KR102491215B1 - Photosensitive coloring composition for forming colored spacer, cured product, colored spacer, and image display device - Google Patents

Abstract

An object of the present invention is to provide a photosensitive coloring composition that can form a pattern having high light-shielding properties and excellent surface smoothness, particularly preferably used for formation of a colored spacer. The photosensitive coloring composition for forming a colored spacer of the present invention includes (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant. It contains, and the said (c) photoinitiator contains the oxime ester type compound represented by following formula (I).

Description

Photosensitive coloring composition for forming colored spacer, cured product, colored spacer, image display device

The present invention relates to a photosensitive coloring composition and the like. In detail, for example, a photosensitive coloring composition suitably used for formation of a colored spacer or the like in a color filter such as a liquid crystal display, a colored spacer obtained by curing the photosensitive colored composition, and an image display device including the colored spacer. it's about

A liquid crystal display (LCD) utilizes the property that the alignment of liquid crystal molecules is switched by turning on/off the voltage to the liquid crystal. On the other hand, each member which comprises the cell of LCD is formed by the method using the photosensitive composition represented by the photolithography method in many cases. Since this photosensitive composition is easy to form a fine structure and easy to process on a substrate for a large screen, its application range tends to widen further in the future.

However, in an LCD manufactured using the photosensitive composition, the voltage applied to the liquid crystal is not maintained due to the electrical properties of the photosensitive composition itself or the influence of impurities contained in the photosensitive composition, thereby causing problems such as uneven display of the display. There are times when In particular, in a member closer to the liquid crystal layer in a color liquid crystal display, for example, a so-called columnar spacer, photo spacer, etc. used to keep the distance between two substrates constant in a liquid crystal panel, Its influence is great.

Conventionally, when a spacer having no light-shielding property is used for a TFT-type LCD, a TFT as a switching element may malfunction due to light passing through the spacer. In order to prevent this, for example, Patent Literature 1 describes a method of using a spacer (colored spacer) having light-shielding properties.

On the other hand, in recent years, with a change in the structure of a panel, a method of collectively forming colored spacers having different heights by a photolithography method has been proposed. For example, in Patent Document 2, a plurality of specific pigment species having different light absorption characteristics are combined to ensure a balance between light absorption in the ultraviolet region and visible region, thereby controlling the shape and level difference while maintaining the light-shielding property and the voltage retention of the liquid crystal. , it is disclosed that adhesion to a substrate can be realized. Further, Patent Literature 3 discloses that a plurality of types of organic color pigments are used for the pigment, and Patent Literature 4 discloses that organic black pigments are used.

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

Japanese Unexamined Patent Publication No. 8-234212 International Publication No. 2013/115268 Korean Patent Registration No. 10-1266295 Japanese Published Patent Publication No. 2014-529652 Japanese Patent Publication No. 2014-500852

In recent years, there has been a demand for further enhancing the light-shielding properties of colored spacers with changes in panel structures. As a method of making light-shielding property high, the method of using a pigment with high light-shielding property, the method of making the pigment content ratio high in a photosensitive coloring composition, etc. are mentioned. As a result of investigation by the present inventors, in the photosensitive coloring compositions described in Patent Literatures 2 to 4, the light-shielding properties of the colored spacers were further increased by using a pigment with high light-shielding properties in combination, etc. As a result, the film surface vicinity and the film bottom were It was found that the crosslinking density difference increased in the vicinity, and wrinkles were generated on the surface of the coating film due to heat shrinkage in the heat curing process, resulting in insufficient surface smoothness.

On the other hand, Patent Document 5 describes using a specific oxime ester compound as a photopolymerization initiator for a color resist. However, in Patent Document 5, it is neither described nor suggested to use this oxime ester compound as a photopolymerization initiator for a photosensitive coloring composition for forming a colored spacer. Therefore, when this oxime ester compound is used as a photopolymerization initiator for a photosensitive coloring composition for forming a colored spacer, it is not clear what kind of effect it has.

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

As a result of the present inventors earnestly examining in order to solve the said subject, in the photosensitive coloring composition, by using a specific oxime ester type compound as a photoinitiator, it discovered that the said subject was solvable, and reached this invention.

That is, the present invention has the constitutions of the following [1] to [14].

[1] A photosensitive coloring composition for forming a colored spacer 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 as,

The said (c) photoinitiator contains the oxime ester type compound represented by following formula (I), The photosensitive coloring composition for colored spacer formation characterized by the above-mentioned.

[Formula 1]

(In the above general formula (I),

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

R ² represents an alkanoyl group which may have a substituent or an aryloyl 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 each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. However, at least any one of R5 and ^R6 is a naphthalene ring which ^may have a substituent.

At least one of R ¹ and R ⁴ has an -OR ⁷ group as a substituent. provided that R ⁷ represents a halogenoalkyl group.

X represents a direct bond or a carbonyl group.

Z represents a direct bond or a carbonyl group.)

[2] The coloring according to [1], wherein the coloring agent (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. A photosensitive coloring composition for spacer formation.

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

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

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

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

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

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

[5] The content ratio of at least one pigment selected from the group consisting of a blue pigment and a purple pigment relative to 100 parts by mass of the colorant (a) is 20 parts by mass or more and 90 parts by mass or less, [2] to [4] The photosensitive colored composition for forming a colored spacer according to any one of the above.

[6] The photosensitive coloring composition for forming a colored spacer according to any one of [1] to [5], wherein the coloring agent (a) 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 formula (1), a geometric isomer thereof, a salt thereof, or a salt of a geometric isomer thereof.

[Formula 2]

(In the above formula (1), R ¹¹ and R ¹⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;

R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are independently of each other 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 ;

In addition, 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 , They may be directly bonded to each other or bonded to each other by an oxygen atom, a sulfur atom, NH or NR ²¹ bridge;

R ²¹ and R ²² are each independently an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, a cycloalkenyl group of 3 to 12 carbon atoms, or an alkynyl group of 2 to 12 carbon atoms)

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

[9] The photosensitive coloring composition for forming a colored spacer according to [1], wherein the coloring agent (a) 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 purple pigment.

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

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

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

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

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

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

[13] The photosensitive coloring composition for forming a colored spacer according to any one of [9] to [12], wherein the carbon black content ratio with respect to 100 parts by mass of the colorant (a) is 5 parts by mass 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 cured coating film has an optical density per 1 µm of film thickness of 1.0 or more.

[15] The photosensitive coloring composition for forming colored spacers according to any one of [1] to [14], which is used to collectively form colored spacers having different heights by a photolithography method.

[16] A cured product obtained by curing the photosensitive colored composition for forming a colored spacer according to any one of [1] to [15].

[17] A colored spacer formed from the cured product according to [16].

[18] An image display device provided with the colored spacer according to [17].

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

Hereinafter, although embodiments of the present invention will be described in detail, the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist.

In the present invention, "(meth)acryl" means "acryl and/or methacryl", and the same applies to "(meth)acrylate" and "(meth)acryloyl".

"(Co)polymer" means containing both a homopolymer (homopolymer) and a copolymer (copolymer), and includes "acid (anhydride)", "(anhydride)... "Acid" means containing both an acid and its anhydride. In the present invention, "acrylic resin" means a (co)polymer containing (meth)acrylic acid and a (co)polymer containing (meth)acrylic acid ester having a carboxyl group.

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

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

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

In addition, in this invention, "amine value" represents the amine value in terms of effective solid content, and is a value expressed by the mass of the base amount and equivalent KOH per 1g of solid content of a dispersing agent, unless there is particular notice. In addition, the measuring method is mentioned later. On the other hand, "acid value" shows an 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 expressed by "mass" has the same meaning as the percentage or part expressed by "weight".

[Photosensitive Coloring Composition]

The photosensitive coloring composition of the present invention,

(a) colorant

(b) Alkali-soluble resin

(c) photopolymerization initiator

(d) ethylenically unsaturated compounds

(e) solvent

(f) dispersant

contains as an essential component. In addition, the photosensitive coloring composition of the present invention, if necessary, further contains other compounding components such as adhesion improvers such as silane coupling agents, applicability improvers, development improvers, ultraviolet absorbers, antioxidants, surfactants, pigment derivatives, etc. In general, each compounding component is used in a state in which it is dissolved or dispersed in a solvent.

Since the photosensitive coloring composition of the present invention can form patterns with high light-shielding properties and excellent surface smoothness, it can be preferably used for forming colored spacers, in short, as a photosensitive coloring composition for forming colored spacers. can

On the other hand, since characteristics such as light-shielding properties and surface smoothness are also required for applications other than colored spacers, such as barrier ribs of light emitting portions of organic EL display devices, particularly colored barrier ribs (color banks), they are not limited to colored spacers. can be used without Although the photosensitive coloring composition of this invention is explained in full detail below, unless there is particular notice, both the colored spacer use and the use other than a colored spacer are demonstrated together.

In the photosensitive coloring composition according to the first aspect of the present invention, (a) the coloring agent comprises at least one selected from the group consisting of a red pigment and an orange pigment, and at least one selected from the group consisting of a blue pigment and a purple pigment. It contains and also contains the oxime ester type compound represented by the formula (I) which (c) photoinitiator mentions later.

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

Moreover, the photosensitive coloring composition which concerns on the 3rd aspect of this invention contains the (a) coloring agent containing an organic pigment and carbon black, and (c) the oxime ester type compound represented by the formula (I) which a photoinitiator mentions later contain

On the other hand, the photosensitive coloring composition concerning the 4th aspect of this invention is a photosensitive coloring composition for colored spacer formation, and (c) contains the oxime ester type compound represented by the formula (I) which a photoinitiator mentions later.

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

<(a) colorant>

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

(a) It is preferable to use a pigment as a coloring agent, and as a pigment, an inorganic pigment may be used and an organic pigment may be used. It is preferable to use an organic pigment from the viewpoint of suppressing a drop in the voltage retention of liquid crystal and suppressing absorption of ultraviolet rays to make it easier to control the shape and level difference.

The chemical structure of these pigments is not particularly limited. For example, in addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can also be used. Hereinafter, specific examples of pigments that can be used are indicated by pigment numbers. "C. Terms such as "I. Pigment Red 2" mean color index (C.I.).

As the red pigment, 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 can

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

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

As orange (orange) pigments, 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 these, C. I. Pigment Orange 38 and 71 are preferable. Moreover, it is preferable to use C. I. Pigment Orange 43, 64, and 72 from a point of dispersibility and light-shielding property. When the photosensitive coloring composition according to the first aspect of the present invention is cured with ultraviolet rays, it is preferable to use those having a low ultraviolet absorption rate as the orange pigment. From this point of view, it is more preferable to use C. I. Pigment Orange 64 or 72.

As the blue pigment, 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 can be heard

Among these, C. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 are preferred, and C. I. Pigment Blue 15: 6 is more preferred.

Moreover, it is preferable to use C. I. Pigment Blue 15:6, 16, 60 from a point of dispersibility or light-shielding property. When the photosensitive coloring composition according to the first aspect of the present invention is cured with ultraviolet light, it is preferable to use a blue pigment having a low ultraviolet absorbance. From this point of view, it is more preferable to use C. I. Pigment Blue 60.

As a purple pigment, 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 these, C. I. Pigment Violet 19 and 23 are preferable, and C. I. Pigment Violet 23 is more preferable.

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

Examples of organic color pigments that can be used other than red pigments, orange pigments, blue pigments, and purple pigments include green pigments and yellow pigments.

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. can Among these, C. I. Pigment Green 7 and 36 are preferable.

As the yellow pigment, 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 1, 128, 129, 133, 134 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170 , 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191 : 1, 192, 193, 194, 195, 196, 197, 198, 199 , 200, 202, 203, 204, 205, 206, 207, 208.

Among these, C. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 are preferred, and C. I. Pigment Yellow 83, 138, 139, 150, 180 are more preferred. there is.

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

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

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

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

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

Moreover, from the viewpoint of light-shielding properties and control of shape and level difference, it is preferable that the red pigment is the following (1), it is preferable that the orange pigment is the following (2), and the blue pigment is the following (3) It is preferable, and it is preferable that the purple pigment is the following (4).

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

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

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

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

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

In addition to these color pigments, a black colorant can be further used.

Among the black colorants, it is preferable to use an organic black pigment from the viewpoint of suppressing the decrease in the voltage retention of the liquid crystal and also suppressing the absorption of ultraviolet rays to make it easy to control the shape and level difference. In particular, from the viewpoint of light-shielding properties, It is preferable to use the organic black pigment which is the salt of the compound represented by following formula (1), its geometric isomer, its salt, or its geometric isomer.

[Formula 3]

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

R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are independently of each other 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 ;

In addition, 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 , They may be directly bonded to each other or bonded to each other by an oxygen atom, a sulfur atom, NH or NR ²¹ bridge;

R ²¹ and R ²² are each independently an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, a cycloalkenyl group of 3 to 12 carbon atoms, or an alkynyl group of 2 to 12 carbon atoms.

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

[Formula 4]

When the compound represented by the general formula (1) is anionic, its charge can be transferred to any known suitable cation, for example, a metal, organic, inorganic or metal-organic cation, specifically an alkali metal, an alkaline earth metal, or a transition metal. , primary ammonium, secondary ammonium, tertiary ammonium such as trialkyl ammonium, quaternary ammonium such as tetraalkyl ammonium, or salts compensated with organometallic complexes are preferred. Moreover, when the geometric isomer of the compound represented by General formula (1) is anionic, it is preferable that it is the same salt.

Since there exists a tendency for a shielding rate to become high in the substituent of General formula (1) and their definition, the following is preferable. This is because the following substituents do not absorb and are considered to have no effect on the hue of the pigment.

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

R ¹³ and R ¹⁸ are each independently preferably a hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , a bromine atom, a chlorine atom, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N(CH ₃ )(C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ^— , more preferably hydrogen atom or SO ₃ H.

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

Preferably, at least one combination selected from the group consisting of R ¹¹ and R ¹⁶ , R ¹² and R ¹⁷ , R ¹³ and R ¹⁸ , R ¹⁴ and R ¹⁹ , and R ¹⁵ and R ²⁰ is the same, more preferably Specifically, 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 the C1-C12 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2 -Ethylhexyl group, nonyl group, decyl group, undecyl group or dodecyl group.

The cycloalkyl group having 3 to 12 carbon atoms is, for example, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a cyclopropyl group, a norbornyl group, a bor A yl group, a norcaryl group, a caryl group, a menthyl group, a norphinyl group, a phynyl group, a 1-adamantyl group or a 2-adamantyl group.

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

Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl group, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, 2,4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4(10)-thuyen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene an en-1-yl group, a 7,7-dimethyl-2,4-norcaradien-3-yl group or a camphenyl group.

An alkynyl group having 2 to 12 carbon atoms, for example, 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, 2-methyl-3-butyn-2-yl group, 1,4-pentadiin-3-yl group, 1,3-pentadiin-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl group, Trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadin-5-yl group, 1-octyn-8-yl group, 1-nonin-9-yl group, 1-decyne- 10-yl group or 1-dodecyn-12-yl group.

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

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

[Formula 5]

As a specific example of such an organic black pigment, Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) is exemplified as a trade name.

This organic black pigment is preferably used after being dispersed by a dispersant, solvent and method described later. In addition, when the sulfonic acid derivative of the general formula (2) is present at the time of dispersion, the dispersibility and storage properties may be improved.

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, and perylene black. there is. Among these, carbon black can be preferably used from the viewpoint of light-shielding properties and image characteristics. As an example of carbon black, the following carbon blacks are mentioned.

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

Made by Degussa: Printex (registered trademark, hereinafter the same) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

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

Made by Colombian Carbon Co.: RAVEN (registered trademark, hereinafter the same) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1010N1000, RAVEN RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

As the carbon black, one coated with a resin may be used. When carbon black coated with resin is used, there is an effect of improving adhesion to a glass substrate and volume resistance value. As carbon black coated with resin, the carbon black described in Unexamined-Japanese-Patent No. 09-71733 etc. can be used suitably, for example. From the viewpoint of volume resistivity or permittivity, resin-coated carbon black is preferably used.

It is preferable that the total content of Na and Ca is 100 ppm or less as the carbon black subjected to the coating treatment with the resin. Carbon black is usually produced from raw material oil or combustion oil (or gas), reaction stop water or granulation water, Na, Ca, K, Mg, Al, Ash content with Fe or the like as a composition is contained in the order of percent. Of these, Na and Ca are generally contained at least several hundred ppm each, but reducing them tends to suppress permeation into the transparent electrode (ITO) and other electrodes and prevent electrical short circuits.

As a method of reducing the content of these ash containing Na or Ca, as raw material oil or fuel oil (or gas) and reaction stop water at the time of producing carbon black, carefully selecting those with the lowest content of these as possible, and structure It is possible by reducing the addition amount of the alkali substance that adjusts as much as possible. As another method, a method of dissolving and removing Na or Ca by washing the carbon black discharged from the furnace with water, hydrochloric acid, or the like is exemplified.

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

Moreover, it is preferable that resin-coated carbon black is so-called acidic carbon black of pH 6 or less. Since the dispersion diameter in water (agglomerate diameter) becomes small, it is possible to coat even microscopic units, which is preferable. It is also preferable that the average particle size is 40 nm or less and the amount of dibutyl phthalate (DBP) absorbed is 140 ml/100 g or less. By setting it within the above range, there is a tendency for a coating film having good light-shielding properties to be obtained. The average particle diameter means the number average particle diameter, and is obtained by particle image analysis in which photographs taken at tens of thousands of times by electron microscopy are taken at various fields of view, and about 2000 to 3000 particles of these photographs are measured by an image processing device. means the equivalent diameter of a circle.

The method for preparing the carbon black coated with the resin is not particularly limited. For example, after appropriately adjusting the blending amount of the carbon black and the resin, 1. Mixing the resin with a solvent such as cyclohexanone, toluene, or xylene, and heating A mixture of the dissolved resin solution and a suspension of carbon black and water is mixed and stirred, the carbon black and water are separated, the water is removed, and the resulting composition is heated and kneaded to form a sheet, pulverized, and then dried. Way ; 2. A method in which the resin solution and suspension prepared in the same manner as above are mixed and stirred to granulate carbon black and resin, and then the obtained granular material is separated and heated to remove residual solvent and water; 3. A carboxylic acid such as maleic acid or fumaric acid is dissolved in the above-exemplified solvent, carbon black is added, mixed, and dried, and the solvent is removed to obtain a carboxylic acid impregnated carbon black. a method of adding and dry blending; 4. A suspension is prepared by high-speed stirring of a reactive group-containing monomer component constituting the resin to be coated and water, cooling after polymerization to obtain a reactive group-containing resin from the polymer suspension, carbon black is added thereto, kneaded, and carbon A method of reacting black with a reactive group (grafting carbon black), cooling and grinding, and the like can be employed.

The type of resin to be coated is not particularly limited, but synthetic resins are common, and resins having a benzene ring in the structure have a stronger amphoteric surfactant function, so they are preferable in terms of dispersibility and dispersion stability.

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

The coating amount of the resin relative to the carbon black is preferably 1 to 30% by mass with respect to the total amount of the carbon black and the resin, and when the amount is equal to or more than the lower limit, the coating tends to be sufficient. On the other hand, there is a tendency that adhesion between resins is prevented and dispersibility can be made good by setting it below the said upper limit.

Carbon black coated with resin in this way can be used as a light-shielding material for a colored spacer by a conventional method, and a color filter containing the colored spacer as a component can be produced by a conventional method. If such carbon black is used, it tends to be able to achieve a colored spacer with a high light-shielding factor and a low surface reflectance at low cost. It is also presumed that by coating the carbon black surface with a resin, there is also a function of trapping Ca or Na in the carbon black.

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

Azo dyes include, for example, C. I. Acid Yellow 11, C. I. Acid Orange 7, C. I. Acid Red 37, C. I. Acid Red 180, C. I. Acid Blue 29, C. I. Direct Red 28, C. I. Direct Red 83, C. I. Direct Yellow 12, C. I. Direct Orange 26, C. I. Direct Green 28, C. I. Direct Green 59, C. I. Reactive Yellow 2, C. I. Reactive Red 17, C. I. Reactive Red 120, C. I. Reactive Black 5, C. I. Disperse Orange 5, C. I. Disperse Red 58 , C. I. Disperse Blue 165, C. I. Basic Blue 41, C. I. Basic Red 18, C. I. Mordant Red 7, C. I. Mordant Yellow 5, C. I. Mordant Black 7, and the like.

Examples of anthraquinone-based dyes include C. I. Vat Blue 4, C. I. Acid Blue 40, C. I. Acid Green 25, C. I. Reactive Blue 19, C. I. Reactive Blue 49, C. I. Disperse Red 60, C. I. Disperse Blue 56, C. I. Disperse Blue 60 etc. are mentioned.

In addition, as phthalocyanine-based dyes, for example, C. I. Pad Blue 5, etc., as quinoneimine-based dyes, for example, C. I. Basic Blue 3, C. I. Basic Blue 9, etc., as quinoline-based dyes, for example, C. I. Solvent Yellow 33, C. I. Acid Yellow 3, C. I. Disperse Yellow 64, etc. as nitro dyes, for example, C. I. Acid Yellow 1, C. I. Acid Orange 3, C. I. Disperse Yellow 42 and the like.

These pigments are preferably used after being dispersed 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 standard for the average particle diameter is the number of pigment particles.

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

On the other hand, (a) the coloring agent used in the photosensitive coloring composition according to the second aspect of the present invention contains an organic black pigment which is a compound represented by the above general formula (1), a geometric isomer thereof, a salt thereof, or a salt of a geometric isomer thereof do. Thus, it is thought that a low dielectric constant and a high light blocking factor can be realized by containing a specific organic black pigment.

(a) The coloring agent used in the 2nd aspect of this invention may contain other coloring agents other than the said organic black pigment. As the other colorant, it is preferable to use a pigment, and the pigment may be an organic pigment or an inorganic pigment, but it suppresses a decrease in the voltage retention of liquid crystal and suppresses absorption of ultraviolet rays to facilitate control of shape and level difference. From a viewpoint, it is more preferable to use an organic pigment. As the organic pigment, those listed in the first aspect can be used.

In addition to these pigments, other black colorants can be further used.

Among other black colorants, from the viewpoint of suppressing the drop in the voltage retention of liquid crystal and suppressing the absorption of ultraviolet rays to make it easier to control the shape and level difference, other than those represented by the general formula (1), other organic Preference is given to using a black pigment. Other organic black pigments include aniline black, perylene black, and cyanine black.

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

In addition, the coloring agent (a) used in the photosensitive coloring composition according to the third aspect of the present invention contains an organic pigment and carbon black. In this way, by using organic pigments with little absorption of ultraviolet rays, it is easy to control the shape and level difference, and high light-shielding properties can be achieved by using carbon black in addition to organic pigments.

Although the kind of organic pigment is not specifically limited, From an adhesive viewpoint, it is preferable to contain at least 1 sort(s) selected from the group which consists of a red pigment, an orange pigment, a blue pigment, and a purple pigment. As a red pigment, an orange pigment, a blue pigment, and a purple pigment, what was mentioned in the 1st aspect can be used.

Among these, it is preferable that it contains at least 1 or more types of the following (1)-(4) from a viewpoint of light-shielding property and control of a shape and level difference.

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

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

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

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

Among these, it is preferable to use a blue pigment and/or a purple pigment from the viewpoint of light-shielding properties in the visible region, particularly in the long wavelength region. In particular, in the absorption spectrum of carbon black, the absorbance decreases from a short wavelength to a long wavelength, and the absorbance in the ultraviolet region is higher than that of organic pigments, so from the viewpoint of achieving both light-shielding properties and platemaking properties, a blue pigment and/or a purple pigment It is preferable to use together with carbon black, and it is more preferable to use together a blue pigment and a purple pigment and carbon black.

Moreover, it is preferable that an organic pigment contains an organic black pigment from a light-shielding viewpoint. As an organic black pigment, what was mentioned in the 1st aspect can be used. Moreover, other organic color pigments mentioned in the first aspect, other black color materials, dyes, and the like can also be used.

In addition, the (a) coloring agent used in the photosensitive coloring composition for forming a colored spacer according to the fourth aspect of the present invention is not particularly limited as long as it can form a desired colored spacer. For example, from the viewpoint of suppressing absorption of ultraviolet rays and making it easy to control the shape and level difference, as a first aspect, at least one selected from the group consisting of red pigments and orange pigments, blue pigments and purple pigments described above. It is preferable to set it as containing at least 1 sort(s) selected from the group which consists of.

Thus, as the (a) coloring agent used in the photosensitive coloring composition for forming a colored spacer according to the fourth aspect, the one described as the (a) coloring agent used in the photosensitive coloring composition according to the first aspect can be applied, and What was described as the (a) coloring agent used in the photosensitive coloring composition concerning the 2nd or 3rd aspect can also be applied.

On the other hand, in the photosensitive coloring composition for forming a colored spacer according to the fourth aspect, from the viewpoint of light-shielding properties, it is preferable to contain at least a black colorant, and more preferably to contain at least carbon black. Moreover, it is more preferable to contain at least the said organic black pigment from a viewpoint of suppressing the fall of the voltage retention of a liquid crystal, and suppressing absorption of an ultraviolet-ray, and making it easy to control a shape and a level difference. Carbon black and organic black pigment may be used together from the viewpoint of coexistence of light-shielding properties, suppression of a drop in voltage retention of liquid crystals, and controllability of shapes and levels.

In the photosensitive coloring composition for forming a colored spacer according to the fourth aspect, as the blending amount of these coloring agents, a preferable value in the photosensitive coloring composition of the present invention described later can be employed. Moreover, it can also be adjusted suitably according to the required optical density, International Publication No. 2013/062011, International Publication No. 2013/115268, Japanese Patent Publication No. 2014-534460, Japanese Patent Publication No. 2014-529652, Japanese Unexamined Patent The values described in Publication No. 2014-146029, International Publication No. 2013/179237, and Japanese Unexamined Patent Publication No. 2011-107707 can also be employed.

<(b) alkali-soluble resin>

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

As the (b) alkali-soluble resin used in the present invention, in particular, the following alkali-soluble resin (b1) and/or alkali-soluble resin (b2) (hereinafter sometimes referred to as “carboxyl group-containing epoxy (meth)acrylate resin”) is preferably used from the viewpoint of excellent platemaking properties.

<Alkali-soluble resin (b1)>

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

<Alkali-soluble resin (b2)>

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

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

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

[Formula 6]

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

[Formula 7]

In the above general formula (B2), b represents an average value and represents a number from 0 to 10. R ¹²¹ represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 8 carbon atoms, a cycloalkyl group of 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.

[Formula 8]

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

[Formula 9]

[Formula 10]

In the general formulas (B3-1) and (B3-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, or a carbon number which may have a substituent An alkyl group of 1 to 12 or a phenyl group which may have a substituent is shown. * represents a bonding hand.

[Formula 11]

In the 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 greater than or equal to 0;

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

Examples of the α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and (meth)acrylic acid. α-position haloalkyl, alkoxyl, halogen, nitro, monocarboxylic acids such as cyano substituents, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipic acid, 2- (meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxypropylsuccinic acid, 2 -(meth)acryloyloxypropyladipic acid, 2-(meth)acryloyloxypropyltetrahydrophthalic acid, 2-(meth)acryloyloxypropylphthalic acid, 2-(meth)acryloyloxypropylmale Acid, 2-(meth)acryloyloxybutylsuccinic acid, 2-(meth)acryloyloxybutyladipic acid, 2-(meth)acryloyloxybutylhydrophthalic acid, 2-(meth)acryloyloxy Lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone are added to butylphthalic acid, 2-(meth)acryloyloxybutylmaleic acid (meth), and acrylic acid. a monomer obtained by adding an acid (anhydride) such as (anhydride) succinic acid, (anhydride) phthalic acid, or (anhydride) maleic acid to a monomer or hydroxyalkyl (meth)acrylate or pentaerythritol tri(meth)acrylate; (meth)acrylic acid dimer etc. are mentioned.

Among these, (meth)acrylic acid is particularly preferred in terms of sensitivity.

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

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

In addition, the epoxy resin, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group, and the esterification catalyst may be used alone or in combination of two or more. You can do it.

The amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1 equivalent of the epoxy group of the epoxy resin. to 1.1 equivalents.

When the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group is small, the amount of unsaturated group introduced becomes insufficient, and the subsequent reaction with the polybasic acid and/or its anhydride becomes insufficient. It is also not advantageous that a large amount of epoxy groups remain. On the other hand, when the amount used is large, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group remains as an unreacted substance. In either case, the tendency for hardening characteristics to deteriorate is confirmed.

Examples of polybasic acids and/or their anhydrides include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetra. One or two or more selected from hydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

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

A known method can also be used for the addition reaction of a polybasic acid and/or its anhydride, and an addition reaction of an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin Under the same conditions, the reaction can be continued to obtain the desired product.

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

In the addition reaction of this polybasic acid and/or its anhydride, polyfunctional alcohols such as trimethylolpropane, pentaerythritol, and dipentaerythritol may be added to introduce a multibranched structure.

A carboxyl group-containing epoxy (meth)acrylate resin is usually prepared by adding a polybasic acid and/or an anhydride thereof to a reaction product of an epoxy resin and an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group. After mixing, or after mixing a polybasic acid and/or its anhydride and a polyfunctional alcohol with a reactant of an epoxy resin and an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group, It is obtained by heating.

In this case, the order of mixing the polybasic acid and/or its anhydride with the polyfunctional alcohol is not particularly limited. By heating, polybasic acids and/or polybasic acids and/or polybasic acids and/or polybasic acids and/or their Anhydride reacts with addition.

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

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

Moreover, you may use it, replacing some of the above-mentioned carboxyl group-containing epoxy (meth)acrylate resin with another binder resin. That is, you may use together the carboxyl group-containing epoxy (meth)acrylate resin and another binder resin. In this case, the ratio of the carboxyl group-containing epoxy (meth)acrylate resin in the (b) alkali-soluble resin is preferably 50% by mass or more, particularly 80% by mass or more.

Other binder resins that can be used in combination with the carboxyl group-containing epoxy (meth)acrylate resin are not limited, and may be selected from resins commonly used in photosensitive coloring compositions. For example, the binder resin of Unexamined-Japanese-Patent No. 2007-271727, Unexamined-Japanese-Patent No. 2007-316620, Unexamined-Japanese-Patent No. 2007-334290 etc. are mentioned. In addition, all other binder resins may be used individually by 1 type, and may be used in combination of 2 or more type.

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

As the acrylic resin, for example, an ethylenically unsaturated monomer having at least one carboxyl group (hereinafter referred to as "unsaturated monomer (b1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (b2)" referred to as) can be mentioned.

Examples of the unsaturated monomer (b1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; Mono[(meth)acryloyloxyalkyl] of divalent or higher polyhydric carboxylic acids such as succinate mono[2-(meth)acryloyloxyethyl] and phthalate mono[2-(meth)acryloyloxyethyl] ester; mono(meth)acrylates of polymers having carboxyl groups and hydroxyl groups at both terminals such as ω-carboxypolycaprolactone mono(meth)acrylate; p-vinyl benzoic acid etc. are mentioned.

These unsaturated monomers (b1) can be used individually or in mixture of 2 or more types.

Moreover, as an unsaturated monomer (b2), N-position substituted maleimide like N-phenyl maleimide and N-cyclohexyl maleimide, for example; aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene;

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

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane vinyl ethers such as; and macromonomers having mono(meth)acryloyl groups at the ends of polymer molecular chains such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane.

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

As a specific example of the copolymer of an unsaturated monomer (b1) and an unsaturated monomer (b2), For example, Unexamined-Japanese-Patent No. 7-140654, Unexamined-Japanese-Patent No. 8-259876, Unexamined-Japanese-Patent No. 10 -31308, Japanese Unexamined Patent Publication No. Hei 10-300922, Japanese Unexamined Patent Publication No. Hei 11-174224, Japanese Unexamined Patent Publication No. Hei 11-258415, Japanese Unexamined Patent Publication No. 2000-56118, Japanese Unexamined Patent Publication 2004-101728 and copolymers disclosed in Ho et al.

Although the copolymer of an unsaturated monomer (b1) and an unsaturated monomer (b2) can be manufactured by a well-known method, For example, Unexamined-Japanese-Patent No. 2003-222717, Unexamined-Japanese-Patent No. 2006-259680, International Publication The structure, Mw, and Mw/Mn can also be controlled by a method disclosed in Japanese Patent No. 2007/029871 or the like.

<(c) photopolymerization initiator>

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

The (c) photoinitiator in the photosensitive coloring composition of this invention contains the oxime ester type compound represented by following formula (I). In this way, by containing the oxime ester compound represented by the following formula (I), the light absorbency to long wavelength light is increased by the naphthalene ring contained in the carbazole skeleton, and the crosslinking density inside the coating film can be increased, and Since it has a halogen atom in its structure, it is considered that the compound is easily distributed on the surface of the coating film, and the excessive increase in crosslinking density on the surface of the film due to the influence of oxygen inhibition can be suppressed.

[Formula 12]

In the general formula (I),

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

R ² represents an alkanoyl group which may have a substituent or an aryloyl 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 each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. However, at least any one of R5 and ^R6 is a naphthalene ring which ^may have a substituent.

At least one of R ¹ and R ⁴ has an -OR ⁷ group as a substituent. provided that R ⁷ represents a halogenoalkyl 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, and it is preferable that it is 6 or more. By setting it below the said upper limit, solubility tends to become favorable, and when setting it below the said lower limit, both sensitivity and solubility tend to become easy.

An aromatic hydrocarbon ring group means an aromatic hydrocarbon ring having one free valence. The aromatic hydrocarbon ring of the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, and a benzpyrene ring. , chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.

In addition, an 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, and examples thereof include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, Oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring , phenanthridine ring, benzoimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like.

As the substituent which an aromatic ring group may have, an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a halogenoalkyl group (an alkyl group in which part or all of hydrogen atoms are substituted with halogen atoms), a halogenoalkoxy group (some or all of hydrogen atoms are alkoxy group substituted with a halogen atom), etc., and a halogen atom, a halogenoalkyl group, or a halogenoalkoxy group is preferable from the viewpoint of surface curability, and unsubstituted is preferable from the viewpoint of ease of synthesis.

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

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

As a specific example of an alkanoyl group, an acetyl group, a propanoyl group, a butanoyl group, etc. are mentioned, Among these, from a viewpoint of a sensitivity, an acetyl group or a propanoyl group is preferable, and an acetyl group is more preferable.

As the substituent that the alkanoyl group may have, a hydroxyl group, an alkoxy group, a halogen atom, etc. are exemplified, and unsubstituted is preferable from the viewpoint of sensitivity.

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

A benzoyl group, a methylbenzoyl group, a naphthoyl group etc. are mentioned as a specific example of an aryloyl group, Among these, from a viewpoint of a sensitivity, a benzoyl group is more preferable.

A hydroxyl group, an alkoxy group, a halogen atom etc. are mentioned as a substituent which an aryloyl group may have, and it is preferable that it is unsubstituted from a viewpoint of a sensitivity.

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 still more preferably an acetyl group.

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

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

Examples of the substituent that the alkyl group may have include a hydroxyl group, an alkoxy group, a halogen atom, and a phosphoric acid group, and from the viewpoint of ease of synthesis, unsubstituted ones are more preferred.

Among these, from a solubility viewpoint, R ³ is preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group, and still more preferably a 2-ethylhexyl group.

Examples of the aromatic ring group for R ⁴ include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. 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, and it is preferable that it is 6 or more. By setting it below the said upper limit, solubility tends to become favorable, and when setting it below the said lower limit, both sensitivity and solubility tend to become easy.

An aromatic hydrocarbon ring group means an aromatic hydrocarbon ring having one free valence. The aromatic hydrocarbon ring of the aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, and a benzpyrene ring. , chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.

In addition, an aromatic heterocyclic group means an aromatic heterocyclic ring having one free valency. 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, p Rolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, benzoimidazole ring, perimidine ring, quinazoline ring, A quinazolinone ring, an azulene ring, etc. are mentioned.

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

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

R ⁵ and R ⁶ each independently represent a benzene ring which may have a substituent or a naphthalene ring. However, at least any one of R5 and ^R6 is a naphthalene ring which ^may have a substituent. Specific combinations include a combination in which R ⁵ is a benzene ring which may have a substituent, and R ⁶ is 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 a benzene ring, a combination in which R ⁵ is a naphthalene ring which may have a substituent, and R ⁶ is a naphthalene ring which may have a substituent are exemplified.

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

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

On the other hand, when R ⁵ is a naphthalene ring which may have a substituent, the X, N atom and R ⁶ bonded to R ⁵ in formula (I) may 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 the N atom is bonded to the 2-position. and an embodiment in which X is bonded to the 6-position.

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 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 and the N atom is bonded to the 2-position. and an embodiment in which Z is bonded to the 6-position.

Examples of the substituents that the benzene ring or naphthalene ring may have in R ⁵ and R ⁶ include hydroxyl groups, alkoxy groups, halogen atoms, and the like, and unsubstituted ones are more preferred from the viewpoint of sensitivity.

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

Although R ⁷ represents a halogenoalkyl group, the number of carbon atoms of the halogenoalkyl group in R ⁷ is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more from the viewpoint of solubility. Moreover, from a compatible viewpoint, it is preferably 10 or less, more preferably 7 or less, and still more preferably 5 or less.

The carbon chain in the halogenoalkyl group may be straight, branched, or cyclic, but from the viewpoint of ease of manufacture, a straight chain is preferable.

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

Specific examples of the halogenoalkyl group include a 2,2,3,3-tetrafluoropropyl group, a 2,2,2-trifluoroethyl group, a 2,2,3,3,4,4,5,5- An octafluoropentyl group etc. are mentioned, Among these, a 2,2,3,3- tetrafluoropropyl group is more preferable from a viewpoint of manufacture ease.

As the substituent which the halogenoalkyl group may have, a hydroxyl group, an alkoxy group, etc. are mentioned, and unsubstituted is preferable from a viewpoint of manufacture ease.

X represents a direct bond or a carbonyl group, but is preferably a direct bond from the viewpoint of adhesiveness, and preferably a carbonyl group from the viewpoint of sensitivity.

Moreover, although Z represents a direct bond or a carbonyl group, it is preferable that it is a direct bond from a viewpoint of adhesiveness, and it is preferable that it is a carbonyl group from a viewpoint of sensitivity.

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

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

(c) The photoinitiator in the photosensitive coloring composition of this invention contains the oxime ester type compound represented by the said General formula (I), but may further contain another photoinitiator.

Examples of other photopolymerization initiators include metallocene compounds containing titanocene compounds described in Japanese Unexamined Patent Publication No. 59-152396 and Japanese Unexamined Patent Publication No. 61-151197; Hexaarylbiimidazole derivatives described in Japanese Unexamined Patent Publication No. 2000-56118; N-aryl-α-amino acids and N-aryl-α-amino acids, such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-phenylglycine described in Japanese Unexamined Patent Publication No. 10-39503 , radical activators such as N-aryl-α-amino acid esters, and α-aminoalkylphenone derivatives; The oxime ester derivative described in Unexamined-Japanese-Patent No. 2000-80068, Unexamined-Japanese-Patent No. 2006-36750, International Publication No. 2008/075564, International Publication No. 2009/131189, etc. are mentioned.

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

To the photopolymerization initiator, if necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source and a polymerization accelerator can be blended for the purpose of increasing the sensitivity. As the sensitizing dye, the xanthene dye described in Japanese Unexamined Patent Publication No. Hei 4-221958 and Japanese Unexamined Patent Publication Hei 4-219756, Japanese Unexamined Patent Publication No. Hei 3-239703, and Japanese Unexamined Patent Publication No. Hei 5-289335 A coumarin dye having a heterocyclic ring, a 3-ketocoumarin compound described in Japanese Unexamined Patent Publication No. Hei 3-239703 and Japanese Unexamined Patent Publication Hei 5-289335, a pyrromethene dye described in Japanese Unexamined Patent Publication No. Hei 6-19240, In addition, Japanese Unexamined Patent Publication No. 47-2528, Japanese Unexamined Patent Publication No. 54-155292, Japanese Unexamined Patent Publication No. 45-37377, Japanese Unexamined Patent Publication No. 48-84183, Japanese Unexamined Patent Publication No. 52-112681 No., Japanese Unexamined Patent Publication No. 58-15503, Japanese Unexamined Patent Publication No. 60-88005, Japanese Unexamined Patent Publication No. 59-56403, Japanese Unexamined Patent Publication No. 2-69, Japanese Unexamined Patent Publication No. 57-168088 No., Japanese Unexamined Patent Publication No. 5-107761, Unexamined-Japanese-Patent No. 5-210240, and Japanese Unexamined Patent Publication No. 4-288818, etc. which have a dialkylaminobenzene skeleton are mentioned.

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

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

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

<(d) ethylenically unsaturated compound>

The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound. (d) Sensitivity is improved by containing an ethylenically unsaturated compound.

The ethylenically unsaturated compound used in the present invention is a compound having at least one ethylenically unsaturated group in its molecule. Specifically, examples thereof include (meth)acrylic acid, (meth)acrylic acid alkyl esters, acrylonitrile, styrene, and monoesters of a carboxylic acid having one ethylenically unsaturated bond and a polyhydric or monohydric alcohol. there is.

In this invention, it is especially preferable to use the polyfunctional ethylenic monomer which has 2 or more ethylenically unsaturated groups in 1 molecule. The number of ethylenically unsaturated groups of the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and more preferably 8 or less. Preferably it is 7 or less. When the value is equal to or higher than the lower limit, the sensitivity tends to be high, and when the value is equal to or lower than the upper limit, the solubility in the solvent tends to be improved.

Examples of polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; and esters obtained by esterification of polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.

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

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

Esters obtained by the esterification reaction of polybasic carboxylic acids and unsaturated carboxylic acids with polyvalent hydroxy compounds are not necessarily single substances, but typical examples include condensates of acrylic acid, phthalic acid, and ethylene glycol, acrylic acid, and maleic acid. A condensate of an acid and diethylene glycol, a condensate of methacrylic acid, terephthalic acid, and pentaerythritol, a condensate of acrylic acid, adipic acid, butanediol, and glycerin, and the like are exemplified.

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

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

Among these, it is preferable to use a (meth)acrylic acid alkyl ester as (d) an ethylenically unsaturated compound from a curable viewpoint, and it is more preferable to use dipentaerythritol hexaacrylate.

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

<(e) Solvent>

The photosensitive coloring composition of the present invention contains (e) a solvent. (e) By containing a solvent, the pigment can be dispersed in the solvent and application 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 others used as needed. Various materials are used in a dissolved or dispersed state in a solvent. Among the solvents, organic solvents are preferred from the viewpoint of dispersibility and coating properties.

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

As such an organic solvent, the following are mentioned, for example.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t- Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl -glycol monoalkyl ethers such as 3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

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

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

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

Alkyl acetates, such as cyclohexanol acetate;

ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether and dihexyl ether;

Acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketones such as ketones, methyl nonyl ketones, and methoxymethylpentanone;

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

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

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

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

Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, Ethyl caprylate, butyl stearate, ethyl benzoate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-methoxypropylpropionate, 3- chain or cyclic esters such as butyl methoxypropionate and γ-butyrolactone;

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

halogenated hydrocarbons such as butyl chloride and amyl chloride;

ether ketones such as methoxymethylpentanone;

nitriles such as acetonitrile and benzonitrile; and the like.

Commercially available organic solvents that correspond to the above include mineral spirits, Barsol #2, Afco #18 solvent, Afco thinner, SoCal solvent No.1 and No.2, Solvesso #150, Shell TS28 solvent, Carbitol , Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve (“Cellosolve” is a registered trademark. The same applies hereinafter), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglyme (all trade names), etc. can be heard

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

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

Among the above organic solvents, glycolalkyl ether acetates are preferred in terms of good balance in coating properties, surface tension, and the like, and relatively high solubility of constituent components in the composition.

Moreover, although glycol alkyl ether acetates may be used independently, you may use other organic solvents together. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferred.

Among them, propylene glycol monomethyl ether is particularly preferred in view of the solubility of constituent components in the composition. In addition, glycol monoalkyl ethers have high polarity, and when the amount of addition is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the colored resin composition obtained thereafter increases, so there is a tendency for glycol monoalkyl ethers in solvents 5 mass % - 30 mass % are preferable, and, as for the ratio, 5 mass % - 20 mass % are more preferable.

Moreover, it is also preferable to use together the organic solvent which has a boiling point of 150 degreeC or more (it may be called a "high boiling point solvent" hereafter). By using such a high boiling point solvent together, the photosensitive coloring composition does not dry well, but there is an effect of preventing the uniform dispersion of the pigment in the composition from being destroyed by rapid drying.

That is, there is an effect of preventing the occurrence of foreign matter defects due to precipitation and solidification of a coloring material or the like at the tip of the slit nozzle, for example. From the viewpoint of such a high effect, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred among the various solvents described above.

The content of the high boiling point solvent in the organic solvent is preferably from 3% by mass to 50% by mass, more preferably from 5% by mass to 40% by mass, particularly preferably from 5% by mass to 30% by mass. By setting it above the lower limit, for example, there is a tendency to suppress the occurrence of foreign matter defects due to precipitation and solidification of colorants or the like at the tip of the slit nozzle, and by setting it below the above upper limit, the drying temperature of the composition is suppressed from slowing down, It tends to be able to suppress problems such as tact defects in the vacuum drying process and pin marks in prebaking.

The high boiling point solvent having a boiling point of 150°C or higher may be glycol alkyl ether acetates or glycol alkyl ethers.

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

<(f) Dispersant>

In the photosensitive coloring composition of the present invention, finely dispersing (a) the colorant and stabilizing the dispersed state are important for securing the stability of quality, and therefore (f) contains a dispersing agent.

(f) As the dispersing agent, a polymeric dispersing agent having a functional group is preferable, and from the viewpoint of dispersion stability, it is a carboxyl group; a phosphoric acid group; sulfonic acid group; or bases thereof; primary, secondary or tertiary amino groups; quaternary ammonium base; A polymeric dispersant having a functional group such as a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, and pyrazine is preferable.

Among them, a primary, secondary or tertiary amino group; quaternary ammonium base; A polymeric dispersant having a basic functional group such as a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, and pyrazine is particularly preferable from the viewpoint that a small amount of the dispersant can be dispersed when dispersing the pigment.

In addition, as the polymer dispersing agent, for example, a urethane-based dispersing agent, an acrylic-based dispersing agent, a polyethyleneimine-based dispersing agent, a polyallylamine-based dispersing agent, a dispersing agent composed of a monomer and a macromonomer having an amino group, a polyoxyethylene alkyl ether-based dispersing agent, polyoxyethylenedi Ester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, and the like are exemplified.

Specific examples of such a dispersant include, as trade names, EFKA (registered trademark. manufactured by BASF), DISPERBYK (registered trademark. manufactured by Big Chemie Co., Ltd.), Disparon (registered trademark. manufactured by Kusumoto Kasei Co., Ltd.), SOLSPERSE (registered trademark. manufactured by Lubrizol Corporation.), KP (produced by Shin-Etsu Chemical Co., Ltd.), Polyflow (produced by Kyoeisha Chemical Co., Ltd.), Ajispur (registered trademark. manufactured by Ajinomoto Corporation.), and the like.

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

The weight average molecular weight (Mw) of the polymeric dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less.

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

In view of dispersibility and storage stability, a polymeric dispersant having a basic functional group and a polyester bond and/or a polyether bond is preferable.

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

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

Examples of the above polyisocyanate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, Aromatic diisocyanates such as tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as dimer acid diisocyanate, isophorone diisocyanate, 4,4' -Methylene bis(cyclohexyl isocyanate), ω,ω'-diisocyanate, alicyclic diisocyanate such as dimethylcyclohexane, xylylene diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate, etc. direction Cyclic aliphatic diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanates such as triisocyanate, tris(isocyanate phenylmethane) and tris(isocyanate phenyl)thiophosphate, trimers thereof, hydrogen adducts, and polyol adducts thereof; and the like.

As the polyisocyanate, a trimer of organic diisocyanate is preferred, and a trimer of tolylene diisocyanate and isophorone diisocyanate are most preferred. These may be used individually by 1 type, and may use 2 or more types together.

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

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 glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and the hydroxyl group at one end of these compounds having 1 to 25 carbon atoms. and those alkoxylated with an alkyl group of , and mixtures of two or more of these.

Examples of the polyether glycol include polyether diols, polyether ester diols, and mixtures of two or more of these. As the polyetherdiol, those obtained by singly or copolymerizing alkylene oxides, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and Mixtures of two or more of them are exemplified.

The polyether ester diol is obtained by reacting an ether group-containing diol or a mixture with another glycol with a dicarboxylic acid or an anhydride thereof, or by reacting an alkylene oxide with polyester glycol, for example, poly(poly Oxytetramethylene) adipate etc. are mentioned.

Polyether glycol is most preferably polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which the hydroxyl group at one terminal of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

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

Examples of polycarbonate glycol include poly(1,6-hexylene)carbonate and poly(3-methyl-1,5-pentylene)carbonate, and examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyolefin glycol. Isoprene glycol etc. are mentioned.

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

The number average molecular weight of the compound 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.

Compounds having an active hydrogen and a tertiary amino group in the same molecule used in the present invention are described.

Examples of the hydrogen atom directly bonded to an active hydrogen, that is, an oxygen atom, a nitrogen atom, or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Atoms are preferred.

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

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

In addition, examples of the nitrogen-containing heterocycle in the case where the tertiary amino group has a nitrogen-containing heterocyclic structure include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, and a benzene ring. Imidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, nitrogen-containing hetero 5-membered ring such as benzothiadiazole ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring , nitrogen-containing hetero 6-membered rings such as an acridine ring and an isoquinoline ring. Among these nitrogen-containing heterocycles, an imidazole ring or a triazole ring is preferable.

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

In addition, if a compound having a triazole ring and an amino group is specifically exemplified, 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1, 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino -1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole, etc. are mentioned.

Among them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3-amino-1,2,4 -Triazoles are preferred.

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

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

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

In the above preparation, a urethanization reaction catalyst is usually used. Examples of the catalyst include tin-based catalysts such as dibutyltindilaurate, dioctyltindilaurate, dibutyltindioctoate and stannous octoate, iron-based catalysts such as iron acetylacetonate and ferric chloride, tri and tertiary amines such as ethylamine and triethylenediamine. These may be used individually by 1 type, and may be used in combination of 2 or more types.

The introduced amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled within the range of 1 to 100 mgKOH/g based on the amine titer after the reaction. More preferably, it is the range of 5-95 mgKOH/g. The amine value is a value obtained by titrating neutralization of a basic amino group with an acid and expressing it in mg number of KOH corresponding to the acid value. When the amine value is lower than the above range, the dispersibility tends to decrease, and when the amine value exceeds the above range, developability tends to decrease.

In addition, in the case where isocyanate groups remain in the polymer dispersant in the above reaction, it is also preferable to break the isocyanate groups with an alcohol or an amino compound because the stability over time of the product is increased.

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. If the molecular weight is less than 1,000, dispersibility and dispersion stability are poor, and if it exceeds 200,000, solubility is lowered, dispersibility is poor, and reaction control becomes difficult.

As the acrylic polymer dispersant, random copolymers and graft copolymers of an unsaturated group-containing monomer having a functional group (the functional group referred to herein is a functional group described above as a functional group contained in the polymer dispersant) and an unsaturated group-containing monomer having no functional group , it is preferred to use a block copolymer. These copolymers can be prepared by known methods.

As the monomer containing an unsaturated group having a functional group, (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxyethylhexane Unsaturated monomers having a carboxyl group such as hydrophthalic acid and acrylic acid dimer, tertiary amino groups such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and quaternary products thereof, and unsaturated monomers having a quaternary ammonium base can be mentioned as a specific example. These may be used individually by 1 type, and may use 2 or more types together.

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

The acrylic polymer dispersant is particularly preferably an A-B or B-A-B block copolymer composed of an A block having a functional group and a B block having no functional group, but in this case, the portion derived from the unsaturated group-containing monomer containing the functional group in the A block In addition to the structure, partial structures derived from unsaturated group-containing monomers that do not contain the above functional groups may be contained, and these may be contained in either random copolymerization or block copolymerization in the A block. Further, the content in the A block of the partial structure not containing a functional group is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.

Although the B block consists of a partial structure derived from an unsaturated group-containing monomer containing no functional group, one B block may contain partial structures derived from two or more types of monomers, and these are random copolymerized in the B block. Or you may contain in any aspect of block copolymerization.

The AB or B-A-B block copolymer is prepared, for example, by a 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 anionic living polymerization method is an anionic polymerization active species, and is represented by, for example, the following scheme.

[Formula 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 greater.

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

[Formula 22]

In the above scheme, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , j and k are each an integer greater than or equal to 1, R ^a is a hydrogen atom or a monovalent organic group, and R ^b is a hydrogen atom different from R ^a or a monovalent organic group.

When synthesizing this acrylic polymer dispersant, Japanese Unexamined Patent Publication No. 9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Ute, Kouichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 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) and the like. there is.

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

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 usually preferably 0.1 to 10 mmol, and good dispersibility can be secured by keeping it within this range. tend to have

In addition, in such a block copolymer, there are cases where amino groups generated during the production process are usually contained, but the amine value is about 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, preferably 10 mgKOH/g or more , More preferably 30 mgKOH/g or more, still more preferably 50 mgKOH/g or more, and also preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably It is 75 mgKOH/g or less.

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

0.5 to 1.5 g of the dispersant sample is precisely weighed in a 100 ml beaker, and dissolved in 50 ml of acetic acid. Using an automatic titrator equipped with a pH electrode, this solution was subjected to neutralization titration with a 0.1 mol/L HClO ₄ acetic acid solution. The inflection point of the titration pH curve is used as the end point of the titration, and the amine titer is determined by the following equation.

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

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

In addition, the acid value of this block copolymer varies depending on the presence or absence and type of the acidic group that is the basis of the acid value, but generally the lower one is preferable, and is usually 10 mgKOH / g or less, and its weight average molecular weight ( Mw) is preferably in the range of 1000 to 100,000. There exists a tendency that favorable dispersibility can be ensured by setting it within the said range.

When it has a quaternary ammonium salt group as a functional group, although it does not specifically limit about the specific structure of a polymer dispersing agent, From a dispersible viewpoint, the repeating unit represented by the following formula (i) (Hereinafter, it may be called "repeating unit (i)". ) is preferred.

[Formula 23]

In the formula (i), R ³¹ to R ³³ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, and among R ³¹ to R ³³ Two or more may be bonded to each other to form a cyclic structure. R ³⁴ is a hydrogen atom or a methyl group. X is a divalent linking group, and Y ^- is a counter anion.

The number of carbon atoms in the alkyl group which may have a substituent in R ³¹ to R ³³ in the formula (i) is not particularly limited, but is usually 1 or more, preferably 10 or less, and more preferably 6 or less.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like. Among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Or it is preferable that it is a hexyl group, and it is more preferable that it is a methyl group, an ethyl group, a propyl group, or a butyl group. Moreover, either a linear form or a branched form may be sufficient. Moreover, you may contain cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group.

The number of carbon atoms in the aryl group which may have a substituent in R ³¹ to R ³³ in the formula (i) is not particularly limited, but is usually 6 or more, preferably 16 or less, and 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, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, or a di It is preferable that it is an ethylphenyl group, and it is more preferable that it is a phenyl group, a methylphenyl group, or an ethylphenyl group.

The number of carbon atoms of the aralkyl group which may have a substituent in R ³¹ to R ³³ in the formula (i) is not particularly limited, but is usually 7 or more, preferably 16 or less, and more preferably 12 or less.

Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenyl isopropylene group. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or It is preferably a phenylbutylene group, and more preferably a phenylmethylene group or a phenylethylene group.

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, R ³¹ and R ³³ are each independently a methyl group or an ethyl group, and R ³² is It is preferably a phenylmethylene group or a phenylethylene group, more preferably R ³¹ and R ³³ are methyl groups, and R ³² is a phenylmethylene group.

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

[Formula 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, and R ³⁵ and R ³⁶ are They may be bonded to each other to form a cyclic structure. R ³⁷ is a hydrogen atom or a methyl group. Z is a divalent linking group.

Moreover, as an alkyl group which may have a substituent in R ³⁵ and R ³⁶ in the formula (ii), those exemplified as R ³¹ to R ³³ in the formula (i) can be preferably employed.

Similarly, as the aryl group which may have a substituent in R ³⁵ and R ³⁶ in the formula (ii), those exemplified as R ³¹ to R ³³ in the formula (i) can be preferably employed. Moreover, as an aralkyl group which may have a substituent in R ³⁵ and R ³⁶ in the formula (ii), those exemplified as R ³¹ to R ³³ in the formula (i) can be preferably employed.

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

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

In the formulas (i) and (ii), examples of the divalent linking group X and Z include an alkylene group of 1 to 10 carbon atoms, an arylene group of 6 to 12 carbon atoms, a -CONH-R ⁴³ - group, and -COOR. ⁴⁴ -group [provided that R ⁴³ and R ⁴⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms]; and the like, preferably -COO- R ⁴⁴ - group.

Moreover, in the said formula (i), as Y< ^- > of a counter anion, Cl- ^, Br- ^{, I- ,} _ClO4- ^, _BF4- ^, _CH3COO- ^, _PF6- etc. are mentioned.

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

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

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

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

[Formula 25]

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

Although the number of carbon atoms of the alkyl group which may have a substituent in R ⁴¹ of the formula (iii) is not particularly limited, it is usually 1 or more, preferably 2 or more. Moreover, it is preferable that it is 10 or less, and it is more preferable that it is 6 or less.

A methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group etc. are mentioned as a specific example of an alkyl group. 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, either a linear form or a branched form may be sufficient. Moreover, you may contain cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group.

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

In addition, the content ratio of the repeating unit represented by the formula (iii) in all the repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and 4 mol% or more. more preferable Moreover, it is preferable that it is 30 mol% or less, it is more preferable that it is 20 mol% or less, and it is still more preferable that it is 10 mol% or less. In the case within the above range, compatibility with binder components such as solvents and dispersion stability tend to be compatible.

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

[Formula 26]

In the formula (iv), R ³⁸ is 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 ³⁹ is a hydrogen atom or a methyl group.

Although the number of carbon atoms of the alkyl group which may have a substituent in R ³⁸ in the formula (iv) is not particularly limited, it is usually 1 or more, preferably 2 or more, and more preferably 4 or more. Moreover, it is preferable that it is 10 or less, and it is more preferable that it is 8 or less.

A methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group etc. are mentioned as a specific example of an alkyl group. 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, either a linear form or a branched form may be sufficient. Moreover, you may contain cyclic structures, such as a cyclohexyl group and a cyclohexylmethyl group.

Although the number of carbon atoms of the aryl group which may have a substituent in R ³⁸ in the formula (iv) is not particularly limited, it is usually 6 or more. Moreover, it is preferable that it is 16 or less, it is more preferable that it is 12 or less, and it is still more preferable that it is 8 or less.

Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthracenyl group, and the like, and among these, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, or a di It is preferable that it is an ethylphenyl group, and it is more preferable that it is a phenyl group, a methylphenyl group, or an ethylphenyl group.

The number of carbon atoms in the aralkyl group which may have a substituent in R ³⁸ in the formula (iv) is not particularly limited, but is usually 7 or more and preferably 16 or less, more preferably 12 or less, and 10 or less. more preferable

Specific examples of the aralkyl group include a phenylmethylene group, a phenylethylene group, a phenylpropylene group, a phenylbutylene group, and a phenyl isopropylene group. Among these, a phenylmethylene group, a phenylethylene group, a phenylpropylene group, or It is preferably a phenylbutylene group, and more preferably a phenylmethylene group or a phenylethylene group.

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-like alkyl group, a halogen atom, an alkoxy group, etc. are mentioned. In addition, both linear and branched chain alkyl groups represented by R ³⁸ are included.

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

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

The polymeric dispersing agent is a block copolymer having an A block having repeating units (i) and repeating units (ii) and a B block having no repeating units (i) and repeating units (ii), from the viewpoint of further enhancing the dispersibility. chain is preferred.

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

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

Further, repeating units other than repeating unit (i) and repeating unit (ii) may be contained in the A block, and examples of such repeating units include repeating units derived from the above-mentioned (meth)acrylic acid ester monomers. can The content of repeating units other than repeating unit (i) and repeating unit (ii) in A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but these repeating units are contained in A block It is best not to.

Repeating units other than repeating units (iii) and (iv) may be contained in the B block, and examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate type monomers such as (meth)acrylic acid chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; Allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from monomers such as N-methacryloylmorpholine.

The content of repeating units other than repeating unit (iii) and repeating unit (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but these repeating units are contained in the B block It is best not to.

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

<Other ingredients of photosensitive coloring composition>

In the photosensitive coloring composition of the present invention, in addition to the components described above, an adhesion improver such as a silane coupling agent, a coating property improver, a developing improver, an ultraviolet absorber, an antioxidant, a surfactant, a pigment derivative, and the like can be suitably blended.

(1) adhesion improver

The photosensitive coloring composition of the present invention may contain an adhesion improver in order to improve adhesion with a substrate. As the adhesion improver, a silane coupling agent, a phosphoric acid group-containing compound, and the like are preferable.

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

As a preferable silane coupling agent, For example, (meth)acryloxysilanes, such as 3-methacryloxypropyl methyl dimethoxysilane and 3-methacryloxypropyl trimethoxysilane, 2-(3,4-epoxycyclohexyl) ) Epoxysilanes such as ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-ureidopropyl Although isocyanate silanes, such as ureidosilanes, such as triethoxysilane, and 3-isocyanate propyl triethoxysilane, are mentioned, Especially preferably, they are silane coupling agents of epoxysilanes.

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

[Formula 27]

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

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

(2) surfactant

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

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

As such a surfactant, for example, TSF4460 (manufactured by GE Toshiba Silicone Co., Ltd.), DFX-18 (manufactured by Neos Co., Ltd.), BYK-300, BYK-325, BYK-330 (manufactured by Big Chemie Co.), KP340 (Shin-Etsu Silicone Co., Ltd.) company), F-470, F-475, F-478, F-559 (manufactured by DIC), SH7PA (manufactured by Toray Silicon Co., Ltd.), DS-401 (manufactured by Daikin Co.), L-77 (manufactured by Nippon Unika Co., Ltd.) ), FC4430 (manufactured by Sumitomo 3M), and the like.

In addition, surfactant may use 1 type, and may use 2 or more types together in arbitrary combinations and ratios.

(3) pigment derivatives

The photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersing aid in order to improve dispersibility and storage stability.

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

Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidemethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton, or alkyl groups, aryl groups, heterocyclic groups, etc. What was bonded via , Preferably it is a sulfonic acid group. In addition, these substituents may be substituted in multiple numbers on one pigment skeleton.

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

(4) Mineral generator

A photoacid generator is a compound capable of generating an acid by ultraviolet rays, and a crosslinking reaction is promoted by the presence of a crosslinking agent such as a melamine compound by the action of an acid generated when exposed to light.

Among these photoacid generators, those with high solubility in solvents, particularly those with high solubility in solvents used for photosensitive coloring compositions, are preferred. For example, diphenyliodonium, ditolyliodonium, phenyl (p-anisyl) iodonium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p- diaryl iodonium such as chlorophenyl)iodonium, bis(n-dodecyl)iodonium, p-isobutylphenyl(p-tolyl)iodonium, p-isopropylphenyl(p-tolyl)iodonium, or tri Chloride, bromide, or boric fluoride salt, hexafluorophosphate salt, hexafluoroarsenate salt, aromatic sulfonate salt, tetrakis (pentafluorophenyl) borate salt, etc. of triarylsulfonium such as phenylsulfonium, di Sulfonium organoboron complexes such as phenylphenacylsulfonium (n-butyl)triphenylborate, or 2-methyl-4,6-bistrichloromethyltriazine, 2-(4-methoxyphenyl)-4,6 - Although triazine compounds, such as bistrichloromethyltriazine, etc. are mentioned, It is not limited to this.

(5) cross-linking agent

A crosslinking agent may be further added to the photosensitive coloring composition of the present invention, and for example, a melamine or guanamine-based compound may be used. Examples of these crosslinking agents include melamine or guanamine-based compounds represented by the following general formula (6).

[Formula 28]

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

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

In the melamine-based compound corresponding to the general formula (6), that is, the compound of the following general formula (6-1), hexamethylolmelamine, pentamethylol X lamin, tetramethylolmelamine, hexamethoxymethylmelamine, pentamene ToxymethylX lamin, tetramethoxymethylmelamine, hexaethoxymethylmelamine, etc. are included.

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

In addition, tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzo in the guanamine-type compound corresponding to general formula (6), ie, the compound in which ^R61 is aryl in general formula (6) Guanamine, tetraethoxymethylbenzoguanamine and the like are included.

A crosslinking agent having a methylol group or a methylolalkyl ether group can also be used. An example is given below.

2,6-bis(hydroxymethyl)-4-methylphenol, 4-tert-butyl-2,6-bis(hydroxymethyl)phenol, 5-ethyl-1,3-bis(hydroxymethyl)perhydro -1,3,5-triazin-2-one (commonly known as N-ethyldimethyloltriazone) or its dimethyl ether form, dimethyloltrimethylene urea or its dimethyl ether form, 3,5-bis(hydroxymethyl) Perhydro-1,3,5-oxadiazin-4-one (commonly known as dimethyloluron) or its dimethyl ether form, tetramethylolglyoxaldiurane 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 type. As for the quantity at the time of using a crosslinking agent, 0.1-15 mass % is preferable with respect to the total solid content of the photosensitive coloring composition, More preferably, it is 0.5-10 mass %.

(6) Mercapto compounds

A mercapto compound may also be added as a polymerization accelerator and to improve the adhesion to the substrate.

Types of mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol Bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane trithioglycolate, butanediol bisthiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trithioglycolate , Pentaerythritol tetrakithiopropionate, pentaerythritol tetrakithioglycolate, trishydroxyethyl trithiopropionate, ethylene glycol bis (3-mercaptobutylate), butanediol bis (3-mercaptobutyl rate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropanetris (3-mercaptobutylate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate) , mercapto having a heterocyclic ring such as 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione compounds or aliphatic polyfunctional mercapto compounds; and the like. These can use various things individually by 1 type or in mixture of 2 or more types.

<Component blending amount in 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 or more with respect to the total solid content in the photosensitive coloring composition. . Moreover, it is preferable that it is 60 mass % or less normally, and it is more preferable that it is 50 mass % or less.

(a) Sufficient optical density (OD) tends to be obtained when the content of the colorant is set at or above the lower limit, and sufficient plate making properties tend to be easily obtained when set at or below the upper limit.

Further, in the first aspect and the fourth aspect, (a) at least one pigment selected from the group consisting of a red pigment and an orange pigment relative to 100 parts by mass of the colorant is preferably 1 part by mass or more, and preferably 2 parts by mass or more More preferably, it is more preferably 3 parts by mass or more. It is also preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, and particularly preferably 7 parts by mass or less. A sufficient optical density (OD) tends to be obtained when the value is equal to or greater than the lower limit, and plate making characteristics tend to be ensured when the value is equal to or less than the upper limit.

In the first aspect and the fourth aspect, (a) at least one pigment selected from the group consisting of a blue pigment and a purple pigment relative to 100 parts by mass of the colorant is preferably 20 parts by mass or more, and preferably 30 parts by mass or more It is 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, it is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 75 parts by mass or less, and particularly preferably 70 parts by mass or less. There is a tendency that the light-shielding property can be ensured by setting the value to be equal to or greater than the lower limit, and the plate making property tends to be ensured by setting the value to be equal to or less than the upper limit.

Further, in the second aspect, (a) the content of the organic black pigment represented by the general formula (1) relative to 100 parts by mass of the colorant is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and 20 parts by mass It is more preferably 40 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, it is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, still more preferably 85 parts by mass or less, and particularly preferably 80 parts by mass or less. There is a tendency that light-shielding properties can be improved by setting the value to be equal to or more than the lower limit, and a decrease in reliability tends to be suppressed by setting to the value equal to or less than the upper limit.

In the third aspect, (a) the amount of organic pigment relative to 100 parts by mass of the colorant 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, and 70 parts by mass or more particularly preferred. 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. When the value is equal to or greater than the lower limit, the plate making properties tend to be ensured, and when the value is equal to or less than the upper limit, a sufficient optical density (OD) tends to be obtained.

Further, in the third aspect, (a) at least one pigment selected from the group consisting of a red pigment and an orange pigment relative to 100 parts by mass of the colorant is preferably 0 parts by mass or more, more preferably 1 part by mass or more, It is more preferable that it is 2 mass parts or more. Moreover, 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. A sufficient optical density (OD) tends to be obtained when the value is equal to or greater than the lower limit, and plate making characteristics tend to be ensured when the value is equal to or less than the upper limit.

In the third aspect, (a) at least one pigment selected from the group consisting of a blue pigment and a purple pigment relative to 100 parts by mass of the colorant is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, It is more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, particularly preferably 60 parts by mass or more, and most preferably 65 parts by mass or more. Moreover, it is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, and still more preferably 80 parts by mass or less. There is a tendency that the light-shielding property can be ensured by setting the value to be equal to or greater than the lower limit, and the plate making property tends to be ensured by setting the value to be equal to or less than the upper limit.

(a) When the colorant contains an organic black pigment, (a) the amount of the organic black pigment relative to 100 parts by mass of the colorant is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more Do. Moreover, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less. A sufficient optical density (OD) tends to be obtained when the value is equal to or greater than the lower limit, and plate making characteristics tend to be secured when the value is equal to or less than the upper limit.

(a) When the colorant contains carbon black, (a) the amount of carbon black relative to 100 parts by mass of the colorant 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, It is especially preferable that it is 20 mass parts or more. Further, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still more preferably 35 parts by mass or less, and still more preferably 30 parts by mass or less. A sufficient optical density (OD) tends to be obtained when the value is equal to or greater than the lower limit, and plate making characteristics tend to be secured when the value is equal to or less than the upper limit.

(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 with respect to the total solid content of the photosensitive coloring composition of the present invention, still more preferably It is 25 mass % or more, Especially preferably, it is 30 mass % or more. Usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, still more preferably 50% by mass or less, particularly preferably 40% by mass below

(b) By making the content of the alkali-soluble resin more than the above lower limit, there is a tendency that a decrease in the solubility of the unexposed portion in the developing solution can be suppressed, and development defects can be suppressed. Moreover, by setting it below the said upper limit, it tends to be able to suppress the penetration|permeability of the developing solution to an exposed area from becoming high, and to suppress the fall of the sharpness and adhesiveness of a pixel.

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

(c) When the content ratio of the photopolymerization initiator is equal to or greater than the lower limit above, a decrease in sensitivity tends to be suppressed, and when the content ratio of the photopolymerization initiator is equal to or less than the upper limit, a decrease in the solubility of the unexposed portion in the developing solution is suppressed and defective development is suppressed. tend to be able to

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

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

When the content ratio of the polymerization accelerator is equal to or greater than the lower limit above, a decrease in the sensitivity to exposure light tends to be suppressed, and when the content ratio of the polymerization accelerator is equal to or less than the upper limit, the decrease in solubility of the unexposed portion in the developing solution is suppressed, and development defects are reduced. It tends to be suppressed.

In addition, the blending ratio of the sensitizing dye in the photosensitive coloring composition of the present invention is usually 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass of the total solid content in the photosensitive coloring composition from the viewpoint of sensitivity. below

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

In the photosensitive coloring composition of the present invention, by using (e) a solvent, the solid concentration is usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 30% by mass. It is liquefied so that it may become % or less.

(f) The content of the dispersing agent is usually 1% by mass or more in the solid content of the photosensitive coloring composition, preferably 3% by mass or more, and more preferably 5% by mass or more. Moreover, usually 30 mass % or less and 20 mass % or less are preferable, 15 mass % or less is more preferable, and 10 mass % or less is still more preferable.

The content ratio of (f) dispersant to 100 parts by mass of (a) colorant is usually 5 parts by mass or more and more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and usually 50 parts by mass. It is preferably less than or equal to 30 parts by mass or less.

(f) When the content ratio of the dispersant is equal to or greater than the lower limit above, sufficient dispersibility tends to be obtained, and when the ratio of the dispersant is equal to or less than the above upper limit, a decrease in sensitivity, platemaking properties, etc., due to a relatively reduced ratio of other components can be suppressed. tend to have

When using an adhesion improver, its content is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0.4 to 2% by mass with respect to the total solid content in the photosensitive coloring composition. When the content ratio of the adhesion improver is set to the above lower limit or more, there is a tendency that the effect of improving adhesion can be sufficiently improved, and when the content is set to the above upper limit or less, the sensitivity is lowered or the remaining residue after development tends to become a defect. there is

In the case of using a surfactant, its content is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.01 to 0.5% by mass, most preferably 0.01 to 0.5% by mass, based on the total solid content in the photosensitive coloring composition. Preferably it is 0.03-0.3 mass %. The smoothness and uniformity of the coating film tend to be easily expressed when the content of the surfactant is set to be equal to or more than the lower limit above, and the smoothness and uniformity of the coating film are easily expressed when the content of the surfactant is set to be equal to or less than the upper limit value, and the deterioration of other characteristics can be suppressed. there is

<Physical properties of photosensitive coloring composition>

The photosensitive coloring composition of the present invention can be preferably used for forming a colored spacer, and from the viewpoint of being used as a colored spacer, it is preferable to exhibit a black color. Further, the optical density (OD) per 1 μm of film thickness of the coating film is preferably 1.0 or more, more preferably 1.2 or more, still more preferably 1.5 or more, and particularly preferably 1.8 or more. It is usually 4.0 or less, preferably 3.0 or less, and more preferably 2.5 or less.

<Method for producing photosensitive coloring composition>

The photosensitive coloring composition (hereinafter sometimes referred to as "resist") of the present invention is produced by a conventional method.

Usually, it is preferable to carry out dispersion treatment of (a) the colorant in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer or the like. By the dispersion treatment (a), since the colorant is finely divided, the coating properties of the resist are improved.

Dispersion treatment is usually preferably carried out in a system in which a part or all of (a) colorant, (e) solvent, (f) dispersant, and (b) alkali-soluble resin are used in combination (hereinafter referred to as dispersion treatment). The mixture and the composition obtained by the treatment are sometimes referred to as "ink" or "pigment dispersion"). Particularly (f) the use of a polymeric dispersant as the dispersant is preferred because the obtained ink and resist are suppressed in thickening over time (dispersion stability is excellent).

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

Further, when a dispersion treatment is performed on a liquid containing all components to be blended in the photosensitive coloring composition, highly reactive components may be denatured due to heat generated during the dispersion treatment. Therefore, it is preferable to carry out the dispersion treatment in a system containing a polymeric dispersant.

When dispersing (a) the coloring agent with a sand grinder, glass beads or zirconia beads having a particle diameter of about 0.1 to 8 mm are preferably used. As for the dispersion treatment conditions, the temperature is usually in the range of 0°C to 100°C, preferably room temperature to 80°C. The dispersing time is appropriately adjusted because the appropriate time differs depending on the composition of the liquid and the size of the dispersing treatment device. Controlling the gloss of the ink so that the 20-degree specular gloss of the resist (JIS Z8741) is in the range of 50 to 300 is a criterion for dispersion.

When the gloss of the resist is low, the dispersion treatment is not sufficient, and coarse pigment (coloring material) particles often remain, and developability, adhesion, resolution, and the like may be insufficient. In addition, if the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so the dispersion stability tends to be rather impaired.

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

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

[cured material]

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

[Colored Spacer]

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

(1) support

As a support for forming the colored spacer, the material is not particularly limited as long as it has appropriate strength. Although a transparent substrate is mainly used, as the material, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, and thermoplastic resins such as polycarbonate, polymethyl methacrylate, and polysulfone. Sheets of thermosetting resins such as epoxy resins, unsaturated polyester resins, poly(meth)acrylic resins, and various types of glass.

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

The support may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane-based resin, etc., as necessary, in order to improve surface properties such as adhesiveness.

The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, and preferably in the range of 0.1 to 7 mm. Further, when performing thin film formation treatment of various resins, the film thickness is usually in the range of 0.01 to 10 µm, preferably 0.05 to 5 µm.

(2) colored spacer

The photosensitive coloring composition of the present invention is used for the same purpose as a known photosensitive coloring composition for color filters. Hereinafter, the case of being used as a colored spacer (black photo-spacer) will be described according to a specific example of a method for forming a black photo-spacer using the photosensitive coloring composition of the present invention.

Usually, a photosensitive coloring composition is supplied in a film form or pattern form by a method such as coating on a substrate on which a black photo-spacer is to be formed, and the solvent is dried. Subsequently, pattern formation is performed by a method such as a photolithography method in which exposure-development is performed. Thereafter, a black photo-spacer is formed on the substrate by performing additional exposure or thermal curing if necessary.

(3) Formation of colored spacers

[1] Supply method to substrate

The photosensitive coloring composition of the present invention is usually supplied onto a substrate in a state of being dissolved or dispersed in a solvent. As the supply method, it can be carried out by a conventionally known method, for example, a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. Moreover, you may supply in the form of a pattern by an inkjet method, a printing method, etc.

Among them, the die coating method is preferable from a comprehensive viewpoint, in that the amount of the coating liquid used is significantly reduced, and there is no influence of mist or the like that adheres when the spin coating method is used, and generation of foreign substances is suppressed.

The application amount varies depending on the application, but, for example, in the case of a black photo spacer, the dry film thickness is usually 0.5 μm to 10 μm, preferably 1 μm to 9 μm, particularly preferably 1 μm to 7 μm. is the range In addition, it is important that the dry film thickness or the height of the finally formed spacer be uniform over the entire substrate. If the deviation is large, non-uniform defects are generated in the liquid crystal panel.

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

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

[2] Drying method

Drying after supplying the photosensitive coloring composition solution onto the substrate is preferably performed by a drying method using a hot plate, IR oven, or convection oven. Moreover, you may combine the reduced-pressure drying method which performs drying in a reduced-pressure chamber, without raising temperature.

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

[3] Exposure method

Exposure is performed by superposing a negative mask pattern on the coating film of the photosensitive coloring composition and irradiating a light source of ultraviolet rays or visible rays through the mask pattern. In the case of exposure using an exposure mask, a method of bringing the exposure mask close to the coating film of the photosensitive coloring composition, or disposing the exposure mask at a position away from the coating film of the photosensitive coloring composition, and passing the exposure mask through the exposure mask It may be based on the method of projecting light light. Moreover, it may be based on the scanning exposure system by the laser beam which does not use a mask pattern.

At this time, if necessary, in order to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen, exposure is performed in a deoxygenated atmosphere or after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer. you can do or do

As a preferred aspect of the present invention, when black photo-spacers having different heights are formed simultaneously by a photolithography method, for example, a light-shielding portion (light transmittance: 0%) and a plurality of openings, the highest average light transmittance An exposure mask having an opening having a small average light transmittance (intermediate transmission opening) relative to the opening (completely transmitting opening) is used. With this method, a difference in remaining film rate is generated by the difference in average light transmittance between the intermediate transmission opening and the full transmission opening, that is, the difference in exposure amount.

A method of manufacturing the intermediate transmission opening by, for example, a matrix light-shielding pattern having minute polygonal light-shielding units is known. In addition, as an absorber, a method of producing a film of a material such as chromium, molybdenum, tungsten, or silicon by controlling the light transmittance is known.

The light source used for said exposure is not specifically limited. As the light source, for example, a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a fluorescent lamp, an argon ion laser, a YAG laser , laser light sources such as excimer lasers, nitrogen lasers, helium cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. In the case of irradiating and using light of a specific wavelength, an optical filter may be used.

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

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

Further, 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 normally 500 micrometers or less, Preferably it is 400 micrometers or less, More preferably, it is 300 micrometers or less.

[4] Development method

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

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

Examples of the surfactant include nonionic interfaces such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. activator; anionic surfactants such as alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkyl sulfates, alkylsulfonic acid salts, and sulfosuccinic acid ester salts; Amphoteric surfactants, such as alkyl betaines and amino acids, are mentioned.

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

The conditions of the development treatment are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C., especially 15 to 45 ° C., particularly preferably 20 to 40 ° C., and the development method is immersion development method or spray development method. , It may be by any method of a brush development method, an ultrasonic development method, and the like.

[5] Additional exposure and heat curing treatment

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

The size, shape, etc. of the colored spacer of the present invention are appropriately adjusted according to the specifications of the color filter to which it is applied, but the photosensitive colored composition of the present invention is, in particular, a black photo in which the height of the spacer and the sub-spacer are different by the photolithography method. It is useful for simultaneously forming a spacer, and in that case, the height of the spacer is usually about 2 to 7 μm, and the sub-spacer has a height that is usually about 0.2 to 1.5 μm lower than that of the spacer.

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

[Color Filter]

The color filter of the present invention is provided with the colored spacer of the present invention as described above, and, for example, on a glass substrate as a transparent substrate, a black matrix, red, green, and blue pixel colored layers, and an overcoat layer These are stacked, and after forming the colored spacers, an alignment film is formed to manufacture the fabric.

A liquid crystal display device provided with the colored spacer of the present invention by bonding the color filter having the colored spacer of the present invention and the substrate on the liquid crystal driving side to form a liquid crystal cell, and injecting liquid crystal into the formed liquid crystal cell. An image display device such as this can be manufactured.

Example

Next, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to the following examples unless departing from the gist thereof.

Components of the photosensitive coloring composition used in the following Examples and Comparative Examples are as follows.

<Organic black pigment>

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

[Formula 30]

<Alkali Soluble Resin-I>

145 parts by mass of propylene glycol monomethyl ether acetate was stirred while substituting with nitrogen, and the temperature was raised to 120°C. To this, 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate, and 66 parts by mass of monoacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton were added dropwise thereto, and 2,2'-azobis- 8.47 parts by mass of 2-methylbutyronitrile was added dropwise over 3 hours, and further stirring was continued at 90°C for 2 hours. Next, the inside of the reaction vessel was replaced with air substitution, 0.7 mass part of trisdimethylaminomethylphenol and 0.12 mass part of hydroquinone were introduced to 43.2 mass parts of acrylic acid, and reaction was continued at 100 degreeC for 12 hours. Then, 56.2 mass parts of tetrahydrophthalic anhydride (THPA) and 0.7 mass part of triethylamine were added, and it was made to react at 100 degreeC for 3.5 hours. The weight average molecular weight Mw of alkali-soluble resin-I obtained in this way measured by GPC was about 8400, and the acid value was 80 mgKOH/g.

<Alkali Soluble Resin-II>

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

<Dispersant-I>

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

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

[Formula 31]

<Dispersant-II>

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

<Pigment derivative>

"Solsperse12000" made by Lubrizol

<Solvent-I>

PGMEA: Propylene glycol monomethyl ether acetate

<Solvent-II>

MB: 3-methoxybutanol

<Photoinitiator-I>

Irgacure OXE03 (manufactured by BASF)

[Formula 32]

<Photoinitiator-II>

[Formula 33]

<Photoinitiator-III>

[Formula 34]

<Photopolymerizable monomer>

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

<Additives>

Nippon Kayaku Co., Ltd., KAYAMER PM-21 (methacryloyl group-containing phosphate)

<Surfactant>

Megafac F-559 manufactured by DIC Co., Ltd.

<Evaluation of Optical Density (OD)>

The optical density (OD) was measured with a transmission densitometer (“D200-II” manufactured by Gretac Macbeth). Further, the film thickness at the measuring point was also measured, and the optical density (unit OD) per unit film thickness (1 μm) was calculated.

<Evaluation of substrate adhesion>

Regarding the target pattern, the value of the aperture diameter (μm) of the one having the smallest aperture diameter among the patterns remaining on the substrate with good resolution was set as the minimum adhesion. It is excellent in board|substrate adhesiveness, so that this value is small.

<Evaluation of surface smoothness>

With respect to the target pattern, the presence or absence of wrinkles on the surface after heating was observed with a visual field of 70 µm x 70 µm using an optical microscope. In addition, the evaluation criteria are as follows.

○: Wrinkles of micron order are not observed on the surface of the pattern

×: Wrinkles of micron order are conspicuous on the surface of the pattern

<Evaluation of surface roughness>

For the target pattern, the surface roughness Sa (arithmetic average roughness , nm) was measured.

<Preparation of Pigment Dispersion 1>

The pigments, dispersants, dispersing aids, alkali-soluble resins, and solvents shown in Table 1 were mixed in a mass ratio shown in Table 1. This solution was subjected to dispersion treatment in the range of 25 to 45°C for 3 hours with a paint shaker. As beads, 0.5 mmφ zirconia beads were used, and 2.5 times the mass of the dispersion liquid was added. After completion of the dispersion, the beads and the dispersion liquid were separated by a filter to prepare a pigment dispersion liquid 1.

<Preparation of Pigment Dispersions 2 and 3>

Pigment dispersions 2 and 3 were prepared in the same manner as in Pigment Dispersion 1, except that the pigments, dispersants, dispersing aids, alkali-soluble resins, and solvents shown in Table 1 were mixed so as to have the mass ratios shown in Table 1.

<Pigment Dispersion 4 (Coated Carbon Black Dispersion)>

Carbon black was manufactured by a conventional oil furnace method. However, as raw material oil, ethylene bottom oil with a small amount of Na, Ca, and S was used, and coke oven gas was used for combustion. In addition, as the reaction stop water, pure water treated with an ion exchange resin was used. 540 g of the obtained carbon black was stirred at 5,000 to 6,000 rpm for 30 minutes using a homomixer together with 14500 g of pure water to obtain a slurry. This slurry was transferred to a container equipped with a screw stirrer, and 600 g of toluene in which 60 g of epoxy resin "Epicoat 828" (manufactured by Mitsubishi Chemical Corporation) was dissolved was added in small portions while mixing at about 1,000 rpm. During about 15 minutes, the carbon black dispersed in water migrated to the toluene side in the total amount, and became particles of about 1 mm.

Next, after draining water with a 60-mesh wire mesh, it was placed in a vacuum dryer and dried at 70°C for 7 hours to completely remove toluene and water.

The obtained coated carbon black, dispersant, pigment derivative, and solvent were mixed in mass ratios shown in Table 2.

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

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

Using the above-prepared pigment dispersions 1 to 4, each component was added so as to have a blending ratio of Table 2, and PGMEA was added so that the solid content was 22% by mass, stirred and dissolved to prepare a photosensitive coloring composition. Evaluation was performed by the method mentioned later using the obtained photosensitive coloring composition. In addition, the value of the upper stage in Table 2 shows the usage-amount of each component. On the other hand, the value of the lower stage represents the solid content of each component as a content ratio with respect to the total solid content of the photosensitive coloring composition.

<Method of collectively forming cured products having different heights>

Each photosensitive coloring composition was applied onto a glass substrate (“AN100” manufactured by AGC) using a spinner. Then, it was heat-dried on a hot plate at 100 degreeC for 70 second, and the coating film was formed.

For the obtained coating film, completely permeable openings in circular patterns of various diameters with a diameter of 5 to 50 μm (5 to 20 μm: 1 μm intervals, 25 μm to 50 μm: 5 μm intervals) and diameters of 5 to 50 μm (5 to 5 μm intervals) 20 μm: 1 μm intervals, 25 μm to 50 μm: 5 μm intervals) of intermediate transmission openings in circular patterns of various diameters, and further, an exposure mask having straight openings (complete transmission) with a width of 100 μm. conducted. The intermediate transmission opening is a thin film of Cr oxide and has a light transmittance of 10 ± 2% at a wavelength of 365 nm. The exposure gap (distance between the mask and the coated surface) was 220 µm. As the irradiation light, an ultraviolet ray having an intensity of 32 mW/cm 2 at a wavelength of 365 nm was used, and the exposure amount was 100 mJ/cm 2 . In addition, ultraviolet irradiation was performed under air.

Subsequently, shower development at a water pressure of 0.15 MPa at 25°C using a developing solution composed of an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a nonionic surfactant ("A-60" manufactured by Kao Corporation). After carrying out, the development was stopped with pure water and washed with water washing spray. The shower developing time was adjusted between 10 and 120 seconds, and it was set as 1.5 times the time for dissolving and removing the unexposed coating film.

By this operation, a pattern was obtained from which unnecessary parts were removed. The board|substrate on which the said pattern was formed was heated in oven at 230 degreeC for 20 minutes, and the pattern was hardened, and the substantially cylindrical spacer pattern was obtained.

The optical density (OD) per unit film thickness (1 μm) of the pattern corresponding to the straight opening was measured by the method described above. In addition, the substrate adhesion was evaluated by the method described above for patterns corresponding to full transmission apertures of a circular pattern of 5 to 50 µm and intermediate transmission apertures of 5 to 50 µm in the same way. In addition, surface smoothness was evaluated by the method described above for the patterns corresponding to the linear openings. In addition, the surface roughness of the patterns corresponding to the straight openings was evaluated by the method described above. Each result was shown in Table 2.

It was confirmed that the coated substrates using the photosensitive coloring compositions of Examples 1 and 2 had a high unit OD, excellent light-shielding properties, and excellent surface smoothness. In addition, the substrate adhesion of the middle transmission opening was also good.

On the other hand, it was confirmed that Comparative Examples 1 to 3 had the same unit OD value as Examples 1 and 2, but had poor surface smoothness and poor substrate adhesion of the intermediate transmission opening.

In general, in order to improve the light-shielding properties of a colored spacer, a method of increasing the concentration of a pigment or a method of using a pigment having high light-shielding properties in combination is known. However, when such a method is applied, the ultraviolet transmittance is lowered, and a difference in crosslinking density occurs in the film thickness direction, so that the crosslinking density of the film surface is higher than that of the bottom of the film, and wrinkles are generated on the film surface due to heat shrinkage during the thermal curing process. , it is considered that the surface smoothness deteriorates.

In the photosensitive coloring composition of the present invention, since the oxime ester compound represented by the formula (I) is used as the photopolymerization initiator, the halogen atom in the chemical structure of the compound causes the compound to have an initiator in the vicinity of the film surface. It is thought that it is easy to distribute and, by being affected by oxygen inhibition, suppresses excessive increase in crosslinking density on the membrane surface and reduces wrinkles on the membrane surface due to heat shrinkage in the thermal curing process.

In addition, the absorption of long-wavelength light is increased by the naphthalene ring in the carbazole skeleton of the compound, and the long-wavelength light contained in the ultraviolet lamp can be used to increase the crosslinking density in the vicinity of the bottom of the film. Even in a pattern formed in an opening having a low transmittance, it is considered that the adhesion to the substrate becomes good.

[Example 3 and Comparative Example 4]

Using the above-prepared pigment dispersions 3 and 4, each component was added so that the ratio in the solid content was the blending ratio shown in Table 3, and PGMEA was added so that the solid content was 22% by mass, stirred and dissolved to obtain a photosensitive coloring composition. prepared. Using the obtained photosensitive coloring composition, evaluation was performed in the same manner as in Example 1 except that the exposure amount in the exposure treatment was 40 mJ/cm 2 . In addition, the value of the upper stage in Table 3 shows the usage-amount of each component. On the other hand, the value of the lower stage represents the solid content of each component as a content ratio with respect to the total solid content of the photosensitive coloring composition. In addition, the visual field for evaluation of surface smoothness was 5 cm x 5 cm.

It was confirmed that the coated substrate using the photosensitive coloring composition of Example 3 had a high unit OD, excellent light-shielding properties, and excellent surface smoothness. In addition, the substrate adhesion of the middle transmission opening was also good.

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

Although this invention was demonstrated in detail using the specific aspect, it is clear for those skilled in the art that various changes and modifications are possible, without leaving|separating the intent and range of this invention. In addition, this application is a Japanese patent application filed on March 11, 2015 (Japanese Patent Application No. 2015-048577), a Japanese patent application filed on March 11, 2015 (Japanese Patent Application No. 2015-048578), and 2015 It is based on the Japanese Patent Application (Japanese Patent Application No. 2015-157456) filed on August 7, the entirety of which is incorporated by reference.

ADVANTAGE OF THE INVENTION According to the photosensitive coloring composition of this invention, the hardened|cured material and colored spacer with high light-shielding property and excellent surface smoothness can be provided, and also the image display apparatus provided with such a colored spacer can be provided. Therefore, the present invention has very high industrial applicability in each field of a photosensitive coloring composition, cured product, colored spacer, and image display device.

Claims (18)

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,
The (a) coloring agent 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 photosensitive coloring composition characterized by the said (c) photoinitiator containing the oxime ester type compound represented by following formula (I).
[Formula 1]

(In the above general formula (I),
R ¹ represents an aromatic ring group which may have a substituent.
R ² represents an alkanoyl group which may have a substituent or an aryloyl 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 each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. However, at least any one of R5 and ^R6 is a naphthalene ring which ^may have a substituent.
At least one of R ¹ and R ⁴ has an -OR ⁷ group as a substituent. provided that R ⁷ represents a halogenoalkyl group.
X represents a direct bond or a carbonyl group.
Z represents a direct bond or a carbonyl group.) delete delete According to claim 1,
The photosensitive coloring composition whose content ratio of at least 1 sort(s) of pigment selected from the group which consists of a red pigment and an orange pigment with respect to 100 mass parts of said (a) coloring agents is 1 mass part or more and 30 mass parts or less. According to claim 1,
The photosensitive coloring composition whose content ratio of at least 1 sort(s) of pigment selected from the group which consists of a blue pigment and a purple pigment with respect to 100 mass parts of said (a) coloring agents is 20 mass parts or more and 90 mass parts or less. According to claim 1,
The photosensitive coloring composition in which the said (a) coloring agent contains an organic black pigment. 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,
The (a) coloring agent contains a compound represented by the following formula (1), a geometric isomer thereof, a salt thereof, or a salt of a geometric isomer thereof, and
The photosensitive coloring composition characterized by the said (c) photoinitiator containing the oxime ester type compound represented by following formula (I).
[Formula 2]

(In the above formula (1), R ¹¹ and R ¹⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are independently of each other 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 ;
In addition, 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 , They may be directly bonded to each other or bonded to each other by an oxygen atom, a sulfur atom, NH or NR ²¹ bridge;
R ²¹ and R ²² are each independently an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, a cycloalkenyl group of 3 to 12 carbon atoms, or an alkynyl group of 2 to 12 carbon atoms)
[Formula 3]

(In the above general formula (I),
R ¹ represents an aromatic ring group which may have a substituent.
R ² represents an alkanoyl group which may have a substituent or an aryloyl 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 each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent. However, at least any one of R5 and ^R6 is a naphthalene ring which ^may have a substituent.
At least one of R ¹ and R ⁴ has an -OR ⁷ group as a substituent. provided that R ⁷ represents a halogenoalkyl group.
X represents a direct bond or a carbonyl group.
Z represents a direct bond or a carbonyl group.) According to claim 1 or 7,
The photosensitive coloring composition in which the said (a) coloring agent contains carbon black. According to claim 7,
The photosensitive coloring composition in which said (a) coloring agent contains an organic pigment further. delete delete delete delete According to claim 1 or 7,
The photosensitive coloring composition whose optical density per 1 micrometer of film thickness of a hardened coating film is 1.0 or more. According to claim 1 or 7,
A photosensitive coloring composition used to collectively form colored spacers having different heights by a photolithography method. A cured product obtained by curing the photosensitive coloring composition according to any one of claims 1, 4 to 7, and 9. A colored spacer formed from the cured product according to claim 16. An image display device comprising the colored spacer according to claim 17.