TW202100665A - Photosensitive colored composition - Google Patents

Abstract

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

Description

Photosensitive coloring composition for forming colored spacer

The present invention relates to a photosensitive coloring composition and the like. In detail, for example, it relates to a photosensitive coloring composition preferably used for forming a coloring spacer in a color filter of a liquid crystal display, etc., a coloring spacer obtained by curing the photosensitive coloring composition, and The image display device of the colored spacer.

The liquid crystal display (LCD) uses the property of switching the arrangement of liquid crystal molecules by turning on and off the voltage of the liquid crystal. On the other hand, most of the components constituting the LCD unit are formed by a method using a photosensitive composition represented by photolithography. The photosensitive composition has a tendency to further expand its application range in the future because it is easy to form a fine structure and is also easy to process substrates for large screens.

However, the LCD manufactured by using the photosensitive composition cannot maintain the voltage applied to the liquid crystal due to the electrical characteristics of the photosensitive composition itself or the influence of the impurities contained in the photosensitive composition, resulting in the display of the display The situation of inequality. Particularly, in color liquid crystal displays, components closer to the liquid crystal layer, such as so-called columnar spacers, optical spacers, etc., used in liquid crystal panels to keep the distance between two substrates constant, have a greater influence.

Previously, when spacers that do not have light-shielding properties are used in thin-film transistor (TFT) LCDs, there are switching elements The TFT malfunctions due to the light passing through the spacer. In order to prevent this, for example, Patent Document 1 describes a method of using a spacer having light-shielding properties (colored spacer).

On the other hand, in recent years, with changes in panel structure, a method of forming colored spacers of different heights at one time by photolithography has been proposed. For example, Patent Document 2 discloses the following: By combining several specific pigment types with different light absorption characteristics to ensure the balance of light absorption in the ultraviolet region and the visible region, the light shielding property and the voltage retention rate of the liquid crystal can be maintained, and Realize the control of the shape or level difference and the adhesion with the substrate. In addition, Patent Document 3 discloses that a plurality of organic coloring pigments are used as a pigment, and Patent Document 4 discloses that an organic black pigment is used.

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

[Prior Technical Literature]

[Patent Literature]

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

Patent Document 2: International Publication No. 2013/115268

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

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

Patent Document 5: Japanese Patent Special Form 2014-500852

In recent years, with the changes in panel structure, it is required to further improve The shading of spacers. As a method of improving the light-shielding property, a method of using a pigment with a higher light-shielding property, a method of increasing the content of the pigment in the photosensitive coloring composition, and the like can be cited. The inventors of the present invention have discovered through research that in the photosensitive coloring composition described in Patent Documents 2 to 4, pigments with higher light-shielding properties are used in combination to further improve the light-shielding properties of the colored spacers. Near the bottom, the difference in crosslinking density becomes larger, and wrinkles are generated on the surface of the coating film due to thermal shrinkage during the thermal hardening process, and the surface smoothness becomes insufficient.

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

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

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

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

The said (c) photopolymerization initiator contains the oxime ester type compound represented by following formula (I).

[化1]

(In the above general formula (I),

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

R ² represents an alkyl group which may have a substituent or an aryl group which may have a substituent.

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

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

R ⁵ and R ⁶ each independently represent an optionally substituted benzene ring or an optionally substituted naphthalene ring. Among them, at least one of R ⁵ and R ⁶ 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. Here, R ⁷ represents a haloalkyl group.

X represents a direct bond or a carbonyl group.

Z represents a direct bond or a carbonyl group. )

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

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

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

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

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

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

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

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

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

[7] The photosensitive coloring composition for forming a colored spacer according to [6], wherein the organic black pigment contains a compound represented by the following formula (1), its geometric isomer, its salt, or its Salt of geometric isomers.

[化2]

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

^{R 12, R 13, R 14} , R 15, R 17, R 18, R 19 and R ²⁰ lines of all other groups are each independently a hydrogen atom, a halogen ^{atom, R 21, COOH, COOR 21} , COO -, CONH _2. CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , COCR ²¹ , OOCNH ₂ , OOCNHR ²¹ , OOCNR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²² , NR ^{21 _{COR 22, N = CH 2,}} N = CHR 21, N = CR 21 R 22, SH, SR 21, SOR 21, SO 2 R 21, SO 3 R 21, SO 3 H, SO 3 -, SO 2 NH 2 , SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² ;

And at least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ Directly bond to each other or to bond to each other through oxygen atom, sulfur atom, NH or NR ²¹ bridge;

R ²¹ and R ²² are independently an alkyl group with 1 to 12 carbons, cycloalkyl with 3 to 12 carbons, alkenyl with 2 to 12 carbons, cycloalkenyl with 3 to 12 carbons, or 2 ~12 alkynyl. )

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

[9] The photosensitive coloring composition for forming a colored spacer according to [1], wherein the (a) colorant contains an organic pigment and carbon black.

[10] The photosensitive coloring composition for forming a colored spacer according to [9], wherein the organic pigment contains at least one selected from the group consisting of a red pigment, an orange pigment, a blue pigment, and a purple pigment .

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

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

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

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

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

[12] The photosensitive paint for forming colored spacers as described in any one of [9] to [11] A color composition in which 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 content ratio of carbon black to 100 parts by mass of the colorant (a) is 5 mass Part or more and 50 parts by mass or less.

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

[15] The photosensitive coloring composition for forming colored spacers as described in any one of [1] to [14], which is used to form colored spacers of different heights at one time by photolithography.

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

[17] A colored spacer formed by the hardened material described in [16].

[18] An image display device comprising the colored spacer described in [17].

According to the present invention, it is possible to provide a photosensitive coloring composition capable of forming a pattern with high light-shielding properties and excellent surface smoothness. In addition, it is possible to provide a cured product and a colored spacer with excellent light-shielding properties and excellent surface smoothness, and further, an image display device provided with such a colored spacer can be provided.

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

The so-called "(co)polymer" means to include both homopolymer and copolymer, and the so-called "...acid (anhydride)" means to include both acid and its anhydride . In addition, in the present invention, the "acrylic resin" means a (co)polymer containing (meth)acrylic acid and a (co)polymer containing (meth)acrylate having a carboxyl group.

In addition, in the present invention, the term "monomer" refers to the term relative to the so-called high-molecular substance (polymer), meaning that in addition to the narrowly defined monomer (monomer), it also includes dimers, trimers, and oligomers. Polymer etc.

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

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

In addition, in the present invention, the so-called "amine value", unless otherwise specified, means the amine value in terms of effective solid content, and is the value expressed by the mass of KOH per 1g of the base equivalent of the solid content of the dispersant . In addition, see below for the measurement method. On the other hand, the so-called "acid value", unless otherwise specified, means the acid value in terms of effective solid content, which is calculated by neutralization titration.

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

[Photosensitive coloring composition]

The photosensitive coloring composition of the present invention contains

(a) Coloring agent

(b) Alkali-soluble resin

(c) Photopolymerization initiator

(d) Ethylene unsaturated compounds

(e) Solvent

(f) Dispersant

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

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

On the other hand, characteristics such as light-shielding and surface smoothness are attributed to the partitions of the light-emitting part of organic electroluminescence (EL, Electroluminescence) display devices, especially color-removing partitions such as colored partitions (banks). The characteristics are also required for other purposes, so it can be used without being limited to colored spacers. The photosensitive coloring composition of the present invention will be described in detail below. Unless otherwise specified, both the use of the colored spacer and the use other than the colored spacer will be described together.

In the photosensitive coloring composition related to the first aspect of the present invention, (a) the colorant contains at least one selected from the group consisting of red pigments and orange pigments, and is composed of blue pigments and purple pigments At least one in the group, and (c) light gathering The combined initiator includes an oxime ester compound represented by the following formula (I).

In addition, in the photosensitive coloring composition related to the second aspect of the present invention, (a) the colorant contains a compound represented by the following general formula (1), its geometric isomer, its salt, or its geometric difference The organic black pigment of the salt of the structure (hereinafter sometimes abbreviated as "organic black pigment represented by general formula (1)").

In addition, in the photosensitive coloring composition related to the third aspect of the present invention, (a) the colorant contains an organic pigment and carbon black, and (c) the photopolymerization initiator contains an oxime represented by the following formula (I) Ester compounds.

On the other hand, the photosensitive coloring composition of the fourth aspect of the present invention is a photosensitive coloring composition for forming a colored spacer, and (c) the photopolymerization initiator contains an oxime ester represented by the following formula (I) Department of compounds.

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

<(a) Colorant>

The (a) colorant used in the photosensitive coloring composition of the first aspect of the present invention contains at least one selected from the group consisting of red pigments and orange pigments, and is selected from the group consisting of blue pigments and purple pigments. Make up at least one of the groups. In this way, the photosensitive coloring composition of the first aspect of the present invention can achieve high light-shielding properties by containing a specific organic coloring pigment.

(A) It is preferable to use a pigment as the coloring agent, and as the pigment, an inorganic pigment or an organic pigment may be used. From the viewpoint of easily suppressing the decrease in the voltage retention of the liquid crystal and suppressing the absorption of ultraviolet rays to control the shape or step difference, it is preferable to use an organic pigment.

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

In addition to organic pigments such as indanthrene, indanthrene, and perylene, various inorganic pigments can also be used. Hereinafter, specific examples of pigments that can be used are indicated by the pigment number. The term "CI Pigment Red 2" listed below means the color index (CI).

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

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

Furthermore, it is preferable to use C.I. Pigment Red 177, 254, and 272 in terms of dispersibility or shading properties. When the photosensitive coloring composition of the first aspect of the present invention is cured by ultraviolet light, it is preferable to use ultraviolet light absorber as the red pigment The lower rate. From this viewpoint, it is more preferable to use C.I. Pigment Red 254 and 272.

Examples of orange pigments include CI pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48 , 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79.

Among them, C.I. Pigment Orange 38 and 71 can be preferably cited. Furthermore, it is preferable to use C.I. Pigment Orange 43, 64, 72 in terms of dispersibility or shading properties. In the case of curing the photosensitive coloring composition of the first aspect of the present invention with ultraviolet rays, it is preferable to use one with a low ultraviolet absorption rate as the orange pigment. From this viewpoint, it is more preferable to use C.I. Pigment Orange 64 and 72.

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

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

Furthermore, it is preferable to use C.I. Pigment Blue 15:6, 16, 60 in terms of dispersibility or shading properties. When the photosensitive coloring composition of the first aspect of the present invention is cured by ultraviolet rays, it is preferable to use a blue pigment having a low ultraviolet absorption rate. From this viewpoint, it is more preferable to use C.I. Pigment Blue 60.

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

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

Furthermore, it is preferable to use C.I. Pigment Violet 23 and 29 in terms of dispersibility or light-shielding property. In the case where the photosensitive coloring composition of the first aspect of the present invention is cured by ultraviolet rays, it is preferable to use a purple pigment having a low ultraviolet absorption rate. From this viewpoint, it is more preferable to use C.I. Pigment Violet 29.

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

Examples of green pigments include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among them, C.I. Pigment Green 7, 36 can be preferably cited.

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

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

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

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

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

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

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

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

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

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

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

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

Furthermore, the combination of colors is not particularly limited. From the viewpoint of light-shielding properties, for example, the combination of red pigment and blue pigment, the combination of blue pigment and orange pigment, blue pigment, orange pigment and purple Combinations of pigments, etc.

Furthermore, in addition to these color pigments, black color materials can be further used. Among the black color materials, it is preferable to use organic black pigments from the viewpoint of easily suppressing the decrease in the voltage retention rate of the liquid crystal and suppressing the absorption of ultraviolet rays to control the shape or the step difference. It is preferable to use an organic black pigment which is a compound represented by the following formula (1), its geometric isomer, its salt, or its geometric isomer salt.

[化3]

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

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

And at least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ Directly bond to each other or to bond to each other through oxygen atom, sulfur atom, NH or NR ²¹ bridge;

R ²¹ and R ²² are independently an alkyl group with 1 to 12 carbons, cycloalkyl with 3 to 12 carbons, alkenyl with 2 to 12 carbons, cycloalkenyl with 3 to 12 carbons, or 2 ~12 alkynyl.

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

[化4]

When the compound represented by the general formula (1) is anionic, it is preferably by any known suitable cation, such as a metal, organic, inorganic or metal organic cation, specifically an alkali metal, alkaline earth metal, Transition metal, tertiary ammonium such as primary ammonium, secondary ammonium, trialkylammonium, quaternary ammonium such as tetraalkylammonium, or organometallic complex salt to compensate its charge. In addition, when the geometric isomers of the compound represented by the general formula (1) are anionic, they are preferably the same salt.

Among the definitions of the substituents of the general formula (1) and the like, since there is a tendency for the shielding ratio to increase, the following are preferred. The reason is that the following substituents have no absorption and will not affect the color tone of the pigment.

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

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

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

Alkyl groups with 1 to 12 carbon atoms are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, tertiary butyl, 2-methylbutyl, n-propyl Pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, heptyl, n-octyl, 1,1,3,3-tetramethylbutyl, 2-ethyl Hexyl, nonyl, decyl, undecyl or dodecyl.

基、

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

base,

Group, norcarnyl, carnyl, menthyl, norpinyl, pinyl, 1-adamantyl or 2-adamantyl.

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

烯-1-基、2,5-降

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

En-1-yl, 2,5-nor

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

The alkynyl group having 2 to 12 carbon atoms is, for example, 1-propyn-3-yl, 1-butyn-4-yl, 1-pentyn-5-yl, 2-methyl-3-butyn-2-yl , 1,4-pentadien-3-yl, 1,3-pentadien-5-yl, 1-hexyn-6-yl, cis-3-methyl-2-pentene-4-yne- 1-yl, trans-3-methyl-2-pentene-4-yn-1-yl, 1,3-hexadiyn-5-yl, 1-octyne-8-yl, 1-nonyne- 9-yl, 1-decyn-10-yl or 1-dodecyn-12-yl.

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

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

[化5]

As a specific example of such an organic black pigment, Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF Corporation) can be cited as a trade name. The organic black pigment is preferably dispersed and used by the following dispersant, solvent, and method. In addition, if the sulfonic acid derivative of the general formula (2) is present during dispersion, the dispersibility or storage properties may be improved.

Examples of black color materials other than the organic black pigment represented by the above general formula (1) include: carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, and perylene Black wait. Among them, carbon black can be preferably used in terms of light shielding properties and image characteristics. As an example of carbon black, the following carbon black can be mentioned.

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

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

Manufactured by Cabot: Monarch (registered trademark, the same below) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, the same below) 99, RECAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, the same below) XC72R, ELFTEX (registered trademark)-8

Manufactured by Columbian Carbon: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22, RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U , RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

Carbon black can also be coated with resin. If carbon black coated with resin is used, it has the effect of improving the adhesion to the glass substrate or the volume resistance. As the carbon black coated with the resin, for example, the carbon black described in JP 09-71733 A, etc. can be preferably used. In terms of volume resistance or permittivity The surface is preferably resin-coated carbon black.

As carbon black used for the coating treatment with the resin, it is preferable that the total content of Na and Ca is 100 ppm or less. Carbon black usually contains Na or Ca, K, Mg, Al, Fe mixed from raw material oil or combustion oil (or gas) at the time of manufacture, reaction stop water or granulation water, and furnace materials of the reaction furnace in percentage levels. As the ash of the composition. Among them, Na or Ca generally contains hundreds of ppm or more each, and by reducing these, there is a tendency to suppress the penetration of transparent electrodes (ITO) or other electrodes and prevent electrical short circuits.

As a method to reduce the content of the ash containing Na or Ca, it can be achieved by the following method, namely, as the raw material oil or fuel oil (or gas) and reaction stop water in the production of carbon black, the content is carefully selected Keep as few as possible; and minimize the amount of alkaline substances that adjust the structure. As another method, a method of washing carbon black produced from the furnace with water or hydrochloric acid to dissolve and remove Na or Ca can be cited.

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

In addition, the resin-coated carbon black is preferably a so-called acid carbon black having a pH of 6 or less. Since the dispersion diameter (coalescence diameter) in water becomes smaller, it is preferable to be able to coat fine cells. Furthermore, it is preferable that the average particle diameter is 40 nm or less, and the dibutyl phthalate (DBP) absorption amount is 140 ml/100g or less. By setting it within the above range, you can get The tendency of coating films with good shading properties. The average particle size means the number average particle size, and means the equivalent circle diameter obtained by the particle image analysis. The particle image analysis is to take photos taken with tens of thousands of magnifications in several fields of view using an electron microscope, and The image processing device is used to measure about 2000 to 3000 particles in these photos.

The preparation method of carbon black coated by resin is not particularly limited. For example, after appropriately adjusting the blending amount of carbon black and resin, the following methods can be used: 1. Mix the resin with solvents such as cyclohexanone, toluene, and xylene. Heat and dissolve to obtain a resin solution, mix and stir the resin solution with a suspension of carbon black and water to separate the carbon black and water, then remove the water and heat and knead to obtain a composition. The material is formed into flakes and pulverized and then dried; 2. The resin solution and suspension prepared in the same manner as above are mixed and stirred to granulate the carbon black and resin, and then the obtained granular material is separated and heated The remaining solvent and water are removed; 3. The carboxylic acid such as maleic acid and fumaric acid is dissolved in the above-exemplified solvent, and carbon black is added, mixed and dried, and the solvent is removed to obtain carboxylic acid-added carbon After the black, add resin to it and dry blend; 4. Stirring the monomer component containing reactive group and water at high speed to prepare a suspension, and then cool it after polymerization to obtain it from the polymer suspension The reactive group-containing resin is then added with carbon black and kneaded to react the carbon black with the reactive group (graft the carbon black), cool and pulverize.

The type of resin to be coated is also not particularly limited. Generally, synthetic resins are used. Furthermore, since the amphoteric surfactants of resins with benzene rings in the structure are more effective, they are better in terms of dispersibility and dispersion stability. good.

As specific synthetic resins, thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glycolphthalate resin, epoxy resin, alkylbenzene resin, etc. can be used, or polystyrene Ethylene, polycarbonate, polyterephthalene Ethylene Diester, Polybutylene Terephthalate, Modified Polyphenylene Ether, Polyurethane, Poly(p-phenylenediamine), Polyimide, Polyimide, Polyamine Thermoplastic resins such as maleimide, polyether benzene, polyarylate, and polyether ether ketone.

The coating amount of the carbon black by the resin is preferably 1 to 30% by mass with respect to the total amount of the carbon black and the resin, and by setting it to be more than the above lower limit value, it tends to be sufficiently coated. On the other hand, by setting it below the above upper limit value, there is a tendency that the adhesion of resins can be prevented and the dispersibility will be good.

The carbon black coated with resin in this way can be used as a light-shielding material of the colored spacer according to a conventional method, and a color filter in which the colored spacer is used as a constituent element can be manufactured by a conventional method. If this type of carbon black is used, there is a tendency to achieve a colored spacer with a high shading rate and a low surface reflectance at low cost. In addition, it is also speculated that by coating the surface of carbon black with resin, it also has the effect of encapsulating Ca or Na in carbon black.

Moreover, in addition to the black color material, a dye may be used for the said organic coloring pigment. Examples of dyes that can be used as color materials include: azo dyes, anthraquinone dyes, phthalocyanine dyes, quinonimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine Basic dyes, etc.

As the azo dyes, for example, CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reaction Yellow 2, CI Reaction Red 17, CI Reaction Red 120, CI Reaction Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Mordant Red 7, CI Mordant Yellow 5, CI Mordant Black 7, etc.

Examples of anthraquinone 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. In addition, as the phthalocyanine-based dye, for example, CI Vat Blue 5 and the like can be cited, as the quinoneimine-based dye, for example, CI Basic Blue 3, CI Basic Blue 9 and the like, and as the quinoline-based dye, for example, CI Solvent Yellow 33, CI Acid Yellow 3, CI Disperse Yellow 64, etc., and examples of nitro dyes include CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42, and the like.

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

Furthermore, in the photosensitive coloring composition of the first aspect of the present invention, the average particle diameter of the pigment is a value obtained from the particle diameter of the pigment measured by dynamic light scattering (DLS). The particle size measurement is performed on the fully diluted photosensitive coloring composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by mass, but if it is the concentration recommended by the measuring device, it is based on the concentration), and it is performed at 25°C Next measurement.

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

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

Furthermore, in addition to these pigments, other black color materials can be further used. Among other black color materials, it is preferable to use organic black other than those expressed by the above general formula (1) from the viewpoint of easily suppressing the decrease in the voltage retention of the liquid crystal and suppressing the absorption of ultraviolet rays to control the shape or step difference. pigment. Examples of other organic black pigments include aniline black, perylene black, cyanine black, and the like.

Furthermore, in the second aspect of the present invention, inorganic black pigments can be used. Examples of inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among them, carbon black can be preferably used in terms of light shielding properties and image characteristics. As an example of carbon black, those listed in the first aspect can be used. In addition, other color materials such as the dyes listed in the first aspect can also be used.

In addition, the (a) colorant used in the photosensitive coloring composition of the third aspect of the present invention contains an organic pigment and carbon black. In this way, by using organic pigments that absorb less ultraviolet light, it is easy to control the shape or level difference; and, by using carbon black in addition to organic pigments, high shading properties can be achieved.

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

Among these, it is preferable to contain at least one of the following (1) to (4) from the viewpoint of light-shielding properties, or control of shape and level difference.

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

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

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

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

Among them, it is preferable to use a blue pigment and/or a purple pigment from the viewpoint of light-shielding in the visible light region, especially in the long wavelength region. In particular, in the absorption spectrum of carbon black, the absorbance decreases from the short wavelength toward the long wavelength, and the absorbance in the ultraviolet region is also higher than that of organic pigments. Therefore, from the viewpoint of both light-shielding and plate-making properties, it is better to use both A blue pigment and/or a purple pigment and carbon black are more preferably used in combination with a blue pigment and a purple pigment and carbon black.

In addition, from the viewpoint of light-shielding properties, the organic pigment preferably contains an organic black pigment. As the organic black pigment, those listed in the first aspect can be used. In addition, other organic coloring pigments, other black color materials, dyes, etc. listed in the first aspect may also be used.

In addition, the (a) colorant used in the photosensitive coloring composition for forming a colored spacer of the fourth aspect of the present invention is not particularly limited as long as it can form the desired colored spacer. For example, from the viewpoint of easily suppressing the absorption of ultraviolet rays and controlling the shape or the level difference, it is preferable to contain at least 1 selected from the group consisting of red pigments and orange pigments as the first aspect described above. Species, and at least one selected from the group consisting of blue pigments and purple pigments.

In this way, as the (a) colorant used in the photosensitive coloring composition for forming colored spacers of the fourth aspect, (a) colorant used in the photosensitive coloring composition of the first aspect can be applied In addition, those described as the (a) colorant used in the photosensitive coloring composition of the second or third aspect can also be applied.

On the other hand, in the photosensitive coloring composition for forming a colored spacer of the fourth aspect, from the viewpoint of light shielding properties, it is preferable to contain at least a black color material, and more preferably to contain at least carbon black. In addition, from the viewpoint of easily suppressing the decrease in the voltage retention rate of the liquid crystal and suppressing the absorption of ultraviolet rays to control the shape or the step difference, it is more preferable to include at least the above The organic black pigment. From the viewpoint of light-shielding properties and consideration of both suppression of the reduction in voltage retention of liquid crystals and control of shapes or steps, carbon black and organic black pigments can also be used in combination.

In the photosensitive coloring composition for forming a colored spacer of the fourth aspect, as the compounding amount of the colorants, the following preferable values in the photosensitive coloring composition of the present invention can be adopted. In addition, it can also be adjusted appropriately 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 No., Japanese Patent Application Publication No. 2014-146029, International Publication No. 2013/179237, Japanese Patent Application Publication No. 2011-107707, etc.

<(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. Examples include epoxy (meth)acrylate resins, acrylic resins, and carboxyl group-containing resins. Epoxy resins, carboxyl group-containing urethane resins, novolac resins, polyvinylphenol resins, etc., among which epoxy (meth)acrylate resins and acrylic resins are preferred. These can be used individually by 1 type or in mixture of a plurality of types.

As the (b) alkali-soluble resin used in the present invention, from the viewpoint of excellent plate-making properties, the following alkali-soluble resin (b1) and/or alkali-soluble resin (b2) (hereinafter, Sometimes called "carboxyl-containing epoxy (meth)acrylate resin").

<Alkali-soluble resin (b1)>

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

<Alkali-soluble resin (b2)>

It is obtained by adding epoxy resin to α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group, and then reacting with polyhydric alcohol, polybasic acid and/or its anhydride The alkali-soluble resin.

As the epoxy resin used as the raw material, for example, bisphenol A type epoxy resin (for example, "Epikote (registered trademark, the same below) 828", "Epikote1001", "Epikote1002" manufactured by Mitsubishi Chemical Corporation, "Epikote1004" etc.), epoxy resins obtained by the reaction of the alcoholic hydroxyl group of bisphenol A epoxy resin with epichlorohydrin (for example, "NER-1302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 323 , Softening point 76℃)), bisphenol F resin (for example, "Epikote807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Mitsubishi Chemical Corporation), by bisphenol F Epoxy resin obtained by the reaction of alcoholic hydroxyl group of epoxy resin with epichlorohydrin (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 resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Company), (ortho, meta, p) cresol novolac type epoxy resin (for example, Nippon Kayaku "EOCN (registered trademark, the same below)-102S", "EOCN-1020", "EOCN-104S"), triglycidyl isocyanurate (for example, "TEPIC( Registered trademark)”), triphenol methane type epoxy resin (for example, “EPPN (registered trademark, below) manufactured by Nippon Kayaku Co., Ltd. Same) -501", "EPN-502", "EPPN-503"), alicyclic epoxy resins ("Celloxide2021P", "Celloxide (registered trademark, the same below) EHPE" manufactured by Daicel Chemical Industry Co., Ltd.), will be manufactured by Epoxy resin obtained by epoxidation of phenol resin obtained by the reaction of dicyclopentadiene and phenol (for example, "EXA-7200" manufactured by DIC Corporation, "NC-7300" manufactured by Nippon Kayaku Co.), The epoxy resin etc. represented by general formula (B1)~(B4).

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

[化6]

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

[化7]

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

[化8]

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

[化9]

[化10]

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

[化11]

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

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

As α, β-unsaturated monocarboxylic acid or α, β-unsaturated monocarboxylic acid ester having a carboxyl group, (meth)acrylic acid, crotonic acid, ortho, meta or p-vinyl benzoic acid, (form Yl) α-position haloalkyl, alkoxy, halogen, nitro, cyano substituted monocarboxylic acids of acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(methyl) )Acrylic oxyethyl adipic acid, 2-(meth)acryloxyethyl phthalic acid, 2-(meth)acryloxyethyl hexahydrophthalic acid, 2-( Meth)acryloxyethyl maleic acid, 2-(meth)acryloxypropyl succinic acid, 2-(meth)acryloxypropyl adipic acid, 2-(methyl) ) Acrylic oxypropyl tetrahydrophthalic acid, 2-(meth) acryloxy propyl phthalic acid, 2-(meth) acryloxy propyl maleic acid, 2-( Meth) acryloxy butyl succinic acid, 2-(meth) acryloxy butyl adipic acid, 2-(meth) acryloxy butyl hydrophthalic acid, 2-( Meth) acryloxy butyl phthalic acid, 2-(meth)acrylic acid Oxybutyl maleic acid, as a single product obtained by adding (meth)acrylic acid to lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone Or add hydroxyalkyl (meth)acrylate, pentaerythritol tri(meth)acrylate and succinic acid (anhydride), phthalic acid (anhydride), maleic acid (anhydride) and other acids (anhydrides) Monomers, (meth)acrylic acid dimers, etc. Among these, (meth)acrylic acid is particularly preferable in terms of sensitivity.

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

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

In addition, epoxy resin, α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having carboxyl group, and esterification catalyst may be used alone, or two or more kinds may be used in combination.

The usage amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group is preferably in the range of 0.5 to 1.2 equivalents relative to 1 equivalent of epoxy group of epoxy resin. Preferably, it is in the range of 0.7 to 1.1 equivalents.

If the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group is small, the introduction amount of unsaturated group is insufficient, and the subsequent use of polybasic acid and/or its anhydride The response also became insufficient. In addition, a large amount of epoxy groups remains unfavorable. On the other hand, if the amount used is large, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxyl group will remain as an unreacted product. In either case, the hardening characteristics tend to deteriorate.

Examples of polybasic acids and/or their anhydrides include those selected from maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, and partial Phenyltricarboxylic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endo-methylene tetrahydrophthalic acid, chlorsaconic acid, methyltetrahydrophthalic acid, biphenyl tetracarboxylic acid , And one or more of these acid anhydrides.

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

With regard to the addition reaction of polybasic acid and/or its anhydride, known methods can also be used. It can be used with epoxy resin and α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester with carboxyl group. Under the same conditions of the addition reaction, continue the reaction to obtain the target product.

Regarding the addition amount of the polybasic acid and/or its acid anhydride component, the acid value of the resulting carboxyl-containing epoxy (meth)acrylate resin is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, and more Preferably, it is 50 mgKOH/g or more. In addition, it is preferably 150 mgKOH/g or less, more preferably 140 mgKOH/g or less, and still more preferably about 120 mgKOH/g. By setting it as the above lower limit value or more, the alkali developability tends to become better, and by setting it as the above upper limit value or less, the curing performance tends to become better.

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

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

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

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

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

In addition, a part of the epoxy (meth)acrylate resin containing carboxyl group may be replaced with another binder resin. That is, a carboxyl group-containing epoxy (meth)acrylate resin and other binder resins may be used in combination. In this case, it is preferable to set the ratio of the carboxyl group-containing epoxy (meth)acrylate resin in (b) alkali-soluble resin to 50% by mass or more, especially 80% by mass or more.

There are no restrictions on other binder resins that can be used in combination with the carboxyl group-containing epoxy (meth)acrylate resin, as long as it is selected from resins generally used in photosensitive coloring compositions. For example, Japanese Patent Laid-Open No. 2007-271727, Japanese Binder resins described in Japanese Patent Application Publication No. 2007-316620 and Japanese Patent Application Publication No. 2007-334290. In addition, all other binder resins may be used individually by 1 type, and may be used in combination of 2 or more types.

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

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

The unsaturated monomer (b1) includes, for example, unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; such as maleic acid, maleic anhydride, and fumaric acid , Itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, the unsaturated dicarboxylic acid of citraconic acid or its anhydride; succinic acid mono[2-(meth)acryloyloxyethyl] ester, Phthalic acid mono[2-(meth)acryloyloxyethyl] mono[(meth)acryloyloxyalkyl] ester of a two-valent or more polycarboxylic acid; such as ω-carboxypolyhexyl Lactone mono(meth)acrylate is a mono(meth)acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends; p-vinyl benzoic acid, etc. These unsaturated monomers (b1) can be used individually or in mixture of 2 or more types.

In addition, as the unsaturated monomer (b2), for example, N-substituted maleimines such as N-phenylmaleimines and N-cyclohexylmaleimines; such as styrene, Aromatic vinyl compounds such as α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether and vinyl naphthalene;

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

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

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

Vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetan Vinyl ethers of alkane; such as polystyrene, poly(methyl)acrylate, poly(n-butyl)acrylate, polysiloxane, which has a single (meth)acrylic acid group at the end of the polymer molecular chain The giant monomer and so on. 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 5-50% by mass, and more preferably 10-40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, there is a tendency to obtain a photosensitive coloring composition excellent in alkaline developability and storage stability.

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

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

<(c) Photopolymerization initiator>

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

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

[化12]

In the above general formula (I),

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

R ² represents an alkyl group which may have a substituent or an aryl group which may have a substituent.

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

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

R ⁵ and R ⁶ each independently represent an optionally substituted benzene ring or an optionally substituted naphthalene ring. Among them, at least one of R ⁵ and R ⁶ 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. Here, R ⁷ represents a haloalkyl group.

X represents a direct bond or a carbonyl group.

Z represents a direct bond or a carbonyl group.

Examples of the aromatic ring group in R ¹ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is preferably 30 or less, more preferably 12 or less, and still more preferably 8 or less. Moreover, it is usually 4 or more, preferably 6 or more. By setting it below the above upper limit value, the solubility tends to become good, and by setting it above the above lower limit value, there is a tendency that both sensitivity and solubility tend to be compatible.

環、聯三伸苯環、乙烷合萘環、熒蒽環、茀環等。 The aromatic hydrocarbon ring group means an aromatic hydrocarbon ring having one free valence. The aromatic hydrocarbon ring as the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, fused tetraphenyl ring, pyrene ring, benzene And pyrene ring,

Ring, terphenylene ring, ethane naphthalene ring, fluoranthene ring, sulphur ring, etc.

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

唑環、苯并異 噻唑環、苯并咪唑環、吡啶環、吡

環、嗒

環、嘧啶環、三

環、喹啉環、異喹啉環、

啉環、喹

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

Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thieno Furan ring, benziso

Azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring

Ring, ta

Ring, pyrimidine ring, three

Ring, quinoline ring, isoquinoline ring,

Quinoline ring

A morpholine ring, a phenanthridine ring, a benzimidazole ring, a piperidine ring, a quinazoline ring, a quinazolinone ring, a azulene ring, etc.

Examples of substituents that the aromatic ring group may have include alkyl groups, hydroxyl groups, alkoxy groups, halogen atoms, haloalkyl groups (an alkyl group in which part or all of the hydrogen atoms are substituted with halogen atoms), and haloalkoxy groups (An alkoxy group in which part or all of the hydrogen atoms are substituted with halogen atoms), etc., from the viewpoint of surface hardenability, a halogen atom, a haloalkyl group or a haloalkoxy group is preferred, and the ease of synthesis From a viewpoint, it is preferable not to be substituted.

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

The carbon number of the alkyl group in R ² is not particularly limited, but from the viewpoint of sensitivity, it is preferably 2 or more. 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.

Specific examples of the alkyl group include acetyl group, propyl group, butyryl group, etc. Among them, from the viewpoint of sensitivity, acetyl group or propyl group is preferred, and acetyl group is more preferred. . Examples of the substituent that the alkanoyl group may have include a hydroxyl group, an alkoxy group, a halogen atom, etc., and from the viewpoint of sensitivity, it is preferably unsubstituted.

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

Specific examples of the aryl group include a benzyl group, a tolyl group, and a naphthyl group. Among these groups, the benzyl group is more preferable from the viewpoint of sensitivity.

Examples of the substituent that the aryl group may have include a hydroxyl group, an alkoxy group, a halogen atom, and the like. From the viewpoint of sensitivity, it is preferably unsubstituted. Among them, from the viewpoint of sensitivity, it is preferable to set R ² as an alkyl group which may have a substituent, more preferably as an unsubstituted alkyl group, and still more preferably as an acetyl group. base.

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

Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, etc. Among these, from the viewpoint of solubility In particular, octyl or 2-ethylhexyl is preferred, and 2-ethylhexyl is more preferred.

Examples of the substituent that the alkyl group may have include a hydroxyl group, an alkoxy group, a halogen atom, a phosphoric acid group, and the like. From the viewpoint of ease of synthesis, it is more preferably unsubstituted. Among them, from the viewpoint of solubility, it is preferable to set R ³ as an alkyl group which may have a substituent, more preferably as an unsubstituted alkyl group, and still more preferably as 2-ethyl Base hexyl.

Examples of the aromatic ring group in R ⁴ include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number is preferably 30 or less, more preferably 12 or less, and still more preferably 8 or less. Moreover, it is usually 4 or more, preferably 6 or more. By setting it below the above upper limit value, the solubility tends to become good, and by setting it above the above lower limit value, there is a tendency that both sensitivity and solubility tend to be compatible.

環、聯三伸苯環、乙烷合萘環、熒蒽環、茀環等。 The aromatic hydrocarbon ring group means an aromatic hydrocarbon ring having one free valence. The aromatic hydrocarbon ring as the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, fused tetraphenyl ring, pyrene ring, benzene And pyrene ring,

Ring, terphenylene ring, ethane naphthalene ring, fluoranthene ring, sulphur ring, etc.

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

唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡

環、嗒

環、嘧啶環、三

環、喹啉環、異喹啉環、

啉環、喹

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

Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thieno Furan ring, benziso

Azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring

Ring, ta

Ring, pyrimidine ring, three

Ring, quinoline ring, isoquinoline ring,

Quinoline ring

A morpholine ring, a phenanthridine ring, a benzimidazole ring, a piperidine ring, a quinazoline ring, a quinazolinone ring, a azulene ring, etc.

Examples of substituents that the aromatic ring group may have include alkyl groups, hydroxyl groups, alkoxy groups, halogen atoms, etc. From the viewpoint of solubility, alkyl groups or alkoxy groups are preferred, and alkyl groups are more preferred. , More preferably a methyl group.

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, and still more preferably 3 or more. Moreover, from the viewpoint of compatibility, it is preferably 10 or less, more preferably 5 or less, and still more preferably 4 or less.

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

R ⁵ and R ⁶ each independently represent a benzene ring or a naphthalene ring which may have a substituent. Among them, at least one of R ⁵ and R ⁶ is a naphthalene ring which may have a substituent. Specific combinations include: R ⁵ is a combination of optionally substituted benzene ring and R ⁶ is optionally substituted naphthalene ring, R ⁵ is optionally substituted naphthalene ring and R ⁶ is optionally substituted The combination of benzene ring, R ⁵ is a naphthalene ring that may have substituents, and R ⁶ is a combination of naphthalene ring that may have substituents.

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

In the case where R ⁵ is a benzene ring which may have a substituent, an N atom is bonded to the 1-position of the benzene ring, R ⁶ is bonded to the 2-position, and X is bonded to the 4-position. Similarly, when R ⁶ is a benzene ring that may have a substituent, it may be exemplified that the N atom is bonded to the 1-position of the benzene ring, R ⁵ is bonded to the 2-position, and Z is bonded to the 4-position.

On the other hand, when R ⁵ is a naphthalene ring which may have a substituent, the X, N atom and R ⁶ bonded to R ⁵ in formula (I) may also be bonded to any position of the naphthalene ring. For example, it can be enumerated in the state where N atom is bonded to the 1-position of the naphthalene ring, R ⁶ is bonded to the 2-position and X is bonded to the 4-position, or R ⁶ is bonded to the 1-position of the naphthalene ring, and R ⁶ is bonded to the 2-position. A state where N atom is bonded to position and X is bonded to position 6, etc.

Similarly, when R ⁶ is a naphthalene ring which may have a substituent, the Z, N atom and R ⁵ bonded to R ⁶ in formula (I) may also be bonded to any position of the naphthalene ring. For example, it can be enumerated in the state where 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 the naphthalene ring is bonded to the 1-position with R ⁵ and 2 The position is bonded with N atom and the 6 position is bonded with Z, etc.

Examples of the substituent that may be possessed by the benzene ring or naphthalene ring in R ⁵ and R ⁶ include a hydroxyl group, an alkoxy group, and a halogen atom. From the viewpoint of sensitivity, it is more preferably unsubstituted.

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

R ⁷ represents a haloalkyl group, and the carbon number of the haloalkyl group in R ⁷ is not particularly limited. From the viewpoint of solubility, it is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. Moreover, from the viewpoint of compatibility, it is preferably 10 or less, more preferably 7 or less, and still more preferably 5 or less. The carbon chain in the haloalkyl group may be linear, branched, or cyclic. From the viewpoint of ease of manufacture, the carbon chain is preferably linear.

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

Specific examples of haloalkyl include: 2,2,3,3-tetrafluoropropyl, 2,2,2-trifluoroethyl, 2,2,3,3,4,4,5,5 -Octafluoropentyl and the like. Among these, 2,2,3,3-tetrafluoropropyl is more preferable from the viewpoint of ease of production. Examples of the substituent that the haloalkyl group may have include a hydroxyl group, an alkoxy group, and the like. From the viewpoint of ease of production, it is preferably unsubstituted.

X represents a direct bond or a carbonyl group, and from the viewpoint of adhesion, a direct bond is preferred, and from the viewpoint of sensitivity, a carbonyl group is preferred. In addition, Z represents a direct bond or a carbonyl group. From the viewpoint of adhesion, a direct bond is preferred, and from the viewpoint of sensitivity, a carbonyl group is preferred.

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

[化13]

[化14]

[化15]

[化16]

[化17]

[化18]

[化19]

[化20]

The (c) photopolymerization initiator in the photosensitive coloring composition of the present invention contains the oxime ester compound represented by the above general formula (I), or may further contain another photopolymerization initiator.

二唑衍生物、鹵甲基-對稱三

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

Diazole derivatives, halomethyl-symmetric three

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

A photopolymerization initiator may be used individually by 1 type, and may be used in combination of 2 or more types. In the photopolymerization initiator, a sensitizing dye and a polymerization accelerator corresponding to the wavelength of the image exposure light source can be prepared as needed to improve the sensitivity. As the sensitizing dye, there may be mentioned: Japanese Patent Laid-Open No. 4-221958, Dibenzopyran pigments described in Japanese Patent Laid-Open No. 4-219756, Japanese Patent Laid-Open No. 3-239703, Japanese Patent Coumarin pigments with heterocycles described in Kaihei 5-289335, Japanese Patent Laid-open No. 3-239703, 3-ketocoumarin compounds described in Japanese Patent Laid-open No. 5-289335, Japanese Patent The pyrromethene dye described in JP 6-19240, and Japanese Patent Publication No. 47-2528, Japanese Patent Publication No. 54-155292, Japanese Patent Publication No. 45-37377, Japan Japanese Patent Application Publication No. 48-84183, Japanese Patent Application Publication No. 52-112681, Japanese Patent Application Publication No. 58-15503, Japanese Patent Application Publication No. 60-88005, Japanese Patent Application Publication No. 59- 56403, Japanese Patent Laid-Open No. 2-69, Japanese Patent Laid-Open No. 57-168088, Japanese Patent Laid-Open No. 5-107761, Japanese Patent Laid-Open No. 5-210240, Japanese The coloring matter having a dialkylaminobenzene skeleton described in Japanese Patent Laid-Open No. 4-288818.

唑、2-(對二乙胺基苯基)苯并

唑、2-(對二甲胺基苯基)苯并[4,5]苯并

唑、2-(對二甲胺基苯基)苯并[6,7]苯并

唑、2,5-雙(對二乙胺基苯基)-1,3,4-

唑、2-(對二甲胺基苯基)苯并噻唑、2-(對二乙胺基苯基)苯并噻唑、2-(對二甲胺基苯基)苯并咪唑、2-(對二乙胺基苯基)苯并咪唑、2,5-雙(對二乙胺基苯基)-1,3,4-噻二唑、(對二甲胺基苯基)吡啶、(對二乙胺基苯基)吡啶、(對二甲胺基苯基)喹啉、(對二乙胺基苯基)喹啉、(對二甲胺基苯基)嘧啶、(對二乙胺基苯基)嘧啶等含對二烷胺基苯基之化合物等。其中最佳者為4,4'-二烷胺基苯并苯酮。又，增感色素可單獨使用1種，亦可併用2種以上。 Among these sensitizing dyes, preferred are amine-containing sensitizing dyes, and more preferred are compounds having an amine group and a phenyl group in the same molecule. Especially preferred are, for example: 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone Benzophenone compounds such as ketone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone; 2- (P-Dimethylaminophenyl)benzo

Azole, 2-(p-diethylaminophenyl)benzo

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

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

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

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

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

<(d) Ethylene Unsaturated Compound>

The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound. By containing (d) an ethylenically unsaturated compound, the sensitivity is improved. Ethylene used in the present invention The unsaturated compound is a compound having at least one ethylenically unsaturated group in the molecule. Specifically, examples include: (meth)acrylic acid, (meth)acrylic acid alkyl esters, acrylonitrile, styrene, and monoesters of carboxylic acids with one ethylenically unsaturated bond and polyhydric or monohydric alcohols Wait.

In the present invention, it is particularly preferable to use a multifunctional ethylenic monomer having two or more ethylenic unsaturated groups in one molecule. The number of ethylenically unsaturated groups contained in the multifunctional ethylenic monomer is not particularly limited, and is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably 8 or less, more preferably 7 or less. By setting it above the above lower limit value, there is a tendency for high sensitivity, and by setting it below the above upper limit value, there is a tendency for the solubility to a solvent to be improved.

Examples of polyfunctional ethylenic monomers include: esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polyols Polyhydric hydroxy compounds such as hydroxy compounds, esters obtained by esterification with unsaturated carboxylic acids and polycarboxylic acids, etc.

Examples of the esters of the above-mentioned aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, and trimethylolethane triacrylate. Acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate and other aliphatic polyhydroxy compound acrylates, Replace the acrylate of the exemplified compounds with methacrylate of methacrylate, similarly with itaconate of itaconate, crotonate of crotonate, or replacement of Malay The maleic acid ester of the acid ester.

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

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

In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl-containing (meth)acrylate or a polyisocyanate compound and a polyol and a hydroxyl-containing (meth) Ethyl (meth)acrylate urethanes obtained by the reaction of acrylates; such as epoxy acrylates which are the addition reactants of polyepoxy compounds and hydroxyl (meth)acrylate or (meth)acrylic acid; Acrylic amides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate are more useful.

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

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

<(e) Solvent>

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

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

Examples of such organic solvents include the following. Such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tertiary butyl ether, two Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-ethyl Glycol monoalkyl ethers of oxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

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

Such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, ethyl 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, two Propylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether of 3-methyl-3-methoxybutyl acetate Acetate;

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

Such as acetone, methyl ethyl ketone, methyl pentanone, methyl isopropyl ketone, methyl isopentanone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl pentanone, methyl Ketones such as methyl butanone, methylhexanone, methylnonanone and methoxymethylpentanone;

Such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl 1-valent or polyhydric alcohols of base alcohols;

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

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

Alkoxy carboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as chlorobutane and chloropentane; such as ether ketones of methoxymethylpentanone; such as Nitriles such as acetonitrile and benzonitrile.

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

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

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

Among them, propylene glycol monomethyl ether is particularly preferred in terms of the solubility of the constituent components in the composition. In addition, glycol monoalkyl ethers have high polarity. If the amount of addition is too large, the pigments tend to agglomerate, and the viscosity of the colored resin composition obtained thereafter will increase. The storage stability tends to decrease. The ratio of the glycol monoalkyl ethers is preferably 5 mass% to 30 mass %, and more preferably 5 mass% to 20 mass %.

Also, use an organic solvent with a boiling point above 150℃ (sometimes below It is also better to call it "high boiling point solvent"). By using such a high boiling point solvent in combination, the photosensitive coloring composition is not easy to dry out, and it has the effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed due to rapid drying.

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

The content of the high-boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. By setting it above the above lower limit value, for example, the tendency of color materials and the like to precipitate and solidify at the tip of the slit nozzle to cause foreign body defects can be suppressed, and by setting it below the above upper limit value, it is possible to suppress the composition The drying temperature becomes slower, which can suppress the tendency of poor tempo during the vacuum drying step or pre-baking pore marks.

Furthermore, the high boiling point solvent with a boiling point above 150°C may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, it may not contain a high boiling point above 150°C. Solvent.

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

<(f) Dispersant>

In the photosensitive coloring composition of the present invention, finely dispersing (a) the colorant and stabilizing the dispersion state are important for ensuring the stability of quality, and therefore includes (f) Dispersant.

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

Such as polymer dispersants derived from functional groups such as nitrogen-containing heterocyclic groups.

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

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

Also, examples of polymer dispersants include: urethane-based dispersants, acrylic-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, and monomers containing amine groups. And macromonomer dispersant, polyoxyethylene alkyl ether dispersant, polyoxyethylene diester dispersant, polyether phosphoric acid dispersant, polyester phosphoric acid dispersant, sorbitan aliphatic ester dispersant , Aliphatic modified polyester dispersant, etc.

As specific examples of such dispersants, trade names include EFKA (registered trademark, manufactured by BASF Corporation), DISPERBYK (registered trademark, manufactured by BYK-Chemie Corporation), Disparlon (registered trademark, manufactured by Kusumoto Chemical Corporation), SOLSPERSE ( Registered trademark, manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Co., Ltd.), etc. 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 polymer dispersant is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50,000 or less. Among them, from the viewpoint of the dispersibility of the pigment, the (f) dispersant is preferably The urethane-based polymer dispersant and/or the acrylic polymer dispersant containing a functional group, particularly preferably an acrylic polymer dispersant. Moreover, in terms of dispersibility and storage properties, a polymer dispersant having a basic functional group and having a polyester bond and/or a polyether bond is preferred.

As urethane-based and acrylic polymer dispersants, for example, DISPERBYK160~166, 182 series (all urethane series), DISPERBYK2000, 2001, LPN21116, etc. (all acrylic-based) (all of the above are Manufactured by BYK-Chemie company).

As a urethane-based polymer dispersant, if a preferable chemical structure is specifically exemplified, for example, a polyisocyanate compound, a compound with a number average molecular weight of 300 to 10,000 having 1 or 2 hydroxyl groups in the molecule can be mentioned. A dispersing resin with a weight average molecular weight of 1,000 to 200,000 obtained by reacting with a compound having active hydrogen and tertiary amine group in the same molecule. By treating these with a quaternary agent such as benzyl chloride, all or part of the tertiary amine group can be turned into a quaternary ammonium base.

Examples of the above-mentioned polyisocyanate compound include: p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate Aromatic diisocyanates such as isocyanate and toluidine diisocyanate, hexamethylene diisocyanate, methyl lysine diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate Aliphatic diisocyanate, isophorone diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), ω,ω'-diisocyanate dimethyl cyclohexane and other alicyclic diisocyanates, benzene two Aliphatic diisocyanates with aromatic rings such as methyl diisocyanate, α,α,α',α'-tetramethylxylylene diisocyanate, lysine triisocyanate, 1,6,11-undecane Triisocyanate, 1,8- Diisocyanato-4-isocyanatomethyl octane, 1,3,6-hexamethylene triisocyanate, dicycloheptane triisocyanate, tris(isocyanatophenylmethane), thiophosphoric acid tris(isocyanatobenzene) Triisocyanates such as cyanoacrylates, such terpolymers, water adducts, and these polyol adducts.

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

As a method for producing isocyanate terpolymers, the following methods can be cited: using appropriate trimerization catalysts for the above-mentioned polyisocyanates, such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates To perform the partial trimerization of isocyanate groups. After the trimerization is stopped by the addition of catalyst poison, the unreacted polyisocyanate is solvent extracted and removed by thin film distillation to obtain the target isocyanate-containing Urate-based polyisocyanate.

As a compound with a number average molecular weight of 300 to 10,000 having 1 or 2 hydroxyl groups in the same molecule, polyether diols, polyester diols, polycarbonate diols, polyolefin diols, etc., and these compounds can be cited The single-terminal hydroxyl group is an alkyl group with 1 to 25 carbon atoms and is alkoxylated and a mixture of these two or more.

Examples of the polyether glycol include polyether glycol, polyether ester glycol, and a mixture of two or more of these. Examples of polyether glycols include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, ethylene glycol-propylene glycol copolymer, polyoxytetramethylene glycol, and polyoxane Methylene glycol, polyoxyoctamethylene glycol and mixtures of two or more of them.

As the polyether ester diol, it can be exemplified by reacting an ether group-containing diol or a mixture with other diols with a dicarboxylic acid or an anhydride such as a polyester diol Those obtained by reacting with alkylene oxide, for example, poly(polyoxytetramethylene) adipate and the like.

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

Examples of polyester diols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and dicarboxylic acids Alcohol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2, 3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol , 2-Butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2, 4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene Diol, 2-methyl-1,8-octamethylene glycol, aliphatic diols such as 1,9-nonanediol, alicyclic diols such as bishydroxymethylcyclohexane, xylylene Diols, aromatic diols such as bishydroxyethoxybenzene, N-alkyl dialkanolamines such as N-methyldiethanolamine, etc.) obtained by polycondensation, such as polyethylene adipate, polyhexane Butylene diacid, polyhexamethylene adipate, polyethylene adipate/propylene glycol, etc., or polyols obtained by using the above-mentioned glycols or monohydric alcohols with 1 to 25 carbon atoms as initiators Lactone diol or polylactone monool, such as polycaprolactone diol, polymethylvalerolactone, and a mixture of two or more of these. As the polyester diol, the best one is polycaprolactone diol or polycaprolactone using an alcohol with carbon number 1 to 25 as the initiator.

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

The number average molecular weight of a compound having 1 or 2 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.

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

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

Examples of such compounds having active hydrogen and tertiary amino groups in the same molecule include: N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3- Propylenediamine, N,N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N -Diethylethylenediamine, N,N-dipropylethylenediamine, N,N-dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N- Diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1,4-butanediamine, etc.

唑環、苯并噻唑環、苯并噻二唑環等含氮雜五元環、吡啶環、嗒

環、嘧啶環、三

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

Azole ring, benzothiazole ring, benzothiadiazole ring and other nitrogen-containing five-membered ring, pyridine ring,

Ring, pyrimidine ring, three

Nitrogen-containing six-membered rings such as ring, quinoline ring, acridine ring and isoquinoline ring. Among the nitrogen-containing heterocycles, the imidazole ring or the triazole ring is preferred.

If specifically exemplified compounds having these imidazole rings and amino groups, 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, 1-(2-aminoethyl) Imidazole and so on.

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. .

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

The preferred blending ratio of the raw materials for the manufacture of urethane-based polymer dispersants is 10 with respect to 100 parts by mass of the polyisocyanate compound, and the number-average molecular weight of the compound having 1 or 2 hydroxyl groups in the same molecule is 10 ~200 parts by mass, preferably 20~190 parts by mass, and more preferably 30~180 parts by mass, 0.2~25 parts by mass, preferably 0.3~24 for compounds having active hydrogen and tertiary amine group in the same molecule Mass parts.

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

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

The introduction amount of the compound having active hydrogen and tertiary amine group in the same molecule is preferably controlled within the range of 1-100 mgKOH/g based on the amine value after the reaction. More preferably, it is in the range of 5 to 95 mgKOH/g. The amine value is a value expressed in mg of KOH corresponding to the acid value by neutralizing the basic amine group by acid. If the amine value is less than the above range, the dispersibility tends to decrease; and if it exceeds the above range, the developability tends to decrease.

Furthermore, in the case where the isocyanate group remains in the polymer dispersant in the above reaction, if the isocyanate group is further eliminated with an alcohol or an amine compound, the stability of the product over time becomes higher, which is preferable. The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually 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, the dispersibility and dispersion stability are poor; if it exceeds 200,000, the solubility is reduced, the dispersibility is poor, and it is difficult to control the reaction.

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

Examples of the unsaturated group-containing monomer having a functional group include (meth)acrylic acid, 2-(meth)acryloxyethyl succinic acid, 2-(meth)acryloxyethyl o-benzene Unsaturated monomers with carboxyl groups such as dicarboxylic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, acrylic acid dimer, dimethylaminoethyl (meth)acrylate, (methyl) ) Unsaturated monomers having tertiary amino groups and quaternary ammonium salt groups such as diethylaminoethyl acrylate and these quaternary products are taken as specific examples. These may be used individually by 1 type, and may use 2 or more types together.

酯、三環癸烷(甲基)丙烯酸酯、(甲基)丙烯酸四氫糠酯、N-乙烯基吡咯啶酮、苯乙烯及其衍生物、α-甲基苯乙烯、N-環己基馬來醯亞胺、N-苯基馬來醯亞胺、N-苄基馬來醯亞胺等N-取代馬來醯亞胺、丙烯腈、乙酸乙烯酯及聚(甲基)丙烯酸甲酯巨單體、聚苯乙烯巨單體、聚(甲基)丙烯酸2-羥基乙酯巨單體、聚乙二醇巨單體、聚丙二醇巨單體、聚己內酯巨單體等巨單體等。該等可單獨使用1種，亦可併用2種以上。 Examples of unsaturated group-containing monomers without functional groups include: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, ( N-Butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate Ester, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isopropyl (meth)acrylate

Ester, tricyclodecane (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexyl horse Leximine, N-phenylmaleimide, N-benzylmaleimide, N-substituted maleimide, acrylonitrile, vinyl acetate and poly(meth)acrylate Monomers, polystyrene macromonomers, poly(meth)acrylate 2-hydroxyethyl macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, polycaprolactone macromonomers and other macromonomers Wait. These may be used individually by 1 type, and may use 2 or more types together.

The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer containing an A block with a functional group and a B block without a functional group. In this case, the A block is derived from the aforementioned functional group In addition to the partial structure of the unsaturated group-containing monomer, it can also include the partial structure of the above-mentioned unsaturated group-containing monomer without functional groups. These can also be random copolymerization or block copolymerization. Contained in the A block. In addition, the content of the functional group-free partial structure in the A block is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.

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

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

[化21]

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

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

[化22]

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

When synthesizing the acrylic polymer dispersant, Japanese Patent Laid-Open No. 9-62002 or P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), BC Anderson, GDAndrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), right hand Koichi, Hatada Koichi, Polymer Processing, 36, 366 (1987), Higashimura Toshinobu, Sawmoto Mitsuo, Polymer Essays, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic , 109, 4737 (1987), Aida Takuzo, Inoue Shohei, Synthetic Organic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987) and other known methods.

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

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

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

Amine value [mgKOH/g]=(561×V)/(W×S)

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

In addition, the amine value of the block copolymer also differs depending on the presence and type of acidic groups that are the basis of the acid value, but generally the lower one is better, usually less than 10 mgKOH/g, and its weight average molecular weight (Mw) is higher Preferably, it is in the range of 1000 to 100,000. By setting it within the above range, there is a tendency to ensure good dispersibility.

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

[化23]

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

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

As specific examples of alkyl groups, methyl, ethyl, propyl, butyl, Pentyl, hexyl, heptyl, octyl, etc., among these, preferred are methyl, ethyl, propyl, butyl, pentyl, or hexyl, and more preferred are methyl, ethyl, propyl, Or butyl. Furthermore, it may be either linear or branched. Moreover, cyclic structures such as cyclohexyl and cyclohexylmethyl may be included.

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

Specific examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, anthryl, etc. Among them, preferred are Phenyl, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl, more preferably phenyl, methylphenyl, or ethylphenyl.

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

Specific examples of the aralkyl group include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, phenylisopropylidene, etc. Among them, phenylethylene is preferred. Methyl, phenylethylene, phenylethylene, or phenylethylene, more preferably phenylmethylene or phenylethylene.

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

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

[化24]

In the above formula (ii), R ³⁵ and R ³⁶ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group, R ³⁵ and R ³⁶ They may be bonded to each other to form a ring structure. R ³⁷ is a hydrogen atom or a methyl group. Z is the linking base of divalent.

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

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

Examples of substituents that may be possessed by the alkyl group, aralkyl group or aryl group in R ³¹ to R ^{33 in the} above formula (i) and R ³⁵ and R ³⁶ in the above formula (ii) include halogen atoms and alkoxy groups , Benzoyl, hydroxyl, etc.

In the above formulas (i) and (ii), as the divalent linking group X and Z, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R ⁴³ -group, -COOR ⁴⁴ -group [wherein, R ⁴³ and R ⁴⁴ are single bonds, alkylene groups with 1 to 10 carbons, or ether groups with 2 to 10 carbons (alkoxyalkyl)], etc., Preferably it is -COO-R ⁴⁴ -group. Further, in the above formula (I), as counter anions Y ^-, include ^{Cl -, Br -, I -} , ClO 4 -, BF 4 -, CH 3 COO -, PF 6 - and the like.

The content ratio of the repeating unit represented by the above formula (i) is not particularly limited. From the viewpoint of dispersibility, the sum of the content ratio of the repeating unit represented by the above formula (i) and the content ratio of the repeating unit represented by the above formula (ii) is preferably 60 mol% or less, more preferably It is 50 mol% or less, more preferably 40 mol% or less, and particularly preferably 35 mol% or less. In addition, 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 above formula (i) to the total repeating units of the polymer dispersant is not particularly limited. From the viewpoint of dispersibility, it is preferably 1 mol% or more, and more It is preferably 5 mol% or more, and more preferably 10 mol% or more. Furthermore, it is preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, and particularly preferably 15 mol% or less.

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

In addition, the polymer dispersant preferably has a repeating unit represented by the following formula (iii) (hereinafter, sometimes referred to as:) from the viewpoint of improving compatibility with binder components such as solvents and improving dispersion stability. Is the "repeated unit (iii)").

[化25]

In the above 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.

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

Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Among these, preferred is methyl, ethyl, propyl, butyl, pentyl, or hexyl, and more preferred is methyl, ethyl, propyl, or butyl. Furthermore, it may be either linear or branched. Moreover, cyclic structures such as cyclohexyl and cyclohexylmethyl may be included.

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

In addition, the content ratio of the repeating unit represented by the above formula (iii) in the total repeating units of the polymer dispersant is not particularly limited, and it is preferably 1 mol% or more, more preferably 2 mol% or more, More preferably, it is 4 mol% or more. Moreover, it is preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less. When it falls within the above range, there is a tendency that compatibility with solvents and other binder components and dispersion stability tend to be compatible.

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

[化26]

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

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

Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl. Among these, preferred is methyl, ethyl, propyl, butyl, pentyl, or hexyl, and more preferred is methyl, ethyl, propyl, or butyl. Furthermore, it may be either linear or branched. Moreover, cyclic structures such as cyclohexyl and cyclohexylmethyl may be included.

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

Specific examples of aryl groups include phenyl, methylphenyl, ethylphenyl, dimethylphenyl, diethylphenyl, naphthyl, anthryl, etc. Among them, preferred are Phenyl, methylphenyl, ethylphenyl, dimethylphenyl, or diethylphenyl, more preferably phenyl, methylphenyl, or ethylphenyl.

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

Specific examples of the aralkyl group include phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene, phenylisopropylidene, etc. Among them, phenylethylene is preferred. Methyl, phenylethylene, phenylethylene, or phenylethylene, more preferably phenylmethylene or phenylethylene.

Among them, 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.

Examples of the substituent that the alkyl group in R ³⁸ may have include a halogen atom and an alkoxy group. Moreover, as a substituent which an aryl group or an aralkyl group may have, a chain alkyl group, a halogen atom, an alkoxy group, etc. are mentioned. In addition, the chain-shaped alkyl group represented by R ³⁸ also includes either linear or branched chain.

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

啉等單體之重複單位。 The polymer dispersant may also have repeating units other than repeating unit (i), repeating unit (ii), repeating unit (iii), and repeating unit (iv). Examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate-based monomers such as (meth)acrylic acid chloride; (meth)acrylic acid (Meth)acrylamide monomers such as amide and N-methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic glycidyl ether; N- Methacrylic acid

Repeating units of monomers such as morpholines.

Regarding the polymer dispersant, from the viewpoint of further improving the dispersibility, it is preferable to include an A block having a repeating unit (i) and a repeating unit (ii), and not having A block copolymer of B block with repeating unit (i) and repeating unit (ii).

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

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

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

啉等單體之重複單位。 Repeating units other than repeating units (iii) and (iv) may also be contained in the B block. Examples of such repeating units include styrene monomers derived from styrene and α-methylstyrene; (Meth)acrylic acid salt monomers such as meth)acrylic acid chloride; (meth)acrylic acid amine monomers such as (meth)acrylic amide and N-methylol acrylamide; vinyl acetate; propylene Nitrile; allyl glycidyl ether, crotonic acid glycidyl ether; N-methacrylic acid

Repeating units of monomers such as morpholines.

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

Also, in terms of improving dispersion stability, (f) the dispersant is preferably Use with the following pigment derivatives.

<Other compounding ingredients of photosensitive coloring composition>

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

(1) Adhesion improver

In the photosensitive coloring composition of the present invention, in order to improve the adhesion to the substrate, an adhesion improving agent may be contained. As the adhesion improving agent, a silane coupling agent, a phosphoric acid group-containing compound, and the like are preferred. As the type of silane coupling agent, various silane coupling agents such as epoxy-based, (meth)acrylic-based, amine-based, etc. can be used alone, or two or more of them can be mixed and used.

As a preferable silane coupling agent, for example, (meth)acrylic acid such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, etc. Oxyoxysilanes, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxy propyl trimethoxy silane, 3-glycidoxy propyl methyl bis Silicone oxides such as ethoxysilane, 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, 3-isocyanatopropyltriethyl Isocyanate-based silanes such as oxysilanes, especially silane coupling agents of epoxy silanes. As the phosphoric acid group-containing compound, a (meth)acrylic acid group-containing phosphoric acid ester is preferred, and one represented by the following general formula (g1), (g2) or (g3) is preferred.

[化27]

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

(2) Surfactant

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

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

Examples of such surfactants include: TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by NEOS), BYK-300, BYK-325, BYK-330 (manufactured by BYK-Chemie), KP340 ( Shin-Etsu Silicones), F-470, F-475, F-478, F-559 (manufactured by DIC), SH7PA (manufactured by Toray Silicone), DS-401 (manufactured by Daikin), L-77 ( Nippon Unicar Corporation), FC4430 (Sumitomo 3M Corporation), etc. Furthermore, one type of surfactant can be used, or two or more types can be used in any combination and ratio And use.

(3) Pigment derivatives

系、蒽醌系、陰丹士林系、苝系、紫環酮系、二酮基吡咯并吡咯系、二

系等衍生物，其中，較佳為酞菁系、喹酞酮系。 In the photosensitive coloring composition of the present invention, in order to improve dispersibility and storage properties, a pigment derivative may be contained as a dispersion aid. Examples of pigment derivatives include: azo series, phthalocyanine series, quinacridone series, benzimidazolone series, quinophthalone series, isoindolinone series, two

Series, anthraquinone series, indanthrene series, perylene series, pericone series, diketopyrrolopyrrole series, two

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

As the substituent of the pigment derivative, sulfonic acid group, sulfonamide group and its quaternary salt, phthaliminomethyl, dialkylaminoalkyl group, hydroxyl group, carboxyl group, amide group, etc. Those formed by bonding to the pigment skeleton directly or via an alkyl group, an aryl group, a heterocyclic group, etc. are preferably a sulfonic acid group. In addition, these substituents may be substituted in plural in one pigment skeleton.

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

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

(4) Photoacid generator

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

、2-(4-甲氧基苯基)-4,6-雙三氯甲基三

等三

化合物等，但並不限於此。 Among the photoacid generators, those having greater solubility in solvents, in particular, solvents used in photosensitive coloring compositions are preferred. Examples include: diphenyl iodonium, xylyl iodonium, phenyl (p-anisyl) iodonium, bis(m-nitrophenyl) iodonium, bis(p-tertiary butylphenyl) iodonium, bis(p-chlorobenzene) Diaryl iodonium, bis(n-dodecyl) iodonium, p-isobutylphenyl (p-tolyl) iodonium, p-isopropylphenyl (p-tolyl) iodonium, or triphenyl amenium Onium and other triarylsulfonium chloride, bromide, or fluoroboride, hexafluorophosphate, hexafluoroarsenate, aromatic sulfonate, tetrakis (pentafluorophenyl) borate, etc., or diphenyl Phosphonium organoboron complexes such as methylbenzylmethylsulfonium(n-butyl)triphenylborate, or 2-methyl-4,6-bistrichloromethyltri

, 2-(4-Methoxyphenyl)-4,6-bistrichloromethyltri

Wait three

Compound etc., but not limited to this.

(5) Crosslinking agent

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

[化28]

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

Here, the aryl group with 6 to 12 carbon atoms is typically phenyl, 1-naphthyl or 2-naphthyl, and these phenyl or naphthyl groups may also be bonded with alkyl, alkoxy, or halogen atoms And other substituents. The alkyl group and the alkoxy group may each have about 1 to 6 carbon atoms. The alkyl group represented by R ⁶⁸ is preferably the above-mentioned methyl or ethyl group, especially methyl group.

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

[化29]

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

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

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

-2-酮(通稱N-乙基二羥甲基三

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

二

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

-2-one (commonly known as N-ethyl dimethylol tri

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

two

-4-one (commonly known as dimethylolurea) or its dimethyl ether body, tetramethylolglyoxal dialkyl urea or its tetramethyl ether body.

In addition, these crosslinking agents may be used individually by 1 type, and may be used in combination of 2 or more types. The amount when the crosslinking agent is used is preferably 0.1 to 15% by mass, and more preferably 0.5 to 10% by mass relative to the total solid content of the photosensitive color composition.

(6) Mercapto compounds

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

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

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

Azole, 2-mercaptobenzimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bismercaptopropionate, butanediol bismercaptoacetate, ethylene glycol Dimercaptoacetate, trimethylolpropane trimercaptoacetate, butanediol bis-methylpropionate, trimethylolpropane trimercaptopropionate, trimethylolpropane trimercaptoacetate, pentaerythritol Tetramercaptopropionate, pentaerythritol tetramercaptoacetate, trihydroxyethyl trimercaptopropionate, ethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), 1 , 4-bis(3-methylbutanoyloxy)butane, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate) Acid ester), ethylene glycol bis(3-mercaptoisobutyrate), butanediol bis(3-mercaptoisobutyrate), trimethylolpropane tris(3-mercaptoisobutyrate), 1, 3,5-Tris(3-mercaptobutoxyethyl)-1,3,5-tris

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

<The amount of ingredients in the photosensitive color composition>

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

By setting the content of (a) colorant to above the above lower limit value, there is a tendency to obtain sufficient optical density (OD); in addition, by setting it below the above upper limit value, it is easy to obtain sufficient plate-making characteristics tendency.

Moreover, in the first aspect and the fourth aspect, relative to 100 parts by mass of the (a) colorant, at least one pigment selected from the group consisting of red pigments and orange pigments is preferably 1 part by mass or more, It is more preferably 2 parts by mass or more, and still more preferably 3 parts by mass or more. Furthermore, 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, still more preferably 10 parts by mass or less, and particularly preferably 7 parts by mass or less. By setting it above the above lower limit value, there is a tendency to obtain a sufficient optical density (OD); by setting it below the above upper limit value, there is a tendency to ensure plate-making characteristics.

In addition, in the first aspect and the fourth aspect, relative to 100 parts by mass of the (a) colorant, at least one pigment selected from the group consisting of blue pigments and purple pigments It is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, still 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, most preferably 65 parts by mass or more . Furthermore, 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. By setting it above the above lower limit value, there is a tendency to ensure light-shielding properties; by setting it below the above upper limit value, there is a tendency to ensure plate making characteristics.

Furthermore, in the second aspect, the content of the organic black pigment represented by the general formula (1) with respect to 100 parts by mass of the (a) colorant is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and It is preferably 20 parts by mass or more, more preferably 40 parts by mass or more, particularly preferably 60 parts by mass or more, and most preferably 70 parts by mass or more. Furthermore, 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. By setting it above the above lower limit value, there is a tendency to improve the light-shielding property; by setting it below the above upper limit value, there is a tendency to suppress the decrease in reliability.

Furthermore, in the third aspect, relative to 100 parts by mass of the (a) colorant, the organic pigment is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more. Furthermore, it is preferably 99 parts by mass or less, more preferably 95 parts by mass or less, still more preferably 90 parts by mass or less, particularly preferably 85 parts by mass or less, and most preferably 80 parts by mass or less. By setting it above the above lower limit value, there is a tendency to ensure plate-making characteristics; by setting it below the above upper limit value, there is a tendency to obtain a sufficient optical density (OD).

In addition, in the third aspect, relative to 100 parts by mass of the (a) colorant, at least one pigment selected from the group consisting of red pigments and orange pigments is preferably 0 parts by mass or more, more preferably 1 part by mass Parts or more, more preferably 2 parts by mass or more. also, It is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, particularly preferably 10 parts by mass or less, and most preferably 0 parts by mass. By setting it above the above lower limit value, there is a tendency to obtain a sufficient optical density (OD); by setting it below the above upper limit value, there is a tendency to ensure plate-making characteristics.

In addition, in the third aspect, relative to 100 parts by mass of the (a) colorant, at least one pigment selected from the group consisting of blue pigments and purple pigments is preferably 20 parts by mass or more, more preferably 30 parts by mass Parts by mass or more, more preferably 40 parts by mass or more, still more preferably 50 parts by mass or more, particularly preferably 60 parts by mass or more, most preferably 65 parts by mass or more. Furthermore, 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. By setting it above the above lower limit value, there is a tendency to ensure light-shielding properties; by setting it below the above upper limit value, there is a tendency to ensure plate making characteristics.

When (a) the colorant contains an organic black pigment, relative to 100 parts by mass of the (a) colorant, the organic black pigment is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 20 parts by mass More than. 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. By setting it above the above lower limit value, there is a tendency to obtain a sufficient optical density (OD); by setting it below the above upper limit value, there is a tendency to ensure plate-making characteristics.

When (a) the colorant contains carbon black, relative to 100 parts by mass of the (a) colorant, the carbon black is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass or more , Particularly preferably 20 parts by mass or more. Furthermore, 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. By setting it above the above lower limit value, there is a tendency to obtain sufficient optical density (OD); by setting it below the above upper limit value, it is possible to ensure The tendency of the version features.

(b) The content of the alkali-soluble resin relative to the total solid content of the photosensitive coloring composition of the present invention is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more, more preferably 30% by mass or more. It is generally 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, and particularly preferably 40% by mass or less.

By setting the content of the (b) alkali-soluble resin to be more than the above lower limit, there is a tendency that the solubility of the unexposed part in the developer can be suppressed and poor development can be suppressed. Moreover, by setting it as below the said upper limit, there exists a tendency for the permeability of a developing solution to an exposure part to be suppressed to become high, and to suppress the sharpness of a pixel or a tendency for adhesiveness to fall.

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

By setting the content ratio of (c) photopolymerization initiator to be higher than the above lower limit, there is a tendency to suppress the decrease in sensitivity; by setting the content of the photopolymerization initiator to be lower than the above upper limit, it is possible to suppress the unexposed part in the developer The solubility is reduced to suppress the tendency of poor development.

(c) The content of the oxime ester compound represented by the general formula (I) contained in the photopolymerization initiator is not particularly limited, but is usually 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, more preferably 70% by mass or less Above, it is particularly preferably 90% by mass or more, and usually 100% by mass or less. By setting it as the above lower limit or more, the surface smoothness of the obtained hardened product tends to become better.

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

By setting the content ratio of the polymerization accelerator to above the above lower limit, there is a tendency to suppress the decrease in sensitivity to exposure light; by setting below the above upper limit, it is possible to suppress the unexposed part in the developer The solubility is reduced to suppress the tendency of poor development. Also, regarding the blending ratio of the sensitizing dye in the photosensitive coloring composition of the present invention, from the viewpoint of sensitivity, the total solid content in the photosensitive coloring composition is usually 20% by mass or less, preferably It is 15% by mass or less, and more preferably 10% by mass or less.

(d) The content of the ethylenically unsaturated compound is generally 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less relative to the total solid content of the photosensitive coloring composition of the present invention. By setting the content ratio of the (d) ethylenically unsaturated compound to the above upper limit or less, there is a tendency that the permeability of the developer to the exposed part can be suppressed from increasing, and a good image tends to be easily obtained. In addition, the lower limit of the content of (d) ethylenically unsaturated compound is usually 1% by mass or more, preferably 5% by mass or more.

Furthermore, the photosensitive coloring composition of the present invention uses the solvent (e) so that the solid content concentration thereof is usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably The liquid is prepared in a manner of 30% by mass or less.

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

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

By setting the content ratio of (f) dispersant to above the above lower limit, it tends to be easy to obtain sufficient dispersibility; by setting below the above upper limit, it is possible to relatively reduce the ratio of other components It suppresses the tendency of decrease in sensitivity and plate making performance.

In the case of using the adhesion improver, its content relative to the total solid content in the photosensitive color composition is usually 0.1 to 5 mass%, preferably 0.2 to 3 mass%, and more preferably 0.4 to 2 mass% . By setting the content ratio of the adhesion improver to be higher than the above lower limit value, there is a tendency that the adhesion improvement effect can be sufficiently obtained; by setting the content ratio of the adhesion improving agent to be lower than the above upper limit value, it is possible to suppress a decrease in sensitivity or residue after development. The tendency to become a defect.

In addition, when a surfactant is used, its content relative to the total solid content in the photosensitive color composition is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, and more preferably 0.01 to 0.5 % By mass, preferably 0.03 to 0.3% by mass. By setting the content of the surfactant to above the above lower limit, the smoothness and uniformity of the coating film tends to be easily expressed; by setting it below the above upper limit, the smoothness of the coating film is easy to express , Uniformity, and also suppress the tendency of other characteristics to deteriorate.

<Physical properties of photosensitive coloring composition>

The photosensitive coloring composition of the present invention can be preferably used to form a colored spacer, and from the viewpoint of use as a colored spacer, it is preferably black. Furthermore, the optical density (OD) per 1 μm of the film thickness of the coating film is preferably 1.0 or more, more preferably 1.2 or more, still more preferably 1.5 or more, 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 manufacturing photosensitive coloring composition>

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

The dispersion treatment is usually preferably carried out in a system in which (a) a colorant, (e) a solvent, and (f) a dispersant, and (b) a part or all of an alkali-soluble resin are used in combination (hereinafter, sometimes provided in The mixture of the dispersion treatment and the composition obtained by the treatment are called "ink" or "pigment dispersion"). In particular, if a polymer dispersant is used as the (f) dispersant, the viscosity increase over time of the obtained ink and photoresist is suppressed (excellent in dispersion stability), which is preferable.

Thus, in the step of manufacturing a photoresist, it is preferable to manufacture a pigment dispersion liquid containing at least (a) a colorant, (e) a solvent, and (f) a dispersant. As the (a) colorant, (e) organic solvent, and (f) dispersant that can be used in the pigment dispersion liquid, those described in the photosensitive coloring composition can be preferably adopted.

Furthermore, when the liquid containing the total components of the photosensitive coloring composition is subjected to dispersion treatment, the heat generated during the dispersion treatment is highly reflective. Possibility to modify the components of the response. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.

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

When the glossiness of the photoresist is low, the dispersion treatment is insufficient, and coarse pigment (color material) particles remain in many cases, and the developability, adhesion, resolution, etc. may become insufficient. In addition, if the dispersion treatment is performed until the gloss value exceeds the above-mentioned range, the pigment is broken and a large number of ultrafine particles are generated, and therefore the dispersion stability tends to be impaired.

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

Next, the ink obtained by the above-mentioned dispersion treatment is mixed with the above-mentioned other components contained in the photoresist to form a uniform solution. In the photoresist manufacturing process, there are many cases where fine dirt is mixed into the liquid. Therefore, it is more desirable to filter the obtained photoresist with a filter or the like.

[Hardened material]

By curing the photosensitive coloring composition of the present invention, a cured product can be obtained. The cured product obtained by curing the photosensitive coloring composition can be preferably used as a coloring spacer.

[Coloring spacer]

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

(1) Support

The material of the support used to form the colored spacer is not particularly limited as long as it has an appropriate strength. Transparent substrates are mainly used. Examples of materials include: polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, and polycarbonate Thermosetting resin sheets such as thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, poly(meth)acrylic resins, and various glasses.

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

In order to improve surface properties such as adhesiveness, the support may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, or urethane-based resin film forming treatment, etc., if necessary. The thickness of the transparent substrate is usually set to 0.05-10 mm, preferably in the range of 0.1-7 mm. In addition, in the case of performing film forming processing of various resins, the film thickness is usually 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 well-known color filters The same purpose as the photosensitive color composition. Hereinafter, the case of using as a colored spacer (black photosensitive spacer) will be described based on a specific example of a method for forming a black photosensitive spacer using the photosensitive colored composition of the present invention.

Generally, the photosensitive coloring composition is supplied in a film or pattern shape by a method such as coating on a substrate on which a black photosensitive spacer is to be provided, and the solvent is dried. Then, pattern formation is performed by methods such as exposure-development photolithography. Thereafter, if necessary, additional exposure or thermal curing treatment is performed, thereby forming a black photosensitive spacer on the substrate.

(3) Formation of colored spacers

[1] How to supply substrates

The photosensitive coloring composition of the present invention is usually supplied on the substrate in a state of being dissolved or dispersed in a solvent. The supply method can be performed by a conventionally known method, such as a spin coater method, a wire bar coating method, a flow coating method, a die nozzle coating method, a roll coating method, a spraying method, and the like. Moreover, it may be supplied in a pattern by an inkjet method, a printing method, or the like.

Among them, if the die nozzle coating method is used, the amount of coating liquid used is greatly reduced, and there is no such comprehensive viewpoint as the influence of mist attached when using the spin coating method, and the suppression of foreign matter generation. Better.

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

However, when using the photosensitive coloring composition of the present invention, When the black photosensitive spacers with different heights are formed at one time by the shadow method, the heights of the black photosensitive spacers finally formed are different.

Furthermore, as the substrate, a known substrate such as a glass substrate can be used. Furthermore, the surface of the substrate is preferably flat.

[2] Drying method

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

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

[3] Exposure method

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

At this time, in order to prevent the decrease in sensitivity of the photopolymerizable layer caused by oxygen as necessary, it can also be carried out in a deoxidized environment, or polyethylene can be formed on the photopolymerizable layer. The oxygen barrier layer such as the alcohol layer is then exposed.

As a preferable aspect of the present invention, when forming black photosensitive spacers with different heights simultaneously by photolithography, for example, a light-shielding part (transmittance of 0%) and a plurality of openings are used It is an exposure mask for openings (middle penetration openings) with a lower average light transmittance than the openings with the highest average light transmittance (complete penetration openings). With this method, the difference in the residual film rate is caused by the difference in the average light transmittance between the middle penetration opening and the complete penetration opening, that is, the difference in exposure.

The intermediate penetration opening is known, for example, by a method of forming a light-shielding pattern with a matrix of light-shielding units having tiny polygons. In addition, a method of controlling the light transmittance by a film of a chromium-based, molybdenum-based, tungsten-based, silicon-based, or other material as an absorber is known.

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

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

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

[4] Development method

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

Examples of basic compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, Potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide and other inorganic alkaline compounds, or single. Double or triethanolamine, single. Double or trimethylamine, single. Double or triethylamine, single or double isopropylamine, n-butylamine, single. Organic basic compounds such as bis or triisopropanolamine, ethyleneimine, ethylenediimide, tetramethylammonium hydroxide (TMAH), choline, etc. These basic compounds may also be a mixture of two or more kinds.

Examples of the above-mentioned surfactant include: polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. Nonionic surfactants such as alkyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfate, alkyl sulfonate, sulfosuccinate and other anionic interface Active agent; amphoteric surfactants such as alkyl betaines and amino acids.

As the organic solvent, for example, isopropanol, benzyl alcohol, ethyl siloxol, butyl siloxol, phenyl siloxol, propylene glycol, diacetone alcohol, etc. The organic solvent may be used alone or in combination with an aqueous solution.

The conditions of the development treatment are not particularly limited. Generally, the development temperature is in the range of 10-50°C, among which 15-45°C is preferred, and 20-40°C is particularly preferred. The developing method can use immersion developing method, jet developing method, Any method such as magnetic brush development method and ultrasonic development method.

[5] Additional exposure and thermal hardening treatment

For the developed substrate, additional exposure may be performed by the same method as the above-mentioned exposure method as needed, and thermal hardening treatment may also be performed. Regarding the thermal hardening treatment conditions at this time, the temperature is selected in the range of 100°C to 280°C, preferably 150°C to 250°C, and the time is selected in the range of 5 minutes to 60 minutes.

The size or shape of the colored spacer of the present invention is appropriately adjusted according to the specifications of the color filter to which the colored spacer is applied. The photosensitive colored composition of the present invention is particularly suitable for forming the spacer simultaneously by photolithography. It is more useful for black photosensitive spacers that are different in height from the sub-spacers. In this case, the height of the spacers is usually about 2~7μm, and the sub-spacers have a height that is usually about 0.2~1.5μm lower than the spacers. .

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

[Color filter]

The color filter of the present invention is one having the coloring spacer of the present invention as described above, for example, a black matrix, red, green, etc. are laminated on a glass substrate as a transparent substrate. The blue pixel colored layer and the protective layer are formed by forming colored spacers and then forming an alignment film.

The color filter with the colored spacer of the present invention is bonded to the liquid crystal drive side substrate to form a liquid crystal cell, and liquid crystal is injected into the formed liquid crystal cell, thereby making it possible to manufacture a liquid crystal with the colored spacer of the present invention Video display devices such as display devices.

Example

Next, examples and comparative examples are given to explain the present invention more specifically, but the present invention is not limited to the following examples as long as it does not exceed the gist. The constituent 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 the chemical structure represented by the following formula (2))

[化30]

<Alkali-soluble resin-I>

The temperature was increased to 120°C while stirring 145 parts by mass of propylene glycol monomethyl ether acetate while replacing it with nitrogen. At this time, 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, and it cost 3 2,2'-azobis-2- 8.47 parts by mass of methyl butyronitrile, and further continued stirring at 90°C for 2 hours. Next, the inside of the reaction vessel was changed to air replacement, 0.7 parts by mass of tris-dimethylaminomethyl phenol and 0.12 parts by mass of hydroquinone were put into 43.2 parts by mass of acrylic acid, and the reaction was continued at 100°C for 12 hours. Then, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added, and the reaction was carried out at 100°C for 3.5 hours. The weight average molecular weight Mw measured by GPC of the alkali-soluble resin-I obtained in this way was about 8,400, and the acid value was 80 mgKOH/g.

<Alkali-soluble resin-II>

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

<Dispersant-I>

"DISPERBYK-LPN21116" manufactured by BYK-Chemie (including the A block with a quaternary ammonium salt group and a tertiary amino group in the side chain and an acrylic AB block without a quaternary ammonium salt group and an amino group Stage copolymer. The amine value is 70mgKOH/g. The acid value is less than 1mgKOH/g.)

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

[化31]

<Dispersant-II>

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

<Pigment Derivatives>

"Solsperse12000" manufactured by Lubrizol

<Solvent-I>

PGMEA: Propylene glycol monomethyl ether acetate

<Solvent-II>

MB: 3-ethoxybutanol

<Photopolymerization Initiator-I>

Irgacure OXE03 (made by BASF Corporation)

[化32]

<Photopolymerization initiator-II>

[化33]

<Photopolymerization initiator-III>

[化34]

<Photopolymerizable monomer>

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

<Additive>

KAYAMER PM-21 (containing methacrylic acid) manufactured by Nippon Kayaku Co., Ltd. Phosphate Ester of Acetone)

<Surfactant>

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

<Evaluation of Optical Density (OD)>

The optical density (OD) was measured by passing through a densitometer (“D200-II” manufactured by GretagMacbeth). Furthermore, the film thickness of the measurement site was also measured, and the optical density (unit OD) per unit film thickness (1 μm) was calculated.

<Evaluation of substrate adhesion>

For the target pattern, the value of the opening diameter (μm) of the smallest opening diameter among those with good resolution and the pattern remaining on the substrate is set as the smallest close contact. The smaller the value, the better the substrate adhesion.

<Evaluation of Surface Smoothness>

For the target pattern, observe whether the heated surface has wrinkles in a field of 70μm×70μm with an optical microscope. In addition, the evaluation criteria are as follows.

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

×: Micron-level wrinkles on the pattern surface are extremely obvious

<Evaluation of surface roughness>

For the target pattern, the three-dimensional non-contact surface shape measurement system Micromap of Ryoka Systems Co., Ltd. uses a 50x optical lens to measure the surface roughness Sa (arithmetic mean roughness) in a field of view of 70μm×70μm in a focus mode. Degrees, nm).

<Preparation of Pigment Dispersion Liquid 1>

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

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

[Table 1]

<Preparation of Pigment Dispersion Liquids 2 and 3>

Except that the pigment, dispersant, dispersing aid, alkali-soluble resin, and solvent described in Table 1 were mixed so that the mass ratio described in Table 1 was mixed, a pigment dispersion liquid 2 was prepared in the same manner as the pigment dispersion liquid 1. And 3.

<Pigment Dispersion 4 (Coated Carbon Black Dispersion)>

Carbon black is manufactured by the usual oil furnace method. Among them, as the feedstock oil, Na, Ethylene bottom oil with less Ca and S content, using coke oven gas for combustion. Furthermore, as the reaction stop water, pure water treated with an ion exchange resin was used. Using a homomixer, 540 g of the obtained carbon black and 14,500 g of pure water were mixed together at 5,000 to 6,000 rpm for 30 minutes to obtain a slurry. This slurry was transferred to a container with a screw-type mixer, and while mixing at about 1,000 rpm, 600 g of toluene in which 60 g of epoxy resin "Epikote 828" (manufactured by Mitsubishi Chemical Corporation) was dissolved was added in small amounts. In about 15 minutes, all the carbon black dispersed in the water moved to the toluene side and became about 1mm particles.

Next, after shaking water with a 60-mesh metal 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 so that the mass ratio described in Table 2 would be obtained.

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

The zirconia beads are used as beads and added with the same mass as the dispersion. After the dispersion is completed, the beads are separated from the dispersion by a filter.

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

Using the pigment dispersions 1 to 4 prepared above, each component was added so that the blending ratios in Table 2 would become, and then PGMEA was added so that the solid content became 22% by mass and stirred and dissolved to prepare a photosensitive coloring composition . Using the obtained photosensitive coloring composition, it evaluated by the following method. Furthermore, the upper row values in Table 2 indicate the usage amount of each ingredient. On the other hand, the value in the lower stage represents the solid content of each component in terms of the content ratio relative to the total solid content of the photosensitive coloring composition.

[Table 2]

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

A spin coater was used to coat each photosensitive coloring composition on a glass substrate ("AN100" manufactured by AGC). Then, it heated and dried on a hotplate at 100 degreeC for 70 second, and formed the coating film. For the obtained coating film, a circular pattern of various diameters with a diameter of 5-50μm (5-20μm: every 1μm; 25μm-50μm: every 5μm) is used with a fully penetrating opening and a diameter of 5-50μm ( 5~20μm: every 1μm; 25μm~50μm: every 5μm) the middle penetration opening of the circular pattern of various diameters, and the exposure mask with a linear opening (complete penetration) with a width of 100μm . The middle penetration opening is a thin film of Cr oxide and the light transmittance at a wavelength of 365nm is set to 10±2%. The exposure gap (the distance between the mask and the coated surface) is 220 μm. As the irradiation light, ultraviolet rays with an intensity of 32 mW/cm ² at a wavelength of 365 nm were used, and the exposure amount was set to 100 mJ/cm ² . In addition, ultraviolet irradiation is performed under air.

Then, using a developer containing an aqueous solution containing 0.05% by mass of potassium hydroxide and 0.08% by mass of a non-ionic surfactant ("A-60" manufactured by Kao Corporation), a water pressure of 0.15MPa at 25°C After the spray development, the development is stopped with pure water and washed with water spray. The spray developing time is adjusted between 10 and 120 seconds, and is set to 1.5 times the time to dissolve and remove the unexposed coating film. Through these operations, the pattern with the excess part removed is obtained. The substrate with the pattern formed was heated in an oven at 230° C. for 20 minutes to harden the pattern to obtain a substantially cylindrical spacer pattern.

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

It was confirmed that the coated substrate using the photosensitive coloring composition of Examples 1 and 2 had a high unit OD, excellent light-shielding properties, and excellent surface smoothness. In addition, the adhesion of the substrate through the opening in the middle is also good. On the other hand, it was confirmed that Comparative Examples 1 to 3 and The unit OD values of Examples 1 and 2 are the same, but the surface smoothness is poor, and the adhesion of the substrate through the opening in the middle is poor.

Generally, in order to improve the light-shielding property of the colored spacer, a method of increasing the pigment concentration or a method of using a pigment with a higher light-shielding property is known. However, it is believed that if this method is applied, the UV transmittance will decrease, resulting in a difference in cross-linking density in the film thickness direction. Compared with the bottom of the film, the cross-linking density of the film surface becomes higher, and the heat shrinks due to the thermal hardening process. On the other hand, wrinkles are generated on the film surface, and the surface smoothness is deteriorated.

In the photosensitive coloring composition of the present invention, it is considered that since the oxime ester compound represented by the above formula (I) is used as the photopolymerization initiator, the compound is easily deposited on the film due to the halogen atom in the chemical structure of the compound. The distribution of the initiator near the surface prevents the crosslinking density of the film surface from becoming excessively high due to the influence of oxygen hindrance, which can reduce the generation of wrinkles on the film surface caused by the heat shrinkage of the thermal hardening process.

In addition, it is believed that the naphthalene ring in the carbazole skeleton of the compound increases the absorption of long-wavelength light. The long-wavelength light contained in an ultraviolet lamp can also be used to increase the crosslinking density near the bottom of the film. The pattern formed by the opening with a lower penetration rate like the middle penetration opening also improves the adhesion of the substrate.

[Example 3 and Comparative Example 4]

Using the pigment dispersions 3 and 4 prepared above, each component was added so that the solid content ratio became the blending ratio in Table 3, and then PGMEA was added so that the solid content became 22% by mass and stirred to dissolve it. Photosensitive coloring composition. Using the obtained photosensitive coloring composition, the evaluation was performed in the same procedure as in Example 1, except that the exposure amount in the exposure treatment was 40 mJ/cm ² . Furthermore, the upper row values in Table 3 indicate the usage amount of each ingredient. On the other hand, the value in the lower stage represents the solid content of each component in terms of the content ratio relative to the total solid content of the photosensitive coloring composition. In addition, the field of view for the evaluation of surface smoothness was set to 5 cm×5 cm.

[table 3]

It was confirmed that the coated substrate using the photosensitive coloring composition of Example 3 had a high unit OD, excellent light shielding properties, and excellent surface smoothness. In addition, the adhesion of the substrate through the opening in the middle is also good. On the other hand, it was confirmed that although the unit OD value of Comparative Example 4 was the same as that of Example 3, the surface smoothness was inferior, and the value of the surface roughness was also large. Furthermore, the adhesion of the substrate in the middle penetration opening was poor.

The present invention is described in detail using a specific aspect, and it is clear to the practitioner that various changes and modifications can be made without departing from the intent and scope of the present invention. Furthermore, this application is based on a Japanese patent application filed on March 11, 2015 (Japanese Patent Application No. 2015-048577), and a Japanese patent application filed on March 11, 2015 (Japanese Patent Application No. 2015-048578) ), and the application submitted on August 7, 2015 Japanese patent application (Japanese Patent Application No. 2015-157456), and the entire content is cited in the form of citation.

(Industrial availability)

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

Claims (4)

A photosensitive coloring composition for forming a colored spacer, which contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, and (e) a solvent , And (f) Dispersant, characterized by: The aforementioned (c) photopolymerization initiator includes an oxime ester compound represented by the following formula (I), [化1]

(In the above general formula (I), R ¹ represents an aromatic ring group which may have a substituent, R ² represents an alkane group which may have a substituent, or an aryl group which may have a substituent, R ³ represents a hydrogen atom or an alkyl group which may have a substituent, R ⁴ represents an aromatic ring group which may have a substituent, R ⁵ and R ⁶ each independently represent an optionally substituted benzene ring or an optionally substituted naphthalene ring, wherein at least one of R ⁵ and R ⁶ is an optionally substituted naphthalene ring, At least one of R ¹ and R ⁴ has a -OR ⁷ group as a substituent, wherein R ⁷ represents a haloalkyl group, X represents a direct bond or a carbonyl group, Z represents a direct bond or a carbonyl group). The photosensitive coloring composition for forming a colored spacer according to claim 1, wherein the (a) colorant contains at least one selected from the group consisting of red pigments and orange pigments, and is selected from blue pigments and purple At least one of the group of pigments. The photosensitive coloring composition for forming a colored spacer of claim 2, wherein the red pigment is the following (1), the orange pigment is the following (2), the blue pigment is the following (3), the above The purple pigment is (4) below, (1) At least one selected from C.I. Pigment Red 177 and 254 (2) At least one selected from C.I. Pigment Orange 43, 64 (3) At least one selected from C.I. Pigment Blue 15: 6, 60 (4) At least one selected from C.I. Pigment Violet 23 and 29. The photosensitive coloring composition for forming a colored spacer according to claim 2 or 3, wherein at least one pigment selected from the group consisting of a red pigment and an orange pigment is contained relative to 100 parts by mass of the colorant (a) The ratio is 1 part by mass or more and 30 parts by mass or less.