CN111690268A

CN111690268A - Azo pigment dispersion containing pigment derivative and coloring composition for forming coating film

Info

Publication number: CN111690268A
Application number: CN202010146270.9A
Authority: CN
Inventors: 山地健太
Original assignee: Sanyo Color Works Ltd
Current assignee: Sanyo Color Works Ltd
Priority date: 2019-03-13
Filing date: 2020-03-05
Publication date: 2020-09-22
Also published as: JP2020147682A; TW202035574A; JP7338127B2; KR20200110208A

Abstract

Provided are an azo pigment dispersion which can suppress a decrease in brightness and can improve contrast compared with conventional contrast, and a coloring composition for forming a coating film containing the azo pigment dispersion. Containing azo pigmentsA pigment dispersion comprising a pigment derivative represented by the following formula (1), a dispersant and a solvent, and a coloring composition for forming a coating film, which comprises the pigment dispersion and a coating film-forming component. (in the formula (1), R¹～R⁴Independently represents a hydrogen atom or a halogen atom, R⁵Represents a group represented by the following formula (1-1) or formula (1-2). n is a real number greater than 0 and 2 or less. ) (in the formula (1-1), Q¹Represents a hydrogen atom, a halogen atom or an alkoxy group, Q²Represents a hydrogen atom, a halogen atom or an alkoxy group, Q³＊ represents a C1-4 alkyl group (in the formula (1-2), ＊ represents a bond.)

Description

Azo pigment dispersion containing pigment derivative and coloring composition for forming coating film

Technical Field

The present invention relates to an azo pigment dispersion containing a pigment derivative and a coloring composition for forming a coating film containing the azo pigment dispersion.

Background

Azo pigments are widely used as colorants such as paints, offset printing inks, gravure printing inks, color toners, recording inkjet inks, and colorants for color filters. In order to improve various characteristics such as brightness and contrast of a coating film formed in these applications, a finely divided azo pigment is sometimes used. However, it is generally known that a colored composition containing a finely divided pigment tends to have poor dispersion stability. Therefore, proposals have been made to improve these various properties while ensuring dispersion stability of pigments and the like (patent documents 1 to 5).

Patent document 1 describes: in the production of a red pigment dispersion for a color filter, which contains an organic pigment, a pigment dispersion aid A which is a sulfonated compound having the same skeleton as the organic pigment, a pigment dispersion aid B having a specific structure, a pigment dispersant, and an organic solvent, the following steps are performed: after the dispersion aid a and the organic pigment are mixed and subjected to a micronization treatment, the pigment dispersion aid B, the pigment dispersant and the organic solvent are mixed and subjected to a dispersion treatment. It is considered that the use of 2 pigment dispersing aids in this way improves the fine dispersibility of the pigment and the subsequent dispersion stability, and enables the achievement of excellent color characteristics, high transmittance, and contrast.

Patent document 2 describes a coloring composition for a color filter, which is characterized by comprising: a colorant (A) containing a red azo pigment (a1) having a maximum refractive index of 1.8 or less in a light wavelength region of 600 to 700 nm; and a resin (B). When such a pigment (a1) is contained, the contrast ratio is high, but the pigment does not need to be excessively finely divided, and therefore, the stability is also excellent.

Patent document 3 describes the following method: a pigment dispersion aid having a specific structure, an acrylic block copolymer having a tertiary amino group and/or a quaternary ammonium group, and an organic solvent are added to fine particles obtained by fine-pulverizing a pigment containing c.i. pigment red 221, and a pigment dispersion is obtained by dispersion, and then a red pigment dispersion resist composition for a color filter is prepared. By this method, the dispersion stability of the fine particles of the pigment containing c.i. pigment red 221 can be significantly improved as compared with the prior art, and a red pigment dispersion resist composition for a color filter excellent in dispersion stability, tinting strength, contrast, brightness, heat resistance and solvent resistance can be provided.

Patent document 4 describes: by surface-treating the naphthol red having the specific structure with a hydrophilic naphthol derivative or a hydrophilic phenol derivative having the specific structure, a naphthol red having excellent dispersibility, color developability, and transparency can be obtained.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2011-162722

Patent document 2: japanese patent laid-open publication No. 2012-198453

Patent document 3: japanese patent laid-open publication No. 2016-61979

Patent document 4: japanese patent laid-open publication No. 2016-108451

Disclosure of Invention

Technical problem to be solved by the invention

For example, in the field of display devices using color filters, the market for high image quality is strongly demanded, and even if the inventions described in patent documents 1 to 4 are adopted, there is still room for improvement. For example, even if the contrast of the coating film can be improved, the brightness may be reduced. The object of the invention is therefore: provided are an azo pigment dispersion which can suppress a decrease in brightness and can improve contrast compared with conventional contrast, and a coloring composition for forming a coating film containing the azo pigment dispersion.

Technical solution for solving technical problem

The present inventors have conducted intensive studies in order to solve the above-mentioned technical problems. As a result, they have found that the use of a specific pigment derivative can suppress the decrease in brightness of a coating film containing the obtained pigment dispersion and can improve the contrast as compared with the conventional contrast, and have completed the present invention.

The first invention of the present invention relates to an azo pigment dispersion containing an azo pigment, a pigment derivative represented by the following formula (1), a dispersant and a solvent.

(in the formula (1), R¹～R⁴Independently represents a hydrogen atom or a halogen atom, R⁵Represents a group represented by the following formula (1-1) or formula (1-2). n is a real number greater than 0 and 2 or less. )

(in the formula (1-1), Q¹Represents a hydrogen atom, a halogen atom or an alkoxy group, Q²Represents a hydrogen atom, a halogen atom or an alkoxy group, Q³＊ represents an alkyl group having 1 to 4 carbon atoms and represents a bond

(in the formula (1-2), symbol represents a valence bond.)

Wherein, in the formulae (1-1) and (1-2), the symbol "represents a valence bond" means that the terminal represented by the symbol "means that the terminal is directly bonded to a nitrogen atom.

In the embodiment of the present invention, the azo pigment may contain 80% by weight or more (based on the solid content) of a reaction product of the substrate represented by the following formula (2) and the coupling agent represented by the following formula (3).

(in the formula (2), R⁶Represents R⁸-NH-C (═ O) -, group, R⁷Represents a halogen atom orR⁹O-is a group represented by. R⁸Represents a hydrogen atom or a phenyl group (-C)₆H₅)。R⁹Represents an alkyl group having 1 to 4 carbon atoms. )

(in the formula (3), R¹⁰Represents a hydrogen atom or R¹¹-NH-C (═ O) -. R¹¹Represents a group represented by the following formula (3-1). )

(in the formula (3-1), R¹²Represents R¹⁴-NH-C (═ O) -or R¹⁴-C (═ O) -NH-, a group represented by R¹³Represents a hydrogen atom, a halogen atom or R¹⁵O-is a group represented by. R¹⁴Represents a hydrogen atom or a phenyl group (-C)₆H₅)。R¹⁵＊ represents an alkyl group having 1 to 4 carbon atoms and represents a bond

Wherein, in the formula (3-1), ＊ represents a bond means that the terminal represented by "＊" is directly bonded to the nitrogen atom, that is, R¹⁰Is R¹¹when-NH-C (═ O) -represents a group, R¹⁰Is a group represented by the following formula (3-2). In the formula (3-2), R¹²、R¹³As described above.

In an embodiment of the present invention, the azo pigment contains a reaction product of a base represented by the above formula (2) or (4) and a coupling agent represented by the above formula (3) or (5), and the content (based on solid content) of the reaction product of the formula (2) or (3) may be 80 to 95% by weight.

(in the formula (5), R¹⁶represents-SO₃H or-COOH, or a group represented by-COOH. )

In an embodiment of the present invention, the weight ratio ((2)/(4)) of the component derived from formula (2) to the component derived from formula (4) may be 90.6/9.4 to 98.9/1.1, and the weight ratio ((3)/(5)) of the component derived from formula (3) to the component derived from formula (5) may be 82.4/17.6 to 96.5/3.5.

In an embodiment of the present invention, the azo pigment may have an average primary particle diameter of 25 to 70 nm.

The second invention of the present invention relates to a coloring composition for forming a coating film, which contains the azo pigment dispersion and a coating film-forming component.

According to the present invention, an azo pigment composition which can suppress a decrease in brightness and can improve contrast compared with conventional contrast, and a method for producing the azo pigment composition can be provided.

Detailed Description

Embodiments of the present invention will be described below.

An azo pigment dispersion according to an embodiment contains an azo pigment, a pigment derivative represented by the following formula (1), a dispersant, and a solvent.

(in the formula (1-2), symbol represents a valence bond.)

By using such a specific pigment derivative, the decrease in brightness of a coating film formed using an azo pigment dispersion is suppressed, and the contrast is improved. The reason for this is not clear, but it is presumed that the presence of the specific pigment derivative can suppress crystallization and crystal growth of the intended azo pigment. It is presumed that by suppressing crystallization or crystal growth in this way, aggregation of the azo pigment can be suppressed, lowering of brightness can be suppressed, and contrast can be improved.

The pigment derivative may be appropriately selected depending on the application, as long as it has the structure represented by formula (1). For example, in the case of color filter applications, since heating to a high temperature of 200 ℃ or higher is sometimes performed during the production process, there is a tendency as follows from the viewpoint of ensuring a good contrast (hereinafter referred to as "heat resistance") even after heating: r in the formula (1)¹～R⁴In the case of a halogen atom, the heat resistance is improved. Examples of the halogen atom include a bromine atom, a chlorine atom, and an iodine atom. These substances may be appropriately selected depending on the use and the like. From the viewpoint of heat resistance, a chlorine atom is preferred.

R in the formula (1)⁵The group represented by the formula (1-1) or the formula (1-2) may be appropriately selected depending on the use and the like. For example, in the case of color filter applications, the group represented by the formula (1-1) is preferable from the viewpoint of heat resistance.

Q in the formula (1-1)¹The hydrogen atom, halogen atom or alkoxy group can be appropriately selected and used according to the use. Among them, alkoxy groups are preferable from the viewpoint of heat resistance. The alkoxy group may have a structure in which a chain or cyclic hydrocarbon group having 1 to 6 carbon atoms is bonded to an oxygen atom. For example, in the case of color filter applications, from the viewpoint of heat resistance, a chain hydrocarbon group having 1 to 6 carbon atoms is preferred, and a methyl group is more preferred. Examples of the halogen atom include a bromine atom, a chlorine atom, and an iodine atom. These substances may be appropriately selected depending on the use and the like. From the viewpoint of heat resistance, a chlorine atom is preferred.

Q in the formula (1-1)²Can be based onThe use thereof is suitably selected from a hydrogen atom, a halogen atom and an alkoxy group. From the viewpoint of heat resistance, a halogen atom is preferable. Examples of the halogen atom include a bromine atom, a chlorine atom, and an iodine atom. These substances may be appropriately selected depending on the use and the like. From the viewpoint of heat resistance, a chlorine atom is more preferable. The alkoxy group may have a structure in which a chain or cyclic hydrocarbon group having 1 to 6 carbon atoms is bonded to an oxygen atom. For example, in the case of color filter applications, from the viewpoint of heat resistance, a chain hydrocarbon group having 1 to 6 carbon atoms is preferred, and a methyl group is more preferred.

Q in the formula (1-1)³The alkyl group may have 1 to 4 carbon atoms, and the number of carbon atoms may be appropriately selected depending on the application. The alkyl group may be linear or branched. For example, in the case of color filter applications, the number of carbon atoms is preferably 1 or 2, more preferably 1, from the viewpoint of heat resistance.

Examples of the group represented by the formula (1-1) include groups represented by the following formulae (1-1-1) to (1-1-4).

In the formula (1), n may be a real number greater than 0 and not greater than 2. From the viewpoint of heat resistance, n is preferably in the range of more than 0.5 and less than 1.5. This is because the effect of improving heat resistance is small when n is less than 0.5, and the effect of improving heat resistance is not easily increased even when n is more than 1.5.

The pigment dispersion according to the embodiment of the present invention may contain a pigment derivative, a dispersion resin, and the like other than the substance represented by formula (1) from the viewpoint of further improving the dispersion stability of the particles in the pigment dispersion or the coloring composition for forming a coating film. The content of the pigment derivative (solid content or active ingredient) is preferably 2 to 15 parts by weight in total based on 100 parts by weight of the azo pigment from the viewpoint of dispersion stability. The dispersion resin is particularly preferably used when the coating film-forming component contains a photopolymerizable component. Examples of such a dispersion resin include alkali-soluble resins described later. The dispersion resin may be the same resin species as the alkali-soluble resin used as the coating film-forming component, or may be a different resin species. The content of the dispersion resin is preferably 10 to 50 parts by weight based on 100 parts by weight of the total of the azo pigment and the pigment derivative. Specific examples of the pigment derivative and the dispersion resin other than the substance represented by the formula (1) will be described later.

The azo pigment is not particularly limited, and a general azo pigment can be used. For example, when the pigment index number is used as an example, the c.i. pigment red 1, 2,3, 4,5,6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 40, 48: 1. 48: 2. 48: 3. 48: 4. 49: 1. 49: 2. 50: 1. 50: 2. 51, 52: 1. 52: 2. 53, 54, 55, 56, 57, 58: 1. 58: 2. 58: 3. 58: 4. 59, 60: 1. 61, 62, 63: 1. 63: 2. 64: 1. 65, 66, 67, 68, 69, 70, 77, 93, 95, 99, 112, 114, 115, 117, 119, 133, 139, 140, 141, 142, 143, 144, 146, 147, 148, 150, 151, 157, 162, 163, 164, 166, 170, 171, 175, 176, 183, 184, 185, 187, 188, 193, 200, 208, 210, 212, 214, 220, 221, 222, 237, 238, 239, 242, 243, 245, 247, 248, 253, 258, 261, 262, 266, 267, 268, 269, 273, 274, and the like.

From the viewpoint of suppressing the decrease in brightness and improving the contrast, an azo pigment containing 80% by weight or more (based on the solid content) of the reaction product of the matrix represented by the following formula (2) and the coupling agent represented by the following formula (3) is preferable.

(in the formula (2), R⁶Represents R⁸-NH-C (═ O) -, group, R⁷Represents a halogen atom or R⁹O-is a group represented by. R⁸Represents a hydrogen atom or a phenyl group (-C)₆H₅)。R⁹Represents an alkyl group having 1 to 4 carbon atoms. )

In the formula (2), R⁶And R⁷The bonding position (2) is not particularly limited. R⁶Is NH₂-C (═ O) -or C₆H₅A group represented by — NH — C (═ O) -, may be used. R⁷Is a halogen atom or R⁹A group represented by O-may be used. The halogen atom may be any of a chlorine atom, a bromine atom and the like. R⁹The alkyl group may be a C1-4 alkyl group, and may be a methyl group, an ethyl group, a propyl group, or a butyl group. The propyl group and the butyl group may be linear or branched. Examples of such a substrate include 3-amino-4-methoxybenzanilide, 2-chloro-5-methoxyaniline, and 3-chloro-6-methoxyaniline.

In the formula (3), R¹⁰Is a hydrogen atom or R¹¹A group represented by — NH — C (═ O) -, may be used. R¹¹May be a functional group represented by the above formula (3-1), wherein R is in the formula (3-1)¹²And R¹³The bonding position (2) is not particularly limited. R¹²May be NH₂-C (═ O) -or C₆H₅-NH-C (═ O) -, or H-C (═ O) -NH-or C₆H₅-C (═ O) -NH-. R¹³May be a halogen atom or R¹⁵O-is a group represented by. The halogen atom may be any of a chlorine atom, a bromine atom and the like. R¹⁵Is alkyl of 1-4 carbon atoms, i.e. AExamples of such a coupling agent include N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide, β naphthol, and the like.

In the formula (3), R¹¹In the case of a group represented by the formula (3-1), R¹⁰Is a group represented by the following formula (3-2). In the formula (3-2), R¹²、R¹³As mentioned above, ＊ represents a bond.

From the viewpoint of suppressing the decrease in brightness and further improving the contrast, the azo pigment is preferably an azo pigment composition containing a reaction product of a matrix represented by the above formula (2) or (4) and a coupling agent represented by the above formula (3) or (5), and the content (based on the solid content) of the reaction product of the formula (2) or (3) is 80 to 95% by weight.

(in the formula (5), R¹⁶represents-SO₃H or-COOH. )

In the formula (4), the bonding position of the sulfonic acid group is not particularly limited. Examples of such a heterogeneous substrate include p-aminobenzoic acid (Sulfanilic acid), anthranilic acid (anthranilic acid), and m-aminobenzoic acid. The different substrates may be used in 1 kind or 2 or more kinds.

In the formula (5), R¹⁶The bonding position (2) is not particularly limited. R¹⁶is-SO₃The coupling agent of such a different species includes, for example, β -naphthol, BON acid, Schaffer's acid, F acid, etc.

The azo pigment composition contains a reaction product obtained by using the coupling agent represented by the formula (2) as a main coupling agent, using the base represented by the formula (3) as a main base, and reacting the main coupling agent with the main base in the presence of a different coupling agent different from the main coupling agent and a different base different from the main base, and may contain a side reaction product of any combination of these and the different coupling agent and the different base in addition to the main reaction product of the main coupling agent and the main base. The side reaction products that may be contained vary depending on the conditions and the like. In this way, by further adding a base and a coupling agent different from the base and the primary coupling agent constituting the specific azo pigment, it is possible to suppress a decrease in luminance and improve contrast. The reason is presumed to be that crystallization and crystal growth of the intended azo pigment (main azo pigment) can be suppressed by the presence of a side reaction product other than the main azo pigment, which is generated by the presence of a different substrate and coupling agent. It is presumed that by suppressing crystallization or crystal growth in this way, aggregation of the main azo pigment can be suppressed, and a decrease in luminance can be suppressed, whereby the contrast can be further improved.

In the composition of the main azo pigment and the by-product contained in the azo pigment, from the viewpoint of exerting the function of the by-product, suppressing the decrease in brightness, and further improving the contrast, it is preferable that the weight ratio ((2)/(4)) of the component derived from formula (2) to the component derived from formula (4) is 90.6/9.4 to 98.9/1.1, and the weight ratio ((3)/(5)) of the component derived from formula (3) to the component derived from formula (5) is 82.4/17.6 to 96.5/3.5.

The composition of the main azo pigment and the by-product can be grasped from the composition ratio of the starting materials, but the obtained azo pigment composition may be used for measurement by gas chromatography-mass spectrometry (GC/MS).

The reaction product of the substrate represented by the formula (2) and the coupling agent represented by the formula (3) can be obtained according to a conventionally known general method for producing an azo pigment. Alternatively, commercially available materials may be used. These substances may be subjected to a micronization treatment described later.

On the other hand, an azo pigment composition which is a reaction product of the main matrix represented by the formula (2), the different matrix represented by the formula (4), the main coupling agent represented by the formula (3), and the different coupling agent represented by the formula (5), and in which the content (based on solid content) of the reaction product of the formula (2) and the formula (3) is 80 to 95% by weight, can be obtained as follows.

For example, when the substrate represented by the above formula (2) is reacted with the coupling agent represented by the above formula (3), it can be obtained by adding the different substrate represented by the above formula (4) and the different coupling agent represented by the above formula (5).

The heterogeneous matrix and the coupling agent may be present in the coupling reaction using the main matrix and the main coupling agent. For example, the following methods can be employed: (1) mixing a solution containing a main base and a foreign base with a solution containing a coupling agent and a foreign coupling agent to carry out a coupling reaction; (2) when a solution of a main base and a solution of a coupling agent containing a main coupling agent are mixed and subjected to a coupling reaction, a solution of a dissimilar base and a solution of a dissimilar coupling agent are separately added to the main base and the main coupling agent, and a coupling reaction is carried out. The substrate is subjected to the reaction of nitriding and coupling under known conditions.

From the viewpoint of obtaining the main azo pigment as a main colorant, securing the characteristics of the main azo pigment, and effectively suppressing the crystallization and crystal growth of the azo pigment by using a product derived from the dissimilar base and the coupling agent as desired, the dissimilar base is preferably added in an amount of 0.5 to 4 parts by weight with respect to 100 parts by weight of the main base.

For the same reason, the mixing ratio of the primary coupling agent and the dissimilar coupling agent is preferably 2 to 20 parts by weight based on 100 parts by weight of the primary coupling agent.

After the coupling reaction, the reaction mixture was filtered, washed with water and dried to obtain a dried product of the azo pigment composition. The dried product can also be used directly as an azo pigment composition. The pulverized product of the pulverized dried product may be used as the azo pigment composition. A finely divided product obtained by micronizing a dried or pulverized product may also be used as the azo pigment composition.

The pulverized material can be obtained by pulverizing with a dispersing machine such as a roll mill or a bead mill. The finely divided product can be obtained by, for example, salt milling. Micronization by the salt milling method, particularly the solvent salt milling method, is carried out by, for example, mixing a dried or pulverized product of the pigment composition, a water-soluble inorganic salt and a water-soluble solvent, mechanically kneading the obtained mixture with a kneader or the like, and grinding the pigment composition with the water-soluble inorganic salt. Such salt mills may employ conditions known in the art. After the salt milling, the pigment composition can be finely pulverized by washing with water to remove the water-soluble inorganic salt and the water-soluble solvent. The water washing is preferably carried out until the water-soluble inorganic salt and the water-soluble solvent are completely removed. Drying may be performed to remove water according to the use.

In the case of performing the micronization treatment, the micronization treatment may be performed in the presence of a surface treatment agent such as a pigment derivative or a resin, from the viewpoint of more effectively suppressing the crystallization or crystal growth of the azo pigment. For example, in the case of the solvent salt milling method described above, the surface-treating agent may be present when the pigment composition is milled by a kneader. The surface treatment agent may be added in a total amount at the start of kneading, or may be added in two or more portions after the start of kneading.

The pigment derivative as the surface treatment agent may be a pigment derivative represented by formula (1), or may be a pigment derivative other than the pigment derivative. Examples of the pigment derivative other than the formula (1) include compounds having an organic pigment other than the azo pigment which is the basic skeleton in the formula (1) as the basic skeleton and having an acidic group or an aromatic group as a substituent introduced into a side chain. Specific examples of the organic pigment to be a matrix skeleton include: quinacridone pigments, phthalocyanine pigments, azo pigments (except those contained in the basic skeleton of formula (1)), quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, dioxazine pigments, and the like. Further, as the matrix skeleton, a pale yellow aromatic polycyclic compound such as a naphthalene-based, anthraquinone-based, triazine-based, or quinoline-based compound which is not called a coloring matter is generally included. Examples of such pigment derivatives include those described in Japanese patent application laid-open Nos. 11-49974, 11-189732, 10-245501, 2006-265528, 8-295810, 11-199796, 2005-234478, 2003-240938, 2001-356210, 2007-186681, 2003-167112, 2013-199470 and the like.

The amount of the pigment derivative added (nonvolatile content or solid content) is preferably 1 to 20 parts by weight based on 100 parts by weight of the azo pigment.

Examples of the resin as the surface treatment agent include vinyl ester resins and acrylic resins. The amount of the resin as the surface treatment agent is preferably 3 to 30 parts by weight based on 100 parts by weight of the azo pigment.

The average primary particle diameter of the finely divided azo pigment is preferably 25 to 70 nm. Such an average primary particle diameter can be obtained as an arithmetic average by selecting arbitrary 50 fine pigment particles from 5 ten thousand times and 10 ten thousand times images obtained by a transmission electron microscope (trade name: JEM-1011, manufactured by JEOL Ltd.), and measuring the maximum particle diameter of each fine pigment particle based on a measuring scale shown in the images.

The pigment derivative represented by the formula (1) and other pigment derivatives may be added and mixed after the micronization treatment, except when the micronization treatment is performed.

Examples of the dispersant include a resin type dispersant and a surfactant type dispersant. Specific examples of the resin type pigment dispersant include oily dispersants such as polyurethanes, polyesters, unsaturated polyamides, phosphoric acid esters, polycarboxylic acids and amine salts, ammonium salts and alkylamine salts thereof, polycarboxylates, hydroxyl-containing polycarboxylates, polysiloxanes, and modified polyacrylates, water-soluble resins such as (meth) acrylic acid- (meth) acrylate copolymers, (meth) acrylic acid-styrene copolymers, and styrene-maleic acid copolymers, and water-soluble polymer compounds.

As the resin type dispersant, commercially available ones can be used. Specific examples of commercially available products are described below, but the commercially available products are not limited thereto.

Manufactured by Lubrizol corporation of Japan: solsperse 3000, 9000, 13240, 17000, 20000, 24000, 26000, 27000, 28000, 32000, 32500, 36000, 38500, 39000, 55000, 41000, and,

BYK-Chemie Japan K.K.: disperbyk 108, 110, 112, 140, 142, 145, 161, 162, 163, 164, 166, 167, 171, 174, 182, 190, 2000, 2001, 2050, 2070, 2150, LPN6919, LPN22101, LPN21116, LPN21715, LPN, pp,

Manufactured by BASF corporation: EFKA 4401, 4403, 4406, 4330, 4340, 4010, 4015, 4046, 4047, 4050, 4055, 4060, 4080, 5064, 5207, 5244, EFKA,

Manufactured by Ajinomoto Fine-Chemicals, Inc.: Ajisper-PB821(F), PB822, PB880, and,

Chuanjia precision chemical Co., Ltd.: HINACT T-8000,

Manufactured by Nanben Kabushiki Kaisha: DISPALON PW-36, DISPALON DA-325, 375, 7301, DISPALON,

Available from Otsuka chemical Co., Ltd: TERPLUS D2015, and the like.

The molecular weight of the resin type dispersant may be appropriately selected in consideration of the characteristics of each component. For example, a substance having a weight average molecular weight of 1000 to 100000 can be used.

Examples of the surfactant type pigment dispersant include anionic surfactants such as naphthalene sulfonic acid formaldehyde condensate salt, aromatic sulfonic acid formaldehyde condensate, polyoxyethylene alkyl phosphate ester, etc., anionic surfactants such as polyoxyethylene alkyl ether, etc., cationic surfactants such as alkylamine salt, quaternary ammonium salt, etc.

As the surfactant type dispersant, commercially available ones can be used. Specific examples of commercially available products are described below, but the commercially available products are not limited thereto.

Manufactured by kao corporation: DEMOL N, RN, MS, SN-B, Emalgen 120, 430, ACETAMINE 24, 86, QUARTAMIN 24P,

Manufactured by heliochemical corporation: NIKKOL BPS-20, BPS-30, DHC-30, BPSH-25, N-methyl-N-propylidene chloride,

First industrial pharmaceutical co: PLYSURF AL, A208F,

Available from Lion corporation: arquad C-50, T-28, T-50, etc.

The dispersant may contain 1 or 2 or more species. The content of the dispersant (solid content or active ingredient) is preferably 10 to 40 parts by weight based on 100 parts by weight of the azo pigment from the viewpoint of dispersion stability. The optimum amount of the dispersant to be added may be appropriately adjusted depending on the combination with the type of the pigment to be used, and the like.

The solvent may be appropriately selected depending on the kind of the coating film forming component described later, and examples thereof include various organic solvents such as aromatic solvents, ketone solvents, ester solvents, glycol ether solvents, alcohol solvents, and aliphatic solvents. Among them, from the viewpoint of film formability, organic solvents selected from aromatic, ketone, ester, and glycol ether are preferable. The number of the organic solvents may be only 1, or 2 or more.

Examples of the aromatic organic solvent include aromatic hydrocarbons such as toluene, xylene, and ethylbenzene.

Examples of the ketone-based organic solvent include methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, acetylacetone, isophorone, acetophenone, and cyclohexanone.

Examples of the ester-based organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, isopropyl acetate, methyl propionate, 3-methoxybutyl acetate, ethyl glycol acetate, propylene glycol monomethyl ether acetate (PMA), propylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, methyl monochloroacetate, ethyl monochloroacetate, butyl monochloroacetate, methyl acetoacetate, ethyl acetoacetate, butyl carbitol acetate, butyl lactate, ethyl-3-ethoxypropionate, ethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate, propyl acetate, and 1, 3-butanediol diacetate.

Examples of the glycol ether-based organic solvent include water-soluble glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol mono-isopropyl ether, diethylene glycol mono-isopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono-t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-isopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-isopropyl ether, propylene glycol mono-n-butyl ether, and dipropylene glycol mono-,

And water-insoluble glycol ethers such as ethylene glycol monohexyl ether, ethylene glycol-2-ethylhexyl ether, ethylene glycol phenyl ether, diethylene glycol n-hexyl ether, diethylene glycol-2-ethylhexyl ether, propylene glycol monobutyl ether, dipropylene glycol propyl ether, and propylene glycol methyl ether propionate.

Examples of the alcohol-based organic solvent include alkyl alcohols having 1 to 4 carbon atoms such as ethanol, methanol, butanol, propanol and isopropanol, and the like,

Ethylene glycol, propylene glycol, diethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene-1, 4-diol, 2-ethyl-1, 3-hexanediol, 2-methyl-2, 4-pentanediol, tripropylene glycol, polyethylene glycol having a molecular weight of 2000 or less, 1, 3-propanediol, isopropylene glycol, isobutylene glycol, 1, 4-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, glycerol, meso-erythritol, pentaerythritol, and the like.

Examples of the aliphatic organic solvent include aliphatic hydrocarbons such as n-pentane, n-hexane, and n-heptane.

The amount of the solvent to be added may be such that the concentration of the solid component containing the azo pigment or the like is 10 to 30% by weight of the total pigment dispersion, from the viewpoint of handling properties.

In an embodiment of the pigment dispersion of the present invention, other additives may be contained in addition to the aforementioned components. Examples of the other additives include other pigments, dyes, antioxidants, anti-aggregation agents, and surface control agents (leveling agents). The other pigment or dye is a pigment or dye used in combination with the aforementioned main azo pigment for toning.

The pigment dispersion can be obtained by, for example, adding the above-described respective components to a known dispersing machine such as a bead mill, a sand mill, a disperser, or the like, and dispersing the components. The method of adding the components is not particularly limited, and a mixture obtained by mixing the components at the same time may be subjected to a dispersion treatment. In the case of using a plurality of pigments, a mixture obtained by mixing each pigment and a solvent with a dispersant and/or other optional components may be dispersed, a pigment dispersion may be prepared for each pigment, and these pigment dispersions may be mixed and then dispersed again. Other methods are also possible.

The azo pigment dispersion as described above can be used as a colorant for paints, offset printing inks, gravure printing inks, color toners, inkjet inks for recording, colorants for color filters, and the like. Since the contrast can be improved compared with the conventional one by suppressing the decrease in luminance, the colorant is particularly suitable as a colorant such as a color filter of an image display device. In recent years, in image display devices using color filters, various light sources such as cold cathode tubes, light emitting diodes, and organic EL elements have been used as backlights of light sources, but since pigments having strong coloring power are used, color reproducibility is good even when any light source is used, and good luminance can be exhibited in various color regions.

The coloring composition for forming a coating film according to an embodiment contains the azo pigment dispersion and a coating film-forming component. By containing the azo pigment dispersion, a decrease in brightness can be suppressed, and a coating film having good contrast can be formed. Therefore, for example, the compound is suitable as a colorant for color filter applications.

Examples of the coating film-forming component include polymers such as thermoplastic polyurethane resins, (meth) acrylic resins, polyamide resins, polyimide resins, styrene-maleic acid resins, polyester resins, silicone resins, and cardo resins, and polymerizable components such as photopolymerizable components.

As the polymer, an alkali-soluble resin showing solubility in a solution in an alkali region is preferable. When the alkali-soluble resin is contained, for example, when the pigment composition is applied to pattern formation in a photolithography step in the production of a color filter, the pattern formability can be further improved.

As such an alkali-soluble resin, the resin disclosed in Japanese patent laid-open No. 2009-179789 can be used. In brief, the alkali-soluble resin may be suitably selected from, for example, alkali-soluble resins which are linear organic high molecular polymers and have a group (for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, or the like) which promotes at least 1 alkali-solubility in a molecule (preferably, a molecule having an acrylic copolymer or a styrene copolymer as a main chain). Among them, development with a weak alkaline aqueous solution soluble in an organic solvent is more preferable.

The alkali-soluble resin preferably has a weight average molecular weight of 5000 to 50000 from the viewpoint of developability.

Various alkali-soluble resins are commercially available, and specific examples thereof are as follows, but the alkali-soluble resins are not limited thereto.

Showa Polymer K.K.: ripoxy SPC-2000,

Manufactured by mitsubishi yang corporation: dianal NR series,

Diamond hamrock co.ltd., system: photomer 6173 (COOH-containing urethane acrylic oligomers),

Osaka organic chemical industry, manufactured by Osaka: viscoat R-264, KS Resist 106, SOP-005, and,

Manufactured by Daiiol chemical industries, Ltd.: CYCLOMER P series, PLACCEL CF200 series,

Manufactured by masson cellulose UCB corporation: ebecryl 3800,

Manufactured by japan catalyst corporation: acrycure (registered trademark) RD-Y-503, RD-Y-702-A, BX-Y-10,

Manufactured by Soken chemical Co., Ltd.: folett (registered trademark) ZAH110, and the like.

The content of the polymer in the coloring composition is preferably 10 to 40% by weight based on the total solid content of the coloring composition. When the dispersion resin is used, the amount is a total amount.

The polymerizable component is preferably a photopolymerizable component since patterning by development (negative development) is easily performed.

The photopolymerizable component contains a photopolymerizable compound and a photopolymerization initiator. As such a photopolymerizable compound and a photopolymerization initiator, those described in, for example, Japanese patent application laid-open No. 2009-179789 can be used. As detailed, such photopolymerizable compounds are addition polymerizable compounds having at least one ethylenically unsaturated double bond, selected from compounds having at least 1, preferably 2 or more terminal ethylenically unsaturated bonds. Such a group of compounds is well known in the art, and in the present invention, these compounds can be used without particular limitation. The photopolymerizable compound has a chemical form such as a monomer, a prepolymer, a dimer, a trimer, and an oligomer, or a mixture thereof, and a copolymer thereof.

Examples of the monomer include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides thereof, and preferably, esters of unsaturated carboxylic acids and aliphatic polyol compounds, and amides of unsaturated carboxylic acids and aliphatic polyamine compounds are used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, mercapto groups, etc. with monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. are also preferably used. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituent groups such as isocyanate group and epoxy group with monofunctional or polyfunctional alcohols, amines and thiols are also preferable, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituent groups such as halogen group and tosyloxy group with monofunctional or polyfunctional alcohols, amines and thiols are further preferable. In addition, as another example, a compound group obtained by replacing the unsaturated carboxylic acid with a saturated phosphonic acid, styrene, vinyl ether, or the like may be used.

The content of the photopolymerizable compound in the coloring composition is preferably 5 to 70 wt% based on the total nonvolatile components in the coloring composition. These may be used alone, or 2 or more of them may be used in combination. In addition, the method of using the photopolymerizable compound may be arbitrarily selected from the viewpoints of the size of inhibition of polymerization with oxygen, resolution, fogging property, refractive index change, surface adhesiveness, and the like, and the appropriate structure, blending amount, and addition amount may be selected.

As the photopolymerization initiator, those described in Japanese patent laid-open publication No. 2009-179789 can be used. Examples thereof include acetophenone type, ketal type, benzophenone type, benzoin type, benzoyl type, xanthone type, active halogen compounds (triazine type, oxadiazole type, coumarin type), acridine type, imidazole type, oxime ester type, and the like.

Specific examples of the benzophenone-based photopolymerization initiator include benzophenone, 4 ' -bis (dimethylamino) benzophenone, 4 ' -bis (diethylamino) benzophenone, and 4,4 ' -dichlorobenzophenone.

The content of the photopolymerization initiator in the colored composition is preferably 0.1 to 10% by mass relative to the total nonvolatile components of the colored composition. When the content of the photopolymerization initiator is within this range, the polymerization reaction can be favorably progressed to form a film having a favorable strength.

When the coloring composition contains a photopolymerizable component as a coating film-forming component, the above-mentioned alkali-soluble resin may be contained.

In the embodiment of the coloring composition for forming a coating film of the present invention, other additives may be contained in addition to the above components. Examples of the other additives include a sensitizer (sensitizing dye), a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a filler, a surfactant, an adhesion promoter, an antioxidant, an anti-aggregation agent, and a surface conditioner (leveling agent). These substances may be appropriately selected depending on the components of the pigment dispersion.

The coating film-forming colored composition can be obtained by adding and dispersing the above-described respective components in a known dispersing machine such as a bead mill, a sand mill, a disperser, or the like.

Examples

Hereinafter, embodiments of the present invention will be described in detail based on examples.

Production example 1

500 parts by weight of concentrated sulfuric acid, 5.3 parts by weight of paraformaldehyde, and 23.5 parts by weight of phthalimide were mixed and stirred at 22 ℃ for 1 hour to effect a reaction. Then, 36.3 parts by weight of 3-amino-4-methoxybenzanilide was added thereto, heated to 50 ℃ and stirred for 3 hours to effect a reaction. The obtained reaction solution was mixed with a large amount of cold water to precipitate crystals. The obtained crystals were separated by filtration and washed with pure water to obtain 285 parts by weight (37% by weight of solid) of a pale yellow slurry.

This pale yellow slurry and 0.5 parts by weight of sulfanilic acid were dispersed in 600 parts by weight of water, and 57.5 parts by weight of 35% aqueous hydrochloric acid solution was added and stirred for 50 minutes. Ice was added to the mixture at a temperature of 0 to 5 ℃, 62 parts by weight of a 19% aqueous solution of sodium nitrite was added thereto, the mixture was stirred for 30 minutes, and 1.2 parts by weight of sulfamic acid for removing excess nitrous acid was added thereto. Further, 60 parts by weight of sodium acetate and 30 parts by weight of 80% acetic acid were added to prepare a bisazo onium salt solution.

Separately, 48 parts by weight of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide and 1.8 parts by weight of BON acid as a heterogeneous coupling agent were dissolved in 1400 parts by weight of water and 25 parts by weight of 30% sodium hydroxide at a temperature of 80 ℃ or lower to prepare a coupling agent solution. The solution was added to the diazoonium salt solution at a temperature of 10 ℃ or lower to perform a coupling reaction, and the resulting solution was subjected to a heat treatment at 85 ℃. The reaction mixture was filtered, washed with water, and dried at 100 ℃. Thereafter, the dried product was pulverized to obtain a pulverized product containing the pigment derivative 1.

Identification of the chemical Structure of the pigment derivative 1 obtained by matrix-assisted laser decomposition of AXIMA-CFRplus type manufactured by Shimadzu corporationIon ionization-time of flight mass spectrometry (MALDI-TOF-MS) was performed by measuring in a positive ion mode using 2, 5-dihydroxybenzoic acid (DHBA) as a matrix. As a result, a molecular ion peak was observed at m/z 740. This value is related to R in the general formula (1)⁵Corresponding to the monoisotopic mass of the group represented by the formula (1-1-1).

By working as above, R in formula (1) is obtained¹～R⁴Is a hydrogen atom, R⁵A pigment derivative 1 having a group represented by the formula (1-1-1) wherein n is 1.0.

Production example 2

A pulverized product containing pigment derivative 2 was obtained in the same manner as in production example 1, except that 30.0 parts by weight of dichlorophthalimide was used instead of 23.5 parts by weight of phthalimide and 1000 parts by weight of concentrated sulfuric acid was used instead of 500 parts by weight. The chemical structure of the obtained pigment derivative 2 was identified by measuring 2, 5-dihydroxybenzoic acid (DHCA) as a matrix in a negative ion mode using an AXIMA-CFR plus matrix assisted laser dissociation ionization-time of flight mass spectrometer (MALDI-TOF-MS) manufactured by shimadzu corporation. As a result, a molecular ion peak was observed at m/z 806. This value is related to R in formula (1)¹、R⁴Corresponding to a hydrogen atom, R²、R³Corresponding to chlorine atom, R⁵Corresponding to the monoisotopic mass of the group represented by the formula (1-1-1).

By working as above, R in formula (1) is obtained¹、R⁴Is a hydrogen atom, R²、R³Is a chlorine atom, R⁵A pigment derivative 2 having a group represented by the formula (1-1-1) and n of 1.0.

(production example 3)

A pulverized product containing pigment derivative 3 was obtained in the same manner as in production example 1, except that 45.4 parts by weight of 3,4,5, 6-tetrachlorophthalimide was used instead of 23.5 parts by weight of phthalimide, and concentrated sulfuric acid was used in an amount of 1000 parts by weight from 500 parts by weight. The chemical structure of pigment derivative 3 was identified in the same manner as in production example 1, and as a result, a molecular ion peak was observed at m/z 876. The value is in accordance with formula (1)R¹～R⁴Corresponding to chlorine atom, R⁵Corresponding to the monoisotopic mass of the group represented by the formula (1-1-1).

By working as above, R in formula (1) is obtained¹～R⁴Is a chlorine atom, R⁵A pigment derivative 3 having a group represented by the formula (1-1-1) and n of 1.0.

Production example 4

A pulverized product containing pigment derivative 4 was obtained in the same manner as in production example 1, except that 48 parts by weight of N- (5-chloro-2, 4-dimethoxyphenyl) -3-hydroxy-2-naphthamide and 52 parts by weight of N- (5-chloro-2, 4-dimethoxyphenyl) -3-hydroxy-2-naphthamide were used instead of 48 parts by weight of N- (5-chloro-2-methoxyphenyl) -2-naphthamide. The chemical structure of pigment derivative 4 was identified in the same manner as in production example 1, and as a result, a molecular ion peak was observed at m/z 770. This value is related to R in formula (1)¹～R⁴Corresponding to a hydrogen atom, R⁵Corresponding to the monoisotopic mass of the group represented by the formula (1-1-1).

By working as above, R in formula (1) is obtained¹～R⁴Is a hydrogen atom, R⁵A pigment derivative 4 having a group represented by the formula (1-1-1) and n of 1.0.

Production example 5

A pulverized product containing pigment derivative 5 was obtained in the same manner as in production example 1, except that 48 parts by weight of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide and 52 parts by weight of N- (4-chloro-2, 5-dimethoxyphenyl) -3-hydroxy-2-naphthamide were used instead of 48 parts by weight of N- (5-chloro-2-methoxyphenyl). The chemical structure of pigment derivative 5 was identified in the same manner as in production example 1, and as a result, a molecular ion peak was observed at m/z 770. This value corresponds to the monoisotopic mass corresponding to the following formula (6). The procedure described above gave pigment derivative 5 represented by the following formula (6).

(production example 6)

A pulverized product containing pigment derivative 6 was obtained in the same manner as in production example 1 except for using 48 parts by weight of N- (2, 3-dihydro-2-oxo-1H-benzimidazol-5-yl) -3-hydroxynaphthalene-2-carboxamide instead of using 48 parts by weight of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide. As a result of identifying the chemical structure in the same manner as in production example 1, a molecular ion peak was observed at m/z 732. This value corresponds to the monoisotopic mass corresponding to the following formula (7). The procedure described above gave pigment derivative 6 represented by the following formula (7).

Production example 7

A pulverized product containing pigment derivative 7 was obtained in the same manner as in production example 1, except for using 48 parts by weight of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide and 46 parts by weight of N- (2-ethoxyphenyl) -3-hydroxy-2-naphthamide instead of using 48 parts by weight of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide. The chemical structure was identified in the same manner as in production example 1, and as a result, a molecular ion peak was observed at m/z 720. This value corresponds to the monoisotopic mass corresponding to the following formula (8). The pigment derivative 7 represented by the following formula (8) was obtained in accordance with the above procedure.

Production example 8

50 parts by weight of 3-amino-4-methoxybenzanilide and 1.2 parts by weight of sulfanilic acid as a heterogeneous substrate were dispersed in 1000 parts by weight of water, ice was added thereto under a temperature condition of 0 to 5 ℃, 55 parts by weight of 35% hydrochloric acid aqueous solution was added thereto, and the mixture was stirred for 30 minutes. Thereafter, 50 parts by weight of a 30% aqueous solution of sodium nitrite was added and stirred for 60 minutes, and then 1.2 parts by weight of sulfamic acid for removing excess nitrous acid was added. Further, 40 parts by weight of sodium acetate and 58 parts by weight of 90% acetic acid were added to prepare a bisazo onium salt solution. Separately, 64g of N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide and 4.4 parts of BON acid as a hetero coupling agent were dissolved at a temperature of 80 ℃ or lower together with 1000 parts of water and 25 parts of sodium hydroxide to prepare a coupling agent solution. The solution was added to the diazoonium salt solution at a temperature of 10 ℃ or lower to perform a coupling reaction, and the resulting solution was subjected to a heat treatment at 90 ℃. The reaction mixture was filtered, washed with water, and dried at 100 ℃. Thereafter, the dried product was pulverized to obtain a pulverized product. The content of pigment Red 269, which is the reaction product of the disazo compound of 3-amino-4-methoxybenzanilide and N- (5-chloro-2-methoxyphenyl) -3-hydroxy-2-naphthamide, was 89.1% by weight. The weight ratio ((1)/(3)) of the components derived from the main matrix (1) and the foreign matrix (3) was 97.1/2.9, and the weight ratio ((2)/(4)) of the components derived from the main coupling agent (2) and the foreign coupling agent (4) was 91.7/8.3.

The obtained pulverized product was subjected to a micronization treatment in accordance with the following procedure to obtain a micronized azo pigment composition. That is, 300g of the pulverized material, 45g of a surface treatment agent (Ripoxy (registered trademark) SPC2000, showa electric corporation, vinyl ester resin), 3000g of mirabilite as a grinding agent, and 800g of ethylene glycol (japan catalyst, manufactured by japan) as a binder were charged into a two-arm kneader (MORIYAMA, 5L kneader Σ, hereinafter referred to as a kneader) and kneaded at a temperature controlled so that the temperature of the kneaded material in the kneader became 40 ℃. When the kneading is completed, the kneaded product is taken out, transferred to a temperature-adjustable tank in which 16L of deionized water is stored in advance, stirred by a stirring device at a rotation speed of 180rpm for 30 minutes, adjusted to pH 2.3 to 2.5 with 35% hydrochloric acid, and then stirred for further 1 hour to disperse the kneaded product. The dispersion was transferred to a Nutsche funnel for filtration, and the residue was washed with deionized water until the conductivity of the wash water became 3. mu.S/cm or less. The residue containing the water after washing was taken out, placed on a drying rack (made of SUS304), transferred to a dryer, and dried at 95 ℃ for 20 hours. The dried product was pulverized by a pulverizer (SMALL pulverizer, sample mill SK-M2, manufactured by Co., Ltd.) to obtain a finely pulverized powdery azo pigment composition. The average primary particle diameter of the particles in the finely divided azo pigment composition is 50 nm.

Production example 9

A dried product was obtained in the same manner as in production example 8 except that sulfanilic acid and BON acid were not added, and then a pulverization treatment was performed to obtain a powdery azo pigment. The average primary particle diameter of the particles in the azo pigment obtained was 90 nm.

Production example 10

300g of c.i. pigment orange 38 (product name NOVOPERM RED HFG, azo pigment, manufactured by Clariant corporation), 45g of surface treatment agent (Ripoxy (registered trademark) SPC2000, showa electric corporation, vinyl ester resin), 3000g of mirabilite as a grinding agent, and 800g of ethylene glycol (manufactured by japan catalyst) as a binder were charged into a two-arm type kneader (manufactured by MORIYAMA, 5L kneader Σ type, hereinafter referred to as kneader.) and kneaded for 9 hours while controlling the temperature so that the temperature of the kneaded material in the kneader becomes 40 ℃. When the kneading is completed, the kneaded product is taken out, transferred to a temperature-adjustable tank in which 16L of deionized water is stored in advance, stirred by a stirring device at a rotation speed of 180rpm for 30 minutes, adjusted to pH 2.3 to 2.5 with 35% hydrochloric acid, and then stirred for further 1 hour to disperse the kneaded product. The dispersion was transferred to a Nutsche funnel for filtration, and the residue was washed with deionized water until the conductivity of the wash water became 3. mu.S/cm or less. The residue containing the water after washing was taken out, placed on a drying rack (made of SUS304), transferred to a dryer, and dried at 95 ℃ for 20 hours. The dried product was pulverized by a pulverizer (SMALL pulverizer, sample mill SK-M2, manufactured by Co., Ltd.) to obtain a finely pulverized powdery azo pigment composition. The average primary particle diameter of the particles in the finely divided azo pigment composition is 40 nm.

[ test example A ]

(example A1)

The azo pigment composition obtained in production example 8: 12.0 wt%, pigment derivative 1 obtained in production example 1: 1.2 wt% (10.0 wt% with respect to the azo pigment composition) (hereinafter, the azo pigment composition and the pigment derivative may be collectively referred to as a colorant component), a polymeric dispersant (product of BYK-Chemie Japan, Disperbyk LPN-21715): the solid content was 40% by weight based on the colorant component, and a dispersion resin (folett (registered trademark) ZAH110, manufactured by seikagaku corporation, 35.0% by weight of the solid content, alkali-soluble): the amount of solid component was 30% by weight based on the colorant component, propylene glycol monomethyl ether (PM) as a solvent: 8% by weight of propylene glycol monomethyl ether acetate (PMA) as solvent: the remaining part was put into a stirrer (single screw mixer) having an internal volume of 550ml, and stirred for 10 minutes. Subsequently, 4 times the amount of zirconia beads (Toray cell balls, manufactured by Toray corporation) having an average particle size of 0.8mm was added thereto, and the mixture was stirred in a thermostatic bath at 40 ℃ for 30 minutes to carry out dispersion treatment. Thereafter, PMA was added so that the azo pigment composition became 19 wt%, stirring was performed for 10 minutes, and the zirconia beads were removed by filtration. Subsequently, zirconia beads (Toray cell balls, manufactured by Toray corporation) having an average particle size of 0.1mm were added in an amount of 4 times the total amount of the beads, and the mixture was stirred in a thermostatic bath at 40 ℃ for 90 minutes to perform dispersion treatment. Thereafter, PMA was added so that the azo pigment composition became 12 wt%, stirring was performed for 10 minutes, and the zirconia beads were removed by filtration using a Filter (PALL HDCII Membrane Filter, manufactured by PALL corporation), thereby obtaining pigment dispersion a 1.

(example A2)

A pigment dispersion a2 was obtained in the same manner as in example a1, except that the azo pigment obtained in production example 9 was used instead of the azo pigment composition obtained in production example 8.

Comparative example A1

Instead of the azo pigment composition obtained in production example 8: 22.5% by weight of pigment derivative 1 obtained in production example 1: 2.5 wt%, using the azo pigment composition obtained in production example 8: pigment dispersion A3 was obtained in the same manner as in example a1, except that 25% by weight was used.

Comparative example A2

Instead of the azo pigment composition obtained in production example 9: 22.5% by weight and pigment derivative 1 obtained in production example 1: 2.5 wt%, using the azo pigment composition obtained in production example 9: pigment dispersion a4 was obtained in the same manner as in example a1, except that 25% by weight was used.

(evaluation)

< preparation of coloring composition for Forming coating film >

To the pigment dispersions a1 to 4, coating film forming components (made by seiko chemical corporation, folett (registered trademark) ZAH110, acrylic polymer, solid content 35.0%, alkali-soluble) and PMA were added so that the azo pigment composition became 12% by weight and the total amount of the dispersion resin and the polymer dispersant became 100% by weight based on the azo pigment composition, to prepare colored compositions a1 to 4.

< formation of coating film >

The obtained colored compositions A1 to 4 were applied to glass plates having a thickness of 1mm and 100mm square, respectively, by using a spin coater (available from MIKASA, MS-150A). At this time, 3 coating films having different chromaticity x were coated with each of the coloring compositions A1 to 4 to prepare 3 coated sheets. That is, the thickness was changed by changing the rotation speed of the spin coater so that the chromaticity x of 1 of the 3 sheets had to be smaller than 0.6850 and the chromaticity x of the other 1 sheet had to be larger than 0.6850. The resulting coated plate was pre-dried at 90 ℃ for 2.5 minutes (Prebake), and further dried at 230 ℃ for 30 minutes (Postbake).

< measurement of chromaticity Y, luminance Y, contrast >

The tristimulus values of the coating films after Postbake were determined by the xyz color method using a colorimeter (U3310, manufactured by hitachi corporation). The contrast ratio (CR ratio) was determined using a color luminance meter (TOPCONTECHNOHOSE, BM-5AS, Co., Ltd.). For each coating film, an approximate straight line (calibration curve) was obtained from the measured values of the 3 coating plates prepared as described above, and the values of chromaticity Y and luminance Y when chromaticity x was 0.6850 were used as the results of each coating film. Wherein, the brightness Y adopts a correction value Y. The CR ratios (a1, a2, A3, a4/A3) of the respective coating films a1 to a4 were determined based on the coating film A3 obtained using the coloring composition A3. The results are shown in Table 1.

[ Table 1]

[ test example B ]

(example B1)

Pigment dispersion B1 was obtained in the same manner as in example a1, except that pigment derivative 2 obtained in production example 2 was used in place of pigment derivative 1 obtained in production example 1.

(evaluation)

As control B1, pigment dispersion B2 was obtained in the same manner as in comparative example a 1. In the same manner as in test example a, using the obtained pigment dispersions B1 and 2, colored compositions B1 and 2 and coating films B1 and 2 were prepared, respectively, and evaluated. The results are shown in Table 2. Further, a CR ratio was determined based on a coating film B2 (control B1) obtained using the coloring composition B2.

[ Table 2]

[ test example C ]

(example C1)

Pigment dispersion C1 was obtained in the same manner as in example a1, except that pigment derivative 3 obtained in production example 3 was used in place of pigment derivative 1 obtained in production example 1.

(evaluation)

As control C1, pigment dispersion C2 was obtained in the same manner as in comparative example a 1. In the same manner as in test example a, using the obtained pigment dispersions C1 and 2, colored compositions C1 and 2 and coating films C1 and 2 were prepared and evaluated, respectively. The results are shown in Table 3. Further, the CR ratio was determined based on the coating film C2 (control C1) obtained using the coloring composition C2.

[ Table 3]

[ test example D ]

(example D1)

Pigment dispersion D1 was obtained in the same manner as in example a1, except that pigment derivative 4 obtained in production example 4 was used in place of pigment derivative 1 obtained in production example 1.

(example D2)

Pigment dispersion D2 was obtained in the same manner as in example a1, except that pigment derivative 5 obtained in production example 5 was used in place of pigment derivative 1 obtained in production example 1.

(evaluation)

As a control D1, a pigment dispersion D3 was obtained in the same manner as in comparative example a 1. In the same manner as in test example A, using the obtained pigment dispersions D1 to 3, colored compositions D1 to 3 and coating films D1 to 3 were prepared and evaluated, respectively. The results are shown in Table 4. Further, the CR ratio was determined based on a coating film D3 (control D1) obtained using the coloring composition D3.

[ Table 4]

[ test example E ]

Example E1

Pigment dispersion E1 was obtained in the same manner as in example a1, except that pigment derivative 6 obtained in production example 6 was used in place of pigment derivative 1 obtained in production example 1.

Example E2

Pigment dispersion E2 was obtained in the same manner as in example a1, except that pigment derivative 7 obtained in production example 7 was used in place of pigment derivative 1 obtained in production example 1.

(evaluation)

As a control E1, a pigment dispersion E3 was obtained in the same manner as in comparative example a 1. In the same manner as in test example A, using the obtained pigment dispersions E1 to 3, colored compositions E1 to 3 and coating films E1 to 3 were prepared and evaluated, respectively. The results are shown in Table 5. Further, the CR ratio was determined based on a coating film E3 (control E1) obtained using the coloring composition E3.

[ Table 5]

[ test example F ]

(example F1)

A pigment dispersion F1 was obtained in the same manner as in example a1, except that the azo pigment composition obtained in production example 10 was used in place of the azo pigment composition obtained in production example 8.

Comparative example F1

Using the azo pigment composition obtained in production example 8: 25% by weight of the azo pigment composition obtained in production example 8: 22.5% by weight and pigment derivative 1 obtained in production example 1: a pigment dispersion F2 was obtained in the same manner as in example F1, except that the content of 2.5% by weight was changed.

(evaluation)

In the same manner as in test example a, using the obtained pigment dispersions F1 and F2, coloring compositions F1 and F2 and coating films F1 and F2 were prepared, respectively, and evaluated. The results are shown in Table 6. Further, a CR ratio was determined based on a coating film F2 (comparative example F1) obtained using the coloring composition F2.

[ Table 6]

As can be seen from tables 1 to 6: by using the pigment derivative represented by the formula (1), a coating film formed from the coloring composition for forming a coating film containing an azo pigment dispersion can suppress a decrease in brightness (Y ″), and improve contrast.

Claims

1. An azo pigment dispersion characterized by:

comprising an azo pigment, a pigment derivative represented by the following formula (1), a dispersant and a solvent,

in the formula (1), R¹～R⁴Independently represents a hydrogen atom or a halogen atom, R⁵Represents a group represented by the following formula (1-1) or formula (1-2), and n is more than 0 and 2 or lessThe real number of (2) is,

in the formula (1-1), Q¹Represents a hydrogen atom, a halogen atom or an alkoxy group, Q²Represents a hydrogen atom, a halogen atom or an alkoxy group, Q³An alkyl group having 1 to 4 carbon atoms, ＊ represents a bond,

in the formula (1-2), the symbol represents a valence bond.

2. The azo pigment dispersion according to claim 1, wherein:

the azo pigment contains a reaction product of a base represented by the following formula (2) and a coupling agent represented by the following formula (3) in an amount of 80% by weight or more based on the solid content,

in the formula (2), R⁶Represents R⁸-NH-C (═ O) -, group, R⁷Represents a halogen atom or R⁹A group represented by O-, R⁸Represents a hydrogen atom or a phenyl group (-C)₆H₅)，R⁹Represents an alkyl group having 1 to 4 carbon atoms,

in the formula (3), R¹⁰Represents a hydrogen atom or R¹¹-NH-C (═ O) -, group, R¹¹Represents a group represented by the following formula (3-1),

in the formula (3-1), R¹²Represents R¹⁴-NH-C (═ O) -or R¹⁴-C (═ O) -NH-, a group represented by R¹³Represents a hydrogen atom, a halogen atom or R¹⁵A group represented by O-, R¹⁴Represents a hydrogen atom or a phenyl group (-C)₆H₅)，R¹⁵Represents an alkyl group having 1 to 4 carbon atoms, and ＊ represents a bond.

3. The azo pigment dispersion according to claim 2, wherein:

the azo pigment comprises a reaction product of a substrate represented by the above formula (2) or (4) and a coupling agent represented by the above formula (3) or (5), wherein the content of the reaction product represented by the above formula (2) or (3) is 80 to 95% by weight based on the solid content,

in the formula (5), R¹⁶represents-SO₃H or-COOH.

4. The azo pigment dispersion according to claim 3, wherein:

the weight ratio of the component derived from formula (2) to the component derived from formula (4) is 90.6/9.4 to 98.9/1.1 in terms of (2)/(4), and the weight ratio of the component derived from formula (3) to the component derived from formula (5) is 82.4/17.6 to 96.5/3.5 in terms of (3)/(5).

5. The azo pigment dispersion according to any one of claims 1 to 4, wherein:

the average primary particle size of the azo pigment is 25-70 nm.

6. A coloring composition for forming a coating film, characterized in that:

comprising the azo pigment dispersion according to any one of claims 1 to 5 and a coating film-forming ingredient.