KR102144939B1 - Anthraquinone pigment synergist, pigment ink composition comprising the same and preparation method thereof - Google Patents

Abstract

The present invention relates to an anthraquinone pigment synergist for a pigment ink and a composition thereof. More particularly, the present invention relates to an anthraquinone-based pigment synergist, a pigment ink composition comprising the same and a manufacturing method thereof. According to the present invention, the pigment synergist has advantages of greatly improving the dispersibility of micronized pigments while having excellent solubility and high output since a nozzle is not clogged during printing. In addition, the pigment synergist can be used as a pigment-synergist for aqueous ink due to improved solubility in water.

Description

Anthraquinone pigment synergist, pigment ink composition comprising the same, and manufacturing method thereof {Anthraquinone pigment synergist, pigment ink composition comprising the same and preparation method thereof]

The present invention relates to an anthraquinone pigment synergist for pigment inks and a composition thereof, and more particularly, to an anthraquinone pigment synergist, a pigment ink composition comprising the same, and a method for producing the same.

The inkjet ink industry for printing is forming a huge market scale as a key component and material of printing culture along with supplying PCs, which was its main business in the 1980s. In the industry, the printing industry, advertisement industry, educational institution, and clothing industry have developed into an industry that plays a leading role in the revolutionary growth of the industry.In the case of recent inkjet printers, the resolution is 2,400 dpi and the printing speed is 70 ppm high-speed technology printer. With the development of technology, ink materials are evolving into pigment types that have heat resistance and light resistance rather than dye types.

As a prior art related to an anthraquinone-based dispersant, Japanese Patent Laid-Open No. 7-33998 (JP1995-033998A) discloses a ring containing -O-, -S-, =N- or -NH- in an organic pigment and anthraquinone skeleton. A composition for improving the coloring of a polymer organic substance is described using an anthraquinone-based dispersant having a structure bonded thereto, and Japanese Patent Laid-Open No. JP2007-231074A for an aqueous pigment dispersion and an ink composition using the same describes dispersion stability and heat resistance of particulate pigments. In order to provide this excellent aqueous pigment dispersion, a pigment derivative in which a sulfonic acid group is introduced into an anthraquinone pigment is described. Recently, Chinese Patent Laid-Open No. CN108587225A, which relates to an anthraquinone dye dispersant and ink for electrowetting displays, discloses ancra A technique of using an anthraquinone dye dispersant having an unsaturated hydrocarbon substituent having 1 to 20 carbon atoms in each of two phenyl groups of quinone has been attempted.

In general, pigmented inks can be expected to have excellent water resistance and light resistance, but have lower solubility than dyes, and dispersion stability due to aggregation and sedimentation of pigments is poor, and high output due to changes over time and clogging of the nozzle of Trinter toner. In the development of pigment inks, there is a disadvantage in that it is difficult to have storage stability. Therefore, the development of a pigment atomization technology constituting the ink by atomizing pigment particles having a size of several tens of µm into a size of several tens of nm, and a technology to improve dispersion stability and solubility is required. Actually.

Japanese Unexamined Patent Application Publication No. Hei 7-33998 (JP1995-033998A) Japanese Unexamined Patent Application Publication No. 2007-231074 (JP2007-231074A) Chinese Patent Publication CN108587225A

The present invention was developed to solve the above problems, and a pigment capable of inducing dispersion stability through interaction with a dispersant and preventing agglomeration between pigments by using an electrostatic or three-dimensional repulsive force of dispersed or micronized pigment particles It aims to provide synergist.

In the present invention, it is intended to provide a pigment ink composition having excellent storage stability and solubility, and at the same time, to provide a pigment ink composition having high output because the nozzle is not clogged during printing.

In addition, it is intended to provide a pigment-synergist having the possibility of use as a pigment-synergist for aqueous ink due to improved solubility in water.

In the present invention, in order to solve the above problems, a pigment synergist having a chemical structure represented by the following Chemical Formula 1 is provided.

<Formula 1>

However, in Formula 1, R ₁ to R ₃ are each independently hydrogen or any one selected from the group consisting of a hydroxyl group and a nitro group, and R ₄ is any one or more selected from the group consisting of a carboxy group, a sulfonic acid group, and a phosphoric acid group.

In addition, in the present invention, pigments; Dispersant; And in the pigment ink composition comprising a solvent, it provides a pigment ink composition further comprising a pigment synergist having a chemical structure represented by the formula (1).

In addition, in the present invention, a pigment dispersion preparation step of dispersing the pigment in a solvent in which the dispersant is dissolved; And it provides a method for producing a pigment ink composition comprising a pigment synergist mixing step of mixing the pigment synergist having a chemical structure represented by the formula (1) in the pigment dispersion.

As described above, the pigment synergist according to the present invention has characteristics of greatly improving the dispersibility and storage stability of the micronized pigment.

In addition, the pigment ink composition containing the pigment synergist according to the present invention has excellent solubility and storage stability, has high output because the nozzle is not clogged during printing, and is used as a pigment for water-based ink-synergist due to improved solubility in water. You can have the possibility.

1 shows the solubility of anthraquinone and pigment synergists of Formulas 2 to 6 in DMSO and water according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail. Terms and words used in the specification and claims should not be construed as limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. Based on the principle that the present invention should be interpreted as a meaning and concept consistent with the technical idea of the present invention.

The term "synergist" used throughout the specification is to prevent agglomeration between pigments by using electrostatic or three-dimensional repulsion of a pigment dispersed in a solvent and induce dispersion stability through interaction with a dispersant. It refers to a compound and has a structure similar to the chemical structure of the whole or part of the compound that forms the pigment, and can strongly adsorb to the pigment through π-π interactions, and the ionic functional groups contained in it By making the surface acidic or basic, it has a function of increasing the effect of a dispersant having a double ion or a pigment carrier.

In the present invention, in order to solve the above problems, a pigment synergist having a chemical structure represented by the following Chemical Formula 1 is provided.

<Formula 1>

However, in Formula 1, R ₁ to R ₃ are each independently hydrogen or any one selected from the group consisting of a hydroxyl group and a nitro group, and R ₄ is any one or more selected from the group consisting of a carboxy group, a sulfonic acid group, and a phosphoric acid group.

In the pigment synergist according to an embodiment of the present invention, a pigment synergist capable of improving the dispersibility of the pigment by introducing an organic acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group directly into the anthraquinone skeleton may be considered. Pigment synergists in which organic acid groups are introduced directly into the anthraquinone skeleton is not preferable because the maximum peak absorbance of the pigment changes due to the introduction of a substituent directly into the anthraquinone skeleton, and in particular, two or more carboxyl groups and sulfonic acid groups And in the introduction of a phosphoric acid group, it is more preferable to introduce a plurality of substituents through an intermediate linking structure such as a separate phenyl group in order to directly introduce a substituent to the anthraquinone skeleton.

The pigment synergist according to an embodiment of the present invention may have a chemical structure represented by any one of the following Chemical Formulas 2 to 6.

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

Pigment ink composition according to an embodiment of the present invention is a pigment; Dispersant; And a pigment synergist composed of a solvent and having a chemical structure represented by Formula 1 above. More specifically, a pigment synergist having a chemical structure represented by Chemical Formulas 2 to 6 may be further included.

The pigment according to an embodiment of the present invention may be an anthraquinone pigment.

The dispersant according to an embodiment of the present invention is polyacrylic acid, polymethacrylic acid, poly(styrene-acrylic acid), poly(styrene-methacrylic acid), poly(styrene-maleic acid), poly(styrene-maleic anhydride) ), acrylic acid or methacrylic acid and a copolymer of alkyl acrylate or methacrylate, poly(ethylene-acrylic acid), or a salt thereof may be one or more selected from the group consisting of.

In the present invention, in order to solve the above problems, a pigment dispersion preparation step of dispersing the pigment in a solvent in which the dispersant is dissolved; And it provides a method for producing a pigment ink composition comprising a pigment synergist mixing step of mixing a pigment synergist having a chemical structure represented by the following formula (1) in the pigment dispersion.

<Formula 1>

However, in Formula 1, R ₁ to R ₃ are each independently hydrogen or any one selected from the group consisting of a hydroxyl group and a nitro group, and R ₄ is any one or more selected from the group consisting of a carboxy group, a sulfonic acid group, and a phosphoric acid group.

The pigment synergist according to an embodiment of the present invention may have a chemical structure represented by any one of the following Chemical Formulas 2 to 6.

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

Pigment ink composition according to an embodiment of the present invention is a pigment; Dispersant; And a pigment synergist composed of a solvent and having a chemical structure represented by Formula 1 above. More specifically, a pigment synergist having a chemical structure represented by Chemical Formulas 2 to 6 may be further included.

The pigment according to an embodiment of the present invention may be an anthraquinone pigment.

The dispersant according to an embodiment of the present invention is polyacrylic acid, polymethacrylic acid, poly(styrene-acrylic acid), poly(styrene-methacrylic acid), poly(styrene-maleic acid), poly(styrene-maleic anhydride) ), acrylic acid or methacrylic acid and a copolymer of alkyl acrylate or methacrylate, poly(ethylene-acrylic acid), or a salt thereof may be one or more selected from the group consisting of.

Hereinafter, implementation examples and examples of the present application will be described in detail so that a person having general knowledge in the technical field to which the present application belongs can easily implement a preferred embodiment of the present invention. In particular, the technical idea of the present invention and its core configuration and operation are not limited by this. In addition, the content of the present invention may be implemented in various different types of equipment, and is not limited to the implementation examples and examples described herein.

<Manufacturing method of pigment synergist>

Preparation Example 1: Preparation method of the compound of formula 2

The compound of Formula 2, which is a pigment synergist according to an embodiment of the present invention, may be prepared according to Reaction Scheme 1 below.

<Formula 2>

<Reaction Scheme 1>

1,8 dihydroxy-4,5 dinitroanthraquinone (25g, 75.71mmol), 4-aminobenzoic acid (25.96g, 189.296mmol) and sodium acetate (12.15g, 148.15mmol) nitrobenzene (750ml) And reacted at 150° C. for 48 hours. While the temperature of the reaction mixture was slowly lowered to room temperature, ethanol was added and stirred overnight. Filter the crystallized material and rinse with water until neutral. (90% or more yield)

Preparation Example 2: Method for preparing the compound of Formula 3

The compound of Formula 3, which is a pigment synergist according to an embodiment of the present invention, may be prepared according to Scheme 2 below.

<Formula 3>

<Reaction Scheme 2>

1-nitroanthraquinone (25g, 98.75mmol), 4-aminobenzoic acid (33.85g, 246.85mmol) and sodium acetate (12.15g, 148.15mmol) were added to nitrobenzene (750ml) and reacted at 150℃ for 48 hours. do. While the temperature of the reaction mixture was slowly lowered to room temperature, ethanol was added and stirred overnight. Filter the crystallized material and rinse with water until neutral. (90% or more yield)

Preparation Example 3: Method for preparing the compound of formula 4

The compound of Formula 4, which is a pigment synergist according to an embodiment of the present invention, may be prepared according to Scheme 3 below.

<Formula 4>

<Reaction Scheme 3>

1-nitroanthraquinone (14g, 55.29mmol), 4-aminophthalic acid (25g, 138.015mmol) and sodium acetate (6.79g, 82.93mmol) were added to nitrobenzene (400ml) and reacted at 150℃ for 48 hours. . While the temperature of the reaction mixture was slowly lowered to room temperature, ethanol was added and stirred overnight. Filter the crystallized material and rinse with water until neutral. (90% or more yield)

Preparation Example 4: Preparation Method of Compound 5

The compound of Formula 5, which is a pigment synergist according to an embodiment of the present invention, may be prepared according to Scheme 4 below.

<Formula 5>

<Reaction Scheme 4>

1-nitroanthraquinone (14g, 55.29mmol), 4-amino isophthalic acid (25g, 138.015mmol) and sodium acetate (6.79g, 82.93mmol) were added to nitrobenzene (400ml) and reacted at 150℃ for 48 hours. do. While the temperature of the reaction mixture was slowly lowered to room temperature, ethanol was added and stirred overnight. Filter the crystallized material and rinse with water until neutral. (90% or more yield)

Preparation Example 5: Method for preparing the compound of formula 6

The compound of Formula 6, which is a pigment synergist according to an embodiment of the present invention, may be prepared according to Scheme 5 below.

<Formula 6>

<Reaction Scheme 5>

1-nitroanthraquinone (14g, 55.29mmol), 4-amino terephthalic acid (25g, 138.015mmol) and sodium acetate (6.79g, 82.93mmol) were added to nitrobenzene (400ml) and reacted at 150℃ for 48 hours. . While the temperature of the reaction mixture was slowly lowered to room temperature, ethanol was added and stirred overnight. Filter the crystallized material and rinse with water until neutral. (90% or more yield)

<Production method of pigment dispersion and pigment ink composition>

1. Solubility test of pigment synergist

1 shows the solubility of anthraquinone and pigment synergists of Formulas 2 to 6 according to an embodiment of the present invention in DMSO and water. The anthraquinone pigment does not dissolve in water, but rises to the top and slightly dissolves in DMSO. Pigment synergists of Chemical Formulas 2 to 6 according to an embodiment of the present invention are dissolved in water and DMSO. Therefore, it can be seen that the solubility of the synthesized anthraquinone pigment-synergist is improved than that of ancraquinone, and it can be seen that there is a possibility of use as a pigment-synergy for aqueous ink.

2. Preparation of pigment dispersion

BASF acrylic dispersant 4.8% is mixed with 71.2 parts by weight of distilled water and stirred until completely dissolved (60 rpm / 1 minute stirring), magenta pigment 24% is added, and mixed with a homomixer (6,000 rpm / 30 minutes stirring). The dispersion was dispersed for 1 hour in a dispersion shaker using a bead mill (Disper DAS-200).

Comparative Example 1 did not use a pigment synergist, Example 1 used the compound of Formula 2 as a pigment synergist, Example 2 used the compound of Formula 3 as a pigment synergist, and Example 3 represented the formula 4 The compound was used as a pigment synergist, Example 4 used the compound of formula 5, and Example 5 used the formula 6.

The composition of the pigment dispersion prepared according to an embodiment of the present invention is summarized and described in Table 1 below.

Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 Pigment Red 122 24.0% 24.0% 24.0% 24.0% 24.0% 24.0% Acrylic dispersant 4.8% 4.8% 4.8% 4.8% 4.8% 4.8% Synergist none 2.4% 2.4% 2.4% 2.4% 2.4% Antifoam 0.53% 0.53% 0.53% 0.53% 0.53% 0.53% Distilled water Balance Balance Balance Balance Balance Balance Dispersion shaker Disper DAS-200 Disper DAS-200 Disper DAS-200 Disper DAS-200 Disper DAS-200 Disper DAS-200

*All materials in the composition are weight percent

3. Preparation of pigment ink composition

To prepare the ink, a) add a moisturizing agent to 50 increments of distilled water in order so that the total weight of glycerin/ethylene glycol/triethylene glycol is 32%, followed by stirring at 60 rpm for 1 minute. b) As a surfactant, 1.2% of the surfactant of the Surfynol series of Airproducts is added and then stirred at 60 rpm for 1 minute. c) As other additives, 0.05% of an antifoam (polysiloxane) and less than 0.1% of a preservative (1,2-Benzisothiazolin-one) were added, followed by stirring at 60 rpm for 1 minute. d) Finally, after adding 2.5% of the pigment dispersion prepared above based on Pigment, the mixture is stirred at 60 rpm for 1 hour.

The composition of the pigment ink composition prepared according to an embodiment of the present invention is summarized and described in Table 2 below.

Experiment number Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 Dispersion
(Pigment) 3.5% 3.5% 3.5% 3.5% 3.5% 3.5% Moisturizer
(Glycerin/ethylene glycol, triethylene glycol) 32.0% 32.0% 32.0% 32.0% 32.0% 32.0% Surfactants
(Surfynol) 1.3% 1.3% 1.3% 1.3% 1.3% 1.3% Antifoam
(Polysiloxane) 0.05% 0.05% 0.05% 0.05% 0.05% 0.05% antiseptic
(1,2-Benzisothiazolinone) Less than 0.1% Less than 0.1% Less than 0.1% Less than 0.1% Less than 0.1% Less than 0.1% Distilled water Balance Balance Balance Balance Balance Balance

*All materials in the composition are weight percent

< Pigment ink properties Analysis>

Pigment-ink prepared according to an embodiment of the present invention was analyzed for initial physical properties and changes over time. The magenta pigment-ink prepared in the present invention was measured as follows for the average particle size, viscosity, and surface tension, which are physical properties. The average particle size was measured by a measurement method using Malvern Zetasizer Nano-S. Viscosity was measured using a Brookfiled DV-2+PRO instrument, and surface tension was measured using a Kruss K8 instrument. Initial pigment ink physical properties were measured immediately after ink preparation, and storage stability over time was evaluated by maintaining one cycle at 20°C to +55°C for 1 day, and repetition of 7 times, that is, after 1 week. Was measured. The continuous output evaluation of the printer was evaluated as the maximum number of printouts without any nozzles clogging when continuously printing A4 plain paper in a 100% full-image pattern under standard mode printing conditions in a high-speed printer with a print speed of 70 ppm or higher.

The initial physical property values, storage stability, and continuous output properties of the magenta pigment ink using the anthraquinone pigment synergist evaluated as described above were evaluated, and the results are summarized in Table 3 below.

division Comparative Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 Initial properties Particle size
[nm] 139.4 175.3 140.3 139.0 139.2 140.0 Viscosity
[cP] 3.67 3.78 3.75 3.60 3.63 3.70 Surface tension [dyne/cm] 34.2 36.4 34.5 34.4 34.2 34.5 Aging Test
[After 7 days/
Rate of change] Particle size [nm]
(Change rate, %) 132.0
(-5.31%) 291.0
(+66.0%) 133.5
(-4.85%) 130.8
(-5.89%) 131.5
(-5.53%) 131.9
(-5.79%) Viscosity [cP]
(Change rate, %) 3.70
(+0.82) 4.2
(+11.1%) 3.75
(0%) 3.59
(-0.27%) 3.60
(-0.83%) 3.69
(-0.27%) Surface tension [dyne/cm]
(Change rate, %) 33.1
(-3.22) 35.0
(-3.85%) 33.5
(-2.89%) 33.0
(-4.07%) 33.1
(-3.22%) 33.1
(-4.06%) 70ppm speed printing result
[HP476DW] A4/normal mode
/Full pattern output
Good
Good/
Color change occurs Good Good Good Good

In the case of Example 1 using the synthesized pigment synergy as a result of analyzing the initial physical properties of the pigment ink composition prepared according to an embodiment of the present invention, the particle size is larger than that of Comparative Example 1 without the synergy and color in output A change has occurred. On the other hand, in the case of Examples 3 and 4, the particle size was smaller than that of Comparative Example 1 in which the synergist was not used, and the nozzle was not clogged, so the output was excellent.

The change over time of the physical properties of the pigment ink composition prepared according to an embodiment of the present invention over time was measured again after 7 days, and in Examples 3, 4, and 5 using the synthesized pigment synergy, it was not used. The storage stability was excellent because the rate of change over time (particle size, viscosity, and surface tension) was less than that of Comparative Example 1.

As a result of testing the continuous printability of the pigment ink composition prepared according to an embodiment of the present invention, Examples 2, 3, 4 and 5 using the synthesized pigment synergist and Comparative Example 1 without using the synergist were all 500 The output of each was good.

As described above, the pigment synergist according to the present invention has characteristics of greatly improving the dispersibility and storage stability of the micronized pigment.

In addition, the pigment ink composition containing the pigment synergist according to the present invention has excellent solubility and has high output because the nozzle is not clogged during printing, and has the possibility of use as a pigment for water-based ink-synergist due to improved solubility in water. I can.

Claims (9)

Anthraquinone pigments; Dispersant; menstruum; And
A pigment ink composition comprising a pigment synergist having a chemical structure represented by the following formula (1):
<Formula 1>

However, in Formula 1, R ₁ to R ₃ are each independently hydrogen or any one selected from the group consisting of a hydroxyl group and a nitro group, and R ₄ is any one or more selected from the group consisting of a carboxy group, a sulfonic acid group, and a phosphoric acid group. The method according to claim 1,
The pigment synergist is a pigment ink composition, characterized in that it has a chemical structure represented by any one of the following Formulas 2 to 6.
<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

delete delete The method according to claim 1,
The dispersant is polyacrylic acid, polymethacrylic acid, poly(styrene-acrylic acid), poly(styrene-methacrylic acid), poly(styrene-maleic acid), poly(styrene-maleic anhydride), acrylic acid or methacrylic acid and alkyl Pigment ink composition, characterized in that at least one selected from the group consisting of a copolymer with acrylate or methacrylate, poly(ethylene-acrylic acid) or a salt thereof. A pigment dispersion preparation step of dispersing an anthraquinone pigment in a solvent in which the dispersant is dissolved; And
A method for producing a pigment ink composition comprising a pigment synergist mixing step of mixing a pigment synergist having a chemical structure represented by the following formula (1) in the pigment dispersion liquid:
<Formula 1>

However, in Formula 1, R ₁ to R ₃ are each independently hydrogen or any one selected from the group consisting of a hydroxyl group and a nitro group, and R ₄ is any one or more selected from the group consisting of a carboxy group, a sulfonic acid group, and a phosphoric acid group. The method of claim 6,
The pigment synergist is a method for producing a pigment ink composition, characterized in that it has a chemical structure represented by any one of the following formulas 2 to 6.
<Formula 2>

<Formula 3>

<Formula 4>

<Formula 5>

<Formula 6>

delete The method of claim 6,
The dispersant is polyacrylic acid, polymethacrylic acid, poly(styrene-acrylic acid), poly(styrene-methacrylic acid), poly(styrene-maleic acid), poly(styrene-maleic anhydride), acrylic acid or methacrylic acid and alkyl A method for producing a pigment ink composition, characterized in that it is at least one selected from the group consisting of acrylate or methacrylate copolymer, poly(ethylene-acrylic acid), or a salt thereof.

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