KR20170136205A - Blue pigment synergist, blue pigment ink composition comprising the same and preparation method thereof - Google Patents

Abstract

The present invention relates to a blue pigment synergist, and a composition thereof, and more particularly, to a phthalocyanine-based pigment synergist having a carboxyl group or a sulfonic acid group, to a blue pigment composition comprising the same, and to a preparation method thereof, wherein the pigment synergist according to the present invention greatly improves the dispersibility of a fine particulate pigment, is excellent in storage stability and can have high output as a nozzle is not clogged during printing.

Description

TECHNICAL FIELD The present invention relates to a blue pigment synergist, a blue pigment ink composition containing the blue pigment synergist, a blue pigment synergist, a blue pigment ink composition,

The present invention relates to a blue pigment synergist for a pigment ink and a composition thereof, and more particularly, to a phthalocyanine pigment synergist having a carboxyl group or a sulfonic acid group, a blue pigment ink composition containing the same, and a process for producing the same.

In the printing inkjet ink industry, along with supply of PC, which is the main business of the 1980s, the large market size is formed as a key component material of printing culture. In the industry, the printing industry, the advertising industry, the educational institution, and the garment industry have developed into industries that play a leading role in the industry's breakthrough growth. In recent years, inkjet printers have achieved high- In addition to technology development, ink materials have evolved into pigment types that have more heat resistance and light resistance than dye type.

 However, since the solubility and dispersion stability of the pigment are lower than that of the dye, there is a problem that the nozzle of the printer toner is clogged and it is difficult to have high output and storage stability. Therefore, in developing pigment ink, pigment particles of several tens of 탆 in size It has been desired to develop a pigment atomization technique for constituting ink and a technique for improving dispersion stability.

Korean Patent No. 10-1195078 Japanese Patent Application Laid-Open No. 2009-114280

The present invention has been developed in order to solve the above problems. It is an object of the present invention to provide a pigment synergist which can induce dispersion stability through interaction with dispersing agent by eating aggregation between pigments using electrostatic or steric repulsion, and to provide a synergist.

In addition, the present invention provides a pigment ink composition having excellent storage stability including such pigment synergists and having high output and dispersion stability because nozzles are not blocked during printing.

The present invention provides a pigment synergist having a chemical structure represented by the following general formula (1).

≪ Formula 1 >

In the above formula (1), M is Cu, Zn, Co. Ni, Sn, Pb, Mg and Fe, L is a simple bond, any one of an alkylene group and an arylene group, and R is any one of a carboxyl group, a sulfonic acid group and a phosphoric acid group.

Also, in the present invention, a pigment; Dispersing agent; And a solvent, wherein the pigment ink composition further comprises a pigment synergist having a chemical structure represented by the general formula (1).

The present invention also provides a process for producing a pigment dispersion comprising dispersing a pigment in a solvent in which a dispersant is dissolved; And a pigment synergist mixing step of mixing the pigment dispersion with a pigment synergist having the chemical structure represented by the formula (1).

As described above, the pigment synergist according to the present invention has characteristics that greatly improve dispersibility and storage stability of the finely divided pigment.

In addition, the pigment ink composition containing the pigment synergist according to the present invention has excellent storage stability and high output because the nozzle is not blocked during printing.

Figure 1 is a graphical representation of a pigment synergist (a) pigment blue 15: 3, (b) a pigment synergist and (c) a pigment synergist DMSO of formula (3) Solubility.

Hereinafter, the present invention will be described in detail. The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

As used throughout this specification, the term "synergist" refers to a pigment that is dispersed in a solvent to prevent aggregation of the pigment using electrostatic or steric repulsion or the like and to induce dispersion stability through interaction with the dispersant Refers to a compound having a structure resembling the chemical structure of all or part of a compound forming a pigment and capable of strongly adsorbing to a pigment through a pi-pi interaction and having an ionic functional group, The surface is made acidic or basic, and has a function of increasing the effect of a dispersant having a bifunctional ion or a pigment carrier.

The present invention provides a pigment synergist having a chemical structure represented by the following general formula (1).

≪ Formula 1 >

In the above formula (1), M is Cu, Zn, Co. Ni, Sn, Pb, Mg and Fe, L is a simple bond, any one of an alkylene group and an arylene group, and R is any one of a carboxyl 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 expressed by the following Chemical Formula 2 or Chemical Formula 3.

(2)

(3)

A pigment ink composition according to one embodiment of the present invention comprises a pigment; Dispersing agent; And a pigment synergist having a chemical structure represented by the general formula (1).

The pigment according to an embodiment of the present invention may be a phthalocyanine blue pigment.

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

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

≪ Formula 1 >

In the above formula (1), M is Cu, Zn, Co. Ni, Sn, Pb, Mg and Fe, L is a simple bond, any one of an alkylene group and an arylene group, and R is any one of a carboxyl 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 Chemical Formula 2 or Chemical Formula 3 as a chemical structure.

(2)

(3)

The pigment according to an embodiment of the present invention may be a phthalocyanine blue pigment.

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

Hereinafter, embodiments and embodiments of the present invention will be described in detail so that those skilled in the art can readily implement the preferred embodiments of the present invention. In particular, the technical idea of the present invention and its core structure and action are not limited by this. In addition, the content of the present invention can be implemented by various other types of equipment, and is not limited to the embodiments and examples described herein.

<Production method of pigment synergist>

Production Example 1: Production method of the formula (2)

The compound of Formula 2, which is a pigment synergist according to one embodiment of the present invention, can be prepared according to the following Reaction Scheme 1.

(2)

<Reaction Scheme 1>

After dissolving the sulfuric acid (140 ml) and the blue pigment 15: 3 (10 g, 17.4 mmol) thoroughly, add benzoic acid (2.12 g, 17.4 mmol) and paraformaldehyde (0.58 g, 19.0 mmol). After the reaction temperature is raised to 60 ° C and the reaction is completed for 2 hours, the reaction is terminated by adding cold water. The precipitate is stirred for 2.5 hours at room temperature and then washed with distilled water. (Yield: 80%)

Production Example 2: Production method of the formula (3)

The compound of Formula 3, which is a pigment synergist according to one embodiment of the present invention, can be prepared according to the following Reaction Formula 2.

(3)

<Reaction Scheme 2>

140.0 ml of sulfuric acid and 10 g of blue pigment 15: 3 are completely dissolved. React the reaction slowly to 90 ° C and react for 6 hours. When the reaction time is over, reduce to 40 ° C and add xylene (23.2 ml, 20 g). After elevating the temperature to 55 ° C and stirring for 0.5 hours, 1000 ml of water is added, and after raising the temperature to 75 ° C, it is thoroughly washed with distilled water after filtration. (Yield: 84.5%)

&Lt; Pigment Dispersion and Method of Manufacturing Pigment Ink Composition >

1. Solubility test of pigment synergist

Figure 1 is a graphical representation of a pigment synergist (a) pigment blue 15: 3, (b) a pigment synergist and (c) a pigment synergist DMSO of formula (3) Solubility. Pigment blue (15: 3) is precipitated in DMSO and does not dissolve in water but floats to the top. The pigment synergist of Formula 2 according to one embodiment of the present invention was settled to DMSO and water. The pigment synergist of Formula 3 according to one embodiment of the present invention has solubility in DMSO and precipitation in water.

2. Preparation of pigment dispersion

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

Comparative Example 1 does not use a pigment synergist, Comparative Example 2 uses a commercially available pigment synergist Solspers 5000, Example 1 uses a compound of Formula 2 as a pigment synergist, Example 2 uses a compound of Formula 3 Is used as a pigment synergist.

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

Comparative Example 1 Comparative Example 2 Example 1 Example 2 Pigment Blue 15: 3 24.0% 24.0% 24.0% 24.0% BASF
Acrylic dispersant 4.8% 4.8% 4.8% 4.8% Synergy none 2.4%
(Solsepers 5000) 2.4%
(2) 2.4%
(Formula 3) Distilled water Balance Balance Balance Balance Dispersion shaker Disper DAS-200 Disper DAS-200 Disper DAS-200 Disper DAS-200

3. Preparation of Pigment Ink Composition

The ink is prepared by a) adding 50 parts by weight of distilled water so that the total amount of glycerin, ethylene glycol, and triethylene glycol as a humectant is 32% by weight, and the mixture is stirred at 60 rpm for 1 minute. b) Surfactant is added 1.2% of surfactant of Surfynol series of Airproducts and stirred at 60 rpm for 1 minute. c) Add 0.05% of defoamer (polysiloxane) and less than 0.1% of preservative (1,2-Benzisothiazolin-one) as other additive and stir at 60 rpm for 1 minute. d) Finally, the pigment dispersion prepared above was added in an amount of 2.5% based on the pigment and stirred at 60 rpm for 1 hour.

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

Experiment number Comparative Example 1 Comparative Example 2 Example 1 Example 2 Pigment 2.5% 2.5% 2.5% 2.5% Moisturizer
(Glycerin / ethylene glycol, triethylene glycol) 32.0% 32.0% 32.0% 32.0% Surfactants
(Surfynol) 1.2% 1.2% 1.2% 1.2% Defoamer
(Polysiloxane) 0.05% 0.05% 0.05% 0.05% antiseptic
(1,2-Benzisothiazoline
-one) Less than 0.1% Less than 0.1% Less than 0.1% Less than 0.1% Distilled water Balance Balance Balance Balance

&Lt; Analysis of Pigment Ink Properties >

Initial physical properties and time-dependent changes of the pigment-ink prepared according to one embodiment of the present invention were analyzed. The average particle size, viscosity and surface tension of the blue pigment-ink prepared in the present invention were measured as follows. The average particle size was measured using a Malvern Zetasizer Nano-S instrument. The viscosity was measured using a Brookfiled DV-2 + PRO instrument and the surface tension was measured using a Kruss K8 instrument. The initial pigment ink properties were measured immediately after the ink was prepared. The aging storage stability evaluation was carried out at 20 ° C to + 55 ° C for 1 day after the ink was manufactured, and the physical properties after 7 repetitions, that is, Respectively. The continuous printability evaluation of the printer was evaluated as the maximum number of prints that did not block any nozzles when continuously printing A4 plain paper in full-size 100% pattern under standard mode output conditions in an ultra-high speed printer with an output speed of 70 ppm or more.

The evaluation results of the initial physical properties, storage stability and continuous output of the blue pigment ink evaluated as above are summarized in Table 3 below.

division Comparative Example  One Comparative Example  2 Example  One Example  2 Initial property Particle size
[nm] 143.4 Gelled
Can not measure
(Gelation) 146.6 137.2 Viscosity
[cP] 3.29 Gelation
No ink production 3.24 3.14 Surface tension [dyne / cm] 34.9 Gelation
No ink production 34.6 34.9 Aging Test
[After 7 days / rate of change] Particle size [nm]
(% Change,%) 187.3
30.6% Gelation
No ink production 162.8
(11.1%) 138.7
(1.1%) Viscosity [cP]
(% Change,%) 3.51
(6.7%) Gelation
No ink production 3.04
(6.2%) 3.22
(2.6%) Surface tension [dyne / cm]
(% Change,%) 32.5
(6.9%) Gelation
No ink production 33.1
(4.3%) 32.2
(7.7%) 70ppm speed printing result
[HP476DW] A4 / Normal mode / Full pattern output Good 500-sheet output Gelation
No ink production Good 500-sheet output Good 500-sheet output

As a result of analyzing the initial physical properties of the pigment ink composition prepared according to one embodiment of the present invention, the particle sizes of Examples 1 and 2 using the synthesized pigment synergist were smaller than those of Comparative Example 1 not using the pigment synergist The nozzles were not clogged and thus the output was excellent. On the other hand, when the commercialized product of Comparative Example 2 was used, gelation was impossible and measurement was impossible.

The time-dependent change of the physical properties of the pigment ink composition prepared according to one embodiment of the present invention over time was measured again after 7 days. In the case of Examples 1 and 2 using the synthesized pigment synergist, 1 (particle size, viscosity, surface tension), and storage stability was superior. On the other hand, Comparative Example 2 using the commercialized product was unable to measure the change over time because gelation was impossible as described above and ink production was impossible.

As a result of testing the continuous printability of the pigment ink composition prepared according to one embodiment of the present invention, the printability of 500 sheets of each of Examples 1 and 2 using the pigment synergists synthesized and Comparative Example 1 not used was good.

As described above, the pigment synergist according to the present invention greatly improves the dispersibility of the finely divided pigment, has excellent storage stability, and is excellent in high output because the nozzles are not clogged during printing.

Claims (9)

A pigment synergist having a chemical structure represented by the following formula (1)
&Lt; Formula 1 >

In the above formula (1), M is Cu, Zn, Co. Ni, Sn, Pb, Mg and Fe, L is a simple bond, any one of an alkylene group and an arylene group, and R is any one of a carboxyl group, a sulfonic acid group and a phosphoric acid group. The method according to claim 1,
Wherein the pigment synergist has a chemical structure expressed by the following general formula (2) or (3).
(2)

(3)

Pigments; Dispersing agent; And a solvent. In the pigment ink composition,
The pigment ink composition according to claim 1, further comprising the pigment synergist according to claim 1. The method of claim 2,
Wherein the pigment is a phthalocyanine-based blue pigment. The method of claim 2,
The dispersant may be selected from the group consisting of polyacrylic acid, polymethacrylic acid, poly (styrene-acrylic acid), poly (styrene-methacrylic acid) Acrylate or methacrylate, and a poly (ethylene-acrylic acid) or a salt thereof. A pigment dispersion preparation step of dispersing the pigment in a solvent in which the dispersant is dissolved; And
And a pigment synergist in which the pigment synergist having the chemical structure represented by the following formula (1) is mixed with the pigment dispersion.
&Lt; Formula 1 >

In the above formula (1), M is Cu, Zn, Co. Ni, Sn, Pb, Mg and Fe, L is a simple bond, any one of an alkylene group and an arylene group, and R is any one of a carboxyl group, a sulfonic acid group and a phosphoric acid group. The method of claim 6,
Wherein the pigment synergist has a chemical structure expressed by the following general formula (2) or (3).
(2)

(3)

The method of claim 6,
Wherein the pigment is a phthalocyanine-based blue pigment. The method of claim 6,
The dispersant may be selected from the group consisting of polyacrylic acid, polymethacrylic acid, poly (styrene-acrylic acid), poly (styrene-methacrylic acid) (Meth) acrylate or methacrylate, and a poly (ethylene-acrylic acid) or a salt thereof.

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