KR100568464B1 - Preparation method of dispersed pigment solution and solvent-based pigment ink therefrom - Google Patents

Abstract

The present invention relates to a method for producing a pigment dispersion, and to minimize the amount of resin required in the process of atomizing the pigment, the pigment concentration is high, the physical property of the inkjet printer for inkjet printers can be easily adjusted to be used in any company's printer It is an object to provide a process for the production of atomized pigment dispersions used in the manufacture of inks.

The atomized pigment dispersion of the present invention comprises a) a vinyl resin having a vinyl chloride content of 10-99.9% by weight and a vinyl acetate content of 10-99.9% with a vinyl resin copolymerized with a vinyl acetate, an acrylic resin or a mixture thereof. A resin dissolving step of dissolving in one or two or more mixed organic solvents; b) a first dispersion step of adding a dispersant and an organic pigment to the solution obtained in step a) and stirring by wetting at high speed; c) grinding the dispersion obtained in step b) with an impact disperser or bead mill.

Oil type inkjet ink, inkjet ink, pigment ink, organic pigment, pigment dispersion, vinyl resin, acrylic resin, inkjet printing, impact mill, bead mill

Description

Preparation method of pigment dispersion and oil-based pigment ink prepared therefrom {Preparation method of dispersed pigment solution and solvent-based pigment ink therefrom}

The present invention relates to a method for preparing a pigment dispersion and an oil-based pigment ink prepared therefrom, and more particularly, to a method for preparing a pigment dispersion used in the preparation of an oil-based pigment ink for an inkjet printer and to an oil-based pigment ink for printing on a polymer material. It is about.

Oil-based pigment inks for inkjet printers were developed for the purpose of printing directly on PVC-based uncoated materials, unlike conventional coatings on which water-based inkjets are used, and are mainly used in inkjet printers or inkjet plotters. Color development, light resistance, and water resistance are superior to molding pigment inks, and the market is rapidly replacing the aqueous pigment ink market.

Due to the properties of these materials, the oil-based pigment ink for inkjet printers has to be adhered to the surface of the material at the moment of contact with the material. After penetrating into the material, the resin contained in the ink should be able to strongly adhere the finely pigmented pigment pigment to the material, and the solvent should dry quickly to prevent smearing or contamination by the external environment.

Most of the pigments of the oil-based pigment ink for inkjet printers use encapsulated particulate pigment chips developed by Ciba Geigy, Penn color, and BASF for screen printing on plastic surfaces. Is prepared by dissolving this encapsulated particulate pigment in a solvent as it is.

Commercially encapsulated particulate pigments, namely chips, include the Microlith K series and the Microlith A series from Ciba Geigy, and the Dispersion SE series from BASF, which are used as pigments in inkjet printers. Since it is used in more than one, there is a disadvantage in that the density of the color is lowered when the viscosity is set for use for an inkjet printer, and the pigment made of the chip has a limited number of colors because it is defined in several colors.

In addition, the oil-based inkjet pigment ink is characterized by the fact that it is not easy to manufacture ink, because each company requires different physical properties such as viscosity and pigment concentration in designing the head of the ink cartridge due to overheating competition among printer companies.

An object of the present invention is to minimize the amount of resin required in the process of atomizing the pigment, the pigment concentration is high, the atomization used in the preparation of the oil-based pigment ink for inkjet printers easy to adjust the physical properties to be used in any company printer To provide a method for producing a pigment dispersion, and an oil-based pigment ink for an inkjet printer prepared therefrom.

Method for producing the atomized pigment dispersion of the present invention for achieving the above object,

a) one or two or more mixed organic solvents of vinyl chloride, acrylic resin, or a mixture of vinyl chloride and vinyl acetate in which the vinyl chloride content is 10-99.9% by weight and the vinyl acetate content is 10-99.9% Dissolving in a resin;

b) a first dispersion step of adding a dispersant and an organic pigment to the solution obtained in step a) and stirring by wetting at high speed;

c) grinding the dispersion obtained in step b) with an impact disperser or bead mill.

Solvents are selected from ketones, amides, esters, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ether acetates, triethylene glycol alkyl ether acetates in consideration of affinity with pigments and resins, compatibility with printing surfaces, and penetration. Or a mixture of propylene glycol alkyl ether acetates and dipropylene glycol alkyl ether acetates. Preferably, cyclohexanone, n-methyl-2-pyrrolidone (n lactone solvents such as -methyl-2-pyrrolidone, 2-pyrrolidone, isophorone, and gamma-butyrolactone, ethylene glycol butyl ether acetate ether acetate), diethylene glycol butyl ether acetate, triethylene glycol butyl ether acetate One or more mixtures of ethylene glycol butyl ether acetate, propylene glycol methyl ether acetate and dipropylene glycol methyl ether acetate are used.

Vinyl resin and acrylic resin are used for encapsulation to atomize the pigment and to strongly fix the pigment in combination with the printing surface when printing. . In particular, the acrylic resin plays a role of giving clarity to the output with inherent optical properties.

The vinyl resin is preferably a copolymer of vinyl chloride and vinyl acetate, and has an average molecular weight of 200,000 or less. For example, commercially available vinyl resins include VYNS-3, VYHH, VYHD, and VMCH. , VMCC, VMCA, VAGH, VAGF, VAGC, and the like.

Acrylic resins have properties similar to those of the above vinyl resins, but commercially available acrylic resins include Mitsubishi Rayon's DIANAL BR series, R & H's ACRYLOID series, Zeneca's NEOCRYL series, Hulls' PLEXIGUM series, ICI's ELVACITE series, and Degussa's DEGALANT Series, Good year's PLIOLITE series.

Organic pigments use organic pigments such as magenta, cyan, yellow, and black as well as orange and green colors. For example, magenta is C.I. Pigment Red 122, C.I. Pigment Red 57: 1, C.I. Pigment Red 185, C.I. Pigment Red 176, C.I. Pigment Red 48: 3, C.I. Pigment Red 247, C.I. Pigment Red 170, C.I. Pigment Red 53: 1, C.I. Pigment Red 149, C.I. Pigment Violet 19, C.I. Pigment Red242, C.I. Pigment Red 37 is selected and used. Yellow is C.I. Pigment Yellow 181, C.I. Pigment Yellow 191, C.I. Pigment Yellow 83, C.I. Pigment Yellow 180, C.I. Pigment Yellow 13, C.I. Pigment Yellow 120, C.I. Pigment Yellow 194, C.I. Pigment Yellow 151, C.I. Pigment Yellow 139, C.I. Pigment Yellow 17, C.I. Pigment Yellow 155 is used and cyan is C.I. Pigment Blue 15: 1, C.I. Select from Pigment Blue 15: 3 and use black as Carbon black C.I. Balck 7, Carbon black C.I. Select from Balck 11 and use orange. C.I. Pigment Orange 13, C.I. Pigment Orange 34, C.I. Pigment Orange 38, C.I. Pigment Orange 72, C.I. Pigment Orange 43, C.I. Pigment Orange 68, C.I. Pigment Orange 74, C.I. Select from Pigment Orange 5 and use green as C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Select from Pigment Green 17.

The organic pigment atomization process consists of two stages. The first stage is the first stage of atomization with mixing the pigment, resin, and solvent and stirring at high speed, and the wetting of the resin and pigment particles is performed, and the second stage is the impact mill. Or in the step of atomizing using a bead mill, the pigment (pigment) is atomized.

In the resin dissolving step of step a), a solvent capable of dissolving 0.01-50.0% by weight of the pigment is used, and a vinyl resin and an acrylic resin or a mixture thereof are used in an amount of 0.01-90% by weight of the solvent.

The dispersant keeps the atomized pigment in a stable dispersion state, and compatibility with the vinyl resin or acrylic resin to be used should be considered and organic pigment to dispersant is used in a weight ratio of 100: 1 to 1: 3.

In the first dispersion stage of step b), the mixer is stirred at 2,000-25,000 rpm, and in the second dispersion stage of step c), when grinding with an impact disperser, the pressure is 4,000-25,000 psi. In particular, step c) is the final step of atomizing the pigment and the most important step to stabilize the dispersion, and the appropriate number of times to repeat the appropriate number of times to maintain the stable dispersion state of the atomized pigment.

When the number of repetitions during milling is small, not only the atomization of the pigment is appropriately performed, but also the dispersion state becomes unstable, and excessive repeat milling causes aggregation or unstable dispersion depending on the pigment.

The oily pigment ink is prepared by blending the pigment dispersion with the ink diluent, preferably blending 1-99% by weight of the atomized pigment dispersion with 1-99% by weight of the ink diluent.

Ink diluents are ketones, amides, esters, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ether acetates, tri Using ethylene glycol alkyl ether acetates, propylene glycol alkyl ether acetates, dipropylene glycol alkyl ether acetates, or mixtures thereof Preferably, cyclohexanone, n-methyl-2-pyrrolidone, 2-pyrrolidone, 2-pyrrolidone, isophorone, gamma-part Tyrolactone (gamma-butyrolactone), ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate ether acetate, triethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, or mixtures thereof Use

In addition to the pigment dispersion and the ink diluent, a vinyl resin, an acrylic resin or a mixture thereof may be added so as to be 0.01-10% by weight of the total weight of the ink. Preferably, the vinyl resin is 70-99.9% by weight of vinyl chloride and 0.1-30% of vinyl acetate. As the copolymerized weight%, those having an average molecular weight of 200,000 or less are used.

Further, the fluorine-based surfactant may be added at 0.001-10% by weight of the total weight of the ink, or the silicone antifoaming agent may be added at 0.001-10% by weight of the total weight of the ink in order to prevent foaming.

The configuration of the present invention will be clearer through the following embodiments.

<Example 1>

1) Resin dissolution step: Vinyl resin VYHH 450gr was added to solvent EBA 8,900gr, and stirred for 60 minutes at a speed of 3000rpm using a high speed mixer to dissolve the resin.

2) First dispersion step: 50 g of the dispersant EFKA-4047 and pigment C.I. Pigment Yellow 120 600gr was added and mixed at 6000rpm for 2 hours.

3) Second Dispersion Step: The pigment was ground by repeating the impact milling process five times.

As a result, a pigment dispersion having a pigment concentration of 6% by weight, a pigment particle size of up to 550 nm, and an average particle size of 90 nm was prepared, and sedimentation or aggregation did not occur even when left for 6 months.

<Example 2-10>

Pigments were each converted to C.I. Pigment Yellow 181 (Example 2), C.I. Pigment Yellow 191 (Example 3), C.I. Pigment Yellow 83 (Example 4), C.I. Pigment Yellow 180 (Example 5), C.I. Pigment Yellow 13 (Example 6), C.I. Pigment Yellow 194 (Example 7), C.I. Pigment Yellow 151 (Example 8), C.I. Pigment Yellow 17 (Example 9), C.I. The same procedure as in Example 1 was carried out except for changing to Pigment Yellow 155 (Example 10).

The dispersion prepared through the above process had a pigment concentration of 6% by weight, a pigment particle size of 300-900 nm at maximum, an average particle size of 40-120 nm, and no sedimentation or aggregation occurred even after 6 months of standing.

<Example 11>

1) Resin dissolution step: The vinyl resin VAGH 400gr was added to the solvent EBA 8920gr, and stirred for 60 minutes at a speed of 2500rpm using a high speed mixer to dissolve the resin.

2) First Dispersion Step: The dispersant BYK-160 80gr and pigment C.I. Pigment Red 176 600gr was added and mixed at 7000rpm for 90 minutes.

3) Second Dispersion Step: The pigment was ground by repeating the bead milling process five times.

As a result, a pigment dispersion having a pigment concentration of 6% by weight, a pigment particle size of up to 680 nm, and an average particle size of 99 nm was prepared, and sedimentation or aggregation did not occur even when left for 6 months.

<Example 12-21>

Pigments were each converted to C.I. Pigment Red 57: 1 (Example 12), C.I. Pigment Red 122 (Example 13), C.I. Pigment Red 185 (Example 14), C.I. Pigment Red 48: 3 (Example 15), C.I. Pigment Red 247 (Example 16), C.I. Pigment Red 170 (Example 17), C.I. Pigment Red 53: 1 (Example 18), C.I. Pigment Red 149 (Example 19), C.I. Pigment Red 242 (Example 20), C.I. A pigment dispersion was prepared in the same manner as in Example 11 except for changing to Pigment Red 37 (Example 21).

As a result, the pigment concentration was 6% by weight, the pigment particle size was up to 350-900nm, the average particle size was 40-130nm, and even after standing for 6 months sedimentation or aggregation did not occur.

<Example 22>

1) Resin dissolution step: The vinyl resin VYHD 355gr was added to solvent EBA 8920gr, and stirred for 60 minutes at a speed of 3000rpm using a high speed mixer to dissolve the resin.

2) First dispersion step: 125 gr of the dispersant EFKA-4046 and C.I. Pigment Blue 15: 3 600gr was added and mixed for 90 minutes at 6000rpm.

3) Secondary Dispersion Step: The first dispersed droplet was finally pulverized at 1200 rpm through a bead milling process.

As a result, a pigment dispersion having a pigment concentration of 6% by weight, a pigment particle size of up to 480 nm, and an average particle size of 75 nm was prepared, and sedimentation or aggregation did not occur even when left for 6 months.

<Example 23>

Pigment is C.I. A pigment dispersion was prepared in the same manner as in Example 22 except for changing to Pigment Blue 15: 4.

As a result, a pigment dispersion having a pigment particle size of up to 305 nm and an average particle size of 73 nm was prepared, and sedimentation or aggregation did not occur even when left for 6 months.

<Example 24>

1) Resin dissolution step: The vinyl resin VMCC 400gr was added to solvent EBA 8920gr, and the resin was dissolved by stirring at a speed of 2000 rpm for 60 minutes with a high speed mixer.

2) Primary Dispersion Step: The dispersant BYK-162 80gr and Carbon black C.I. Balck 7 600gr was added and mixed for 90 minutes at 5000rpm.

3) Secondary Dispersion Step: The first dispersed droplets were finally milled again through an impact milling process.

As a result, a pigment dispersion having a pigment particle size of up to 370 nm and an average particle size of 65 nm was prepared, and sedimentation or aggregation did not occur even when left for 6 months.

<Example 25>

Pigments are carbon black C.I. A pigment dispersion was prepared in the same manner as in Example 24 except for changing to Black 11.

As a result, a pigment dispersion having a pigment particle size of up to 480 nm and an average particle size of 75 nm was prepared, and sedimentation or aggregation did not occur even when left for 6 months.

Example 26

1) Resin dissolving step: Vinyl resin VYHH 400gr was added to solvent EBA 8920gr, and stirred for 60 minutes at a speed of 2500rpm using a high speed mixer to dissolve the resin.

2) First dispersion step: Dispersant BYK-162 80gr and C.I. Pigment Orange 13 600gr was added and mixed at 5000rpm for 90 minutes.

3) Secondary Dispersion Step: The first dispersed droplets were finally milled again through an impact milling process.

As a result, a pigment dispersion having a pigment particle size of up to 370 nm and an average particle size of 65 nm was prepared, and sedimentation or aggregation did not occur even when left for 6 months.

<Example 27-32>

Pigments were each converted to C.I. Pigment Orange 34 (Example 27), C.I. Pigment Orange 38 (Example 28), C.I. Pigment Orange 72 (Example 29), C.I. Pigment Orange 43 (Example 30), C.I. Pigment Orange 68 (Example 31), C.I. A pigment dispersion was prepared in the same manner as in Example 26 except for changing to Pigment Orange 74 (Example 32).

As a result, a pigment dispersion having a pigment particle size of 300-850 nm at maximum and an average particle size of 40-115 nm was prepared, and no sedimentation or aggregation occurred even when left for 6 months.

<Example 33>

1) Resin dissolving step: The vinyl resin VAGH 400gr was added to the solvent EBA 8920gr and stirred for 60 minutes at a speed of 3000rpm using a high speed mixer to dissolve the resin.

2) First dispersion step: Dispersant BYK-162 80gr and C.I. Pigment Green 7 600gr was added and mixed for 90 minutes at 7000rpm.

3) Secondary Dispersion Step: The first dispersed droplet is finally milled at 1600 rpm in the bead milling process.

As a result, a pigment dispersion having a pigment particle size of up to 370 nm and an average particle size of 65 nm was prepared, and sedimentation or aggregation did not occur even when left for 6 months.

<Example 34>

Pigments were each converted to C.I. A pigment dispersion was prepared in the same manner as in Example 26 except for changing to Pigment Green 36.

As a result, a pigment dispersion having a pigment particle size of up to 420 nm and an average particle size of 55 nm was prepared, and sedimentation or aggregation did not occur even when left for 6 months.

     <Example 35>

      In order to prepare an oil-based pigment ink, 500 g of the dispersion solution of <Example 1>, EBA 478 gr, 1 gr of a fluorine-based surfactant, 1 gr of a silicone antifoaming agent, and 20 gr of an acrylic resin were stirred at a high speed homomixer at 7000 rpm for 2 hours.

      The stirred ink was filtered through an Adventec 5C filter paper to produce an oily pigment ink having a viscosity of 3.8 cps and a surface tension of 28.

      The prepared ink was injected into the ink cartridge and output from the MIMAKI JV-3 160, showing a stable output of 30 m or more.

The dispersion of <Example 2-34> was prepared by ink in the same manner to obtain a stable output result.

According to the present invention, in the preparation of the oil-based pigment ink, the limitations on the viscosity characteristics and the concentration limitation of the color can be overcome to produce a high concentration of the oil-based pigment ink.

In particular, the excellent dispersibility and stability of the finely pigmented pigment does not cause sediment or agglomeration even after long-term storage for more than 6 months, easy to control the physical properties can be easily applied to any company printer.

Claims (14)

a) one or two or more mixed organic solvents of vinyl chloride, acrylic resin, or a mixture of vinyl chloride and vinyl acetate in which vinyl chloride content is 10-99.9% by weight and vinyl acetate content is 10-99.9% Dissolving in a resin; b) a first dispersion step of adding a dispersant and an organic pigment to the solution obtained in step a) and stirring by wetting at high speed; c) grinding the dispersion obtained in step b) with an impact disperser or bead mill.     The method of claim 1, wherein in step a), the vinyl resin, the acrylic resin, or a mixture thereof is dissolved in 0.01-90% by weight of the solvent. The method of claim 1, wherein the ratio of the organic pigment to the vinyl resin or the acrylic resin or a mixed resin thereof is 100: 1 _to 1: 3 by weight in step b). The method of claim 1, wherein the stirring speed of the mixer in step b) is 2,000-25,000 rpm. The method of claim 1, wherein the grinding pressure of the impact disperser in step c) is 4,000-25,000 psi. The method of claim 1, wherein cyclohexanone, n-methyl-2-pyrrolidone, 2-pyrrolidone, iso Isophorone, gamma-butyrolactone, ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate, triethylene glycol butyl ether acetate ( triethylene glycol butyl ether acetate, propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, ethylene glycol butyl ether, diethylene glycol butyl ether (diethylene glycol butyl ether), propylene glycol butyl ether, propylene glycol methyl ether 1 kinds or method of the atomized pigment dispersion characterized by using two or more in admixture. delete         The pigment of claim 1 wherein the magenta is a pigment used in step b). Pigment Red 122, C.I. Pigment Red 57: 1, C.I. Pigment Red 185, C.I. Pigment Red 176, C.I. Pigment Red 48: 3, C.I. Pigment Red 247, C.I. Pigment Red 170, C.I. Pigment Red 53: 1, C.I. Pigment Red 149, C.I. Pigment Red242, C.I. Pigment Violet 19, C.I. Pigment Red 37 is selected and used. Yellow is C.I. Pigment Yellow 181, C.I. Pigment Yellow 191, C.I. Pigment Yellow 83, C.I. Pigment Yellow 180, C.I. Pigment Yellow 13, C.I. Pigment Yellow 120, C.I. Pigment Yellow 194, C.I. Pigment Yellow 151, C.I. Pigment Yellow 139, C.I. Pigment Yellow 17, C.I. Pigment Yellow 155 is used and cyan is C.I. Pigment Blue 15: 1, C.I. Select from Pigment Blue 15: 3 and use black as Carbon black C.I. Balck 7, Carbon black C.I. Select from Balck 11 and use orange. C.I. Pigment Orange 13, C.I. Pigment Orange 34, C.I. Pigment Orange 38, C.I. Pigment Orange 72, C.I. Pigment Orange 43, C.I. Pigment Orange 68, C.I. Pigment Orange 74, C.I. Select from Pigment Orange 5 and use green as C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 17 A method for producing an atomized pigment dispersion, characterized in that for use. 1 to 99% by weight of the atomized pigment dispersion prepared according to any one of claims 1 to 8, ketones, amides, esters, ethylene glycol alkyl ether acetates (ethylene) glycol alkyl ether acetates, diethylene glycol alkyl ether acetates, triethylene glycol alkyl ether acetates, propylene glycol alkyl ether acetates, Oil-based pigment ink prepared by blending 1-99% by weight of an ink diluent selected from dipropylene glycol alkyl ether acetates, or mixtures thereof. 10. The method of claim 9, wherein the ink diluent is cyclohexanone, n-methyl-2-pyrrolidone, 2-pyrrolidone, isophorone ), Gamma-butyrolactone, ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate, triethylene glycol butyl ether acetate ether acetate), propylene glycol methyl ether acetate, dipropylene glycol methyl ether acetate, or a mixture thereof. 10. The oil type pigment ink according to claim 9, wherein 0.01-10% by weight of the total weight of the ink is added to the vinyl resin, the acrylic resin, or a mixture thereof. 12. The oil-based pigment ink according to claim 11, wherein the vinyl resin is copolymerized with 70-99.9% by weight of vinyl chloride and 0.1-30% by weight of vinyl acetate, and has an average molecular weight of 200,000 or less. 10. The oil type pigment ink according to claim 9, wherein the fluorine-based surfactant is added in an amount of 0.001 to 10% by weight based on the total weight of the ink. 10. The oil type pigment ink according to claim 9, wherein the silicone antifoaming agent is added in an amount of 0.001 to 10% by weight based on the total weight of the ink.