KR20020059920A - Composition of pigment ink having superior dispersion stability - Google Patents

Abstract

PURPOSE: A pigment-type ink composition and its preparation method are provided, to improve the dispersion stability, the image density, the spraying characteristic, the continuous printing stability and the storage stability. CONSTITUTION: The pigment-type ink composition comprises 0.1-10 parts by weight of a pigment; 0.5-50 parts by weight of a polyalkyl acryl-based compound represented by the formula 1: (CHX1-CX1Y1)m-(CHX2-CX2COOY2)n-; 5-20 parts by weight of a moisturizing agent; and 1-20 parts by weight of a penetration promoter. In the formula 1, m and n are independent each other and are a natural number; X1 is H, CH3, COOCH3, C6H5, COOC6H5 or COO-M¬+; Y1 IS H, CH3, C6H5, CONH2, COO-M¬+, COO-C6H5, OCOCH3 or an alkylcarboxyl group; X2 IS H, CH3, COOCH3, C6H5, COOC6H5 or COO-M¬+; and Y2 IS H, CH3, C6H5, CONH2, a metal ion or an alkyl group. The method comprises the steps of mixing 0.1-10 parts by weight of the pigment, 0.5-50 parts by weight of the polyalkyl acryl-based compound and 1-5 parts by weight of diethylene glycol to prepare a pigment dispersive solution; and mixing 5-20 parts by weight of the obtained pigment dispersive solution and 5-30 parts by weight of a mixture consisting of 5-20 parts by weight of the moisturizing agent and 1-20 parts by weight of the penetration promoter.

Description

Pigment type ink composition with excellent dispersion stability {COMPOSITION OF PIGMENT INK HAVING SUPERIOR DISPERSION STABILITY}

[Industrial use]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigmented ink composition having excellent dispersion stability, and more particularly to a pigmented ink composition having excellent image density, spraying characteristics, continuous printing stability, and storage stability in printing.

[Prior art]

[0003] The inkjet printer has two types of recording methods: a thermal spray method for forming bubbles and ejecting ink with the force, and a piezo method for ejecting ink by controlling the volume change using a piezoelectric element. Until now, inkjet inks have been concentrated in office printers and home printers, but in addition, the use of commercial printers or industrial printers that can be applied to various materials as well as printing large widths is increasing.

In order to use for this purpose, various conditions have to be satisfied. Typical examples are light fastness and water fastness. Inks for the advertising industry or for outdoor printers should not change their properties or colors even when exposed to weather or excessive amounts of sunlight. Of course, basic conditions that can be printed on the printer must be met. Unlike the general ink, the pigment-type ink used for this purpose must satisfy basic properties such as viscosity, surface tension and pH. Typically, it can be divided into dye type ink and pigment type ink. In the case of the dye type ink, the dye used is a method of producing an ink using a water-soluble dye. Since the dye is easily dissolved in water, ink production is easy, and color, physical properties, and purity should be excellent as dye dye ink. Can be used. It also has the advantage that the color is very bright, vivid and vivid color by using water-soluble pigments, but since it is easily dissolved in water, it dissolves easily in water after printing and easily spreads when adhered to paper and the pigment is present in the dye molecule state. Because of this, there is a disadvantage that the color is easily decomposed by the light.

On the other hand, the pigment-type ink has an advantage that the structure is in a crystalline form, so that it is not easily soluble in water, does not bleed, and is not easily decomposed by light. However, unlike the dye-type ink, insoluble fine pigment particles have to be maintained in a stable dispersion state, there is a problem that the manufacturing is difficult. At present, the ink for inkjet printers, which are used as water-soluble constituents, are mostly made of dyes, but due to the advantages of pigmented inks, much of them are converted to pigmented inks. Pigment-type inks are resistant to water and light, so their use has been further developed from general office ink or indoor ink to outdoor advertising or industrial ink.

Since various pigment inks currently developed and marketed are mostly lacking in dispersion stability, problems such as continuous printing or precipitation during long-term storage occur. This is because dispersion stability is not achieved because of various phenomena depending on the type and characteristics of the dispersant used. Therefore, there is a need for research and development on pigment-type inks excellent in dispersion stability, long-term storage, and stability in continuous printing.

In view of the problems of the prior art, an object of the present invention is to provide a pigmented ink composition which can provide dispersion stability, long-term storage, and stability during chain printing.

In addition, the present invention provides a method for producing a pigmented ink excellent in dispersion stability.

[Means for solving the problem]

The present invention, in order to achieve the above object, in the pigment type ink composition,

a) pigments;

b) a polyalkylacrylic compound represented by Chemical Formula 1

[Formula 1]

(In Formula 1,

Each m, n is a positive integer,

X ₁ is H, CH ₃ , COOCH ₃ , C ₆ H ₅ , COOC ₆ H ₅ , or COO-M ⁺ ,

Y ₁ is H, CH ₃ , C ₆ H ₅ , CONH ₂ , COO-M ⁺ , COO-C ₆ H ₅ , OCOCH ₃ , or an alkylcarboxyl group,

X ₂ is H, CH ₃ , COOCH ₃ , C ₆ H ₅ , COOC ₆ H ₅ , or COO-M ⁺ ,

Y ₂ is H, CH ₃ , C ₆ H ₅ , CONH ₂ , metal ion, or alkyl);

c) humectants; And

d) penetration accelerator

It provides a pigmented ink composition comprising a.

In addition, the present invention is a method for producing a pigmented ink,

a) iii) pigments;

Ii) a polyalkylacrylic compound represented by Chemical Formula 1; And

보) moisturizer

Preparing a pigment dispersion containing a; And

b) to the pigment dispersion of a)

Iii) humectants; And

Iii) penetration accelerator

Adding a mixed solvent to disperse

It provides a method for producing a pigment-type ink comprising a.

Hereinafter, the present invention will be described in detail.

[Action]

In inkjet inks, a method of dispersing a pigmented ink in an aqueous solution state uses a substance such as a surfactant or a dispersant. In general, surfactants used in pigment dispersion may be divided into hydrophilic and hydrophobic moieties. The fact that the hydrophilic part is in an aqueous state and the hydrophobic part is in contact with the surface of the pigment to maintain dispersion stability is known through many data and papers. Since the bond strength of the pigment and dispersant is mostly van der Waals force, it is very weak than other chemical bonds and can be easily dropped by heat or other external force. Therefore, dispersion stabilization is a difficult task.

Most of the dispersants used vary widely, but basically, these two or more different parts exist as block copolymers or random copolymers to stabilize in aqueous solution. It may be considered that the more hydrophobic part is advantageous because the more the force or binding seat combined with the pigment can be achieved to stabilize the dispersion, but in that case, they may be agglomerated with each other to increase the particle size or precipitate.

In general, there are two techniques for achieving stabilization of dispersion: stabilization by electrostatic repulsion and stabilization by steric hindrance. In the former case, the dispersion is stabilized by preventing the particles from colliding with each other or entanglement by using an electrostatic force that the dispersant is polarized and repels the same polarities. In the latter case, since it has a considerably large three-dimensional structure, it is a method of achieving dispersion stabilization by preventing entanglement or agglomeration of each other by irregularization. In general, in the case of pigment dispersion used in pigment type ink, the dispersion stabilization method is stabilized by electrostatic repulsive force.

There are many kinds of dispersants used to produce pigmented inks based on this technique.

Anionic surfactants include fatty acid salts, alkyl dicarboxylates, alkyl sulfate ester salts, alkyl sulfate salts, polyhydric ester alcohol salts, alkyl naphthalene sulfate salts, alkylbenzene sulfate salts, alkyl naphthalene sulfate salts, alkyl sulfon succinic acid salts, Naphthenic acid salts, alkyl ether carboxylates, acylated peptides, alpha olefin sulfates, N-acylmethyltaurine salts, alkyl ether sulfates, secondary polyhydric alcohol ethoxy sulfates, polyoxyethylene alkylphenyl ether sulfates, monogly sulfates, Alkyl ether phosphoric acid ester salts, alkyl phosphoric acid ester salts, and the like.

Cationic surfactants include alkylamine salts, quaternary ammonium salts, alkylpyridium salts, alkylimidazolium salts, and the like.

Nonionic surfactants include fluorine, silicone, acrylic acid polymers, polyoxyethylene alkyl ethers, polyoxyethylene dihydric alcohol ethers, polyoxyethylene sterol ethers, lanolin derivatives of polyoxyethylene, and polyoxyethylene / polyoxypropylene air. Copolymer, polyoxyethylene sorbitan fatty acid ester, monoglyceride fatty acid ester, sucrose fatty acid ester, alkanolamide fatty acid, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, and the like.

Polymeric surfactants include polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, carboxyl group-containing water-soluble polyesters, hydroxyl group-containing cellulose resins, acrylic resins, vinyl acetate-based resins, butadiene resins, acrylic acid esters, and styrenes. Acrylic, polyester, polyamide, polyurethane, and the like.

Other surfactants include amphoteric surfactants such as alkylbetaine, alkylamine oxide, and phosphatidylcholine.

The present invention relates to a pigment ink, which is prepared by diluting a pigment dispersion obtained by dispersing a polyalkylacrylic compound and a dispersant containing diethylene glycol in a pigment, and having excellent dispersion stability, storage stability, and long-term stability during continuous printing. Ink compositions can be provided.

More specifically

The composition of the pigment ink composition of the present invention is

a) 0.1 to 10 parts by weight of pigment;

b) 0.5 to 50 parts by weight of the polyalkylacrylic compound represented by Formula 1; And

c) 5 to 20 parts by weight of a humectant; And

d) 1 to 20 parts by weight of penetration accelerator

It is preferable to include.

In addition, the present invention, the pigment-type ink is prepared by the pigment 1 to 30 parts by weight; 0.5 to 50 parts by weight of a polyalkylacrylic compound represented by Formula 1; And 5 to 20 parts by weight of a moisturizer 5 to 20 parts by weight of a pigment dispersion prepared by dispersing a mixture of 1 to 5 parts by weight of diethylene glycol; And 5 to 30 parts by weight of a mixed solvent in which 1 to 20 parts by weight of a penetration accelerator are mixed are preferably dispersed.

The molecular weight of the polyalkylacrylic compound represented by Chemical Formula 1 of a) ii) is determined based on m and n, and in order to obtain excellent dispersion stability, a compound having a molecular weight of 3 to 23 in the sum of m and n of Chemical Formula 1 ( A), a compound (B) in which the sum of m and n in the formula (1) is 23 to 70, and a compound (C) in which the sum of m and n in the formula (1) is 70 to 200, or a copolymer thereof, preferably Preferably a mixture of a compound in which the sum of m and n in the formula 1 is 6-15, a compound in which the sum of m and n in the formula 1 is 37-60, and a compound in which the sum of m and n in the formula 1 is 70-114, Or copolymers thereof.

Three combination ratios of the sum of m and n in the formula (1) is excellent dispersion stability when 1 to 5% by weight of the compound of A, 90 to 98% by weight of the compound of B, and 1 to 5% by weight of the compound of C It is possible to obtain, preferably 2 to 4% by weight of the compound of A, 91 to 95% by weight of the compound of B, and 3 to 5% by weight of the compound of C.

When the compound of A is less than 1% by weight, the viscosity is severe and stability is lowered. When it exceeds 5% by weight, the initial viscosity is very high, making it difficult to achieve dispersion stability. In addition, when the compound of B is used in excess of 98% by weight, the viscosity is maintained to some extent, but the concentration change after centrifugation is severe, and the long-term stability is lowered. When it is used at less than 90% by weight, dispersion stability and thermal stability are lowered. This causes nozzle clogging. When the compound of C is used in less than 1% by weight, the initial viscosity is low, but the particles are easily entangled, the viscosity rises sharply, and when it exceeds 5% by weight, the initial viscosity is not high to achieve dispersion stability.

In the polyalkylacrylic compound of a) ii), a dispersant is used in the pigment at 0.5 to 50 parts by weight of the total concentration, and preferably 2 to 20 parts by weight.

As the pigment of a) iii), black and color are used, and in the case of black, carbon black is used. Examples include Monarch 280, Monarch 120, Regal 350R, Regal 99R from Cabot; Special black 550, Special black 4, Special black 6, FW1, FW2, FW2V, FW18, XBF 285, S-160, S-170, Printex 90, Printex 95, Printex 80, Printex 75 from Degussa; And Raven 7000, Raven 5000UltraII, Raven 2600Ultra, Raven 3000, Raven 1255, Raven CD-5008, Raven C-975Ultra, Raven 1040, and Raven 1500 from Colombia Chemicals. In the case of color, pigments such as BASF, Clariant, CIBA, Aztech, Sum Chemical, DIC, and Daehan Switzerland are used. For example, CIPigment Blue 15, 15: 1, 15: 3, 15 based on CINo. : 4, 15: 6, 16, 22, 56, 60, 64, CIPigment Red 9, 17, 97, 122, 123, 149, 166, 168, 177, 180, 192, 202, 209, 215, 137, 138, 150, 153, 154, 155, 166, 168, 180 are used.

The moisturizers a) iii) and b) iii) use a high boiling point organic solvent to prevent evaporation of water, and examples thereof include glycerin, ethylene glycol, diethylene glycol, and triethylene, which are solvents used in pigment-type inks. 1 type from the group consisting of glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 1,5-pentanediol, 2-pyrrolidone, and N-methyl-2-pyrrolidone It is preferable to be selected more than.

The moisturizing agent of a) iii) is preferably diethylene glycol (DEG), and it is preferable to use 1 to 5 parts by weight together with the polyalkylacrylic compound of a) ii). It lowers the solubility to improve the binding strength with the pigment and prevents drying.

In the preparation of the pigment dispersion of step a), the remaining portion other than the pigment of a) iii), the polyalkylacrylic compound of a) ii), and diethylene glycol of a) iii) may be ion exchanged water or distilled water. To 100 parts by weight.

The penetration promoter of b) iii) is for promoting penetration into paper or other media, and includes ethylene glycol monomethyl ethyl ether, diethylene glycol monomethyl ethyl ether, triethylene glycol monomethyl propyl ether, and propylene glycol monomethyl ethyl. It is preferable to select 1 or more types from the group which consists of an ether and dipropylene glycol dimethyldiethyl ether.

The solvent of b) is used in an amount of 5 to 30 parts by weight, and mixed solvent mixed in a ratio of diethylene glycol monobutyl ether = 0.1 to 12, which is a permeation accelerator of diethylene glycol / b) It is preferable to use 6-17 weight part and to mix | blend the composition ratio in ratio of DEG / DEGBE = 0.5-7.

The present invention may be added to the anti-foaming antifoaming agent, anti-foaming agent to prevent mold or bacterial growth during long-term storage, such as non-ionic surfactant, other additives to enhance the permeability and control the surface tension as needed.

As the nonionic surfactant, a silicone, fluorine, or alkyl unsaturated fatty acid having antifoaming property is used. Examples include surfynol series (Air products), zonyl series (Dupont) and bio At least one selected from the group consisting of a series (bayowet series, BAYER), sodium lauryl sulfate, amine oxide type, and silicone type surfactant is preferable.

In addition, when dispersing the pigment using the above-mentioned surfactant, ball mill, bead mill, roll mill, two-roll mill, three-roll mill ( It is preferably carried out in dispersers such as three-roll mills, sand mills, dyno mills, horizontal milling machines, vertical milling machines, homogenizers and high-pressure mills. The bead used in the bead mill is sand, high purity sand, iron ball, glass ball, zirconia, alumina and the like. In some cases, a high speed homogenizer or a high pressure microfluidizer is used.

The dispersion of the present invention was prepared using a dyno mill or high hardness glass beads, and the milling time is 5 to 7 hours until the dispersion is sufficient.

In addition, the viscosity of the ink prepared by the above method is preferably 1.3 to 4.0 cp.

The present invention will be described in more detail with reference to the following examples and comparative examples. However, an Example is for illustrating this invention and is not limited only to these.

EXAMPLE

Example 1

Poly (stylene-co-methylmetacrylate) copolymer (A-1) 3 wherein the sum of m and n in the formula (1) is a polyalkylacrylic compound in 10 parts by weight of black carbon black (Printex 90, Degussa) as a pigment. Wt%, compound poly (stylene-co-methylmetacrylate) copolymer (B-1) 94-% by weight, sum of m and n of formula (1) is 37-47 compound poly, sum of m and n of formula (1), 74-90 10 parts by weight of a dispersant having a combination ratio of 3% by weight (stylene-co-methylmetacrylate) copolymer (C-1) was added. The remainder was added to 100 parts by weight of water and diethylene glycol to adjust the pigment concentration to 10%. Prepared.

Example 2

Pigment dispersion liquid was carried out in the same manner as in Example 1, except that a dispersant having a combined composition ratio of 1.5 wt% of A-1, 97 wt% of B-1, and 1.5 wt% of C-1 was used as the polyalkylacrylic compound. Was prepared.

Example 3

Pigment dispersion was carried out in the same manner as in Example 1, except that a dispersant having a combination ratio of 4% by weight of A-1, 92% by weight of B-1, and 4% by weight of C-1 was used as the polyalkylacrylic compound. Was prepared.

Example 4

2% by weight of A-1 as a polyalkylacrylic compound, 95% by weight of a compound poly (acrylic acid, sodium salt) (B-2) having a sum of m and n in the general formula (1) from 42 to 46, and 3% by weight of C-1 A pigment dispersion was prepared in the same manner as in Example 1 except that a dispersant having a combination ratio of was used.

Example 5

2% by weight of the compound poly (acrylc acid, sodium salt) (A-2), B-2 95% by weight, and C-1 3% by weight, wherein the sum of m and n in the general formula (1) is 10-13 as the polyalkylacrylic compound A pigment dispersion was prepared in the same manner as in Example 1, except that a dispersant having a combined composition ratio of was used.

Example 6

Polyalkylacrylic compound, 2% by weight of A-1, 95% by weight of B-1, 3% by weight of compound poly (acrylic acid, sodium salt) (C-2) having a sum of m and n A pigment dispersion was prepared in the same manner as in Example 1, except that a dispersant having a combined composition ratio was used.

Example 7

A pigment dispersion was carried out in the same manner as in Example 1 except that a polyalkylacrylic compound was used as a dispersant having a combination ratio of A-2 2% by weight, B-1 95% by weight, and C-2 3% by weight. Prepared.

Example 8

Except for using a dispersing agent having a combination composition of 2% by weight of A-1, 2% by weight of B-1, 50% by weight of B-1 and 45% by weight of B-2, and 2% by weight of C-1 Was carried out in the same manner as in Example 1 to prepare a pigment dispersion.

Example 9

Except for using a dispersing agent having a combination composition of 2% by weight of A-2, 2% by weight of B-1 and 50% by weight of B-1 and 45% by weight of B-2, and 3% by weight of C-2 In the same manner as in Example 1, a pigment dispersion was prepared.

Example 10

Except for using a dispersing agent having a combination composition of 2% by weight of A-1, 80% by weight of B-1, 15% by weight of B-1 and 15% by weight of B-2, and 3% by weight of C-1 Was carried out in the same manner as in Example 1 to prepare a pigment dispersion.

Example 11

Except for using a dispersing agent having a combination composition of 2% by weight of A-2, 80% by weight of B-1 and 15% by weight of B-2 and 95% by weight of a mixture of C-1 3% by weight Was carried out in the same manner as in Example 1 to prepare a pigment dispersion.

Example 12

Except for using a dispersing agent having a combination ratio of 2% by weight of A-1, 2% by weight of B-1 and 15% by weight of B-1 and 80% by weight of B-2, and 95% by weight of C-1 3% by weight of the polyalkylacrylic compound Was carried out in the same manner as in Example 1 to prepare a pigment dispersion.

Example 13

Except for using a dispersing agent having a combination composition of 2% by weight of A-2, 2% by weight of B-1 and 15% by weight of B-1 and 80% by weight of B-2, and 95% by weight of C-2 3% by weight. Was carried out in the same manner as in Example 1 to prepare a pigment dispersion.

Comparative Example 1

Pigment dispersion was carried out in the same manner as in Example 1, except that a dispersant having a combination ratio of 0.5 wt% of A-1, 95 wt% of B-1, and 4.5 wt% of C-1 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 2

Pigment dispersion was carried out in the same manner as in Example 1, except that a dispersant having a combination ratio of 4.5 wt% A-1, 95 wt% B-1, and 0.5 wt% C-1 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 3

Pigment dispersion was carried out in the same manner as in Example 1, except that a dispersant having a combination ratio of 7-1 wt% of A-1, 90 wt% of B-1, and 3-1 wt% of C-1 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 4

Pigment dispersion was carried out in the same manner as in Example 1, except that a dispersant having a combined composition ratio of 3% by weight of A-1, 90% by weight of B-1, and 7% by weight of C-1 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 5

A pigment dispersion was prepared in the same manner as in Example 1, except that a dispersant having a combined composition ratio of 10 wt% of A-1 and 90 wt% of B-1 was used as the polyalkylacrylic compound.

Comparative Example 6

A pigment dispersion was prepared in the same manner as in Example 1, except that a dispersant having a combined composition ratio of 90 wt% of B-1 and 10 wt% of C-1 was used as the polyalkylacrylic compound.

Comparative Example 7

Pigment dispersion was carried out in the same manner as in Example 1, except that a dispersant having a combination ratio of 10 wt% of A-1, 80 wt% of B-1, and 10 wt% of C-1 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 8

A pigment dispersion was prepared in the same manner as in Example 1 except that B-1 100 wt% of a dispersant was used as the polyalkylacrylic compound.

Comparative Example 9

The pigment dispersion was carried out in the same manner as in Example 1, except that a dispersant having a combination ratio of 0.5 wt% A-2, 95 wt% B-2, and 4.5 wt% C-2 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 10

Pigment dispersion was carried out in the same manner as in Example 1, except that a dispersant having a combination ratio of 4.5-2 wt% A-2, 95 wt% B-2 and 0.5 wt% C-2 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 11

Pigment dispersion was carried out in the same manner as in Example 1, except that a dispersant having a combination ratio of A-2 7 wt%, B-2 90 wt%, and C-2 3 wt% was used as the polyalkylacrylic compound. Prepared.

Comparative Example 12

Pigment dispersion was carried out in the same manner as in Example 1, except that a dispersant having a combination ratio of 3-2 wt% A-2, 90 wt% B-2 and 7 wt% C-2 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 13

A pigment dispersion was prepared in the same manner as in Example 1, except that a dispersing agent having a combined composition ratio of 10% by weight of A-2 and 90% by weight of B-2 was used as the polyalkylacrylic compound.

Comparative Example 14

A pigment dispersion was prepared in the same manner as in Example 1, except that a dispersant having a combined composition ratio of B-2 90 wt% and C-2 10 wt% was used as the polyalkylacrylic compound.

Comparative Example 15

Pigment dispersion was carried out in the same manner as in Example 1, except that a dispersant having a combined composition ratio of 10% by weight of A-2, 80% by weight of B-2, and 10% by weight of C-2 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 16

A pigment dispersion was prepared in the same manner as in Example 1, except that 100 wt% of B-2 was used as the polyalkylacrylic compound.

Comparative Example 17

Except that a polyalkylacrylic compound was used as a dispersant having a composition ratio of 0.5% by weight of A-1, 50% by weight of B-1 and 45% by weight of B-2, and 95% by weight of C-1 4.5% by weight of C-1. Was carried out in the same manner as in Example 1 to prepare a pigment dispersion.

Comparative Example 18

Except for using a dispersing agent having a combination composition of 4.5% by weight of A-1, 50% by weight of B-1 and 45% by weight of B-2, and 95% by weight of C-1 0.5% by weight of the polyalkylacrylic compound. Was carried out in the same manner as in Example 1 to prepare a pigment dispersion.

Comparative Example 19

Except for using a dispersing agent having a combination composition of 7% by weight of A-1, 50% by weight of B-1 and 40% by weight of B-2, and 90% by weight of C-1 3% by weight of the polyalkylacrylic compound. Was carried out in the same manner as in Example 1 to prepare a pigment dispersion.

Comparative Example 20

Except for using a dispersing agent having a composition ratio of 3% by weight of A-1, 90% by weight of a mixture of 50% by weight of B-1 and 40% by weight of B-2, and 7% by weight of C-1 Was carried out in the same manner as in Example 1 to prepare a pigment dispersion.

Comparative Example 21

Same as Example 1 except that a polyalkylacrylic compound was used as a dispersant having a composition ratio of 10% by weight of A-1, 90% by weight of a mixture of 50% by weight of B-1 and 40% by weight of B-2. A pigment dispersion was prepared by the method.

Comparative Example 22

Except for using a dispersing agent having a combination composition of 90% by weight, C-1 10% by weight of a mixture of 50% by weight of B-1 and 40% by weight of B-2 as a polyalkylacrylic compound, It was carried out by the method to prepare a pigment dispersion.

Comparative Example 23

Except for using a dispersing agent having a combined composition ratio of 10% by weight of A-1, 40% by weight of B-1 and 40% by weight of B-2, and 80% by weight of C-1 10% by weight of the polyalkylacrylic compound. Was carried out in the same manner as in Example 1 to prepare a pigment dispersion.

Comparative Example 24

A pigment dispersion was prepared in the same manner as in Example 1, except that 100 wt% of a mixture of 50 wt% of B-1 and 50 wt% of B-2 was used as the polyalkylacrylic compound.

The dispersion stability and particle stability of the pigment dispersions prepared in Examples 1 to 13, and Comparative Examples 1 to 24 were measured by the methods of a) and b), and the results are shown in Table 1 below.

A) Dispersion stability: Dispersion stability was evaluated by accelerating long-term storage using a centrifuge. After centrifugation at 8000 rpm for 10 minutes, the density change of the pigment dispersion was measured by using an UV / VIS spectrophotometer (Cary, Varian) to measure OD (Optical Density).

○ (stable): 80% or more comparing the concentration before and after centrifugation

△ (unstable): 50-80% or more by comparing the concentration before and after centrifugation

× (very unstable): Less than 50% comparing the concentration before and after centrifugation

B) Particle stability: The particle stability of the pigment dispersion was measured by viscosity change, and freezing-heating test was performed to accelerate the particle stability. Viscosity change was measured by repeating three times with one cycle at a temperature of minus 5 ℃ and image 60 ℃ each day. The viscosity was measured using a programmable DV-II ⁺ Viscometer (Brookfield) while controlling the temperature with 25 ℃ constant temperature water.

TABLE 1

division Concentration change (%) Particle Stability (Viscosity Change (cp)) Dispersion stability Before centrifugation After centrifugation Early 1 cycle 3 cycles Example 1 100 85 1.80 2.20 3.26 ○ Example 2 100 84 1.65 2.05 3.11 ○ Example 3 100 82 1.92 2.40 3.52 ○ Example 4 100 82 2.20 2.70 3.25 ○ Example 5 100 86 2.36 2.75 3.41 ○ Example 6 100 81 2.35 2.68 3.22 ○ Example 7 100 86 2.34 2.60 3.17 ○ Example 8 100 84 2.45 2.86 3.35 ○ Example 9 100 86 2.48 2.92 3.50 ○ Example 10 100 84 1.89 2.65 3.46 ○ Example 11 100 82 1.92 2.86 3.68 ○ Example 12 100 79 1.74 2.25 3.02 ○ Example 13 100 81 1.76 2.45 3.24 ○ Comparative Example 1 100 75 1.97 2.75 4.05 △ Comparative Example 2 100 70 2.16 2.89 4.92 △ Comparative Example 3 100 65 2.17 2.42 4.16 △ Comparative Example 4 100 65 2.38 3.63 4.55 △ Comparative Example 5 100 58 2.12 3.82 5.46 △ Comparative Example 6 100 56 2.45 3.70 5.88 △ Comparative Example 7 100 50 3.02 4.67 6.45 × Comparative Example 8 100 46 2.11 3.25 5.46 × Comparative Example 9 100 63 1.95 3.26 4.58 △ Comparative Example 10 100 58 1.84 3.01 4.71 △ Comparative Example 11 100 44 2.24 3.22 4.86 × Comparative Example 12 100 59 2.36 3.15 4.52 △ Comparative Example 13 100 52 1.72 2.56 4.60 △ Comparative Example 14 100 43 2.54 3.77 6.15 × Comparative Example 15 100 51 2.42 4.55 8.12 × Comparative Example 16 100 42 1.79 2.95 4.56 △ Comparative Example 17 100 63 1.76 2.74 4.25 △ Comparative Example 18 100 65 1.82 2.87 4.84 △ Comparative Example 19 100 73 1.86 2.98 4.76 △ Comparative Example 20 100 67 2.34 3.84 5.04 △ Comparative Example 21 100 43 1.95 4.76 7.56 × Comparative Example 22 100 44 2.65 5.12 9.26 × Comparative Example 23 100 45 2.59 5.02 9.52 × Comparative Example 24 100 38 2.06 3.77 5.96 ×

Through Table 1, 1 to 5% by weight of the compound having m + n = 3 to 23 of the polyalkylacrylic compound, 90 to 98% by weight of the compound having m + n = 23 to 70, m + n = 70 to 200 In Examples 1 to 13 in which phosphorus compounds were mixed in a combination ratio of 1 to 5% by weight, the dispersion stability was superior to 80% or more as a result of comparing the concentrations before and after centrifugation, and the results of the freezing-heating test were also slightly It was confirmed that the viscosity change or the viscosity increase was not large. However, in Comparative Examples 1 to 24, the concentration before and after centrifugation was found to be less than 80%, and the variation in viscosity also varied according to the amount of use and composition of the dispersant, indicating that the dispersion stability was unstable or very unstable. Could.

Example 14

4 weight% of a compound poly (stylene-co-methylmetacrylate) copolymer (A-1) having a sum of m and n in the general formula (1) as a polyalkylacrylic compound in 10 parts by weight of the color pigment Red 122 (Hostaperm, Clariant), 92% by weight of the compound poly (stylene-co-methylmetacrylate) copolymer (B-1) in which the sum of m and n in the formula (1) is 37 to 47, and the compound poly (stylene-) in which the sum of m and n in the formula (1) is 74 to 90. 20 parts by weight of a dispersant having a combined composition ratio of 4% by weight of co-methylmetacrylate) copolymer (C-1) was added, and a balance of 10% by weight of water and diethylene glycol was added to prepare a pigment dispersion having a pigment concentration of 10%.

Example 15

Pigment dispersion was carried out in the same manner as in Example 14, except that a dispersant having a combination ratio of 2.5 wt% of A-1, 95 wt% of B-1, and 2.5 wt% of C-1 was used as the polyalkylacrylic compound. Prepared.

Example 16

The pigment dispersion was carried out in the same manner as in Example 14, except that a dispersant having a combination ratio of 1.5 wt% of A-1, 95 wt% of B-1, and 3.5 wt% of C-1 was used as the polyalkylacrylic compound. Prepared.

Example 17

A pigment dispersion was carried out in the same manner as in Example 14, except that a dispersant having a combination ratio of 3.5 wt% A-1, 95 wt% B-1, and 1.5 wt% C-1 was used as the polyalkylacrylic compound. Prepared.

Example 18

Except for using a dispersing agent having a combination composition of 2% by weight of A-1, 2% by weight of B-1, 50% by weight of B-1 and 45% by weight of B-2, and 3% by weight of C-1 Was carried out in the same manner as in Example 14 to prepare a pigment dispersion.

Example 19

Except for using a dispersing agent having a combination composition of 3% by weight of A-1, 3% by weight of B-1, 50% by weight of B-1 and 45% by weight of B-2, and 2% by weight of C-1 Was carried out in the same manner as in Example 14 to prepare a pigment dispersion.

Example 20

Except for using a dispersing agent having a combination composition of 2% by weight of A-2, 50% by weight of B-1 and 45% by weight of B-2, and 95% by weight of mixture of C-2 3% by weight Was carried out in the same manner as in Example 14 to prepare a pigment dispersion.

Example 21

Except for using a dispersing agent having a combination composition of 3% by weight of A-2, 3% by weight of B-2, 50% by weight of B-1 and 45% by weight of B-2, and 2% by weight of C-2 Was carried out in the same manner as in Example 14 to prepare a pigment dispersion.

Example 22

Except for using a dispersing agent having a combination composition of 2% by weight of A-2, 80% by weight of B-1 and 15% by weight of B-2, and 95% by weight of mixture of C-2 3% by weight Was carried out in the same manner as in Example 14 to prepare a pigment dispersion.

Example 23

Except for using a dispersing agent having a combination composition of 3% by weight of A-2, 80% by weight of B-1 and 15% by weight of B-2 and 95% by weight of a mixture of C-2 and 2% by weight of C-2. Was carried out in the same manner as in Example 14 to prepare a pigment dispersion.

Example 24

Except for using a dispersing agent having a combination composition of 2% by weight of A-1, 15% by weight of B-1 and 80% by weight of B-2 and 95% by weight of a mixture of C-1 3% by weight Was carried out in the same manner as in Example 14 to prepare a pigment dispersion.

Example 25

Except for using a dispersing agent having a combination composition of 3% by weight of A-1, 15% by weight of B-1, 80% by weight of B-1 and 80% by weight of B-2, and 2% by weight of C-1 Was carried out in the same manner as in Example 14 to prepare a pigment dispersion.

Comparative Example 25

Pigment dispersion was carried out in the same manner as in Example 14, except that a dispersant having a combination ratio of 0.5 wt% of A-1, 95 wt% of B-1, and 4.5 wt% of C-1 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 26

Pigment dispersion was carried out in the same manner as in Example 14, except that a dispersant having a combination ratio of 4.5 wt% of A-1, 95 wt% of B-1, and 0.5 wt% of C-1 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 27

A pigment dispersion was carried out in the same manner as in Example 14, except that a dispersant having a combination ratio of A-1 7 wt%, B-1 90 wt%, and C-1 3 wt% was used as the polyalkylacrylic compound. Prepared.

Comparative Example 28

Pigment dispersion was carried out in the same manner as in Example 14, except that a dispersant having a combination ratio of 3-1 wt% A-1, 90 wt% B-1, and 7 wt% C-1 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 29

A pigment dispersion was prepared in the same manner as in Example 14, except that a dispersing agent having a combined composition ratio of 10 wt% of A-1 and 90 wt% of B-1 was used as the polyalkylacrylic compound.

Comparative Example 30

A pigment dispersion was prepared in the same manner as in Example 14, except that a dispersing agent having a combined composition ratio of 90 wt% of B-1 and 10 wt% of C-1 was used as the polyalkylacrylic compound.

Comparative Example 31

Pigment dispersion was carried out in the same manner as in Example 14, except that a dispersant having a combination ratio of 10 wt% of A-1, 80 wt% of B-1, and 10 wt% of C-1 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 32

A pigment dispersion was prepared in the same manner as in Example 14, except that B-1 100 wt% of a polyalkylacrylic compound was used as a dispersant.

Comparative Example 33

Pigment dispersion was carried out in the same manner as in Example 14, except that a dispersant having a combination ratio of 0.5-2 wt% A-2, 95 wt% B-2 and 4.5 wt% C-2 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 34

Pigment dispersion was carried out in the same manner as in Example 14, except that a dispersant having a combination ratio of 4.5 wt% A-2, 95 wt% B-2, and 0.5 wt% C-2 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 35

Pigment dispersion was carried out in the same manner as in Example 14, except that a dispersant having a combination ratio of A-2 7 wt%, B-2 90 wt%, and C-2 3 wt% was used as the polyalkylacrylic compound. Prepared.

Comparative Example 36

Pigment dispersion was carried out in the same manner as in Example 14, except that a dispersant having a combination ratio of 3% by weight of A-2, 90% by weight of B-2, and 7% by weight of C-2 was used as the polyalkylacrylic compound. Prepared.

Comparative Example 37

A pigment dispersion was prepared in the same manner as in Example 14, except that a dispersing agent having a combined composition ratio of 10% by weight of A-2 and 90% by weight of B-2 was used as the polyalkylacrylic compound.

Comparative Example 38

A pigment dispersion was prepared in the same manner as in Example 14 except for using a dispersing agent having a combined composition ratio of B-2 90% by weight and C-2 10% by weight as the polyalkylacrylic compound.

Comparative Example 39

A pigment dispersion was prepared in the same manner as in Example 14, except that a dispersing agent having a combined composition ratio of 10% by weight of A-2 and 90% by weight of B-2 was used as the polyalkylacrylic compound.

Comparative Example 40

A pigment dispersion was prepared in the same manner as in Example 14, except that B-2 100 wt% of a polyalkylacrylic compound was used as a dispersant.

Comparative Example 41

Except for using a dispersing agent having a combination ratio of 7% by weight of A-1, 50% by weight of B-1 and 40% by weight of B-2 and 90% by weight of C-1 3% by weight of the polyalkylacrylic compound Was carried out in the same manner as in Example 14 to prepare a pigment dispersion.

Comparative Example 42

Except for using a dispersing agent having a combination ratio of 10% by weight of A-1, 10% by weight of B-1 and 40% by weight of B-1 and 40% by weight of B-2, and 10% by weight of C-1 Was carried out in the same manner as in Example 14 to prepare a pigment dispersion.

Comparative Example 43

A pigment dispersion was prepared in the same manner as in Example 14, except that 100 v% of a mixture mixed with 50 wt% of B-1 and 50 wt% of B-2 was used as the polyalkylacrylic compound.

Comparative Example 44

Except for using a dispersing agent having a combination composition of 90% by weight of the mixture of 3% by weight of A-2, 50% by weight of B-1 and 40% by weight of B-2, and 7% by weight of C-2 Was carried out in the same manner as in Example 14 to prepare a pigment dispersion.

Comparative Example 45

Except for using a dispersing agent having a combination ratio of 7% by weight of A-2, 7% by weight of B-1 and 50% by weight of B-1 and 40% by weight of B-2, and 3% by weight of C-2 Was carried out in the same manner as in Example 14 to prepare a pigment dispersion.

The dispersion stability and particle stability of the pigment dispersions prepared in Examples 14 to 25 and Comparative Examples 25 to 45 were measured by the methods of a) and b), and the results are shown in Table 2 below.

TABLE 2

Concentration change (%) Particle Stability (Viscosity Change (cp)) Dispersion stability Before centrifugation After centrifugation Early 1 cycle 3 cycles Example 14 100 85 3.08 3.89 4.42 ○ Example 15 100 84 3.25 4.04 4.84 ○ Example 16 100 82 2.87 3.94 4.80 ○ Example 17 100 82 2.65 3.89 4.46 ○ Example 18 100 86 2.56 3.73 4.32 ○ Example 19 100 84 2.67 3.91 4.52 ○ Example 20 100 81 2.45 3.64 4.13 ○ Example 21 100 83 2.74 3.85 4.88 ○ Example 22 100 78 2.94 4.12 5.06 ○ Example 23 100 84 2.86 4.05 4.92 ○ Example 24 100 82 2.34 3.56 4.56 ○ Example 25 100 87 2.42 3.76 4.68 ○ Comparative Example 25 100 75 2.89 3.97 5.23 △ Comparative Example 26 100 74 2.56 4.01 5.45 △ Comparative Example 27 100 74 3.24 4.26 5.62 △ Comparative Example 28 100 73 3.48 4.85 5.95 △ Comparative Example 29 100 65 3.62 4.35 5.43 △ Comparative Example 30 100 68 3.51 4.95 6.12 △ Comparative Example 31 100 54 3.97 5.56 7.84 × Comparative Example 32 100 48 2.97 4.67 5.64 △ Comparative Example 33 100 72 2.87 4.12 5.25 △ Comparative Example 34 100 74 2.63 4.05 5.16 △ Comparative Example 35 100 63 3.72 4.77 6.34 △ Comparative Example 36 100 65 3.54 4.82 6.64 △ Comparative Example 37 100 69 3.61 4.65 6.21 △ Comparative Example 38 100 63 3.77 4.81 6.72 △ Comparative Example 39 100 47 3.84 5.12 7.53 × Comparative Example 40 100 45 2.99 3.87 5.02 △ Comparative Example 41 100 62 3.24 4.73 6.72 △ Comparative Example 42 100 47 3.72 5.17 7.66 × Comparative Example 43 100 42 2.88 4.56 6.35 × Comparative Example 44 100 56 3.45 4.98 6.46 △ Comparative Example 45 100 50 3.36 4.87 6.35 △

Through Table 2, 1 to 5% by weight of the compound of m and n of the polyalkylacrylic compound represented by the formula (1) is 3 to 23, 90 to 98% by weight of the compound of m and n is 23 to 70, And Examples 14 to 25, which are mixed in a combination ratio of 1 to 5% by weight of a compound in which the sum of m and n are 70 to 200, have excellent dispersion stability of 80% or more as a result of comparing the concentration before and after centrifugation. The results of the freezing-heating test also showed a small change in viscosity or a small increase in viscosity. However, in the case of Comparative Examples 25 to 45, the concentration before and after centrifugation was found to be less than 80%, and the variation of the viscosity also varied according to the amount of the dispersant used and the composition ratio, so that the dispersion stability was unstable or very unstable. Could.

Production Example

Preparation Example 1

15 parts by weight of a mixture of 10 parts by weight of diethylene glycol (DEG) and 5 parts by weight of diethylene glycol monobutyl ether (DEGBE), and 10 parts by weight of a pigment dispersion prepared using carbon black, and sulfinol 465 as a surfactant. 0.01% by weight of 10% solution, Ari products company), or DC 193 (Aldrich) was used, and 100 parts by weight of water was added to prepare a pigmented ink.

Preparation Example 2

To 10 parts by weight of a pigment dispersion prepared using carbon black, 8 parts by weight of DEG, 8 parts by weight of a mixed solvent, 16 parts by weight of a mixed solvent, and 0.01 parts by weight of a surfactant were used, and 100 parts by weight of water was added to prepare a pigmented ink. .

Preparation Example 3

To 10 parts by weight of a pigment dispersion prepared using carbon black, 7 parts by weight of DEG, 4 parts by weight of DEGBE, 13 parts by weight of a mixed solvent of 2 parts by weight of glycerol (Aldrich), and 0.01 parts by weight of a surfactant were used, and 100 parts by weight of water was added thereto. Pigment-type inks were prepared accordingly.

Preparation Example 4

4 parts by weight of DEG, 9 parts by weight of DEGBE, 15 parts by weight of a mixed solvent of 15 parts by weight of a mixed solvent, and 0.01 parts by weight of a surfactant were added to 10 parts by weight of a pigment dispersion prepared using carbon black, and 100 parts by weight of water were added to the pigment. Mold ink was prepared.

Preparation Example 5

8 parts by weight of DEG, 6 parts by weight of DEGBE, 2 parts by weight of 2-Py (2-pyrolidinone, Aldrich), 16 parts by weight of a mixed solvent, and 0.01 part by weight of a surfactant , 100 parts by weight of water was added to prepare a pigmented ink.

Preparation Example 6

6 parts by weight of DEG and 6 parts by weight of DEGBE, 2 parts by weight of glycerol, 16 parts by weight of a mixed solvent of 16 parts by weight of 2-Py and 2 parts by weight of a pigment dispersion prepared using carbon black, and 0.01 parts by weight of surfactant 100 parts by weight was added to prepare a pigmented ink.

Preparation Example 7

15 parts by weight of a mixed solvent of 15 parts by weight of DEG, 6 parts by weight of DEGBE, and 0.1 parts by weight of surfactant were used in 15 parts by weight of the pigment dispersion prepared using Red 122, and 100 parts by weight of water was added to prepare a pigment-type ink. .

Preparation Example 8

To 15 parts by weight of the pigment dispersion prepared using Red 122, 6 parts by weight of DEG, 9 parts by weight of DEGBE and 15 parts by weight of a mixed solvent, and 0.1 parts by weight of surfactant were used, and 100 parts by weight of water was added to prepare a pigmented ink. .

Preparation Example 9

To 15 parts by weight of the pigment dispersion prepared using Red 122, 8 parts by weight of DEG, 8 parts by weight of DEGBE and 16 parts by weight of a mixed solvent, and 0.1 parts by weight of surfactant were used, and 100 parts by weight of water was added to prepare a pigmented ink. .

Preparation Example 10

15 parts by weight of the pigment dispersion prepared using Red 122 6 parts by weight of DEG and 6 parts by weight of DEGBE, 2 parts by weight of glycerol, 16 parts by weight of a mixed solvent of 2-Py, and 0.1 parts by weight of a surfactant 100 parts by weight was added to prepare a pigmented ink.

Preparation Example 11

15 parts by weight of a pigment dispersion prepared using Blue 15: 3 (Daihan, Switzerland), 16 parts by weight of a mixed solvent of DEG and 8 parts by weight of DEGBE, and 0.1 part by weight of a surfactant, and 100 parts by weight of water The pigment-like ink was prepared according to the unit.

Preparation Example 12

10 parts by weight of DEG and 6 parts by weight of a mixed solvent, 16 parts by weight of a mixed solvent, and 0.1 parts by weight of a surfactant were added to 15 parts by weight of a pigment dispersion prepared using Blue 15: 3, and 100 parts by weight of water was added to give a pigmented ink. Prepared.

Preparation Example 13

6 parts by weight of DEG, 8 parts by weight of DEGBE, 16 parts by weight of a mixed solvent of 16 parts by weight of a mixed solvent, and 0.1 parts by weight of a surfactant were used, and 100 parts by weight of water was added to 15 parts by weight of the pigment dispersion prepared using Blue 15: 3. Pigment-type inks were prepared accordingly.

Preparation Example 14

To 15 parts by weight of the pigment dispersion prepared using Blue 15: 3, 9 parts by weight of DEG, 5 parts by weight of DEGBE, 16 parts by weight of a mixed solvent of 2-Py, and 0.1 parts by weight of surfactant were used, and water was added. According to the weight part, a pigmented ink was prepared.

Preparation Example 15

To 14 parts by weight of the pigment dispersion prepared using Yellow74, 9 parts by weight of DEG, 6 parts by weight of DEGBE, and 16 parts by weight of a mixed solvent, and 0.1 parts by weight of surfactant were added, and 100 parts by weight of water was added to prepare a pigmented ink.

Preparation Example 16

To 14 parts by weight of the pigment dispersion prepared using Yellow74, 6 parts by weight of DEG, 9 parts by weight of DEGBE, and 16 parts by weight of a mixed solvent, and 0.1 parts by weight of surfactant were added, and 100 parts by weight of water was added to prepare a pigmented ink.

Preparation Example 17

To 14 parts by weight of the pigment dispersion prepared using Yellow74, 8 parts by weight of DEG, 16 parts by weight of a mixed solvent of DEGBE8, and 0.1 parts by weight of surfactant were used, and 100 parts by weight of water was added to prepare a pigmented ink.

Preparation Example 18

To 14 parts by weight of a pigment dispersion prepared using Yellow74, 7 parts by weight of DEG, 7 parts by weight of DEGBE, 16 parts by weight of a mixed solvent of glycerol, and 0.1 parts by weight of a surfactant were used, and 100 parts by weight of water was added to form a pigment. Ink was prepared.

Comparative Example 1

15 parts by weight of DEGBE and 0.01 parts by weight of surfactant were used for 10 parts by weight of the pigment dispersion prepared using carbon black, and 100 parts by weight of water was added to prepare a pigmented ink.

Comparative Example 2

15 parts by weight of DEG and 0.01 parts by weight of surfactant were used in 10 parts by weight of the pigment dispersion prepared using carbon black, and 100 parts by weight of water was added to prepare a pigment-type ink.

Comparative Example 3

To 10 parts by weight of a pigment dispersion prepared using carbon black, 1 part by weight of DEG, 11 parts by weight of DEGBE, 16 parts by weight of a mixed solvent and 4 parts by weight of a mixed solvent and 0.01 parts by weight of a surfactant are added, and 100 parts by weight of water is added to the pigment type. Ink was prepared.

Comparative Example 4

10 parts by weight of a pigment dispersion prepared using carbon black, 12 parts by weight of DEG, 1 part by weight of DEGBE, 16 parts by weight of a mixed solvent of glycerol, and 0.01 part by weight of a surfactant, and 100 parts by weight of water to add a pigment ink. Was prepared.

Comparative Example 5

To 10 parts by weight of a pigment dispersion prepared using carbon black, 1 part by weight of DEG, 1 part by weight of DEGBE, 15 parts by weight of a mixed solvent and 13 parts by weight of a mixed solvent and 0.01 part by weight of a surfactant are added, and 100 parts by weight of water is added to form a pigment. Ink was prepared.

Comparative Example 6

10 parts by weight of DEG, 1 part by weight of DEGBE, 13 parts by weight of a mixed solvent, and 15 parts by weight of a mixed solvent and 0.01 part by weight of surfactant were used for 10 parts by weight of a pigment dispersion prepared using carbon black. Pigment-type inks were prepared.

Comparative Example 7

2 parts by weight of DEG, 2 parts by weight of DEGBE, 6 parts by weight of glycerol, 6 parts by weight of mixed solvent and 16 parts by weight of a mixed solvent and 0.01 parts by weight of surfactant were used. 100 parts by weight was added to prepare a pigmented ink.

Comparative Example 8

To 10 parts by weight of a pigment dispersion prepared using carbon black, 9 parts by weight of glycerol, 15 parts by weight of 2-Py 6 parts by weight of a mixed solvent, and 0.01 parts by weight of surfactant were used, and 100 parts by weight of water was added to prepare a pigment-type ink. It was.

Comparative Example 9

To 10 parts by weight of a pigment dispersion prepared using carbon black, 6 parts by weight of glycerol, 15 parts by weight of 2-Py 9 parts by weight of a mixed solvent and 0.01 parts by weight of a surfactant were used, and 100 parts by weight of water was added to prepare a pigmented ink. It was.

Comparative Example 10

To 15 parts by weight of the pigment dispersion prepared using Red 122, 1 part by weight of DEG, 1 part by weight of DEGBE, 12 parts by weight of a mixed solvent, 14 parts by weight of a mixed solvent, and 0.01 part by weight of a surfactant were added. Ink was prepared.

Comparative Example 11

To 15 parts by weight of the pigment dispersion prepared using Red 122, 2 parts by weight of DEG, 2 parts by weight of DEGBE, 16 parts by weight of a mixed solvent of 2-Py and 0.01 parts by weight of surfactant were used, and 100 parts by weight of water were added. Pigment-type inks were prepared.

Comparative Example 12

15 parts by weight of DEG and 15 parts by weight of surfactant were used in 15 parts by weight of the pigment dispersion prepared using Red 122, and 100 parts by weight of water was added to prepare a pigmented ink.

Comparative Example 13

15 parts by weight of DEGBE and 0.01 parts by weight of surfactant were used in 15 parts by weight of the pigment dispersion prepared using Red 122, and 100 parts by weight of water was added to prepare a pigmented ink.

Comparative Example 14

To 15 parts by weight of the pigment dispersion prepared using Red 122, 9 parts by weight of glycerol, 15 parts by weight of a mixed solvent of 2-Py, and 0.01 parts by weight of a surfactant are used, and 100 parts by weight of water is added to the pigment ink. Prepared.

Comparative Example 15

To 15 parts by weight of the pigment dispersion prepared using Red 122, 6 parts by weight of glycerol, 16 parts by weight of 2-Py 9 parts by weight of a mixed solvent, and 0.01 parts by weight of surfactant were used, and 100 parts by weight of water was added to give a pigmented ink. Prepared.

Comparative Example 16

12 parts by weight of glycerol and 0.01 parts by weight of a surfactant were used in 15 parts by weight of the pigment dispersion prepared using Red 122, and 100 parts by weight of water was added to prepare a pigmented ink.

Comparative Example 17

12 parts by weight of 2-Py and 0.01 parts by weight of surfactant were used in 15 parts by weight of the pigment dispersion prepared using Red 122, and 100 parts by weight of water was added to prepare a pigment-type ink.

Comparative Example 18

5 parts by weight of DEG, 15 parts by weight of a mixed solvent, and 0.01 parts by weight of a surfactant were used for 15 parts by weight of a pigment dispersion prepared using Red 122, and 100 parts by weight of water was added to prepare a pigment-type ink. .

Comparative Example 19

15 parts by weight of DEG, 15 parts by weight of 2-Py mixed solvent and 0.01 parts by weight of surfactant were used for 15 parts by weight of the pigment dispersion prepared using Red 122, and 100 parts by weight of water was added to prepare a pigmented ink. It was.

Comparative Example 20

5 parts by weight of DEGBE, 15 parts by weight of a mixed solvent, and 0.01 parts by weight of surfactant were used for 15 parts by weight of the pigment dispersion prepared using Red 122, and 100 parts by weight of water was added to prepare a pigment-type ink. .

Comparative Example 21

5 parts by weight of DEGBE, 15 parts by weight of 2-Py 10 parts by weight of a mixed solvent, and 0.01 parts by weight of surfactant were used for 15 parts by weight of the pigment dispersion prepared using Red 122, and 100 parts by weight of water was added to give a pigmented ink. Prepared.

Comparative Example 22

15 parts by weight of DEG, and 0.01 parts by weight of surfactant were used in 15 parts by weight of the pigment dispersion prepared using Blue 15: 3, and 100 parts by weight of water was added to prepare a pigmented ink.

Comparative Example 23

15 parts by weight of DEGBE and 0.01 parts by weight of surfactant were used in 15 parts by weight of the pigment dispersion prepared using Blue 15: 3, and 100 parts by weight of water was added to prepare a pigmented ink.

Comparative Example 24

To 15 parts by weight of the pigment dispersion prepared using Blue 15: 3, 9 parts by weight of glycerol, 15 parts by weight of 2-Py 6 parts by weight of a mixed solvent, and 0.01 parts by weight of a surfactant were added, and 100 parts by weight of water was added to form a pigment. Ink was prepared.

Comparative Example 25

To 15 parts by weight of pigment dispersion prepared using Blue 15: 3, 6 parts by weight of glycerol, 15 parts by weight of 2-Py 8 parts by weight of a mixed solvent, and 0.01 parts by weight of surfactant were used, and 100 parts by weight of water was added to form a pigment. Ink was prepared.

Comparative Example 26

To 15 parts by weight of the pigment dispersion prepared using Blue 15: 3, 8 parts by weight of glycerol, 16 parts by weight of 2-Py 8 parts by weight of a mixed solvent, and 0.01 parts by weight of a surfactant were used, and 100 parts by weight of water was added to form a pigment. Ink was prepared.

Comparative Example 27

15 parts by weight of DEG was added to 14 parts by weight of the pigment dispersion prepared using Yellow74, and water was added to prepare 100 parts by weight of a pigment ink.

Comparative Example 28

15 parts by weight of DEGBE was added to 14 parts by weight of the pigment dispersion prepared using Yellow74, and 100 parts by weight of water was added to prepare a pigmented ink.

Comparative Example 29

To 14 parts by weight of the pigment dispersion prepared using Yellow74, 8 parts by weight of glycerol and 14 parts by weight of a mixed solvent of 2-Py were added, and 100 parts by weight of water was added to prepare a pigmented ink.

Comparative Example 30

6 parts by weight of glycerol and 14 parts by weight of a mixed solvent of 14 parts by weight of 2-Py were added to 14 parts by weight of the pigment dispersion prepared using Yellow74, and 100 parts by weight of water was added to prepare a pigmented ink.

Comparative Example 31

14 parts by weight of DEG, 2 parts by weight of DEGBE, 5 parts by weight of glycerol, and 5 parts by weight of 2-Py mixed solvent were added to 14 parts by weight of the pigment dispersion prepared using Yellow74. Was prepared.

Using the inks prepared in Preparation Examples 1 to 18 and Comparative Examples 1 to 31, measured by the following methods a), b), c), d), m), b), and m). The results are shown in Table 3 below.

A) Drop formation: It was measured to see if the spraying was properly performed as a pigment type ink.

○: initial injection

×: No initial injection

B) Continuous printing: In order to find out whether the dispersion dissolves in the thermal resistor due to heat and precipitates or debris is formed to block the nozzle holes and prevent ink injection, the SOLID image is 1.5 m in width and length using ENCAD NOVAJET 730 printer. When printing at a high speed of 10 m size, it was measured whether the injection was performed well without clogging the nozzle.

○: Print more than 10 m

△: 5 to 10 m printing

×: 5 m or less printing

C) Image density: ID of SOLID image was printed here using GO Vinyl Calendered Water Resistant media of ENCAD, and the value was shown using Densitometer (RD918, Macbeth). The ID is usually required to have a density of 1.3 or more for black and 0.9 to 1.4 for color.

D) Nozzle state: In order to measure the phenomenon that the nozzle is clogged after leaving for a long time without printing, the nozzle was checked after 48 hours after printing.

If the nozzles were clogged, nozzle recovery was attempted through a printer self test.

◎: 0 blocked nozzles

○: 1 or 2 clogged nozzles (recovered)

△: 2 or more clogged nozzles (recovered)

×: 2 or more clogged nozzles (no recovery)

ㅁ) ID retention: The difference was measured by comparing the difference between the initial concentration of the ID and the ID concentration of the final printing.

○: ± 0.05 (ID retention)

×:> ± 0.05 (ID not maintained)

I) Removal of crust: The degree of crust occurring under the nozzle after continuous printing was measured.

○: slightly occurs

△: often occurs, but easily wiped

×: not generated and not wiped

G) Drying speed: To determine the phenomenon of smearing or staining on the back side according to the drying speed after printing, it was measured by determining the degree of contamination when the image was buried using the same media after 10 cm after printing. .

○: no pollution

△: slightly dirty

×: much pollution

TABLE 3

division drop formation Continuous printing Burn density Nozzle Condition Keep identity crust removal Drying speed Preparation Example 1 ○ ○ 1.34 ◎ ○ ○ ○ Preparation Example 2 ○ ○ 1.31 ◎ ○ ○ ○ Preparation Example 3 ○ ○ 1.32 ○ ○ ○ ○ Preparation Example 4 ○ ○ 1.29 ○ ○ ○ ○ Preparation Example 5 ○ ○ 1.30 ○ ○ ○ ○ Preparation Example 6 ○ ○ 1.31 ○ ○ △ ○ Preparation Example 7 ○ ○ 1.01 ◎ ○ ○ ○ Preparation Example 8 ○ ○ 0.98 ◎ ○ ○ ○ Preparation Example 9 ○ ○ 0.99 ◎ ○ ○ ○ Preparation Example 10 ○ ○ 1.03 ○ ○ △ ○ Preparation Example 11 ○ ○ 1.01 ◎ ○ ○ ○ Preparation Example 12 ○ ○ 1.05 ◎ ○ ○ ○ Preparation Example 13 ○ ○ 1.02 ○ ○ ○ ○ Preparation Example 14 ○ ○ 1.03 ○ ○ ○ ○ Preparation Example 15 ○ ○ 0.96 ◎ ○ ○ ○ Preparation Example 16 ○ ○ 0.92 ◎ ○ ○ ○ Preparation Example 17 ○ ○ 0.95 ◎ ○ ○ ○ Preparation Example 18 ○ ○ 0.94 ○ ○ ○ ○ Comparative Example 1 ○ × 0.76 × ○ ○ ○ Comparative Example 2 ○ ○ 1.22 ○ ○ ○ △ Comparative Example 3 ○ × 0.80 × ○ △ ○ Comparative Example 4 ○ ○ 1.26 ○ ○ △ △ Comparative Example 5 ○ △ 1.36 ○ ○ × × Comparative Example 6 ○ △ 1.32 ○ ○ × △ Comparative Example 7 ○ △ 1.22 ○ ○ △ ○

Comparative Example 8 ○ △ 1.24 △ ○ △ ○ Comparative Example 9 ○ △ 1.23 △ ○ △ ○ Comparative Example 10 ○ × 0.85 × × × × Comparative Example 11 ○ × 0.89 × × × △ Comparative Example 12 ○ × 0.81 △ × ○ △ Comparative Example 13 ○ × 0.63 × × ○ ○ Comparative Example 14 ○ × 0.70 △ × △ △ Comparative Example 15 ○ × 0.77 △ × △ ○ Comparative Example 16 ○ × 0.79 △ × × × Comparative Example 17 ○ × 0.76 △ × × ○ Comparative Example 18 ○ △ 0.96 △ ○ × × Comparative Example 19 ○ △ 0.81 △ ○ × ○ Comparative Example 20 ○ △ 0.94 △ × × × Comparative Example 21 ○ △ 0.93 △ × × ○ Comparative Example 22 ○ △ 0.92 △ × ○ △ Comparative Example 23 ○ × 0.66 × × ○ ○ Comparative Example 24 ○ △ 0.88 △ × △ △ Comparative Example 25 ○ △ 0.89 △ ○ △ ○ Comparative Example 26 ○ △ 0.83 △ × △ ○ Comparative Example 27 ○ × 0.62 × × ○ ○ Comparative Example 28 ○ △ 0.85 △ ○ ○ △ Comparative Example 29 ○ × 0.91 △ × △ △ Comparative Example 30 ○ △ 0.92 × ○ △ ○ Comparative Example 31 ○ △ 0.95 △ ○ ○ △

Through Table 3, in Preparation Examples 1 to 18 using a solvent in which diethylene glycol (DEG) and diethylene glycol monobutyl ether (DEGBE) were mixed, DEG or DEGBE was used alone, or with other solvents. Compared to the production of Comparative Examples 1 to 31 used by mixing showed a high ID, it was confirmed that the excellent in the chain printing stability, image concentration, nozzle condition, drying speed, and crust removal.

The present invention can provide a pigmented ink composition excellent in dispersion stability, storage stability, and long-term stability in continuous printing.

Claims (9)

In the pigment type ink composition, a) pigments; b) a polyalkylacrylic compound represented by Chemical Formula 1 [Formula 1] (In Formula 1, Each m, n is a positive integer, X ₁ is H, CH ₃ , COOCH ₃ , C ₆ H ₅ , COOC ₆ H ₅ , or COO-M ⁺ , Y ₁ is H, CH ₃ , C ₆ H ₅ , CONH ₂ , COO-M ⁺ , COO-C ₆ H ₅ , OCOCH ₃ , or an alkylcarboxyl group, X ₂ is H, CH ₃ , COOCH ₃ , C ₆ H ₅ , COOC ₆ H ₅ , or COO-M ⁺ , Y ₂ is H, CH ₃ , C ₆ H ₅ , CONH ₂ , metal ion, or alkyl); c) humectants; And d) penetration accelerator Pigment type ink composition comprising a. The method of claim 1, a) 0.1 to 10 parts by weight of pigment; b) 0.5 to 50 parts by weight of the polyalkylacrylic compound represented by Formula 1; And c) 5 to 20 parts by weight of a humectant; And d) 1 to 20 parts by weight of penetration accelerator Pigment type ink composition comprising a. The method of claim 1, The polyalkylacrylic compound of b) V) 1 to 5% by weight of the compound of formula 1 in which the sum of m and n is 3 to 23; Ii) 90 to 98% by weight of the compound of formula 1 in which the sum of m and n is from 23 to 70; And Iii) 1 to 5% by weight of the compound of formula (1) in which the sum of m and n is 70 to 200; Pigment mixtures, or mixtures thereof. The method of claim 1, The moisturizing agent of c) is glycerin, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 1,5-pentanediol, 2-pyrrolidone And at least one pigment-based ink composition selected from the group consisting of N-methyl-2-pyrrolidone. The method of claim 1, The permeation accelerator of d) is ethylene glycol monomethyl ethyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ethyl ether, triethylene glycol monomethyl propyl ether, propylene glycol monomethyl ethyl ether, and dipropylene glycol dimethyldi Pigment type ink composition selected from the group consisting of ethyl ether. The method of claim 1, Pigment type ink composition whose viscosity of the said ink is 1.3-4.0cp. In the method for producing a pigmented ink, a) iii) 0.1 to 10 parts by weight of pigment; Ii) 0.5 to 50 parts by weight of a polyalkylacrylic compound represented by Formula 1 below [Formula 1] (In Formula 1, Each m, n is a positive integer, X ₁ is H, CH ₃ , COOCH ₃ , C ₆ H ₅ , COOC ₆ H ₅ , or COO-M ⁺ , Y ₁ is H, CH ₃ , C ₆ H ₅ , CONH ₂ , COO-M ⁺ , COO-C ₆ H ₅ , OCOCH ₃ , or an alkylcarboxyl group, X ₂ is H, CH ₃ , COOCH ₃ , C ₆ H ₅ , COOC ₆ H ₅ , or COO-M ⁺ , Y ₂ is H, CH ₃ , C ₆ H ₅ , CONH ₂ , metal ion, or alkyl); And V) 1 to 5 parts by weight of diethylene glycol Dispersing a mixture of the above to prepare a pigment dispersion; And b) 5 to 20 parts by weight of the pigment dispersion of a) Iii) 5 to 20 parts by weight of a humectant; And 내지) 1 to 20 parts by weight of penetration accelerator Adding 5 to 30 parts by weight of a mixed solvent of Pigment type ink manufacturing method comprising a. The method of claim 7, wherein The mixed solvent of b) is a method of producing a pigment-type ink, which is contained in a proportion of diethylene glycol monobutyl ether = 0.1 to 12 diethylene glycol / b) ') permeation accelerator of moisturizing agent b)). The method of claim 7, wherein The pigment dispersion of step a) is ball mill, bead mill, roll mill, 2-roll mill, 3-roll mill, sand mill, dyno mill, horizontal grinder, vertical grinder, homogenizer, high pressure grinder, micropullui A method for producing a pigmented ink which is carried out in a mill selected from the group consisting of low grader.