KR100538235B1 - Colorant coordinated with antibacterial moiety and liquid composition comprising the same - Google Patents

Abstract

The present invention relates to a metal complex colorant containing an antibacterial function and a liquid composition comprising the same. The antimicrobial colorant is obtained by combining an antimicrobial material and a colorant through coordination bonds with a metal, and the liquid composition prepared by using the antimicrobial colorant may improve fastness of light resistance, water resistance, etc. as well as antimicrobial properties.

Description

Colorant coordinated with antibacterial moiety and liquid composition comprising the same

The present invention relates to an antimicrobial metal complex colorant and an antimicrobial liquid composition comprising the same, and more particularly, to an antimicrobial colorant and an antimicrobial liquid composition comprising the same by coordinating a carbendazim derivative with a metal complex colorant to give antimicrobial activity to the colorant molecule itself. It is about.

In general, inkjet printing is one of the non-impact printing methods, and has less advantages than the contact printing method, and has the advantage of easier color implementation than the laser beam printer.

Such contactless printing methods can be further classified into continuous inkjet methods and drop-on-demand (DOD) methods. Continuous inkjet printing is a method of printing by controlling the ink direction by inducing a change in the electromagnetic field while continuously ejecting the ink. On the other hand, the drop-on-demand method is a method in which ink is sprayed and printed per minute drop, and is divided into a thermal-bubble ink-jet method and a piezoelectric inkjet method. The heat-bubble inkjet method uses the pressure generated from the expansion of the bubble generated by heating the ink, whereas the piezoelectric inkjet method generates pressure by using a piezoelectric plate that dynamically deforms by electricity. Spray it.

Recently, there is a tendency to reduce the dot size of an inkjet printer in order to obtain a high quality printed product at a high resolution. To this end, the head of the inkjet printer has a smaller nozzle opening, which is easy to clog and the performance is influenced by deposits and the like affecting the size of the inkjet droplets. It is known that the components of the ink formulations affect the clogging of the nozzles, and in order to prevent this, wetting agents are usually added to the inkjet ink.

On the other hand, the ink composition for an inkjet printer basically contains a colorant, a solvent and an additive to impart color. When a dye is used as the colorant, the light resistance and water resistance of the printed product are inferior, but the range of colors that can be realized is wide. In contrast, in the case of using a pigment as a colorant, water resistance and light resistance are better than those of the dye, but there is a disadvantage in that the range of colors that can be realized is narrower than that of the dye.

In the case of the ink composition including the above dye or pigment as a colorant, the generation of bacteria or the like causes deterioration of ink properties and problems such as long-term storage stability. Therefore, a separate antimicrobial agent is added to the ink composition to suppress the production and growth of bacteria, etc., but there is a problem that another side effect occurs due to the antimicrobial agent. In other words, when the antimicrobial agent is added to the inkjet ink composition, the nozzle clogging due to ink entanglement is significantly increased, and homogeneity is also difficult to secure. In addition, in the case of using an antimicrobial agent that can suppress such side effects, there is a problem in that it is difficult to realize the optimal color because the antimicrobial properties are weak and the long-term storage stability is lowered or the dye or pigment having excellent compatibility with the antimicrobial agent is difficult to select.

The technical problem to be achieved by the present invention is to provide a colorant imparting antimicrobial properties by binding the antimicrobial material to the metal complex colorant through a coordination bond.

Another technical problem to be achieved by the present invention is to provide an antimicrobial liquid composition containing the antimicrobial colorant.

The present invention to achieve the above technical problem,

It provides an antimicrobial colorant of formula (1) characterized in that it is obtained by coordinating an antimicrobial substance and a colorant with a metal:

The coloring agent forms a coordination bond with the metal (Me), and includes one or more azo groups of the formula (2),

The metal (Me) represents a polyvalent transition metal,

L represents a ligand forming a coordination bond with a metal (Me),

A represents an antimicrobial ligand that coordinates to the metal directly or via a linker Y,

n represents a number from 1 to 3, m represents a number from 0 to 2, m + n = a number from 1 to 3,

In Formula 2, X ₁ and X ₂ each independently represent a hydroxy, amino group, carboxyl group or alkoxy group having 1 to 2 carbon atoms, ring A and B represents an unsubstituted or substituted C5-C30 cycloalkenylene group.

The ligand A is preferably a carbendazide derivative represented by the following formula (3).

In Formula 3, R ₁ represents a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, or a phosphoric acid or a salt thereof, and R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a substituted or unsubstituted group An alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl or alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted Or an unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms.

In Formula 1, Y may be represented as Formula 4 below as a linker that may be involved when A, which is an antimicrobial substance, does not form a direct coordination bond with a metal (Me) coordinated with a colorant.

In Chemical Formula 4, Z is a functional group capable of coordinating with a metal (Me), particularly a hydroxy, amino group, carboxyl group or alkoxy group having 1 to 2 carbon atoms, and R ₈ is substituted or unsubstituted with 1 to 30 carbon atoms. Alkylene group, substituted or unsubstituted alkenylene group having 2 to 30 carbon atoms, substituted or unsubstituted alkynylene group having 2 to 30 carbon atoms, substituted or unsubstituted arylene group having 6 to 30 carbon atoms, substituted with 6 to 20 carbon atoms Or an unsubstituted arylalkylene group, a substituted or unsubstituted heteroalkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 4 to 20 carbon atoms, a substituted or unsubstituted heteroarylalkylene having 4 to 20 carbon atoms Is selected from the group consisting of

J is a junction group bonded with the antimicrobial substance A as a single bond, -C (= 0) -NR _9- , -NR ₉ -C (= 0)-, -NH-C (= 0) -R ₁₀ -C (= O) -O-, -OC (= O) -R ₁₀ -C (= O) -NH-, -OC (= O) -R ₁₀ -C (= O) O-, -C (= O) -O-, -OC (= O)-, -O-, -S-, -P-, -NH-, -C = C-, -C≡C-, R ₉ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, R ₁₀ is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 30 carbon atoms, 2 carbon atoms Substituted or unsubstituted alkynylene group having from 30 to 30 carbon atoms, substituted or unsubstituted arylene group having 6 to 20 carbon atoms, substituted or unsubstituted arylalkylene group having 6 to 20 carbon atoms, substituted or unsubstituted hetero atom having 1 to 30 carbon atoms An alkylene group, a substituted or unsubstituted heteroarylene group having 4 to 20 carbon atoms, a substituted or unsubstituted heteroarylalkylene group having 4 to 20 carbon atoms, and Emitter is selected.

In order to achieve the other technical problem of the present invention, the present invention

Antimicrobial metal complex colorants;

Liquid medium; And / or

Contains additives,

The antimicrobial metal complex colorant provides a liquid composition, which is obtained by combining an antimicrobial material and a colorant through coordination bonds with a metal.

Hereinafter, the present invention will be described in more detail.

The antimicrobial metal complex colorant of the present invention binds the antimicrobial material and the colorant through a coordination bond with the metal to impart antimicrobial activity to the colorant molecule. That is, the antimicrobial colorant of the present invention is obtained by combining a carbendazide derivative and a colorant through coordination bonds with metals. The antimicrobial colorants are excellent in antimicrobial properties, and thus, long-term storage stability can be secured without a separate antimicrobial agent during ink production. Therefore, the fastness of water resistance, light resistance and the like can be improved.

Antimicrobial colorant according to the present invention,

An antimicrobial colorant of Formula 1 characterized in that the antimicrobial substance and the colorant are obtained by coordinating a coordination bond with a metal:

<Formula 1>

The coloring agent forms a coordination bond with the metal (Me), and includes one or more azo groups of the formula (2),

The metal (Me) represents a polyvalent transition metal,

L represents a ligand forming a coordination bond with a metal (Me),

A represents an antimicrobial ligand that coordinates to the metal directly or via a linker Y,

n represents a number from 1 to 3, m represents a number from 0 to 2, m + n = a number from 1 to 3,

<Formula 2>

In Formula 2, X ₁ and X ₂ each independently represent a hydroxy, amino group, carboxyl group or alkoxy group having 1 to 2 carbon atoms, ring A and B represents an unsubstituted or substituted C5-C30 cycloalkenylene group.

More specifically, in the compound of Formula 1, metal (Me) represents Ni, Cu, Zn, Fe, Cr, Pd, Pt, Co, etc. as a polyvalent transition metal, and L and (Y) A are metals (Me). Ligand which forms a coordination bond with

Examples of the ligand L include, but are not limited to, neutral ligands such as water, ammonia, pyridine, bipyridine, terpyridine, and morpholine, and anionic ligands such as acetate, iminodiacetate, and glycine.

The ligand A is preferably a carbendazine derivative represented by the following Chemical Formula 3 as an antimicrobial substance capable of coordinating a metal Me directly or through a linker Y.

<Formula 3>

In Formula 3, R ₁ represents a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, or a phosphoric acid or a salt thereof, and R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ Are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a substituted or unsubstituted group An alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl or alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted Or an unsubstituted arylalkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms.

In Formula 1, Y may be represented as Formula 4 below as a linker that may be involved when A, which is an antimicrobial substance, does not form a direct coordination bond with a metal (Me) coordinated with a colorant.

<Formula 4>

In Chemical Formula 4, Z is a functional group capable of coordinating with a metal (Me), particularly a hydroxy, amino group, carboxyl group or alkoxy group having 1 to 2 carbon atoms, and R ₈ is substituted or unsubstituted with 1 to 30 carbon atoms. Alkylene group, substituted or unsubstituted alkenylene group having 2 to 30 carbon atoms, substituted or unsubstituted alkynylene group having 2 to 30 carbon atoms, substituted or unsubstituted arylene group having 6 to 30 carbon atoms, substituted with 6 to 20 carbon atoms Or an unsubstituted arylalkylene group, a substituted or unsubstituted heteroalkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 4 to 20 carbon atoms, a substituted or unsubstituted heteroarylalkylene having 4 to 20 carbon atoms Is selected from the group consisting of

J is a junction group bonded with the antimicrobial substance A as a single bond, -C (= 0) -NR _9- , -NR ₉ -C (= 0)-, -NH-C (= 0) -R ₁₀ -C (= O) -O-, -OC (= O) -R ₁₀ -C (= O) -NH-, -OC (= O) -R ₁₀ -C (= O) O-, -C (= O) -O-, -OC (= O)-, -O-, -S-, -P-, -NH-, -C = C-, -C≡C-, R ₉ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, R ₁₀ is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 30 carbon atoms, 2 carbon atoms Substituted or unsubstituted alkynylene group having from 30 to 30 carbon atoms, substituted or unsubstituted arylene group having 6 to 20 carbon atoms, substituted or unsubstituted arylalkylene group having 6 to 20 carbon atoms, substituted or unsubstituted hetero atom having 1 to 30 carbon atoms An alkylene group, a substituted or unsubstituted heteroarylene group having 4 to 20 carbon atoms, a substituted or unsubstituted heteroarylalkylene group having 4 to 20 carbon atoms, and Emitter is selected.

As the colorant which binds to the antimicrobial substance through coordination with the metal, any colorant may be used without limitation as long as it has at least one azo group capable of forming a metal complex salt among commonly used colorants. In addition, the antimicrobial coloring agent is bound to one or more of the antimicrobial substance to one azo group contained in the colorant through a coordination bond with the metal, or each of the at least one antimicrobial substance to the two or more azo groups contained in the colorant is combined with the metal It is preferred to combine through coordination to form an antimicrobial metal complex colorant, but is not necessarily limited thereto.

The alkylene group used as a substituent in the compound of the present invention is a divalent compound obtained by removing two hydrogen atoms at both ends of a normal paraffinic hydrocarbon, and refers to a straight or branched alkylene group having 1 to 20 carbon atoms, and from 1 to about Preferred are straight-chain or branched alkylene groups having 12 carbon atoms. More preferred alkylene groups are lower alkylene groups having 1 to 6 carbon atoms. At least one hydrogen atom of the alkylene group may be substituted with a halogen atom, hydroxy group, nitro group, cyano group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof have.

The heteroalkylene group used as a substituent in the compound of the present invention means that the alkylene group as defined above contains a nitrogen atom, a sulfur atom, an oxygen atom or a person atom. At least one hydrogen atom of the heteroalkylene group may be substituted with a halogen atom, a hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine, a hydrazone, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof. Can be.

The arylene group used as a substituent in the compound of the present invention refers to a divalent compound obtained by separating two hydrogen atoms from an aromatic hydrocarbon having 6 to 20 carbon atoms containing one or more rings. The arylene group may have 1 to 3 substituents such as hydroxy, halo, haloalkyl, nitro, cyano, alkoxy and lower alkylamino.

The hetero arylene group used as a substituent in the compound of the present invention means that the arylene group as defined above contains a nitrogen atom, a sulfur atom, an oxygen atom or a person atom.

The alkyl group used as a substituent in the compound of the present invention refers to a straight or branched alkyl group having 1 to 20 carbon atoms, and a straight or branched alkyl group having 1 to about 12 carbon atoms is preferable. More preferred alkyl groups are lower alkyl groups having 1 to 6 carbon atoms. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, iso-amyl, hexyl, and the like. More preferred is a lower alkyl group having. At least one hydrogen atom of the alkyl group may be substituted with a halogen atom, hydroxy group, nitro group, cyano group, amino group, amidino group, hydrazine, hydrazone, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof. .

The heteroalkyl group which is a substituent used in the compound of the present invention means that the alkyl group as defined above contains a nitrogen atom, a sulfur atom or an oxygen atom. For example hydroxymethyl, acetoxymethyl, 3-hydroxypropyl, 1,2-dihydroxyethyl, 2-methoxyethyl, 2-aminoethyl, 2-dimethylaminoethyl, 2-acetylaminoethyl, 3 -(Pyrrolidin-1-yl) -ethyl, etc. are mentioned.

The cycloalkenylene group, which is a substituent used in the compound of the present invention, is a ring having at least one double bond in the ring, and may form a 5- to 9-membered ring, and may also form a fused ring such as a double ring or a triple ring. Do.

The present invention also provides a liquid composition comprising the antimicrobial colorant. The liquid composition of the present invention comprises an antimicrobial colorant, a liquid medium and / or an additive, and the antimicrobial colorant is characterized in that the antimicrobial metal complex colorant obtained by combining the antimicrobial material and the colorant through coordination of metal.

Hereinafter, only an ink composition which is one embodiment of the liquid composition will be described in detail, but the present invention is not necessarily limited thereto.

In the ink composition according to the embodiment of the present invention, the content ratio of each component is preferably 1 to 20 parts by weight of the antimicrobial colorant based on 100 parts by weight of the ink composition, and based on 100 parts by weight of the ink composition. It is more preferable that the said antimicrobial coloring agent is 1-10 weight part.

An ink composition according to another embodiment of the present invention is an ink composition comprising both a conventional colorant and an antimicrobial colorant according to the present invention as a colorant. That is, the ink composition according to another embodiment of the present invention is a conventional colorant; At least one antimicrobial metal complex colorant selected from the group consisting of antimicrobial colorants according to the invention represented by Formula 1; Aqueous liquid medium and / or additives.

In the ink composition according to another embodiment of the present invention, the content ratio of each component is 1 to 15 parts by weight of the conventional colorant and 1 to 15 parts by weight of the antimicrobial colorant based on 100 parts by weight of the ink composition. It is preferable that the total amount of the conventional colorant and the antimicrobial colorant according to the present invention is 2 to 20 parts by weight based on 100 parts by weight of the ink composition. The total content of the conventional colorant and the antimicrobial colorant according to the present invention is more preferably 2 to 10 parts by weight based on 100 parts by weight of the ink composition.

In the ink compositions according to one and other embodiments of the present invention, the colorant and the antimicrobial colorant according to the present invention are dissolved or dispersed in an aqueous liquid medium.

The aqueous liquid medium is water alone; Or a mixture of 5 to 50 parts by weight of the organic solvent and 50 to 95 parts by weight of water.

The amount of water and organic solvent added to the aqueous liquid medium can vary depending on various factors, such as viscosity, surface tension, drying rate, etc., depending on the properties of the ink composition, and these properties depend on the inkjet printing method in which the ink is used. And may also vary depending on the type of substrate on which the ink is printed.

The organic solvent may be an alcohol compound of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol or isobutyl alcohol; Ketone compounds of acetone, methyl ethyl ketone, diethyl ketone or diacetone alcohol; Ester compounds of methyl acetate, ethyl acetate or ethyl lactate; Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,2,4-butanetriol, 1,5-pentanediol, 1,2,6-hexanetriol Polyhydric alcohol compounds of hexylene glycol, glycerol, glycerol ethoxylate or trimethylolpropane ethoxylate; Ether compounds of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, triethylene glycol monomethyl ether or triethylene glycol monoethyl ether; Nitrogen compounds of 2-pyrrolidone or N-methyl-2-pyrrolidone; And sulfur-containing compounds of dimethyl sulfoxide, tetramethylenesulfone or thioglycol.

The ink composition according to one embodiment and another embodiment according to the present invention may further include at least one selected from the group consisting of a dispersant, a viscosity modifier, a surfactant, a storage stabilizer and a wetting agent.

When the colorant is a pigment or a dye that is not soluble in water, it may include one or more dispersants as necessary for the dispersion stability of the colorant. There is no particular limitation on the dispersant usable in the present invention. That is, a dispersant having a relatively simple structure and a low molecular weight, as well as a dispersant having a large molecular weight such as a block copolymer which may limit the physical properties, stability and functionality of the ink, may be used in the ink composition of the present invention.

Specific examples of dispersants having a relatively low molecular weight and simple structure include polyvinyl alcohol (PVA), cellulose polymers, phenol oxide polymers modified with ethylene oxide, ethylene oxide / propylene oxide polymers, sodium poly Acrylate solution (TEGO, disperse 715W), modified polyacrylic resin solution (TEGO, disperse 735W), alkylol ammonium salt solution of low molecular polycarboxylic acid polymer (BYK-Chemie, Disperbyk), alkylol ammonium solution of multifunctional polymer ( BYK-Chemie, Disperbyk-181), or mixtures thereof, and the like, but is not necessarily limited thereto.

Specific examples of the dispersant having a complicated structure and a high molecular weight include siloxane series such as polyether siloxane copolymer (TEGO, Wet KL 245 / Wet 260); Hydrophilic polymer of AB or BAB structure, wherein A is a hydrophobic homopolymer or copolymer of an unsubstituted or substituted C1-C30 acrylic monomer, and B is an unsubstituted or substituted C1 AB or BAB polymer of the hydrophilic polymer or copolymer of the acrylic monomer of 30 to 30) and the like, but is not necessarily limited thereto. More specific examples of the above-mentioned complex and molecular weight dispersants include acrylic acid / acrylate copolymers, methacrylic acid / methacrylate copolymers, and acrylic acid / polydialkylsiloxanes. / Acrylate block copolymer (acrylic acid / polydialkylsiloxane / acrylate block copolymer) or a mixture thereof may be used, but is not necessarily limited thereto.

In the ink composition according to one embodiment and the other embodiment of the present invention, the content of the dispersant is preferably 1 to 20 parts by weight based on 100 parts by weight of the ink composition.

Viscosity modifiers serve to adjust the viscosity of the ink composition so that smooth jetting can be maintained. As specific examples thereof, casein, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose and the like can be used. The content of the viscosity modifier is preferably 0.1 to 5.0 parts by weight based on 100 parts by weight of the ink composition.

In the ink composition according to one embodiment and the other embodiment of the present invention, the content of the surfactant is preferably 0.5 to 5 parts by weight based on 100 parts by weight of the ink composition.

The surfactant is to stabilize the jetting performance at the nozzle by controlling the surface tension of the ink composition, and it is preferable to use anionic surfactant, cationic surfactant or nonionic surfactant.

Examples of the anionic surfactants include salts of alkyl carboxylic acids having 1 to 1000 carbon atoms (preferably salts of alkyl carboxylic acids having 10 to 200 carbon atoms) and salts of alcohol sulfonic acid esters having 1 to 1000 carbon atoms. Salts of alcohol sulfonic acid esters of 10 to 200 carbon atoms, salts of alkyl sulfonic acids of 1 to 1000 carbon atoms (preferably salts of alkyl sulfonic acids of 10 to 200 carbon atoms), salts of alkylbenzenesulfonic acids of 1 to 1000 carbon atoms (preferably Salts of alkylbenzenesulfonic acids having 10 to 200 carbon atoms), or mixtures thereof.

Examples of the cationic surfactant include fatty acid amine salts, quaternary ammonium salts, sulfonium salts, phosphonium salts, or mixtures thereof.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, where alkyl is an alkyl group having 1 to 1000 carbon atoms, preferably an alkyl group having 10 to 200 carbon atoms, and polyoxyethylene alkyl phenyl ether (where alkyl is 1 carbon atom). To alkyl groups, preferably alkyl groups having 10 to 200 carbon atoms, polyoxyethylene secondary alcohol ethers, polyoxyethylene-oxypropylene block copolymers, polyglycerol fatty acid esters, sorbitan fatty acid esters, or mixtures thereof. have.

In the ink composition according to one embodiment and another embodiment of the present invention, the content of the surfactant is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the ink composition.

The humectant is for preventing the ink composition from clogging at the nozzle, and polyhydric alcohol is preferable. Specific examples of humectants include glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2- Butene-1,4-diol, 2-methyl-2-pentanediol and mixtures thereof.

In the ink composition according to one embodiment and the other embodiment of the present invention, the content of the humectant is preferably 5 to 30 parts by weight based on 100 parts by weight of the ink composition.

On the other hand, in the ink composition of one embodiment and another embodiment of the present invention, the total content of one or more additives selected from the group consisting of the dispersant, viscosity modifier, surfactant, storage stabilizer, and wetting agent is based on 100 parts by weight of the ink composition It is preferable that it is 0.5-40 weight part.

Hereinafter, a method of preparing an ink composition according to one embodiment and another embodiment of the present invention described above will be described.

The antimicrobial colorant and / or the usual colorant are placed in a carrier medium, and other additives such as a dispersant, a viscosity modifier, and a surfactant are mixed as necessary, followed by sufficiently stirring to prepare a uniform ink composition. Thereafter, the composition is passed through a filter of 0.45 to 0.8 mu m and filtered to finally obtain an ink composition according to the present invention.

Hereinafter, the present invention will be described in detail with reference to the following examples, but the present invention is not limited to the following examples. The present invention reveals that the characteristics are evaluated based on the ink, and the method of the evaluation can be applied to liquid toner, dry toner, paint and / or coating liquid, in addition to ink. Hereinafter, only the ink will be described as a representative of the embodiment of the composition to which the antimicrobial metal complex colorant is applied, which means that the practice of the present invention is not limited to the ink.

Synthesis Example 1

(1) Put 80g of ammonia in the water 1500ml, dissolved into a CuCl ₂ 2H ₂ O o of 34g herein. 83 g of a colorant of the following Chemical Formula 5 was added to the solution, heated to 80 ° C., sufficiently mixed, and 140 g of ammonium chloride and 700 ml of hot water were added thereto. NaCl was added thereto to precipitate, filtered, and dried in an oven to obtain 77 g of a copper complex colorant.

(2) 50 g of the copper complex colorant obtained in (1) was dissolved in 200 ml of DMF, and 18 g of the carbendazide derivative represented by the following formula (6) was added thereto, and then the mixed solution was refluxed at 100 ° C. for 6 hours or more. After the solvent of the reaction solution was removed in vacuo, the remaining reactant was washed and dried to obtain 47 g of an antimicrobial copper complex colorant in which one of the ligands was substituted with a carbendazide derivative, which is an antimicrobial substance.

Synthesis Example 2

(1) 25 g of CuSO ₄ dissolved in water after adding 99 g of colorant of the following formula (7) to 1000 ml of water and heating at 90 ° C. 5H ₂ O and 25 g of ammonia solution (30%) were added sequentially, and the mixture was sufficiently mixed at pH 8 for 20 hours. 100 g of ammonium chloride was added to the reaction solution, filtered, washed, and dried in an oven to obtain 79 g of a copper complex colorant.

(2) 53 g of the copper complex colorant obtained in (1) was dissolved in 200 ml of DMF, and 15 g of the carbendazide derivative represented by the following formula (8) was added thereto, and the mixed solution was refluxed at 100 ° C. for 6 hours or more. After the solvent of the reaction solution was removed in vacuo, the remaining reactant was washed and dried to obtain 41 g of an antimicrobial copper complex colorant in which one of the ligands was substituted with a carbendazide derivative, which is an antimicrobial substance.

Synthesis Example 3

(1) Colorant 72g of formula 9 with an aqueous ammonia solution (30%), 25g of ethylene glycol of 800ml, and then this was added to Co (CH ₃ COO) ₂ o 4H ₂ O 25g on was sufficiently mixed at 100 ℃. 800 ml of hot water and 100 g of ammonium chloride were added to the reaction solution, followed by precipitation, filtration and washing, followed by drying in an oven to obtain 58 g of a cobalt complex colorant.

(2) 47 g of the cobalt complex colorant obtained in (1) was dissolved in 200 ml of DMF, and 30 g of carbendazide derivatives of the following Chemical Formula 10 were added thereto, and the mixed solution was refluxed at 100 ° C. for 6 hours or more. After the solvent of the reaction solution was removed in vacuo, the remaining reactant was washed and dried to obtain 53 g of an antimicrobial cobalt complex colorant in which two of the ligands were substituted with a carbendazide derivative which is an antimicrobial substance.

Synthesis Example 4

(1) 89 g of a colorant represented by the following Formula 11, CuSO ₄ ㅇ Using 45 g of 5H ₂ O, experimenting was carried out in the same manner as in Synthesis Example 2 (1) to obtain 70 g of a copper complex colorant in which two copper atoms were bound per molecule of colorant.

(2) 55 g of the copper complex colorant obtained in (1) was dissolved in 200 ml of DMF, and 19 g of the carbendazide derivative represented by the following Formula 12 was added thereto, and the mixed solution was refluxed at 100 ° C. for 6 hours or more. After the solvent of the reaction solution was removed in vacuo, the remaining reactant was washed and dried to obtain 48 g of an antimicrobial copper complex colorant containing two carbendazide derivatives per molecule of colorant.

Synthesis Example 5

(1) Dissolve 83 g of the coloring agent of Chemical Formula 5 in 800 ml of water, and add CrCl ₃ ㅇ Add 53 g of 6H ₂ O. After refluxing this solution at pH 3 for 6 hours or more, the reaction solution was treated with pH 6 to precipitate, and the precipitate was filtered and washed to obtain 73 g of a chromium complex colorant.

(2) 51 g of the chromium complex colorant obtained in (1) was dissolved in 200 ml of DMF, and 24 g of a carbendazide derivative represented by the following formula (13) was added thereto, and the mixed solution was refluxed at 100 ° C. for 6 hours or more. After the solvent of this reaction solution was removed in vacuo, the remaining reactant was washed and dried to obtain 50 g of an antimicrobial chromium complex colorant.

Example 1

Ink composition

4 g of the antimicrobial metal complex colorant of Synthesis Example 1 (2)

77 g of water

3 g of isopropyl alcohol

10 g of ethylene glycol

Glycerin 6g

The components were mixed and stirred for at least 30 minutes in a stirrer to make a uniform state. Thereafter, the resultant was passed through a 0.45 μm filter to prepare an antimicrobial ink composition of the present invention.

Example 2

An ink composition was prepared in the same manner as in Example 1, using the antimicrobial metal complex colorant of Synthesis Example 2 (2) instead of the antimicrobial metal complex colorant of Synthesis Example 1 (2) in Example 1.

Example 3

In Example 1, an ink composition was prepared in the same manner as in Example 1, except that the antimicrobial metal complex colorant of Synthesis Example 3 (2) was used instead of the antimicrobial metal complex colorant of Synthesis Example 1 (2).

Example 4

In Example 1, an ink composition was prepared in the same manner as in Example 1, except that the antimicrobial metal complex colorant of Synthesis Example 4 (2) was used instead of the antimicrobial metal complex colorant of Synthesis Example 1 (2).

Example 5

In Example 1, an ink composition was prepared in the same manner as in Example 1, except that the antimicrobial metal complex colorant of Synthesis Example 5 (2) was used instead of the antimicrobial metal complex colorant of Synthesis Example 1 (2).

Comparative Example 1

In Example 1, except that the metal complex colorant of Synthesis Example 1 (1) was used instead of the antimicrobial metal complex colorant of Synthesis Example 1 (2) and 0.5 wt.% Of the antimicrobial agent (BIT) was separately added. An ink composition was prepared in the same manner as in 1. In this case, however, the amount of water was reduced by the amount of the antimicrobial agent used.

Comparative Example 2

In Comparative Example 1, an ink composition was prepared in the same manner as in Comparative Example 1, except that the metal complex colorant of Synthesis Example 2 (1) was used instead of the metal complex colorant of Synthesis Example 1 (1).

Comparative Example 3

In Comparative Example 1, an ink composition was prepared in the same manner as in Comparative Example 1, except that the metal complex colorant of Synthesis Example 3 (1) was used instead of the antimicrobial metal complex colorant of Synthesis Example 1 (1).

Comparative Example 4

In Comparative Example 1, an ink composition was prepared in the same manner as in Comparative Example 1, except that the metal complex colorant of Synthesis Example 4 (1) was used instead of the antimicrobial metal complex colorant of Synthesis Example 1 (1).

Comparative Example 5

In Comparative Example 1, an ink composition was prepared in the same manner as in Comparative Example 1, except that the metal complex colorant of Synthesis Example 5 (1) was used instead of the antimicrobial metal complex colorant of Synthesis Example 1 (1).

Comparative Example 6

In Example 1, an ink composition was prepared in the same manner as in Example 1, except that the coloring agent of Formula 5 was used instead of the antimicrobial metal complex coloring agent of Synthesis Example 1 (2).

Comparative Example 7

In Example 1, an ink composition was prepared in the same manner as in Example 1, except that the coloring agent of Formula 7 was used instead of the antimicrobial metal complex coloring agent of Synthesis Example 1 (2).

The properties of the ink compositions prepared according to the above Examples and Comparative Examples were evaluated according to the following methods.

Experimental Example 1: Long-term storage stability test

100 ml of each of the ink compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 7 were put in a heat resistant glass bottle, and sealed, and then stored in a 60 ° C. thermostatic bath. After leaving it for 2 months, the presence or absence of sedimentation on the bottom was evaluated and evaluated as follows.

○: no precipitate. X: There is a precipitate.

division Example Comparative example One 2 3 4 5 One 2 3 4 5 6 7 Storage stability ○ ○ ○ ○ ○ X X X X X X X

Referring to Table 1, in Examples 1 to 5, which are ink compositions obtained by using the antimicrobial metal complex colorant of the present invention, Comparative Examples 1 to 5 using conventional antimicrobial substances and Comparative Examples without using antimicrobial substances Compared with the case of 6 to 7, no precipitation formation was observed, indicating that the storage stability is excellent.

Experimental Example 2: Ames test

TA98 was added to the ink compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 7 and incubated in a dark room at 37 ° C. for 48 hours, and the number of denatured colonies was measured.

division Example Comparative example One 2 3 4 5 One 2 3 4 5 6 7 Colony count 83 94 85 90 79 93 80 91 92 83 389 408

Referring to Table 2, in Examples 1 to 5, which are ink compositions obtained by using the antimicrobial metal complex colorant of the present invention, Comparative Example 1 using a conventional antimicrobial agent as compared with Comparative Examples 6 and 7 without using an antimicrobial agent. It can be seen that the antimicrobial properties appear as in the case of the 5 to.

As described above, the antimicrobial metal complex colorant of the present invention is obtained by combining an antimicrobial substance and a colorant through coordination bond with a metal, and the liquid composition prepared by using the antimicrobial agent improves not only antimicrobial but also fastness of storage stability, light resistance, water resistance, and the like. It can be useful because it can be.

Claims (17)

delete An antimicrobial colorant of the general formula (1) characterized by obtained by coordinating an antimicrobial substance and a colorant with a metal: <Formula 1> The coloring agent forms a coordination bond with the metal (Me), and includes one or more azo groups of the formula (2), The metal (Me) represents a polyvalent transition metal, L represents a ligand forming a coordination bond with a metal (Me), A represents a carbendazide derivative represented by the following Chemical Formula 3 as an antimicrobial ligand that is coordinated to a metal directly or through a linker Y, n represents a number from 1 to 3, m represents a number from 0 to 2, m + n = a number from 1 to 3, <Formula 2> In the compound of Formula 2, X ₁ and X ₂ each independently represent a hydroxy, amino group, carboxyl group or alkoxy group having 1 to 2 carbon atoms, ring A and B is an unsubstituted or substituted C5-C30 cycloalkenylene group Indicates, <Formula 3> In the compound of Formula 3, R ₁ represents a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, or a phosphoric acid or a salt thereof, and R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₇ is independently a hydrogen atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a substitution or a non- A substituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl or alkynyl group having 2 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms , Substituted or unsubstituted arylalkyl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms, or substituted or unsubstituted heteroarylalkyl group having 6 to 30 carbon atoms; Produce. The antimicrobial colorant of claim 2 wherein the linker Y has a structure of Formula 4: <Formula 4> In Chemical Formula 4, Z is a functional group capable of coordinating with a metal (Me), particularly a hydroxy, amino group, carboxyl group or alkoxy group having 1 to 2 carbon atoms, and R ₈ is substituted or unsubstituted with 1 to 30 carbon atoms. Alkylene group, substituted or unsubstituted alkenylene group having 2 to 30 carbon atoms, substituted or unsubstituted alkynylene group having 2 to 30 carbon atoms, substituted or unsubstituted arylene group having 6 to 30 carbon atoms, substituted with 6 to 20 carbon atoms Or an unsubstituted arylalkylene group, a substituted or unsubstituted heteroalkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 4 to 20 carbon atoms, a substituted or unsubstituted heteroarylalkylene having 4 to 20 carbon atoms Is selected from the group consisting of J is a junction group bonded with the antimicrobial substance A as a single bond, -C (= 0) -NR _9- , -NR ₉ -C (= 0)-, -NH-C (= 0) -R ₁₀ -C (= O) -O-, -OC (= O) -R ₁₀ -C (= O) -NH-, -OC (= O) -R ₁₀ -C (= O) O-, -C (= O) -O-, -OC (= O)-, -O-, -S-, -P-, -NH-, -C = C-, -C≡C-, R ₉ is hydrogen or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms, R ₁₀ is a substituted or unsubstituted alkylene group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 30 carbon atoms, 2 carbon atoms Substituted or unsubstituted alkynylene group having from 30 to 30 carbon atoms, substituted or unsubstituted arylene group having 6 to 20 carbon atoms, substituted or unsubstituted arylalkylene group having 6 to 20 carbon atoms, substituted or unsubstituted hetero atom having 1 to 30 carbon atoms An alkylene group, a substituted or unsubstituted heteroarylene group having 4 to 20 carbon atoms, a substituted or unsubstituted heteroarylalkylene group having 4 to 20 carbon atoms, and Emitter is selected. delete The antimicrobial coloring agent according to claim 2, wherein the metal (Me) is Ni, Cu, Zn, Fe, Cr, Pd, Pt, or Co. The method of claim 2, wherein the ligand L is at least one ligand selected from the group consisting of a neutral ligand of water, ammonia, pyridine, bipyridine, terpyridine or morpholine and an anionic ligand of acetate, iminodiacetate or glycine. Antimicrobial colorant, characterized in that. delete At least one antimicrobial colorant selected from the group consisting of the antimicrobial colorants according to any one of claims 2, 3, 5 and 6; And An antimicrobial liquid composition comprising a liquid medium, The liquid medium is to use water alone or a mixture of one or more organic solvents, The antimicrobial liquid composition, characterized in that 1 to 20 parts by weight based on 100 parts by weight of the liquid composition. delete The antimicrobial liquid composition according to claim 8, wherein the total amount of the organic solvent in the liquid medium is 5 to 50 parts by weight based on 100 parts by weight of the liquid composition. delete coloring agent; At least one antimicrobial colorant selected from the group consisting of the antimicrobial colorants according to any one of claims 2, 3, 5 and 6; And An antimicrobial liquid composition comprising a liquid medium, The liquid medium is to use water alone or a mixture of one or more organic solvents, The colorant is 1 to 15 parts by weight based on 100 parts by weight of the liquid composition, the content of the antimicrobial colorant is 1 to 15 parts by weight, and the total content of the colorant and the antimicrobial colorant is 100 parts by weight of the liquid composition. Antibacterial liquid composition, characterized in that 2 to 20 parts by weight on the basis. delete The antimicrobial liquid composition according to claim 12, wherein the total content of the organic solvent in the liquid medium is 5 to 50 parts by weight based on 100 parts by weight of the liquid composition. The organic solvent according to any one of claims 8, 10, 12 and 14, wherein the organic solvent is methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol. alcohol compounds of t-butyl alcohol or isobutyl alcohol; Aliphatic ketone compounds of acetone, methyl ethyl ketone, diethyl ketone or diacetone alcohol; Ester compounds of methyl acetate, ethyl acetate or ethyl lactate; Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,2,4-butanetriol, 1,5-pentanediol, 1,2,6-hexanetriol Polyhydric alcohol compounds of hexylene glycol, glycerol, glycerol ethoxylate or trimethylolpropane ethoxylate; Ether compounds of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, triethylene glycol monomethyl ether or triethylene glycol monoethyl ether; Nitrogen compounds of 2-pyrrolidone or N-methyl-2-pyrrolidone; And sulfur-containing compounds of dimethyl sulfoxide, tetramethylenesulfone or thioglycol. The liquid composition of claim 8, wherein the liquid composition further comprises 0.5 to 40 parts by weight based on 100 parts by weight of the liquid composition, at least one additive selected from the group consisting of a dispersant, a viscosity modifier, a surfactant, a storage stabilizer, and a humectant. An antimicrobial liquid composition. The liquid composition of claim 12, wherein the liquid composition further comprises 0.5 to 40 parts by weight based on 100 parts by weight of the liquid composition, at least one additive selected from the group consisting of a dispersant, a viscosity modifier, a surfactant, a storage stabilizer, and a humectant. An antimicrobial liquid composition.