KR100513858B1 - Antibiotic additive and ink composition comprising the same - Google Patents

Abstract

An antimicrobial additive and an ink composition comprising the same are disclosed. The present antimicrobial additive is a compound in which an antimicrobial substance having the following chemical formula and a predetermined additive are chemically bound to each other, and the ink composition is an antimicrobial additive which is a compound in which the antimicrobial substance having the following chemical formula and a predetermined additive are combined by chemical reaction. It includes. According to the present invention, it is possible to provide an antimicrobial additive having excellent compatibility with general dyes and pigments and an ink composition including the same, while preventing surface drying, promoting storage stability, and preventing generation and growth of bacteria in the ink.

Description

Antimicrobial additives and ink composition comprising same {Antibiotic additive and ink composition comprising the same}

The present invention relates to an antimicrobial additive and an ink composition comprising the same. More specifically, the present invention relates to an antimicrobial additive to which antimicrobial is imparted by combining a compound having an antimicrobial function with a wetting agent or a storage stabilizer in the ink composition and an ink composition including the same.

The field of use of the antimicrobial additive and the ink composition including the same according to the present invention is, for example, paints, paints, inks, etc. Among them, ink compositions for printers, in particular ink compositions for inkjet printers are representative. The case of using as an ink composition for inkjet printers is looked at in detail.

There are two types of printing by printers, a non-impact printing method and a contact printing method. Among these, inkjet printing is one of the non-contact printing methods, which has the advantages of lower noise and easier color implementation than laser beam printers as compared to the contact printing method.

There are two types of inkjet printing methods, continuous stream inkjet (continuous stream) and drop-on-demand (DOD) method. In the continuous jet inkjet method, ink is continuously jetted by pressure at an orifice or nozzle. The ejected ink is disturbed by forming drops at a predetermined distance from the orifice. These droplets are dispersed and charged to the digital data signal and passed through the electromagnetic field so that the orbits of each droplet are adjusted and recycled or directed to a gutter on a certain location on the recording medium. In the drop-on-demand scheme, droplets are ejected directly from the orifice to a location on the recording medium in accordance with the digital data signal. Droplets that do not eject onto the recording medium are not formed or released.

The drop-on-demand method is much simpler than the continuous jet method since it does not require ink recovery, charge, or deflection. There are two types of drop-on-demand inkjet methods, thermal inkjet (also called bubble ink) and piezoelectric inkjet.

In the thermal inkjet method, the ink is sprayed by using the pressure generated in the expansion of the bubble generated by heating the ink. The thermal inkjet method produces droplets of high speed and allows for very close spacing of the nozzles. The introduction of the thermal inkjet method enables the drop-on-demand method to provide a printer that is simpler and cheaper than the continuous jet method and maintains high printing speed.

On the other hand, the piezoelectric inkjet method generates pressure by using a piezoelectric plate that dynamically deforms the droplets by electricity and injects ink. This piezoelectric inkjet method results in the relatively large size of the piezoelectric plate obstructing the adjacent spacing of the nozzles, and the physical limitation of the piezoelectric plate results in a drop in the speed of ink droplets. Low drop rates severely reduce the resistance to drop rate changes, which also affects providing good print quality. It is also pointed out that the drop-on-demand method using the piezoelectric inkjet method has a slow printing speed.

On the other hand, in recent years, the dot size of an inkjet printer tends to be small, and high quality printing at high resolution is required. In order to obtain a smaller dot size, the head of an inkjet printer has fewer nozzle openings, which are likely to be clogged, and inkjet droplets are performance dependent on deposits and the like affecting size. 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.

 In addition, the ink composition for an inkjet printer basically consists of colorants, solvents and additives. However, in order to apply it to an inkjet printer and apply it to color printing, the ink composition should have the property of jetting as expected in the printer, and after being jetted, the ink composition should be well adsorbed or absorbed by the target medium to display the image as expected. Therefore, the ink composition may have viscosity, surface tension, optical density, dot uniformity, jetting stability, drying time, bleeding, and storage stability. satisfactory performance in terms of storage stability, hue, lightness, saturation, affinity with the print head and recording media, smear fastness, and water fastness of the image. In order to mix the various additives. Among these, as one of the additives for implementing the storage stability of the ink composition, 2-pyrrolidone, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3 Methods have been proposed using various heterocyclic compounds, including nitrogen, such as -dimethyl-2-imidazole (1,3-dimethyl-2-imidazolidinone) (US Pat. Nos. 5,108,503, 5,858,075, 5,980,622, 5,990,202, 6057,384, 5,641,346, 5,972,086, 6,039,796, 6,095,645). Heterocyclic compounds including nitrogen as additives according to the patents disclosed herein, such as 2-pyrrolidone, N-methyl pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone When using, there is an effect that the storage stability, wettability and drying properties are improved.

In the case of using a dye as a colorant in the ink composition for an inkjet printer, its use is limited because the ink has poor water resistance and light resistance. On the other hand, in the case of using a pigment as a colorant, the water resistance and light resistance of the ink are superior to those in the case of using a dye. Ink compositions containing such dyes or pigments as colorants have deteriorated ink properties and problems with long-term storage stability due to the production of bacteria and the like. Therefore, a method of adding a separate antimicrobial agent has been proposed to inhibit the production and growth of bacteria and the like. However, when such an antimicrobial agent is added to the ink composition, since the antimicrobial agent is combined with other additives in the ink composition to form macromolecules, nozzle clogging due to ink entanglement is remarkably increased and it is difficult to secure homogeneity. In addition, in the case of using an antimicrobial agent that can suppress such side effects, the antimicrobial properties are weak, the storage stability may be reduced for a long time, it is difficult to implement the optimal color due to the difficult selection of dyes or pigments excellent compatibility with the antimicrobial agent.

The present invention has been made to solve the above problems, and an object of the present invention is to provide an antimicrobial additive that combines an antimicrobial compound through a chemical reaction with a substance added as a wetting agent or a storage stabilizer in the ink composition, The present invention provides an antimicrobial additive and an ink composition containing the same, which are excellent in compatibility with general dyes and pigments while preventing drying, promoting storage stability, and preventing the formation and growth of bacteria in the ink.

The antimicrobial additive according to the present invention for achieving the above object is characterized in that the antimicrobial substance having a chemical formula of the following [Formula 1] and a predetermined additive is a compound combined by chemical reaction.

In the above formula,

R ₁ is any one selected from the group consisting of a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group and a salt thereof, a sulfonic acid group and a salt thereof, phosphoric acid and 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 hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group and Salts, sulfonic acid groups and salts thereof, phosphoric acid and salts thereof, substituted or unsubstituted C1 to C30 alkyl groups, substituted or unsubstituted C1 to C30 alkenyl, substituted or unsubstituted C1 to C30 alkynyl groups, Substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylalkyl group, substituted or unsubstituted C6 to C30 hetero An aryl group, and a substituted or unsubstituted C6 to C30 heteroarylalkyl group.

Substituted or unsubstituted C1 to C30 alkyl groups may include C1 to C30 straight or branched alkyl radicals.

Examples of alkyl radicals include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, iso-amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl Including but not limited to.

Wherein substituted C1 to C30 alkyl group, substituted C1 to C30 alkenyl group, substituted C1 to C30 alkynyl group, substituted C1 to C30 heteroalkyl group, substituted C1 to C30 aryl group, substituted C1 to The C30 arylalkyl group, substituted C1 to C30 heteroaryl group, and substituted C1 to C30 heteroarylalkyl group each independently have at least one hydrogen atom selected from halogen atom, hydroxy group, nitro group, cyano group, amino group, and amidino group. , Hydrazine group, hydrazone group, carboxyl group and salt thereof, sulfonic acid group and salt thereof, phosphoric acid and salt thereof, alkyl group of C1 to C20, alkenyl group of C1 to C20, alkynyl group of C1 to C20, heteroalkyl group of C1 to C20, C6 It is preferably substituted with any one selected from the group consisting of an aryl group of C20 to C20, an arylalkyl group of C6 to C20, a heteroaryl group of C6 to C20, and a heteroarylalkyl group of C6 to C20.

The additive chemically reacting with the antimicrobial substance of [Formula 1] is a wetting agent or a storage stabilizer.

Here, the humectant preferably includes at least one selected from the group consisting of alcohols, diols, triols, polyols, polyethylene glycols, and polypropylene glycols.

Storage stabilizers are substituted or unsubstituted 2-pyrrolidone, N-methyl pyrrolidone, pyridine, imidazole, piperidine, 2-pyrrolidinone, primary amine, secondary amine, tertiary amine, amide It is preferable to include at least one selected from the nitrogen-containing compound consisting of, lactone, and lactam. In this case, the substituted nitrogen-containing compound has at least one hydrogen atom selected from halogen atom, hydroxy group, nitro group, cyano group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group and salt thereof, sulfonic acid group and salt thereof, phosphoric acid and salt thereof, C1 to C20 alkyl group, C1 to C20 alkenyl group, C1 to C20 alkynyl group, C1 to C20 heteroalkyl group, C6 to C20 aryl group, C6 to C20 arylalkyl group, C6 to C20 heteroaryl group, and It is substituted with any one selected from the group consisting of C6 to C20 heteroarylalkyl group.

In addition, the antimicrobial additives of the present invention may include at least one or more of the antimicrobial additives chemically bonded to the humectant and the antimicrobial additives chemically bonded to the storage stabilizer, and may include both types of antimicrobial additives.

In addition, an ink composition comprising an antimicrobial additive according to the present invention for the second object of the present invention includes a colorant, a solvent and an antimicrobial additive, and the antimicrobial additive included in the ink composition is an antimicrobial substance having the chemical formula [1]. And a predetermined additive is a compound which is bonded by chemical reaction.

In [Formula 1],

R ₁ is any one selected from the group consisting of a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group and a salt thereof, a sulfonic acid group and a salt thereof, phosphoric acid and 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 hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group and Salts, sulfonic acid groups and salts thereof, phosphoric acid and salts thereof, substituted or unsubstituted C1 to C30 alkyl groups, substituted or unsubstituted C1 to C30 alkenyl, substituted or unsubstituted C1 to C30 alkynyl groups, Substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylalkyl group, substituted or unsubstituted C6 to C30 hetero An aryl group, and a substituted or unsubstituted C6 to C30 heteroarylalkyl group.

Wherein the substituted or unsubstituted C1 to C30 alkyl group may comprise C1 to C30 straight or branched alkyl radicals, which alkyl methyl, ethyl, n-propyl, isopropyl, n-butyl, Groups including, but not limited to, isobutyl, sec-butyl, t-butyl, pentyl, iso-amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and the like.

Wherein substituted C1 to C30 alkyl group, substituted C1 to C30 alkenyl group, substituted C1 to C30 alkynyl group, substituted C1 to C30 heteroalkyl group, substituted C1 to C30 aryl group, substituted C1 to The C30 arylalkyl group, substituted C1 to C30 heteroaryl group, and substituted C1 to C30 heteroarylalkyl group each independently have at least one hydrogen atom selected from halogen atom, hydroxy group, nitro group, cyano group, amino group, and amidino group. , Hydrazine group, hydrazone group, carboxyl group and salt thereof, sulfonic acid group and salt thereof, phosphoric acid and salt thereof, alkyl group of C1 to C20, alkenyl group of C1 to C20, alkynyl group of C1 to C20, heteroalkyl group of C1 to C20, C6 It is preferably substituted with any one selected from the group consisting of an aryl group of C20 to C20, an arylalkyl group of C6 to C20, a heteroaryl group of C6 to C20, and a heteroarylalkyl group of C6 to C20.

In the antimicrobial additive included in the ink composition of the present invention, the additive chemically reacting with the antimicrobial substance of [Formula 1] is a wetting agent or a storage stabilizer.

Here, the humectant preferably includes at least one selected from the group consisting of alcohols, diols, triols, polyols, polyethylene glycols, and polypropylene glycols.

Storage stabilizers are substituted or unsubstituted 2-pyrrolidone, N-methyl pyrrolidone, pyridine, imidazole, piperidine, 2-pyrrolidinone, primary amine, secondary amine, tertiary amine, amide It is preferable to include at least one selected from the nitrogen-containing compound consisting of, lactone, and lactam. In this case, the substituted nitrogen-containing compound has at least one hydrogen atom selected from halogen atom, hydroxy group, nitro group, cyano group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group and salt thereof, sulfonic acid group and salt thereof, phosphoric acid and salt thereof, C1 to C20 alkyl group, C1 to C20 alkenyl group, C1 to C20 alkynyl group, C1 to C20 heteroalkyl group, C6 to C20 aryl group, C6 to C20 arylalkyl group, C6 to C20 heteroaryl group, and It is substituted with any one selected from the group consisting of C6 to C20 heteroarylalkyl group.

In addition, the antimicrobial additives of the ink composition including the antimicrobial additive of the present invention may include at least one or more of the antimicrobial additives chemically bonded to the humectant and the antimicrobial additives chemically bonded to the storage stabilizer, and include both types of antimicrobial additives. can do.

In the ink composition including the antimicrobial additive of the present invention, the antimicrobial additive is preferably in the range of 0.1 part by weight to 30 parts by weight with respect to 100 parts by weight of the ink composition.

The solvent may be used alone or in a mixture of water and an organic solvent.

When using a mixture of water and an organic solvent, the content of the organic solvent is preferably within the range of 5 parts by weight to 50 parts by weight with respect to 100 parts by weight of the ink composition.

In addition, the organic solvent may be an alcohol solvent composed of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, isobutyl alcohol; Ketone solvents composed of acetone, methyl ethyl ketone and diacetone alcohol; Ester solvents composed of ethyl acetate and 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 solvents composed of hexylene glycol, glycerol, glycerol ethoxylate, trimethylpropane ethoxylate; Alkyl ether solvents composed of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl; Nitrogen-containing solvent consisting of 2-pyrrolidone, N-methyl pyrrolidone, N-methyl-2-pyrrolidone; And a sulfur-containing solvent composed of dimethyl sulfoxide, tetramethylene sulfone, and thioglycol.

When the colorant in the ink composition according to the invention is a pigment, the ink composition preferably further comprises a dispersant.

In this case, the dispersing agent is polyvinyl alcohol, cellulose polymer, phenolic polymer modified with ethylene oxide, ethylene oxide polymer, propylene oxide polymer, sodium polyacrylate solution, modified polyacrylic resin solution, alkylol of low molecular weight polycarboxylic acid polymer. Ammonium salt solution, alkylol ammonium solution of the multifunctional polymer; Polyether siloxane copolymers; And A is a substituted or unsubstituted hydrophobic homopolymer of C1 to C30 acrylic monomer or a copolymer of acrylic monomer, and B is substituted or unsubstituted hydrophilic polymer or copolymer of acrylic monomer to C1 to C30 acrylic monomer. It is preferable to include a material selected from the group consisting of; AB polymer having an AB structure and a BAB polymer having a BAB structure, which is a hydrophilic polymer consisting of, in particular, the AB polymer is acrylic acid / acrylate copolymer, methacrylic acid / methacryl It is any one selected from the rate copolymers, and it is preferable that the BAB polymer is an acrylic acid / polydialkylsiloxane / acrylate block copolymer.

The ink composition according to the present invention may further include a viscosity modifier. When the ink composition further comprises a viscosity modifier, the content of the viscosity modifier is preferably within the range of 0.1 parts by weight to 10.0 parts by weight with respect to 100 parts by weight of the ink composition. In addition, the viscosity modifier more preferably comprises a material selected from the group consisting of casein, carboxymethyl cellulose, polyethylene glycol, polypropylene glycol, polyvinylpyrrolidone, polyethyleneimine, polyvinyl alcohol.

In addition, the ink composition according to the present invention may further include a surfactant.

If the ink composition further comprises a surfactant, the surfactant is a salt of an alkylcarboxylic acid of C1 to C1000, a salt of alkylsulfonic acid of C1 to C1000, a salt of an alkylsulfonic acid ester of C1 to C1000, an alkylbenzenesulfonic acid of C1 to C1000 Anionic surfactants composed of salts; And polyoxyethylene alkyl ethers having alkyl groups of C1 to C1000, polyoxyethylene alkylphenyl ethers having alkyl groups of C1 to C1000, polyoxyethylene secondary alcohol ethers, polyoxyethylene-oxypropylene block copolymers, polyglycerine fatty acid esters, sorbitan Nonionic surfactants consisting of fatty acid esters; preferably includes, but is not limited to, a material selected from the group consisting of.

In addition, the content of the surfactant is preferably within the range of 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the ink composition.

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

The present invention relates to an antimicrobial additive in which an antimicrobial substance having a specific functional group and a predetermined additive are combined by chemical reaction, and an ink containing the antimicrobial additive.

The antimicrobial additive according to the present invention combines the antimicrobial material with other additives in a chemical reaction, and retains the original function of the additive which combines with the antimicrobial material, while also having an antimicrobial function. The antimicrobial material used in the preparation of the antimicrobial additives according to the present invention is a compound having a chemical formula of the following [Formula 2]. This compound is also called the benzoimidazole.

here,

R ₁ is any one selected from the group consisting of a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group and a salt thereof, a sulfonic acid group and a salt thereof, phosphoric acid and 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 hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group and Salts, sulfonic acid groups and salts thereof, phosphoric acid and salts thereof, substituted or unsubstituted C1 to C30 alkyl groups, substituted or unsubstituted C1 to C30 alkenyl, substituted or unsubstituted C1 to C30 alkynyl groups, Substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylalkyl group, substituted or unsubstituted C6 to C30 hetero An aryl group, and a substituted or unsubstituted C6 to C30 heteroarylalkyl group.

It is more preferable to use the compound shown by following [Formula 3] as an antimicrobial substance among the compound shown by [Formula 2].

here,

R ₁ is any one selected from the group consisting of a hydrogen atom, a hydroxyl group, an amino group and a carboxyl group; And R ₂ and R ₁₀ each independently represent 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 and a salt thereof, a sulfonic acid group and a salt thereof, phosphoric acid and a salt thereof , Substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C1 to C30 alkenyl, substituted or unsubstituted C1 to C30 alkynyl group, substituted or unsubstituted C1 to C30 hetero Alkyl groups, substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C6 to C30 arylalkyl groups, substituted or unsubstituted C6 to C30 heteroaryl groups, and substituted or unsubstituted C6 To C30 heteroarylalkyl group.

Looking at the R group of the compounds of [Formula 2] and [Formula 3] in detail as follows.

Alkyl groups include straight or branched radicals of C1 to C30, preferably straight or branched radicals of C1 to C20. More preferred are alkyl groups comprising radicals of C1 to C12. These radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, iso-amyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, etc. Including but not limited to.

In addition, at least one hydrogen atom of the alkyl group may be 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 and a salt thereof, a sulfonic acid group and a salt thereof, a phosphoric acid and a salt thereof, and C 1 to C 20 Alkyl group, C1 to C20 alkenyl group, C1 to C20 alkynyl group, C1 to C20 heteroalkyl group, C6 to C20 aryl group, C6 to C20 arylalkyl group, C6 to C20 heteroaryl group, and C6 to C20 It may be substituted with any one selected from the group consisting of heteroarylalkyl group.

Alkenyl group or alkynyl group means that the alkyl group contains a carbon double bond or a carbon triple bond at the middle or the end of the alkyl group. For example, ethylene, propylene, butylene, hexylene, acetylene and the like. At least one hydrogen atom of the alkenyl group or alkynyl group may be 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 and a salt thereof, a sulfonic acid group and a salt thereof, phosphoric acid and a salt thereof, C1 to C20 alkyl group, C1 to C20 alkenyl group, C1 to C20 alkynyl group, C1 to C20 heteroalkyl group, C6 to C20 aryl group, C6 to C20 arylalkyl group, C6 to C20 heteroaryl group, and It may be substituted with any one selected from the group consisting of C6 to C20 heteroarylalkyl group.

Heteroalkyl group means that the above alkyl group contains any one selected from a nitrogen atom, a sulfur atom, an oxygen atom, and a phosphorus atom. For example, methoxy, ethoxy, propoxy, butoxy and t-butoxy are mentioned. Examples of heteroalkyl groups having substituents include haloalkoxy radicals such as fluoromethoxy, chloromethoxy, trifluoromethoxy, trifluoroethoxy, fluoroethoxy and fluoropropoxy. At least one hydrogen atom of the heteroalkyl group is a halogen atom, hydroxy group, nitro group, cyano group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group and salts thereof, sulfonic acid group and salts thereof, phosphoric acid and salts thereof, C1 to C20 Alkyl group, C1 to C20 alkenyl group, C1 to C20 alkynyl group, C1 to C20 heteroalkyl group, C6 to C20 aryl group, C6 to C20 arylalkyl group, C6 to C20 heteroaryl group, and C6 to C20 It may be substituted with any one selected from the group consisting of a heteroarylalkyl group.

An aryl group refers to a C6 to C30 carbocycle aromatic system comprising one or more rings, which rings may be attached or fused together in a pendant manner. The term aryl includes similar aromatic radicals such as phenyl, naphthyl, indane and biphenyl. The aryl group is preferably phenyl or naphthyl. In addition, at least one hydrogen atom of the aryl group may be 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 and salts thereof, sulfonic acid groups and salts thereof, phosphoric acid and salts thereof, and C1 to C20 alkyl group, C1 to C20 alkenyl group, C1 to C20 alkynyl group, C1 to C20 heteroalkyl group, C6 to C20 aryl group, C6 to C20 arylalkyl group, C6 to C20 heteroaryl group, and C6 to C20 It may be substituted with any one selected from the group consisting of C20 heteroarylalkyl group.

An arylalkyl group means that some of the hydrogen atoms of the aryl group in such an aryl group are substituted with lower alkyl, that is, radicals such as methyl, ethyl or propyl. For example, benzyl, phenylethyl, phenylpropyl, phenylisopropyl and the like may be used. At least one hydrogen atom of the arylalkyl group may be a halogen atom, a hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, Hydrazone group, carboxyl group and salt thereof, sulfonic acid group and salt thereof, phosphoric acid and salt thereof, C1 to C20 alkyl group, C1 to C20 alkenyl group, C1 to C20 alkynyl group, C1 to C20 heteroalkyl group, C6 to C20 aryl Group, a C6 to C20 arylalkyl group, a C6 to C20 heteroaryl group, and a C6 to C20 heteroarylalkyl group.

Heteroaryl groups include at least one hetero atom selected from the group consisting of N, O, P, and S and the remaining ring atoms refer to monovalent monocyclic or bicyclic aromatic radicals having 3 to 30 carbon atoms as carbon atoms. The term heteroaryl also refers to monovalent monocyclic or bicyclic aromatic radicals in which heteroatoms in the ring are oxidized or quaternized, ie, form N-oxides or quaternary salts. For example, thienyl, benzothienyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, quinoxalinyl, imidazolyl, furanyl, benzofuranyl, thiazolyl, isoxazolyl , Benzisoxazolyl, benzimidazolyl, triazolyl, pyrazolyl, pyrrolyl, indolyl, 2-pyridonyl, 4-pyridonyl, N-alkyl-2-pyridonyl, pyrazinyl, pyrida Genonyl, pyrimidinyl, oxazoloyl, N-oxides corresponding to the materials exemplified above (eg pyridyl N-oxide, quinolinyl N-oxide), and each of the four exemplified materials Tea salts, and the like, but is not necessarily limited thereto.

At least one hydrogen atom in the heteroaryl group is a halogen atom, hydroxy group, nitro group, cyano group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group and salts thereof, sulfonic acid group and salts thereof, phosphoric acid and salts thereof, C1 to C20 alkyl group, C1 to C20 alkenyl group, C1 to C20 alkynyl group, C1 to C20 heteroalkyl group, C6 to C20 aryl group, C6 to C20 arylalkyl group, C6 to C20 heteroaryl group, C6 to C20 It may be substituted with any one selected from the group consisting of a heteroarylalkyl group.

Heteroarylalkyl group means that a hydrogen atom of some of the above heteroaryl group is substituted with an alkyl group. At least one hydrogen atom of the heteroarylalkyl group may be 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 and a salt thereof, a sulfonic acid group and a salt thereof, a phosphoric acid and a salt thereof, C 1 to C20 alkyl group, C1 to C20 alkenyl group, C1 to C20 alkynyl group, C1 to C20 heteroalkyl group, C6 to C20 aryl group, C6 to C20 arylalkyl group, C6 to C20 heteroaryl group, C6 to C20 It may be substituted with any one selected from the group consisting of a heteroarylalkyl group.

Alkylene group, alkenylene group, alkynylene group, heteroalkylene group, arylene group, arylalkylene group, heteroarylene group, and heteroarylalkylene group, which are substituents of the R group used in the present invention, are defined as the alkyl group, alkenyl group, respectively. , Alkynyl group, heteroalkyl group, aryl group, arylalkyl group, heteroaryl group, and heteroarylalkyl group. However, in the case of the substituent of the R group, it is different from the radical in the form of being inserted into the intermediate portion of the bond of the compound rather than being connected to the final terminal.

The antimicrobial additive according to the present invention is preferably included within the range of 0.1 parts by weight to 30 parts by weight with respect to 100 parts by weight of the ink composition for inkjet printers. If the weight part of the antimicrobial additive is greater than 30 parts by weight, there is a problem in that the viscosity cannot be adjusted. If the weight part of the antimicrobial additive is less than 0.1 part by weight, there is a problem in that the antimicrobial effect does not appear.

The antimicrobial additive according to the present invention is a compound in which the antimicrobial substance of the above [Formula 2] or [Formula 3] and a predetermined additive are bonded by a chemical reaction, that is, a benzimidazole derivative.

Preferred examples of the antimicrobial additives of the present invention are those in which the predetermined additive which binds the antimicrobial substance is a substance added as a humectant to the ink composition. As one of the chemical reactions, there is a reaction formula shown in the following [Scheme 1], for example.

In the reaction product of [Scheme 1], A-OH is a humectant, and the compound on the left side of the compound of Formula 3 is substituted with R ₁ to a carboxyl group, and R ₂ and R ₁₀ are each independently a hydrogen atom, a halogen atom, or a hydroxyl group. , Nitro group, cyano group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group and salt thereof, sulfonic acid group and salt thereof, phosphoric acid and salt thereof, substituted or unsubstituted C1 to C30 alkyl group, substituted or substituted Unsubstituted C1 to C30 alkenyl groups, substituted or unsubstituted C1 to C30 alkynyl groups, substituted or unsubstituted C1 to C30 heteroalkyl groups, substituted or unsubstituted C6 to C30 aryl groups, substituted Or an unsubstituted C6 to C30 arylalkyl group, a substituted or unsubstituted C6 to C30 heteroaryl group, a substituted or unsubstituted C6 to C30 heteroarylalkyl group Any one selected from the group.

In the above [Reaction Scheme 1], a product in which the carboxyl group of the antimicrobial substance and the hydroxyl group of the humectant are esterified to bind is an antimicrobial additive. Of these antimicrobial additives, -COOA functions as a humectant, and the rest of the structure functions as an antimicrobial agent.

Wetting agents may be used any one or a mixture of two or more selected from the group consisting of alcohols, diols, triols, polyols, polyethylene glycols, polypropylene glycols. Such wetting agents may be selected to take into account the reactivity with the antimicrobial substances of [Formula 2] and [Formula 3], the stability of the product after the reaction and the like. The humectant used to provide the antimicrobial additive according to the invention is therefore not limited to that illustrated above.

In addition, another preferred example of the antimicrobial additive according to the present invention is the case where the additive to be combined with the antimicrobial material is a substance added as a storage stabilizer to the ink composition. One of such chemical reactions is, for example, the reaction formula shown in [Scheme 2].

In the reaction product of [Scheme 2], A-NH ₂ is a storage stabilizer, and the compound on the left side of the compound of [Formula 3] is substituted with R ₁ to a carboxyl group, and R ₂ and R ₁₀ are each independently a hydrogen atom or a halogen atom. , Hydroxy group, nitro group, cyano group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group and salt thereof, sulfonic acid group and salt thereof, phosphoric acid and salt thereof, substituted or unsubstituted C1 to C30 alkyl group, substituted Or an unsubstituted C1 to C30 alkenyl group, a substituted or unsubstituted C1 to C30 alkynyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C6 to C30 aryl group, Substituted or unsubstituted C6 to C30 arylalkyl group, substituted or unsubstituted C6 to C30 heteroaryl group, substituted or unsubstituted C6 to C30 heteroarylalkyl group It is one selected from the group.

In the above [Reaction Scheme 2], a product in which the carboxyl group of the antimicrobial substance and the amino group of the storage stabilizer are bound by amide reaction becomes an antimicrobial additive. Of these antimicrobial additives, -CONHA functions as a storage stabilizer and the rest of the structure functions as an antimicrobial agent.

Storage stabilizers are substituted or unsubstituted 2-pyrrolidone, N-methyl pyrrolidone, pyridine, imidazole, piperidine, 2-pyrrolidinone, primary amine, secondary amine, tertiary amine, amide Any one or a mixture of two or more selected from the group consisting of, lactones, and lactams can be used. Such storage stabilizers may be selected to consider the reactivity with the antimicrobial substances of [Formula 2] and [Formula 3], the stability of the product after the reaction and the like. The storage stabilizer used to provide the antimicrobial additive according to the invention is therefore not limited to that illustrated above.

The antimicrobial additive according to the present invention may be a compound in which the antimicrobial substance is chemically reacted with a humectant or a compound in which the antimicrobial substance is chemically reacted with a storage stabilizer, and a mixture thereof may be used.

Another object of the present invention is to provide an ink composition comprising the antimicrobial additive prepared as described above. Therefore, the antimicrobial additive contained in the ink composition containing the antimicrobial additive according to the present invention has the characteristics as described above.

As the solvent used in the ink composition comprising the antimicrobial additive according to the present invention, an aqueous liquid medium is used. The aqueous liquid medium can be used alone or in combination with water and one or more organic solvents. When using an organic solvent, the total content of the organic solvent is preferably within the range of 5 parts by weight to 50 parts by weight with respect to 100 parts by weight of the ink composition.

The amount of water and organic solvent added to the aqueous liquid medium can vary depending on various factors, such as the properties of the ink composition, such as viscosity, surface tension, and degree of permeation of the ink. These characteristics may vary depending on the inkjet printing method in which the ink is used, and may also vary according to the type of substrate on which the ink is printed. In the case of the ink composition according to the present invention, the content of the organic solvent may be increased in consideration of these characteristics. It is preferable to use as.

The organic solvent used in the aqueous liquid medium which is the solvent according to the present invention is composed of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, isobutyl alcohol. Alcohol solvents; Ketone solvents composed of acetone, methyl ethyl ketone and diacetone alcohol; Ester solvents composed of ethyl acetate and ethyl lactate; Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,2,4-butanediol, 1,5-pentanediol, 1,2,6-hexanetriol, hex Polyhydric alcohol solvents composed of silylene glycol, glycerol, glycerol ethoxylate, trimethylpropane ethoxylate; Lower alkyl ether solvents composed of ethylene glycol, monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether; Nitrogen-containing solvents composed of 2-pyrrolidone, N-methyl pyrrolidone and N-methyl-2-pyrrolidone; It is selected from the group consisting of; sulfur-containing compound solvent consisting of dimethyl sulfoxide, tetramethylene sulfone, thioglycol. However, it is not limited to the said organic solvent.

When the pigment is used as a colorant in the ink composition including the antimicrobial additive of the present invention, a dispersant may be further included for dispersion stability of the colorant, and there is no particular limitation on the dispersant usable in the present invention. That is, the dispersant of the present invention is not only a dispersant having a relatively simple structure and a low molecular weight, but also a dispersant of a large molecular weight such as a block copolymer which may limit the physical properties, stability, and functionality of the ink when directly contained in the ink composition. Can be used as.

For example, dispersants having a relatively low molecular weight and simple structure include polyvinyl alcohol (PVA), cellulosics, ethylene oxide modified phenols, ethylene oxide / propylene oxide polymers, Sodium polyacrylate 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 salt of multifunctional polymer Any one selected from the solution (BYK-Chemie, Disperbyk-181) or a mixture thereof may be used, but is not limited thereto.

In addition, examples of the dispersant having a complicated structure and a large molecular weight are as follows. Siloxane series such as polyether siloxane copolymers (TEGO, Wet KL 245 / Wet 260) can be used. In addition, it has the structure of AB or BAB, wherein A is a hydrophobic homopolymer or copolymer of substituted or unsubstituted C1 to C30 acrylic monomer, and B is substituted or unsubstituted AB polymers or BAB polymers which are hydrophilic polymers of acrylic monomers of C1 to C30 or copolymers of acrylic monomers are possible. Examples of AB polymers or BAB polymers include acrylic acid / acrylate copolymers, methacrylic acid / methacrylate copolymers, acrylic acid / polydialkylsiloxanes / acrylates Block copolymers (acrylic acid / polydialkylsiloxane / acrylate block copolymer), and mixtures of these polymers may be used. However, the above list is only an example of a dispersant having a complicated structure and a large molecular weight, but is not necessarily limited thereto.

The content of the dispersant used in the present invention is preferably within the range of 1 part by weight to 20 parts by weight with respect to 100 parts by weight of the ink composition. When the dispersant is included in the weight part within this range, the dispersing effect of preventing the pigment from being entangled is excellent.

The ink composition according to the present invention may further include additives such as viscosity modifiers, surfactants, and metal oxides as necessary.

Viscosity modifiers are substances that serve to control viscosity so that smooth jetting can be maintained. Viscosity modifiers according to the invention may be used casein or carboxymethylcellulose. The content of the viscosity modifier is preferably within the range of 0.1 parts by weight to 5.0 parts by weight with respect to 100 parts by weight of the ink composition.

The surfactant serves to stabilize the jetting performance at the nozzle by adjusting the surface tension of the ink composition. As the surfactant, anionic surfactants or nonionic surfactants are used.

Anionic surfactants used in the present invention are salts of alkylcarboxylic acids of C1 to C1000, salts of alkylsulfonic acid esters of C1 to C1000, salts of alkylsulfonic acids of C1 to C1000, and salts of alkylbenzenesulfonic acids of C1 to C1000. Any one selected from the group consisting of or mixtures thereof. Preferably any one selected from the group consisting of salts of alkylcarboxylic acids of C10 to C200, salts of alkylsulfonic acid esters of C10 to C200, salts of alkylsulfonic acids of C10 to C200, salts of alkylbenzenesulfonic acids of C10 to C200, or That is a mixture.

The nonionic surfactants used in the present invention are polyoxyethylene alkyl ethers having an alkyl group of C1 to C1000, polyoxyethylene alkyl phenyl ethers having a alkyl group of C1 to C1000, polyoxyethylene secondary alcohol ethers, polyoxyethylene-oxypropylene block copolymers. Any one selected from the group consisting of polymers, polyglycerol fatty acid esters, sorbitan fatty acid esters, or mixtures thereof. Preferably, the alkyl group is C10 to C200 polyoxyethylene alkyl ether, the alkyl group is C10 to C200 polyoxyethylene alkyl phenyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene-oxypropylene block copolymer, polyglycerine fatty acid ester, Sorbitan fatty acid esters, any one selected from the group consisting of or mixtures thereof.

The amount of the surfactant is preferably within the range of 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the ink composition.

Looking at the manufacturing method of the ink composition having the above-described composition is as follows.

First, an antimicrobial additive according to the present invention is prepared as a compound in which an antimicrobial substance and a humectant are bound through a chemical reaction, a compound in which the antimicrobial substance and a storage stabilizer are bound through a chemical reaction, or a mixture thereof.

The colorant and the antimicrobial additives prepared above are then mixed with additives such as dispersants, viscosity modifiers, surfactants and the like into the aqueous liquid medium. The mixture is then sufficiently stirred in a stirrer to bring it into a uniform state. The resultant is then filtered through a 0.45 μm or 0.8 μm filter to obtain an ink composition comprising the antimicrobial additive according to the present invention.

Hereinafter, the present invention will be described in more detail with reference to the following examples.

{Example}

Example 1

Preparation of Antimicrobial Additives

27.6 g of glycerin, 300 mL of DMSO, and 18.0 g of a carbendazim derivative of the following [Formula 4] were added and dissolved in a 500 mL Erlenmeyer flask. One to two boiling stones were added thereto, and 30 ml of concentrated sulfuric acid was slowly added dropwise thereto, and the Erlenmeyer flask was connected to a reflux condenser and allowed to react sufficiently at 80 ° C for at least 8 hours. After cooling this reaction liquid to room temperature, the crystal | crystallization which generated excess methanol was filtered through the suction filter. To remove the unreacted substance, the crystals were dissolved in DMSO again, and methanol was added to the resulting crystals. The crystals were filtered through a suction filter and dried in an oven to obtain 24.5 g of the antimicrobial additive of [Formula 5].

[Production of Ink Composition]

In order to prepare an ink composition including the antimicrobial additive of [Formula 5], each of the following components were mixed and sufficiently stirred for 30 minutes or more in a stirrer to make a uniform state. Then, an ink composition containing an antimicrobial additive was prepared by filtration with a filter of 0.45 mu m.

3.5 g of C.I.direct black 168

8.0 g of the antimicrobial additive of the above [Formula 5]

Isopropyl Alcohol 2.0g

2-pyrrolidone 10.0 g

76.5 g of distilled water

Example 2

Preparation of Antimicrobial Additives

In a 500 mL Erlenmeyer flask, 300 mL of DMSO and 18.4 g of the carbendazide derivative of [Formula 4] were added and dissolved. 7.1 g of SOCl ₂ was added thereto and reacted at room temperature for 1 hour or longer to obtain an A solution. Then, a solution of 57.2 g of 2, 2, 6, and 6-tetramethyl-4-piperidinol of [Formula 6] in 200 ml of DMSO was added to the solution A, followed by adding 1 to 2 boiling stones to the reflux condenser. 6 hours or longer at 80 ° C. After cooling this reaction liquid to room temperature, the crystal | crystallization which generated excess methanol was filtered through the suction filter. In order to remove the unreacted substance, the crystals were dissolved in DMSO again, and methanol was added to the resulting crystals. The crystals were similarly filtered through a suction filter and dried in an oven to obtain 12.6 g of the antimicrobial additive of [Formula 7].

[Production of Ink Composition]

In order to prepare an ink composition including the antimicrobial additive of [Formula 7], each of the following components were mixed and sufficiently stirred for 30 minutes or more in a stirrer to make a uniform state. Then, an ink composition containing an antimicrobial additive was prepared by filtration with a filter of 0.45 mu m.

C.I. direct black 9 2.0 g

C.I.direct black 168 2.0 g

6.0 g of the antimicrobial additive of [Formula 7]

Isopropyl Alcohol 2.0g

Propylene Glycol 8.0g

Polyethylene glycol 4.0 g

Distilled water 76g

Example 3

Preparation of Antimicrobial Additives

In a 500 mL Erlenmeyer flask, 100 mL of DMSO and 18.0 g of a carbendazide derivative of [Formula 8] were added and dissolved. 4.2 g of SOCl ₂ was added thereto and reacted at room temperature for 1 hour or longer to obtain a C solution. Then, a solution of 12.9 g of 2-pyrrolidone-5-carboxylic acid of [Formula 9] in 200 ml of DMSO was added to the above C solution, and then 1 to 2 boiling stones were added thereto. It was made to react sufficiently over time. After cooling the reaction solution to room temperature, excess methanol was added and the Sangig crystals were filtered through a suction filter. In order to remove the unreacted substance, the crystals were dissolved in DMSO again, and methanol was added to the resulting crystals. The crystals were similarly filtered through a suction filter and dried in an oven to obtain 12.5 g of the antimicrobial additive of [Formula 10].

[Production of Ink Composition]

In order to prepare an ink composition including the antimicrobial additive of [Formula 10], each of the following components were mixed and sufficiently stirred for 30 minutes or more in a stirrer to make a uniform state. Then, an ink composition containing an antimicrobial additive was prepared by filtration with a filter of 0.45 mu m.

C.I. direct black 199 4.0 g

8.0 g of the antimicrobial additive of [Formula 10]

Isopropyl Alcohol 4.0g

1,5-pentanediol 10.0 g

74 g of distilled water

Example 4

Preparation of Antimicrobial Additives

100 ml of DMSO in a 500 ml Erlenmeyer flask and the following carbendazide derivative 4

5 g was added to dissolve. 7.7 g of SOCl ₂ was added thereto and reacted at room temperature for 1 hour or longer to obtain an E solution. The solution of 47.6 g of the ethylene glycol derivative of [Formula 12] was dissolved in 200 ml of DMSO, was added to the above E solution, 1 to 2 boiling stones were added, and the mixture was connected to a reflux condenser and reacted at 80 ° C. for at least 6 hours. After cooling this reaction liquid to room temperature, the crystal | crystallization which generated excess methanol was filtered through the suction filter. In order to remove the unreacted substance, the crystals were dissolved in DMSO again, and methanol was added to the resulting crystals. The crystals were similarly filtered through a suction filter and dried in an oven to obtain 75.2 g of the antimicrobial additive of [Formula 13].

[Production of Ink Composition]

In order to prepare an ink composition including the antimicrobial additive of [Formula 13], each of the following components were mixed and sufficiently stirred for 30 minutes or more in a stirrer to make a uniform state. Then, an ink composition containing an antimicrobial additive was prepared by filtration with a filter of 0.45 mu m.

C.I.Reactive Red 180 4.5g

10 g of the antimicrobial additive of [Formula 13]

Ethanol 3.0g

6.0 g N-methyl pyrrolidone

76.5 g of distilled water

Example 5

Preparation of Antimicrobial Additives

25.8 g of the pyrrolidone carboxylic acid of [Chemical Formula 9], 300 ml of DMSO and 24.2 g of the carbendazide derivative of [Formula 14] were dissolved in a 500 ml Erlenmeyer flask. One to two boiling stones were added thereto, and 30 ml of concentrated sulfuric acid was slowly dropped, and then connected to a reflux condenser, followed by sufficient reaction at 80 ° C. for at least 8 hours. After cooling this reaction liquid to room temperature, the crystal | crystallization which generated excess methanol was filtered through the suction filter. In order to remove the unreacted substance, the crystals were dissolved in DMSO again, and methanol was added to the resulting crystals. The crystals were dried in an oven with a suction filter to obtain 26.0 g of the antimicrobial additive of [Formula 15].

[Production of Ink Composition]

In order to prepare an ink composition including the antimicrobial additive of [Formula 15], each of the following components were mixed and sufficiently stirred for 30 minutes or more in a stirrer to make a uniform state. Then, an ink composition containing an antimicrobial additive was prepared by filtration with a filter of 0.45 mu m.

C.I. Acid Yellow 23 3.0 g

8.0 g of the antimicrobial additive of [Formula 15]

Ethylene Glycol 4.0g

Propylene Glycol 5.0g

Distilled water 80.0g

Example 6

Preparation of Antimicrobial Additives

The antimicrobial additive of Example 6 is a compound of [Formula 13] prepared by the same method as the preparation of the antimicrobial additive of Example 4 .

[Production of Ink]

The following components were mixed to prepare an ink composition comprising the antimicrobial additive of [Formula 13].

4.0 g of carbon black

Styrene / Acrylic Copolymer 4.0g

0.5 g of monoetherolamine

8.0 g of the antimicrobial additive of [Formula 13]

2-pyrrolidone 4.0g

Polyethylene glycol 2.0 g

Isopropyl alcohol 4.0 g

Distilled water 73.5g

After mixing the components, the mixture was dispersed under the following conditions.

Dispersing Equipment: Sand Mill

Dispersion medium: Glass beads (diameter 1㎛)

Dispersion medium application rate: 50% (volume ratio)

Dispersion time: 3 hours

Finally, centrifugation was carried out at a speed of 12,000 rpm for 20 minutes to secure a dispersion ink having a particle size of 0.1 μm or less, and all large particles were removed.

Example 7

Preparation of Antimicrobial Additives

The antimicrobial additive of Example 7 is a compound of [Formula 5] prepared by the same method as the preparation of the antimicrobial additive of Example 1 .

[Production of Ink]

The following components were mixed to prepare an ink including the antimicrobial additive of [Formula 5].

Phthalocyanine Blue 4.5g

Styrene / Acrylic Copolymer 3.5g

0.3 g of trietarolamine

10.0 g of the antimicrobial additive of [Formula 5]

6.0 g N-methyl pyrrolidone

Polyethylene glycol 2.0 g

3.0 g of isopropyl alcohol

Distilled water 70.7g

After mixing the components, the mixture was dispersed under the following conditions.

Dispersing Equipment: Sand Mill

Dispersion medium: Glass beads (diameter 1㎛)

Dispersion medium application rate: 50% (volume ratio)

Dispersion time: 3 hours

Finally, centrifugation was carried out at a speed of 12,000 rpm for 20 minutes to secure a dispersion ink having a particle size of 0.1 μm or less, and all large particles were removed.

{Comparative Example}

Comparative Example 1

Except, instead of anti-microbial additives of the above-mentioned [Chemical Formula 5] in Example 1 was used to form the ethylene glycol and diethylene glycol 4g 6g was prepared in the ink in the same manner as in Example 1.

Comparative Example 2

In Example 2, except for using N- methyl pyrrolidone 6.0g, instead of anti-microbial additives of the above-mentioned [Chemical Formula 7] was prepared in the ink in the same manner as in Example 2.

Comparative Example 3

Except in Example 3 was used to form 2-pyrrolidone 8.0g, instead of anti-microbial additives of the above-mentioned [Chemical Formula 10] was prepared in the ink in the same manner as in Example 3.

Comparative Example 4

In Example 4, except that the BIT 0.2g in the above [Formula 13] instead of the anti-microbial additives to 10.0g of diethylene glycol and antimicrobial agent to prepare an ink in the same manner as in Example 4.

Comparative Example 5

An ink was prepared in the same manner as in Example 1 , except that 8.0 g of caprolactam and BIT 0.1 g were used as an antimicrobial agent instead of the antimicrobial additive of [Formula 15] in Example 5 .

Comparative Example 6

An ink composition in the same manner as in Example 6, except for using 8.0g of diethylene glycol in place of the antimicrobial additive in the [formula 13] in Example 6 was prepared.

Comparative Example 7

An ink composition in Example 7 wherein the ethylene glycol in place of the antimicrobial additive in the [formula 5] 3.0g, 7.0g of diethylene glycol, and in the same manner as in Example 7 except that the biocide was prepared as a 0.1g BIT .

{evaluation}

Rating 1

When the inks according to Examples 1 to 7 and Comparative Examples 1 to 7 were left to be stored, the test results for the presence or absence of precipitation of each ink are shown in the following [Table 1]. In this experiment, 100 ml of the ink of Examples 1 to 7 and Comparative Examples 1 to 7 were contained in 14 250 ml bottles, and the inlet was sealed and stored in a 60 ° C thermostat. While leaving it for a certain time while checking the presence or absence of precipitation of the bottom of each bottle containing the ink is shown in the following [Table 1].

ink Precipitation presence by standing time (O, ×) 7 days 14 days 30 days 60 days 120 days 180 days 360 days Example 1 O O O O O O O Example 2 O O O O O O O Example 3 O O O O O O O Example 4 O O O O O O O Example 5 O O O O O O O Example 6 O O O O O O O Example 7 O O O O O O O Comparative Example 1 O O O × × × × Comparative Example 2 O O × × × × × Comparative Example 3 O O × × × × × Comparative Example 4 × × × × × × × Comparative Example 5 × × × × × × × Comparative Example 6 O O × × × × × Comparative Example 7 × × × × × × ×

Here, O represents the case where there is no precipitate, and x represents the case where there is a precipitate.

According to the above [Table 1], the ink containing the antimicrobial additives according to Examples 1 to 7 according to the present invention did not occur precipitation by the antimicrobial additives according to the present invention. On the other hand, the ink containing no antimicrobial additives of Comparative Examples 1 to 3 and 6 has no precipitates when stored for a short period of time, but mold or precipitates are formed when stored for a long period of time. In 5 and Comparative Example 7, it was confirmed that the precipitate is formed from the beginning. As a result, the antimicrobial additives according to Examples 1 to 7 according to the present invention exhibited good antimicrobial function in the ink composition while having good compatibility with other components in the ink composition including the antimicrobial additive. Able to know.

Evaluation 2

Experimental results for nozzle clogging when the ink according to Examples 1 to 7 and Comparative Examples 1 to 7 were applied to the cartridge are shown in the following [Table 2]. In this experiment, the ink of Examples 1 to 7 and Comparative Examples 1 to 7 was filled in each of 14 Laxmark cartridges by 50 ml, and then left at room temperature. After a predetermined time elapsed, a pattern was taken from the nozzle with a Lexmark printer to confirm whether the nozzle was clogged.

ink Nozzle clogging (O, △, ×) 1 day 3 days 7 days 14 days 21st 28 days 60 days Example 1 O O O O O O O Example 2 O O O O O O O Example 3 O O O O O O O Example 4 O O O O O O O Example 5 O O O O O O O Example 6 O O O O O O O Example 7 O O O O O O O Comparative Example 1 O O △ × × × × Comparative Example 2 O O △ × × × × Comparative Example 3 O O △ × × × × Comparative Example 4 × × × × × × × Comparative Example 5 × × × × × × × Comparative Example 6 O O △ × × × × Comparative Example 7 × × × × × × ×

Here, O denotes that there is no nozzle clogging, Δ denotes that a part of nozzle clogging is present, and x denotes that most of the nozzle clogging occurs.

According to the above [Table 2], the ink containing the antimicrobial additives of Examples 1 to 7 according to the present invention did not cause nozzle clogging when applied to the cartridge for long term storage. On the other hand, in the ink of Comparative Examples 1 to 7, some or most of the nozzle clogging occurred, it can be seen that the ink of Comparative Examples 1 to 7 is not stable. In other words, the antimicrobial additives of Examples 1 to 7 according to the present invention have good compatibility with other components in the ink composition including the antimicrobial additives, and the additives inherent function added to prepare the antimicrobial additives are wetting agents or storage. It can be seen that the stabilizer functions properly.

Evaluation 3

In the present invention, a halo zone test was used to measure the antimicrobial efficacy of the ink composition including the antimicrobial additive according to the present invention. In the halo area test, first, agar medium of potato dextrose was prepared in a sterile petri dish (10 cm in diameter), and then Examples 1 to 7 and Comparative Examples 1 to 3 , Aspergillus sneeger spore solution was applied thinly on the OHP films printed with the ink, except for dyes and pigments in Comparative Example 6, respectively. Then, 20 μl of distilled water solution was dropped onto the OHP film on which the ink made without the colorant was printed, and left for 1 hour on a clean bench under ultraviolet light. This paper was placed in the center of agar medium coated with Aspergillus niger and incubated for 72 hours in an incubator at 30 ° C. Then, the growth of Aspergillus niger was observed around the eye. Inks containing the antimicrobial additives of Examples 1 to 7 did not grow mold and maintained transparent areas. On the other hand, the ink that does not contain the antimicrobial additives of Comparative Examples 1 to 3 and Comparative Example 6 is not grown because the mold grows and propagates. Therefore, it can be seen that the antimicrobial additives of Examples 1 to 7 exhibit an antibacterial function, and the ink composition including the same also has high antimicrobial properties.

The light transmittance was evaluated and the results are shown in the following [Table 3]. The ink of Examples is the ink of Examples 1 to 7, and the ink of Comparative Example is the ink of Comparative Examples 1 to 3, and Comparative Example 6.

division Light transmission before culture (% T) Light transmission after incubation (% T) Apparent light transmittance after incubation Example 80 80 Transparency Comparative example 79 51 opacity

As shown in [Table 3], the antimicrobial properties of the ink composition including the antimicrobial additives of Examples 1 to 7 did not change the light transmittance because the concentration of the bacteria was not increased after culturing the bacteria. On the other hand, in the ink that does not contain the antimicrobial inks of Comparative Examples 1 to 3 and Comparative Example 6, it can be seen that germs propagate to decrease the light transmittance.

According to the present invention as described above, by combining the humectant or storage stabilizer contained in the ink composition with a compound having an antimicrobial function to provide an antimicrobial additive and by providing an ink composition comprising the same, the additive inherent functions and antibacterial There is an effect that can provide an antimicrobial additive and an ink composition comprising the same can exert a function at the same time. In addition, when the commercially available antimicrobial agent is simply added to the ink, the antimicrobial agent is a polymer material, so that the storage stability of the ink is anxious. In the present invention, the ink composition includes an antimicrobial additive having a storage stability that does not cause precipitation even during long-term storage. There is an effect that can provide.

Although the above has been illustrated and described with respect to the preferred embodiment of the present invention, the present invention is not limited to the specific preferred embodiment described above, the present invention without departing from the gist of the invention claimed in the claims Various modifications can be made by those skilled in the art, and such changes are within the scope of the claims.

Claims (26)

Represented by the following formula, Wherein R ₁ is any one selected from the group consisting of a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group and a salt thereof, a sulfonic acid group and a salt thereof, phosphoric acid and 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 hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group and Salts, sulfonic acid groups and salts thereof, phosphoric acid and salts thereof, substituted or unsubstituted C1 to C30 alkyl groups, substituted or unsubstituted C1 to C30 alkenyl, substituted or unsubstituted C1 to C30 alkynyl groups, Substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylalkyl group, substituted or unsubstituted C6 to C30 hetero An aryl group and any one selected from the group consisting of a substituted or unsubstituted C6 to C30 heteroarylalkyl group; Alcohol, diol, triol, polyol, polyethylene glycol, polypropylene glycol, substituted or unsubstituted 2-pyrrolidone, N-pyrrolidone, pyridine, imidazole, piperidine, 2-pyrrolidinone, 1 An antimicrobial additive, characterized in that the compound by the chemical reaction of any one selected from the group consisting of secondary amine, secondary amine, tertiary amine, amide, lactone, and lactam. The method of claim 1, The alkyl group is an antimicrobial additive, characterized in that it comprises a straight or branched alkyl radical of C1 to C30. The method of claim 1, The substituted C1 to C30 alkyl group, the substituted C1 to C30 alkenyl group, substituted C1 to C30 alkynyl group, substituted C1 to C30 heteroalkyl group, substituted C1 to C30 aryl group, substituted C1 to The C30 arylalkyl group, substituted C1 to C30 heteroaryl group, and substituted C1 to C30 heteroarylalkyl group each independently have at least one hydrogen atom selected from halogen atom, hydroxy group, nitro group, cyano group, amino group, and amidino group. , Hydrazine group, hydrazone group, carboxyl group and salt thereof, sulfonic acid group and salt thereof, phosphoric acid and salt thereof, C1 to C20 alkyl group, C1 to C20 alkenyl group, C1 to C20 alkynyl group, C1 to C20 heteroalkyl group, C6 To C20 aryl, C6 to C20 arylalkyl, C6 to C20 heteroaryl, and C6 to C20 heteroarylalkyl group It is an antimicrobial additive. delete delete delete delete The method of claim 1, The substituted 2-pyrrolidone, N-pyrrolidone, pyridine, imidazole, piperidine, 2-pyrrolidinone, primary amine, secondary amine, tertiary amine, amide, lactone, and lactam are at least At least one hydrogen atom is a halogen atom, hydroxy group, nitro group, cyano group, amino group, amidino group, hydrazine group, hydrazone group, carboxyl group and salts thereof, sulfonic acid group and salts thereof, phosphoric acid and salts thereof, alkyl groups of C1 to C20, C1 to C20 C20 alkenyl group, C1 to C20 alkynyl group, C1 to C20 heteroalkyl group, C6 to C20 aryl group, C6 to C20 arylalkyl group, C6 to C20 heteroaryl group, and C6 to C20 heteroarylalkyl group Antimicrobial additive, characterized in that substituted with any one selected from the group consisting of. delete An ink composition comprising a colorant, a solvent and an antimicrobial additive, The antimicrobial additive is represented by the following formula, R ₁ is any one selected from the group consisting of a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group and a salt thereof, a sulfonic acid group and a salt thereof, phosphoric acid and 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 hydroxy group, a nitro group, a cyano group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group and Salts, sulfonic acid groups and salts thereof, phosphoric acid and salts thereof, substituted or unsubstituted C1 to C30 alkyl groups, substituted or unsubstituted C1 to C30 alkenyl, substituted or unsubstituted C1 to C30 alkynyl groups, Substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 arylalkyl group, substituted or unsubstituted C6 to C30 hetero An aryl group and any one selected from the group consisting of a substituted or unsubstituted C6 to C30 heteroarylalkyl group; Alcohol, diol, triol, polyol, polyethylene glycol, polypropylene glycol, substituted or unsubstituted 2-pyrrolidone, N-pyrrolidone, pyridine, imidazole, piperidine, 2-pyrrolidinone, 1 It is a compound combined by chemical reaction of any one selected from the group consisting of primary amine, secondary amine, tertiary amine, amide, lactone, and lactam, The antimicrobial additive is an ink composition comprising an antimicrobial additive, characterized in that within the range of 0.1 to 30 parts by weight based on 100 parts by weight of the ink composition. The method of claim 10, Wherein said alkyl group comprises a straight or branched alkyl radical of C1 to C30. The method of claim 10, The substituted C1 to C30 alkyl group, the substituted C1 to C30 alkenyl group, substituted C1 to C30 alkynyl group, substituted C1 to C30 heteroalkyl group, substituted C1 to C30 aryl group, substituted C1 to The C30 arylalkyl group, substituted C1 to C30 heteroaryl group, and substituted C1 to C30 heteroarylalkyl group each independently have at least one hydrogen atom selected from halogen atom, hydroxy group, nitro group, cyano group, amino group, and amidino group. , Hydrazine group, hydrazone group, carboxyl group and salt thereof, sulfonic acid group and salt thereof, phosphoric acid and salt thereof, C1 to C20 alkyl group, C1 to C20 alkenyl group, C1 to C20 alkynyl group, C1 to C20 heteroalkyl group, C6 To C20 aryl, C6 to C20 arylalkyl, C6 to C20 heteroaryl, and C6 to C20 heteroarylalkyl group An ink composition comprising an antibacterial additive. delete delete delete delete delete delete delete The method of claim 10, The solvent is an ink composition comprising an antimicrobial additive, characterized in that water is used alone. The method of claim 10, The solvent is an ink composition comprising an antimicrobial additive, characterized in that used by mixing water and an organic solvent. The method of claim 21, An ink composition comprising an antimicrobial additive, characterized in that the content of the organic solvent is within the range of 5 parts by weight to 50 parts by weight with respect to 100 parts by weight of the ink composition. The method of claim 21, The organic solvent, Alcohol solvents consisting of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol and isobutyl alcohol; Ketone solvents composed of acetone, methyl ethyl ketone and diacetone alcohol; Ester solvents composed of ethyl acetate and 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 solvents composed of hexylene glycol, glycerol, glycerol ethoxylate, trimethylpropane ethoxylate; Alkyl ether solvents composed of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl; Nitrogen-containing solvent consisting of 2-pyrrolidone, N-methyl pyrrolidone, N-methyl-2-pyrrolidone; And An ink composition comprising an antimicrobial additive, characterized in that the solvent is made of a compound selected from the group consisting of; a sulfur-containing solvent consisting of dimethyl sulfoxide, tetramethylene sulfone, thioglycol. The method of claim 10, An ink composition comprising an antimicrobial additive, wherein the colorant is a pigment and the ink composition further comprises a dispersant. The method of claim 10, Ink composition comprising an antimicrobial additive, characterized in that the ink composition further comprises a viscosity modifier. The method of claim 10, Ink composition comprising an antimicrobial additive, characterized in that the ink composition further comprises a surfactant.