KR20180079575A - anthraquinone dyes and sublimation transferring ink comprising thereof - Google Patents

Abstract

The present invention relates to a sublimation transfer ink used in digital textile printing (DTP), and provides an anthraquinone-based disperse dye represented by chemical formula 1 and a sublimation transfer ink comprising the anthraquinone-based disperse dye. In chemical formula 1, R_1 is an alkyl group having 6 to 8 carbon atoms, and R_3, R_4 and R_5 are each H, OH, NH_2, and NHCH_3. According to the present invention, the anthraquinone-based disperse dye and a transfer ink comprising the anthraquinone-based disperse dye can be used as a transfer ink specified to DTP since the anthraquinone-based disperse dye and the transfer ink comprising the anthraquinone-based disperse dye are not only excellent in transfer efficiency for fabrics such as a polyester fabric and the like, but also very excellent in washing fastness and light fastness.

Description

Anthraquinone dyes and sublimation transferring ink compositions containing the same,

The present invention relates to a sublimation transfer ink used in digital textile printing (DTP), and more particularly, to an anthraquinone-based dispersion dye and a sublimation transfer ink for DTP containing the same.

The digital textile printing (DTP) technique uses a inkjet printer to print the transfer ink first on a transfer paper and then dry the paper. Then, the dried transfer paper is placed on the fabric and a high heat of about 170 ° C or higher is applied to sublimate the ink, It is a technology that is transferred to the fabric by penetration.

DTP is able to express fine image realistically compared with traditional dyeing method and it is possible to produce small quantity of many kinds compared to existing dyeing method by digitizing printing process so that it can respond effectively to rapid change of fashion, It is eco-friendly because processing problems are reduced.

DTP was developed in 1991, and Korean companies are actively growing in the field of textile and fashion as domestic companies have localized DTP technology in the early 2000s.

Sublimation transfer inks used in DTP are prepared by dispersing a dispersion dye in water or a solvent using a dispersant and mixing additives such as a penetrating agent and a moisturizer.

The dyes are classified into azo dyes, anthraquinone dyes, quinophthalone dyes, and phthalocyanine dyes. The dyes are classified into various substituents at various positions of the matrix of these dyes, such as azo dyes, anthraquinone dyes, quinophthalone dyes, A number of dyes have been developed and commercially available.

Anthraquinone dyes are relatively expensive but have a merit of showing a clear color and are used not only as a traditional fiber dye but also as a dye for sublimation transfer ink.

Since DTP is a dye sublimation method through transfer paper, the transfer efficiency of transfer ink is very important for improving the color of DTP. Since the transfer efficiency is influenced not only by the characteristics of the transfer paper but also by the dye structure and characteristics of the sublimation dye, development of a dye having high transfer efficiency is continuously required.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide an anthraquinone disperse dye having improved transfer efficiency in digital textile printing and a transfer ink containing the disperse dye.

In order to achieve the above object, the present invention provides an anthraquinone disperse dye represented by the following formula (1).

[Chemical Formula 1]

In this formula,

R ₁ is a C ₆ to C ₈ alkyl group,

R ₄ , R ₃ , R ₄ and R ₅ are each independently H, OH, NH ₂ or NHCH ₃ .

The anthraquinone disperse dye is preferably an anthraquinone disperse dye represented by the following formula (2) or (3).

(2)

R ₁ is a C ₆ to C ₈ alkyl group,

R ₄ and R ₅ are each independently H, OH, NH ₂ , NHCH ₃ .

(3)

In this formula,

R ₁ is a C ₆ to C ₈ alkyl group.

The present invention provides a sublimation transfer ink composition comprising the anthraquinone based dispersion dye.

The sublimation transfer ink composition according to the present invention may further comprise an aqueous polymer, a dispersant, a wetting agent and a solvent.

The aqueous polymer may be a polymer containing a urethane group, a copolymer containing a urethane group, a polymer containing an acryl group, a copolymer containing an acrylic group, and a mixture thereof.

The dispersant may be selected from anionic dispersants including formaldehyde condensates of lignin sulfonic acid, formaldehyde condensates of alkyl naphthalene sulfonic acid, and formaldehyde condensates of creosote oil sulfonic acid.

The solvent may be water, deionized water, a water-soluble organic solvent and a water-miscible organic solvent. The organic solvent may be an alcohol solvent, a ketone solvent, a polyhydric alcohol solvent, a nitrogenous solvent, dimethylsulfoxide, And a sulfur compound of thioglycol.

The wetting agent may include diethylene glycol, glycerol, and diethylene glycol monobutyl ether.

The anthraquinone disperse dye according to the present invention and the transfer ink containing the dyestuff according to the present invention have excellent transfer efficiency to fabrics such as polyester fibers and are excellent in washing fastness and light fastness and can be used for digital textile printing ) Can be used.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a diagram showing a transfer step of a sublimation transfer ink produced according to the present invention. FIG.
2 is a graph showing the relationship between the apparent density (K / S) of the transfer paper before and after transfer using a colorimeter (Computer Color Matching System, Coloreye-3100, Macbeth) Measurement results.
3 is a graph showing the relationship between the apparent density (K / S) of the transfer paper before and after transfer using a colorimeter (Computer Color Matching System, Coloreye-3100, Macbeth) Measurement results.

The present invention is directed to an anthraquinone dye.

The present inventors have conducted various studies based on known anthraquinone dyes in order to develop sublimation transfer inks, and have found that the anthraquinone methyl group (C ₁ ), propoxy group (C ₃ ), hexyl group (C ₆ ) (C ₈ ). As a result, it was confirmed that when the alkyl group having a long chain having 6 or more carbon atoms was introduced, not only the transcription efficiency was significantly increased in DTP but also the washing fastness and light fastness were excellent. Respectively.

The present invention provides a transfer ink comprising an anthraquinone disperse dye represented by the following formula (1).

[Chemical Formula 1]

In this formula,

R ₁ is a C ₆ to C ₈ alkyl group,

R ₄ , R ₃ , R ₄ and R ₅ are each independently H, OH, NH ₂ or NHCH ₃ .

The disperse dye according to the present invention is preferably 3 to 10% by weight based on 100% by weight of the entire transfer ink. When the amount of the disperse dye is less than 3% by weight, the color may not be clear after the transfer, and if it exceeds 10% by weight, dispersion may be difficult and the transferability may be lowered.

The sublimation transfer ink composition according to the present invention comprises a dispersing agent. The dispersant may comprise one or two components.

The dispersant may be an aqueous polymer. When dispersed dyes are dispersed and atomized into nano-size, they tend to aggregate to lower the energy of the surface. The water-based polymer surrounds the disperse dye which is in an atomized state, and disturbs the tendency of the disperse dye to aggregate with each other to increase dispersibility .

The aqueous polymer may comprise a polymer containing a urethane group, a copolymer containing a urethane group, a polymer containing an acrylic group, a copolymer containing an acrylic group, and a mixture thereof. Known water-soluble polymers include, but are not limited to, ONCRYL® 50, JONCRYL® 60, JONCRYL® 61, JONCRYL® 63, JONCRYL® 67, JONCRYL® 611 and JONCRYL® 690. The aqueous polymer may comprise water, typically deionized water. For a variety of uses, the aqueous polymer may include one or more water-soluble or water-miscible organic solvents that are dispersed and mixed in water.

The aqueous polymer is preferably 0.5 to 10% by weight based on 100% by weight of the entire transfer ink. If the amount of the aqueous polymer is less than 0.5% by weight, the dispersibility may be deteriorated, and if it is more than 10% by weight, the problem of layer separation of the ink may occur.

The dispersant may be an anionic dispersant such as lecithin, formaldehyde condensates of lignin sulfonic acid, formaldehyde condensates of alkyl naphthalene sulfonic acid, formaldehyde condensates of creosote oil sulfonic acid, and the like. The anionic dispersant is not limited, but polymeric sulfonic acids, preferably formalin condensates of aromatic sulfonic acids, and formalin condensates of lignin sulfonic acid can be used.

The sublimation transfer ink composition according to the present invention includes a solvent.

The solvent may be water, an organic solvent or a mixture thereof. The solvent is preferably deionized water. As the organic solvent, at least one selected from the group consisting of an alcohol-based solvent, a ketone-based solvent, a polyhydric alcohol-based solvent, a nitrogen-containing solvent, dimethylsulfoxide, tetramethylsulfone and a thioglycol sulfide compound can be used.

As the alcoholic solvent usable as an organic solvent, examples of the monohydric alcohol include lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, s-butyl alcohol and t- Ethyl alcohol, iso-propyl alcohol and n-butyl alcohol are particularly preferable.

Examples of the polyhydric alcohol solvent include alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butylene glycol and glycerol, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, Glycol. Examples of the polyhydric alcohol derivative include lower alkyl ethers of the above-described polyhydric alcohols such as ethylene glycol methyl ether and the like, and lower polyhydric alcohols such as ethylene glycol diacetates.

The solvent is adjusted to be in the range of 50 to 95% by weight based on 100% by weight of the entire transfer ink.

The sublimation transfer ink composition according to the present invention may contain a wetting agent.

The wetting agent serves to prevent the ink from drying out or clogging the printer nozzle. Examples of the wetting agent include polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, tetraethylene glycol, polyethylene glycol, glycerol, 2-methyl- Hexanetriol, thioglycol, and the like. Lower alkyl mono- or di-ethers derived from alkylene glycols such as ethylene glycol mono-methyl ether or mono-ethyl ether, diethylene glycol mono-methyl ether or mono-ethyl ether, propylene glycol mono-methyl ether Or mono-ethyl ether, triethylene glycol mono-methyl ether or mono-ethyl ether, diethylene glycol di-methyl ether or di-ethyl ether and diethylene glycol monobutyl ether.

The wetting agent is preferably 10 to 50% by weight based on 100% by weight of the entire transfer ink. When the wetting agent is less than 10% by weight, the drying speed is increased to cause nozzle clogging problem in the inkjet head, and when it exceeds 50% by weight, the dispersibility may be lowered.

The sublimation transfer ink composition according to the present invention may further contain small amounts of additives such as a surface modifier, a surfactant, a bactericide, a viscosity modifier, a pH adjuster, a buffer, an antioxidant and a conductivity modifier.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are provided to illustrate the present invention, and the present invention is not limited to the following examples.

Example 1: 1 -amino-2- ( hexyloxy )-4- hidroxyanthracene -9,10- dione (Formula 1-1)  Produce

[Formula 1-1]

In a round flask, 58.3 g of 1-amino-2-bromo-4-hydroxyanthracene-9,10-dione was added and 34.5 g of potassium carbonate was added. After the addition, the temperature was raised to 70 ° C to completely dissolve the solution, and 25.9 g of n-hexanol was further stirred to complete the reaction. The pH was adjusted with an aqueous solution of sodium hydroxide, followed by filtration and washing with water to obtain a red solid dye.

Example 2: 1 -amino-4- hydroxy -2-( octyloxy ) anthracene -9,10- dione (Formula 1-2)  Produce

[Formula 1-2]

In Example 1, 26.4 g of n-octanol was added instead of n-hexanol, and the same procedure was followed to obtain a red solid dye.

Example 3: 1 , 5- diamino -2-( hexyloxy ) -4,8- 디 디시 xyanthracene -9,10- dione (Formula 1-3)  Produce

[Formula 1-3]

In a round flask, 64.7 g of 1,5-diamino-2-chloro-4,8-dihydroxyanthracene-9,10-dione was added and 42.5 g of potassium carbonate was added. After the addition, the temperature was raised to 70 ° C to completely dissolve the solution, and 25.9 g of n-hexanol was further stirred to complete the reaction. The pH was adjusted with an aqueous solution of sodium hydroxide, followed by filtration and washing with water to obtain a red solid dye.

Example 4: 1 , 5- diamino -4,8- dihydroxy -2-( octyloxy ) anthracene -9,10- dione (Formula 1-4)  Produce

[Formula 1-4]

In Example 3, 26.4 g of n-octanol was added instead of n-hexanol, and the same procedure was followed to obtain a red solid dye.

Comparative Example 1: 1 -amino-4- hydroxy -2- 메틸oxyantracene -9,10- dione (C.I. Disperse Red 5)  Ready

[Formula 1-5]

Commercially available CI Disperse Red 4 was prepared.

Comparative Example 2: 1 -amino-4- hydroxy -2- propoxyanthracene -9,10- dione (Formula 1-6)  Produce

[Chemical Formula 1-6]

In Example 1, 26.4 g of n-propanol was added in place of n-hexanol, and the same procedure was followed to obtain a red solid dye.

Comparative Example 3: 1 , 5- diamino -4,8- dihydroxy -2- 메틸oxyantracene -9,10- dione (Formula 1-7)  Produce

[Chemical Formula 1-7]

In Example 3, 22.4 g of methanol was added instead of n-hexanol, and the same procedure was carried out to obtain a red solid dye.

Comparative Example 4: 1 , 5- diamino -4,8- dihydroxy -2- propoxyanthracene -9,10- dione (Formula 1-8)  Produce

[Chemical Formula 1-8]

In Example 3, 22.4 g of methanol was added instead of n-hexanol, and the same procedure was carried out to obtain a red solid dye.

Example  5: Preparation of sublimation transfer ink composition

The disperse dyes of the prepared examples and comparative examples were mixed in the mixing ratios shown in Table 1 below to prepare transfer inks.

ingredient content(%) dyes The disperse dyes of Examples and Comparative Examples 5.0 Dispersant JONCRYL 67 1.0 Lecithin Powder 1.5 solvent deionized water 67.3 1,2-propane diol 25.0 Surface conditioner BYK-348 0.2

Experimental Example  One: Dischargeability  exam

In order to test the discharging properties of the transfer inks of the Examples and Comparative Examples, the ink was ejected using an inkjet nozzle having a size of 50 mu m, and the time of continuous ejection until the ejection amount was reduced by 5% was measured. , All of which met the requirements of inkjet printing.

Experimental Example  2: Transfer rate test

As shown in Fig. 2, the sublimation transfer ink prepared according to the present invention was mounted on an inkjet printer (Epson, Japan), printed on a transfer paper (Hansol Paper), and dried for 30 hours. The printed transfer paper was placed in a thermocompression press and transferred to a polyester fabric at 190 ° C.

The transfer ratio of the sublimation transfer ink was measured by using a colorimeter (Computer Color Matching System, Coloreye-3100, Macbeth) to measure the apparent density (K / S) of the transfer paper before and after transferring, , 2), and FIG. 3 (Examples 3 and 4, Comparative Examples 3 and 4), and the transfer rates are shown in Table 2 below.

Example Transfer rate Example 1 96.78% Example 2 96.97% Example 3 97.12% Example 4 97.39% Comparative Example 1 93.21% Comparative Example 2 94.27% Comparative Example 3 94.85% Comparative Example 4 95.01%

As shown in FIGS. 2 to 3 and Table 2, the sublimation transfer ink of the comparative example shows a transfer ratio of 95% or less, while the sublimation transfer ink of the present invention shows a significant difference at a high transfer rate of 97% or more can do. It can be seen that, when the amine position of the coupler is replaced by an alkyl group having 6 or more carbon atoms, the transfer ratio in DTP is significantly increased as in the present invention.

Claims (10)

An anthraquinone disperse dye represented by the following formula (1).
[Chemical Formula 1]

In this formula,
R ₁ is a C ₆ to C ₈ alkyl group,
R ₄ , R ₃ , R ₄ and R ₅ are each independently H, OH, NH ₂ or NHCH ₃ .
The method according to claim 1,
An anthraquinone disperse dye represented by the following formula (2).
(2)

R ₁ is a C ₆ to C ₈ alkyl group,
R ₄ and R ₅ are each independently H, OH, NH ₂ , NHCH ₃ .
The method according to claim 1,
An anthraquinone disperse dye represented by the following formula (3).
(3)

In this formula,
R ₁ is a C ₆ to C ₈ alkyl group. A sublimation transfer ink composition comprising the anthraquinone based dispersion dye according to any one of claims 1 to 3.
The sublimation transfer ink composition according to claim 4, further comprising an aqueous polymer, a dispersant, a wetting agent and a solvent.
6. The method of claim 5,
The aqueous polymer is a sublimation transfer ink composition wherein the polymer comprises a urethane group, a copolymer containing a urethane group, a polymer containing an acrylic group, a copolymer containing an acrylic group, and a mixture thereof.
6. The method of claim 5,
Wherein the dispersant is an anionic dispersant comprising a formaldehyde condensate of lignin sulfonic acid, a formaldehyde condensate of alkyl naphthalene sulfonic acid, and a formaldehyde condensate of creosote oil sulfonic acid.
6. The method of claim 5,
Wherein the solvent is water, deionized water, a water-soluble organic solvent, and a water-miscible organic solvent.
9. The method of claim 8,
Wherein the organic solvent is a sulfur compound of an alcohol-based solvent, a ketone-based solvent, a polyhydric alcohol-based solvent, a nitrogen-containing solvent, dimethylsulfoxide, tetramethylsulfone and thioglycol.
6. The method of claim 5,
Wherein the wetting agent comprises diethylene glycol, glycerol, and diethylene glycol monobutyl ether.

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