TW202124606A - Coloring liquid, coloring liquid set, recording medium, and coloring method - Google Patents

Abstract

The present invention provides a coloring liquid containing C. I. Acid Red 260 and a triethylene glycol alkyl ether compound, a coloring liquid set including the coloring liquid, a recording medium to which the coloring liquid is attached, and a coloring method using the coloring liquid or the coloring liquid set.

Description

Coloring liquid, coloring liquid set, recording medium and coloring method

The present invention relates to a coloring liquid, a coloring liquid set provided with the coloring liquid, a recording medium attached with the coloring liquid, and a coloring method using the coloring liquid or the coloring liquid set.

The inkjet recording method is a recording method in which ink droplets fly from an inkjet head toward a recording medium (paper, cloth, etc.), and the ink droplets adhere to the recording medium. The inkjet recording method has the following advantages: its mechanism is relatively simple and inexpensive; it can form high-definition and high-quality images; it can record at high speeds; it has less noise during recording; it is easy to record colors. Therefore, it has been rapidly popularized in recent years. Gradually develop. The inkjet recording method has a continuous method for making droplets fly continuously, and an ON-DEMAND method for making droplets fly according to image information signals. In addition, the discharge method can include: the method of applying pressure by a piezoelectric element to discharge the liquid drop; the method of discharging the liquid droplet by generating bubbles in the ink by heat; the method of using ultrasonic waves; the method of attracting by electrostatic force And the way to spit out droplets, etc. Examples of inks suitable for such inkjet recording include water-based inks, oil-based inks, solid (melt type) inks, and the like.

In addition, the printing and dyeing methods for printing images on cloth and the like are known: screen printing and dyeing method, roller printing and dyeing method, rotary screen printing and dyeing method, transfer printing and dyeing method, etc. However, these printing and dyeing methods must prepare expensive screen frames, engraving rollers, transfer paper, etc. each time the image design is changed. Therefore, it is not suitable for multi-item and small-scale production in terms of cost, and it is difficult to respond quickly. The diversification of fashion. In order to solve the shortcomings of such conventional printing and dyeing methods, a technique has been developed to read samples with a scanner, perform image processing with a computer, and print the results by inkjet recording (hereinafter, also referred to as "inkjet printing and dyeing"). "). If such an inkjet recording method is applied, there is no need to make a plate required by the previous printing and dyeing method, and an image with excellent color gradation can be formed quickly, so it can cope with shortened delivery time, multiple items, and low-volume production. In addition, the inkjet printing and dyeing system uses only the necessary amount of ink when forming an image, so compared to the previous screen printing and the like, it also has environmental advantages such as less waste liquid. On the other hand, the ink used in inkjet printing and dyeing is required to have dye solubility, storage stability, wet fastness, light resistance and other properties.

C.I. Acid Red 260 is a dye with excellent wet fastness and light fastness, but it has the problem of poor solubility or poor storage stability when used as a coloring liquid. At the same time, when the coloring liquid is used for inkjet recording, it is required to have excellent discharge stability. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2000-265097 A [Patent Document 2] Japanese Special Publication No. 2007-515561

[The problem to be solved by the invention]

The subject of the present invention is to provide a coloring liquid, a coloring liquid set provided with the coloring liquid, a recording medium attached with the coloring liquid, and a coloring method using the coloring liquid or the coloring liquid set, the coloring liquid containing CI acid Red 260 has excellent storage stability and excellent discharge stability when used in inkjet recording. [Means to solve the problem]

The specific methods used to solve the above-mentioned problems include the following implementation aspects. 1) A coloring solution containing C.I. Acid Red 260 and a triethylene glycol alkyl ether compound. 2) The coloring liquid according to 1), wherein the triethylene glycol alkyl ether compound is a triethylene glycol monoalkyl ether compound. 3) The coloring solution according to 2), wherein the triethylene glycol monoalkyl ether compound includes at least one selected from triethylene glycol monobutyl ether and triethylene glycol monomethyl ether. 4) The coloring solution as described in any one of 1) to 3), which contains a compound whose LogP value is less than 1. 5) The coloring solution described in 4) contains more than two compounds with a LogP value of less than 1. 6) The coloring solution according to 4) or 5), wherein the aforementioned compound with a LogP value of less than 1 includes the group selected from the group consisting of triethylene glycol, diethylene glycol, and diethylene glycol alkyl ether compounds At least one of the group. 7) The coloring liquid according to any one of 1) to 6), which contains at least one selected from a moisturizer and a surfactant. 8) A coloring liquid set comprising the coloring liquid described in any one of 1) to 7) and a coloring liquid of at least one different hue from the coloring liquid phase. 9) A recording medium to which the coloring liquid described in any one of 1) to 7) is attached. 10) The recording medium according to 9), wherein the recording medium is cloth. 11) A coloring method in which the coloring liquid described in any one of 1) to 7) or the coloring liquid set included in the coloring liquid set described in 8) is attached to a recording medium for coloring. [Effects of Invention]

According to the present invention, it is possible to provide a coloring liquid, a coloring liquid set provided with the coloring liquid, a recording medium attached with the coloring liquid, and a coloring method using the coloring liquid or the coloring liquid set, the coloring liquid containing CI acid Red 260 has excellent storage stability and excellent discharge stability when used in inkjet recording.

＜Coloring liquid＞ The coloring solution of this embodiment contains C.I. Acid Red 260 and a triethylene glycol alkyl ether compound. "C.I." is the abbreviation for color index. Hereinafter, each component contained in the coloring liquid of this embodiment will be explained in detail.

[C.I. Acid Red 260] Relative to the total mass of the coloring liquid, the content of C.I. Acid Red 260 is preferably 0.2 to 20% by mass, and more preferably 1 to 10% by mass.

[Triethylene glycol alkyl ether compound] Examples of triethylene glycol alkyl ether compounds include: triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monoisopropyl ether, Triethylene glycol monobutyl ether, triethylene glycol monododecyl ether and other triethylene glycol monoalkyl ether compounds; triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol Triethylene glycol dialkyl ether compounds such as ethylene glycol dibutyl ether and triethylene glycol butyl methyl ether. These compounds may be used singly, or two or more of them may be used in combination. Among the triethylene glycol alkyl ether compounds, triethylene glycol monoalkyl ether compounds are preferred, and at least one selected from triethylene glycol monomethyl ether and triethylene glycol monobutyl ether is more preferred. good.

Relative to the total mass of the coloring liquid, the total content of the triethylene glycol alkyl ether compound is preferably 0.5 to 90% by mass, more preferably 1 to 80% by mass, and even more preferably 2 to 50% by mass good.

[Compounds with LogP value less than 1] The coloring solution of this embodiment preferably further contains a compound with a LogP value of less than 1. The LogP value is the logarithmic value of the 1-octanol/water partition coefficient, which is an indicator of the hydrophilicity/hydrophobicity of a substance. The LogP value can use either the calculated value or the actual measured value.

Compounds with a LogP value of less than 1 include, for example, monohydric alcohols such as methanol, ethanol, and isopropyl alcohol; ketones or ketone alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; diethylene glycol , Triethylene glycol, tetraethylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol and other ethylene oxide or propylene oxide addition polymers; ethylene glycol, propylene glycol, 1,3-propylene glycol, butylene glycol , Hexanediol and other C2-6 alkanediols; 1,2,6-hexanetriol and other triols; glycerol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethyl Lower alkyl ethers of polyols such as glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether Lower dialkyl ethers of polyols such as ether, tetraethylene glycol dimethyl ether, and tetraethylene glycol diethyl ether; 2-pyrrolidone, ε-caprolactam, N-methyl-2- Pyrrolidone and other compounds having a lactam structure. These compounds may be used singly or in combination of two or more, preferably two or more in combination.

Among the compounds whose LogP value is less than 1, the coloring solution of this embodiment preferably contains at least 1 selected from the group consisting of triethylene glycol, diethylene glycol, and diethylene glycol alkyl ether compounds Species (hereinafter, also referred to as "triethylene glycol, etc."), and more preferably contain triethylene glycol. Examples of the diethylene glycol alkyl ether compound include diethylene glycol monoalkyl ether compounds and diethylene glycol dialkyl ether compounds.

In addition, when the coloring solution of the present embodiment contains triethylene glycol or the like, it is preferable to adjust the ratio of triethylene glycol or the like to the above-mentioned triethylene glycol alkyl ether compound. For example, the ratio of triethylene glycol to triethylene glycol alkyl ether compound in the coloring liquid is preferably 10:1 to 1:10 in terms of mass ratio, and more preferably 5:1 to 1:5 Best, 2:1 to 1:2 is even better. Moreover, when the content of C.I. Acid Red 260 in the coloring liquid is set to 1 part by mass, the content of triethylene glycol and triethylene glycol alkyl ether compound is preferably 0.5 parts by mass or more.

Relative to the total mass of the coloring liquid, the total content of compounds with a LogP value of less than 1 is preferably 0.5 to 90% by mass, more preferably 1 to 80% by mass, and even more preferably 2 to 50% by mass .

[Humectant and Surfactant] The coloring liquid of this embodiment preferably further contains at least one selected from a moisturizer and a surfactant, and more preferably contains both a moisturizer and a surfactant.

Examples of humectants include methyl urea, ethyl urea, N,N'-diethyl urea, urea, thiourea, ethylene urea, N,N'-dihydroxy ethyl urea, diglycerin, polyglycerin, polyglyceryl Ether compounds (SC-P750, SC-P1000, SC-P1600, etc. manufactured by Sakamoto Pharmaceutical Co., Ltd.), etc.

When the coloring liquid of this embodiment contains a humectant, the content of the coloring liquid is preferably 1 to 20% by mass, and more preferably 3 to 10% by mass relative to the total mass of the coloring liquid.

Examples of the surfactant system include various surfactants such as anionic, cationic, amphoteric, and nonionic. Among these, nonionic surfactants are preferred.

The anionic surfactant system includes, for example, alkylsulfonate, α-olefin sulfonate, polyoxyethylene alkyl ether acetate, N-amino acid or its salt, and N-acyl methyl cattle. Sulfonate, Alkyl Sulfate Polyoxyalkyl Ether Sulfate, Alkyl Sulfate Polyoxyethylene Alkyl Ether Phosphate, Rosinic Acid Stone Ion, Castor Oil Sulfate, Lauryl Alcohol Sulfate, Alkylphenol Type Phosphoric acid ester, alkyl phosphate, alkyl aryl sulfonate, diethyl sulfosuccinate, diethylhexyl sulfosuccinate, dioctyl sulfosuccinate, etc.

Examples of the cationic surfactant system include 2-vinylpyridine derivatives and poly4-vinylpyridine derivatives.

Amphoteric surfactants include, for example, lauryl dimethyl amino acetate betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolium betaine, coconut oil fatty acid amide propyl dimethyl Betaine, polyoctylpolyaminoethylglycine, imidazoline derivatives, etc.

Examples of nonionic surfactants include: polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, Polyoxyethylene lauryl ether, polyoxyethylene alkyl ether and other ether series; polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate Esters, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, etc.; 2,4,7,9-tetra Methyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3- Alcohols and other acetylene alcohols; product names Surfynol 104, 105PG50, 82, 420, 440, 465, 485, OLFINE STG, etc. manufactured by Nissin Chemical Industry Co., Ltd. Among these, Surfynol is preferred, Surfynol 104PG50, Surfynol 440, and Surfynol 465 are more preferred, and Surfynol 440 and Surfynol 465 are even more preferred.

When the coloring liquid of this embodiment contains a surfactant, the content of the coloring liquid is preferably 0.01 to 1% by mass, and more preferably 0.1 to 1% by mass relative to the total mass of the coloring liquid.

[water] The coloring liquid of this embodiment preferably further contains water. The water is preferably one with less impurities such as ion-exchanged water and distilled water.

When the coloring liquid of this embodiment contains water, the content of the coloring liquid is preferably 10 to 95% by mass, and more preferably 25 to 85% by mass relative to the total mass of the coloring liquid.

[Other ingredients] In addition to the above, the coloring liquid system of this embodiment may further contain preparation agents such as a pH adjuster and an antiseptic and antifungal agent. With respect to the total mass of the coloring liquid, the total content of these preparations is usually 0 to 10% by mass, preferably about 0.05 to 5% by mass.

As long as the pH adjuster is one whose pH of the colorable liquid is controlled in the range of 6.0 to 11.0, any substance can be used. Examples of pH adjusting agents include alkanolamines such as diethanolamine, dimethylethanolamine, diethylethanolamine, and triethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonium hydroxide (Ammonia); carbonates of alkali metals such as lithium carbonate, sodium carbonate, potassium carbonate, etc.; ginseng (hydroxymethyl) aminomethane, etc. Among these, triethanolamine is preferred. Relative to the total mass of the coloring liquid, the content of the pH adjuster is usually 0.01 to 2% by mass, preferably 0.05 to 1% by mass.

Examples of antiseptic and antifungal agents include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2-benzisothiazoline- 3-ketone, 1-benzisothiazolin-3-one amine salt, PROXEL GXL, PROXEL XL2 manufactured by LONZA JAPAN Co., Ltd., etc. Among these, PROXEL GXL and PROXEL XL2 are preferred.

[Preparation method of coloring liquid, etc.] The coloring liquid of this embodiment is obtained by mixing the above-mentioned components to form a solution. The order of adding each component is not particularly limited. When a coloring liquid is used as the ink for inkjet recording described later, it is preferable to perform precision filtration using a filter membrane or the like. The pore size of the filter membrane is usually 0.1 to 1 μm, preferably 0.1 to 0.8 μm.

When the viscosity of the coloring solution of this embodiment is measured with an E-type viscometer at 25°C, it is preferably 30 mPa·s or less. In addition, when the surface tension of the coloring solution of the present embodiment is measured by the plate method at 25°C, it is preferably about 20 to 70 mN/m, and more preferably about 25 to 60 mN/m. When the coloring liquid is used as the ink for inkjet recording described later, it is better to adjust to appropriate values in consideration of the discharge volume, response speed, flight characteristics of droplets, and inkjet head characteristics of the inkjet printer used.

[Use of coloring liquid] The coloring liquid of this embodiment can be used for various recording purposes such as printing, photocopying, marking, writing, drawing, and printing, but is particularly suitable for inkjet recording.

When the coloring liquid of this embodiment is used as ink for inkjet recording, the coloring liquid of this embodiment can be used directly, or other additives can be added as needed. Other additives include, for example, drying inhibitors (wetting agents), fading inhibitors, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, antifungal agents, pH adjusters, surface tension adjusters, and defoamers , Viscosity adjusters, dispersants, dispersion stabilizers, rust inhibitors, chelating agents, moisturizers, solubilizers and other well-known additives. In the case of water-based inks, these various additives are directly added to the ink. When the oil-soluble dye is used in the form of a dispersion, these various additives are generally added after the preparation of the dye dispersion, but it can also be added to the oil phase or the water phase when the dye dispersion is prepared.

When using the coloring liquid of this embodiment as the ink for inkjet recording, it is preferable to contain 0.2 to 10% by mass of C.I. Acid Red 260 in the ink for inkjet recording. C.I. Acid Red 260 and other pigments can also be used together in the ink system for inkjet recording. When two or more dyes are used in combination, the total content of the dyes is preferably in the above range.

＜Coloring liquid set＞ The coloring liquid of this embodiment can be used not only for monochromatic image formation, but also for full-color image formation. For example, in order to form a full-color image, the coloring liquid of this embodiment is used as the magenta coloring liquid. It can be set as a three-primary color coloring liquid set with blue coloring liquid and yellow coloring liquid added, and furthermore, it can be set as A coloring liquid set of 4 colors including black coloring liquid added to it. In addition, in order to form a higher-definition image, the coloring liquid of this embodiment is used as the red coloring liquid. It can also be added with magenta coloring liquid, light magenta coloring liquid, blue coloring liquid, and green coloring. Coloring liquid set of liquid, orange coloring liquid, dark yellow coloring liquid, gray coloring liquid, etc. In particular, it is preferable to use the coloring liquid of this embodiment as a magenta coloring liquid, and it is preferable to set it as a coloring liquid set to which a blue coloring liquid is added. Moreover, using the coloring liquid of this embodiment as a magenta coloring liquid, a red coloring liquid, or a ruby coloring liquid, it can also be set as a coloring liquid set which added the coloring liquid of a different hue. For example, the coloring liquid of this embodiment may be used as a magenta coloring liquid to form a set with a red coloring liquid, or the coloring liquid of this embodiment may be used as a red coloring liquid and combined with a magenta coloring liquid to form a set. The coloring liquid of the form is used as rubin red coloring liquid and forms a set with magenta coloring liquid or red coloring liquid. Examples of the pigment system contained in the coloring solution that forms a set with the coloring solution of this embodiment include: known yellow pigments, known magenta pigments, known blue pigments, and known black pigments.

Known yellow pigments include, for example, azo pigments having aryl and/or heteroaryl groups; methine pigments such as benzylidene pigments and monomethine oxonol pigments; naphthalene Quinone pigments, anthraquinone pigments and other quinone pigments; quinophthalone pigments; nitro/nitroso pigments; acridine pigments; acridinone pigments, etc.

Well-known magenta pigments can be arbitrarily selected from pigments having structures other than CI Acid Red 260, and examples include: azo pigments having aryl and/or heteroaryl groups; azomethine pigments; Aryl pigments, styryl pigments, merocyanine pigments, cyanine pigments, oxonol pigments and other methine pigments; diphenylmethane pigments, triphenylmethane pigments, dibenzo Carbocation pigments such as xanthene pigments; quinone pigments such as naphthoquinone, anthraquinone, and anthrapyridone; condensed polycyclic pigments such as dioxazine pigments; etc.

Known blue pigments include, for example: phthalocyanine pigments, naphthalocyanine pigments, azo pigments having aryl and/or heteroaryl groups; azomethine pigments; arylene pigments, styrene Methine pigments such as merocyanine pigments, cyanine pigments, and oxacyanine pigments; carbocations such as diphenylmethane pigments, triphenylmethane pigments, and xanthene pigments Dyes; quinone dyes such as naphthoquinone, anthraquinone, and anthrapyridone; condensed polycyclic dyes such as dioxazine dyes, etc.

Known black pigments include: metal-containing azo compounds, azo pigments such as disazo, trisazo, or tetraazo; sulfur dyes; carbon black dispersions.

When using the coloring liquid of this embodiment as a magenta coloring liquid, a red coloring liquid, or a Rubin red coloring liquid, use a coloring liquid other than the coloring liquid of CI Acid Red 260, and choose any coloring liquid other than CI Acid Red 260. The structure of the pigment is used.

The coloring liquid system of this embodiment can be used by mixing the above-mentioned pigments and toning. Each coloring liquid used in the coloring liquid set can also be used by mixing the above-mentioned pigments and toning.

＜Coloring method, recording medium＞ The coloring method of the present embodiment is a method of attaching the coloring liquid of the present embodiment or each coloring liquid included in the coloring liquid set to the recording medium to perform coloring. In addition, the recording medium of this embodiment has the coloring solution of this embodiment adhered to it.

Recording media include: plain paper, resin-coated paper, inkjet paper, glossy paper, glossy film, electronic photo sharing paper and other information transmission sheets; fiber (cotton, linen, nylon, wool, silk, etc.), cloth ; Glass; Metal; Ceramics; Leather; Substrates for color filters, etc. The recording medium is preferably a sheet-like one, but it may have a three-dimensional shape such as a spherical shape or a rectangular parallelepiped shape other than the sheet-like shape.

The method of adhering the coloring liquid to the recording medium is not particularly limited, and, for example, an inkjet recording method is preferable.

When forming an inkjet recording image, simply fill a container containing a coloring liquid (ink for inkjet recording) in a predetermined position of the inkjet printer, and discharge droplets of the coloring liquid to the recording medium to adhere to it. To form a recorded image. Inkjet printers include: a piezoelectric printer that uses mechanical vibration; a bubble jet printer (registered trademark) printer that uses bubbles generated by heating. Either method can be used.

Suitable recording media that can be used for inkjet recording include, for example, those having an ink-receiving layer on a substrate such as paper, synthetic paper, and film. The ink-receiving layer is made by impregnating or coating the above-mentioned substrate with a cationic polymer; combining porous silica, alumina sol, special ceramics, and other inorganic particles that can absorb the pigment in the coloring liquid, and polyvinyl alcohol , Polyvinylpyrrolidone and other hydrophilic polymers are applied to the surface of the substrate together. The recording medium provided with such an ink-receiving layer is generally called inkjet paper (film), glossy paper (film), and the like. Representative examples of special papers that can be obtained from commercially available products are: Cannon Co., Ltd. product name: Photo paper, glossy Pro "platinum grade", photo paper, glossy gold; Seiko Epson Co., Ltd. product name Photo paper Crispia (high gloss), photo paper (gloss), photo matte paper; Japanese Hewlett-Packard Co., Ltd. product name is Advance photo paper (gloss); Brother Co., Ltd. product name is Premium plus glossy photo paper etc. In addition, of course, plain paper can also be used. Specifically, it can be listed: Cannon Co., Ltd. product name is PB paper GF500; SEIKO EPSON Co., Ltd. product name is two-sided plain paper; PPC (plain paper copy) Use paper etc.

When forming an inkjet recording image, for the purpose of imparting gloss or water resistance to the image, or for improving weather resistance, a polymer fine particle dispersion (also referred to as a polymer emulsion) can also be used. The timing of applying the polymer emulsion to the recording medium may be before, after, or at the same time when the ink is applied to the recording medium. In other words, it is possible to record with ink for inkjet recording on a recording medium containing a polymer emulsion, or it may be possible to include a polymer emulsion in the printing ink. In addition, the polymer emulsion can be applied to the recording medium as a single liquid substance before or after recording on the recording medium by the ink.

In addition, a preferable recording medium used for inkjet recording includes cloth. The fabric system preferably contains cellulose-based fibers, polyamide-based fibers, and the like. Examples of the cellulosic fiber system include cotton, hemp, rayon, polynosic, and the like. Examples of polyamide-based fibers include silk, wool, nylon, and the like. The fabric containing cellulose-based fibers or polyamide-based fibers is preferably 100% cellulose-based fibers or polyamide-based fibers, but may also include other raw materials. The blending ratio of cellulose fibers or polyamide fibers is preferably 30% or more, and more preferably 50% or more.

＜Inkjet printing and dyeing method of fabric＞ The inkjet printing and dyeing method of fabric includes using the coloring solution of this embodiment as the printing ink, and performing at least the following steps in sequence.

[Printing and Dyeing Step] The inkjet printing and dyeing method of fabric includes a printing and dyeing step of applying coloring liquid to the fabric. The fabric is preferably a fabric containing cellulose fibers or polyamide fibers.

[Pre-processing steps] The inkjet printing and dyeing method of the fabric may also include the step of applying a pretreatment agent to the fabric as a step before the printing and dyeing step in order to promote the immobilization reaction of the dye in the printing and dyeing step.

(Pretreatment agent) Examples of the pretreatment agent system include those containing components such as a solubilizing agent, a water-soluble metal salt, a pH adjuster, a pH buffering agent, a polymer component, and a surfactant.

The solubilizing agent generally plays a role of increasing the color density of the image when the cloth to which the coloring liquid is imparted is heated under steam. Examples of the solubilizing agent system include urea, alkyl urea, ethylene urea, propylene urea, thiourea, guanidine salt, and tetraalkylammonium halide.

Examples of water-soluble metal salts include compounds that form typical ionic crystals like halides of alkali metals or alkaline earth metals, and have a pH of 4 to 10. Representative examples of such compounds include alkali metal salt systems such as NaCl, Na ₂ SO ₄ , KCl, and CH ₃ COONa, and alkaline earth metal salt systems include CaCl ₂ , MgCl ₂ and the like. Among them, salts of Na, K, and Ca are preferred.

The pH adjuster generally plays a role in improving the immobilization reaction of various dyes to the fabric. Here, the so-called pH adjuster is a compound or composition that adjusts the pH of the printing ink applied to the fabric, and changes the pH of the printing ink. Examples of the pH adjusting agent include alkali, acid, or a combination of alkali and acid.

The pH buffer system, like the pH adjuster, plays a role in improving the immobilization reaction of various dyes to the fabric. Examples of the pH buffer system include sodium bicarbonate, sodium carbonate, ammonium sulfate, and sodium acetate.

The polymer component generally plays a role as a paste for imparting various dyes to the fabric. The polymer component may be either a natural polymer compound or a synthetic polymer compound, but when the coloring liquid contains water, a water-soluble polymer is preferred. Examples of water-soluble polymer systems include starch materials such as corn and wheat; cellulose polymer compounds such as carboxymethyl cellulose, methyl cellulose, and hydroxyethyl cellulose; sodium alginate, acacia gum, and locust bean gum , Trant gum (trant gum), guar gum, Tamarindus (Tamarindus) seeds and other polysaccharide-based water-soluble polymer compounds; gelatin, casein and other protein-based substances; tannic acid-based substances; lignin-based substances and other natural Water-soluble polymer compound. In addition, the synthetic water-soluble polymer compound system includes, for example, known polyvinyl alcohol-based compounds, polyethylene oxide-based compounds, acrylic acid-based water-soluble polymer compounds, and maleic anhydride-based water-based polymer compounds. Among these, polysaccharide-based water-soluble polymer compounds or cellulose-based polymer compounds are preferred.

Surfactants include: anionic, nonionic, cationic, and amphoteric surfactants. The anionic, nonionic, and amphoteric surfactants can be the same as those listed in the ink composition. In particular, nonionic surfactants with an HLB value of 12.5 or more are preferred, and the HLB value is 14 The above nonionic surfactants are more preferable. As the cationic surfactant system, alkylamine salts, quaternary ammonium salts, etc. can be used. The amphoteric surfactant system uses betaine type and the like.

The pre-treatment agent can also contain additives such as anti-reducing agent, antioxidant, leveling agent, heavy dyeing agent, etc. according to the characteristics of the dye used.

The pretreatment agent may be a mixture prepared by mixing various components such as a solubilizing agent and a surfactant to the fabric, or each component may be sequentially applied to the fabric.

The method of applying the pretreatment agent to the fabric includes a dipping method, a flat paddle method, a coating method, a spraying method, an inkjet method, and the like. Among these, the pretreatment agent is applied at a drawing rate of 5 to 150%, preferably in the range of 10 to 130%.

[Post-processing steps] The fabric after the printing and dyeing step preferably undergoes a post-treatment step, thereby promoting the nailing of the dye to the fabric, and thereafter, it is better to sufficiently remove the unfixed dye, other components, and the pretreatment agent. The post-processing steps are usually divided into several steps. For example, it can be set as a post-processing step by sequentially performing a preliminary drying step, a steaming step, a washing step, and a drying step.

(Preparatory drying step) First, after the printing and dyeing step, it is preferable to place the fabric to which the coloring liquid has been applied at room temperature to 150°C for 0.5 to 30 minutes, and to preliminarily dry the coloring liquid. This preliminary drying can increase the printing density and effectively prevent bleeding. The preliminary drying system also includes the penetration of the coloring liquid into the fabric. In addition, heating and drying can also be carried out in continuous steps. For example, the fabric is formed into a roll and supplied to an inkjet printer for printing. After that, the fabric on which an image has been formed can be dried using a dryer. The dryer can be directly connected to the inkjet printer or separated from the inkjet printer. The drying of the fabric on which the image has been formed is preferably carried out at room temperature to 150°C for 0.5 to 30 minutes. Preferable drying methods include: air convection method, direct contact heating roller method, irradiation method, and the like.

(Steam step) The steaming step is a step of exposing the fabric to which the coloring liquid has been given to saturated steam to promote the immobilization of the dye on the fabric. In the steaming step in the post-treatment, it is preferable to change the conditions, especially the time, according to the type of fabric. For example, when the cloth is wool, the time of the steaming step is preferably 1 to 120 minutes, more preferably 3 to 60 minutes. Moreover, when the fabric is polyamide, the time of the steaming step is preferably about 1 to 30 minutes.

(Washing step) Through the above steps, most of the dye is fixed to the fabric, but some of the dye is not dyed to the fabric. It is better to rinse off the unfixed dye first. The removal of unfixed dyes can be done by conventionally known cleaning methods. For example, it is preferable to use water or warm water in the range of normal temperature to 100°C, or to use an anionic or nonionic soaping agent. When the unfixed dye is not completely removed, good results may not be obtained in various wet fastnesses, such as washing fastness and sweat fastness.

(Drying step (drying after washing)) The cloth must be dried after washing. The drying step is to squeeze or dewater the washed cloth, and then dry it or use a dryer, heating roller, electric iron, etc. to dry it.

The inkjet printing method described above is preferably a method of applying the coloring solution of this embodiment to a fabric containing polyamide fibers or cellulose fibers. By applying the coloring liquid of the present embodiment to a fabric containing polyamide fibers or cellulose fibers, a good hue can be exhibited, and a colored portion with excellent color rendering and fastness can be formed. In addition, the dyed part of the fabric printed with the coloring liquid of this embodiment exhibits a good hue, and is excellent in color rendering and fastness. In particular, when printing on a fabric containing polyamide fibers, a dyed portion exhibiting high color rendering properties, excellent color rendering properties, and printing characteristics can be formed on the fabric compared to using conventional coloring liquids.

＜Dyeing method of fabric other than inkjet printing＞ The dyeing method of cloth is roughly divided into dip dyeing method and printing dyeing method. The so-called dip dyeing method is a dyeing method in which the dyed fabric is immersed in a dye solution in which the dye is dissolved or dispersed in a solvent, uniformly adsorbed on the surface of the fiber, and the dye is diffused into the fiber, and then dyed by bonding. The so-called printing and dyeing method is a method in which dyes or pigments are applied to the dyed cloth to obtain a pattern. The dyeing method is used to dye or fix the dye to produce a dyed product with a pattern. The pattern effect appears on the cloth. Nowadays, in the industry, screen printing and dyeing with rollers, transfer printing with transfer paper, and inkjet printing without plate making are carried out in the industry.

[Screen printing and dyeing, roller printing and dyeing, transfer printing and dyeing] When performing screen printing, roller printing, or transfer printing, the above-mentioned coloring liquid is used as a color paste, and the color paste is printed on a fabric through a printing plate or transfer paper. The fabric printing and dyeing method preferably includes at least the following steps (1) to (4). (1) The step of adding a coloring liquid to a liquid containing at least a polymer compound and water to prepare a color paste, (2) The step of printing the color paste of (1) above on the fabric, (3) The step of blowing steam onto the printed fabric, (4) The step of washing the printed fabric with water and drying the washed fabric.

The color paste preferably satisfies the printability that is suitable for printing on a printing plate, and the necessary printing and dyeing properties such as dyeing and washing. Therefore, for the purpose of imparting printability and printability, the color paste system may include pastes, solvents, dyeing auxiliary agents, etc., in addition to dyes.

The paste is preferably a water-soluble polymer. Examples of the water-soluble polymer system include well-known natural polymers such as starches, seaweeds, natural gums, cellulose derivatives, sodium alginate, protein materials, tannic acid-based materials, and wood-based materials. In addition, well-known synthetic polymers such as polyvinyl alcohol-based compounds, polyethylene oxide-based compounds, acrylic water-based polymers, styrene-based water-based polymers, and maleic anhydride-based water-based polymers are also used as pastes.

For the solvent system, for example, it is preferable to use a water-soluble solvent, and it is preferable to use a solvent containing at least water.

Examples of dyeing auxiliary agents include: developer (acid, alkali, etc.), dye solubilizer, wetting agent, humectant, heavy dye, anti-reduction agent, metal ion blocking agent, ultraviolet absorber, dispersant, level dyeing Agents, de-staining agents, preservatives, anti-mold agents, antioxidants, migration inhibitors, dye fixatives, defoamers, etc.

The step of preparing the color paste is preferably to add a dyeing auxiliary to the paste solution in which the paste is dissolved or dispersed in a solvent, and then add the dye solution in which the dye is dissolved or dispersed in the solvent and stir to prepare the color paste.

The printing and dyeing method is different from the dip-dyeing method. After the fabric is printed with the color paste (the step of printing the color paste on the fabric), the color material printed on the fabric is dyed to the fiber. This step is called the "color development step". There are methods that use heated air, and methods that use saturated steam at normal pressure or superheated steam. The method using saturated steam at normal pressure is preferred. In the step of blowing out steam on the printed fabric, the temperature and time for steam treatment vary according to the type of color paste or the type of fabric, but the temperature is preferably from 90 to 140°C, and from 100 to 108°C For better. The time is preferably 1 to 60 minutes, more preferably 10 to 40 minutes. After blowing out the steam on the printed fabric, it goes through the same washing and drying steps as the dip dyeing method to obtain the printed fabric. [Example]

Hereinafter, the present invention will be explained in more detail through examples, but the present invention is not limited by the examples. As long as there is no special statement in the examples, "parts" means parts by mass, and "%" means% by mass. In addition, the printing ink in each embodiment is contained in the above-mentioned coloring liquid.

<Examples 1 to 9, Comparative Examples 1 to 4: Preparation of coloring liquid> The components shown in the following Tables 1 and 2 were mixed and stirred for 1 hour while maintaining at about 50°C, thereby preparing 13 types of coloring liquids of Examples 1 to 9 and Comparative Examples 1 to 4. The "water" ion-exchange water used for the preparation of the coloring liquid is adjusted by adding water so that the total amount becomes 100 parts. The abbreviations in Tables 1 and 2 respectively indicate the following. TEG: Triethylene glycol (manufactured by Kanto Chemical Co., Ltd.) TEGMBE: Triethylene glycol monobutyl ether (manufactured by Kanto Chemical Co., Ltd.) TEGMME: Triethylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.) 2Py: 2-pyrrolidone (manufactured by Tokyo Chemical Industry Co., Ltd.) Gly: Glycerin (manufactured by Kanto Chemical Co., Ltd.)

[Table 1] Example 1 2 3 4 5 6 7 8 9 CI Acid Red 260 10 10 10 10 10 10 10 10 10 TEG 5 10 15 20 15 30 10 20 - TEGMBE 5 10 15 20 - 30 20 10 20 TEGMME - - - - 15 - - - - 2Py - - - - - - - - - Gly - - - - - - - - - water Remnants Remnants Remnants Remnants Remnants Remnants Remnants Remnants Remnants total 100 100 100 100 100 100 100 100 100

[Table 2] Comparative example 1 2 3 4 CI Acid Red 260 10 10 10 10 TEG - - 17 15 TEGMBE - - - - TEGMME - - - - 2Py 20 - - 15 Gly - 20 - - water Remnants Remnants Remnants Remnants total 100 100 100 100

＜Evaluation＞ [Solubility Evaluation Test] The solubility of the coloring liquids obtained in Examples 1 to 9 and Comparative Examples 1 to 4 was evaluated. Specifically, the coloring liquid was filtered, the filter residue on the filter paper was visually confirmed, and the evaluation was performed based on the following evaluation criteria. The results are shown in Tables 3 and 4 below. -Assessment benchmarks- A: There is no filter residue and can be completely dissolved. B: There is a little filtering residue. C: There are many filtering residues, but it can be filtered. D: Unable to filter.

[Stability evaluation test over time] The stability over time of the coloring liquids obtained in Examples 1 to 9 and Comparative Examples 1 to 4 was evaluated. Specifically, after leaving the coloring liquid at room temperature for 10 days, it was filtered and the filter residue on the filter paper was visually confirmed, and the evaluation was performed based on the same evaluation criteria as the above-mentioned [Solubility Evaluation Test]. The results are shown in Tables 3 and 4 below.

[Low-temperature stability evaluation test] The low-temperature stability of the coloring solutions obtained in Examples 1 to 9 and Comparative Examples 1 to 4 were evaluated. Specifically, after placing the coloring liquid in a freezer at -8°C for 10 days, it was filtered and the filter residue on the filter paper was visually confirmed, and evaluated based on the same evaluation criteria as the above-mentioned [Solubility Evaluation Test]. The results are shown in Tables 3 and 4 below.

[table 3] Example 1 2 3 4 5 6 7 8 9 Solubility C A A A A A A A A Stability over time C B A A B A A B A Low temperature stability C B A A B A A B C

[Table 4] Comparative example 1 2 3 4 Solubility D A D D Stability over time D D D D Low temperature stability D D D D

It can be seen from Tables 3 and 4 that, compared to the coloring liquids of Comparative Examples 1 to 4, the coloring liquids of Examples 1 to 9 have excellent stability over time and low temperature.

<Examples 10 to 15: Preparation of ink for inkjet recording> The components shown in Table 5 below were mixed and stirred for 1 hour, and filtered with a filter membrane (trade name: cellulose acetate filter paper, manufactured by ADVANTECH) with a pore size of 0.45 μm, thereby preparing Example 10 There are 6 types of inks from 15 to 15. The "water" ion-exchange water used for the preparation of the ink is added and adjusted so that the total amount becomes 100 parts. The abbreviations in Table 5 respectively indicate the following. TEG: Triethylene glycol TEGMBE: Triethylene glycol monobutyl ether 2Py: 2-pyrrolidone Gly: Glycerin TEA: Triethanolamine Surfynol 465: Surfactant (manufactured by Nissin Chemical Industry Co., Ltd.) PROXEL XL2: Antifungal agent (manufactured by LONZA JAPAN Co., Ltd.)

[table 5] Example 10 11 12 13 14 15 CI Acid Red 260 5 5 5 5 5 5 TEG 5 7 10 2 10 10 TEGMBE 10 14 17 19 10 5 Urea 5 5 5 5 5 5 Surfynol 465 0.2 0.2 0.2 0.2 0.2 0.2 Proxel XL2 0.1 0.1 0.1 0.1 0.1 0.1 TEA 0.5 0.5 0.5 0.5 0.5 0.5 2Py 4 4 4 4 4 4 Gly 8 8 8 8 8 8 water Remnants Remnants Remnants Remnants Remnants Remnants total 100 100 100 100 100 100

＜Evaluation＞ [Evaluation test of paper discharge stability] The container filled with the inks of Examples 10 to 15 was filled in an inkjet printer PX-205 (manufactured by SEIKO EPSON Co., Ltd.) to obtain 100%, 80%, 60%, 40%, and 20% of each In the method of 5 levels of density, a gradation image pattern is produced, and inkjet recording is performed on the following 3 types of paper, thereby obtaining a red test print. Paper A: manufactured by SEIKO EPSON Co., Ltd., "photo paper <gloss>" Paper B: Made by Fuji Film Co., Ltd., "Color Painting/Photo Finishing Pro" Paper C: Plain paper

Visually observe the obtained test print, and evaluate whether the image is reproducible according to the following evaluation criteria. The results are shown in Table 6 below. -Assessment benchmarks- A: The image can be reproduced. B: There are several "stripes" or "stripes". C: The image is largely lacking.

[Evaluation test of printing characteristics of test printed matter] Observe the test prints obtained in the above-mentioned [Discharge Stability Evaluation Test on Paper] with a microscope, and evaluate whether the dot diameter is uniform according to the following evaluation criteria. The results are shown in Table 6 below. -Assessment benchmarks- A: The dot diameter is uniform. B: The spot diameter is uneven. C: Unable to print.

[Evaluation test of vomiting stability of cloth] A pretreatment agent containing 2 parts of guar gum, 2 parts of ammonium sulfate, 5 parts of urea, and 91 parts of water was prepared, and the silk cloth was pretreated by the flat slurry method. Specifically, the silk cloth is immersed in the pretreatment agent, and after squeezing off the excess liquid with a rubber roller, it is dried at 60°C. The container filled with the inks of Examples 10 to 15 was filled in an inkjet printer PX-205 (manufactured by SEIKO EPSON Co., Ltd.) to obtain 100%, 80%, 60%, 40%, and 20% of each The five-stage color gradation of the density is used to make a gradual image pattern, which is printed and dyed on the silk cloth after the pre-treatment. After pre-drying the obtained printed matter at 60 to 80°C, it is steamed for 30 minutes under the conditions of a humidity of more than 90% and 100 to 103°C. Thereafter, the printed material was washed with cold water for 5 minutes, and then dried to obtain a red test dyed cloth.

The test dyed cloth obtained by visual observation was evaluated according to the following evaluation criteria to evaluate whether the image is reproducible. The results are shown in Table 6 below. -Assessment benchmarks- A: The image can be reproduced. B: There are several "stripes" or "stripes". C: The image is largely lacking.

[Table 6] Example 10 11 12 13 14 15 Stability of paper spit out A A A A A A Stability of vomiting to cloth A A A A A A Test the printing characteristics of printed matter A A A B A A

It can be seen from Table 6 that the ink systems of Examples 10 to 15 have excellent ejection stability to paper and fabric, and can reproduce images. In addition, the ink-based printing characteristics of Examples 10 to 12, 14, and 15 are also excellent, and test prints with uniform dot diameters can be obtained.

No schema in this case

Claims (11)

A coloring liquid containing C.I. Acid Red 260 and triethylene glycol alkyl ether compound. The coloring solution according to claim 1, wherein the triethylene glycol alkyl ether compound is a triethylene glycol monoalkyl ether compound. The coloring solution according to claim 2, wherein the triethylene glycol monoalkyl ether compound includes at least one selected from the group consisting of triethylene glycol monobutyl ether and triethylene glycol monomethyl ether. The coloring liquid as described in claim 1 or 2 contains a compound whose LogP value is less than 1. The coloring solution described in claim 4 contains two or more compounds with a LogP value of less than 1. The coloring solution according to claim 4, wherein the compound whose LogP value is less than 1 includes at least 1 selected from the group consisting of triethylene glycol, diethylene glycol, and diethylene glycol alkyl ether compounds kind. The coloring liquid according to claim 1 or 2 contains at least one selected from a moisturizer and a surfactant. A coloring liquid kit is provided with the coloring liquid described in any one of claims 1 to 7 and a coloring liquid of at least one different hue from the coloring liquid phase. A recording medium to which the coloring liquid described in any one of claims 1 to 7 is attached. The recording medium according to claim 9, wherein the recording medium is cloth. A coloring method is to apply the coloring liquid described in any one of claims 1 to 7 or each coloring liquid included in the coloring liquid set described in claim 8 to a recording medium to perform coloring.