JP2014080539A - Ink for sublimation transfer, manufacturing method of dyed product and dyed product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink for sublimation transfer having excellent color development property as inkjet ink, especially excellent color tone and chroma as a cyan ink while showing negativity at the Ames test, to provide a manufacturing method of a dyed product using the ink for sublimation transfer, and a dyed product manufactured by using the method.SOLUTION: The ink for sublimation transfer is discharged by an inkjet method and contains water, a water-soluble organic solvent and a sublimable dye, and the sublimable dye contains at least one kind of C.I Solvent Blue 63 and C.I. Solvent Blue 11 and C.I. Disperse Violet 28.

Description

  The present invention relates to a sublimation transfer ink, a method for producing a dyed article, and a dyed article.

  Dyeing of fabrics and the like using sublimation transfer is widely performed. As a dyeing method using such sublimation transfer, printing is performed on a sheet-like intermediate transfer medium such as paper by an ink jet method, and then the intermediate medium is superimposed on an object to be dyed such as a cloth, and sublimation transfer is performed by heating. For example, the ink receiving layer of the object to be dyed (film product etc.) provided with a peelable ink receiving layer is subjected to ink jet printing, and then heated as it is to sublimate and diffuse into the object to be dyed on the lower layer side. There is a method of performing dyeing and then peeling off the ink receiving layer, etc., and ink containing sublimation dye (ink for sublimation transfer) is used for these dyeing methods.

  Conventionally, for dyeing fabrics and the like, a method of coloring using a quinone dye having an auxiliary color group only on one aromatic ring of an anthraquinone structure has been proposed. In addition, it is disclosed that an anthraquinone structure dye has excellent performance as a cyan dye for thermal recording (see, for example, Patent Document 1 and Patent Document 2).

  On the other hand, many anthraquinone dyes are positive in the Ames test used to detect mutagenicity, which is a standard for easily determining whether a substance is carcinogenic. Still has a problem in terms of safety (for example, see Patent Document 3).

JP 2005-126861 A JP-A-8-244366 Japanese Patent Laid-Open No. 11-124510

  An object of the present invention is to provide a sublimation transfer ink which shows negative in the Ames test and has excellent color developability as an inkjet ink, in particular, excellent hue and saturation as a cyan ink, and uses the sublimation transfer ink. Another object of the present invention is to provide a dyed product produced using the above method.

  As a result of intensive studies on the above problems, the present inventor has found that the above object can be achieved by the following present invention.

  The sublimation transfer ink of the present invention is ejected using an ink jet method, and includes water, a water-soluble organic solvent, and a sublimation dye, and the sublimation dye is C.I. I. Solvent Blue 63 or C.I. I. At least one of Solvent Blue 11 and C.I. I. Disperse Violet 28.

  Accordingly, it is possible to provide an ink for sublimation transfer which shows negative in the Ames test and has excellent color developability as an inkjet ink, particularly excellent hue and saturation as a cyan ink. The sublimable dye is C.I. I. Solvent Blue 63, C.I. I. Disperse violet 28 is more preferable.

  In the sublimation transfer ink of the present invention, the C.I. I. Solvent Blue 63 or C.I. I. The content of Solvent Blue 11 or the C.I. I. Solvent Blue 63 and the C.I. I. The content of Solvent Blue 11 and the C.I. I. The weight ratio with respect to the content of the disperse violet 28 is preferably in the range of 1: 1 to 4: 1.

  Thereby, the hue and saturation as a cyan ink can be made more excellent. Note that C.I. I. Solvent Blue 63 or C.I. I. The content of Solvent Blue 11 or C.I. I. Solvent Blue 63 and C.I. I. The content of Solvent Blue 11 and the C.I. I. The weight ratio with respect to the content of disperse violet 28 is more preferably in the range of 1.5: 1 to 2: 1.

  The method for producing a dyed product of the present invention includes an ink application step of applying the sublimation transfer ink of the present invention to an intermediate transfer medium using an inkjet method, and the intermediate transfer medium to which the sublimation transfer ink is applied, A heating step in which the surface to which the sublimation transfer ink is applied and the dyed surface of the object to be dyed are opposed to each other, and the sublimation dye constituting the sublimation transfer ink is transferred to the object to be dyed. It is characterized by having.

  Thereby, the manufacturing method of the dyeing | staining thing using the sublimation transfer ink which can manufacture a dyeing | staining thing with sufficient productivity can be provided.

  In the manufacturing method of the dyeing | staining thing of this invention, it is preferable that the heating temperature in the said transfer process is 160 degreeC or more and 220 degrees C or less.

  Thereby, energy sufficient to transfer the sublimation dye to the dyed object can be obtained, and the productivity of the dyed object can be made particularly excellent. In addition, it is more preferable that the said heating temperature is 170 degreeC or more and 200 degrees C or less.

  The dyed product of the present invention is produced using the sublimation transfer ink of the present invention.

  Thereby, the dyeing | staining excellent in color developability can be provided.

  A preferred embodiment of the sublimation transfer ink according to the present invention is ejected using an ink jet method, and includes water, a water-soluble organic solvent, and a sublimation dye, and the sublimation dye is C. . I. Solvent Blue 63 or C.I. I. At least one of Solvent Blue 11 and C.I. I. Disperse violet 28.

  Accordingly, it is possible to provide a sublimation transfer ink which shows negative in the Ames test and has excellent color developability as an inkjet ink, in particular, excellent hue and saturation as a cyan ink.

≪Ink for sublimation transfer≫
First, the sublimation transfer ink of the present invention will be described.
As a method of dyeing a cloth or the like using sublimation transfer, printing is performed on a sheet-like intermediate transfer medium such as paper by an ink jet method, and then the intermediate medium is superimposed on an object to be dyed such as a cloth and sublimated by heating. For example, the ink receiving layer of a dyed object (film product, etc.) provided with a releasable ink receiving layer is subjected to ink jet printing, and heated as it is, and sublimation diffusion dyeing is performed on the lower dyed object. And then the ink receiving layer is peeled off. In these dyeing methods, ink containing a sublimable dye (ink for sublimation transfer) is used.
In general, sublimation transfer inks contain water in addition to sublimation dyes. In addition, inks containing water-soluble organic solvents are widely used to prevent clogging of nozzles of inkjet heads and ensure ejection stability. It has been.

  Hereinafter, each component constituting the sublimation transfer ink of the present invention will be described.

<Water>
The sublimation transfer ink of the present invention contains water. Water functions as a dispersion medium for dispersing a sublimable dye, which will be described in detail later, and a solvent for dissolving a water-soluble organic solvent.

  By including water in the sublimation transfer ink, the viscosity and surface tension of the sublimation transfer ink can be suitably adjusted so as to be included in a preferable range, and the sublimation transfer ink has excellent dischargeability by the ink jet method. Can be. Moreover, since water is a component that can be easily removed after ejection by the ink jet method, it is also important for increasing the productivity of the dyed product. In addition, since water is a substance that is extremely safe for the human body and the like, it is important for ensuring the safety of workers in the production of dyed products.

  The content of water in the sublimation transfer ink is not particularly limited, but is preferably 50% by mass or more and 90% by mass or less, and more preferably 55% by mass or more and 70% by mass or less.

<Water-soluble organic solvent>
The sublimation transfer ink of the present invention contains a water-soluble organic solvent. Accordingly, it is possible to effectively suppress the evaporation of moisture from the head when left for a long period of time while improving the ejection stability of the ink for sublimation transfer by the ink jet method.

  Examples of the water-soluble organic solvent include polyol compounds, glycol ethers, saccharides, and betaine compounds.

  Examples of the polyol compound include a polyol compound (preferably a diol compound) having 2 to 6 carbon atoms in the molecule and having one ether bond in the molecule. Specific examples include glycerin, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol. 2,3-butanediol, 3-methyl-1,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 3-methyl-1, Examples include 5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, and the like.

  As the glycol ether, for example, a monoalkyl ether of glycol selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol and tripropylene glycol is preferable. More specifically, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monopropyl ether and the like can be preferably exemplified.

  Saccharides refer to monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides. Examples of sugars include threose, erythrulose, erythrose, arabinose, ribulose, ribose, xylose, xylulose, lyxose, glucose, fructose, mannose, idose, sorbose, gulose, talose, tagatose, galactose, allose, psicose, altrose, maltose. , Isomaltose, cellobiose, lactose, sucrose, trehalose, isotrehalose, gentiobiose, melibiose, tulanose, sophorose, isosaccharose, glucan, fructan, mannan, xylan, galacturonan, mannuronan, N-acetylglucosamine polymers, dihetero Heteroglycans such as glycans and triheteroglycans, maltotriose, isomalttrio Scan, panose, maltotetraose, maltopentaose and the like, preferably, trehalose and the like.

  A betaine compound is a compound that has a positive charge and a negative charge at non-adjacent positions in the same molecule, and has no positively charged hydrogen atoms bonded to dissociable hydrogen atoms, so that the molecule as a whole has no charge. (Inner salt). Preferred betaine compounds are N-alkyl substituted amino acids, more preferably N-trialkyl substituted amino acids. Examples of the betaine compound include trimethylglycine (also referred to as “glycine betaine”), γ-butyrobetaine, homarine, trigonelline, carnitine, homoserine betaine, valine betaine, lysine betaine, ornithine betaine, alanine betaine, stachydrine, and betaine glutamate. Preferably, a trimethylglycine etc. can be illustrated.

  The content of the water-soluble organic solvent used in the present invention is preferably 1% by weight to 40% by weight with respect to the total weight of the ink, preferably 5% by weight, from the viewpoint of adjusting the viscosity of the ink and preventing clogging due to the moisturizing effect. More preferably, it is 30 mass% or less. These may be used alone or in combination of two or more.

<Sublimation dye>
The sublimable dye is a dye having a property of sublimation by heating. As the sublimation dye, a disperse dye, a solvent dye or the like having the above properties can be used.

  The sublimation transfer ink of the present invention is C.I. I. Solvent Blue 63 or C.I. I. At least one of Solvent Blue 11 and C.I. I. Disperse violet 28 is included. Any of these sublimation dyes shows a negative result in the Ames test, whereby the sublimation transfer ink of the present invention can provide a sublimation transfer ink that shows a negative result in the Ames test.

  By the way, the Ames test is a mutagenicity test using bacteria. The strain used for the Ames test is a histidine-requiring strain (his-) that cannot synthesize histidine among Salmonella. As a result of the test substance acting on the strain, histidine can be synthesized again. The number of colonies of non-histidine-requiring (his +) revertants is counted to determine the mutagenicity of the substance. Currently, among these strains, TA1535, TA1537, TA100, TA98 or WP2uvrA- are generally used. Of these strains, when TA98 is used, it is often positive with dyes such as anthraquinone structure dyes. The Ames test generally incorporates a direct test in which the substance to be tested acts directly on the microbial cells, and a drug metabolic activation enzyme (so-called S9Mix) obtained from the liver of rats and the like in order to bring the drug metabolism system in microorganisms closer to that of mammals. A metabolic activation test is performed in combination. Usually, a test substance is determined to have a positive Ames test when the number of return colonies in the test of the test substance is more than twice the number of return colonies in the solvent control test (test with the solvent alone). The Ames test in the present invention indicates a test with TA98 and TA100 incorporating S9Mix.

  In addition, C.I. I. Solvent Blue 63 or C.I. I. At least one of Solvent Blue 11 and C.I. I. By including the disperse violet 28, excellent color developability as an inkjet ink, in particular, excellent hue and saturation as a cyan ink can be obtained. Accordingly, it is possible to provide an ink for sublimation transfer which shows negative in the Ames test and has excellent color developability as an inkjet ink, particularly excellent hue and saturation as a cyan ink.

The hue excellent as the cyan ink in the sublimation transfer ink of the present invention is that the hue angle ∠H ° defined in the CIELAB color space on the object to be dyed is in the range of about 250 ° to about 280 °. It shall be shown.
[The hue angle ∠H ° is given by ∠H ° = tan ⁻¹ (b * / a * + 180 (when a * <0) or ∠H ° = tan ⁻¹ (b * / a *) + 360 (a *> 0, where a * and b * represent the perceptual chromaticity index defined in the CIELAB color space.]

Further, the saturation excellent as the cyan ink in the sublimation transfer ink of the present invention indicates that the saturation C * defined in the CIELAB color space on the object to be dyed is 45 or more, and 50 or more. Is more preferable.
[The saturation C * is obtained by C * = [(a *) ² + (b *) ² ] ^1/2 . ]

<Other ingredients>
The sublimation transfer ink of the present invention may contain components other than those described above (other components). Examples of such components include a dispersant, an antiseptic / antifungal agent, a pH adjuster, a chelating reagent, a rust preventive agent, an ultraviolet absorber, an antifoaming agent, a surface tension adjuster, and a polysiloxane compound.

  When the sublimation transfer ink contains a dispersant, the dispersion stability of the sublimation dye in the sublimation transfer ink can be made particularly excellent, the storage stability of the sublimation transfer ink, and the long-term of the sublimation transfer ink. In particular, the discharge stability can be made particularly excellent. In addition, the reliability of the dyed product produced using the sublimation transfer ink can be made particularly excellent.

  The dispersant is not particularly limited, and examples thereof include an anionic dispersant, a nonionic dispersant, and a polymer dispersant.

  Preferred examples of the anionic dispersant include a formalin condensate of aromatic sulfonic acid. Examples of the “aromatic sulfonic acid” in the formalin condensate of aromatic sulfonic acid include creosote oil sulfonic acid, cresol sulfonic acid, phenol sulfonic acid, β-naphthol sulfonic acid, methyl naphthalene sulfonic acid, butyl naphthalene sulfonic acid and the like. Alkylnaphthalenesulfonic acid, a mixture of β-naphthalenesulfonic acid and β-naphtholsulfonic acid, a mixture of cresolsulfonic acid and 2-naphthol-6-sulfonic acid, and ligninsulfonic acid.

  As the anionic dispersant, a formalin condensate of β-naphthalene sulfonic acid, a formalin condensate of alkyl naphthalene sulfonic acid, and a formalin condensate of creosote oil sulfonic acid are preferable.

  Examples of nonionic dispersants include phytosterol ethylene oxide adducts and cholestanol ethylene oxide adducts.

  Examples of the polymer dispersant include polyacrylic acid partial alkyl esters, polyalkylene polyamines, polyacrylates, styrene-acrylic acid copolymers, vinyl naphthalene-maleic acid copolymers, and the like.

  Examples of antiseptic / antifungal agents include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8- Oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, brominated indanone And compounds such as benzyl bromacetate and inorganic salts. Examples of the organic halogen compound include sodium pentachlorophenol, and examples of the pyridine oxide compound include sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, and isothiazoline-based compounds. Examples of the compound include an amine salt of 1-benzisothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, and 5-chloro-2-methyl. -4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4 -Isothiazoline-3-one calcium chloride and the like . Other antiseptic / antifungal agents include sodium dehydroacetate, sodium sorbate, sodium benzoate and the like.

  When the sublimation transfer ink contains a pH adjuster, the storage stability of the sublimation transfer ink can be made particularly excellent. In addition, the reliability of the dyed product produced using the sublimation transfer ink can be made particularly excellent.

  As the pH adjuster, for example, an agent capable of controlling the pH of the sublimation transfer ink in the range of 6.0 to 11.0 can be suitably used. Examples of such pH adjusters include alkanolamines such as diethanolamine, triethanolamine, dimethylethanolamine, and diethylethanolamine; alkaline metal water such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and lithium hydroxide. Examples thereof include oxides; ammonium hydroxide; carbonates of alkali metals such as lithium carbonate, sodium carbonate, and potassium carbonate; aminosulfonic acids such as taurine;

  Examples of the chelating reagent include disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate, and the like.

  Examples of the antirust agent include acidic sulfites, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and benzotriazole compounds.

  Examples of ultraviolet absorbers include benzophenone compounds, cinnamic acid compounds, triazine compounds, stilbene compounds, so-called fluorescent brighteners (compounds that absorb ultraviolet rays typified by benzoxazole compounds), and the like. Is mentioned.

  Examples of antifoaming agents include highly oxidized oil compounds, glycerin fatty acid ester compounds, fluorine compounds, silicone compounds, and acetylene compounds.

  Examples of the surface tension adjusting agent include a surfactant, and examples thereof include an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant.

  Examples of the anionic surfactant include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acylmethyl taurate, alkyl sulfate poly Oxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfonate, diethyl Examples include sulfosuccinate, diethylhexylsylsulfosuccinate, and dioctylsulfosuccinate.

  Examples of the amphoteric surfactant include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, and others. Examples include imidazoline derivatives.

  Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

  Nonionic surfactants include, for example, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and the like. Ether surfactants: polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate Ester surfactants such as rate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne- , 6-diol, 3,5-dimethyl-1-hexyne-3-acetylene glycol (alcohol) based surfactants such as ol.

  By including the polysiloxane compound in the sublimation transfer ink, it is possible to improve the discharge response of the droplet discharge by the ink jet method. Examples of the polysiloxane compound include polyether-modified siloxane and polyether-modified polydimethylsiloxane.

  The surface tension (surface tension at 25 ° C.) of the sublimation transfer ink of the present invention is preferably 20 mN / m or more and 50 mN / m or less, and more preferably 25 mN / m or more and 40 mN / m or less. Note that the surface tension of the sublimation transfer ink can be determined, for example, by measurement according to JIS K3362 using a surface tension meter CBVP-A3 (manufactured by Kyowa Interface Science Co., Ltd.).

  Further, the viscosity (viscosity at 25 ° C.) of the sublimation transfer ink of the present invention is preferably 2 mPa · s or more and 20 mPa · s or less. As a result, the discharge stability of the sublimation transfer ink (discharge volume stability, flight characteristics of droplets, etc.), discharge response (response speed, high frequency compatibility (frequency characteristics), etc.), etc. are particularly excellent. be able to. The viscosity of the sublimation transfer ink can be determined by measurement in accordance with JIS Z8809 using a vibration viscometer.

≪Dye production method≫
Next, the manufacturing method of the dyeing | staining thing of this invention is demonstrated.

  According to the method for producing a dyed product of the present invention, an ink application step (1a) of applying the sublimation transfer ink of the present invention as described above to an intermediate transfer medium using an inkjet method, and the sublimation transfer ink are applied. The intermediate transfer medium is heated in a state where the surface to which the sublimation transfer ink is applied and the dyed surface of the object to be dyed are opposed to each other, thereby transferring the sublimation dye to the object to be dyed (1b). ). Thereby, the manufacturing method of the dyeing | staining thing using the sublimation transfer ink which can manufacture a dyeing | staining thing with sufficient productivity can be provided. Hereinafter, each step will be described in detail.

<Ink application process>
In this step, the sublimation transfer ink of the present invention is applied to the intermediate transfer medium using an inkjet method (1a).

  The ink for sublimation transfer by the inkjet method can be discharged using a known droplet discharge device.

  As a droplet discharge method (inkjet method), a piezo method or a method of discharging ink by bubbles generated by heating the ink can be used. From the viewpoint of difficulty, the piezo method is preferable.

As the intermediate transfer medium, for example, paper such as plain paper, a recording medium provided with an ink receiving layer (referred to as exclusive ink jet paper, coated paper, etc.), etc. can be used. Paper having an ink receiving layer is preferred. Thereby, in the process of drying the sublimation transfer ink applied to the intermediate transfer medium, it is possible to obtain an intermediate recorded matter in which bleeding or the like is suppressed, and in the subsequent transfer step, the sublimation dye is more sublimated. Proceed smoothly.
In this step, a plurality of types of inks may be used. Thereby, for example, the color gamut that can be expressed can be made wider.

<Transfer process>
Thereafter, the intermediate transfer medium to which the sublimation transfer ink has been applied is heated while facing the object to be dyed, and the sublimation dye constituting the sublimation transfer ink is transferred to the object to be dyed (1b). Thereby, a dyeing | staining thing is obtained.

  The heating temperature in this step is not particularly defined, but is preferably 160 ° C. or higher and 220 ° C. or lower, and more preferably 170 ° C. or higher and 200 ° C. or lower. Thereby, sufficient energy can be obtained to transfer the sublimation dye to the object to be dyed, and the productivity of the dyed object can be made particularly excellent.

  Although the heating time in this step depends on the heating temperature, it is preferably 30 seconds or longer and 90 seconds or shorter, more preferably 45 seconds or longer and 60 seconds or shorter. Thereby, sufficient energy can be obtained to transfer the sublimation dye to the object to be dyed, and the productivity of the dyed object can be made particularly excellent.

  Further, this step may be performed by heating the intermediate transfer medium provided with the sublimation transfer ink in a state of facing the object to be dyed, but the intermediate transfer medium and the object to be dyed are brought into close contact with each other. It is preferable to carry out by heating in the state. As a result, the energy required for transfer can be reduced and the productivity of dyed products can be made particularly excellent.

  Any material may be used as the material to be dyed. For example, a sheet-like material such as a fabric (hydrophobic fiber fabric, etc.), a resin (plastic) film, paper, or the like is preferably used. An object having a three-dimensional shape such as a rectangular parallelepiped shape may be used.

  Further, as the object to be dyed, for example, glass, metal, ceramics may be used in addition to those made of resin, plastic, paper or the like.

  Examples of the fibers constituting the fabric as the object to be dyed include polyester fibers, nylon fibers, triacetate fibers, diacetate fibers, polyamide fibers, and blended products using two or more of these fibers. Moreover, you may use the blended products of these with regenerated fibers, such as rayon, or natural fibers, such as cotton, silk, and wool.

  Examples of the resin (plastic) film as the object to be dyed include a polyester film, a polyurethane film, a polycarbonate film, a polyphenylene sulfide film, a polyimide film, and a polyamideimide film. The resin (plastic) film may be a laminate in which a plurality of layers are laminated, or may be composed of a gradient material in which the composition of the material changes in a gradient manner.

≪Dyeing≫
Next, the dyeing | staining thing of this invention is demonstrated.

  The dyed product of the present invention is produced using the above-described sublimation transfer ink of the present invention. Thereby, the dyeing | staining excellent in color developability can be provided.

  The dyed product of the present invention may be used for any purpose, and examples thereof include clothing such as T-shirts and trainers, and banners.

[1] Production of sublimation transfer ink A sublimation transfer ink was produced as follows.

Example 1
First, a sublimable dye described in Table 1, a formalin condensate of β-naphthalenesulfonic acid as an anionic dispersant, and ion-exchanged water was mixed with 0.2 mm glass beads in a sand mill. Under cooling, the dispersion treatment was performed for about 15 hours. After the dispersion treatment, ion-exchanged water is added for dilution, and then the dispersion is filtered through glass fiber filter paper GC-50 (manufactured by Toyo Filter Paper Co., Ltd., filter pore size 0.5 μm) to remove components having a large particle size. An aqueous dispersion was obtained.

  Next, sublimation transfer ink was obtained by mixing the aqueous dispersion obtained as described above, glycerin, triethylene glycol monomethyl ether, and ion-exchanged water in the proportions shown in Table 1.

(Examples 2 to 4)
The sublimation transfer ink was prepared in the same manner as in Example 1, except that the composition shown in Table 1 was obtained by adjusting the type and amount of the aqueous dispersion used for the preparation of the sublimation transfer ink. Manufactured.

(Comparative Examples 1-5)
The sublimation transfer ink was prepared in the same manner as in Example 1, except that the composition shown in Table 1 was obtained by adjusting the type and amount of the aqueous dispersion used for the preparation of the sublimation transfer ink. Manufactured.

Table 1 summarizes the compositions of the sublimation transfer inks of the respective Examples and Comparative Examples.
In the table,
C. I. Solvent Blue 63 (sublimation dye) is “SB63”,
C. I. Solvent Blue 11 (sublimation dye) is “SB11”,
C. I. Disperse violet 28 (sublimation dye) is "DV28",
C. I. Disperse Blue 14 (sublimation dye) is “DB14”,
C. I. Solvent Blue 36 (sublimation dye) is “SB36”,
Formalin condensate (anionic dispersant) of β-naphthalenesulfonic acid is “NS”,
Glycerin is “GL”,
Triethylene glycol monomethyl ether is indicated by “TEGMME”.

[2] Implementation of Ames Test Ames test was performed using the sublimation transfer inks of each Example and Comparative Example as follows.

As the Ames test, a metabolic activation test using a test strain (TA98 or TA100) and S9mix was performed. The sublimation transfer inks of Examples and Comparative Examples produced in [1] above were dissolved in dimethyl sulfoxide, respectively, and the sublimation transfer ink concentrations were 1.2, 4.9, 20, 78, 313, and 1250, respectively. And a test solution was prepared so as to be 7 doses of 5000 (μg / plate), and a metabolic activation test as an Ames test was performed twice (2 plates) using a preincubation method. The average value of the two plates of the number of revertant colonies generated was calculated for each test strain. In addition, a solvent control test (test using only the solvent) was performed in the same manner, and the average value of the obtained number of revertant colonies for two plates was calculated. The obtained calculation results were evaluated according to the following criteria.
Positive: In any one or more of the two types of test strains used (TA98 or TA100), the number of revertant colonies on the plate containing the test substance is 2 relative to the number of revertant colonies in the solvent control test. More than double.
Negative: The number of revertant colonies on the plate containing the test substance in both of the two test strains used (TA98 or TA100) is less than twice the number of revertant colonies in the solvent control test.
These results are shown in Table 2.

[3] Manufacture of dyed goods Dyeings were manufactured as follows using the ink for sublimation transfer of each Example and a comparative example.

First, sublimation transfer ink was put into an ink jet apparatus. Thereafter, a paper having an ink receiving layer made of a material containing silica is prepared as an intermediate transfer medium, and the ink receiving layer of the intermediate transfer medium is 100% duty, 50% at 1440 × 720 dpi (dot per inch). Sublimation transfer ink was ejected at a duty of 5% (ink application step). “Duty” is defined by the following formula (A) and indicates a unit of the calculated value D.
D = {(actual printing dot number) / (vertical resolution × horizontal resolution)} × 100 (duty) (A)

  Thereafter, the ink receiving layer of the intermediate transfer medium provided with the sublimation transfer ink is brought into intimate contact with a fabric (a material to be dyed) made of polyester fibers, and in this state, a heat press TP-608M manufactured by Taiyo Seiki Co., Ltd. Was heated under the conditions of 200 ° C. × 60 seconds to perform sublimation transfer (transfer process). This gave a dyed product.

[4] Measurement of hue of dyed portion For the dyed product produced in [3] above, a *, b * defined in the CIELAB color space of the dyed portion on the side facing the intermediate transfer medium, and The hue angle ∠H ° was determined by measurement using SpectroScan (manufactured by GretagMacbeth) and evaluated according to the following criteria. At this time, the hue angles ∠H ° of the dyed portion of the dyed product obtained with 100% duty, 50% duty, and 5% duty are ∠H ° (100), ∠H ° (50), and ∠H °, respectively. (5).
A: The hue angles ∠H ° (100), ∠H ° (50), and ∠H ° (5) of the dyed portion are all in the range of about 250 ° to about 280 °.
B: Any one or two of hue angles ∠H ° (100), ∠H ° (50), and ∠H ° (5) of the dyeing portion are in the range of about 250 ° to about 280 °.
C: The hue angles 染色 H ° (100), ∠H ° (50), and ∠H ° (5) of the dyed portion are all outside the range of about 250 ° to about 280 °.
These results are shown in Table 2.

[5] Measurement of Saturation of Staining Part For the dyed product produced in [3] above, a *, b *, defined in the CIELAB color space of the dyeing part on the side facing the intermediate transfer medium In addition, saturation C * was determined by measurement using SpectroScan (manufactured by GretagMacbeth) and evaluated according to the following criteria. At this time, the chroma C * of the dyed portion of the dyed product obtained with 100% duty was defined as C * (100).
A: The chroma C * (100) of the stained part is 50 or more.
B: The chroma C * (100) of the dyed portion is 45 or more and less than 50.
C: The chroma C * (100) of the dyed portion is less than 45.
These results are shown in Table 2.

  As is apparent from Table 2, the sublimation transfer ink of the present invention is negative in the Ames test and provides a dyed product having excellent color developability as an inkjet ink, particularly excellent hue and chroma as a cyan ink. Could be ink.

  The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method, and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that achieves the same effect as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

  The present invention can be suitably used, for example, in sublimation transfer without using an intermediate transfer medium. Sublimation transfer without using an intermediate transfer medium is a method in which a printed matter is obtained by directly attaching to a fabric using an ink jet method and then performing a heating step. Even in this case, it is needless to say that excellent color developability as an inkjet ink, in particular, excellent hue and saturation as a cyan ink.

  Further, for example, in the manufacturing method of the present invention, in addition to the steps as described above, there may be further steps (a pretreatment step, an intermediate treatment step, a post treatment step).

  In the above-described embodiment, the ink application process for applying the sublimation transfer ink according to the present invention to the intermediate transfer medium using the ink jet method, and the intermediate transfer medium to which the sublimation transfer ink has been applied are applied. Typically, a dyed product is produced using a method comprising heating in a state facing a dyed product and transferring a sublimation dye constituting the sublimation transfer ink to the dyed product. Although explained, the dyeing | staining of this invention is not limited to what was manufactured using such a method. For example, the dyed material of the present invention is obtained by applying the sublimation transfer ink according to the present invention to the ink receiving layer of a material to be dyed (film product or the like) provided with a releasable ink receiving layer by an ink jet method. Alternatively, it may be produced by using a method in which the dyed material on the lower layer side is subjected to sublimation diffusion dyeing by heating as it is, and then the ink receiving layer is peeled off.

Claims (5)

Sublimation transfer ink ejected using an inkjet method,
water and,
A water-soluble organic solvent,
A sublimable dye,
The sublimable dye is C.I. I. Solvent Blue 63 or C.I. I. At least one of Solvent Blue 11 and
C. I. Disperse violet 28, and a sublimation transfer ink.   The sublimation transfer ink is the C.I. I. Solvent Blue 63 or C.I. I. The content of Solvent Blue 11 or the C.I. I. Solvent Blue 63 and the C.I. I. The content of Solvent Blue 11 and the C.I. I. 2. The sublimation transfer ink according to claim 1, wherein a weight ratio with respect to a content of the disperse violet 28 is in a range of 1: 1 to 4: 1. An ink application step of applying the sublimation transfer ink according to claim 1 or 2 to an intermediate transfer medium using an inkjet method;
The intermediate transfer medium to which the sublimation transfer ink has been applied is heated in a state where the surface to which the sublimation transfer ink has been applied and the dyed surface of the object to be dyed face each other to constitute the sublimation transfer ink. And a transfer step of transferring a sublimation dye to the dyed article.   The method for producing a dyed product according to claim 3, wherein a heating temperature in the transfer step is 160 ° C or higher and 220 ° C or lower.   A dyed product produced using the sublimation transfer ink according to claim 1.