JP2004107648A - Inkjet recording ink for sublimation transfer printing and printing technique - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inkjet recording ink excellent in preventing nozzle clogging and having good dispersion stability and giving stable discharge after operating for a long time or stopping for a long time with keeping various performance such as preserrvation stability, high quality recorded images and the like and reducing environmental pollution and provide a sublimation transfer printing technique using the same. <P>SOLUTION: After carrying out an inkjet printing on a sheet-like medium by using the inkjet recording ink for sublimation transfer printing, containing water, a sugar alcohol having ≥4 hydroxy groups, a sublimating dye, a dispersant and a compound expressed by chemical formula (I): R-O-(CH<SB>2</SB>CH<SB>2</SB>O)n-H (wherein R expresses a 25-150C alkyl; n expresses 2-100), the sheet-like medium is heated to transfer and print the sublimating dye to an object to be dyed. <P>COPYRIGHT: (C)2004,JPO

Description

The present invention relates to an ink for ink-jet recording for sublimation transfer in an ink-jet recording system, and a sublimation transfer dyeing method using the same. More specifically, an inkjet recording ink for sublimation transfer using a sublimable dye used in a piezo-type inkjet system, which has reduced environmental pollution, and is excellent in preventing clogging of nozzles of a recording head and storage stability of ink, and sublimation. It relates to a transfer staining method.

Aqueous inkjet recording inks generally take the form of a solution of a water-soluble dye or a liquid in which a water-insoluble colorant is dispersed in an aqueous solution containing water or a water-soluble organic solvent. In addition, a dyeing method in which ink-jet printing is performed on a sheet-like medium such as paper, and then the medium is overlaid on a hydrophobic fiber or a resin film product by sublimation transfer, for example, sublimation diffusion dyeing having a peelable ink receiving layer Inkjet printing on a possible film product, sublimation diffusion dyeing on the lower film product by heating as it is, then peeling the ink receiving layer, dyeing using sublimation transfer such as dyeing method, sublimation Ink jet recording inks using dyes have been used (see Patent Document 1 below).

The sublimable dye ink generally has a form in which the sublimable dye is dispersed in an aqueous solution containing water, a water-soluble organic solvent and a dispersant, but the sublimable dye is inkjet-printed on the paper medium. After that, it is superimposed on the transfer target, sublimated by heating and dyed by sublimation transfer, or ink jet printing is performed on the ink receiving layer of a sublimable diffusion dyeable film product having a peelable ink receiving layer, as it is When heating and sublimating the sublimable dye to diffuse and dye the lower layer film product, the water-soluble organic solvent evaporates together with water during the heat treatment. This is a point different from inkjet printing for the purpose of general printing only. In a dyeing method using sublimation transfer, a high boiling point organic solvent is used because the temperature is higher than the sublimation temperature of the sublimable dye and heating is performed for a certain time. But it will volatilize. In particular, in the case of a high-boiling organic solvent such as glycerin, the temperature drops to the condensation point as soon as the volatile solvent is released into the atmosphere, resulting in the generation of smoke-like vapor. This looks very bad. In order to avoid this, it is conceivable to use a low-boiling organic solvent that does not form a smoke.However, since the volatile solvent is released to the atmosphere, it is the same in both cases. The problem of environmental pollution arises.

Items required for the performance of the ink jet recording ink include (1) nozzle clogging prevention and ejection stability, (2) ink storage stability, (3) ink ejection direction, ejection amount, and the like. High-quality recorded images having a fixed dot shape, (4) ink drying property, fixing property (5) high print density, and the like.

(4) In the ink jet recording method, since the ink needs to be ejected from a thin nozzle as a small droplet of ink, (1) in the above item is particularly important. In particular, in the on-demand system, since the ejection of ink from the nozzles is temporarily stopped even during the continuous operation, there is a problem that a discharge failure occurs during the long-time continuous operation.

  Also, in the case of the ink for inkjet recording for sublimation transfer using a sublimable dye, unlike the case where a water-soluble dye is used, precipitation (aggregate) due to deterioration of dispersion stability, evaporation of water in a nozzle, etc. Is likely to cause clogging. In particular, when the apparatus is put in a state where the operation is suspended for a long time, clogging due to evaporation of water is likely to occur.

Therefore, humectants are added to suppress evaporation of water. These humectants include high-boiling organic solvents such as glycols such as glycerin and polyethylene glycol, and sugars.

However, as described above, in the sublimation transfer method, since it is necessary to increase the temperature to the sublimation temperature of the sublimable dye and heat it for a certain period of time, even when a high-boiling organic solvent is used as a humectant, the heating temperature during sublimation transfer is low. There is a problem that it volatilizes and pollutes the environment. Therefore, a humectant other than the organic solvent, which does not volatilize during heating during sublimation transfer, and which does not adversely affect the above items (1) to (5) required for the performance of the ink. You need to choose.

例 An example of using a humectant other than a water-soluble organic solvent is an aqueous inkjet ink containing a water-soluble dye and sorbitol (see Patent Document 2 below). Further, an aqueous pigment ink containing a pigment and sorbitol has also been proposed (see Patent Documents 3 and 4 below). Further, a water-based ink for a ballpoint pen to which maltitol is added using a water-soluble dye or pigment as a coloring agent has been proposed (see Patent Document 5 below). Further, an ink using xylitol and a water-soluble organic solvent in a carbon black dispersion has been proposed (see Patent Document 6 below).

In the above prior art, there is an example in which a sugar alcohol is used as a humectant in a pigment ink or a water-soluble dye ink, but whether or not there is applicability when a sublimable dye is used in an ink dispersed with a dispersant. Is not shown at all. Further, no consideration has been given to an environment-friendly sublimable dye ink by reducing the content of a water-soluble organic solvent as much as possible, and there is no technique proposed to solve the problem that arises in that case. . In addition, when used as a humectant, it is necessary to consider a substance that is considered to have no adverse effect such as oxidation-reduction on the sublimable dye.

In addition, water, a coloring agent, and the following formula (II)
_{R-A- (CH 2 CH 2} O) x -H (II)
Wherein R is a straight-chain saturated hydrocarbon having 14 to 23 carbon atoms, A is O or OCO, and x is an integer of 1 to 3; Accordingly, an inkjet ink comprising a humectant has been proposed (see Patent Document 7 below).

However, these can be used as "colorants for various dyes, pigments, colored polymers / waxes, etc. Among them, it is preferable to use water-soluble dyes. Although acid dyes and direct dyes can be used, acid dyes and direct dyes are more preferable. ", And it is apparent from the fact that only acid dyes are actually used in Examples. No description is given for use in sublimable dye inks. Further, even when a polyoxyethylene higher alkyl ether having 23 or less carbon atoms in the above formula is used, when a sublimable dye is used as a coloring material, an ink composition having good redispersibility cannot be obtained.
JP-A-2002-79751 JP-A-57-57762 JP-A-60-72968 JP-A-62-101672 JP-A-2-214785 JP-A-2001-115070 JP 2000-265098 A

The present invention solves the problems of the conventional ink for ink jet recording using a sublimable dye as described above, reduces environmental pollution, maintains storage stability originally required, and maintains the performance of high-quality recorded images and the like. Ink jet recording with excellent nozzle disturbing property, good dispersion stability, and stable ejection even after long-time continuous operation even after long-time continuous operation. And a sublimation transfer dyeing method using the same.

That is, the ink for inkjet recording for sublimation transfer of the present invention comprises water, a sugar alcohol having four or more OH groups, a sublimable dye, a dispersant, and the following chemical formula (I).
_{R-O- (CH 2 CH 2} O) n -H (I)
(Wherein, R represents an alkyl group having 25 to 150 carbon atoms, and n represents 2 to 100).

In addition, the sublimation transfer dyeing method of the present invention is that, after performing ink-jet printing on a sheet-shaped medium using the ink for sublimation transfer-based ink jet recording described above, the sheet-shaped medium is heated and the sublimable dye is subjected to dyeing. It is characterized by sublimation transfer to an object.

The ink for inkjet recording using the sublimable dye of the present invention as a coloring material component has good re-dispersibility with reduced environmental pollution while maintaining the originally required storage stability and performance of high-quality recorded images. Inkjet recording for sublimation transfer that provides ink and has excellent nozzle clogging prevention properties, and stable ejection can be obtained by normal cleaning even after a long period of continuous operation even after long hours of continuous operation. Ink can be provided.

In addition, the sublimation transfer dyeing method of the present invention performs sublimation transfer after performing inkjet printing using the ink for sublimation transfer inkjet recording described above, so that the storage stability originally required for the ink used for dyeing is required. Sublimation transfer dyeing method with reduced environmental pollution while maintaining the performance of high quality, high quality recorded images, etc., improved redispersibility of the ink used, excellent nozzle clogging prevention properties, and It is possible to provide an excellent sublimation transfer dyeing method in which dyeing can be performed and stable ink discharge can be obtained by ordinary cleaning even after a long-time continuous operation or after a long operation suspension of the apparatus.

In the inkjet recording ink for sublimation transfer and the sublimation transfer dyeing method using the same according to the present invention, the sugar alcohol having four or more OH groups is at least one selected from D-sorbitol, xylitol and maltitol. Is preferred.

Further, in the ink for sublimation transfer inkjet recording of the present invention and the sublimation transfer dyeing method using the same, in the compound represented by the chemical formula (I), R represents an alkyl group having 30 to 50 carbon atoms, and n represents Compounds represented by 10 to 50 are preferred.

In addition, in the ink for sublimation transfer inkjet recording of the present invention and the sublimation transfer dyeing method using the same, the compound represented by the chemical formula (I) is preferably a compound having an HLB of 10 or more.

In the sublimation transfer inkjet recording ink and the sublimation transfer dyeing method using the same according to the present invention, the sublimable dye may be at least one selected from the group consisting of disperse dyes and oil-soluble dyes. preferable.

In the sublimation transfer inkjet recording ink and the sublimation transfer dyeing method using the same according to the present invention, the dispersant comprises an anionic surfactant, a nonionic surfactant, and a polymer surfactant. It is preferably at least one selected from the group.

In the ink for sublimation transfer inkjet recording of the present invention and the sublimation transfer dyeing method using the same, the content of the sugar alcohol having four or more OH groups is 0.5 to 50% based on the total weight of the ink. % By weight.

In the ink for sublimation transfer inkjet recording of the present invention and the sublimation transfer dyeing method using the same, a sugar alcohol having four or more OH groups, a sublimable dye, a dispersant, and a chemical formula (I) are used. The content of the compound is 0.5 to 50% by weight of a sugar alcohol having four or more OH groups, 0.2 to 12% by weight of a sublimable dye, and 0.1 to 20% by weight of the total weight of the ink. %, And 0.1 to 8% by weight of the compound represented by the chemical formula (I).

In the sublimation transfer inkjet recording ink and the sublimation transfer dyeing method using the same according to the present invention, the ink contains substantially no water-soluble organic solvent (that is, the content of the water-soluble organic solvent is substantially zero). 0% by weight).

That is, the present invention provides a water-soluble organic solvent by dispersing a sublimable dye with a dispersant, and including a sugar alcohol having four or more OH groups as a humectant in the ink containing the chemical formula (I). The sublimation dye content is as low as possible to make it practical as an environmentally friendly sublimable dye ink.

  The compound represented by the chemical formula (I) used in the present invention has an alkyl group having 25 or more carbon atoms, unlike polyoxyethylene higher alkyl ethers conventionally used in ink jet recording inks. The upper limit of the carbon number of the alkyl group is usually 150 or less. As a conventional example, natural alcohol-based or synthetic alcohol-based compounds are commercially available, but generally, these alkyl groups have about 12 to 18 carbon atoms. JP-A-2000-265098 describes a polyoxyethylene alkyl ether compound having an alkyl group having 14 to 23 carbon atoms.

However, even when these polyoxyethylene higher alkyl ethers having less than 25 carbon atoms are used, when a sublimable dye is used as a coloring material, an ink composition having good redispersibility cannot be obtained. Therefore, in the present invention, it is necessary to use a compound in which R is an alkyl group having 25 to 150 carbon atoms as the compound represented by the chemical formula (I).

糖 As the sugar alcohol used in the present invention, a sugar alcohol derived from a monosaccharide or a sugar alcohol derived from a disaccharide is preferable. Examples of monosaccharide-derived sugar alcohols include threitol, erythritol, arabitol, ribitol, xylitol, lyxitol, sorbitol, mannitol, iditol, glitol, talitol, galactitol, allitol, and altitol. Examples of sugar alcohols derived from disaccharides include maltitol, isomaltitol, lactitol, and tranitol. In the present invention, it is necessary to use a sugar alcohol having four or more OH groups, and when a sugar alcohol having less than four OH groups, for example, glycerin, is used, heating during sublimation transfer Volatilizes, which is not preferred. Among these, D-sorbitol, xylitol and maltitol are preferred, and D-sorbitol is particularly preferred from the viewpoint of solubility and economy. These may be used alone or as a mixture of two or more kinds. However, the content of the sugar alcohol used in the present invention depends on the viscosity of the ink and the total weight of the ink from the viewpoint of preventing clogging due to the moisturizing effect. Is preferably 0.5 to 50% by weight. It is more preferably 2 to 40% by weight, particularly preferably 5 to 25% by weight.

In the present invention, it is preferable not to use a water-soluble organic solvent (substantially, the content of the water-soluble organic solvent is 0% by weight), but as long as the purpose of the present invention is not impaired, the water-soluble organic solvent is used in combination with the sugar alcohol. Solvents may be used. Examples of the water-soluble organic solvent include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, and glycerin, and ethylene glycol monomethyl ether. Glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether and propylene glycol monomethyl ether; alcohols such as isopropyl alcohol, methanol and ethanol; bases such as N-methyl-2-pyrrolidone and triethanolamine. Solvents.

  Among the water-soluble organic solvents, glycerin, diethylene glycol, polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, and propylene glycol are preferable from the viewpoint of moisture retention.

  These may be used alone or in combination of two or more.

In the compound represented by the following chemical formula (I) used in the present invention, R represents an alkyl group having 25 to 150 carbon atoms, and by using a compound having 25 or more carbon atoms of R, an inkjet having good redispersibility can be obtained. It can be a recording ink composition. It is preferable to use the compound represented by the following chemical formula (I) also from the viewpoint of continuous discharge stability, discharge property after leaving for a long time, and long-term storage stability. Further, from the viewpoint of solubility in the aqueous ink composition, R having a carbon number of 150 or less is suitable. The carbon number of R is preferably 30 to 50 carbon atoms, and particularly preferably an alkyl group having 30 to 35 carbon atoms. n is 2 to 100, preferably 10 to 50, particularly preferably 20 to 50. The alkyl group may be linear or branched, but is preferably a linear alkyl group.

HLB is 4 or more, preferably 10 or more, and particularly preferably 14 to 18, from the viewpoint of solubility in water.

_{R-O- (CH 2 CH 2} O) n -H (I)
The compound of the formula (I) is preferably used in an amount of 0.1 to 8% by weight, more preferably 0.1 to 6% by weight, and particularly preferably 0.2 to 4% by weight, based on the total amount of the ink. preferable. When used in the range of 0.1 to 8% by weight, there is no problem that the viscosity of the ink becomes too high due to too much addition amount, and the intended effect can be exhibited, which is preferable.

  Examples of the compound of the formula (I) include "Unitox 420" (R is a linear alkyl group having 31 to 32 carbon atoms, n is about 3, HLB = 4) manufactured by Petrolite of the United States, and "Unitox 450". "(R is a linear alkyl group having 31 to 32 carbon atoms, n is about 10, HLB = 10)," Unitox 480 "(R is a linear alkyl group having 31 to 32 carbon atoms, n is about 40, HLB = 16), "Unitox 520" (R is a linear alkyl group having 38 carbon atoms, n is about 3, HLB = 4), "Unitox 550" (R is a linear alkyl group having 38 carbon atoms, n Is about 12, HLB = 10), "Unitox 720" (R is a linear alkyl group having 48 to 49 carbon atoms, n is about 4, HLB = 4), "Unitox 750" (R is 48 to 49 carbon atoms) A linear alkyl group, n is about 16, H B = 10), and the like.

  As the sublimable dye, a disperse dye having a sublimability and an oil-soluble dye are preferable, and these may be used alone or in combination.However, disperse dyes are particularly preferable from the viewpoint of dispersibility and dyeability. It is preferably used.

染料 As an example of the sublimable dye, a dye that sublimates or evaporates at 70 to 260 ° C. under atmospheric pressure is preferable. For example, there are dyes such as azo, anthraquinone, quinophthalone, styryl, di- or triphenylmethane, oxazine, triazine, xanthene, methine, azomethine, acridine, diazine and the like. Among them, examples of yellow disperse dyes include C.I. I. Disperse Yellow 51, 54, 60, 64, 65, 82, 98, 119, 160, 211 and the like. Examples of red disperse dyes include C.I. I. Disperse Red 4, 22, 55, 59, 60, 146, 152, 191, 302, Vat Red 41, and the like. Examples of blue disperse dyes include C.I. I. Disperse Blue 14, 28, 56, 60, 72, 73, 77, 334, 359, 366, and the like. Other color components include Violet # 27, 28, and the like. Other oil-soluble dyes include C.I. I. Solvent Orange 25, 60, Red 155, Blue 35, 36, 97, 104, and the like.

  Generally, the content of these sublimable dyes is preferably from 0.2 to 12% by weight based on the total weight of the ink, since dispersion stability is maintained and a required print density is obtained. More preferably, it is 0.5 to 8% by weight.

The dispersant used in the present invention also has a function of dispersing a sublimable dye in an aqueous medium and maintaining the dispersion stability of the finely divided sublimable dye. The dispersant to be used is not particularly limited, but may be any one suitable for the combination of the sugar alcohol and the compound represented by the formula (I), and may be an anionic surfactant, a nonionic surfactant, or a polymer. Surfactants and the like can be used alone or as a mixture. In particular, an anionic surfactant or a nonionic surfactant is preferable for dispersing a disperse dye or an oil-soluble dye, and an anionic surfactant is particularly preferable.

Examples of the anionic surfactant include formalin condensate of naphthalene sulfonate, lignin sulfonate, and formalin condensate of special aromatic sulfonate (formalin condensate of sodium alkyl naphthalene sulfonate such as butyl naphthalene and sodium naphthalene sulfonate) Condensate, formalin condensate of sodium cresol sulfonate and sodium 2 naphthol-6-sulfonate, formalin condensate of sodium cresol sulfonate, formalin condensate of creosote oil sodium sulfonate, etc.), polyoxyethylene alkyl ether sulfate And the like.

Examples of the nonionic surfactant include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene acetylene glycol, polyoxyethylene derivative, and oxyethylene / oxypropylene block copolymer. .

高分子 Further, examples of the polymeric surfactant include a polyalkyl acid partial alkyl ester, a polyalkylene polyamine, a polyacrylate, a styrene-acrylic acid copolymer, and a vinyl naphthalene-maleic acid copolymer.

The content of these dispersants is preferably 0.1 to 20% by weight based on the total weight of the ink for the purpose of maintaining good dispersion stability of the sublimable dye. More preferably, it is 0.1 to 12% by weight.

そ の 他 Various other additives can be added to the ink of the present invention, as needed, as long as the object of the present invention is not hindered. For example, there are a surface conditioner, a hydrotrope agent, a pH adjuster, a viscosity adjuster, a preservative, a fungicide, a light stabilizer, a chelating agent, an antifoaming agent and the like.

  Among the above additives, examples of the surface modifier include a fluorine-based surfactant, a polyether-modified polydimethylsiloxane, and an acrylic polymer. In the case of the present invention, particularly, the polyether-modified polydimethylsiloxane and the acrylic Polymers are preferred. These surface conditioners are effective in adjusting the surface tension of the ink and making the ink easily wet with the ink flow path material, but are preferably 0.05 to 1% by weight, more preferably 0.05 to 1% by weight based on the total weight of the ink. Preferably, it is used in the range of 0.1 to 0.5% by weight. If the amount is less than 0.05% by weight, the effect tends to decrease, and even if the amount exceeds 1% by weight, the effect tends not to increase so much.

The method for adjusting the ink jet recording ink of the present invention is not particularly limited, but is preferably adjusted by the method described below. That is, first,
(1) A subdispersible dye, the sugar alcohol, the compound of the formula (I), a dispersant, water, and, if necessary, a water-soluble organic solvent and the additives are mixed and stirred to prepare a preliminary dispersion. And then
(2) Sublimation dye is finely divided and dispersed in a wet medium mill such as a sand mill in the preliminary dispersion to obtain a dye dispersion.
(3) After adjusting the concentration by adding water, a water-soluble organic solvent and the above-mentioned additives to the dye dispersion, and then filtering the mixture with a filter paper or the like, the dye dispersion is used.

  In the above method, the sugar alcohol may be added at the time of micronization or may be added at the time of concentration adjustment, or may be added in portions, but from the viewpoint of workability, an aqueous solution prepared in advance or a commercially available aqueous solution is used. Is preferred.

The compound of the formula (I) may be added at the time of micronization, may be added at the time of concentration adjustment, or may be added in divided portions. % Of an aqueous solution is preferably used.

  The average particle diameter of the sublimable dye obtained by the above method is preferably 0.5 μm or less, more preferably 0.05 to 0.2 μm.

As described above, the specific examples of the sublimable dye, the sugar alcohol having four or more OH groups, the dispersant, and other components have been described. However, the present invention is limited to only the specific examples. Not something.

As a method of performing sublimation transfer dyeing using the ink for sublimation transfer ink jet recording of the present invention as described above, the ink is subjected to ink jet printing on a sheet-like medium using the ink for sublimation transfer ink jet recording, and then the sheet A method is employed in which a sublimable dye is sublimated and transferred to an object to be dyed by heating a linear medium.

The object to be dyed is not particularly limited in its shape and material as long as it is capable of sublimation transfer dyeing. Generally, a sheet material such as a hydrophobic fiber cloth or a resin film, paper, or the like is used. However, the present invention can be applied to a three-dimensional object such as a spherical or cubic object instead of a sheet.

One method of performing sublimation transfer dyeing using the inkjet recording ink for sublimation transfer of the present invention is to perform inkjet printing on a sheet-like medium such as paper and then subject the dyeable object such as a hydrophobic fiber or a resin film product to dyeing. There is a dyeing method in which the medium is superimposed and transferred to an object by sublimation transfer. In addition, ink-jet printing is performed on a sublimable diffusion-dyeable film product having a peelable ink-receiving layer as described above, and after heating as it is, sublimation diffusion-dyeing is performed on the lower film product. The dyeing method of peeling is also included in the present invention.

As the sheet-like medium used in the former method, not only a non-recording sheet-like medium such as plain paper, but also a sheet-like support having at least a coating layer containing a hydrophilic polymer and / or an inorganic porous material. And a recording medium in the form of a sheet.

シ ー ト The sheet-like medium used in the latter method corresponds to a releasable ink receiving layer, and the object to be dyed corresponds to a film product on the lower layer side.

The ink-receiving layer in this case is, for example, a layer mainly composed of a water-soluble resin capable of rapidly absorbing and receiving ink, and the water-soluble resin component is a water-soluble or hydrophilic natural or synthetic polymer. For example, polyvinyl alcohol resin; polyurethane resin; polyvinyl acetal resin; polyvinyl methyl ether; vinyl methyl ether-maleic anhydride copolymer; polyvinyl pyrrolidone; vinyl pyrrolidone-styrene copolymer; vinyl pyrrolidone-vinyl acetate copolymer; Water-soluble acrylic resin synthesized from monomers such as acrylic acid, methacrylic acid, acrylic acid ester, methacrylic acid ester and other monomers; vinyl resins such as polyacrylamide; polyethylene oxide; synthetic resins such as polyglutamic acid : Carboxymethylcellulose; semi-synthetic resins such as cellulose derivatives such as methylcellulose: Chitin; chitosan; starch; natural resins such as gelatin, etc. Can. Polyacrylic acid, polyelectrolyte polymer electrolytes such as alkali metal salts such as polystyrene sulfonic acid, or polycation polymer electrolytes such as polyethyleneimine, polyvinylamine, polyallylamine, polyvinylalkylammonium halide, polyvinylbenzylalkylammonium halide, Alternatively, an amphoteric polymer electrolyte can also be used. Further, from the viewpoint of ink absorbability, a porous pigment such as silica, clay, talc, diatomaceous earth, zeolite, calcium carbonate, alumina, zinc oxide, and titanium oxide may be added.

Further, as a film product on the lower layer side corresponding to an object to be dyed, a polyester film, a polyurethane film, a polycarbonate film, a polyphenylene sulfide film, a polyimide film, a polyamideimide film, and the like, as well as a sublimable dye on the surface of these films. A film of a material that can be dyed by sublimation without melting or remarkably shrinking by heat during sublimation transfer, such as a film in which a non-affinity resin, for example, a fluorine resin or the like is laminated, is used.

(4) The heating temperature at the time of sublimation transfer differs depending on the type of the sublimable dye used and the like, so it is difficult to unconditionally define it. However, usually, the heating temperature is about 150 to 200 ° C., and the heating time is about 2 to 10 minutes.

本 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following examples, "parts" means "parts by weight" unless otherwise specified, and "%" means "% by weight" unless otherwise specified.

20 parts of a red disperse dye precursor (CI Disperse Red 60), 12 parts of a formalin condensate of a special aromatic sodium sulfonate as an anionic surfactant (“Demol SNB” manufactured by Kao Corporation) as a dispersant, 5 units of “Unitox 480” (a compound of the formula (I) manufactured by Petrolite, USA, where R is a straight-chain alkyl group having 31 to 32 carbon atoms, n is about 40 and HLB is 16), and 123 parts of water Using a mixture of 330 parts of zircon beads having a diameter of 0.4 mm, the mixture was pulverized with a sand mill for 35 hours to obtain a dispersion.

To this dispersion, 5 parts of "Unitox 480", 85 parts of "Sorbitol S" (D-sorbitol 70% aqueous solution manufactured by Niken Kagaku Co., Ltd.), and a polyether-modified polydimethylsiloxane (BIC Chemie Japan) as a surface conditioner 2.0 parts of "BYK-348" manufactured by K.K.) was further added to the ink to prepare an ink whose dye concentration was adjusted to 5%. The average particle size of the dye was 0.10 μm.

Fine particles were formed in the same manner as in Example 1 except that 20 parts of a yellow disperse dye base material (CI Disperse Yellow 54) was used instead of the red disperse dye base material. ), 25 parts of "Unitox 480", 215 parts of "Sorbitol S", 2.5 parts of "BYK-348" as a surface conditioner, and water were added to adjust the dye concentration to 2%. . The average particle size of the dye was 0.12 μm.

20 parts of a blue disperse dye base (CI Disperse Blue 72), 12 parts of a formalin condensate of sodium β-naphthalenesulfonate as an anionic surfactant (“Demol N” manufactured by Kao Corporation) as a dispersant, Using a mixture of 5 parts of "Unitox 480" as the compound of the formula (I) and 123 parts of water and 330 parts of zircon beads having a diameter of 0.4 mm, the mixture was made into fine particles in the same manner as in Example 1 and dispersed. To the solution, 15 parts of "Unitox 480", 130 parts of "Sorbitol S", 2.4 parts of an acrylic polymer ("BYK-381" manufactured by BYK Japan KK) as a surface conditioner, and water are further added. An ink was prepared with the dye concentration adjusted to 3.3%. The average particle size of the dye was 0.08 μm.

In 40 parts of the dispersion obtained by micronization in the same manner as in Example 1, 10 parts of "Unitox 480" as the compound of the formula (I), 85 parts of "sorbitol S", and "BYK-348" as the surface conditioner Was added, and water was further added to prepare an ink having a dye concentration adjusted to 1.25%.

イ ン ク An ink was prepared in the same manner as in Example 1, except that 60 parts of xylitol was used instead of “sorbitol S” in Example 1.

イ ン ク An ink was prepared in the same manner as in Example 1 except that 60 parts of maltitol was used instead of “sorbitol S” of Example 1.

20 parts of a red disperse dye precursor (CI Disperse Red 60), 12 parts of a formalin condensate of a special aromatic sodium sulfonate as an anionic surfactant (“Demol SNB” manufactured by Kao Corporation) as a dispersant, Using a mixture of 3 parts of “Unitox 480” and 125 parts of water, 330 parts of zircon beads having a diameter of 0.4 mm were used to pulverize in a sand mill for 35 hours to obtain a dispersion.

８５ To this dispersion was added 85 parts of “Sorbitol S”, 2.0 parts of “BYK-348” as a surface conditioner), and further water to prepare an ink whose dye concentration was adjusted to 5%. The average particle size of the dye was 0.10 μm.

Fine particles were formed in the same manner as in Example 5 except that 20 parts of a yellow disperse dye base (CI Disperse Yellow 54), 4 parts of "Unitox 480" and 124 parts of water were used instead of the red disperse dye base. Then, 215 parts of "sorbitol S", 2.5 parts of "BYK-348" as a surface conditioner, and water were added to the dispersion to prepare an ink whose dye concentration was adjusted to 2%. The average particle size of the dye was 0.12 μm.

In 40 parts of the dispersion liquid obtained by micronization in the same manner as in Example 7, 3.3 parts of "Unitox 480" as the compound of the formula (I), 85 parts of "sorbitol S", and "BYK-" as the surface conditioner 348 '' was added to 0.4 parts, and water was further added to prepare an ink having a dye concentration adjusted to 1.25%.

Comparative Example 1

イ ン ク An ink was prepared in the same manner as in Example 1 except that 60 parts of glycerin was used in place of “sorbitol S” in Example 1.

Comparative Example 2

イ ン ク An ink was prepared in the same manner as in Example 1 except that 60 parts of diethylene glycol was used instead of “sorbitol S” in Example 1.

Comparative Example 3

Same as Example 1 except that the same amount of a formalin condensate of a special aromatic sodium sulfonate as an anionic surfactant (“Demol SNB” manufactured by Kao Corporation) was used instead of “Unitox 480” in Example 1. Ink was created.

Comparative Example 4

イ ン ク An ink was prepared in the same manner as in Example 1 except that the same amount of “Unitox 480” was used instead of “Demol SNB” in Example 1. The particle size of the dye was 1 μm or more. When the obtained ink was allowed to stand, the dye gradually aggregated, and a precipitate was formed. Therefore, when the dispersant was not used, the storage stability of the ink was inferior and could not be used as an ink for inkjet recording.

Table 1 shows the ratio of components other than water for the ink compositions of Examples 1 to 9 and Comparative Examples 1 to 3.

Furthermore, the inks prepared in Examples 1 to 9 and Comparative Examples 1 to 3 were subjected to the following tests. Table 2 shows the test results.

(1) Redispersibility test After 0.5 g of the ink composition was spread thinly on the surface of a watch glass (φ90 mm), the ink composition was left in a thermo-hygrostat adjusted to a temperature of 30 ° C. and a relative humidity of 20%. Three hours later, the watch glass is removed from the dryer, and the state when the ink is gently rinsed with a small amount of water from the outside of the peripheral portion where the ink has dried is observed.
Evaluation criteria: (○) Redispersion promptly without aggregation. (Ii) Some small thin film aggregates are observed, but do not adhere to the glass surface. (X) Significant aggregates are observed and remain attached to the glass surface.

(2) Continuous ejection stability test Using "JV2-130" (piezo system) manufactured by Mimaki Engineering Co., Ltd. as a commercially available large-format inkjet plotter, a printing resolution of 720 × 720 dpi, a monochromatic / fill-in printing, and a printing width of 1200 mm Under the conditions, continuous printing was performed until printing defects such as missing dots were recognized.

Evaluation criteria: (：) No clogging for 5 hours or more. (△) Clogging occurred in 30 minutes to 1 hour. (X) Clogging occurred within 30 minutes.

(3) Ejection property after leaving for a long time After running continuously for 30 minutes under the printing conditions described above, it was left as it was for 48 hours, and after normal cleaning, a printing test was performed again to confirm whether printing was normally performed under the same conditions.
Evaluation criteria: (○) Normal printing was possible by one predetermined head cleaning of the ink jet plotter. (△) Cleaning is required several times. (X) No recovery after further cleaning.

(4) Sublimation transfer dyeing test A film product (50 μm) capable of sublimation transfer dyeing having a peelable ink receiving layer using the ink for sublimation transfer inkjet recording prepared in Examples 1 to 9 and Comparative Examples 1 to 3. A polyurethane resin-based dye-fixing layer is coated to a thickness of 30 μm on a support polyester film having a thickness of 30 μm, dried, and then a fluoroolefin-based copolymer resin layer is coated to a thickness of 20 μm to be crosslinked. After adhering a pressure-sensitive adhesive layer and release paper to the film, a cross-linkable urethane-based inkjet coating agent “Paterracol IJ-50” (trademark, manufactured by Dainippon Ink and Chemicals, Inc.) as an ink-receiving layer on the film surface has a thickness of 20 μm. The large-format inkjet plotter (piezo method) was formed on the ink receiving layer of The image is printed by a “Minaki Engineering Co., Ltd.“ JV2-130 ”) and heated for about 7 minutes in a hot air dryer (“ Fine Oven DF62 ”manufactured by Yamato Scientific Co., Ltd.) set to about 170 ° C. in advance. Carried out. During the heat treatment, the condition of the heated steam spouting from the ventilation port of the dryer was observed. Thereafter, when the ink receiving layer was peeled off, a film product in which an image was sublimated and diffused and dyed in the film product was obtained.

Evaluation criteria: (○) No smoke-like vapor is generated. (Ii) Smoke-like steam is slightly generated. (X) Significant smoke-like vapor was observed.

　　　
　これらの試験結果から明らかなように、本発明の実施例１〜９は、加熱処理実施中に煙状の蒸気の発生は認められず、再分散性が良好で、連続吐出安定性及び長時間放置後の吐出性にも優れていた。Ｄ−ソルビールをグリセリンまたはジエチレングリコールに置き換えた比較例１及び２は、かなり煙状の蒸気の発生が認められた。式（Ｉ）の化合物を使用しないで、アニオン性分散剤に置き換えた比較例３は、煙状の蒸気の発生は認められなかったが、再分散性が悪く、連続吐出安定性及び長時間放置後の吐出性も悪かった。

As is clear from these test results, in Examples 1 to 9 of the present invention, no smoke-like vapor was generated during the heat treatment, redispersibility was good, continuous discharge stability and long time The ejection property after standing was excellent. In Comparative Examples 1 and 2 in which D-sol beer was replaced with glycerin or diethylene glycol, generation of a considerably smoky vapor was observed. In Comparative Example 3 in which the compound of the formula (I) was not used and the anionic dispersant was used, generation of smoke-like vapor was not recognized, but redispersibility was poor, continuous discharge stability and long-term standing The later ejection property was also poor.

The ink for inkjet recording using the sublimable dye of the present invention as a coloring material component has good re-dispersibility with reduced environmental pollution while maintaining the originally required storage stability and performance of high-quality recorded images. Ink is obtained, excellent in preventing clogging of nozzles, and has an effect that stable ejection can be obtained by ordinary cleaning even after long-time continuous operation even after long-time continuous operation. Therefore, it is suitable for an ink jet recording ink using a sublimable dye as a coloring material component.

In addition, the sublimation transfer dyeing method of the present invention performs sublimation transfer after performing inkjet printing using the ink for sublimation transfer inkjet recording described above, so that the storage stability originally required for the ink used for dyeing is required. Sublimation transfer dyeing method with reduced environmental pollution while maintaining the performance of high quality, high quality recorded images, etc., improved redispersibility of the ink used, excellent nozzle clogging prevention properties, and It is possible to provide an excellent sublimation transfer dyeing method in which dyeing can be performed and stable ink discharge can be obtained by ordinary cleaning even after a long-time continuous operation or after a long operation suspension of the apparatus. Therefore, the sublimation transfer dyeing method of the present invention is suitable for inkjet printing using the inkjet recording ink for sublimation transfer.

Claims (10)

Water, a sugar alcohol having four or more OH groups, a sublimable dye, a dispersant, and the following chemical formula (I)
_{R-O- (CH 2 CH 2} O) n -H (I)
(Wherein, R represents an alkyl group having 25 to 150 carbon atoms, and n represents 2 to 100). An ink for inkjet recording for sublimation transfer, comprising: The ink for inkjet recording for sublimation transfer according to claim 1, wherein the sugar alcohol having four or more OH groups is at least one selected from D-sorbitol, xylitol, and maltitol. The ink for sublimation transfer according to any one of claims 1 to 2, wherein the compound represented by the chemical formula (I) is a compound wherein R represents an alkyl group having 30 to 50 carbon atoms and n represents 10 to 50. Recording ink. The ink for inkjet recording for sublimation transfer according to any one of claims 1 to 3, wherein the compound represented by the chemical formula (I) is a compound having an HLB of 10 or more. The ink for inkjet recording for sublimation transfer according to any one of claims 1 to 4, wherein the sublimable dye is at least one selected from the group consisting of a disperse dye and an oil-soluble dye. The sublimation transfer inkjet according to any one of claims 1 to 5, wherein the dispersant is at least one selected from the group consisting of an anionic surfactant, a nonionic surfactant, and a polymer surfactant. Recording ink. The ink for inkjet recording for sublimation transfer according to any one of claims 1 to 6, wherein the content of the sugar alcohol having four or more OH groups is 0.5 to 50% by weight based on the total weight of the ink. When the content of the sugar alcohol having four or more OH groups, the sublimable dye, the dispersant, and the compound represented by the chemical formula (I) is at least 0.1% based on the total weight of the ink, the content of the sugar alcohol having four or more OH groups is 0.1%. 5 to 50% by weight, 0.2 to 12% by weight of a sublimable dye, 0.1 to 20% by weight of a dispersant, and 0.1 to 8% by weight of a compound represented by the formula (I). The ink for inkjet recording for sublimation transfer according to any one of the above. The ink for inkjet recording for sublimation transfer according to any one of claims 1 to 8, which does not substantially contain a water-soluble organic solvent. After performing inkjet printing on a sheet-like medium using the ink for sublimation transfer inkjet recording according to any one of claims 1 to 9, the sheet-like medium is heated to sublimate a sublimable dye to an object to be dyed. A sublimation transfer dyeing method characterized by transferring.