JP3515779B1 - Inkjet recording ink for sublimation transfer and dyeing method - Google Patents

Abstract

Abstract: PROBLEM TO BE SOLVED: To reduce environmental pollution, have excellent nozzle clogging prevention property, have good dispersion stability, and maintain good storage stability, high quality recorded image performance, etc. Provided are an ink jet recording ink having good re-dispersibility, which enables stable ejection even after a long pause, and a sublimation transfer dyeing method using the ink. SOLUTION: Water, a sugar alcohol having four or more OH groups, a sublimable dye, a dispersant, and a compound represented by the following formula (I)
_{O- (CH 2 CH 2 O)} n -H ( wherein, R 25 carbon atoms
Represents an alkyl group of 150, and n represents 2 to 100. )
After ink-jet printing is performed on a sheet-like medium using the ink for sublimation transfer ink-jet recording containing the compound represented by formula (1), the sheet-like medium is heated to sublimate-transfer the sublimable dye to an object to be dyed.

Description

Detailed Description of the Invention 【Technical field】

The present invention relates to an inkjet recording ink for sublimation transfer in an inkjet recording system and a sublimation transfer dyeing method using the same. More specifically, it is an inkjet recording ink for sublimation transfer and a sublimation transfer ink that uses a sublimable dye used in a piezo inkjet method, which is excellent in the prevention of clogging of nozzles of the recording head and the storage stability of the ink, which reduces environmental pollution. The present invention relates to a transfer dyeing method.

[Background technology]

Aqueous ink jet recording inks generally take the form of a solution of a water-soluble dye or a liquid in which a water-insoluble coloring material is dispersed in water or an aqueous solution containing a water-soluble organic solvent. In addition, a dyeing method of performing sublimation transfer by superposing the medium on a hydrophobic fiber or a resin film product after performing inkjet printing on a sheet-shaped medium such as paper, for example, sublimation diffusion dyeing having a peelable ink receiving layer Inkjet printing on a possible film product, heating it as it is to perform sublimation diffusion dyeing on the lower layer film product, then peeling the ink receiving layer, dyeing using sublimation transfer such as dyeing method, sublimability Ink jet recording inks using dyes are used (Patent Document 1 below)
reference).

The sublimation dye ink is generally in the form of a sublimation dye dispersed in an aqueous solution containing water, a water-soluble organic solvent and a dispersant. After ink-jet printing, the ink-jet printing is performed on the ink-receiving layer of a film product that can be sublimated and transferred by superimposing on a transfer target by heating and dyeing, or a sublimation diffusion dyeable film product having a peelable ink-receiving layer. When the heat treatment is carried out and the sublimable dye is sublimated by heating as it is to perform diffusion dyeing on the lower layer film product, the water-soluble organic solvent is volatilized together with water during the heat treatment. This is a point different from inkjet printing intended only for general printing, and in the dyeing method utilizing sublimation transfer, the temperature is raised above the sublimation temperature of the sublimable dye and heated for a certain period of time, so a high boiling organic solvent is used. But it will be volatilized. In particular, in the case of a high-boiling point organic solvent such as glycerin, as soon as the volatilized solvent is released into the atmosphere, the temperature drops to the condensation point, resulting in the production of smoke-like vapor. This looks very unimpressive. To avoid this, it is possible to use a low-boiling organic solvent that does not become smoke-like, but it is the same in that the volatilized solvent is released into the atmosphere. Environmental pollution issues arise.

Further, items required for the performance of ink jet recording inks are (1) prevention of nozzle clogging, ejection stability, (2) ink storage stability, (3) directionality of ink ejection, Examples include high-quality recorded images in which the ejection amount and the dot shape are constant, (4) ink drying properties, and fixability (5) high print density.

In the ink jet recording method, since it is necessary to eject the ink as a small droplet of the ink from a thin nozzle, the above item (1) is particularly important. Particularly, in the on-demand type system, since the ejection of ink from the nozzle is temporarily stopped even during continuous operation, there is a problem that ejection failure occurs during continuous operation for a long time.

Further, in the case of an ink-jet recording ink for sublimation transfer using a sublimable dye, unlike the case of using a water-soluble dye, a precipitate (aggregate) is generated due to deterioration of dispersion stability and water content in a nozzle. It is easy to cause clogging due to the evaporation of water. In particular, when the operation of the device is left for a long time, clogging easily occurs due to evaporation of water.

Therefore, a moisturizing agent is added to suppress evaporation of water. Examples of these moisturizers include high boiling organic solvents such as glycerin and glycols such as polyethylene glycol, and sugars.

However, as described above, in the sublimation transfer method, it is necessary to raise the temperature to the sublimation temperature of the sublimable dye and heat it for a certain period of time. Therefore, even when a high boiling point organic solvent is used as a moisturizing agent, the sublimation transfer method is performed. There is a problem that it volatilizes at the heating temperature and pollutes the environment. Therefore, a moisturizing agent other than an organic solvent, which does not volatilize upon heating during sublimation transfer, and which does not adversely affect the above-mentioned items (1) to (5) required for ink performance. Must be selected.

An example of using a moisturizer other than the water-soluble organic solvent is an aqueous ink-jet ink containing a water-soluble dye and sorbitol (see Patent Document 2 below). 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 ballpoint pens in which maltitol is added using a water-soluble dye or pigment as a colorant has also been proposed (see Patent Document 5 below). In addition, an ink using xylitol and a water-soluble organic solvent in a carbon black dispersion liquid has also been proposed (see Patent Document 6 below).

In the above-mentioned prior art, there is an example in which sugar alcohol is used as a moisturizing agent in pigment ink or water-soluble dye ink, but it may be applied when used in ink in which a sublimable dye is dispersed with a dispersant. There is no indication as to whether or not. In addition, no consideration has been given to environmentally friendly sublimable dye inks by reducing the content of the water-soluble organic solvent as much as possible, and there is no technique that has been suggested as to how to solve the problems that occur in that case. . In addition, when used as a moisturizer, it is also necessary to consider those which are considered to have no adverse effects such as redox on sublimable dyes.

Further, water, a colorant, and the following formula (II) RA- (CH ₂ CH ₂ O) _x -H (II) (wherein, R is a saturated linear chain having 14 to 23 carbon atoms) Hydrocarbons, A is O or OCO, and x is an integer of 1 to 3), and an ink jet ink comprising a moisturizer if necessary (below) is also proposed. See Patent Document 7).

However, these can be used in various dyes, pigments, colored polymers / waxes, etc. as colorants. Of these, water-soluble dyes are preferably used. -Any of them can be used, but acid dyes and direct dyes are more preferable. "And also because only the acid dyes are actually used in the examples. Obviously, its use in sublimable dye inks is not mentioned. Further, even when polyoxyethylene higher alkyl ethers having R of 23 or less in the above formula are used, an ink composition having good redispersibility cannot be obtained when a sublimable dye is used as a coloring material.

[Patent Document 1] Japanese Unexamined Patent Application Publication No. 2002-77951

[Patent Document 2] Japanese Patent Laid-Open No. 57-57762

[Patent Document 3] Japanese Patent Laid-Open No. 60-72968

[Patent Document 4] JP-A-62-101672

[Patent Document 5] JP-A-2-214785

[Patent Document 6] JP 2001-115070 A

[Patent Document 7] Japanese Patent Laid-Open No. 2000-265098

DISCLOSURE OF THE INVENTION [Problems to be Solved by the Invention]

The present invention solves the problems of the ink jet recording ink using the conventional sublimable dye as described above,
There is little environmental pollution, while maintaining the originally required storage stability and performance such as high-quality recorded images, it has excellent nozzle clogging prevention properties, good dispersion stability, and even during long-term continuous operation. The present invention provides an ink jet recording ink having good redispersibility, which enables stable ejection even after the operation of the apparatus is stopped for a long time, and a sublimation transfer dyeing method using the same.

[Means for Solving the Problems]

That is, the sublimation transfer ink jet recording ink of the present invention comprises water, a sugar alcohol having 4 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 of 25 to 150 carbon atoms,
n represents 2 to 100. ) It is characterized by containing the compound shown by.

Further, in the sublimation transfer dyeing method of the present invention, after the ink jet recording ink for sublimation transfer described above is used to perform ink jet printing on a sheet medium, the sheet medium is heated to form a sublimable dye. It is characterized by sublimation transfer to an object to be dyed.

【The invention's effect】

The ink for ink jet recording using the sublimable dye of the present invention as a coloring material component is a redispersion which reduces environmental pollution while maintaining the originally required storage stability and performance such as high quality recorded images. Excellent sublimation transfer that provides good ink quality, has excellent nozzle clogging prevention properties, and provides stable ejection during normal cleaning even during long continuous operation, even after a long period of non-operation of the device. Ink for inkjet recording can be provided.

Further, the sublimation transfer dyeing method of the present invention is originally required for an ink used for dyeing, because sublimation transfer is carried out after ink jet printing is carried out using the above-mentioned ink for sublimation transfer ink jet recording. Storage stability, while maintaining performance such as high-quality recorded images, it is possible to provide a sublimation transfer dyeing method with reduced environmental pollution, the redispersibility of the ink used is improved, and the nozzle clogging prevention is excellent, Therefore, it is possible to provide an excellent sublimation transfer dyeing method in which dyeing can be carried out at all times, and stable ink ejection can be obtained by normal cleaning even during long-term continuous operation and even after the apparatus is stopped for a long time. .

BEST MODE FOR CARRYING OUT THE INVENTION

In the sublimation transfer ink jet recording ink of the present invention and the sublimation transfer dyeing method using the same, the sugar alcohol having four or more OH groups is D.
-It is preferably at least one selected from sorbitol, xylitol and maltitol.

In the sublimation transfer ink jet recording ink 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. , N is preferably a compound represented by 10 to 50.

In the sublimation transfer ink jet recording ink of the present invention and the sublimation transfer dyeing method using the same, the compound represented by the chemical formula (I) is HLB.
Is preferably a compound of 10 or more.

In the sublimation transfer ink jet recording ink of the present invention and the sublimation transfer dyeing method using the same, the sublimation dye is at least one selected from the group consisting of disperse dyes and oil-soluble dyes. Preferably there is.

In the sublimation transfer ink jet recording ink of the present invention and the sublimation transfer dyeing method using the same, the dispersant is an anionic surfactant, a nonionic surfactant, and a polymer surfactant. It is preferably at least one selected from the group consisting of agents.

In the sublimation transfer ink jet recording ink of the present invention and the sublimation transfer dyeing method using the same, the content of the sugar alcohol having 4 or more OH groups is 0. It is preferably 5 to 50% by weight.

In the sublimation transfer ink jet recording ink of the present invention and the sublimation transfer dyeing method using the same, a sugar alcohol having 4 or more OH groups,
The content of the sublimable dye, the dispersant, and the compound represented by the chemical formula (I) is 0.5 to 50% by weight of a sugar alcohol having 4 or more OH groups, based on the total weight of the ink. It is preferable that the content is 2 to 12% by weight, the dispersant is 0.1 to 20% by weight, and the compound represented by the chemical formula (I) is 0.1 to 8% by weight.

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

That is, according to the present invention, a sublimation dye is dispersed with a dispersant, and a sugar alcohol having four or more OH groups is contained as a moisturizing agent in the ink containing the chemical formula (I) to prepare a water-soluble agent. The content of the organic solvent is reduced as much as possible so that it can be put into practical use as a sublimation dye ink in consideration of the environment.

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, a natural alcohol-based compound or a synthetic alcohol-based compound is commercially available, but the number of carbon atoms of these alkyl groups is generally about 12 to 18. In addition, JP 20
In 00-265098, the alkyl group has 1 carbon atom.
4 to 23 polyoxyethylene alkyl ether type compounds are described.

However, even if 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, R is 25 carbon atoms in the compound represented by the chemical formula (I).
It is necessary to use compounds which are ~ 150 alkyl groups.

The sugar alcohol used in the present invention is preferably a sugar alcohol derived from a monosaccharide or a sugar alcohol derived from a disaccharide. Examples of sugar alcohols derived from monosaccharides 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 turanitol. In the present invention, it is necessary to use a sugar alcohol having 4 or more OH groups. When sugar alcohol having less than 4 OH groups, for example, glycerin, is used, the sugar alcohol may be heated during sublimation transfer. It is not preferable because it volatilizes. Among these, D-
Sorbitol, xylitol, and maltitol are preferable, and D-sorbitol is particularly preferable in terms of solubility and economy. These may be used alone or as a mixture of two or more thereof, but the content of the sugar alcohol used in the present invention is the total weight of the ink from the viewpoint of adjusting the viscosity of the ink and preventing clogging due to the moisturizing effect. Is preferably 0.5 to 50% by weight. More preferably 2 to 40% by weight, 5
-25% by weight is particularly preferred.

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 in a range that does not impair the gist of the present invention, it is used in combination with the sugar alcohol. Water-soluble organic 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, ethylene glycol monomethyl ether. Glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether,
Examples thereof include alcohols such as isopropyl alcohol, methanol and ethanol, and basic solvents such as N-methyl-2-pyrrolidone and triethanolamine.

Of the above 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 admixture 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 in which R has 25 or more carbon atoms, redispersibility is improved. A good ink composition for inkjet recording can be obtained. It is preferable to use the compound represented by the following chemical formula (I) from the viewpoints of continuous discharge stability, discharge property after being left for a long time, and long-term storage stability. Further, from the viewpoint of solubility in the water-based 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 1
00, preferably 10 to 50, particularly preferably 2
0 to 50. The alkyl group may be linear or branched, but a linear alkyl group is preferable.

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

R—O— (CH ₂ CH ₂ O) _n —H (I) The compound represented by the chemical formula (I) is preferably used in an amount of 0.1 to 8% by weight based on the total amount of the ink, and more preferably It is preferably 0.1 to 6% by weight, and particularly preferably 0.2 to 4% by weight. By using it 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 the excessive addition amount, and the desired effect can be exhibited, which is preferable.

Examples of the compound of the above formula (I) are:
"Unitox 420" manufactured by Petrolite Inc. (R is a linear alkyl group having 31 to 32 carbon atoms, n is about 3, HL
B = 4), "Unitox 450" (R is carbon number 31 to 31)
32 linear alkyl groups, n is about 10, HLB = 1
0), "Unitox 480" (R is carbon number 31-32
A linear alkyl group of n, about 40, HLB = 16),
"Unitox 520" (R is a linear alkyl group having 38 carbon atoms, n is about 3, HLB = 4), "Unitox 55"
0 "(R is a linear alkyl group having 38 carbon atoms, n is about 1
2, 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 a carbon number of 48 to 4)
9 is a linear alkyl group, n is about 16, HLB = 10), and the like.

The sublimable dye is preferably a sublimable disperse dye or an oil-soluble dye, which may be used alone or as a mixture, but is particularly preferable in view of dispersibility and dyeability. Disperse dyes are preferably used.

An example of the sublimable dye is 70 at atmospheric pressure.
Dyes that sublime or evaporate at ~ 260 ° C are preferred. For example, azo, anthraquinone, quinophthalone, styryl,
Di- or triphenylmethane, oxazine, triazine,
There are dyes such as xanthene, methine, azomethine, acridine, and diazine. Among these, examples of yellow disperse dyes include C.I. I. Disperse Yellow
51, 54, 60, 64, 65, 82, 98, 11
9,160,211 etc. are mentioned. Examples of red disperse dyes include C.I. I. Disperse Red
4, 22, 55, 59, 60, 146, 152, 19
1, 302, Vat Red 41 and the like. Examples of blue disperse dyes include C.I. I. Dispers
e Blue 14, 28, 56, 60, 72, 73,
77, 334, 359, 366 and the like. Other color components include Violet 27, 28 and the like. Oil-soluble dyes other than the above include C.I. I. S
solvent Orange 25, 60, Red 1
55, Blue 35, 36, 97, 104 and the like.

The content of these sublimable dyes is generally
From the viewpoint of maintaining the dispersion stability and obtaining the required printing density, 0.2 to 12% by weight is preferable with respect to the total weight of the ink. It is more preferably 0.5 to 8% by weight.

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

As the anionic surfactant, a formalin condensate of naphthalene sulfonate, a lignin sulfonate, a formalin condensate of a special aromatic sulfonate (sodium alkylnaphthalenesulfonate such as butylnaphthalene and sodium naphthalenesulfonate) is used. With formalin condensate, sodium cresol sulfonate with sodium 2-naphthol-6-sulfonate, formalin condensate with sodium cresol sulfonate, formalin condensate with creosote oil sodium sulfonate, etc.), polyoxyethylene alkyl Ether sulfate and the like can be mentioned.

As the nonionic surfactant, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene acetylene glycol, polyoxyethylene derivative, oxyethylene / oxypropylene block copolymer, etc. Is mentioned.

Examples of the polymeric surfactants include polyacrylic acid partial alkyl esters, polyalkylene polyamines, polyacrylic acid salts, styrene-acrylic acid copolymers, vinylnaphthalene-maleic acid copolymers and the like. .

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 0.
It is 1 to 12% by weight.

Various other additives can be added to the ink of the present invention, if necessary, within a range not hindering the achievement of the object of the present invention. For example, surface modifiers, hydrotropes, pH modifiers, viscosity modifiers, preservatives, fungicides, light stabilizers, chelating agents, defoamers and the like.

Among the above additives, the surface conditioner includes
Examples of the surfactant include fluorine-based surfactants, polyether-modified polydimethylsiloxane, and acrylic polymers. In the present invention, polyether-modified polydimethylsiloxane and acrylic polymers are particularly preferable. These surface modifiers are effective in adjusting the surface tension of the ink and making the ink easily wet with the ink flow path system material, but preferably 0.05 to 1% by weight based on the total weight of the ink, It is preferably used in the range of 0.1 to 0.5% by weight. 0.0
If it is less than 5% by weight, the effect tends to decrease, and if it exceeds 1% by weight, the effect tends not to increase so much.

The method for adjusting the ink for ink jet recording of the present invention is not particularly limited, but it is preferably adjusted by the method described below. That is, first, (1) a sublimation dye, the sugar alcohol, the compound of the chemical formula (I), a dispersant, water, and, if necessary, a water-soluble organic solvent and the additive are mixed and stirred to prepare a preliminary mixture. A dispersion liquid is prepared, and then (2) the sublimation dye is made into fine particles by a wet medium mill such as a sand mill and dispersed to obtain a dye dispersion liquid. (3) Water, water-soluble organic solvent and the above-mentioned additives are added to the dye dispersion liquid to adjust the concentration, and then filtered with a filter paper or the like before use.

In the above method, the sugar alcohol may be added at the time of forming the fine particles, at the time of adjusting the concentration, 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 preferably used.

Further, the compound of the chemical formula (I) may be added at the time of forming the fine particles, at the time of adjusting the concentration, or may be added in a divided manner. It is preferable to use an aqueous solution of about 15% by weight.

The sublimable dye obtained by the above method preferably has an average particle size of 0.5 μm or less, more preferably 0.0
It is 5 to 0.2 μm.

The sublimation dye, the sugar alcohol having four or more OH groups, the dispersant, and the other components have been described above by way of specific examples, but the present invention is only those exemplified by these specific examples. It is not limited to.

As a method for dyeing by sublimation transfer using the ink for ink-jet recording for sublimation transfer of the present invention as described above, after ink-jet printing on a sheet-like medium using the ink for ink-jet recording for sublimation transfer, A method of heating the sheet medium to sublimate and transfer the sublimable dye to the object to be dyed is adopted.

The object to be dyed is not particularly limited in its shape and material as long as it can be dyed by sublimation transfer dyeing. Generally, a hydrophobic fiber cloth or resin film,
Sheets such as paper are used, but not sheets
It is also possible to apply to a three-dimensional object such as a spherical object or a cubic object.

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

The sheet-like medium used in the former method has a coating layer containing at least a hydrophilic polymer and / or an inorganic porous material, as well as a non-coated recording sheet-like medium such as plain paper. An example of the recording sheet medium is a sheet support.

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

In this case, the ink receiving layer is, for example, a layer mainly composed of a water-soluble resin capable of absorbing and receiving ink rapidly, and the water-soluble resin component is a water-soluble or hydrophilic natural or synthetic polymer. is there. 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 resin such as polyacrylamide; polyethylene oxide; synthetic resin such as polyglutamic acid : Carboxymethyl cellulose; Semi-synthetic resins such as cellulose derivatives such as methyl cellulose:
Chitin; chitosan; starch; one or more appropriately selected from natural resins such as gelatin and the like can be used. Polyacrylic acid, polyelectrolyte polyelectrolytes such as alkali metal salts such as polystyrene sulfonic acid, or polycation polyelectrolytes such as polyethyleneimine, polyvinylamine, polyallylamine, polyvinylalkylammonium halides, polyvinylbenzylalkylammonium halides, Alternatively, amphoteric polyelectrolytes can be used. Further, from the viewpoint of ink absorbability, porous pigments such as silica, clay, talc, diatomaceous earth, zeolite, calcium carbonate, alumina, zinc oxide and titanium oxide may be added.

As the lower layer film product corresponding to the object to be dyed, polyester film, polyurethane film, polycarbonate film, polyphenylene sulfide film, polyimide film, polyamide imide film, etc., and sublimation on the surface of these films A film made of a material capable of being dyed by sublimation without being melted by heat at the time of sublimation transfer or being significantly shrunk, such as a film in which a resin having no affinity for the functional dye, for example, a fluorine resin is laminated is used.

The heating temperature for sublimation transfer differs depending on the type of the sublimable dye used, and thus it is difficult to define it in a general manner, but it is usually about 150 to 200 ° C., and the heating time is 2 to
It takes about 10 minutes.

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

[Example 1]

Red disperse dye base (CI Dispe
20 parts, formalin condensate of special aromatic sodium sulfonate as an anionic surfactant as a dispersant (“Demol SNB” manufactured by Kao Corporation) 12
Part, "Unitox 480" (Compound of the chemical formula (I) manufactured by US Petrolite Co., Ltd., R is a linear alkyl group having 31 to 32 carbon atoms, n is about 40, and HLB is 16) 5
And 330 parts of water were used to prepare 330 parts of zircon beads having a diameter of 0.4 mm, and the mixture was atomized for 35 hours in a sand mill to obtain a dispersion liquid.

To this dispersion, 5 parts of "Unitox 480", 85 parts of "sorbitol S" (70% aqueous solution of D-sorbitol manufactured by Niken Chemical Co., Ltd.), and a polyether-modified polydimethylsiloxane ( An ink was prepared by adding 2.0 parts of "BYK-348" manufactured by Big Chemie Japan Co., Ltd.) and water to adjust the dye concentration to 5%. The average particle size of the dye was 0.10 μm.

Example 2

Instead of the red disperse dye base, a yellow disperse dye base (CI Disperse Yellow) was used.
54) Microparticulation was performed in the same manner as in Example 1 except that 20 parts were used, and 25 parts of "Unitox 480" as the compound of the above chemical formula (I), "215 parts of" sorbitol S "and surface preparation were added to the dispersion. 2.5 parts of "BYK-348" as an agent was further added with water to prepare an ink having a dye concentration adjusted to 2%. The average particle size of the dye was 0.12 μm.

Example 3

Blue Disperse Dye Constituent (CI Dispe
20 parts, formalin condensate of sodium β-naphthalenesulfonate as an anionic surfactant as a dispersant (“Demol N” manufactured by Kao Corporation) 1
A mixture of 2 parts, 5 parts of "Unitox 480" as the compound of the above chemical formula (I) and 123 parts of water has a diameter of 0.
Example 1 using 330 parts of 4 mm zircon beads
Microparticulate in the same manner as described above, and 15 parts of "Unitox 480", 130 parts of "sorbitol S", and an acrylic polymer as a surface conditioner ("BYK-381" manufactured by BYK Japan KK) in this dispersion liquid. Was added to prepare an ink in which the dye concentration was adjusted to 3.3%. The average particle size of the dye was 0.08 μm.

Example 4

To 40 parts of the dispersion obtained by atomizing in the same manner as in Example 1, 10 parts of "Unitox 480" as the compound of the above chemical formula (I) and "sorbitol S" 85 were added.
Part, 0.4 part of "BYK-348" as a surface conditioner,
Further, water was added to prepare an ink having a dye concentration adjusted to 1.25%.

Example 5

An ink was prepared in the same manner as in Example 1 except that 60 parts of xylitol was used in place of "sorbitol S" in Example 1.

Example 6

An ink was prepared in the same manner as in Example 1 except that 60 parts of maltitol was used in place of "sorbitol S" in Example 1.

Example 7

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

To this dispersion, "sorbitol S" 85
Part, "BYK-348" as a surface conditioner) 2.0 parts,
Further, water was added to prepare an ink having a dye concentration adjusted to 5%. The average particle size of the dye was 0.10 μm.

Example 8

Instead of the red disperse dye base, a yellow disperse dye base (CI Disperse Yellow) was used.
54) 20 parts, 4 parts of "Unitox 480", 1 part of water
Microparticulation was performed in the same manner as in Example 5 except that 24 parts were used, and 215 parts of "sorbitol S", 2.5 parts of "BYK-348" as a surface conditioner, and water were further added to the dispersion to obtain a dye concentration. Was adjusted to 2% to prepare an ink. The average particle size of the dye was 0.12 μm.

[Example 9]

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

[Comparative Example 1]

An ink was prepared in the same manner as in Example 1 except that 60 parts of glycerin was used instead of "sorbitol S" in Example 1.

[Comparative Example 2]

Example 1 except that 60 parts of diethylene glycol was used instead of "sorbitol S" of Example 1.
Ink was created in the same manner as.

[Comparative Example 3]

Instead of "Unitox 480" of Example 1, a formalin condensate of special aromatic sodium sulfonate as an anionic surfactant ("Demol manufactured by Kao Corporation")
An ink was prepared in the same manner as in Example 1 except that the same amount of SNB ″) was used.

[Comparative Example 4]

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. Dye particle size is 1 μm
That was all. When the ink obtained was left to stand, the dyes gradually aggregated to form a precipitate. Therefore, when the dispersant was not used, the ink was inferior in storage stability and could not be used as an ink for inkjet recording.

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

Further, the above Examples 1 to 9 and Comparative Examples 1 to
The following tests were conducted on the ink prepared in 3. The test results are shown in Table 2.

(1) Redispersibility test 0.5 g of the ink composition was thinly spread on the surface of a watch glass (φ 90 mm), and then the temperature was 30 ° C. and the relative humidity was 20.
Put it in a constant temperature and humidity chamber adjusted to%, and leave it for a while. After 3 hours, the watch glass is taken out of the dryer, and the state in which the ink is gently rinsed with a small amount of water from the outside of the peripheral portion where the ink has become dry is observed. Evaluation criteria: (○) Redispersion is carried out immediately without agglomeration. (A) A small thin film-like aggregate is observed, but it does not adhere to the glass surface. (X) A considerable amount of aggregates were observed and remained attached to the glass surface.

(2) Continuous Discharge Stability Test Using a commercially available large-sized inkjet plotter "JV2-130" (Piezo method) manufactured by Mimaki Engineering Co., Ltd., a printing resolution of 720 x 720 dpi, solid color, solid printing, printing Continuous printing was performed under the condition of a width of 1200 mm until defective printing such as missing dots was 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) Ejectability after being left for a long time After being continuously operated for 30 minutes under the above printing conditions, it is left as it is for 48 hours, and after a normal cleaning, a printing test is again performed to see if normal printing can be performed under the same conditions. went. Evaluation criteria:
(∘) Normal printing was possible with a single predetermined head cleaning of the inkjet plotter. (△) Needs cleaning several times. (X) Does not recover even after further cleaning.

(4) Sublimation transfer dyeing test Using the ink-jet recording inks for sublimation transfer prepared in Examples 1 to 9 and Comparative Examples 1 to 3, films capable of sublimation transfer dyeing having a releasable ink-receiving layer were used. Product (on a support polyester film with a thickness of 50 μm,
A polyurethane resin-based dye fixing layer is coated to a thickness of 30 μm and dried, and then a fluoroolefin-based copolymer resin layer is coated to a thickness of 20 μm and crosslinked,
Furthermore, after sticking an adhesive layer and a release paper on the back surface of the film, a cross-linking type urethane-based inkjet coating agent "Pateracol IJ-50" (trademark, manufactured by Dainippon Ink and Chemicals, Inc.) is used as an ink receiving layer on the film surface. It was formed by stacking layers with a thickness of 20 μm. ), The large-sized inkjet plotter (piezo type, manufactured by Mimaki Engineering Co., Ltd. “JV2-13”).
0 ") is used to print the image, and the temperature is approximately 170 ° C
Hot air dryer set to (Fine Oven manufactured by Yamato Scientific Co., Ltd.
DF62 ") heat treatment was performed for about 7 minutes. During the heat treatment, the state of heated steam ejected from the ventilation port of the dryer was observed. After that, when the ink receiving layer was peeled off, the film product was formed. A film product was obtained in which the image was sublimation diffusion dyed.

Evaluation criteria: (◯) No smoke-like vapor was observed. (△) Smoke-like vapor is slightly generated. (×) A considerable amount of smoke-like vapor was observed.

[0084]

[Table 1]

[0085]

[Table 2] As is clear from these test results, in Examples 1 to 9 of the present invention, generation of smoke-like vapor was not observed during the heat treatment, redispersibility was good, continuous discharge stability and long-term discharge were stable. It was also excellent in dischargeability after standing. Comparative Example 1 in which D-sorb beer was replaced with glycerin or diethylene glycol
In Nos. 2 and 3, generation of considerably smoky vapor was observed. In Comparative Example 3 in which the compound of the formula (I) was replaced with the anionic dispersant, generation of smoke-like vapor was not observed, but redispersibility was poor, continuous ejection stability and leaving for a long time were left. The dischargeability afterwards was also poor.

[Industrial availability]

The ink for ink jet recording using the sublimable dye of the present invention as a coloring material component is a redispersion which reduces environmental pollution while maintaining the originally required storage stability and performance such as a high quality recorded image. Ink having excellent properties can be obtained, nozzle clogging prevention is excellent, and stable ejection can be obtained by normal cleaning even during long-term continuous operation and even after the apparatus has been stopped for a long time. Therefore, it is suitable for an inkjet recording ink using a sublimable dye as a coloring material component.

Further, the sublimation transfer dyeing method of the present invention is originally required for the ink used for dyeing, because sublimation transfer is carried out after ink jet printing is carried out using the above described sublimation transfer ink jet recording ink. Storage stability, while maintaining performance such as high-quality recorded images, it is possible to provide a sublimation transfer dyeing method with reduced environmental pollution, the redispersibility of the ink used is improved, and the nozzle clogging prevention is excellent, Therefore, it is possible to provide an excellent sublimation transfer dyeing method in which dyeing can be carried out at all times, and stable ink ejection can be obtained by normal cleaning even during long-term continuous operation and even after the apparatus is stopped for a long time. . Therefore, the sublimation transfer dyeing method of the present invention is suitable for inkjet printing using the inkjet recording ink for sublimation transfer.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 2000-351924 (JP, A) JP 54-74105 (JP, A) JP 2001-329195 (JP, A) JP 8-325495 ( JP, A) JP 2002-30092 (JP, A) JP 2001-226617 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09D 11/00 B41J 2/01 B41M 5 / 00

Claims (10)

(57) [Claims] 1. Water, a sugar alcohol having 4 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) (formula). R represents an alkyl group having 25 to 150 carbon atoms,
n represents 2 to 100. ) An ink for inkjet recording for sublimation transfer, which comprises a compound represented by 2. The ink for inkjet recording for sublimation transfer according to claim 1, wherein the sugar alcohol having 4 or more OH groups is at least one selected from D-sorbitol, xylitol and maltitol. 3. The compound according to claim 1, wherein the compound represented by the chemical formula (I) is a compound in which R represents an alkyl group having 30 to 50 carbon atoms and n represents 10 to 50. Inkjet recording ink for sublimation transfer. 4. A compound represented by the chemical formula (I) is HLB.
Is a compound of 10 or more, and the inkjet recording ink for sublimation transfer according to claim 1. 5. The sublimation dye is at least one selected from the group consisting of disperse dyes and oil-soluble dyes.
5. The ink for inkjet recording for sublimation transfer according to any one of 4 to 4. 6. The dispersant is at least one selected from the group consisting of anionic surfactants, nonionic surfactants, and polymer surfactants. Inkjet recording ink for sublimation transfer. 7. The inkjet recording for sublimation transfer according to claim 1, wherein the content of the sugar alcohol having 4 or more OH groups is 0.5 to 50% by weight based on the total weight of the ink. Ink. 8. A sugar alcohol having 4 or more OH groups,
The content of the sublimable dye, the dispersant, and the compound represented by the chemical formula (I) is 0.5 to 50% by weight of a sugar alcohol having 4 or more OH groups, based on the total weight of the ink. 2 to 12% by weight, a dispersant of 0.1 to 20% by weight, and a compound represented by the chemical formula (I) in an amount of 0.1 to 8% by weight. Ink. 9. The inkjet recording ink for sublimation transfer according to claim 1, which contains substantially no water-soluble organic solvent. 10. A sheet-shaped medium is inkjet-printed by using the inkjet recording ink for sublimation transfer according to claim 1, and then the sheet-shaped medium is heated to cover the sublimable dye. A sublimation transfer dyeing method characterized by sublimation transfer to an object to be dyed.