JP6831690B2 - Recording system with ink for inkjet and an inkjet printer - Google Patents

Description

The present invention uses a recording system including an inkjet ink containing a specific amine compound, a resin dispersant, and a sublimating dye, a thermal inkjet printer that records by applying thermal energy, and inkjet recording. Regarding the attached recording media.

The inkjet recording (dyeing) method for hydrophobic fibers typified by polyester fibers can be roughly classified into the following two methods. That is, a direct dyeing method in which the ink is directly applied to the fibers and then the dye in the ink is dyed on the fibers by heat treatment such as high temperature steaming, and after the ink is applied to an intermediate recording medium (dedicated transfer paper or the like), the ink is applied. This is a sublimation transfer dyeing method in which the ink-applied surface of the intermediate recording medium and the hydrophobic fibers are superposed, and then the dye is transferred from the intermediate recording medium to the fiber side by heat.

Of these two methods, the sublimation transfer dyeing method is mainly used for dyeing ordinary banners and the like, and an easy sublimation type dye having excellent transfer suitability to polyester by heat treatment is used in the ink. In sublimation transfer dyeing, in general,
(1) Printing process:
The process of applying the dye in the ink to the intermediate recording medium with an inkjet printer,
(2) Transfer process:
A step of transferring and dyeing a dye applied to an intermediate recording medium by heat treatment from the medium to fibers.
Two steps are required.
On the other hand, in direct dyeing, since ink is directly applied to the fibers, it is common practice to perform pretreatment on the fibers before applying ink for the purpose of preventing dye bleeding and the like. It is also indispensable to wash the dyed fibers for the purpose of removing ink components other than the paste and dyes added by the pretreatment step from the dyed fibers. However, in sublimation transfer dyeing, since recording is performed on an intermediate recording medium and then transferred to fibers, a pretreatment step or a washing step of fibers is not required. In addition, at the time of transfer dyeing, since the dye applied to the intermediate recording medium is sublimated and transferred to the fiber by heating, a cleaning step of removing the glue and ink components other than the dye applied to the fiber is required as in direct dyeing. There are advantages such as not being able to widely use commercially available transfer paper as an intermediate recording medium.

Various types of inkjet inks for direct dyeing and sublimation transfer dyeing have been conventionally developed. Of these, the performance required for water-based dispersed inks containing disperse dyes and oil-soluble dyes, which are insoluble or sparingly soluble dyes in water, includes ejection stability during inkjet recording, increased ink viscosity, and separation. Not storage stability; etc.

Discharge defects during inkjet recording are often caused by the evaporation of water in the ink near the nozzle plate. When the ejection is poor, the ink may fly and bend, which causes problems such as deterioration of the quality of the inkjet recorded image. Therefore, improving the ejection stability during inkjet recording is one of the important issues.

The selection of the dispersant in the ink composition is also important for improving the ejection stability. For example, when a conventionally used dispersant such as an anion dispersant or a nonionic dispersant is used, in sublimation transfer dyeing, an odor is generated due to volatilization of the dispersant due to heating during transfer, and in direct dyeing, If the dispersant remains on the recording medium after dyeing, there is a problem that black bleeding occurs due to contact with water such as rainwater, and it is required to select a dispersant that can solve these problems. In addition to this, the thermal inkjet method, in which heat energy is applied to perform recording, requires higher thermal stability for the ink than the piezo method.

Patent Document 1 discloses an aqueous inkjet ink for sublimation transfer using a polyglycerin and a polyol compound in combination with an anion dispersant and a nonionic dispersant, and describes that it is excellent in ejection stability. .. However, the anion dispersants used (creosote oil sulfonic acid, methylnaphthalene sulfonic acid) generate an odor when heated, and therefore have a problem in workability. Patent Document 2 discloses an ink using a resin dispersant, and describes that it is possible to suppress the occurrence of bleeding during the formation of a color image. However, the improvement effect on discharge stability is not described.

Japanese Unexamined Patent Publication No. 2011-21133 Japanese Unexamined Patent Publication No. 2001-81376

An object of the present invention is to provide a recording system including an ink for inkjet and an inkjet printer having excellent ejection stability, and a recording medium to which ink is attached by inkjet recording.

As a result of diligent studies to solve the above problems, the present inventors have made a specific amine compound, a resin dispersant, and a sublimating dye into an ink for an inkjet, so that the ink for an inkjet has excellent ejection stability. We have found that the above problems can be solved by making it possible to obtain ink and providing a recording system including an inkjet printer using the ink, performing inkjet recording by the system, and adhering the ink to a recording medium. It was completed.

That is, the present invention relates to the following 1) to 14).
1)
A recording provided with an ink containing an amine compound represented by the following formula (1), a resin dispersant, and at least one type of sublimating dye, and a thermal inkjet printer for recording by applying thermal energy. system. However, the resin dispersant is a resin dispersant neutralized with an amine compound represented by the following formula (1).

(R ^{1 to} R ³ in the formula (1) are independently selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group, and a heterocyclic group. Represents the group to be
2)
Recording including the ink according to 1) in which at least one or more of R ^{1 to} R ³ in the formula (1) is other than a hydrogen atom, and a thermal inkjet printer for recording by applying thermal energy. system.
3)
The ink and thermal energy according to 1) or 2), wherein at least one or more of R ^{1 to} R ³ in the formula (1) is an aliphatic hydrocarbon group which may have a substituent, acts. A recording system equipped with a thermal inkjet printer for recording.
4)
The ink according to any one of 1) to 3), wherein the aliphatic hydrocarbon group which may have a substituent is an alkyl group of C1-C6 which may have a substituent. A recording system equipped with a thermal inkjet printer that performs recording by applying thermal energy.
5)
At least one or more of R ^{1 to} R ³ in the formula (1) substitutes a group selected from the group consisting of a hydroxyl group, an amino group, a sulfo group, and a heterocyclic group which may have a substituent. A recording system including the ink according to 4), which is an alkyl group of C1-C6 having a group, and a thermal inkjet type inkjet printer that performs recording by applying thermal energy.
6)
R ¹ in the formula (1) is an alkyl group of C1-C6 having a group selected from the group consisting of a hydroxyl group, a sulfo group, and a heterocyclic group which may have a substituent as a substituent, and R ² and R ³ are alkyl groups of C1-C6 each having a hydrogen atom or a group selected from the group consisting of a heterocyclic group which may have a hydroxyl group, a sulfo group and a substituent as a substituent. 5) A recording system including the above-mentioned ink and a thermal inkjet type inkjet printer that performs recording by applying thermal energy.
7)
R ¹ in the formula (1) is an alkyl group of C1-C3 having a group selected from the group consisting of a hydroxyl group, a sulfo group, and a heterocyclic group which may have a substituent as a substituent, and R ² and R ³ are alkyl groups of C1-C3 having a hydrogen atom or a group selected from the group consisting of a heterocyclic group which may have a hydroxyl group, a sulfo group and a substituent as a substituent, respectively. , 6) A recording system including the above-mentioned ink and a thermal inkjet type inkjet printer that performs recording by applying thermal energy.
8)
In formula (1), R ¹ is a group selected from the group consisting of a 2-hydroxyethyl group, a 2-sulfoethyl group, and a frill group, and R ² and R ³ are independently hydrogen atoms or 2-hydroxy. A recording system including the ink according to any one of 1) to 7), which is an ethyl group, and a thermal inkjet printer for recording by applying thermal energy.
9)
In formula (1), R ¹ , R ² and R ³ are 2-hydroxyethyl groups, respectively, or R ¹ and R ² are 2-hydroxyethyl groups, respectively, and R ³ is a hydrogen atom, or R ¹ is a frill. R ² and R ³ are hydrogen atoms, respectively, or R ¹ is a 2-sulfoethyl group, R ² and R ³ are hydrogen atoms, respectively, and R ¹ is a 2- (methylamino) ethanol group, R ² and A recording system comprising the ink according to any one of 1) to 8), wherein R ³ is each a combination of hydrogen atoms, and a thermal inkjet printer for recording by applying thermal energy.
10)
A recording system including the ink according to any one of 1) to 9), wherein the resin dispersant is a styrene-acrylic resin dispersant, and a thermal inkjet printer for recording by applying thermal energy.
11)
The ink according to any one of 1) to 10), wherein the resin dispersant is a styrene-acrylic resin dispersant having a carboxyl group in the molecule, and a thermal inkjet type inkjet that records by applying thermal energy. A recording system with a printer.
12)
The ink according to any one of 1) to 11), wherein the dye having sublimation property is a disperse dye, an oil-soluble dye, and a vat dye, and a thermal inkjet printer for recording by applying thermal energy. System with.
13)
In the system according to any one of 1) to 12), the ink according to any one of 1) to 12) is ejected by the inkjet printer according to any one of 1) to 12). An inkjet recording method for recording by attaching it to a recording medium.
14)
13) A recording medium recorded by the recording method described.

The recording system including the inkjet ink and the inkjet printer of the present invention is extremely excellent in ejection stability of the inkjet ink and is useful in recording on a recording medium.

The inkjet ink of the present invention contains an amine compound represented by the formula (1), a resin dispersant, and at least one type of dye having sublimation properties. However, the resin dispersant is a resin dispersant neutralized with the amine compound represented by the formula (1). In addition, the system including the inkjet printer of the present invention is configured to require a thermal inkjet printer that records by applying thermal energy.

In the present specification, unless otherwise specified, the acidic functional group among the ionic hydrophilic groups is represented in the form of a free acid including Examples and the like. Further, in the present specification, unless otherwise specified, "compound" having an ionic hydrophilic group is used as a meaning including both "compound or a salt thereof". Further, in the present specification, unless otherwise specified, "%" and "part" are based on mass including examples and the like.

The inkjet ink of the present invention contains an amine compound represented by the formula (1). R ^{1 to} R ³ in the formula (1) are independently selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group, and a heterocyclic group. Represents a group. In the present invention, the "hydrogen atom" is treated as a substituent.

Examples of the aliphatic hydrocarbon group which may have a substituent in the formula (1) include saturated or unsaturated linear, branched or cyclic alkyl groups, and C1-C36 alkyl groups. It is preferably an alkyl group of C1-C18, more preferably an alkyl group of C1-C6, and even more preferably an alkyl group of C1-C3. Examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-decyl group and an n-octadecyl group. Can be mentioned. Examples of the branched alkyl group include an isopropyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a 2-ethyl-hexyl group, a 1-methylbutyl group, a 1-ethylpropyl group, an isopentyl group, an isohexyl group, and 1-. Examples thereof include a methylpentyl group, a 1-ethylbutyl group and an isoheptyl group. Examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, a 2-methylcyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a 2,4-dimethylcyclohexyl group, and 3 , 5-Dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 3,3,5-trimethylcyclohexyl group, 4-t-butylcyclohexyl group, 2-ethylcyclohexyl group and the like. ..

Examples of the aromatic hydrocarbon group which may have a substituent in the formula (1) include a phenyl group, a naphthyl group, an anthracenyl group, a fluorene group, a quinone group, a benzyl group, a trill group and the like.

Examples of the heterocyclic group which may have a substituent in the formula (1) include a five-membered heterocyclic group such as a frill group, a tetrahydrofuryl group, a thienyl group, a tenyl group and a pyrrole group, a pyridyl group and a piperidyl group. , A six-membered heterocyclic group such as a tetrahydropyranyl group and a quinolino group.

Examples of the substituent which the aliphatic hydrocarbon group, the aromatic hydrocarbon group and the heterocyclic group may have in the formula (1) include a hydroxyl group, a halogen atom, a cyano group, a carboxyl group and a sulfo group. , Phosphate group, aliphatic hydrocarbon group, aromatic hydrocarbon group, heterocyclic group, amino group, alkoxyl group, aryloxy group, etc., and are hydroxyl group, amino group, sulfo group, heterocyclic group. Is preferable, a hydroxyl group, a sulfo group, and a heterocyclic group are more preferable, and a hydroxyl group, a sulfo group, and a frill group are particularly preferable. The aliphatic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group may be the same as described above.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the amino group include a substituted or unsubstituted amino group. Examples of the substituted amino group include an amino group substituted with an aliphatic hydrocarbon group such as a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a benzylamino group, a dibenzylamino group and a methylethylamino group, and phenylamino. Cyclic amino groups such as amino groups substituted with aromatic hydrocarbon groups such as groups and diphenylamino groups, monothiophenoamino groups, dithiophenoamino groups, difurylamino groups, amino groups substituted with heterocyclic groups, morpholine, piperidine and the like. And so on. The aliphatic hydrocarbon group, aromatic hydrocarbon group, and heterocyclic group may be the same as described above.

As the alkoxyl group, for example, an aliphatic hydrocarbon group such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, and an oxygen atom are bonded. The group is mentioned. The aliphatic hydrocarbon group may be the same as described above.

Examples of the aryloxy group include groups in which an aromatic hydrocarbon group and an oxygen atom are bonded, such as a phenoxy group, a naphthoxy group, and a p-tolyloxy group. The aromatic hydrocarbon group may be the same as described above.

As a combination of ^{R 1} to ^{R 3} in the formula (1), it is desirable or at least one one of ^{R 1} to ^{R 3} is other than hydrogen atom, or at least one one of ^{R 1} to ^{R 3} is It is preferably an aliphatic hydrocarbon group which may have a substituent, and at least one or more of R ^{1 to} R ³ is an alkyl group of C1-C6 which may have a substituent. More preferably, a group selected from the group consisting of a heterocyclic group in which at least one or more of R ^{1 to} R ³ may have a hydroxyl group, an amino group, a sulfo group, or a substituent is used as a substituent. It is particularly preferable that it is an alkyl group of C1-C6 having as a substituent, and R ¹ has a group selected from the group consisting of a hydroxyl group, a sulfo group, and a heterocyclic group which may have a substituent as a substituent. a of C1-C6 alkyl group, each R ² and R ^3, a hydrogen atom or a hydroxyl group, a sulfo group, a group selected from the group consisting of heterocyclic group which may have a substituent group substituent It is more preferable that it is an alkyl group of C1-C6 having as a substituent, and R ¹ has a group selected from the group consisting of a hydroxyl group, a sulfo group, and a heterocyclic group which may have a substituent as a substituent. a C1-C3 alkyl group, each R ² and R ^3, a hydrogen atom or a hydroxyl group, a sulfo group, a group selected from the group consisting of heterocyclic group which may have a substituent group substituent It is very preferable that it is an alkyl group of C1-C3, in which R ¹ is a group selected from the group consisting of a 2-hydroxyethyl group, a 2-sulfoethyl group and a frill group, and R ² and R ³ are. It is highly preferable that they are independently hydrogen atoms or 2-hydroxyethyl groups, and R ¹ , R ² and R ³ are 2-hydroxyethyl groups, respectively, or R ¹ and R ² are 2-hydroxyethyl groups, respectively. There ^{R 3} is a hydrogen atom, or ^{R 1} is furyl and ^{R 2} and ^{R 3} are each a hydrogen atom, or, ^{R 1} is 2-sulfoethyl radical ^{R 2} and ^{R 3} are each a hydrogen atom, ^{R 1} is Most preferably, it is a combination of a 2- (methylamino) ethanol group and R ² and R ³ are hydrogen atoms, respectively.

Specific examples of the above-mentioned alkyl group of C1-C6 having a hydroxyl group as a substituent include a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, and 3 -Hydroxybutyl group, 2-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group, hydroxyethoxymethyl group, 2-hydroxyethoxyethyl group, 3-hydroxyethoxypropyl group, 3-hydroxyethoxybutyl group, 2 -Hydroxyethoxybutyl group and the like can be mentioned, and a 2-hydroxyethyl group is preferable.

Specific examples of the above-mentioned alkyl group of C1-C6 having an amino group as a substituent include an aminomethyl group, a 2-aminoethyl group, a 3-aminopropyl group, a 2-aminopropyl group, a 4-aminobutyl group, and 3 Examples thereof include a −aminobutyl group, a 2-aminobutyl group, a 5-aminopentyl group, a 6-aminohexyl group and the like, and a 2-aminoethyl group is preferable.

Specific examples of the above-mentioned alkyl group of C1-C6 having a sulfo group as a substituent include a sulfomethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, a 2-sulfopropyl group, a 4-sulfobutyl group and a 3-sulfobutyl group. , 2-sulfobutyl group, 5-sulfopentyl group, 6-sulfohexyl group and the like, and 2-sulfoethyl group is preferable.

Specific examples of the above-mentioned alkyl group of C1-C6 having a heterocyclic group which may have a substituent as a substituent include a furfuryl group, a 2-furylethyl group, a 3-furylpropyl group and a 4-furylbutyl group. , 2-furylbutyl group, 3-furylbutyl group, thienylmethyl group, 2-thienylethyl group, 3-thienylpropyl group, pyrylmethyl group, tetrahydrofurylmethyl group and the like, and a fulfuryl group is preferable. Examples of the substituents that the heterocyclic group may have include the substituents that the aliphatic hydrocarbon group, the aromatic hydrocarbon group, and the heterocyclic group in the formula (1) may have, respectively. It can be the same as the one. The furfuryl group, a group furan bonded via a methylene, _{i.e., C 4 H 3 O-CH} 2 - group, wherein for example, the furfuryl group is substituted one to ammonia (NH _3), a furfuryl amine ..

The amine compound represented by the formula (1) can be used alone or in combination of two or more, and can be appropriately selected in the above-mentioned inkjet ink by a combination with a resin dispersant, a dye having sublimation property, or the like.

The above-mentioned inkjet ink contains a resin dispersant. Examples of the resin dispersant include styrene, styrene derivatives, vinylnaphthalene, vinylnaphthalene derivatives, aliphatic alkyl esters of α and β-ethylenically unsaturated carboxylic acids, acrylic acids and their derivatives, maleic acid and its derivatives, and itacons. Block copolymers, random copolymers and block copolymers consisting of at least two or more monomers selected from acids and derivatives thereof, fumaric acid and derivatives thereof, vinyl acetate, vinyl alcohol, vinylpyrrolidone, acrylamide, derivatives thereof and the like. Graft copolymers, and block polymers containing these salts, polyethyleneimine, polyvinyl ether structures, acrylic block polymers, methacrylic block polymers, polyoxyethylene, block polymers with blocks of polyoxyalkylene, styrene-acrylic resin dispersion Examples thereof include a styrene-acrylic resin dispersant, and a styrene-acrylic resin dispersant is preferable. In the above-mentioned inkjet ink, these resin dispersants can be used alone or in combination of two or more.

Examples of the styrene-acrylic resin dispersant include block copolymers composed of monomers of styrene and acrylic acid, random copolymers and graft copolymers, which are represented by the following formula (2) or formula (3). It is preferable that the structure is formed.

In the above equation (2), n ^{1 to} n ³ represent integers of 1 to 30, respectively. Further, m ¹ and m ² in the above formula (3) represent integers of 1 to 43, respectively. The styrene-acrylic resin dispersant represented by the formulas (2) and (3) preferably has a molecular weight of 5,000 or more. Examples of the carboxyl group-containing styrene-acrylic resin dispersant particularly preferably used in the present invention include John Krill 678 (manufactured by BASF, molecular weight = 8,500, solid acid value = 215), John Krill 611 (BASF). Co., Ltd., molecular weight = 8,100, solid acid value = 53), John Krill 819 (BASF, molecular weight = 14,500, solid acid value = 75), John Krill 690 (BASF, molecular weight = 16) , 500, solid acid value = 240) and the like, and John Krill 678 is more preferable.

As the sublimation dye contained in the above ink, it is preferable to select and use a dye having sublimation transfer suitability from known disperse dyes, oil-soluble dyes and vat dyes. For dyes with sublimation transfer suitability, the test results of the dry heat treatment test (method C) contamination (polyester) in the dyeing fastness test method for JIS L 0879 dry treatment are preferably grade 3-4 or lower, more preferably grade 3. The following dyes. Specific examples of such dyes include C.I. I. Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, 86; C.I. I. Disperse Orange 1, 1: 1, 5, 20, 25, 25: 1, 33, 56, 60, 76; C.I. I. Disperse Brown 2, 27; C.I. I. Disperse threads 4, 11, 50, 53, 55, 55: 1, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190: 1, 207, 239, 240; C.I. I. Bat Red 41; C.I. I. Disperse Violet 8, 17, 23, 27, 28, 29, 36, 57; C.I. I. Disperse Blue 19, 26, 26: 1, 35, 55, 56, 58, 64, 64: 1, 72, 72: 1, 81, 81: 1, 91, 95, 108, 131, 141, 145, 359 360; C.I. I. Solvent blue 36, 63, 105, 111; and the like. These may be used alone or in combination of two or more.
Of the above, from the viewpoint of storage stability of the ink, C.I. I. Disperse Yellow 3, 7, 8, 23, 51, 54, 60, 71, 86; C.I. I. Disperse Orange 20, 25, 25: 1, 56, 60, 76; C.I. I. Disperse Brown 2, 27; C.I. I. Disperse threads 4, 11, 53, 55, 55: 1, 59, 60, 65, 70, 75, 146, 190, 190: 1, 207, 239, 240; C.I. I. Bat Red 41; C.I. I. Disperse Violet 8, 17, 23, 27, 28, 29, 36, 57; C.I. I. Disperse Blue 26, 26: 1, 55, 56, 58, 64, 64: 1, 72, 72: 1, 81, 81: 1, 91, 95, 108, 131, 141, 145, 359, 360; C .. I. Solvent blue 36, 63, 105, 111; is more preferred.

The above-mentioned sublimation dye may be in the form of powder or lump, or in any state of dryness, wet cake, and slurry, and further, a small amount of dispersant is used for the purpose of suppressing aggregation of dye particles during and after synthesis of the dye. It may be contained. In addition, for the purpose of suppressing adverse effects on dispersion stability and ink ejection accuracy, chlorides of metal cations contained as impurities as much as possible, such as sodium chloride; sulfate, for example, sodium sulfate; and other inorganic impurities are contained in a small amount. Is preferably used. In this case, for example, the total content of sodium chloride and sodium sulfate may be about 1% by mass or less with respect to the total mass of the dye, and the lower limit may be 0% by mass, that is, below the detection limit of the detection device. As a method for producing a compound having a small amount of inorganic impurities, for example, a method using a back-penetrating film known per se; or a dried product of the dye used or a wet cake, for example, a C1-C4 alcohol such as acetone or methanol (for example, Methods such as suspension purification or crystallization by adding to a water-soluble organic solvent such as methanol, ethanol, isopropanol, etc., or a water-containing water-soluble organic solvent; etc., and desalting treatment, etc. by these methods can be mentioned. Just do it.

The above sublimative dye may be blended. For example, in the preparation of black ink, an orange dye and a red dye are appropriately blended mainly with a blue dye to adjust the color to black, and this is used as a black dye. Can be done. Further, a plurality of dyes may be blended for the purpose of finely adjusting the color tone of, for example, blue, orange, red, violet, or black to a more preferred color tone.

The above ink is prepared by adding an amine compound represented by the formula (1), a resin dispersant, a sublimable dye, and, if necessary, other additives and the like to the extent that the effects obtained by the ink of the present invention are not impaired. It can be prepared by dispersing in addition to.

Known additives such as antiseptic and antifungal agents, pH adjusters, chelating reagents, rust preventives, ultraviolet absorbers, defoamers, and surface tension regulators may be contained in the above inks. Can be mentioned.

Examples of antiseptic and antifungal agents include organic sulfur type, organic nitrogen sulfur type, organic halogen type, haloallyl sulfone type, iodopropagil type, N-haloalkylthio type, benzothiazole type, nitrile type, pyridine type, 8- Oxyquinoline-based, isothiazoline-based, dithiol-based, pyridineoxide-based, nitropropane-based, organotin-based, phenol-based, tetraammonium salt-based, triazine-based, thiadiadin-based, anilide-based, adamantan-based, dithiocarbamate-based, brominated indanone Examples thereof include compounds such as a system, a benzyl bromacetate system, and an inorganic salt system. Examples of the organic halogen-based compound include pentachlorophenol sodium, examples of the pyridine oxide-based compound include sodium pyridinethione-1-oxide and zinc pyridinethione-1-oxide, and examples of the isothiazolin-based compound include isothiazolinone. For example, an amine salt of 1-benzisothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 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-isothiazolin-3-3 Examples include on-calcium chloride. Other preservatives and fungicides include sodium dehydroacetate, sodium sorbate, sodium benzoate; and the like, as well as the trade names Proxel ^RTM GXL (S) and Proxel ^RTM XL-2 (S); manufactured by Arch Chemical Co., Ltd. Each is listed.

As the pH adjuster, any substance can be used as long as the pH of the ink can be controlled in the range of 6.0 to 11.0 for the purpose of improving the storage stability of the ink. For example, alkanolamines such as diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium hydroxide; ammonium hydroxide; or carbonates. Alkali metal carbonates such as lithium, sodium carbonate and potassium carbonate; aminosulfonic acids such as taurine; and the like can be mentioned.

Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetic acid, sodium hydroxyethylethylenediamine triacetate, sodium diethylenetriamine pentaacetate, sodium uracil diacetate and the like.

Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.

Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds and stilbene compounds, or compounds that absorb ultraviolet rays and emit fluorescence, such as benzoxazole compounds. , So-called fluorescent whitening agents and the like can also be used.

Examples of the defoaming agent include highly oxidized oil-based compounds, glycerin fatty acid ester-based compounds, fluorine-based compounds, silicone-based compounds, and acetylene-based compounds.

Examples of the surface tension adjusting agent include anionic surfactants, amphoteric surfactants, cationic surfactants, nonionic surfactants and the like.

Anionic surfactants include alkyl sulfocarboxylic acid salts, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acylamino acids and their salts, N-acylmethyl taurine salts, alkyl sulfates, polyoxyalkyl ether sulfates. Salt, alkyl sulfate polyoxyethylene alkyl ether phosphate, loginate soap, castor oil sulfate, lauryl alcohol sulfate, alkylphenol type phosphate, alkyl type phosphoric acid ester, alkylaryl sulfonate, diethyl sulfo sulfonate , Diethylhekirsyl sulfo sulphate, dioctyl sulfo sulphate and the like.
It is preferably a sulfosuccinic acid type, and examples of commercial products thereof include Lion Corporation, trade name Lipearl 835I, 860K, 870P, NTD, MSC; Adeca Co., Ltd., trade name. Adecacol EC8600; Kao Corporation product name Perex OT-P, CS, TA, TR; Shin Nihon Rika Co., Ltd., Rika Mild ES-100, ES-200, Rika Surf P-10, M-30, M-75, M-300, G-30, G-600; manufactured by Toho Chemical Industry Co., Ltd., Kohakunor L-300, L-40, L-400, same NL-400; and the like. Among these commercially available products, the Perex series (preferably Perex OT-P) and Adecacol EC8600 are particularly preferable.

Examples of amphoteric surfactants include betaine lauryldimethylaminoacetic acid, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, betaine palm oil fatty acid amide propyldimethylaminoacetic acid, polyoctylpolyaminoethylglycine, and other imidazoline derivatives. Can be mentioned.

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

Examples of the nonionic surfactant include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether; Ethers such as polyoxyethylene oleic acid ester, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-Tetramethyl-5-decine-4,7-diol, 3,6-dimethyl-4-octin-3,6-diol, 3,5-dimethyl-1-hexin-3-ol Etc. acetylene glycol (alcohol) type; trade name Surfinol ^RTM 104, 82, 465 manufactured by Nisshin Kagaku Kogyo Co., Ltd .; Orfin ^RTM STG; trade name Ethergitol ^RTM 15-S-7 manufactured by SIGMA-ALDRICH; etc. Can be mentioned.
Of the above, acetylene glycol-based or acetylene alcohol-based is preferable, acetylene glycol-based is more preferable, and the trade name Surfinol series manufactured by Nissin Chemical Industry Co., Ltd. is particularly preferable.

The above additives can be used alone or in combination. The content of the additive is 0 to 5%, preferably 0 to 3%, based on the mass, based on the total mass of the ink of the present invention. The surface tension of the ink of the present invention is usually adjusted to 20 to 70 mN / m, preferably 20 to 50 mN / m, and the viscosity is preferably adjusted to 2 to 20 mPa · s from the viewpoint of ejection responsiveness and the like. In detail, it is preferable to make fine adjustments to appropriate physical property values in consideration of the ejection amount of the printer to be used, the response speed, the flight characteristics of ink droplets, and the like. The viscosity may be adjusted by the content of the dispersant, and the surface tension may be adjusted by the above-mentioned surfactant or the like.

The above-mentioned inkjet inks dissolve dyes; prevent the composition from drying (maintaining a wet state); adjust the viscosity of the composition; promote the penetration of the dye into the recording medium; adjust the surface tension of the composition; adjust the composition. It may have the effect of defoaming things. Therefore, the ink preferably contains a water-soluble organic solvent. Examples of the water-soluble organic solvent include C1-C4 alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, second butanol, and third butanol; N, N-dimethylformamide, N, N. -Amids such as dimethylacetamide; 2-pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidine-2-one or 1,3-dimethylhexahydropyrimido-2 Heterocyclic ketones such as -one; ketones such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentane-4-one or keto alcohols; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol, 1,2-propanediol, 1,3-Propanediol, 2-methyl-1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,5-pentanediol, 1,2- Mono, oligo, or polyalkylene having C2-C6 alkylene units such as hexanediol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, etc. Glycol or thioglycol; polyols such as trimethylolpropane, glycerin, hexane-1,2,6-triol (preferably triol); ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Examples thereof include C1-C4 monoalkyl ethers of polyhydric alcohols such as monobutyl ether (butyl carbitol), triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether; γ-butyrolactone; dimethylsulfoxide; and the like.

The above-mentioned water-soluble organic solvent also contains a substance that is solid at room temperature, such as trimethylolpropane. That is, a substance that is water-soluble even if it is solid at room temperature, and an aqueous solution containing the substance exhibits the same properties as a water-soluble organic solvent and can be used with the expectation of the same effect. In the present specification, it is a water-soluble organic solvent. Examples of such substances include solid polyhydric alcohols, sugars, amino acids and the like.

The content of the water-soluble organic solvent is usually 0 to 60%, preferably 10 to 50%, based on the total mass of the ink. The ink contains a water-soluble organic solvent and additives, if necessary, and the rest is water.

In the production of the above-mentioned inkjet ink, the water used for preparing the ink is preferably a water having few impurities such as ion-exchanged water or distilled water. Further, after the ink is prepared, microfiltration may be performed using a membrane filter or the like to remove impurities in the ink composition. Since the ink of the present invention is used as an ink for inkjet recording, it is preferable to perform microfiltration. The pore size of the filter used for microfiltration is usually 1 μm to 0.1 μm, preferably 0.8 μm to 0.1 μm.

In the production of the above-mentioned inkjet ink, the order in which each chemical such as an additive is added is not particularly limited, but after preparing an aqueous dispersion by adding a sublimating dye and a dispersant to water and dispersing them, this It is preferable to prepare the ink by adding the above-mentioned additives and the like to the dispersion liquid as needed. Examples of the method for dispersing the sublimation dye include a method using a sand mill (bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer and the like, and among these, a sand mill (bead mill) is preferable. Further, it is preferable to prepare the aqueous dispersion using a sand mill (bead mill) under the condition that beads having a small diameter (approximately 0.01 mm to 1 mm in diameter) are used and the filling rate of the beads is increased. By performing dispersion under such conditions, the particle size of the dye can be reduced, and a dispersion liquid having good dispersibility can be obtained. Further, after preparing the dispersion, it is also preferable to remove components such as dyes having a large particle size by filtration and / or centrifugation or the like. Further, for the purpose of suppressing foaming during preparation of the dispersion, a very small amount of the above-mentioned silicone-based or acetylene-based defoaming agent may be added.

The above-mentioned inkjet ink can be satisfactorily used in a thermal inkjet method in which thermal energy is applied to perform recording. Moreover, either continuous type or on-demand type method may be used. Further, the ink of the present invention can also be used in a recording method in which the ink is adhered to an intermediate recording medium and then transferred to a final recording medium such as paper.

The above-mentioned inkjet ink gives an image with very clear, high saturation and print density, and an ideal hue when recorded on various recording media. Therefore, it is possible to faithfully reproduce a color image of photographic image quality on a recording medium. In addition, there is no solid precipitation, physical property change, hue change, etc. after long-term storage, and the storage stability is extremely good. Furthermore, the precipitation of solids due to drying is extremely unlikely to occur. Therefore, the ink of the present invention does not cause clogging of the injector (recording head) of the inkjet printer. The ink of the present invention does not cause a change in physical properties in a continuous inkjet printer in which the ink is recirculated at a relatively long time interval or in an intermittent use by an on-demand inkjet printer.

Images recorded on a recording medium having an ink receiving layer using the above-mentioned inkjet ink have good robustness such as water resistance, moisture resistance, ozone gas resistance, rubbing resistance, and light resistance. For this reason, the long-term storage stability of images recorded with photographic image quality is also excellent.

An image recorded on a recording medium having no ink receiving layer using the above-mentioned inkjet ink is also excellent in color development such as saturation, brightness, and print density.

The above-mentioned ink can be prepared by mixing each of the above-mentioned components as necessary. The order in which each component is added is not particularly limited. The water used for preparing the ink is preferably water having few impurities such as ion-exchanged water and distilled water. In addition, the prepared ink can be microfiltered using a membrane filter or the like. When the ink is used as an inkjet ink, it is preferable to perform microfiltration for the purpose of preventing nozzle clogging and the like. The pore size of the filter used for microfiltration is usually 1 μm to 0.1 μm, preferably 0.8 μm to 0.1 μm.

The above-mentioned inkjet ink can be used for various purposes such as printing, copying, marking, writing, drafting, stamping, and recording. Among those applications, it is suitable for use in inkjet recording.

Next, a recording system including the above-mentioned inkjet printer will be described.
The above-mentioned inkjet printer using the inkjet ink is a thermal inkjet printer that performs recording by applying thermal energy. The system including the printer is composed of the printer and recording data creating means (not shown, computer, etc.), and the printer receives the recorded data in the program memory. The recorded data may be image or character information itself to be recorded, compressed information of the information, or encoded information.

Next, the recording medium recorded by the recording system including the above-mentioned inkjet printer will be described. The recording media that can be used in the present invention are roughly classified into those having an ink receiving layer and those having no ink receiving layer, and any of these is preferable. Specific recording media include, for example, paper, film, fibers and cloth (cellulose, nylon, wool, etc.), leather, a base material for a color filter, and the like. The ink receiving layer is installed on a recording medium for the purpose of absorbing ink and accelerating its drying. The ink receiving layer is, for example, a method of impregnating or coating the recording medium with a cationic polymer; inorganic fine particles capable of absorbing the dye in the ink are placed on the surface of the recording medium together with a hydrophilic polymer such as polyvinyl alcohol or polyvinylpyrrolidone. It is installed by the method of coating; etc. Examples of the inorganic fine particles capable of absorbing the dye in the ink include porous silica, alumina sol, and special ceramics. A recording medium having such an ink receiving layer is usually called an inkjet dedicated paper, an inkjet dedicated film, a glossy paper, a glossy film, or the like. Typical commercially available examples of recording media having an ink receiving layer include Canon Corporation, trade name Professional Photo Paper, Canon Photo Paper / Glossy Pro [Platinum Grade], and Glossy Gold; Seiko Epson Corporation, products. Name photo paper Crispia (high gloss), photo paper (gloss); manufactured by Nippon Hulett Packard Co., Ltd., product name Advanced Photo Paper (gloss); manufactured by Fujifilm Co., Ltd. , Product name: Photo glossy paper BP71G; and the like. Further, as a paper having no ink receiving layer, plain paper or the like can be mentioned. Among the plain papers on the market, for inkjet recording, double-sided high-quality plain paper (manufactured by Seiko Epson Corporation); PB PAPER GF-500 (manufactured by Canon Inc.); (Manufactured by Hewlett-Packard Co., Ltd.) and the like. In addition, plain paper copy (PPC) paper and the like are also plain paper. Further, in sublimation transfer dyeing, ink is attached to an intermediate recording medium such as transfer paper or a transfer film, and then the ink is transferred to the recording medium by thermal transfer.

When the above-mentioned inkjet recording method is a sublimation transfer dyeing method, plain paper or the like can be used as the intermediate recording medium, but the dye does not aggregate on the paper surface in the process of drying the ink applied to the medium. Moreover, it is preferable that the dye does not interfere with the sublimation of the dye during the next transfer. As such an intermediate recording medium, for example, paper in which an ink receiving layer is formed on the surface of inorganic fine particles such as silica is preferable, and special paper for inkjet is preferably used. The present invention includes an intermediate recording medium (that is, a medium before transfer to the recording medium of the present invention) recorded by the above-mentioned inkjet recording method of the present invention.

In the above sublimation transfer dyeing method, the intermediate recording medium of the present invention and the hydrophobic material are superposed and heated, and the dye applied to the medium is transferred to the hydrophobic material to dye the hydrophobic material. The method. Examples of the hydrophobic material include hydrophobic fibers (preferably polyester fibers and blended fibers containing polyester), films and sheets made of hydrophobic resin, cloth coated with hydrophobic resin, glass, metal, ceramics and the like. Among these, hydrophobic fibers are preferable. The heating temperature at the time of transferring the dye is preferably about 190 to 200 ° C.

The recording system of the present invention is excellent in stability regarding continuous ink ejection, and can suppress pin chipping due to ink clogging during printing, poor ink droplet ejection, and deterioration of landing accuracy. It is presumed that this is because it is possible to minimize the cogation of the heater element portion in the thermal inkjet print head and the precipitation and adhesion of the sublimation dye. In addition, when recorded on various recording media, it gives an image of very clear, high saturation and print density, and an ideal hue. Therefore, it is possible to faithfully reproduce a color image of photographic image quality on a recording medium. Further, there is no solid precipitation, change in physical properties, change in hue, etc. after long-term storage, and the storage stability is extremely good. In addition, solid precipitation due to drying is very unlikely to occur. Therefore, neither the continuous inkjet printer in which the ink is recirculated at a relatively long time interval or the intermittent use by the on-demand inkjet printer causes a change in physical properties.

The recorded image recorded on paper by the recording system of the present invention has high image quality, is excellent in various robustness such as water resistance, moisture resistance, ozone gas resistance, abrasion resistance and light resistance, and is an image recorded with photographic image quality. It has excellent long-term storage stability, and also has excellent color development such as saturation, brightness, and print density. In addition, the recorded image recorded on the fiber also has high image quality, and is excellent in washing fastness, light fastness, sweat light resistance, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified in the examples, "parts" means parts by mass and "%" means% by mass.

[Preparation of emulsion]
48% lithium hydroxide (3.2 parts), ion-exchanged water (56.8 parts), propylene glycol (20 parts) to Joncryl 678 (manufactured by BASF, styrene having the skeleton of formula (1) in the molecule- ( Meta) Acrylic copolymer, weight average molecular weight = 8,500, glass transition point = 85 ° C., acid value = 215 mgKOH / g) 20 parts were added, the temperature was raised to 90-120 ° C., and the mixture was stirred for 5 hours. , Joncryl 678 emulsion was obtained.

[Example 1]
(Step 1)
C. I. A mixture consisting of Disperse Red 60 (30 parts), the obtained emulsion (60 parts), Proxel GXL (0.4 parts), Surfinol 104PG50 (0.4 parts), and ion-exchanged water (9 parts) is 0. A dispersion treatment was carried out for about 15 hours under cooling in a sand mill using 2 mm diameter glass beads. After adjusting the dye content to 15% by adding ion-exchanged water (70 parts), emulsion liquid (30 parts), and diethanolamine (3.0 parts) as the amine represented by the formula (1) to the obtained liquid. , Glass fiber filter paper GC-50 (manufactured by Toyo Filter Paper Co., Ltd., filter pore size 0.5 μm) was used for filtration to obtain dispersion liquid 1.
(Step 2)
In the dispersion liquid 1 (30 parts) obtained in the above (step 1), tetraethylene glycol (5 parts), 1- (2 hydroxyethyl) -2-pyrrolidone (5 parts), 1,6-hexanediol (5 parts) ), 2-Methyl-1,3-propanediol (5 parts), Perex OT-P (0.12 parts), Proxel GXL (0.2 parts), and dye content by adding ion-exchanged water. Was adjusted to 5.0% to prepare the aqueous magenta ink of Example 1.

[Examples 2 to 8]
The aqueous magenta inks of Examples 2 to 8 were prepared in the same manner as in Example 1 except that the amines shown in Table 1 below were added.

[Comparative Example 1]
The aqueous magenta ink of Comparative Example 1 was prepared in the same manner as in Example 1 except that amine was not added in Example 1.

The following evaluation tests were performed on the inks prepared in Examples 1 to 8 above. The test results are shown in Table 1 below.

[Dischargeability evaluation test]
Each magenta ink was filled in a thermal type inkjet printer (manufactured by HP Inc., trade name: Deskjet D4160), and solid printing was performed 15 times as a 100% Duty image on PPC paper (TP PAPER, NBS Ricoh). The ejection stability at the time of printing was evaluated for how much continuous ejection was possible without pin chipping, and evaluated according to the following four criteria. The evaluation results are shown in Table 1 below.
A: The number of sheets that can be continuously ejected is 12 or more B: The number of sheets that can be continuously ejected is 8 or more and less than 12 sheets, and a slight pin chipping is observed C: The number of sheets that can be continuously ejected is 8 More than 12 sheets and less than 12 sheets, and pin chipping is seen D: The number of sheets that can be continuously ejected is less than 7, and there are very many pin chips.

As is clear from the above results, it was confirmed that the ink of each example was superior in ejection stability as compared with the ink of the comparative example.

The thermal type inkjet printer system using the dispersion liquid of the present invention has high ejection stability, and is extremely useful for various recordings, especially for fiber dyeing using an inkjet printer.

Claims (9)

A recording provided with an ink containing an amine compound represented by the following formula (1), a resin dispersant, and at least one type of sublimating dye, and a thermal inkjet printer for recording by applying thermal energy. system. However, the resin dispersant is a resin dispersant neutralized with an amine compound represented by the following formula (1).
(A group selected from the group consisting of a heterocyclic group in which at least one or more of R ^{1 to} R ³ in the formula (1) may have a hydroxyl group, an amino group, a sulfo group, or a substituent. It is an alkyl group of C1-C6 having as a substituent, and the others are independently hydrogen atoms, from an aliphatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group, and a heterocyclic group. Represents a group selected from the group.) R ¹ in the formula (1) is an alkyl group of C1-C6 having a group selected from the group consisting of a hydroxyl group, a sulfo group, and a heterocyclic group which may have a substituent as a substituent, and R ² and R ³ are alkyl groups of C1-C6 each having a hydrogen atom or a group selected from the group consisting of a heterocyclic group which may have a hydroxyl group, a sulfo group and a substituent as a substituent. , A recording system comprising a thermal inkjet type inkjet printer for recording by applying the ink and thermal energy according to claim 1 . R ¹ in the formula (1) is an alkyl group of C1-C3 having a group selected from the group consisting of a hydroxyl group, a sulfo group, and a heterocyclic group which may have a substituent as a substituent, and R ² and R ³ are alkyl groups of C1-C3 having a hydrogen atom or a group selected from the group consisting of a heterocyclic group which may have a hydroxyl group, a sulfo group and a substituent as a substituent, respectively. , A recording system comprising a thermal inkjet type inkjet printer for recording by applying the ink and thermal energy according to claim 2 . In formula (1), R ¹ is a group selected from the group consisting of a 2-hydroxyethyl group, a 2-sulfoethyl group, and a frill group, and R ² and R ³ are independently hydrogen atoms or 2-hydroxy. A recording system including a thermal inkjet printer that records by applying the ink and thermal energy according to any one of claims 1 to 3 , which are ethyl groups. In formula (1), R ¹ , R ² and R ³ are 2-hydroxyethyl groups, respectively, or R ¹ and R ² are 2-hydroxyethyl groups, respectively, and R ³ is a hydrogen atom, or R ¹ is a frill. R ² and R ³ are hydrogen atoms, respectively, or R ¹ is a 2-sulfoethyl group, R ² and R ³ are hydrogen atoms, and R ¹ is a 2- (methylamino) ethanol group, R ² and A recording system including a thermal inkjet printer for recording by applying the ink and thermal energy according to any one of claims 1 to 4 , wherein R ³ is each a combination of hydrogen atoms. A recording system including the ink according to any one of claims 1 to 5 , wherein the resin dispersant is a styrene-acrylic resin dispersant, and a thermal inkjet printer for recording by applying thermal energy. The ink according to any one of claims 1 to 6 , wherein the resin dispersant is a styrene-acrylic resin dispersant having a carboxyl group in the molecule, and a thermal inkjet type inkjet that records by applying thermal energy. A recording system with a printer. The ink according to any one of claims 1 to 7 , wherein the dye having sublimation property is a disperse dye, an oil-soluble dye, and a vat dye, and a thermal inkjet printer for recording by applying thermal energy. System with. A system as claimed in any one of claims 1 to 8, the ink according to any one of claims 1 to 8, ejected by an ink jet printer according to any one of claims 1 to 8 An inkjet recording method for recording by adhering to a recording medium.