JP2022161260A - Ink composition, ink container, printing method, and printer - Google Patents

Abstract

To provide an ink composition that has excellent discharge stability and storage stability and is capable of forming a printed material having excellent scratch resistance and flexibility.SOLUTION: A printing ink composition is an ink that contains water, organic solvents, resin particles, a colorant, and a silicone compound and is used for printing to fabric, where at least one of the organic solvents is a dimethyl amide compound. The dimethyl amide compound is preferably a compound represented by the following structural formula (1). In the structural formula (1), R is a C1-4 alkyl group.SELECTED DRAWING: None

Description

The present invention relates to an ink composition, an ink container, a printing method, and a printing apparatus.

The inkjet recording method is a recording method in which ink droplets are ejected from fine nozzles and deposited on a recording member to form characters and images. 2. Description of the Related Art In recent years, ink-jet textile printing using fabric as a recording member has been widely used. There are two types of ink used in inkjet printers: pigment ink and dye ink. Inkjet textile printing using pigment ink does not require washing with water after coloring, which is necessary for textile printing with dye ink, and does not generate waste water. Therefore, it is excellent as a recording method.

However, in a printed image printed with a pigment ink, the flexibility of the image portion is greatly reduced compared to an image printed with a dye ink.

On the other hand, Patent Document 1 discloses a titanium dioxide slurry having a solid content of 10% by mass, a urethane resin having a solid content of 11.2% by mass, a silicone emulsion having a content of 1.55% by mass, and glycerin having a content of 5% by mass. , 8% by mass of triethylene glycol, 1% by mass of triethylene glycol monobutyl ether, and 0.3% by mass of BYK-348, and is said to have excellent flexibility. there is

However, the ink disclosed in Patent Document 1, to which a silicone compound is added and which has excellent flexibility on fabric, has a problem that at least one of ejection stability and storage stability is inferior to ink to which a silicone compound is not added. occurs.

An object of the present invention is to provide an ink composition which is excellent in ejection stability and storage stability, and which can form a printed material excellent in abrasion resistance and flexibility.

That is, the present invention relates to ink compositions as described below.
An ink composition comprising water, an organic solvent, resin particles, a coloring material, and a silicone compound, wherein the organic solvent comprises a dimethylamide compound.

According to the present invention, it is possible to provide an ink composition which is excellent in ejection stability and storage stability, and which forms a printed matter excellent in abrasion resistance and flexibility.

1 is a diagram showing an example of an image forming apparatus using the ink of the present invention; FIG. 1 is a perspective view of a main tank containing ink of the present invention; FIG.

DETAILED DESCRIPTION OF THE INVENTION Embodiments for carrying out the present invention will be described in detail below. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

In the present invention, “inkjet textile printing” refers to recording (printing) ink on fabric, which is a type of recording medium, using an inkjet method. A “recorded matter” refers to a recording medium on which ink is recorded to form an image.

As used herein, the term “storage stability” refers to the property that the viscosity of the ink does not easily change before and after storage when the ink is stored at 60° C. for 7 days. The term “scratch resistance” refers to the property that the printed image is not easily peeled off or scratched from the fabric when the printed image is rubbed. “Flexibility” refers to the property of being easily bent when the image is bent.

[Ink composition for textile printing]
The ink composition of the invention contains water, an organic solvent, resin particles, a coloring material, and a silicone compound, and the organic solvent contains a dimethylamide compound.
A preferred embodiment of the present invention is a textile printing ink composition (hereinafter also simply referred to as "ink composition" or "ink"). A preferred embodiment of the ink composition comprises a coloring material, resin particles, a dimethylamide compound having a content of 1.0% by mass or more and 10.0% by mass, and a content of 0.1% by mass or more and 5.0% by mass. % or less silicone compound.

Organic solvents, water, coloring materials, resins, additives, and the like that are contained or may be contained in the ink composition are described below.

（上記式中、Ｒは炭素数１以上４以下のアルキル基を表す。） <Dimethylamide compound>
The dimethylamide compound in the present invention is an amphipathic solvent having a high dissolving power having an amide group, an alkyl group and an ether bond, and is represented by the following structural formula (1).

(In the above formula, R represents an alkyl group having 1 to 4 carbon atoms.)

By adding the dimethylamide compound, the compatibility between the water-soluble organic solvent and the resin particles described later is enhanced, the dispersibility is improved, and even when the silicone compound described later is added, the wettability of the nozzle surface of the ejection head is improved. can be lowered.
In addition, since the dimethylamide compound has a high equilibrium water content, a high moisturizing power, and a high boiling point, the ink does not easily dry, the moisturizing power is improved, and the ejection stability is improved.

As the dimethylamide compound, a commercially available product can be used, for example, Equamid: M100 (manufactured by Idemitsu Kosan), Equamid: B100 (manufactured by Idemitsu Kosan), or the like can be used.
The content of the dimethylamide compound in the ink composition is preferably 1.0% by mass or more and 10% by mass or less, and more preferably 5.0% by mass or more and 10.0% by mass or less.

<Silicone compound>
The silicone compound in the present invention means a polymer having a siloxane skeleton as a repeating unit and having a siloxane bond and an organic functional group in the same molecule.

Specific examples of silicone compounds include amino-modified silicone, alkyl-modified silicone, alkylpolyether-modified silicone, epoxy-modified silicone, epoxypolyether-modified silicone, carboxy-modified silicone, carbinol-modified silicone, dimethyl silicone, polyether-modified silicone, reaction At least one selected from type silicones is preferred.

（上記式中、Ｒは炭素数１０以上１５以下のアルキル基を表し、ｎは５以上１２以下の整数を表す。） More preferably, the silicone compound is an emulsion-type dimethylsilicone compound dispersed in water by a nonionic polyalkoxyethylene represented by the following structural formula (2).

(In the above formula, R represents an alkyl group having 10 to 15 carbon atoms, and n represents an integer of 5 to 12.)

<Organic solvent>
The organic solvent used in the present invention is not particularly limited, and any water-soluble organic solvent can be used. Examples thereof include polyhydric alcohols, ethers such as polyhydric alcohol alkyl ethers and polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, and sulfur-containing compounds.
Specific examples of water-soluble organic solvents include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane. Diol, 2,3-butanediol, 3-methyl-1,3-butanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol , 2,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,3-hexanediol, 2,5-hexanediol, 1,5-hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl-1,2,4-butanetriol, 1,2,3-butanetriol, 2,2,4-trimethyl- Polyhydric alcohols such as 1,3-pentanediol and petriol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl Polyhydric alcohol alkyl ethers such as ethers, polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone , 1,3-dimethyl-2-imidazolidinone, ε-caprolactam, nitrogen-containing heterocyclic compounds such as γ-butyrolactone, formamide, N-methylformamide, N,N-dimethylformamide, 3-methoxy-N,N- Amides such as dimethylpropionamide and 3-butoxy-N,N-dimethylpropionamide, amines such as monoethanolamine, diethanolamine, and triethylamine, sulfur-containing compounds such as dimethylsulfoxide, sulfolane, and thiodiethanol, propylene carbonate, and ethylene carbonate. etc.
It is preferable to use an organic solvent having a boiling point of 250° C. or less because it not only functions as a wetting agent but also provides good drying properties.

Polyol compounds having 8 or more carbon atoms and glycol ether compounds are also preferably used. Specific examples of polyol compounds having 8 or more carbon atoms include 2-ethyl-1,3-hexanediol and 2,2,4-trimethyl-1,3-pentanediol.
Specific examples of glycol ether compounds include polyhydric alcohol alkyls such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether. Ethers; polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, and the like.

A polyol compound having 8 or more carbon atoms and a glycol ether compound can improve ink permeability when paper is used as a recording medium.

The content of the organic solvent in the ink is not particularly limited and can be appropriately selected according to the purpose. 20% by mass or more and 60% by mass or less is more preferable.

<Water>
The content of water in the ink is not particularly limited and can be appropriately selected according to the purpose. % to 60% by mass is more preferred.

<Color material>
The coloring material is not particularly limited, and pigments and dyes can be used.
An inorganic pigment or an organic pigment can be used as the pigment. These may be used individually by 1 type, and may use 2 or more types together. Mixed crystals may also be used.
Examples of pigments that can be used include black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, glossy color pigments such as gold and silver, and metallic pigments.
As inorganic pigments, in addition to titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, carbon black produced by known methods such as contact method, furnace method, thermal method, etc. can be used.
Organic pigments include azo pigments, polycyclic pigments (e.g., phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc.). , dye chelates (eg, basic dye chelates, acid dye chelates, etc.), nitro pigments, nitroso pigments, aniline black, and the like. Among these pigments, those having good affinity with the solvent are preferably used. In addition, resin hollow particles and inorganic hollow particles can also be used.
Specific examples of pigments for black include carbon blacks (C.I. Pigment Black 7) such as furnace black, lamp black, acetylene black and channel black, or copper and iron (C.I. Pigment Black 11). , metals such as titanium oxide, and organic pigments such as aniline black (C.I. Pigment Black 1).
Further, for color, C.I. I. Pigment yellow 1, 3, 12, 13, 14, 17, 24, 34, 35, 37, 42 (yellow iron oxide), 53, 55, 74, 81, 83, 95, 97, 98, 100, 101, 104 , 108, 109, 110, 117, 120, 138, 150, 153, 155, 180, 185, 213, C.I. I. Pigment Orange 5, 13, 16, 17, 36, 43, 51, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22, 23, 31, 38, 48:2, 48:2 (Permanent Red 2B (Ca)), 48:3, 48:4, 49:1, 52: 2, 53:1, 57:1 (brilliant carmine 6B), 60:1, 63:1, 63:2, 64:1, 81, 83, 88, 101 (red red), 104, 105, 106, 108 ( cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 184, 185, 190, 193, 202, 207, 208, 209, 213, 219, 224, 254, 264, C.I. I. Pigment Violet 1 (rhodamine lake), 3, 5:1, 16, 19, 23, 38, C.I. I. Pigment Blue 1, 2, 15 (phthalocyanine blue), 15:1, 15:2, 15:3, 15:4 (phthalocyanine blue), 16, 17:1, 56, 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc.
As dyes, acid dyes, direct dyes, reactive dyes, and basic dyes can be used without particular limitation, and may be used singly or in combination of two or more.
Examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142, C.I. I. Acid Red 52, 80, 82, 249, 254, 289, C.I. I. Acid Blue 9,45,249, C.I. I. Acid Black 1, 2, 24, 94, C.I. I. Food Black 1, 2, C.I. I. Direct Yellow 1, 12, 24, 33, 50, 55, 58, 86, 132, 142, 144, 173, C.I. I. Direct Red 1, 4, 9, 80, 81, 225, 227, C.I. I. Direct Blue 1, 2, 15, 71, 86, 87, 98, 165, 199, 202, C.I. I. Direct Black 19, 38, 51, 71, 154, 168, 171, 195, C.I. I. Reactive Red 14, 32, 55, 79, 249, C.I. I. and Reactive Black 3,4,35.

The content of the coloring material in the ink is preferably 0.1% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass or less, from the viewpoints of improving image density, good fixability and ejection stability. is.

In order to disperse the pigment and obtain an ink, there are a method of introducing a hydrophilic functional group into the pigment to make it a self-dispersing pigment, a method of coating the surface of the pigment with a resin for dispersion, and a method of dispersing using a dispersant. method, etc.
As a method of making a self-dispersing pigment by introducing a hydrophilic functional group into a pigment, for example, a method of adding a functional group such as a sulfone group or a carboxyl group to a pigment (for example, carbon) to make it dispersible in water. is mentioned.
As a method of coating the surface of a pigment with a resin and dispersing it, there is a method of encapsulating the pigment in microcapsules to make it dispersible in water. This can be rephrased as a resin-coated pigment. In this case, all the pigments mixed in the ink need not be coated with a resin, and uncoated pigments or partially coated pigments may be dispersed in the ink as long as the effects of the present invention are not impaired. may be
Examples of the method of dispersing using a dispersant include a method of dispersing using a known low-molecular-weight dispersant and high-molecular-weight dispersant typified by surfactants.
As the dispersant, it is possible to use, for example, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc. depending on the pigment.
RT-100 (nonionic surfactant) manufactured by Takemoto Yushi Co., Ltd. and sodium naphthalenesulfonate formalin condensate can also be suitably used as a dispersant.
A dispersing agent may be used individually by 1 type, or may use 2 or more types together.

<Pigment dispersion>
Inks can be obtained by mixing materials such as water and organic solvents with pigments. Ink can also be produced by mixing a pigment, water, a dispersant, and the like to form a pigment dispersion, and then mixing materials such as water and an organic solvent.
The pigment dispersion is obtained by mixing and dispersing water, a pigment, a pigment dispersant, and optionally other components, and adjusting the particle size. Dispersion should be carried out using a disperser.
The particle diameter of the pigment in the pigment dispersion is not particularly limited, but the dispersion stability of the pigment is improved, and the image quality such as ejection stability and image density is improved. 500 nm or less is preferable, and 20 nm or more and 150 nm or less is more preferable. The particle size of the pigment can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).
The content of the pigment in the pigment dispersion is not particularly limited and can be appropriately selected according to the purpose. % or more and 50 mass % or less is preferable, and 0.1 mass % or more and 30 mass % or less is more preferable.
The pigment dispersion is preferably degassed by filtering coarse particles with a filter, a centrifugal separator, or the like, if necessary.

<Resin>
The type of resin contained in the ink is not particularly limited and can be appropriately selected according to the purpose. resins, styrene-butadiene-based resins, vinyl chloride-based resins, acrylic-styrene-based resins, acrylic-silicone-based resins, and the like.
Resin particles made of these resins may also be used. Ink can be obtained by mixing resin particles in a resin emulsion state in which water is dispersed as a dispersion medium with a material such as a coloring material or an organic solvent. As the resin particles, appropriately synthesized ones may be used, or commercially available products may be used. Moreover, these may be used individually by 1 type, or may be used in combination of 2 or more types of resin particles.

The volume average particle diameter of the resin particles is not particularly limited and can be appropriately selected according to the intended purpose. 200 nm or less is more preferable, and 10 nm or more and 100 nm or less is particularly preferable.
The volume average particle diameter can be measured, for example, using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

The content of the resin is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of fixability and storage stability of the ink, the content is 1% by mass or more and 30% by mass or less based on the total amount of the ink. is preferable, and 5% by mass or more and 20% by mass or less is more preferable.

The particle size of the solid content in the ink is not particularly limited and can be appropriately selected according to the purpose. is preferably 20 nm or more and 1000 nm or less, more preferably 20 nm or more and 150 nm or less. The solid content includes resin particles, pigment particles, and the like. The particle size can be measured using a particle size analyzer (Nanotrack Wave-UT151, manufactured by Microtrack Bell Co., Ltd.).

<Additive>
Surfactants, antifoaming agents, antiseptic antifungal agents, anticorrosive agents, pH adjusters, etc. may be added to the ink as necessary.

<Surfactant>
Any of silicone surfactants, fluorine surfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants can be used as surfactants.
The silicone-based surfactant is not particularly limited and can be appropriately selected depending on the purpose. Among them, those that do not decompose even at high pH are preferable. Those having an oxyethylene group or a polyoxyethylene polyoxypropylene group are particularly preferred because they exhibit good properties as water-based surfactants. As the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include compounds in which a polyalkylene oxide structure is introduced into the side chain of the Si portion of dimethylsiloxane.
Examples of fluorine-based surfactants include perfluoroalkylsulfonic acid compounds, perfluoroalkylcarboxylic acid compounds, perfluoroalkylphosphoric acid ester compounds, perfluoroalkylethylene oxide adducts, and perfluoroalkyl ether groups in side chains. Polyoxyalkylene ether polymer compounds are particularly preferred due to their low foaming properties. Examples of the perfluoroalkylsulfonic acid compound include perfluoroalkylsulfonic acid and perfluoroalkylsulfonate. Examples of the perfluoroalkylcarboxylic acid compounds include perfluoroalkylcarboxylic acids and perfluoroalkylcarboxylic acid salts. As the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain, a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in a side chain, and a perfluoroalkyl ether group in a side chain Examples thereof include salts of polyoxyalkylene ether polymers. Counter ions of salts in these _{fluorosurfactants} include Li, Na, K, _NH4 , _NH3CH2CH2OH , _{NH2 ( CH2CH2OH} ) ₂ , and _{NH ( CH2CH2OH} ). ₃ and the like.
Examples of amphoteric surfactants include laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, lauryldihydroxyethylbetaine and the like.
Nonionic surfactants include, for example, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene propylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan Examples include fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of anionic surfactants include polyoxyethylene alkyl ether acetates, dodecylbenzene sulfonates, laurates, and salts of polyoxyethylene alkyl ether sulfates.
These may be used individually by 1 type, or may use 2 or more types together.

（但し、一般式（Ｓ－１）式中、ｍ、ｎ、ａ、及びｂは、それぞれ独立に、整数を表わし、Ｒは、アルキレン基を表し、Ｒ’は、アルキル基を表す。）
上記のポリエーテル変性シリコーン系界面活性剤としては、市販品を用いることができ、例えば、ＫＦ－６１８、ＫＦ－６４２、ＫＦ－６４３（信越化学工業株式会社）、ＥＭＡＬＥＸ－ＳＳ－５６０２、ＳＳ－１９０６ＥＸ（日本エマルジョン株式会社）、ＦＺ－２１０５、ＦＺ－２１１８、ＦＺ－２１５４、ＦＺ－２１６１、ＦＺ－２１６２、ＦＺ－２１６３、ＦＺ－２１６４（東レ・ダウコーニング・シリコーン株式会社）、ＢＹＫ－３３、ＢＹＫ－３８７（ビックケミー株式会社）、ＴＳＦ４４４０、ＴＳＦ４４５２、ＴＳＦ４４５３（東芝シリコン株式会社）などが挙げられる。 The silicone-based surfactant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples include polydimethylsiloxane modified at both chain ends, and polyether-modified silicone-based surfactants having polyoxyethylene groups or polyoxyethylene-polyoxypropylene groups as modifying groups exhibit excellent properties as water-based surfactants. preferable.
As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. Commercially available products are available from, for example, BYK Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Silicone Co., Ltd., Nihon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd., and the like.
The above polyether-modified silicone-based surfactant is not particularly limited and can be appropriately selected according to the purpose. Examples include those introduced into the side chain of the Si portion of siloxane.

(However, in general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R' represents an alkyl group.)
Commercially available products can be used as the above polyether-modified silicone-based surfactants. 1906EX (Japan Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (Dow Corning Toray Silicone Co., Ltd.), BYK-33, BYK-387 (BYK-Chemie Corporation), TSF4440, TSF4452, TSF4453 (Toshiba Silicon Co., Ltd.) and the like.

上記一般式（Ｆ－１）で表される化合物において、水溶性を付与するためにｍは０～１０の整数が好ましく、ｎは０～４０の整数が好ましい。
一般式（Ｆ－２）
Ｃ_ｎＦ_{２ｎ＋１－}ＣＨ_２ＣＨ（ＯＨ）ＣＨ_２－Ｏ－（ＣＨ_２ＣＨ_２Ｏ）_ａ－Ｙ
上記一般式（Ｆ－２）で表される化合物において、ＹはＨ、又はＣｍＦ_２ｍ＋１でｍは１～６の整数、又はＣＨ_２ＣＨ（ＯＨ）ＣＨ_２－ＣｍＦ_２ｍ＋１でｍは４～６の整数、又はＣｐＨ_２ｐ＋１でｐは１～１９の整数である。ｎは１～６の整数である。ａは４～１４の整数である。
上記のフッ素系界面活性剤としては市販品を使用してもよい。この市販品としては、例えば、サーフロンＳ－１１１、Ｓ－１１２、Ｓ－１１３、Ｓ－１２１、Ｓ－１３１、Ｓ－１３２、Ｓ－１４１、Ｓ－１４５（いずれも、旭硝子株式会社製）；フルラードＦＣ－９３、ＦＣ－９５、ＦＣ－９８、ＦＣ－１２９、ＦＣ－１３５、ＦＣ－１７０Ｃ、ＦＣ－４３０、ＦＣ－４３１（いずれも、住友スリーエム株式会社製）；メガファックＦ－４７０、Ｆ－１４０５、Ｆ－４７４（いずれも、大日本インキ化学工業株式会社製）；ゾニール（Ｚｏｎｙｌ）ＴＢＳ、ＦＳＰ、ＦＳＡ、ＦＳＮ－１００、ＦＳＮ、ＦＳＯ－１００、ＦＳＯ、ＦＳ－３００、ＵＲ、キャプストーンＦＳ－３０、ＦＳ－３１、ＦＳ－３１００、ＦＳ－３４、ＦＳ－３５（いずれも、Ｃｈｅｍｏｕｒｓ社製）；ＦＴ－１１０、ＦＴ－２５０、ＦＴ－２５１、ＦＴ－４００Ｓ、ＦＴ－１５０、ＦＴ－４００ＳＷ（いずれも、株式会社ネオス社製）、ポリフォックスＰＦ－１３６Ａ，ＰＦ－１５６Ａ、ＰＦ－１５１Ｎ、ＰＦ－１５４、ＰＦ－１５９（オムノバ社製）、ユニダインＤＳＮ－４０３Ｎ（ダイキン工業株式会社製）などが挙げられ、これらの中でも、良好な印字品質、特に発色性、紙に対する浸透性、濡れ性、均染性が著しく向上する点から、Ｃｈｅｍｏｕｒｓ社製のＦＳ－３１００、ＦＳ－３４、ＦＳ－３００、株式会社ネオス製のＦＴ－１１０、ＦＴ－２５０、ＦＴ－２５１、ＦＴ－４００Ｓ、ＦＴ－１５０、ＦＴ－４００ＳＷ、オムノバ社製のポリフォックスＰＦ－１５１Ｎ及びダイキン工業株式会社製のユニダインＤＳＮ－４０３Ｎが特に好ましい。 As the fluorosurfactant, a fluorine-substituted compound having 2 to 16 carbon atoms is preferable, and a fluorine-substituted compound having 4 to 16 carbon atoms is more preferable.
Examples of fluorine-based surfactants include perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in side chains. Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain is preferable because of its low foamability, and in particular, fluorine-based compounds represented by general formulas (F-1) and (F-2) Surfactants are preferred.

In the compound represented by the general formula (F-1), m is preferably an integer of 0 to 10 and n is preferably an integer of 0 to 40 in order to impart water solubility.
General formula (F-2)
_{CnF2n +1-} CH2CH(OH) _{CH2 -} O-( _CH2CH2O ) _{a -} Y
In the compound represented by the above general formula (F-2), Y is H, or CmF _2m+1 and m is an integer of 1 to 6, or CH ₂ CH(OH)CH ₂ -CmF _2m+1 and m is 4 to 6 Integer, or CpH _2p+1 where p is an integer from 1-19. n is an integer of 1-6. a is an integer from 4 to 14;
Commercially available products may be used as the fluorosurfactant. Examples of commercially available products include Surflon S-111, S-112, S-113, S-121, S-131, S-132, S-141, and S-145 (all manufactured by Asahi Glass Co., Ltd.); Fleurard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (both manufactured by Sumitomo 3M); Megafac F-470, F -1405, F-474 (both manufactured by Dainippon Ink and Chemicals); Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR, Capstone FS-30, FS-31, FS-3100, FS-34, FS-35 (all manufactured by Chemours); FT-110, FT-250, FT-251, FT-400S, FT-150, FT- 400SW (all manufactured by Neos Co., Ltd.), Polyfox PF-136A, PF-156A, PF-151N, PF-154, PF-159 (manufactured by Omnova), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.) Among these, Chemours FS-3100, FS-34, FS- 300, FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW manufactured by Neos Co., Ltd., Polyfox PF-151N manufactured by Omnova Co., Ltd. and Unidyne DSN- manufactured by Daikin Industries, Ltd. 403N is particularly preferred.

The content of the surfactant in the ink is not particularly limited and can be appropriately selected according to the purpose. % or more and 5 mass % or less is preferable, and 0.05 mass % or more and 5 mass % or less is more preferable.

<Antifoaming agent>
The antifoaming agent is not particularly limited, and examples thereof include silicone antifoaming agents, polyether antifoaming agents, and fatty acid ester antifoaming agents. These may be used individually by 1 type, or may use 2 or more types together. Among these, silicone-based antifoaming agents are preferred because of their excellent foam breaking effect.

<Preservative and antifungal agent>
The antiseptic and antifungal agent is not particularly limited, and examples thereof include 1,2-benzisothiazolin-3-one.

<Antirust agent>
The rust inhibitor is not particularly limited, and examples thereof include acidic sulfites and sodium thiosulfate.

<pH adjuster>
The pH adjuster is not particularly limited as long as it can adjust the pH to 7 or higher, and examples thereof include amines such as diethanolamine and triethanolamine.

The physical properties of the ink are not particularly limited and can be appropriately selected depending on the intended purpose. For example, viscosity, surface tension, pH and the like are preferably within the following ranges.
The viscosity of the ink at 25° C. is preferably 5 mPa·s or more and 30 mPa·s or less, more preferably 5 mPa·s or more and 25 mPa·s or less, from the viewpoint of improving the print density and character quality and obtaining good ejection properties. more preferred. Here, the viscosity can be measured using, for example, a rotational viscometer (RE-80L manufactured by Toki Sangyo Co., Ltd.). Measurement conditions are 25° C., standard cone rotor (1°34′×R24), sample liquid volume 1.2 mL, rotation speed 50 rpm, 3 minutes.
The surface tension of the ink is preferably 35 mN/m or less, more preferably 32 mN/m or less at 25° C., from the viewpoint that the ink is appropriately leveled on the recording medium and the drying time of the ink is shortened.
The pH of the ink is preferably from 7 to 12, more preferably from 8 to 11, from the viewpoint of preventing corrosion of metal members in contact with the liquid.

<Pretreatment liquid>
The pretreatment liquid contains a flocculant, an organic solvent, and water, and may optionally contain a surfactant, an antifoaming agent, a pH adjuster, an antiseptic agent, an antirust agent, and the like.
Organic solvents, surfactants, antifoaming agents, pH adjusters, antiseptic antifungal agents, and antirust agents can be the same materials as those used for inks, and other materials used for known treatment liquids can be used. .
The type of flocculant is not particularly limited, and examples thereof include water-soluble cationic polymers, acids, polyvalent metal salts, and the like.

<Post-treatment liquid>
The post-treatment liquid is not particularly limited as long as it can form a transparent layer. The post-treatment liquid is obtained by selecting and mixing organic solvents, water, resins, surfactants, antifoaming agents, pH adjusters, antiseptic antifungal agents, anticorrosive agents, etc., as necessary. Further, the post-treatment liquid may be applied to the entire recording area formed on the recording medium, or may be applied only to the area where the ink image is formed.

<Records>
The ink recorded matter of the present invention has an image formed on a recording medium using the ink of the present invention.
A recorded matter can be obtained by recording with an inkjet recording apparatus and an inkjet recording method.

<Recording device, recording method>
The ink of the present invention can be suitably used for various inkjet recording apparatuses, such as printers, facsimile machines, copiers, printer/facsimile/copier complex machines, stereolithography machines, and the like.
In the present invention, a recording apparatus and a recording method refer to an apparatus capable of ejecting ink, various treatment liquids, and the like onto a recording medium, and a method of performing recording using the apparatus. A recording medium means a medium to which ink or various processing liquids can adhere even temporarily.
This recording apparatus can include not only a head portion for ejecting ink, but also means for feeding, conveying, and discharging a recording medium, and other devices called pre-processing devices and post-processing devices. .
The recording apparatus and recording method may have heating means used in the heating process and drying means used in the drying process. The heating means and drying means include, for example, means for heating and drying the printing surface and the back surface of the recording medium. The heating means and drying means are not particularly limited, but for example, hot air heaters and infrared heaters can be used. Heating and drying can be performed before, during, or after printing.
Also, the recording apparatus and recording method are not limited to those that visualize significant images such as characters and graphics with ink. For example, it includes those that form patterns such as geometric patterns, and those that form three-dimensional images.
In addition, unless otherwise specified, the recording apparatus includes both a serial type apparatus in which the ejection head is moved and a line type apparatus in which the ejection head is not moved.
Furthermore, this recording device can be used not only as a desktop type, but also as a wide recording device that can print on A0 size recording media, and for example, can use continuous paper wound into a roll as a recording medium. A continuous feed printer is also included.
An example of a recording apparatus will be described with reference to FIGS. 1 and 2. FIG. FIG. 1 is a perspective explanatory view of the device. FIG. 2 is a perspective explanatory view of the main tank. An image forming apparatus 400 as an example of a recording apparatus is a serial image forming apparatus. A mechanical unit 420 is provided inside the exterior 401 of the image forming apparatus 400 . Each ink container 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is packed with, for example, an aluminum laminated film. It is made up of members. The ink containing portion 411 is housed, for example, in a container case 414 made of plastic. Thus, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided on the far side of the opening when the cover 401c of the apparatus main body is opened. A main tank 410 is detachably attached to the cartridge holder 404 . As a result, each ink discharge port 413 of the main tank 410 communicates with the ejection head 434 for each color via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 onto the printing medium.

This recording apparatus can include not only a portion that ejects ink, but also devices called pre-processing devices and post-processing devices.
As an aspect of the pre-treatment device and the post-treatment device, it has a pre-treatment liquid and a post-treatment liquid in the same manner as in the case of inks such as black (K), cyan (C), magenta (M), and yellow (Y). There is a mode in which a liquid container and a liquid ejection head are added, and the pretreatment liquid and the posttreatment liquid are ejected by an inkjet recording method.
As another aspect of the pre-treatment device and the post-treatment device, there is an aspect in which a pre-treatment device and a post-treatment device using a method other than the inkjet recording method, such as a blade coating method, a roll coating method, and a spray coating method, are provided.

It should be noted that the method of using the ink is not limited to the ink jet recording method, and can be widely used. In addition to the inkjet recording method, for example, a blade coating method, a gravure coating method, a bar coating method, a roll coating method, a dip coating method, a curtain coating method, a slide coating method, a die coating method and a spray coating method can be used.

The use of the ink of the present invention is not particularly limited and can be appropriately selected according to the intended purpose. Furthermore, it can be used not only as an ink to form two-dimensional characters and images, but also as a three-dimensional modeling material for forming a three-dimensional three-dimensional image (three-dimensional object).
A known three-dimensional modeling apparatus for forming three-dimensional objects can be used, and is not particularly limited. be able to. The three-dimensional object includes a three-dimensional object obtained by applying ink repeatedly. It also includes a molded product obtained by processing a structure obtained by applying ink onto a base material such as a recording medium. The molded product is, for example, a sheet-shaped or film-shaped recorded matter or structure that has been subjected to molding such as heat stretching or punching.・Suitably used for applications where molding is performed after the surface is decorated, such as electronic equipment, meters for cameras, and operation panels.

Image formation, recording, printing, printing, etc. in the terms of the present invention are all synonymous.

The terms recording medium, medium, and printed material are all synonymous.

EXAMPLES Hereinafter, embodiments of the present invention will be described in more detail with reference to examples, but the present embodiments are not limited only to these examples.

(Materials used for ink composition preparation)
[Pigment]
・Black pigment (solid content concentration 25% by mass)
・ Cyan pigment (solid content concentration 20% by mass)

[Urethane resin emulsion]
・ Polycarbonate-based polyurethane resin, solid content concentration 30% by mass
・Polyester polyurethane resin, solid content concentration 40% by mass

[Emulsion type silicone compound]
The silicone emulsion was prepared by conventionally known emulsion polymerization method and phase inversion emulsification method using polyalkoxyethylene as an emulsifier.
・ Silicone A: dimethyl silicone emulsion (solid content concentration 34% by mass)
・ Silicone B: amino-modified silicone emulsion (solid content concentration 39% by mass)
・ Silicone C: Epoxy-modified silicone emulsion (solid content concentration 38% by mass)
・ Silicone D: Reactive silicone emulsion (solid content concentration 30% by mass)

[Dimethylamide compound]
・ Equamid M100 [manufactured by Idemitsu Kosan Co., Ltd.]
・ Equamid B100 [manufactured by Idemitsu Kosan Co., Ltd.]

[moisturizer]
・Glycerin ・Propylene glycol ・Butanediol

[Surfactant]
・ Fluorinated surfactant (Polyfox manufactured by OMNOVA)

The materials shown in Tables 1 and 2 below were mixed at the contents shown in each table (unit: % by mass) and thoroughly stirred. This stirred liquid was filtered through a membrane filter with a pore size of 0.8 mm, and then degassed using a vacuum pump to obtain each ink composition used in Examples and Comparative Examples.

[Evaluation of ink and printed matter]
For each ink prepared above, a printer (Ri-100 manufactured by Ricoh) is used to print on an A4 size cotton broadcloth. In the 5% chart, the ink prepared above was printed at 100% duty. Each printed material was evaluated for abrasion resistance, ejection stability, and flexibility.

[Ink viscosity measurement]
Using a viscometer (RE-550L), the viscosity of each of the above inks was measured at 25° C. and taken as the initial viscosity.

[Storage stability]
Each of the inks prepared above was placed in a 50 mL glass container and sealed, and then the glass bottle was placed in a constant temperature bath at 60° C. and allowed to stand for 7 days. After 7 days, it was taken out, and after sufficiently returning to room temperature, the viscosity was measured in the same manner as in the "ink viscosity measurement". Then, the rate of increase in viscosity after standing for 7 days with respect to the initial viscosity was calculated. Evaluation criteria are as follows. The evaluation results are shown in Tables 1 and 2 below.
(Evaluation criteria)
○: Less than +5% △: +5% or more and less than 15% ×: +15% or more

[Scratch resistance of printed material]
Using a dyeing rubbing fastness tester AR-2 (manufactured by Intec), a printer (Ri-100 manufactured by Ricoh) is used to print on an A4 size cotton broadcloth, and the print pattern is printed in the image area. A rubbing resistance test was performed on an image printed with the above-prepared ink at a duty of 100% on a chart in which the printed area of each color was 5% of the total area of the paper.
A metal cloth was placed on the image surface and rubbed with a load of 200 g, and the transfer on the metal cloth side after rubbing was visually observed. It was evaluated as follows.
(Evaluation criteria)
⊚: No transfer to gold cloth side. There was neither peeling nor damage on the image surface.
◯: A small amount of transfer was observed on the metal cloth side. There was neither peeling nor damage on the image surface.
Δ: Moderate transfer to gold cloth side was observed. Peeling and scratches on the image surface were linearly present.
x: A large amount of transfer was observed on the metal cloth side. Peeling and scratches on the image surface were present on the surface.

[Ejection stability]
Using a printer (Ri-100 manufactured by Ricoh), printing is performed on an A4 size cotton broadcloth, and the printing pattern is in the image area, the printing area is the total area of the paper, and the printing area of each color is 5%. The ink prepared in was printed at 100% duty.
The printing conditions were a recording density of 600 dpi and one-pass printing.
After printing 20 sheets of the above chart continuously, it was put into a resting state without discharging for 20 minutes, and this was repeated 50 times. After printing a total of 1000 sheets, the chart was printed again. The presence or absence of streaks, white spots, and discharge disturbance was visually evaluated.
(Evaluation criteria)
◎: No streaks, white spots, or discharge disturbances in the solid area ○: Streaks, white spots, or discharge disturbances are seen in the solid areas of 1ch or more in the 1st scan △: Streaks, white spots, or discharge disturbances in the 1st scan Disturbance is observed ×: Streaks, white spots, and discharge disturbance are observed throughout the solid area

[Flexibility of printed material]
A 200 mm×200 mm test piece was sampled from the image surface of each of the printed fabrics obtained above according to the handle-o-meter method. The slot width of the handle-o-meter type testing machine is 10 mm, and the vertical and horizontal directions are measured at a position of 67 mm (1/3 of the test width) from either side of the test piece, and the maximum indicated by the recorder A value (N) was read. A rate of change in the value of the printed image portion with respect to the value of the original fabric was calculated.
Evaluation criteria are as follows.
(Evaluation criteria)
⊚: less than +10% ○: less than +20% △: less than +30% ×: less than +50% The evaluation results are shown in Tables 1 and 2 below.

From the above results, the ink compositions of Examples containing a dimethylsilicone compound and a dimethylamide compound are superior to the ink compositions of Comparative Examples in ejection stability, storage stability, abrasion resistance, and flexibility. I found out.

（上記式中、Ｒは炭素数１以上４以下のアルキル基を表す。）
（３）前記ジメチルアミド化合物をインク組成物の総量に対して１．０質量％以上１０．０質量％以下含有する、上記（１）又は（２）に記載のインク組成物。
（４）前記シリコーン化合物はジメチルシリコーン化合物であり、前記ジメチルシリコーン化合物を前記インク組成物の総量に対して０．１質量％以上５．０質量％以下含有する、上記（１）乃至（３）のいずれか１項に記載のインク組成物。
（５）下記構造式（２）で表される非イオン性ポリアルコキシエチレンを含む、上記（１）乃至（４）のいずれか１項に記載のインク組成物。

（上記式中、Ｒは炭素数１０以上１５以下のアルキル基を表し、ｎは５以上１２以下の整数を表す。）
（６）上記（１）乃至（５）のいずれか１項に記載のインク組成物を容器中に収容したことを特徴とするインク収容容器。
（７）上記（１）乃至（５）のいずれか１項に記載のインク組成物を用いてインクジェットにより布帛を印刷する工程を含むことを特徴とする印刷方法。
（８）上記（６）に記載のインク収容容器と、前記インク収容容器から供給されるインクを吐出する吐出手段と、を有することを特徴とする印刷装置。 The present invention relates to the ink described in (1) below, but includes the following (2) to (8) as embodiments of the invention.
(1) An ink composition containing water, an organic solvent, resin particles, a coloring material, and a silicone compound, wherein the organic solvent contains a dimethylamide compound.
(2) The ink composition according to (1) above, wherein the dimethylamide compound is a compound represented by the following structural formula (1).

(In the above formula, R represents an alkyl group having 1 to 4 carbon atoms.)
(3) The ink composition according to (1) or (2) above, containing 1.0% by mass or more and 10.0% by mass or less of the dimethylamide compound relative to the total amount of the ink composition.
(4) The above (1) to (3), wherein the silicone compound is a dimethyl silicone compound and contains 0.1% by mass or more and 5.0% by mass or less of the dimethyl silicone compound relative to the total amount of the ink composition. The ink composition according to any one of .
(5) The ink composition according to any one of (1) to (4) above, containing a nonionic polyalkoxyethylene represented by the following structural formula (2).

(In the above formula, R represents an alkyl group having 10 to 15 carbon atoms, and n represents an integer of 5 to 12.)
(6) An ink container containing the ink composition according to any one of (1) to (5) above.
(7) A printing method comprising a step of printing a fabric by inkjet using the ink composition according to any one of (1) to (5) above.
(8) A printing apparatus comprising the ink container described in (6) above and an ejection means for ejecting the ink supplied from the ink container.

400 Image forming apparatus 401 Exterior of image forming apparatus 401c Cover of apparatus main body 404 Cartridge holder 410 Main tank 410k, 410c, 410m, 410y For black (K), cyan (C), magenta (M), and yellow (Y) main tank 411 ink storage unit 413 ink discharge port 414 storage container case 420 mechanism unit 434 ejection head 436 supply tube

JP 2013-194222 A

Claims (8)

An ink composition comprising water, an organic solvent, resin particles, a coloring material, and a silicone compound, wherein the organic solvent comprises a dimethylamide compound. The ink composition according to claim 1, wherein the dimethylamide compound is a compound represented by the following structural formula (1).

(In the above formula, R represents an alkyl group having 1 to 4 carbon atoms.) 3. The ink composition according to claim 1, wherein the dimethylamide compound is contained in an amount of 1.0% by mass or more and 10.0% by mass or less based on the total amount of the ink composition. 4. The method according to any one of claims 1 to 3, wherein the silicone compound is a dimethyl silicone compound, and contains 0.1% by mass or more and 5.0% by mass or less of the dimethyl silicone compound relative to the total amount of the ink composition. The described ink composition. 5. The ink composition according to any one of claims 1 to 4, comprising a nonionic polyalkoxyethylene represented by the following structural formula (2).

(In the above formula, R represents an alkyl group having 10 to 15 carbon atoms, and n represents an integer of 5 to 12.) 6. An ink container containing the ink composition according to any one of claims 1 to 5. A printing method comprising the step of printing a fabric by inkjet using the ink composition according to any one of claims 1 to 5. 7. A printing apparatus comprising: the ink container according to claim 6; and ejection means for ejecting ink supplied from the ink container.

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