JP6776775B2 - Printing Ink Composition and Recording Method - Google Patents

Description

The present invention relates to a printing inkjet ink composition and a recording method.

The inkjet recording method is a method in which small droplets of ink are ejected from a fine nozzle and adhered to a recording medium for recording. This method has a feature that a high-resolution and high-quality image can be recorded at high speed with a relatively inexpensive device. In the inkjet recording method, there are numerous factors to be examined, such as the properties of the ink used, the stability in recording, and the quality of the obtained image, and research on not only the inkjet recording device but also the ink composition to be used is active. is there.

In addition, dyeing (printing) of fabrics and the like is also performed using an inkjet recording method. Conventionally, screen printing, roller printing, etc. have been used as recording methods for fabrics (woven fabrics and non-woven fabrics), but from the viewpoint of high-mix low-volume productivity and immediate printability, the inkjet recording method should be applied. Is advantageous, so various studies have been conducted.

So-called pigment printing, in which a pigment and a fixing resin are mixed with an ink composition and printed on a fabric, has also been studied. In the case of pigment printing, it is important to physically fix the pigment to the fibers of the fabric or the like.

On the other hand, for example, Patent Document 1 prints with an ink composition containing at least one coloring material selected from hollow resin particles and metal compound particles and a polyurethane resin having a glass transition temperature of 65 ° C. or lower. An image forming method characterized by the above is described. In this document, it is stated that by using a polyurethane resin having a specific glass transition temperature, a coloring material can be firmly fixed on a recording medium and an image having excellent fastness can be obtained.

Japanese Unexamined Patent Publication No. 2010-188597

However, the improvement of toughness is insufficient only by using a polyurethane resin having a specific glass transition temperature. Therefore, the applicant has found that a crosslinkable resin is used for further improvement of the fastness. However, when the crosslinkable resin is used, the frictional fastness of the image is improved, but the crosslinkable resin is contained. Since the ink has a high drying property, it has been clarified that the nozzle for ejecting the ink is likely to be clogged. Therefore, it was considered to add a moisturizer, but it became clear that depending on the type of moisturizer, clogging may occur due to drying or thickening of the ink, or ejection stability may decrease. It was also clarified that the frictional fastness may be lowered due to the residual moisturizer remaining on the recording surface. Although the thickening of the ink could be reduced by heating at the time of recording, the crosslinkable component of the resin contained in the ink may react with heat, and heating at the time of recording is not preferable.

Therefore, in some aspects of the present invention, by solving at least a part of the above-mentioned problems, a printed matter having excellent clogging property and discharge stability, and excellent friction fastness and washing fastness can be obtained. It is an object of the present invention to provide a printing inkjet ink composition and a recording method.

The present invention has been made to solve at least a part of the above-mentioned problems, and can be realized as the following aspects or application examples.

[Application example 1]
One aspect of the printing inkjet ink composition according to the present invention is
Contains a resin dispersion and a moisturizer,
The resin dispersion contains a urethane resin containing a crosslinkable group,
The moisturizer contains an organic solvent having a standard boiling point of 280 ° C. or higher and at least one of a room temperature solid polyhydric alcohol or betaine.

According to the printing inkjet ink composition of Application Example 1, it contains a urethane resin containing a crosslinkable group, an organic solvent having a standard boiling point of 280 ° C. or higher, and at least one of a polyhydric alcohol or betaine which is a solid at room temperature. As a result, the drying property, redispersibility, and viscosity of the ink can be appropriately adjusted, and a printed material having excellent clogging property and ejection stability and excellent friction fastness can be obtained.

[Application example 2]
In the above application example
The content ratio of the room temperature solid polyhydric alcohol or betaine to the organic solvent having a standard boiling point of 280 ° C. or higher can be 1: 2 to 1: 5.

According to Application Example 2, the content ratio of the polyhydric alcohol or betaine solid at room temperature to the organic solvent having a standard boiling point of 280 ° C. or higher is in the range of 1: 2 to 1: 5, resulting in excellent frictional fastness. A printed product can be obtained, and a printed inkjet ink composition that is less likely to be clogged and has excellent ejection stability can be obtained.

[Application example 3]
In the above application example
The content ratio of the room temperature solid polyhydric alcohol or betaine to the urethane resin containing the crosslinkable group can be 1: 1 to 1: 2.

According to Application Example 3, the content ratio of the polyhydric alcohol or betaine solid at room temperature to the urethane resin containing a crosslinkable group is in the range of 1: 1 to 1: 2, so that the friction fastness is excellent. A printed product can be obtained, and a printed inkjet ink composition that is less likely to cause clogging and has excellent ejection stability can be obtained in a wider temperature range.

[Application example 4]
In the above application example
Further pigments can be contained.

According to Application Example 4, in pigment printing, a printing inkjet ink composition capable of obtaining a printed product having excellent clogging property and ejection stability and excellent friction fastness can be obtained.

[Application example 5]
In the above application example
The room temperature solid multivalent alcohol can contain trimethylolpropane.

According to Application Example 5, a printing inkjet ink composition capable of obtaining a printed material having excellent clogging property and ejection stability and excellent friction fastness can be obtained.

[Application example 6]
In the above application example
The solid content concentration of the urethane resin containing the crosslinkable group can be 3.0% by mass or more and 6.0% by mass or less.

According to Application Example 6, when the solid content concentration of the urethane resin containing a crosslinkable group is 3.0% by mass or more and 6.0% by mass or less, a printed material having more excellent frictional fastness can be obtained. At the same time, a printing inkjet ink composition that is less likely to cause clogging and has excellent ejection stability can be obtained.

[Application 7]
In the above application example
The concentration of the organic solvent having a standard boiling point of 280 ° C. or higher can be 6.0% by mass or more and 20.0% by mass or less.

According to Application Example 7, when the concentration of the organic solvent having a standard boiling point of 280 ° C. or higher is 6.0% by mass or more and 20.0% by mass or less, clogging is less likely to occur and printing is excellent in discharge stability. An inkjet ink composition is obtained.

[Application Example 8]
In the above application example
The concentration of the polyhydric alcohol or betaine of the room temperature solid can be 2.5% by mass or more and 9.0% by mass or less.

According to Application Example 8, when the concentration of polyhydric alcohol or betaine as a solid at room temperature is 2.5% by mass or more and 9.0% by mass or less, clogging is less likely to occur and the printing ink is excellent in ejection stability. An ink composition is obtained.

[Application 9]
In the above application example
The urethane resin containing a crosslinkable group can be a polycarbonate-based urethane resin or a polyether-based urethane resin.

According to Application Example 9, a printed matter having further good frictional fastness can be obtained.

[Application Example 10]
One aspect of the recording method according to the present invention is
The printing inkjet ink composition according to any one of Application Examples 1 to 9 is attached to a cloth and recorded.

According to Application Example 10, since recording is performed using the printing inkjet ink composition according to the above application example, printing is stable, clogging is unlikely to occur, ejection stability is excellent, and friction fastness is excellent. A recording method for obtaining an object is obtained.

[Application Example 11]
In the above application example
It can be done without heating.

According to Application Example 11, since recording is performed using the printing inkjet ink composition according to the above application example, ejection is stable even without heating, clogging is unlikely to occur, ejection stability is excellent, and further. A recording method can be obtained that can obtain a printed material having excellent frictional fastness.

[Application 12]
In the above application example
Recording can be performed in a temperature range of 15 ° C. or higher and 35 ° C. or lower.

According to Application Example 12, by recording in a temperature range of 15 ° C. or higher and 35 ° C. or lower, a recording method that is less likely to cause clogging and has excellent discharge stability can be obtained.

Some embodiments of the present invention will be described below. The embodiments described below describe an example of the present invention. The present invention is not limited to the following embodiments, and includes various modifications implemented without changing the gist of the present invention. It should be noted that not all of the configurations described below are essential configurations of the present invention.

1. 1. Printing Ink Ink Composition The printing inkjet ink composition of the present embodiment contains a resin dispersion and a moisturizing agent, the resin dispersion contains a urethane resin containing a crosslinkable group, and the moisturizing agent is used. It contains an organic solvent having a standard boiling point of 280 ° C. or higher and at least one of a polyhydric alcohol or betaine which is a solid at room temperature. This printing inkjet ink composition is used in a recording method for recording by adhering it to a cloth without heating. Hereinafter, the printing inkjet ink composition (hereinafter, also simply referred to as “printing ink composition”, “ink composition”, or “ink”) will be described.

1.1. Resin Dispersion The printing inkjet ink composition of the present embodiment contains a resin dispersion. The resin contained in the resin dispersion has a function of improving the fixing property of the image formed by the ink composition by forming a resin film, and can improve the washing fastness and the friction fastness of the image. .. As the resin dispersion, both an emulsion state and a solution state can be used, but it is preferable to use an emulsion state from the viewpoint of suppressing an increase in the viscosity of the ink.

The resin contained in the resin dispersion is not particularly limited, but at least the resin dispersion contains a urethane resin containing a crosslinkable group. Crosslinkable groups (isocyanate groups) are chemically protected (capping or blocking) and are deprotected and activated by the application of heat to form bonds (eg, urethane bonds, urea bonds, allophanate bonds, etc.). Will form.

Further, since three or more crosslinkable groups of the urethane resin having a crosslinkable group are provided in one molecule, a crosslinked structure is formed by the reaction of the crosslinkable group. In the present specification, the urethane-based resin is a urethane bond or a urea bond formed by reacting an isocyanate group with another reactive group (for example, a hydroxyl group, an amino group, a urethane bonding group, a carboxyl group, etc.). , Refers to a resin containing an allophanate bond, etc. (However, it has an unreacted isocyanate group and a blocked isocyanate group that contribute to the cross-linking reaction). Therefore, in the present specification, for example, urea resin is included in urethane-based resin. The urethane-based resin is preferably a compound having a urethane bond obtained by reacting a compound having an isocyanate group with a compound having a hydroxyl group.

Blocked isocyanate (chemically protected isocyanate) contains a latent isocyanate group in which the isocyanate group is blocked by a blocking agent, and can be obtained, for example, by reacting a polyisocyanate compound with a blocking agent.

Examples of the polyisocyanate compound include a polyisocyanate monomer and a polyisocyanate derivative. Examples of the polyisocyanate monomer include polyisocyanates such as aromatic polyisocyanates, aromatic aliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. These polyisocyanate monomers can be used alone or in combination of two or more.

Examples of the polyisocyanate derivative include multimers of the above-mentioned polyisocyanate monomers (for example, dimer and trimeric (for example, isocyanurate modified and iminooxadiazinedione modified), pentamer and 7). Quantities, etc.), allophanate modified products (for example, allophanate modified products produced by the reaction of the above-mentioned polyisocyanate monomer with a low molecular weight polyol described later), polyol modified products (for example, polyisocyanate monomer and described later). Polyisocyanate modified product (alcohol adduct) produced by reaction with low molecular weight polyol, etc.), biuret modified product (for example, biuret modified product produced by reaction of the above-mentioned polyisocyanate monomer with water or amines, etc. ), Urea modified product (for example, urea modified product produced by the reaction of the above-mentioned polyisocyanate monomer with diamine), oxadiazine trione modified product (for example, the above-mentioned polyisocyanate monomer and carbon dioxide gas). Examples thereof include oxadiazine trione produced by the reaction), carbodiimide modified product (carbodiimide modified product produced by the decarbonate condensation reaction of the polyisocyanate monomer described above), uretdione modified product, uretonimine modified product and the like.

When two or more types of polyisocyanate compounds are used in combination, for example, two or more types of polyisocyanate compounds may be reacted at the same time during the production of blocked isocyanate, or each polyisocyanate compound may be used individually. The obtained blocked isocyanate may be mixed.

The blocking agent blocks and inactivates the isocyanate group, while regenerating or activating the isocyanate group after deblocking, and activating the isocyanate group in the blocked and deblocked state of the isocyanate group. It also has a catalytic action.

Examples of the blocking agent include imidazole compounds, imidazoline compounds, pyrimidine compounds, guanidine compounds, alcohol compounds, phenol compounds, active methylene compounds, amine compounds, imine compounds, oxime compounds, and carbamate compounds. , Urea compounds, acid amide compounds (lactam compounds), acid imide compounds, triazole compounds, pyrazole compounds, mercaptan compounds, barrous sulfate and the like.

Examples of the imidazole-based compound include imidazole (dissociation temperature 100 ° C.), benzimidazole (dissociation temperature 120 ° C.), 2-methylimidazole (dissociation temperature 70 ° C.), 4-methylimidazole (dissociation temperature 100 ° C.), and 2-ethyl. Examples thereof include imidazole (dissociation temperature 70 ° C.), 2-isopropylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole and the like.

Examples of the imidazoline-based compound include 2-methylimidazoline (dissociation temperature 110 ° C.), 2-phenylimidazoline and the like.

Examples of the pyrimidine-based compound include 2-methyl-1,4,5,6-tetrahydropyrimidine.

Examples of the guanidine compound include 3,3-dialkylguanidine such as 3,3-dimethylguanidine, and 1,1,3, for example, 1,1,3,3-tetramethylguanidine (dissociation temperature 120 ° C.) and the like. Examples thereof include 3-tetraalkylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene and the like.

Examples of alcohol-based compounds include methanol, ethanol, 2-propanol, n-butanol, s-butanol, 2-ethylhexyl alcohol, 1- or 2-octanol, cyclohexyl alcohol, ethylene glycol, benzyl alcohol, 2,2. , 2-Trifluoroethanol, 2,2,2-trichloroethanol, 2- (hydroxymethyl) furan, 2-methoxyethanol, methoxypropanol, 2-ethoxyethanol, n-propoxyethanol, 2-butoxyethanol, 2-ethoxy Ethoxyethanol, 2-ethoxybutoxyethanol, butoxyethoxyethanol, 2-butoxyethylethanol, 2-butoxyethoxyethanol, N, N-dibutyl-2-hydroxyacetamide, N-hydroxysuccinimide, N-morpholinethanol, 2,2- Dimethyl-1,3-dioxolan-4-methanol, 3-oxazolidineethanol, 2-hydroxymethylpyridine (dissociation temperature 140 ° C.), furfuryl alcohol, 12-hydroxystearic acid, triphenylsilanol, 2-hydroxyethyl methacrylate, etc. Can be mentioned.

Examples of phenolic compounds include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, s-butylphenol, t-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, n. -Nonylphenol, di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-s-butylphenol, di-t-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, di-n -Nonylphenol, nitrophenol, bromophenol, chlorophenol, fluorophenol, dimethylphenol, styrenated phenol, methylsalicylate, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2-ethylhexyl hydroxybenzoate, 4- [(Dimethylamino) methyl] phenol, 4-[(dimethylamino) methyl] nonylphenol, bis (4-hydroxyphenyl) acetic acid, 2-hydroxypyridine (dissociation temperature 80 ° C.), 2- or 8-hydroxyquinolin, 2- Examples thereof include chloro-3-pyridinol and pyridine-2-thiol (dissociation temperature 70 ° C.).

Examples of the active methylene compound include meldrum acid and dialkyl malonate (for example, dimethyl malonate, diethyl malonate, di-butyl malate, di-t-butyl malate, di2-ethylhexyl malonate and malonic acid). Methyl n-butyl, ethyl n-butyl malonate, methyl s-butyl malate, ethyl s-butyl malonate, methyl t-butyl malate, ethyl t-butyl malonate, diethyl methylmalonate, dibenzyl malonate, malon Diphenyl acid, benzylmethyl malonate, ethylphenyl malonate, t-butylphenyl malonate, isopropylidene malonate, etc.), alkyl acetoacetate (eg, methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate) , N-Butyl acetoacetate, t-butyl acetoacetate, benzyl acetoacetate, phenyl acetoacetate, etc.), 2-acetoacetoxyethyl methacrylate, acetylacetone, ethyl cyanoacetate and the like.

Examples of amine-based compounds include dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis (2,2,6,6-tetramethylpiperidinyl) amine, di-n-propylamine, and diisopropylamine ( Dissociation temperature 130 ° C.), isopropylethylamine, 2,2,4-, or 2,2,5-trimethylhexamethyleneamine, N-isopropylcyclohexylamine (dissociation temperature 140 ° C.), dicyclohexylamine (dissociation temperature 130 ° C.), Bis (3,5,5-trimethylcyclohexyl) amine, piperidine, 2,6-dimethylpiperidine (dissociation temperature 130 ° C), t-butylmethylamine, t-butylethylamine (dissociation temperature 120 ° C), t-butylpropylamine , T-butylbutylamine, t-butylbenzylamine (dissociation temperature 120 ° C.), t-butylphenylamine, 2,2,6-trimethylpiperidin, 2,2,6,6-tetramethylpiperidin (dissociation temperature 80 ° C.) , (Dimethylamino) -2,2,6,6-tetramethylpiperidin, 2,2,6,6-tetramethyl-4-piperidin, 6-methyl-2-piperidin, 6-aminocaproic acid and the like.

Examples of the imine compound include ethyleneimine, polyethyleneimine, 1,4,5,6-tetrahydropyrimidine, guanidine and the like.

Examples of oxime compounds include formaldehyde, acetoaldoxime, acetooxime, methylethylketooxime (dissociation temperature 130 ° C.), cyclohexanone oxime, diacetylmonooxime, penzophenooxime, 2,2,6,6-tetramethyl. Cyclohexanone oxime, diisopropyl ketone oxime, methyl t-butyl ketone oxime, diisobutyl ketone oxime, methyl isobutyl ketone oxime, methyl isopropyl ketone oxime, methyl 2,4-dimethylpentyl ketone oxime, methyl 3-ethyl heptyl ketone oxime, methyl isoamyl ketone Examples thereof include oxime, n-amylketone oxime, 2,2,4,4-tetramethyl-1,3-cyclobutanedione monooxime, 4,4'-dimethoxybenzophenone oxime, 2-heptanone oxime and the like.

Examples of the carbamic acid-based compound include phenyl N-phenylcarbamate and the like.

Examples of the urea compound include urea, thiourea, ethylene urea and the like.

Examples of the acid amide-based (lactam-based) compound include acetanilide, N-methylacetamide, acetate amide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, pyrrolidone, 2,5-piperazindione, laurolactam and the like. Be done.

Examples of the acidimide-based compound include succinate imide, maleate imide, and phthalimide.

Examples of the triazole-based compound include 1,2,4-triazole, benzotriazole and the like.

Examples of the pyrazole-based compound include pyrazole, 3,5-dimethylpyrazole (dissociation temperature 120 ° C.), 3,5-diisopropylpyrazole, 3,5-diphenylpyrazole, 3,5-di-t-butylpyrazole, 3-. Examples thereof include methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, 3-methyl-5-phenylpyrazole and the like.

Examples of the mercaptan-based compound include butyl mercaptan, dodecyl mercaptan, and hexyl mercaptan.

Examples of the sodium bisulfite include sodium bisulfite and the like.

Further, the blocking agent is not limited to the above, and examples thereof include other blocking agents such as benzoxazolone, isatoic anhydride, and tetrabutylphosphonium-acetate.

For some of the above-exemplified compounds, the dissociation temperature is also described as the temperature at which the isocyanate group is regenerated.

Such blocking agents can be used alone or in combination of two or more. The dissociation temperature of the blocking agent can be appropriately selected. The dissociation temperature is, for example, 60 ° C. or higher and 230 ° C. or lower, preferably 80 ° C. or higher and 200 ° C. or lower, more preferably 100 ° C. or higher and 180 ° C. or lower, and further preferably 110 ° C. or higher and 160 ° C. or lower. Within such a temperature range, the pot life of the printing inkjet ink composition can be sufficiently lengthened, and the temperature in the heating step can be prevented from becoming too high.

The main chain of the urethane-based resin having a crosslinkable group may be any of a polyether type containing an ether bond, a polyester type containing an ester bond, a polycarbonate type containing a carbonate bond, and the like. When a urethane resin having a crosslinkable group is crosslinked (crosslinked body), the elongation at break point and 100% modulus can be adjusted by changing the density of the crosslink points and the type of such a main chain. .. Of these, the polycarbonate-based skeleton or the urethane-based resin having a crosslinkable group having a polyether skeleton has a good balance between fracture point elongation and 100% modulus, and has good friction fastness of images and imprints. It is more preferable because it is easy to improve the texture of. In particular, a urethane resin having a polycarbonate-based skeleton tends to have good frictional fastness and is preferable.

Further, the urethane resin having a crosslinkable group has a breaking point elongation of 150% or more, preferably 170% or more, more preferably 200% or more, still more preferably 200% or more, after the crosslink is formed (crosslinked body). , 300% or more is preferable. By selecting the density of the cross-linking points and the type of the main chain so as to have such a breaking point elongation, the texture of the printed matter can be improved.

Here, the elongation at break is determined, for example, by curing a urethane resin emulsion having a crosslinkable group to prepare a film having a thickness of about 60 μm, under the conditions of a tensile test gauge length of 20 mm and a tensile speed of 100 mm / min. The value obtained by measuring with can be adopted. Further, as the 100% modulus, a value obtained by measuring the tensile stress when the film is stretched 100% with respect to the original length in the tensile test can be adopted. The film to be measured may be formed by using a urethane resin emulsion having a crosslinkable group, or may be formed by molding using the same type of resin, but it is preferably formed by using an emulsion resin.

The urethane-based resin having a crosslinkable group may be blended in the form of an emulsion. Such a resin emulsion is a so-called self-reactive urethane-based resin emulsion, and a commercially available urethane-based resin emulsion having an isocyanate group blocked with a blocking agent having a hydrophilic group can be used.

Commercially available urethane-based resins with crosslinkable groups include Takelac WS-6021 (trade name manufactured by Mitsui Chemicals Polyurethane Co., Ltd., urethane-based resin emulsion, polyether-based polyurethane having a polyether-derived skeleton), WS-5100 (Mitsui). Product name manufactured by Chemical Polyurethane Co., Ltd., urethane-based resin emulsion, polycarbonate-based polyurethane having a polycarbonate-derived skeleton), Elastron E-37, H-3 (the above are polyester-based polyurethanes whose main chain has a polyester-derived skeleton), Elastron H- 38, BAP, C-52, F-29, W-11P (the above are polyether polyurethanes whose main chain has a polyether-derived skeleton) (trade name manufactured by Daiichi Kogyo Seiyaku Co., Ltd., urethane resin emulsion), Superflex 870, 800, 150, 420, 460, 470, 610, 700 (trade name manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyurethane resin emulsion), Permarin UA-150 (manufactured by Sanyo Kasei Kogyo Co., Ltd., urethane resin emulsion), Sun Cure 2710 (manufactured by Nippon Lubrizol, urethane-based resin emulsion), NeoRez R-9660, R-9637, R-940 (manufactured by Kusumoto Kasei Co., Ltd., urethane-based resin emulsion), Adecabon Titter HUX-380, 290K (stock) Company ADEKA, urethane-based resin emulsion), etc. can be exemplified.

In the present embodiment, the solid content concentration of the urethane resin containing a crosslinkable group is 1.0% by mass or more and 10.0% by mass or less when the total mass of the printing inkjet ink composition is 100% by mass. It may be 3.0 mass% or more and 6.0 mass% or less, and more preferably 4.0 mass% or more and 5.0 mass% or less.

In addition, these urethane-based resins may be contained in the pretreatment liquid when the pretreatment liquid is used in the recording method of this embodiment described later, and in that case, urethane contained in the pretreatment liquid. The based resin and the urethane-based resin contained in the printing inkjet ink composition may be the same or different.

Further, the temperature of the heating step in the recording method of the present embodiment described later is at least a part of the crosslinkable groups in consideration of the deprotection temperature (dissociation temperature) of the isocyanate groups of the urethane-based resin having these crosslinkable groups. Is set to be activated.

1.2. Moisturizer The textile printing inkjet ink composition according to the present embodiment contains a moisturizer. Since the ink contains a moisturizer, it is possible to stabilize the ejection of the ink by the inkjet method at room temperature (for example, a temperature of about 23 ° C.), and it is not necessary to heat the ink to reduce its viscosity. Further, it is possible to effectively suppress the evaporation of water from the inkjet head when left for a long period of time.

The moisturizing agent is preferably a water-soluble organic solvent, and examples thereof include polyol compounds, glycol ethers, and betaines. In the present embodiment, at least an organic solvent having a standard boiling point of 280 ° C. or higher and room temperature are used. Contains at least one of solid polyhydric alcohols or betaines.

Examples of the polyol compound include a polyol compound (preferably a diol compound) having 2 or more and 6 or less carbon atoms in the molecule and which may have one ether bond in the molecule. Specific examples include diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, polyoxyethylene polyoxypropylene glycol, trimethylolpropane, and methyltriglycol (triethylene glycol monomethyl ether). , Butyl triglycol (triethylene glycol monobutyl ether), butyl diglycol (diethylene glycol monobutyl ether), dipropylene glycol monopropyl ether, glycerin, 1,2-hexanediol, 1,2-heptanediol, 1,3-propane Diol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-3-phenoxy-1,2-propanediol, 3- (3- (3-) Methylphenoxy) -1,2-propanediol, 3-hexyloxy-1,2-propanediol, 2-hydroxymethyl-2-phenoxymethyl-1,3-propanediol, 3-methyl-1,3-butanediol , 1,3-Propanediol, 1,2-Butanediol, 1,2-Pentanediol, 1,4-Butanediol, 1,5-Pentanediol, 1,6-Hexanediol, 2-Methyl-2,4 Examples thereof include glycols such as -pentanediol and 3-methyl-1,5-pentanediol.

Examples of the glycol ether include monoalkyl ethers of glycols selected from ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol. preferable. More preferably, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, dipropylene glycol monopropyl ether and the like can be mentioned.

A betaine is, in a broad sense, an atom having a stable positive and negative charge in the molecule (bilayer ion), having a positive charge and a negative charge at non-adjacent positions in the same molecule, and having a positive charge. Is a compound (intramolecular salt) that does not have a dissociable hydrogen atom bonded to it and has no electric charge as a whole molecule. Preferred betaines are N-alkyl substitutions of amino acids, more preferably N-trialkyl substitutions of amino acids. Examples of betaine include trimethylglycine (also referred to as "glycine betaine"), γ-butyrobetaine, homarin, trigonerin, carnitine, homoserine betaine, valine betaine, lysine betaine, ornithine betaine, alanine betaine, stachidrine and betamate glutamate. And preferably, trimethylglycine and the like can be exemplified.

Moreover, you may use a pyrrolidone derivative as a water-soluble organic solvent. Examples of the pyrrolidone derivative include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-butyl-2-pyrrolidone, and 5-methyl-2-pyrrolidone. And so on.

Examples of the organic solvent having a standard boiling point of 280 ° C. or higher include glycerin among the above-mentioned water-soluble organic solvents. When glycerin is contained, the moisturizing property of the ink can be maintained, so that it is possible to prevent the inkjet head from drying and to provide a recording method having excellent clogging property and ejection stability in the recording method described later.

In the present embodiment, the concentration of the organic solvent having a standard boiling point of 280 ° C. or higher is 6.0% by mass or more and 20.0% by mass or less when the total mass of the printing inkjet ink composition is 100% by mass. Is more preferable, and it is more preferably 8.0% by mass or more and 18.0% by mass or less, and further preferably 10.0% by mass or more and 16.0% by mass or less. Within the above range, it is possible to prevent the nozzle of the inkjet head from drying out and to have excellent ejection stability.

Examples of the room temperature solid polyhydric alcohol include trimethylolpropane among the above-mentioned water-soluble organic solvents. Other compounds include, for example, botanical moisturizers such as trehalose and raffinose. Examples of the betaine that is solid at room temperature include trimethylglycine among the above-mentioned betaines. In addition, as a polyhydric alcohol or betaine which is a solid at room temperature, an organic solvent having a standard boiling point of 280 ° C. or higher is excluded.

Here, in the present specification, "normal temperature" means room temperature and means around 23 ° C. It is preferably 18 to 28 ° C, more preferably 20 to 26 ° C, and even more preferably 21 to 25 ° C. By adding these compounds to the ink, the thickening of the ink can be alleviated. Thereby, it is possible to prevent the nozzle of the inkjet head from drying and clogging, and to provide a recording method having excellent ejection stability.

The concentration of polyhydric alcohol or betaine solid at room temperature is preferably 2.5% by mass or more and 9.0% by mass or less when the total mass of the printing inkjet ink composition is 100% by mass, preferably 3.5. It is more preferably mass% or more and 8.0 mass% or less, and further preferably 4.0 mass% or more and 7.0 mass% or less. Within the above range, it is possible to prevent the nozzle of the inkjet head from drying out and to have excellent ejection stability.

In the present embodiment, a urethane resin containing a crosslinkable group is contained in order to improve the frictional fastness of the ink, and the ink containing the urethane resin containing the crosslinkable group has high drying property (redispersion). Since the property is low), the nozzle that ejects ink is likely to be clogged. Therefore, the printing inkjet ink composition according to the present embodiment contains as a moisturizing agent in combination with an organic solvent having a standard boiling point of 280 ° C. or higher and a polyhydric alcohol or betaine which is a solid at room temperature, thereby increasing the viscosity of the ink. Is appropriately adjusted, and drying and thickening of the ink are suppressed. Therefore, in the recording method described later, it is not necessary to heat the ink to prevent the ink from becoming low in viscosity. Further, it is possible to prevent clogging due to drying and thickening of the ink and deterioration of ejection stability. The crosslinkable component of the resin contained in the ink may react with heat, and heating at the time of recording is not preferable. Therefore, the printing inkjet ink composition according to the present embodiment, which can be recorded without heating, is a recording method for obtaining a printed material having excellent clogging property and ejection stability and excellent friction fastness. It is suitable.

In the present embodiment, the content ratio of the room temperature solid polyhydric alcohol or betaine contained as a moisturizer to the organic solvent having a standard boiling point of 280 ° C. or higher is 1: 2 to 1: 5 (mass ratio). Is preferable. When the content ratio of the polyhydric alcohol or betaine solid at room temperature to the organic solvent having a standard boiling point of 280 ° C. or higher is in the range of 1: 2 to 1: 5, a printed material having excellent friction fastness can be obtained. It is possible to prevent clogging of the nozzle due to drying and thickening of the ink, and to provide a recording method having excellent ejection stability in a wide temperature range. More preferably, the content ratio of the normal temperature solid polyhydric alcohol or betaine to the organic solvent having a standard boiling point of 280 ° C. or higher is 1: 3 to 1: 4.

When the content ratio of the organic solvent having a standard boiling point of 280 ° C. or higher to the polyhydric alcohol or betaine of a solid at room temperature is 2 or more, the moisturizing effect of the organic solvent having a standard boiling point of 280 ° C. or higher becomes suitable, and the nozzle dries. The risk of clogging can be suppressed, and the discharge stability at low temperatures can be ensured.

When the content ratio of the organic solvent having a standard boiling point of 280 ° C. or higher to the polyhydric alcohol or betaine of a solid at room temperature is 5 or less, the organic solvent having a standard boiling point of 280 ° C. or higher remains excessively in the recording medium. It can be suppressed and robustness can be guaranteed. In addition, thickening can be suppressed, discharge stability at high temperatures can be ensured, and the risk of clogging can be suppressed.

Further, in the present embodiment, the content ratio of the room temperature solid polyhydric alcohol or betaine contained as a moisturizing agent to the urethane resin containing a crosslinkable group is 1: 1 to 1: 2 (mass ratio). Is preferable. When the content ratio of the polyhydric alcohol or betaine solid at room temperature to the urethane resin containing a crosslinkable group is in the range of 1: 1 to 1: 2, a printed material having excellent friction fastness can be obtained, and at the same time, a printed material having excellent friction fastness can be obtained. In a wider temperature range, clogging is less likely to occur and discharge stability is excellent. When the content ratio of the polyhydric alcohol or betaine solid at room temperature to the urethane resin containing a crosslinkable group is 1: 1 to 1: 1.5, the discharge stability in a lower temperature range is excellent. It becomes.

When the content ratio of the urethane resin containing a crosslinkable group to the polyhydric alcohol or betaine which is a solid at room temperature is 1 or more, the discharge stability at a low temperature can be ensured.
When the content ratio of the urethane resin containing a crosslinkable group to the polyhydric alcohol or betaine which is a solid at room temperature is 2 or less, the thickening is suppressed, the discharge stability at high temperature can be ensured, and the eyes The risk of clogging can be reduced.

As described above, in the present embodiment, the organic solvent having a standard boiling point of 280 ° C. or higher contained as a moisturizer and the polyhydric alcohol or betaine which is a solid at room temperature are contained in a specific ratio in a wide temperature range (for example). , 15 ° C or higher and 35 ° C or lower), the discharge can be stabilized.

The total amount of the moisturizing agent is 10.0 mass with respect to the total amount of the printing inkjet ink composition from the viewpoint of adjusting the viscosity of the printing inkjet ink composition, preventing clogging due to the moisturizing effect, and discharging stability. % Or more and 30% by mass or less, more preferably 12.0% by mass or more and 24% by mass or less, and further preferably 15.0% by mass or more and 20.0% by mass or less.

1.3. Other ingredients 13.1. Pigments The printing inkjet ink composition of the present embodiment may contain pigments. When the pigment is attached to the fabric, the fabric is printed and a printed product (printed product) is formed.

The pigment is not particularly limited, and either an inorganic pigment or an organic pigment can be used. Examples of pigments include organic pigments such as azo-based, phthalocyanine-based, condensed polycyclic, nitro-based, nitroso-based, hollow resin particles, and polymer particles (Brilliant Carmine 6B, Lake Red C, Watching Red, Disazo Yellow, Hansa). Yellow, phthalocyanine blue, phthalocyanine green, alkaline blue, aniline black, etc.); metals such as cobalt, iron, chromium, copper, zinc, lead, titanium, vanadium, manganese, and nickel, titanium oxide, zinc oxide, antimony oxide, etc. Metal oxides and sulfides such as zinc oxide and zinc oxide, carbon blacks such as furnace carbon black, lamp black, acetylene black, and channel black (CI pigment black 7), as well as ocher, ultramarine, And inorganic pigments such as dark blue can be used.

The carbon black used as the black pigment is No. 2300, No. 900, MCF88, No. 33, No. 40, No. 45, No. 52, MA7, MA8, MA100, No. 2200B, etc. (all manufactured by Mitsubishi Chemical Corporation), Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven
1255, Raven 700, etc. (above, manufactured by Columbia Carbon Co., Ltd.), Rega1 400R, Rega1 330R, Rega1 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1100, Monarch 1100, Monarch 1100 (The above is made by Cabot), Color
Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color B1ack S150, Color Black S160, Color Black S160, Color Black S170, PrintS170, Print , Special Black 4A, Special Black 4 (all manufactured by Degussa) and the like.

As a white pigment, C.I. I. Pigment White 1 (basic lead carbonate), 4 (zinc oxide), 5 (mixture of zinc sulfide and barium sulfate), 6 (titanium oxide), 6: 1 (titanium oxide containing other metal oxides), 7 (Zinc sulfide), 18 (calcium carbonate), 19 (clay), 20 (titanium dioxide), 21 (barium sulfate), 22 (natural barium sulfate), 23 (gloss white), 24 (alumina white), 25 (plaster) ), 26 (magnesium oxide / silicon oxide), 27 (silica), 28 (anhydrous calcium silicate) and the like.

Examples of the yellow pigment include C.I. I. Pigment Yellow 1,2,3,4,5,6,7,10,11,12,13,14,16,17,24,34,35,37,53,55,65,73,74,75, 81, 83, 93, 94, 95, 97, 98, 99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 129, 133, 138, 139, 147, 151, 153, 154, 167, 172, 180 and the like can be mentioned.

Examples of magenta pigments include C.I. I. Pigment Red 1,2,3,4,5,6,7,8,9,10,11,12,14,15,16,17,18,19,21,22,23,30,31,32, 37, 38, 40, 41, 42, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 144, 146, 149, 150, 166, 168 , 170, 171, 175, 176, 177, 178, 179, 184, 185, 187, 202, 209, 219, 224, 245, and C.I. I. Pigment violets 19, 23, 32, 33, 36, 38, 43, 50 and the like.

Examples of the cyan pigment include C.I. I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16, 18, 22, 25, 60, 65, 66, and C.I. I. Bat blue 4, 60 and the like can be mentioned.

Pigments other than black, white, yellow, magenta and cyan include, for example, C.I. I. Pigment Greens 7, 10, and C.I. I. Pigment Brown 3, 5, 25, 26, and C.I. I. Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63 and the like.

A plurality of types of these illustrated pigments may be mixed and used. The total content of pigments (solids) in the printing inkjet ink composition varies depending on the pigment type used, but from the viewpoint of obtaining good color development, the total mass of the printing inkjet ink composition is set to 100% by mass. Occasionally, it is preferably 1 to 30% by mass, more preferably 2 to 15% by mass.

When preparing the printing inkjet ink composition, a pigment dispersion liquid in which pigments are dispersed may be prepared in advance, and the pigment dispersion liquid may be added to the printing inkjet ink composition. As a method for obtaining such a pigment dispersion, a method of dispersing a self-dispersing pigment in a dispersion medium without using a dispersant, or a method of dispersing a pigment in a dispersion medium using a polymer dispersant (resin dispersant). There are a method, a method of dispersing the surface-treated pigment in a dispersion medium, and the like.

(Resin dispersant)
Of these, the resin dispersant is not particularly limited, and is, for example, polyvinyl alcohols, polyvinylpyrrolidones, polyacrylic acid, acrylic acid-acrylic nitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid. -Acrylic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene -Α-Methylstyrene-acrylic acid-acrylic acid ester copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinylnaphthalene-acrylic acid copolymer, vinylnaphthalene-maleic acid copolymer , Vinyl acetate-maleic acid ester copolymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic acid copolymer and the like, and salts thereof. Among these, a copolymer of a monomer having a hydrophobic functional group and a monomer having a hydrophilic functional group, and a polymer composed of a monomer having both a hydrophobic functional group and a hydrophilic functional group are particularly preferable. Further, as the form of the copolymer, any form of a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer can be used.

A commercially available product can also be used as the resin dispersant. Specifically, John Krill 67 (weight average molecular weight: 12,500, acid value: 213), John Krill 678 (weight average molecular weight: 8,500, acid value: 215), John Krill 586 (weight average molecular weight: 4). , 600, acid value: 108), John krill 611 (weight average molecular weight: 8,100, acid value: 53), John krill 680 (weight average molecular weight: 4,900, acid value: 215), John krill 682 (weight) Average molecular weight: 1,700, acid value: 238), John Krill 683 (weight average molecular weight: 8,000, acid value: 160), John Krill 690 (weight average molecular weight: 16,500, acid value: 240) (or more) Product name, manufactured by BASF Japan Co., Ltd.) and the like.

1.3.2. Water The printing inkjet ink composition of the present embodiment may contain water. Examples of water include pure water such as ion-exchanged water, ultra-filtered water, reverse osmosis water, and distilled water, and ultrapure water from which ionic impurities have been removed as much as possible. Further, when water sterilized by ultraviolet irradiation or addition of hydrogen peroxide or the like is used, it is possible to prevent the growth of bacteria and fungi when the printed inkjet ink composition is stored for a long period of time.

The content of water is 40% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, based on the total amount of the printing inkjet ink composition. .. The water in the printing inkjet ink composition includes, for example, a resin particle dispersion used as a raw material and water to be added. When the water content is 40% by mass or more, the printing inkjet ink composition can have a relatively low viscosity. The upper limit of the water content is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less, based on the total amount of the printing inkjet ink composition.

1.3.3. Inorganic Alkaline Compound The printing inkjet ink composition of the present embodiment preferably contains an inorganic alkaline compound (inorganic base compound). The inorganic alkaline compound has a property of increasing the pH of the printing inkjet ink composition. Further, the inorganic alkali compound has at least a function of improving the dispersion stability of the urethane-based resin having a crosslinkable group and / or a function of improving the redispersibility of the urethane-based resin having a crosslinkable group.

Examples of the inorganic alkali compound include alkali metal hydroxide or alkaline earth metal hydroxide, alkali metal carbonate or alkaline earth metal carbonate, alkali metal phosphate or alkaline earth metal phosphoric acid. Examples include salt.

Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. Examples of the hydroxide of the alkaline earth metal include calcium hydroxide and magnesium hydroxide.

Examples of the alkali metal carbonate include lithium carbonate, lithium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate and the like. Examples of carbonates of alkaline earth metals include calcium carbonate and the like.

Examples of the alkali metal phosphate include lithium phosphate, potassium phosphate, trisodium phosphate, disodium hydrogen phosphate and the like. Examples of the phosphate of the alkaline earth metal include calcium phosphate and calcium hydrogen phosphate.

A plurality of types of the above-exemplified inorganic alkaline compounds may be used in the printing inkjet ink composition of the present embodiment. The total content of the inorganic alkali compounds is 0.01% by mass or more and 0.8% by mass or less, preferably 0.02% by mass or more and 0.6% by mass or less, based on the total amount of the printing inkjet ink composition. It is preferably 0.03% by mass or more and 0.4% by mass or less, more preferably 0.04% by mass or more and 0.3% by mass or less, particularly preferably 0.05% by mass or more and 0.2% by mass or less, and particularly preferably. It is 0.05% by mass or more and 0.1% by mass or less.

As long as the blending amount of the inorganic alkaline compound is within the above range, the pH of the printing inkjet ink composition can be sufficiently increased, and the function of enhancing the dispersion stability of the urethane-based resin having a crosslinkable group and / or the crosslinkability It is possible to exert a function of improving the redispersibility of the urethane-based resin having a group. The pH of the printing inkjet ink composition will be described in the section on physical properties.

1.3.4. Surfactant The printing inkjet ink composition of the present embodiment may contain a surfactant. As the surfactant, any of nonionic surfactant, anionic surfactant, cationic surfactant, and amphoteric surfactant can be used, and these may be used in combination. The surfactant can reduce the interfacial tension of the printing inkjet ink composition and increase the permeability to the fabric. However, as for the cationic surfactant, since the components of the printing inkjet ink composition may be aggregated, it is more preferable to use a trace amount or another kind of surfactant.

As the nonionic surfactant, at least one of an acetylene glycol-based surfactant, an acetylene alcohol-based surfactant, a fluorine-based surfactant, and a polysiloxane-based surfactant is preferable. When the ink composition contains these surfactants, the wettability to the fabric and the dispersion stability of the pigment are further improved. Further, the acetylene glycol-based surfactant is more preferable for the purpose of further improving the color development property of the image because the permeability to the fabric can be relatively reduced.

The above-mentioned acetylene glycol-based surfactant and acetylene alcohol-based surfactant are not limited to the following, but are 2,4,7,9-tetramethyl-5-decine-4,7-diol and 2,4,7. , 9-Tetramethyl-5-decine-4,7-diol alkylene oxide adduct, and 2,4-dimethyl-5-decine-4-ol and 2,4-dimethyl-5-decine-4-ol, Selected from alkylene oxide adducts of 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexin-3ol, and 2,4-dimethyl-5-hexin-3-ol. Can exemplify more than one type. Commercially available products can also be used as the acetylene glycol-based surfactant and the acetylene alcohol-based surfactant, and surfinol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50, 104S, 420, 440. , 465, 485, SE, SE-F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA (all of the above are trade names, manufactured by AirProductsandChemicals. Inc.), Orfin B, Y, P, A. , STG, SPC, E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, S
Examples thereof include K-14, AE-3 (all product names, manufactured by Nisshin Kagaku Kogyo Co., Ltd.), acetylenol E00, E00P, E40, E100 (all product names, manufactured by Kawaken Fine Chemical Co., Ltd.) and the like.

As the fluorine-based surfactant, a commercially available one may be used, and examples thereof include Megafuck F-479 (manufactured by DIC Corporation) and BYK-340 (manufactured by Big Chemie Japan Co., Ltd.).

As the polyorganosiloxane-based surfactant, commercially available ones can be used. For example, Orfin PD-501, Orfin PD-502, Orfin PD-570 (all manufactured by Nisshin Chemical Industry Co., Ltd.), BYK-347, BYK-348, BYK-302 (all manufactured by Big Chemie Co., Ltd.) and the like can be mentioned.

Further, examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, alkyl glucoside, polyoxyalkylene glycol alkyl ether, polyoxyalkylene glycol, polyoxyalkylene glycol alkyl phenyl ether, and sucrose fatty acid. Estel, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene acetylene glycol, polyoxyalkylene glycol alkylamine, polyoxyethylene alkylamine, polyoxyethylene alkylamine oxide, fatty acid alkanolamide, alcohol Roll amide, polyoxyethylene polyoxypropylene block polymer and the like may be used.

Examples of anionic surfactants include higher fatty acid salts, soaps, α-sulfo fatty acid methyl ester salts, linear alkylbenzene sulfonates, alkyl sulfate ester salts, alkyl ether sulfate ester salts, monoalkyl phosphate ester salts, and α. -Olefin sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, naphthalene sulfonate, alkane sulfonate, polyoxyethylene alkyl ether sulfate, sulfosuccinate, polyoxyalkylene glycol alkyl ether phosphate, etc. Can be mentioned.

Examples of the amphoteric surfactant include an alkylamino fatty acid salt as an amino acid type, an alkylcarboxylate betaine as a betaine type, and an alkylamine oxide as an amine oxide type. Amphoteric surfactants are not limited to these.

A plurality of types of the above-exemplified surfactants may be mixed and used.

In addition, it is more preferable to consider the HLB value when selecting a surfactant. That is, the HLB value of the surfactant to be blended in the printing inkjet ink composition is 8 or more, preferably 10 or more, and more preferably 11 or more. Surfactants having an HLB value in such a range have higher hydrophilicity and are more likely to suppress the penetration of the printing inkjet ink composition into the fabric. Therefore, the color development property may be further improved.

The HLB value in the present specification is the following formula (1) from the ratio of the non-polar value (I) to the polar value (O) in the organic conceptual diagram (hereinafter, also simply referred to as “I / O value”). It is a value calculated by.

HLB value = (non-polar value (I) / polar value (O)) × 10 ... (1)
Specifically, the I / O values are given by Akira Fujita, "Systematic Organic Qualitative Analysis Mixtures", Kazama Shobo, 1974; Nobuhiko Kuroki, "Staining Theoretical Chemistry", Maki Shoten, 1966; Hiroo Inoue. , "Organic compound separation method", Shokabo, 1990, can be calculated based on each document.

When a surfactant is blended in the printing inkjet ink composition, the total amount of the surfactant is 0.01% by mass or more and 3% by mass or less, preferably 0.05% by mass, based on the entire printing inkjet ink composition. It is preferably blended in an amount of 2% by mass or less, more preferably 0.1% by mass or more and 1% by mass or less, and particularly preferably 0.2% by mass or more and 0.5% by mass or less.

1.3.5. Chelating Agent The printing inkjet ink composition of the present embodiment may contain a chelating agent. The chelating agent has the property of capturing ions. Examples of such a chelating agent include ethylenediaminetetraacetate (EDTA), nitrilotriacetate of ethylenediamine, hexametaphosphate, pyrophosphate, metaphosphate and the like.

1.3.6. Preservative The printing inkjet ink composition of the present embodiment may contain a preservative. By containing the preservative, the growth of mold and bacteria can be suppressed, and the storage stability of the ink composition becomes better. This makes it easier to use, for example, the printing inkjet ink composition as a maintenance liquid for long-term maintenance without using a printer. Preferred examples of preservatives include Proxel CRL, Proxel BDN, Proxel GXL, Proxel XL-2, Proxel IB, Proxel TN and the like.

1.3.7. pH Adjuster The printing inkjet ink composition of the present embodiment may contain a pH adjuster. By containing the pH adjuster, for example, the elution of impurities from the member forming the ink flow path can be suppressed or promoted, and the detergency of the printing inkjet ink composition can be adjusted. .. Examples of the pH adjuster include morpholins, piperazines, and amino alcohols such as triethanolamine.

1.3.8. Other Ingredients The textile printing inkjet ink composition according to the present embodiment may contain a resin emulsion (such as a urethane resin having no crosslinkable group) other than that used in the above-mentioned moisturizing agent, and further, a viscosity modifier, Various additives such as a solubilizing agent, an antioxidant, and an antifungal agent can be appropriately contained.

1.4. Method for Preparing Ink Composition The printing inkjet ink composition used in the present embodiment is obtained by mixing the above-mentioned components in an arbitrary order and, if necessary, filtering or the like to remove impurities. As a method of mixing each component, a method of sequentially adding materials to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirring and mixing them is preferably used. As the filtration method, centrifugal filtration, filter filtration and the like can be performed as needed.

1.5. Physical Properties of the Printing Ink Composition The printing inkjet ink composition according to the present embodiment is applied to the fabric by an inkjet method. Therefore, the surface tension of the printing inkjet ink composition at 25 ° C. is preferably 10 mN / m or more and 40 mN / m or less, preferably 25 mN / m, from the viewpoint of the balance between the recording quality and the reliability as the ink for inkjet recording. More preferably, it is m or more and 40 mN / m or less. To measure the surface tension, for example, use an automatic surface tension meter CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.) to check the surface tension when the platinum plate is wetted with ink in an environment of 25 ° C. It can be measured by.

From the same viewpoint, the viscosity of the printing inkjet ink composition at 20 ° C. is preferably 2 mPa · s or more and 15 mPa · s or less, more preferably 2 mPa · s or more and 5 mPa · s or less, and 2 mPa · s. More preferably, it is s or more and 3.6 mPa · s or less. The viscosity can be measured by using, for example, a viscoelasticity tester MCR-300 (trade name, manufactured by Pysica) in an environment of 40 ° C. or 20 ° C.

2. Recording Method The recording method according to the present embodiment is characterized in that the printing inkjet ink composition according to the present embodiment is attached to a cloth and recorded without heating. Hereinafter, the recording method according to the present embodiment will be described in the order of cloth and recording method.

2.1. Cloth The recording method according to this embodiment is performed using a cloth. The material constituting the fabric is not particularly limited, and for example, natural fibers such as cotton, linen, wool and silk, synthetic fibers such as polypropylene, polyester, acetate, triacetate, polyamide and polyurethane, and biodegradability such as polylactic acid. Examples thereof include fibers, and these blended fibers may be used. As the cloth, the fibers listed above may be in any form such as a woven fabric, a knitted fabric, and a non-woven fabric. Of these, the fabric used in the present embodiment is more preferably formed of fibers containing cellulose such as cotton and linen. By using such a cloth, it is possible to obtain better fixability of the pigment.

The basis weight of the fabric used in the present embodiment is 1.0 oz (ounce) or more and 10.0 oz or less, preferably 2.0 oz or more and 9.0 oz or less, more preferably 3.0 oz or more and 8.0 oz or less, still more preferable. Is in the range of 4.0 oz or more and 7.0 oz or less. In the recording method of the present embodiment, good recording (printing) can be performed if the basis weight of the fabric is in such a range. Further, the recording method of the present embodiment can be applied to a plurality of types of fabrics having different basis weights, and good recording can be performed.

2.2. Recording Method Next, the recording method according to this embodiment will be described for each step.

2.2.1. Ink Adhesion Step The ink adhesion step is a step of adhering a printing inkjet ink composition to a cloth from a nozzle of an inkjet head and recording the ink. In this step, an image is recorded on the cloth by adhering droplets of ink to the cloth. Is what you do. As a result, a recorded material (printed product, printed product) in which an image composed of the ink composition is recorded on the cloth can be obtained.

In the present embodiment, since the printing is performed using the above-mentioned printing inkjet ink composition, it is not necessary to heat the ink to reduce the viscosity and ensure the ejection stability when the ink adheres, and the ink is ejected without heating. Is stable and clogging is less likely to occur. In addition, excessive heating during recording is not preferable because the crosslinkable component of the resin contained in the ink may react with heat. Therefore, the recording method according to the present embodiment can provide a recording method capable of obtaining a printed material which is less likely to be clogged, has excellent discharge stability, and has excellent frictional fastness without heating.

The term “heating” as used herein refers to heating at least one of the ink, the inkjet head, and the cloth by a heating mechanism such as a heater when the ink composition is ejected from the inkjet head and the ink is adhered to the recording medium. This means that the surface temperature of the ink, the inkjet head, or the fabric is higher than that of the recording in the unheated state.

As a heating method, for example, it can be heated by a heater attached to a cloth support portion (platen).

The temperature is measured, for example, by measuring the cloth surface temperature (the surface temperature of the cloth at a position facing the head in the cloth transport direction) at the time of ink adhesion (printing) with a non-contact thermometer (for example, trade name "IT2-80"). It can be done by measuring with (manufactured by Keyence Co., Ltd.). When the fabric support portion (platen) is heated by the heater, the temperature of the surrounding atmosphere also rises, and the inkjet head and the ink may also be in a heated state.

The recording method according to the present embodiment can record in a temperature range of 15 ° C. or higher and 40 ° C. or lower, preferably in a temperature range of 15 ° C. or higher and 35 ° C. or lower, and 20 ° C. or higher and 30 ° C. or lower. It is more preferable to record in the temperature range. In the recording method according to the present embodiment, since the printing is performed using the above-mentioned printing inkjet ink composition, clogging is unlikely to occur in a wide temperature range and the ejection stability is excellent, but the temperature range is 15 ° C. or higher and 35 ° C. or lower. Then, clogging is less likely to occur, and the recording method is excellent in discharge stability. In addition, the obtained recorded material has excellent frictional fastness.

The temperature range is the temperature range of the cloth surface temperature at the time of ink adhesion (during printing), and the temperature of the cloth surface is non-contact with the surface temperature of the cloth at a position facing the head in the cloth transport direction. It was measured with a thermometer (for example, trade name "IT2-80", manufactured by Keyence Co., Ltd.).

Further, when the pretreatment step described later is provided, the ink composition for inkjet printing can be attached to the fabric to at least a part of the region to which the pretreatment liquid is applied by the pretreatment step. As a result, the components such as the coloring material contained in the ink composition react with the coagulant contained in the pretreatment liquid, so that the components such as the coloring material coagulate on the fabric and an image having excellent color development property can be obtained. Be done. Furthermore, the frictional fastness of the recorded image is improved by reacting with the color material and the coagulant of the pretreatment liquid.

The inkjet recording method for ejecting the ink composition may be any method, and examples thereof include a charge deflection method, a continuous method, and an onden mand method (piezo method, bubble jet (registered trademark) method). Among these inkjet recording methods, a method using a piezo type inkjet recording device is particularly preferable.

In the ink adhesion step, it is preferable to apply the ink composition to the fabric so that the adhesion amount of the ink composition is 1.5 mg / cm ² or more and 6 mg / cm ² or less, and 2 mg / cm ² or more and 5 mg / cm ² or less. It is more preferable to apply it to the fabric so as to be. When the amount of the ink composition adhered is 1.5 mg / cm ² , the color development of the recorded image becomes good, the dryness of the recorded image becomes good, and the blurring of the image can be suppressed.

2.2.2. Step of Heating the Fabric The recording method according to the present embodiment may include a heating step of heating the ink composition (image) applied to the fabric.

The heating method for heating the ink composition applied to the fabric is not particularly limited, and examples thereof include a heat press method, a normal pressure steam method, a high pressure steam method, a hot air drying method, and a thermofix method. .. Further, the heat source for heating is not limited to the following, and examples thereof include infrared rays (lamps).

The heating temperature when heating the ink composition applied to the fabric is not limited to this, but is preferably 80 ° C. or higher and 200 ° C. or lower, and more preferably 100 ° C. or higher and 180 ° C. or lower. preferable. However, the heating temperature (reached temperature) is at least a temperature equal to or higher than the temperature at which the crosslinkable group of the urethane resin having the above-mentioned crosslinkable group is activated. Such crosslinkable groups are chemically protected (capping or blocking) and are deprotected and activated by application of heat to form bonds (eg urethane bonds, urea bonds, allophanate bonds, etc.). Become. Further, since three or more crosslinkable groups of the urethane resin having a crosslinkable group are provided in one molecule, a crosslinked structure is formed by the reaction of the crosslinkable group.

By this step, the crosslinkable group of the urethane-based resin having a crosslinkable group contained in the printing ink composition is activated, and a crosslinked structure of the urethane-based resin is generated. As a result, a robust film of urethane-based resin is formed, and for example, a coloring material is fixed to the fabric. In addition, when the pretreatment liquid is attached to the fabric, when a cationic organic compound is used as the flocculant contained in the pretreatment liquid, this penetrates into the mesh of the crosslinked urethane resin. In some cases, the phenomenon described above may occur, and the image may be more firmly fixed to the fabric.

When the heating temperature is within the above range, damage to the fabric can be reduced, and film formation of the resin (which may contain other resins) contained in the printing inkjet ink composition can be promoted. The heating temperature in this heating step refers to the temperature of the image surface formed on the fabric, and is measured using, for example, a non-contact thermometer (trade name "IT2-80", manufactured by Keyence Co., Ltd.). Can be done. The heating time is not limited to this, but can be, for example, 30 seconds or more and 20 minutes or less.

2.2.3. Step of Adhering Pretreatment Liquid to Fabric The recording method according to the present embodiment may include a step of adhering the pretreatment liquid to the fabric before the ink adhesion step. The step of adhering the pretreatment liquid to the cloth is a step of applying the pretreatment liquid to at least a part of the area of the cloth.

Here, the pretreatment liquid is not particularly limited as long as it contains a coagulant that aggregates the components of the printing inkjet ink composition, and is, for example, a polyvalent metal salt, an organic acid, or a cationic compound (cationic resin, Cationic surfactants, etc.). These coagulants may be used alone or in combination of two or more. Among these coagulants, at least one coagulant selected from the group consisting of polyvalent metal salts and organic acids is used because it has excellent reactivity with resin fine particles contained in the printing inkjet ink composition. Is preferable. Further, the pretreatment liquid may also contain a urethane resin having a crosslinkable group contained in the ink composition. In that case, the urethane resin contained in the pretreatment liquid and the printing inkjet ink composition may be contained. It may be the same as or different from the urethane resin contained in the product.

Examples of the method of applying the pretreatment liquid to the cloth include a method of immersing the cloth in the pretreatment liquid (immersion coating) and a method of applying the pretreatment liquid with a spatula, a roller, a brush, a roll coater or the like (roller coating). ), A method of spraying the pretreatment liquid by a spray device or the like (spray coating), a method of spraying the pretreatment liquid by an inkjet method (injection coating), and the like, and any of these methods may be used. Among these, it is preferable to use contact-type or non-contact-type methods such as immersion coating, roller coating, and spray coating because the apparatus configuration is simple and the pretreatment liquid can be quickly applied. The methods may be combined. Further, according to the inkjet coating, the pretreatment liquid can be easily and accurately applied to a predetermined position, and the amount of the pretreatment liquid used can be reduced, which is more preferable.

The printing method according to the present embodiment may include a drying step of the pretreatment liquid for drying the pretreatment liquid applied to the fabric after the step of adhering the pretreatment liquid. The pretreatment liquid may be dried naturally, but it is preferably dried with heating from the viewpoint of improving the drying speed. When heating is involved in the drying step of the pretreatment liquid, the heating method is not particularly limited, and examples thereof include a heat press method, a normal pressure steam method, a high pressure steam method, and a thermofix method. Further, the heat source for heating is not limited to the following, and examples thereof include infrared rays (lamps).

2.3. Action Effect According to the recording method of the present embodiment, since recording is performed using the above-mentioned printing inkjet ink composition in which the dryness and viscosity of the ink are appropriately adjusted, it is necessary to heat the ink in order to reduce the viscosity. Therefore, the discharge is stable even without heating, and clogging is less likely to occur. Therefore, in the recording method according to the present embodiment, it is possible to obtain a recording method capable of obtaining a printed material which is less likely to cause clogging, has excellent discharge stability, and has excellent frictional fastness. Further, when the moisturizer of the above-mentioned printing inkjet ink composition is contained in a specific content ratio, clogging is less likely to occur in a wide temperature range and the ejection stability is excellent, particularly at 15 ° C. or higher and 35 ° C. or higher. In the temperature range of ° C. or lower, clogging is less likely to occur, and the recording method is excellent in discharge stability.

3. 3. Examples and Comparative Examples Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

3.1. Preparation of printing inkjet ink composition Each component is placed in a container so as to have the composition shown in Table 1, mixed and stirred with a magnetic stirrer for 2 hours, and then further subjected to a bead mill filled with zirconia beads having a diameter of 0.3 mm. It was thoroughly mixed by performing a dispersion treatment. After stirring for 1 hour, each printing inkjet ink composition was obtained by filtering using a 5 μm PTFE membrane filter. The numerical values in Table 1 indicate mass%, and pure water (ion-exchanged water) was added so that the mass of each printing inkjet ink composition was 100% by mass.

In Table 1, as the pigment dispersion, C.I. I. Pigment Blue 15: 3, 65 parts by John Krill 611 (trade name: manufactured by BASF Japan Co., Ltd.), which is a styrene-acrylic acid-based dispersion resin, 1.70 parts of potassium hydroxide, by ion exchange method and reverse osmosis method. 250 parts of purified ultrapure water is mixed, dispersed for 10 hours with a ball mill using zirconia beads, and filtered with glass fiber filter paper GA-100 (trade name: manufactured by Advantech Toyo Co., Ltd.) to remove coarse particles and pigment concentration. Was adjusted to be 15% by mass, and the amount was adjusted so that the concentration of the pigment in the printing inkjet ink composition was 4.5% by mass.

Further, in Table 1, Takelac is a resin dispersion of urethane resin, and the details thereof are as follows. The numerical value in Table 1 is the solid content of the urethane resin.
-Takelac WS-6021 (trade name, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., a polyether urethane resin containing blocked isocyanate as a crosslinkable group)
-Takelac WS-5100 (trade name, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., polycarbonate-based urethane resin containing blocked isocyanate as a crosslinkable group)
-Takelac WS-6110 (trade name, manufactured by Mitsui Chemicals Polyurethane Co., Ltd., urethane resin that does not contain blocked isocyanate as a crosslinkable group)

In Table 1, GL / T represents the content ratio (mass ratio) of glycerin to polyhydric alcohol or betaine (trimethylolpropane, trehalose or trimethylglycine) which is a solid at room temperature, and urethane resin / T refers to urethane resin / T. It represents the content ratio (mass ratio) of a urethane resin (Takelac WS-6021, 5100, 6110) to a polyhydric alcohol or betaine (trimethylolpropane, trehalose or trimethylglycine) which is a solid at room temperature.

Further, in Table 1, EDTA is ethylenediaminetetraacetic acid salt, the inorganic alkali is potassium hydroxide, and the surfactant is BYK-348 (manufactured by Big Chemie Japan).

3.2. Evaluation test 3.2.1. A modified machine of SC-F2000 (manufactured by Seiko Epson Corporation) was prepared as a printer for making stamps. A heater was attached to the fabric support (platen) so that the surface temperature of the fabric when ink was attached (during printing) could be controlled to the value in parentheses for ejection reliability in Table 1. That is, the temperature of the cloth surface is measured by a non-contact thermometer (trade name "IT2-80", manufactured by Keyence Co., Ltd.) at a position facing the head in the cloth transport direction. The platen heater was adjusted so that the surface temperature became the target temperature (discharge reliability temperature in Table 1). It should be noted that the heating by the heater is not performed at 25 ° C. (normal temperature) or lower. In the case of 20 ° C. and 15 ° C., the temperature was adjusted by appropriately lowering the room temperature.

Using the above printer, printing was performed on a fabric (heavy weight manufactured by Haines, 100% cotton, white fabric) under the conditions shown in Table 1 at a resolution of 1440 dpi × 1440 dpi and a coating amount of 200 mg / inch ² . After the printing, heat treatment was performed at 165 ° C. for 5 minutes in a conveyor oven (hot air drying method) to fix the stamped material.

3.2.2. Friction fastness test A dyeing fastness test against friction was carried out on the stamped material of each example using a type I (clock meter) tester according to the method specified in ISO-105 X12. Dry friction was tested according to the drying test specified in ISO-105 X12 and evaluated using contaminated grayscale. The evaluation criteria are as follows, and the results are shown in Table 1.
⊚: Friction fastness is 4th grade or higher.
◯: Friction fastness is grade 3 or higher and lower than grade 4.
Δ: Friction fastness is grade 2 or higher and lower than grade 3.
X: Friction fastness is less than grade 2.

3.2.3. Clogging property test For each printing inkjet ink composition shown in Table 1, the above printing was continuously performed for 1 hour under the condition of a cloth surface temperature of 25 ° C. (normal temperature), and after completion, 1 nozzle row (360 pieces). The nozzle) was inspected for abnormal discharge (non-discharge). Before the start of recording, all nozzles were started in a normal state and evaluated based on the following criteria.
⊚: The number of abnormal discharge nozzles is 0.
◯: The number of abnormal discharge nozzles is 1 to 2.
Δ: The number of abnormal discharge nozzles is 3 to 5.
X: The number of abnormal discharge nozzles is 5 or more.

32.4. Discharge reliability (discharge stability) test The imprinted surface of the imprint obtained under the temperature conditions shown in Table 1 was visually observed and evaluated based on the following criteria.
⊚: No missing dots or misalignment of landing position is observed. Excellent discharge reliability.
◯: The landing position is deviated, but it recovers naturally. Good discharge reliability.
Δ: Misalignment of the landing position is observed. There is no problem in practical use.
X: Dot missing occurs. Not practical.

3.2.5. Washing fastness test A washing fastness test was carried out on the stamped material of each example in accordance with the A-2 method of JIS L 0844 (dyeing fastness test method for washing). Specifically, after washing, rinsing, dehydrating, and drying, the discoloration and fading of the printed portion in the test piece was determined. The discoloration and fading was evaluated according to the discoloration and fading gray scale of JIS L0804: 2004 (ISO 105-A02: 1993) based on the following criteria.
⊚: Friction fastness is 4th grade or higher.
◯: Friction fastness is grade 3 or higher and lower than grade 4.
Δ: Friction fastness is grade 2 or higher and lower than grade 3.
X: Friction fastness is less than grade 2.

3.3. Evaluation Results In the examples in which the resin dispersion contains a urethane resin containing a crosslinkable group and contains glycerin and a room temperature solid polyhydric alcohol or betaine as a moisturizing agent, all of them have friction fastness, washing fastness and normal temperature. The result was excellent in discharge reliability. In particular, in the case where the GL / T is in the range of 2 to 5 and the urethane resin / T is in the range of 1 to 2, clogging is unlikely to occur, and the discharge reliability in a wide range of 15 to 35 ° C. is excellent. The result was.

On the other hand, in Comparative Example 1 using a resin having no crosslinkability, the friction fastness and the washing fastness were insufficient. Further, in Comparative Example 2 in which glycerin was not contained as a moisturizer, clogging occurred and the discharge reliability at room temperature was inferior. In particular, since trimethylolpropane is solid at room temperature, the discharge reliability at 15 ° C. is inferior. Further, in Comparative Example 3 in which the moisturizer does not contain a solid polyhydric alcohol or betaine at room temperature, the nozzles are easily dried and the ink is thickened, so that both friction fastness and washing fastness are ejection reliability at room temperature. Was also inadequate. In particular, by containing only glycerin in a high concentration, the results were inferior in discharge reliability, friction fastness, and washing fastness at high temperatures.

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

Claims (12)

Contains a resin dispersion and a moisturizer,
The resin dispersion contains a urethane resin containing a crosslinkable group,
A printing inkjet ink composition in which the moisturizer contains an organic solvent having a standard boiling point of 280 ° C. or higher and at least one of a room temperature solid polyhydric alcohol or betaine. The printing inkjet ink composition according to claim 1, wherein the content ratio of the room temperature solid polyhydric alcohol or betaine to the organic solvent having a standard boiling point of 280 ° C. or higher is 1: 2 to 1: 5. The printing inkjet ink composition according to claim 1 or 2, wherein the content ratio of the room temperature solid polyhydric alcohol or betaine to the urethane resin containing the crosslinkable group is 1: 1 to 1: 2. Stuff. The printing inkjet ink composition according to any one of claims 1 to 3, further containing a pigment. The printing inkjet ink composition according to any one of claims 1 to 4, wherein the room temperature solid multivalent alcohol contains trimethylolpropane. Any of claims 1 to 5, wherein the solid content concentration of the urethane resin containing the crosslinkable group is 3.0% by mass or more and 6.0% by mass or less with respect to the total mass of the ink composition. The printing inkjet ink composition according to item 1. Any one of claims 1 to 6, wherein the concentration of the organic solvent having a standard boiling point of 280 ° C. or higher is 6.0% by mass or more and 20.0% by mass or less with respect to the total mass of the ink composition. The printing inkjet ink composition according to the section. Any one of claims 1 to 7, wherein the concentration of the polyhydric alcohol or betaine of the room temperature solid is 2.5% by mass or more and 9.0% by mass or less with respect to the total mass of the ink composition. The printing inkjet ink composition according to the above. The printing inkjet ink composition according to any one of claims 1 to 8, wherein the urethane resin containing a crosslinkable group is a polycarbonate-based urethane resin or a polyether-based urethane resin. A recording method in which the printing inkjet ink composition according to any one of claims 1 to 9 is attached to a cloth and recorded. The recording method according to claim 10, wherein recording is performed without heating. The recording method according to claim 10 or 11, wherein recording is performed in a temperature range of 15 ° C. or higher and 35 ° C. or lower.