JP6794746B2 - 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 is characterized in that high-resolution and high-quality images 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, fabrics and the like are also dyed (printed) using an inkjet recording method. Conventionally, screen printing, roller printing, etc. have been used as printing 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

In the above prior art document, an attempt is made to improve the fastness of an image by incorporating a crosslinkable resin into an ink composition. However, the improvement of toughness is not sufficient only by using a polyurethane resin having a specific glass transition temperature. Therefore, the applicant has found that a crosslinkable resin is used in order to further improve the fastness. However, when the crosslinkable resin is used, the frictional fastness of the image is improved, but the crosslinkable resin is an ink. When the dispersion in the inside was insufficient, it was sometimes difficult to disperse again. According to the inventors, it has been found that it is effective to add an alkaline (basic) compound in order to enhance the redispersibility of the resin. On the other hand, when the alkalinity is strong, the redispersibility of the crosslinkable resin is improved, but there is a concern about adverse effects such as corrosion of the members of the recording device.

One of the objects according to some aspects of the present invention is to provide a printing ink composition capable of forming an image having good fastness and also having excellent redispersibility and a recording method using the same. ..

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.

One aspect of the printing inkjet ink composition according to the present invention is
A urethane-based resin dispersion having a crosslinkable group and
Inorganic alkaline compounds and
With organic alkaline compounds
Contains.

According to such a printing ink composition, an image having good fastness can be formed by the urethane-based resin dispersion having a crosslinkable group. Further, since the printing inkjet ink composition contains an organic alkaline compound and an inorganic alkaline compound, it can be easily re-dispersed even if the dispersion of the urethane-based resin dispersion having a crosslinkable group becomes poor due to storage or drying. It can be dispersed and has excellent redispersibility.

In the printing inkjet ink composition according to the present invention
Pigments may be further included.

According to such a printing inkjet ink composition, it is possible to easily obtain a printed product on which an image having good fastness is formed.

In the printing inkjet ink composition according to the present invention
A resin dispersant for pigment dispersion may be further contained.

According to such a printing inkjet ink composition, the dispersibility of the pigment is better.

In the printing inkjet ink composition according to the present invention
An acetylene glycol-based surfactant may be further contained.

The inclusion of the organic alkaline compound may increase the permeability of the printing inkjet ink composition to the recording medium too much. According to such a printing inkjet ink composition, it is possible to prevent the acetylene glycol-based surfactant from excessively increasing the permeability of the printing inkjet ink composition to the recording medium. As a result, strike-through of the printed matter can be suppressed and color development can be enhanced.

In the printing inkjet ink composition according to the present invention
The HLB value of the acetylene glycol-based surfactant may be 10 or more.

According to such a printing inkjet ink composition, the effect of suppressing the penetration of the printing inkjet ink composition into the recording medium is even better.

In the printing inkjet ink composition according to the present invention
The pH of the printing inkjet ink composition may be 11.5 or less.

According to such a printing inkjet ink composition, the corrosiveness of members such as recording devices can be further suppressed.

In the printing inkjet ink composition according to the present invention
The urethane-based resin dispersion may have a polycarbonate-based skeleton or a polyether-based skeleton.

According to such a printing inkjet ink composition, it is possible to obtain a printed material having further good friction fastness and texture.

In the printing inkjet ink composition according to the present invention
The urethane-based resin is a printing inkjet ink composition having a breaking point elongation of 170% or more.

According to such a printing inkjet ink composition, a printed product having a better texture can be obtained.

One aspect of the recording method according to the present invention is to attach the above-mentioned printing inkjet ink composition to a cloth for recording.

According to such a recording method, an image having good fastness can be formed by the action of the urethane-based resin dispersion having a crosslinkable group contained in the printing inkjet ink composition used. Further, since the printing inkjet ink composition contains an organic alkaline compound and an inorganic alkaline compound, even if the dispersion of the urethane-based resin dispersion having a crosslinkable group becomes poor due to storage or drying, even if the dispersion becomes poor. It can be easily redispersed and has excellent redispersibility of the printing inkjet ink composition.

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 (hereinafter, also referred to as a printing ink composition, an ink composition, etc.) is prepared by adhering the pretreatment liquid of the present embodiment, which will be described later, to the fabric, and then the printing. The ink composition is used by adhering it to a cloth by an inkjet method. First, the printing ink composition will be described. The printing ink composition of the present embodiment contains a urethane-based resin dispersion having a crosslinkable group, an organic alkaline compound, and an inorganic alkaline compound.

1.1. Urethane-based resin dispersion having a crosslinkable group The printing ink composition of the present embodiment contains a urethane-based resin dispersion having a crosslinkable group (hereinafter, also referred to as a urethane-based resin having a crosslinkable group or a resin dispersion). To do. 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. Crosslinkable groups (isocyanate groups) are chemically protected (capping or blocking) and are deprotected and activated by heat application to form bonds (eg urethane bonds, urea bonds, allophanate bonds, etc.). Will be done.

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.). , A resin that may contain an allophanate bond or the like (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). Measures, 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, 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), a carbodiimide modified product (such as a carbodiimide modified product produced by the decarbonate condensation reaction of the polyisocyanate monomer described above), a uretdione modified product, and a uretonimine modified product.

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-based compounds, acid-amide-based (lactam-based) compounds, acid-imide-based compounds, triazole-based compounds, pyrazole-based compounds, mercaptan-based compounds, heavy sulfites, 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 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.). 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), flufuryl 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 malate (for example, dimethyl malate, 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, and guanidine.

Examples of oxime compounds include formaldehyde, acetaldoxime, acetoxime, 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, and 2-heptanone oxime.

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

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 and benzotriazole.

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 ink composition can be sufficiently extended, 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. The break point elongation and 100% modulus when a urethane resin having a crosslinkable group is crosslinked (crosslinked body) 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 break 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.

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.

Further, the urethane resin having a crosslinkable group preferably has a 100% modulus of 1 MPa or more, more preferably 3 MPa or more, and 10 MPa or more after the crosslink is formed (crosslinked body). Is even more preferable. By selecting the density of the cross-linking points and the type of the main chain so as to have such a modulus, the dry friction fastness and the wet friction fastness can be improved.

Here, the breaking point elongation 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.

As a commercially available urethane-based resin having a crosslinkable group,
Takelac WS-6021 (trade name manufactured by Mitsui Chemicals Polyurethane Co., Ltd., urethane-based resin emulsion, polyether-based polyurethane having a skeleton derived from polyether),
WS-5100 (trade name manufactured by Mitsui Chemicals Polyurethane Co., Ltd., urethane-based resin emulsion, polycarbonate-based polyurethane having a polycarbonate-derived skeleton),
Erastron E-37, H-3 (The above are polyester polyurethanes whose main chain has a polyester-derived skeleton (trade name manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., urethane resin emulsion),
Elastron H-38, BAP, C-52, F-29, W-11P (the above are polyether polyurethanes whose main chain has a skeleton derived from polyether) (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 Dai-ichi Kogyo Seiyaku Co., Ltd., urethane resin emulsion),
Permarin UA-150 (manufactured by Sanyo Chemical Industries, Ltd., urethane resin emulsion),
Suncure 2710 (manufactured by Japan Lubrizol, urethane-based resin emulsion),
NeoRez R-9660, R-9637, R-940 (Urethane resin emulsion manufactured by Kusumoto Kasei Co., Ltd.),
Examples thereof include ADEKA Bontiter HUX-380, 290K (manufactured by ADEKA Corporation, urethane-based resin emulsion).

These urethane-based resins may be contained in the pretreatment liquid, and in that case, the urethane-based resin contained in the pretreatment liquid and the urethane-based resin contained in the printing ink composition may be the same. It may be different.

Further, the temperature of the heating step in the inkjet printing method of the present embodiment described later is at least one of the crosslinkable groups in consideration of the deprotection temperature (dissociation temperature) of the isocyanate group of the urethane resin having these crosslinkable groups. The part is set to be activated.

The content of the urethane-based resin having a crosslinkable group is preferably 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, and 4% by mass, based on the total amount of the printing inkjet ink composition. More than 10% by mass is more preferable, and 7% by mass or less is particularly preferable. When the content of the urethane resin having a crosslinkable group is at least the lower limit value, the friction fastness can be improved, and when it is at least the upper limit value, the texture and redispersibility can be improved. It is preferable because it can be used.

1.2. Inorganic Alkaline Compound The printing ink composition of the present embodiment contains an inorganic alkaline compound (inorganic base compound). The inorganic alkaline compound has a property of increasing the pH of the printing 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.

According to the studies by the inventors, it is known that the inorganic alkaline compound has the above-mentioned actions and functions, but the mechanism thereof is not always clear at this time. For example, it is unclear whether the factor for improving the redispersibility is due to an increase in pH or other factors are involved. However, it is considered that such an action / function of the inorganic alkaline compound is caused by an interaction with a functional group or a protecting group of a urethane resin having at least a crosslinkable group. In addition, many pigment dispersions and resin emulsions are neutralized with an alkaline compound to improve dispersion stability in water. Therefore, by adding a material having an alkaline compound, the effect of further enhancing the dispersion stability in water can be expected.

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 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, more preferably, based on the total amount of the printing ink composition. Is 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 0. It is 0.05% by mass or more and 0.1% by mass or less.

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

1.3. Organic Alkaline Compound The printing ink composition of the present embodiment contains an organic alkaline compound. The organic alkaline compound has a property of increasing the pH of the printing ink composition. Further, the organic alkaline compound acts so as not to raise the pH of the printing ink composition too much by being combined with the above-mentioned inorganic alkaline compound. If the inorganic alkaline compound alone has a function of improving the redispersibility of the urethane-based resin having a crosslinkable group, the pH may become too high. However, by combining the organic alkaline compound and the inorganic alkaline compound, it is possible to suppress an excessive increase in pH, and it is possible to suppress corrosion of members such as containers and devices due to the printing ink composition.

Further, the organic alkaline compound has 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, similarly to the inorganic alkali compound. Have at least.

According to the studies by the inventors, it has been found that the ability of the organic alkaline compound alone to enhance the redispersibility is insufficient, and that good redispersibility can be obtained by combining with the above-mentioned inorganic alkali compound. It has been found that such a combination has the above-mentioned actions and functions, but the mechanism has not always been clarified at this time. In addition, it is not clear at this time whether the above-mentioned actions / functions are caused only by an increase in pH or whether other factors are involved. However, it is considered that such an action / function is caused by an interaction between a functional group or a protective group of a urethane resin having at least a crosslinkable group, an organic alkaline compound and an inorganic alkaline compound.

Examples of the organic alkaline compound include ammonia, aliphatic amines, aromatic amines, aliphatic ammonium, aromatic ammonium, heterocyclic compounds and their hydroxides, carbonates and phosphates. Examples of the organic alkaline compound include ammonia, hydrazine, methylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, diaminoethane, diaminopropane, diaminobutane, diaminopentane, diaminohexane, cyclohexylamine, and aniline. Tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, pyridine, N, N-dimethyl-4-aminopyridine, ammonium carbonate, ammonium hydrogencarbonate, phosphorus Examples thereof include diammonium hydrogenate, piperidine, diethanolamine, triethanolamine, propanolamine, morpholin and the like, and modified products thereof.

In the printing ink composition of the present embodiment, a plurality of types of the above-exemplified organic alkaline compounds may be used. The total content of the organic alkaline compounds is 0.05% by mass or more and 2% by mass or less, preferably 0.1% by mass or more and 1.5% by mass or less, more preferably 0, based on the total amount of the printing ink composition. .3% by mass or more and 1.3% by mass or less, more preferably 0.4% by mass or more and 1.2% by mass or less, particularly preferably 0.4% by mass or more and 1.1% by mass or less, and particularly preferably 0.5. It is mass% or more and 1 mass% or less.

As long as the blending amount of the organic alkaline compound is within the relevant range, the function of enhancing the dispersion stability of the urethane-based resin having a crosslinkable group in combination with the inorganic alkaline compound without raising the pH of the printing ink composition too much. And / or, the function of improving the redispersibility of the urethane-based resin having a crosslinkable group can be exhibited. The pH of the printing ink composition will be described in the section on physical properties.

The mixing amount ratio of the inorganic alkaline compound and the organic alkaline compound is preferably 1:20 to 1: 1 in mass ratio, more preferably 1: 15 to 1: 3, and 1: 10 to 1. : 5 is more preferable. When the blending amount ratio of the inorganic alkali compound and the organic alkali compound is within the above range, the redispersibility of the ink composition containing the crosslinkable group-containing urethane resin dispersion becomes better.

1.4. Other components 1.4.1. Pigments The printing ink composition of the present embodiment may contain pigments, dyes and the like as coloring materials. In the printing ink composition of the present embodiment, the coloring material can be physically fixed to the recording medium by the urethane-based resin having the above-mentioned crosslinkable group, and therefore a pigment is more preferable as the coloring material to be used. When the pigment is attached to the fabric, the fabric (recording medium) is printed and a printed material (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 sulfide and zirconium 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 navy 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, Monarch 1100, Monarch 1 (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, 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. Pigment Green 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 (solid content) in the printing ink composition varies depending on the pigment type used, but from the viewpoint of obtaining good color development, when the total mass of the printing ink composition is 100% by mass. , It is preferably 1 to 30% by mass, and more preferably 2 to 15% by mass.

When preparing the printing ink composition, a pigment dispersion liquid in which the pigment is dispersed may be prepared in advance, and the pigment dispersion liquid may be added to the printing 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 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.

1.4.2. Water The printing ink composition according to 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 irradiation with ultraviolet rays or addition of hydrogen peroxide or the like is used, it is possible to prevent the outbreak of bacteria and fungi when the printing ink composition is stored for a long period of time.

The water content is 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, and further preferably 50% by mass or more, based on the total amount of the printing ink composition. The term "water" in the printing ink composition includes, for example, a resin particle dispersion used as a raw material and water to be added. When the water content is 30% by mass or more, the printing 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 ink composition.

14.3. Surfactant The textile printing ink composition according to this 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 ink composition and increase the permeability to the fabric. However, as for the cationic surfactant, it is more preferable to use a trace amount or another kind of surfactant because the components of the printing ink composition may be aggregated.

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, SK-14, AE-3 (all product names above, manufactured by Nisshin Kagaku Kogyo Co., Ltd.), acetylenol E00, E00P, E40, E100 (all product names above, all product names, 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.), KF-6011 (manufactured by Shinetsu Silicone 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. Esters, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyoxyalkylene acetylene glycols, polyoxyalkylene glycol alkylamines, polyoxyethylene alkylamines, polyoxyethylene alkylamine oxides, fatty acid alkanolamides, archi 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 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 permeability of the printing 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 written 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 ink composition, the total amount of the surfactants is 0.01% by mass or more and 3% by mass or less, preferably 0.05% by mass or more 2 with respect to the entire printing ink composition. It is preferably blended in an amount of mass% or less, more preferably 0.1% by mass or more and 1.5% by mass or less, and particularly preferably 0.2% by mass or more and 1% by mass or less.

Since the printing ink composition contains a surfactant, the stability when ejecting ink from the head tends to increase. In addition, the use of an appropriate amount of surfactant may improve the permeability to the fabric and increase the contact with the pretreatment liquid. As a result, for example, thickening of the printing ink composition is likely to occur, and the color development property of the printing material can be further improved.

In the present embodiment, the content ratio of the surfactant to the above-mentioned organic alkaline compound is preferably 1: 6 to 1: 1 and more preferably 1: 5 to 1: 2 in terms of mass ratio. It is preferably 1: 4 to 1: 3, and more preferably 1: 4 to 1: 3.

In the present embodiment, the content ratio of the surfactant to the above-mentioned inorganic alkaline compound is preferably 20: 1 to 1: 1 and more preferably 19: 1 to 2: 1 in terms of mass ratio. It is preferably 18: 1-3: 1, and more preferably.

Since the content ratios of the surfactant and the organic alkaline compound and the inorganic alkaline compound are in the above range, the redispersibility can be improved and the color can be excellent.

1.4.4. Water-soluble organic solvent The printing ink composition of the present embodiment may contain a water-soluble organic solvent. By containing the water-soluble organic solvent, it is possible to effectively suppress the evaporation of water from the recording head after being left for a long period of time, while improving the ejection stability of the printing ink composition by the inkjet method.

Examples of the water-soluble organic solvent include polyol compounds, glycol ethers, betaine compounds and the like.

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, glycerin, 1,2-hexanediol, 1 , 2-Heptanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-3-phenoxy-1 , 2-Propanediol, 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-pentanediol, 3-methyl-1,5-pentanediol, 1,2,6-hexanetriol, 2-butene-1,4-diol, 2-ethyl-1,3 Examples thereof include polyhydric alcohols such as −hexanediol, 2-methyl-2,4-pentanediol and 4-methyl-1,2-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, methyl triglycol (triethylene glycol monomethyl ether), butyl triglycol (triethylene glycol monobutyl ether), butyl diglycol (diethylene glycol monobutyl ether), dipropylene glycol monopropyl ether and the like can be mentioned.

A betaine compound is a compound that has positive and negative charges at non-adjacent positions in the same molecule, does not have a dissociable hydrogen atom bonded to an atom with a positive charge, and has no charge as a whole molecule. (Intramolecular salt). A preferred betaine compound is an N-alkyl substituent of an amino acid, more preferably an N-trialkyl substituent of an amino acid. Examples of the betaine compound 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 betaine glutamate. Examples thereof are preferably made of trimethylglycine and the like.

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.

A plurality of types of water-soluble organic solvents may be mixed and used. In addition, the total amount of the water-soluble organic solvent is 0.2% by mass or more and 30% by mass or more in total with respect to the total amount of the printing ink composition from the viewpoint of adjusting the viscosity of the printing ink composition and preventing clogging due to the moisturizing effect. It is mass% or less, preferably 0.4 mass% or more and 20 mass% or less, more preferably 0.5 mass% or more and 15 mass% or less, and further preferably 0.7 mass% or more and 10 mass% or less.

1.4.5. Others (preservatives)
The printing 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 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.

(Chelating agent)
The printing 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, and metaphosphate.

(PH regulator)
The printing ink composition of the present embodiment may contain a pH adjuster. By containing a pH adjuster, fluctuations in the pH of the printing ink composition can be suppressed. As the pH adjuster, a known buffer can be used.

(Resin emulsion)
The printing ink composition according to the present embodiment may contain a resin emulsion (a urethane-based resin having no crosslinkable group or the like).

Examples of the resin emulsion include, but are not limited to, at least one resin emulsion selected from urethane-based, styrene-acrylic-based, acrylic-based, and vinyl chloride-vinyl acetate-based.

The urethane resin emulsion is not particularly limited as long as it has a urethane bond in the molecule, but in addition to the urethane bond, a polyester type urethane resin emulsion containing an ether bond in the main chain and an ester bond in the main chain are used. A polyester type urethane resin emulsion containing a polyester type urethane resin emulsion, a polycarbonate type urethane resin emulsion containing a carbonate bond in the main chain, and the like can also be used. In addition to the urethane-based resin emulsion having a crosslinkable group described above, a resin emulsion as shown below can be selected.

As a commercial product of resin emulsion,
Microgel E-1002, E-5002 (trade name manufactured by Nippon Paint Co., Ltd., styrene-acrylic resin emulsion),
Boncoat 4001 (DIC trade name, acrylic resin emulsion), Boncoat 5454 (DIC trade name, styrene-acrylic resin emulsion),
Polysol AM-710, AM-920, AM-2300, AP-4735, AT-860, PSASE-4210E (acrylic resin emulsion),
Polysol AP-7020 (styrene / acrylic resin emulsion),
Polysol SH-502 (vinyl acetate resin emulsion),
Polysol AD-13, AD-2, AD-10, AD-96, AD-17, AD-70 (ethylene-vinyl acetate resin emulsion),
Polysol PSASE-6010 (ethylene / vinyl acetate resin emulsion) (trade name manufactured by Showa Denko KK),
Polysol SAE1014 (trade name, styrene-acrylic resin emulsion, manufactured by Zeon Corporation),
Cybinol SK-200 (trade name, acrylic resin emulsion, manufactured by Saiden Chemical Co., Ltd.),
AE-120A (trade name manufactured by JSR, acrylic resin emulsion),
AE373D (trade name manufactured by E-Tech, carboxy-modified styrene / acrylic resin emulsion),
Seikadyne 1900W (trade name manufactured by Dainichiseika Kogyo Co., Ltd., ethylene-vinyl acetate resin emulsion),
Viniblanc 2682 (acrylic resin emulsion),
Vinibran 2886 (vinyl acetate / acrylic resin emulsion),
Vinibran 5202 (acrylic acetate resin emulsion) (trade name manufactured by Nissin Chemical Industry Co., Ltd.),
Elitel KA-5071S, KT-8803, KT-9204, KT-8701, KT-8904, KT-0507 (trade name manufactured by Unitika, polyester resin emulsion), Hi-Tech SN-2002 (trade name, polyester resin manufactured by Toho Chemical Industry Co., Ltd.) Emulsion),
Takelac W-6020, W-635, W-6061, W-605, W-635, W-6110 (trade name manufactured by Mitsui Chemicals Polyurethane Co., Ltd., urethane resin emulsion),
Superflex 870, 800, 150, 420, 460, 470, 610, 700 (trade name manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., urethane resin emulsion),
Movinyl 966A, Movinyl 7320 (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.),
John Krill 7100, 390, 711, 511, 7001, 632, 741, 450, 840, 74J, HRC-1645J, 734, 852, 7600, 775, 537J, 1535, PDX-7630A, 352J, 352D, PDX-7145, 538J, 7640, 7641, 631, 790, 780, 7610 (above, manufactured by BASF),
NK binder R-5HN (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), etc. can be mentioned.

When the printing ink composition contains a resin emulsion, the content of the resin emulsion in the printing ink composition in terms of solid content is preferably 100% by mass when the total mass of the printing ink composition is 100% by mass. It is 1 to 20% by mass, more preferably 1.5 to 15% by mass, still more preferably 2 to 10% by mass. When the content of the resin emulsion in terms of solid content is within the above range, the washing durability of the image becomes even better. The amount in terms of solid content means the amount of the resin emulsion excluding substances other than the resin (solid content).

In the case where the printing ink composition contains a resin emulsion and the resin emulsion is mixed in the pretreatment liquid, both resin emulsions may be of the same type or different types.

(Other ingredients)
The textile printing ink composition according to the present embodiment can further appropriately contain various additives such as a moisturizer, a viscosity modifier, a solubilizing agent, an antioxidant, and a fungicide.

1.5. Physical properties of the printing ink composition The printing ink composition according to the present embodiment is applied to the fabric by an inkjet method. Therefore, the printing ink composition preferably has a surface tension of 10 mN / m or more and 40 mN / m or less at 25 ° C. from the viewpoint of a balance between recording quality and reliability as an ink for inkjet recording, and is 25 mN / m. It is more preferably 40 mN / m or less.

From the same viewpoint, the viscosity of the printing 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 3.6 mPa · s or less.

The pH of the printing ink composition of the present embodiment is 12.5 or less, preferably 12 or less, more preferably 11.5 or less, still more preferably 11 or less, from the viewpoint of suppressing corrosion of members such as containers and recording devices. , Especially preferably 10.5 or less. Further, as a range in which redispersibility can be obtained, the lower limit of pH is 8 or more, preferably 9 or more. The pH of the printing ink composition can be adjusted by changing the blending amounts of the above-mentioned inorganic alkaline compound and organic alkaline compound, and the blending amount of other substances.

1.6. Action Effect According to the printing ink composition according to the present embodiment, the friction fastness of the formed image is good by containing the urethane-based resin having a crosslinkable group. Further, since the printing ink composition contains an organic alkaline compound and an inorganic alkaline compound, it can be easily redispersed even when the urethane-based resin having a crosslinkable group is poorly dispersed due to storage or drying. It can be redispersed and has excellent redispersibility.

2. 2. Inkjet printing method (recording method)
In the inkjet printing method of the present embodiment, for example, a step of treating the fabric with a pretreatment liquid containing a coagulant, a step of adhering the above-mentioned printing ink composition to the treated fabric, and the step of adhering the fabric to the treated fabric. It has a step of heating. Hereinafter, the printing method according to the present embodiment will be described in the order of the fabric, the printing method, and the pretreatment liquid.

2.1. Cloth The inkjet printing method according to the present embodiment is performed using a cloth (recording medium). 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 printing method of the present embodiment, since the pretreatment liquid described later is used, the flocculant can be appropriately arranged when the pretreatment liquid is applied to the fabric having a basis weight in such a range, which is good. It is possible to realize various pigment printing. In other words, if the basis weight of the fabric is within such a range, the pretreatment liquid can be sufficiently applied, and good printing can be performed by the printing method of the present embodiment. Further, since the printing method of the present embodiment uses the pretreatment liquid, it can be applied to a plurality of types of fabrics having different basis weights, and good printing can be performed.

2.2. Printing method Next, the printing method according to the present embodiment will be described for each step.

2.2.1. Step of Adhering Pretreatment Liquid to Fabric In the present embodiment, the step of adhering the pretreatment liquid (described later) to the fabric is arbitrarily performed. The step of adhering the pretreatment liquid (described later) to the cloth is a step of applying the pretreatment liquid to at least a part of the area of the cloth. In this step, the amount of the pretreatment liquid adhered is preferably 100 mg / inch ² or more and 3000 mg / inch ² or less, and more preferably 130 mg / inch ² or more and 1500 mg / inch ² or less. preferably, it is more preferable to apply such that the 193 mg / inch ² or more 500 mg / inch ² or less. By setting the adhesion amount of the pretreatment liquid to 0.02 g / cm ² or more, it becomes easy to uniformly apply the pretreatment liquid to the fabric, so that color unevenness of the image can be suppressed. Further, by setting the adhesion amount of the pretreatment liquid to 0.5 g / cm ² or less, blurring of the image can be suppressed. The amount of the pretreatment liquid adhered is preferably 70% by mass or more and 100% by mass or less, and more preferably 80% by mass or more and 100% by mass or less with respect to the mass per area of the fabric.

In this step, the amount of deposition of the coagulant contained in the pretreatment liquid was applied to the fabric, but it is preferable to apply such that the 7.5μmol / cm ² or more 40 [mu] mol / cm ² or less, 12 [mu] mol / cm ² or more 30 [mu] mol / It is more preferable to give it so that it is cm ² or less. By applying the flocculant so that the amount of the coagulant adhered is 10 μmol / cm ² or more, the color development of the recorded image becomes good. Further, by applying the flocculant so that the amount of the coagulant adhered is 40 μmol / cm ² or less, the fastness of the recorded image is further improved.

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.

When the step of adhering the pretreatment liquid is adopted in the printing method according to the present embodiment, the step of adhering the pretreatment liquid may include a step of drying the pretreatment liquid for drying the pretreatment liquid applied to the fabric. Good. 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).

2.2.2. Step of Attaching the Printing Ink Composition to the Fabric by the Inkjet Method The step of attaching the printing ink composition to the fabric by the inkjet method is a step of applying the printing ink composition to at least a part of the fabric by the inkjet method. In the step of adhering the printing ink composition to the fabric by the inkjet method, the printing ink composition may be applied to at least a part of the region to which the pretreatment liquid is applied by the step of adhering the pretreatment liquid by the inkjet method. .. As a result, the components such as pigments contained in the printing ink composition react or interact with the coagulant to cause the components such as pigments to coagulate, so that an image having more excellent color development can be obtained.

In this step, a droplet of the printing ink composition is ejected from a nozzle of the head for inkjet recording, and the droplet is adhered to the fabric to print an image on the fabric. As a result, a stamped product (printed product) in which an image composed of the printing ink composition is printed on the cloth can be obtained.

Any of the inkjet recording methods for ejecting the printing ink composition may be used, and examples thereof include a charge deflection method, a continuous method, and an on-denmand method (piezo method, bubble jet (registered trademark) method). Among these inkjet recording methods, a method using a piezo type inkjet recording device is more preferable from the viewpoint of high definition and miniaturization of the device.

In this step, it is preferable to apply the printing ink composition to the fabric so that the amount of adhesion 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 give it to the fabric. When the adhesion amount of the printing ink composition is 1.5 mg / cm ² , the color development of the recorded image tends to be good, and the adhesion amount of the printing ink composition is 6 mg / cm ² or less. As a result, the dryness of the recorded image becomes good, and for example, blurring of the image can be suppressed.

2.2.3. Step of Heating the Fabric The printing 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 heat application 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. Further, when the pretreatment liquid is attached to the fabric and a cationic organic compound is used as the pretreatment liquid, a phenomenon such as invasion of the crosslinked body of the urethane resin occurs. In some cases, the image can 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 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 CORPORATION). 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.

2.3. Action Effect According to the inkjet printing method (recording method) of the present embodiment, an image having good fastness can be formed by the action of the urethane-based resin dispersion having a crosslinkable group contained in the printing inkjet ink composition to be used. .. Further, since the printing inkjet ink composition contains an organic alkaline compound and an inorganic alkaline compound, even if the dispersion of the urethane-based resin dispersion having a crosslinkable group becomes poor due to storage or drying, even if the dispersion becomes poor. It can be easily redispersed and has excellent redispersibility of the printing inkjet ink composition. Further, when the pretreatment liquid is used, the components of the printing ink composition are retained near the surface of the fabric, and for example, an image having sufficient color development (printed product) can be obtained and has a crosslinkable group. By cross-linking the urethane resin by heating, the components of the printing ink composition can be sufficiently fixed to the fabric, and an image (printed product) having better fastness can be obtained. ..

3. 3. Pretreatment Liquid The pretreatment liquid according to the present embodiment is used in the above-mentioned inkjet printing method in which the above-mentioned printing ink composition is adhered to a fabric by an inkjet method. More specifically, the pretreatment liquid may be attached to the fabric, and in that case, the printing ink composition is subsequently attached to the fabric by an inkjet method and used for printing the fabric.

3.1. Coagulant The pretreatment liquid of the present embodiment contains at least a coagulant. The coagulant coagulates or thickens the components of the printing ink composition. That is, the coagulant has a function of coagulating the pigment by interacting with at least a part of the components such as the pigment and the resin contained in the printing ink composition. As a result, at least the color development of the image recorded by the printing ink composition can be improved.

Further, the coagulant can increase the viscosity (thickening) of the printing ink composition by interacting with at least a part of the components (resin, pigment, etc.) contained in the printing ink composition. As a result, it is possible to prevent the printing ink composition from penetrating too much into the inside of the fabric and improve the color development property. In addition, bleeding and bleeding may be reduced by thickening the printing ink composition.

The flocculant is not particularly limited, and examples thereof include metal salts, inorganic acids, organic acids, and cationic compounds. Examples of the cationic compound include a cationic resin (cationic polymer) and a cationic surface activity. Agents and the like (in the present specification, the concept including a cationic resin and a cationic surfactant may be referred to as a cationic organic compound) can be used.

The metal salt is preferably a polyvalent metal salt, but a metal salt other than the polyvalent metal salt can also be used. Among these coagulants, it is preferable to use at least one selected from a metal salt and an organic acid from the viewpoint of excellent reactivity with the components contained in the printing ink composition. Further, among these coagulants, it is preferable to use a cationic polymer from the viewpoint of being easily dissolved in the pretreatment liquid. In addition, a plurality of types of flocculants can be used in combination.

By neutralizing the surface charge of the components contained in the printing ink composition or changing the pH of the printing ink composition with a coagulant, the coagulant reacts with these components to coagulate and precipitate the components to thicken the printing ink composition. be able to.

The polyvalent metal compound among the metal salts is not limited to the following, and includes, for example, titanium compounds, chromium compounds, copper compounds, cobalt compounds, strontium compounds, barium compounds, iron compounds, aluminum compounds, calcium compounds, and magnesium compounds. In addition, these salts (polyvalent metal salts) can be mentioned. Among these polyvalent metal compounds, one or more selected from the group consisting of aluminum compounds, calcium compounds, magnesium compounds, and salts thereof is preferable because pigments can be effectively aggregated, and calcium, magnesium, and the like are preferable. The dissociable salt of the alkaline earth metal of the above is more preferable, and at least one of a calcium salt and a magnesium salt is further preferable.

The multivalent metal salt is a compound composed of a divalent or higher metal ion and an anion. Examples of the divalent or higher metal ion include ions such as calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, and iron. Among the metal ions constituting these polyvalent metal salts, at least one of calcium ions and magnesium ions is preferable from the viewpoint of excellent cohesiveness of the coloring material and the like.

Inorganic ions are the anions that make up the polyvalent metal salt. That is, the polyvalent metal salt is composed of inorganic ions and polyvalent metals. Examples of such inorganic ions include chloride ions, bromine ions, iodine ions, nitrate ions, sulfate ions, and hydroxide ions.

The polyvalent metal compound is preferably an ionic polyvalent metal salt, and in particular, when the polyvalent metal salt is a magnesium salt or a calcium salt, the stability of the reaction solution becomes better. The counterion of the polyvalent metal may be either an inorganic acid ion or an organic acid ion.

Examples of the divalent or higher polyvalent metal ion of the above polyvalent metal salt include Ca ²⁺ , Mg ²⁺ , Cu ²⁺ , Ni ²⁺ , Zn ²⁺ , Ba ²⁺ , and Al ³⁺ . Examples of the anion include Cl ⁻ , NO ^3- , CH ₃ COO ⁻ , I ⁻ , Br ⁻ , ClO ₃ ^{− and the} like. Among these, it is preferable to use magnesium salt, calcium salt, and aluminum salt, which have a high aggregation effect. Specific examples of preferable polyvalent metal salts include calcium carbonate such as heavy calcium carbonate and light calcium carbonate, CaCl ₂ (calcium chloride), calcium nitrate, calcium sulfate, magnesium sulfate, calcium hydroxide, and magnesium chloride. Examples thereof include magnesium carbonate, barium sulfate, barium chloride, zinc carbonate, zinc sulfide, aluminum silicate, calcium silicate, magnesium silicate, and copper nitrate. These polyvalent metal salts may be used alone or in combination of two or more. Among these, at least one of magnesium sulfate, calcium nitrate and calcium chloride is more preferable because sufficient solubility in water can be ensured and traces left by the pretreatment liquid are reduced (traces become inconspicuous). ..

Examples of metal salts other than polyvalent metal salts include monovalent metal salts such as sodium salt and potassium salt. Examples include sodium sulfate and potassium sulfate.

In addition to the above, polyvalent metal compounds include choke, kaolin, calcined clay, talc, titanium oxide, zinc oxide, zinc sulfide, synthetic silica, aluminum hydroxide, alumina, sericite, white carbon, saponite, and calcium. Examples thereof include inorganic pigments such as montmorillonite, sodium montmorillonite, and bentonite, and organic pigments such as acrylic plastic pigments and urea polymer substances.

Examples of organic acids include poly (meth) acrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartaric acid, lactic acid, and sulfonic acid. Preferable examples thereof include ortholic acid, pyrrolidone carboxylic acid, pyron carboxylic acid, pyrrol carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumarin acid, thiophene carboxylic acid, nicotinic acid, derivatives of these compounds, and salts thereof. .. The organic acid may be used alone or in combination of two or more.

Preferable examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and salts thereof. The inorganic acid may be used alone or in combination of two or more.

The cationic organic compound is not particularly limited, but an organic acid salt, a cationic resin, a cationic surfactant and the like can be used. Among the cationic organic compounds, it is preferable to use at least one selected from the cationic resin and the cationic surfactant from the viewpoint of excellent reactivity with the components contained in the printing ink composition.

Examples of organic acid salts include polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, tartrate acid, lactic acid, sulfonic acid, ortholic acid. , Pyrrolidone carboxylic acid, pyron carboxylic acid, pyrrol carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumarin acid, thiophene carboxylic acid, nicotinic acid and other salts can be exemplified. The counterion (cation) of the organic acid salt is not particularly limited, and examples thereof include ions such as sodium, potassium, calcium, magnesium, copper, nickel, zinc, barium, aluminum, titanium, strontium, chromium, cobalt, and iron. The organic acid salt may be used alone or in combination of two or more.

Examples of the cationic resin include a cationic urethane resin, a cationic olefin resin, and a cationic allylamine resin.

As the cationic urethane resin, known ones can be appropriately selected and used. Examples of the cationic urethane resin include Hydran CP-7010, CP-7020, CP-7030, CP-7040, CP-7050, CP-7060, CP-7610 (trade name, Dainippon Ink and Chemicals Co., Ltd.). , Superflex 600, 610, 620, 630, 640, 650 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), urethane emulsion WBR-2120C, WBR-2122C (trade name, manufactured by Taisei Fine Chemical Co., Ltd.), etc. Can be used.

The cationic olefin resin has an olefin such as ethylene or propylene in its structural skeleton, and known ones can be appropriately selected and used. Further, the cationic olefin resin may be in an emulsion state in which it is dispersed in a solvent containing water, an organic solvent and the like. As the cationic olefin resin, a commercially available product can be used, and examples thereof include arrow base CB-1200 and CD-1200 (trade name, manufactured by Unitika Ltd.).

As the cationic allylamine-based resin, known ones can be appropriately selected and used, for example, polyallylamine hydrochloride, polyallylamine amide sulfate, allylamine hydrochloride / diallylamine hydrochloride copolymer, allylamine acetate / diallylamine acetate. Salt copolymer, allylamine acetate / diallylamine acetate copolymer, allylamine hydrochloride / dimethylallylamine hydrochloride copolymer, allylamine / dimethylallylamine copolymer, polydialylamine hydrochloride, polymethyldiallylamine hydrochloride, polymethyldialylamineamide sulfate, polymethyldiallylamine acetate Salt, polyallylamine dimethylammonium chloride, diallylamine acetate / sulfur dioxide copolymer, diallylmethylethylammonium ethylsulfate / sulfur dioxide copolymer, methyldiallylamine hydrochloride / sulfur dioxide copolymer, diallyldimethylammonium chloride / sulfur dioxide copolymer, diallyldimethylammonium chloride -The acrylamide copolymer and the like can be mentioned.

Commercially available products can be used as such cationic allylamine-based resins. For example, PAA-HCL-01, PAA-HCL-03, PAA-HCL-05, PAA-HCL-3L, PAA-HCL- 10L, PAA-H-HCL, PAA-SA, PAA-01, PAA-03, PAA-05, PAA-08, PAA-15, PAA-15C, PAA-25, PAA-H-10C, PAA-D11- HCL, PAA-D41-HCL, PAA-D19-HCL, PAS-21CL, PAS-M-1L, PAS-M-1, PAS-22SA, PAS-M-1A, PAS-H-1L, PAS-H- 5L, PAS-H-10L, PAS-92, PAS-92A, PAS-J-81L, PAS-J-81 (trade name, manufactured by Nittobo Medical Co., Ltd.), Hymo Neo-600, Hymorok Q-101, Q-311 , Q-501, Himax SC-505, SC-505 (trade name, manufactured by Himo Co., Ltd.) and the like can be used.

Examples of the cationic surfactant include primary, secondary and tertiary amine salt type compounds, alkylamine salts, dialkylamine salts, aliphatic amine salts, fatty acid amide amines, benzalconium salts, and quaternary amine salts. Examples thereof include ammonium salt, quaternary alkylammonium salt, alkylpyridinium salt, sulfonium salt, phosphonium salt, onium salt, imidazolinium salt, alkylbetaine, fatty acid amide betaine, and alkylamine oxide. Specific examples thereof include alkyltrimethylammonium salts, dialkyldimethylammonium salts and alkyldimethylbenzylammonium salts as quaternary ammonium salts, and N-methylbishydrochiethylamine fatty acid ester hydrochlorides as amine salt systems. Further, for example, lauryl Hydrochlorides such as amines, palmamines and rosinamines, acetates and the like, lauryltrimethylammonium chloride, cetyltrimethylammonium chloride, benzyltributylammonium chloride, benzalkonium chloride, dimethylethyllaurylammoniumethylsulfate, dimethylethyloctylammoniumethylsulfate, Trimethyllaurylammonium hydrochloride, cetylpyridinium chloride, cetylpyridinium bromide, dihydroxyethyllaurylamine, decyldimethylbenzylammonium chloride, dodecyldimethylbenzylammonium chloride, tetradecyldimethylammonium chloride, hexadecyldimethylammonium chloride, octadecyldimethylammonium chloride, etc. Be done.

As such a cationic surfactant, a commercially available product can be used, for example, Catiogen TML, Catiogen TMP, Catiogen TMS, Catiogen ES-O, Catiogen ES-L, Catiogen ES-L-9, Catiogen ES. -P (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Amogen SH, Amogen K, Amogen CB-H, Amogen HB-C, Amogen AOL (all manufactured by Dai-ichi Kogyo Pharmaceutical Co., Ltd.) and the like.

The total content (solid content) of the cationic organic compound with respect to the entire pretreatment liquid of the present embodiment can be appropriately determined so as to exert the above-mentioned effect, and is, for example, the total mass of the pretreatment liquid. On the other hand, it is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.5% by mass or more and 25% by mass or less, still more preferably 1% by mass or more and 20% by mass or less, and particularly preferably 1% by mass. % Or more and 15% by mass or less.

3.2. Other ingredients 3.2.1. Water The pretreatment liquid of the present embodiment may contain water. The water is the same as described in the above-mentioned printing ink composition. The content of water is 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, and further preferably 50% by mass or more, based on the total amount of the pretreatment liquid.

3.2.2. Water-soluble organic solvent The pretreatment liquid of the present embodiment may contain a water-soluble organic solvent. The water-soluble organic solvent may be able to improve the wettability of the pretreatment liquid with respect to the recording medium. Examples of the water-soluble organic solvent include at least one of esters, alkylene glycol ethers, cyclic esters and alkoxyalkylamides. Further, as the water-soluble organic solvent, nitrogen-containing compounds, saccharides, amines and the like other than these may be used. In addition, the pretreatment liquid may contain a water-soluble organic solvent that can be used in the above-mentioned printing ink composition.

The pretreatment liquid may contain a plurality of types of water-soluble organic solvents. When a water-soluble organic solvent is contained, the total content of the water-soluble organic solvent with respect to the entire pretreatment liquid is 0.1% by mass or more and 20% by mass or less, preferably 0.3% by mass or more and 15% by mass or less. It is more preferably 0.5% by mass or more and 10% by mass or less, and further preferably 1% by mass or more and 7% by mass or less.

3.2.3. Resin emulsion The pretreatment liquid may contain a resin emulsion. By containing the resin emulsion, it may be possible to further enhance the fixing (fixing) property of the self-dispersing pigment contained in the printing ink composition to the fabric. Further, the resin emulsion may function as a sealant for suppressing the penetration of the pretreatment liquid and / or the printing ink composition into the fabric.

Examples of such a resin emulsion include, but are not limited to, at least one resin emulsion selected from urethane-based, styrene-acrylic-based, acrylic-based, and vinyl chloride-vinyl acetate-based. In the pretreatment liquid, one or more of these resin emulsions can be used.

The urethane resin emulsion is not particularly limited as long as it has a urethane bond in the molecule, but in addition to the urethane bond, a polyester type urethane resin emulsion containing an ether bond in the main chain and an ester bond in the main chain are used. A polyester type urethane resin emulsion containing a polyester type urethane resin emulsion, a polycarbonate type urethane resin emulsion containing a carbonate bond in the main chain, and the like can also be used. In addition, a urethane resin emulsion having a crosslinkable group to be blended in the printing ink composition described later may be included.

When the pretreatment liquid contains a resin emulsion, the content of the resin emulsion in the pretreatment liquid in terms of solid content is preferably 1 to 20 when the total mass of the pretreatment liquid is 100% by mass. It is by mass, more preferably 1.5 to 15% by mass, still more preferably 2 to 10% by mass. When the content of the resin emulsion in terms of solid content is within the above range, the washing durability of the image may be further improved. The amount in terms of solid content means the amount of the resin emulsion excluding substances other than the resin (solid content).

When the pretreatment liquid contains a resin emulsion and the printing ink composition contains the resin emulsion, both resin emulsions may be of the same type or different types.

32.4. Surfactant The pretreatment liquid of the present embodiment may contain a surfactant. The surfactant is the same as described in the above-mentioned printing ink composition. When a surfactant is blended in the pretreatment liquid, the total amount of the surfactant is 0.01% by mass or more and 3% by mass or less, preferably 0.05% by mass or more and 2% by mass, based on the entire pretreatment liquid. Hereinafter, it is more preferable to blend 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.

Since the pretreatment liquid contains a surfactant, the stability when ejecting ink from the head tends to increase. Also, the use of an appropriate amount of surfactant improves the permeability to the fabric and allows the flocculant to be more evenly distributed. As a result, agglutination of the self-dispersing pigment and thickening of the printing ink composition are likely to occur, and the color development of the printed material can be further improved.

3.2.5. Other Ingredients In the pretreatment liquid of the present embodiment, various additives such as a chelating agent, a preservative, a pH adjusting agent, a viscosity adjusting agent, an antioxidant, and an antifungal agent are appropriately added as necessary. Can be done.

3.3. Physical Properties of Pretreatment Liquid The surface tension of the pretreatment liquid according to the present embodiment is 30 mN / m or more, preferably 35 mN / m or more, more preferably 35 mN / m or more, from the viewpoint of making the permeability into the fabric appropriate. Is 38 mN / m or more, more preferably 40 mN / m or more. The surface tension is measured by checking the surface tension when the platinum plate is wetted with the composition in an environment of 25 ° C. using an automatic surface tension meter CBVP-Z (manufactured by Kyowa Interface Science Co., Ltd.). can do.

Further, the pretreatment liquid may be attached to the fabric by an inkjet method, and in such a case, the viscosity at 20 ° C. is preferably 1.5 mPa · s or more and 15 mPa · s or less. It is more preferably 5 mPa · s or more and 5 mPa · s or less, and more preferably 1.5 mPa · s or more and 3.6 mPa · s or less.

On the other hand, the pretreatment liquid may be carried out by a method other than the inkjet method. Such methods include a method of applying the pretreatment liquid to the fabric using various sprays, a method of immersing the cloth in the pretreatment liquid and applying the treatment liquid, a method of applying the treatment liquid to the fabric by a brush or the like, and the like. Examples thereof include a contact type, a contact type, or a combination thereof.

When the pretreatment liquid is attached to the fabric by a method other than the inkjet method, the viscosity at 20 ° C. may be higher than that obtained by the inkjet method, for example, 1.5 mPa · s or more and 100 mPa · s. Hereinafter, it is preferably 1.5 mPa · s or more and 50 mPa · s or less, and more preferably 1.5 mPa · s or more and 20 mPa · s or less. The viscosity is measured by increasing the Shear Rate to 10 to 1000 in an environment of 20 ° C. using a viscoelasticity tester MCR-300 (manufactured by Pysica) and reading the viscosity at Shear Rate 200. Can be measured.
4. 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.

4.2. Preparation of Printing Ink Composition Each component is placed in a container so as to have the compositions shown in Tables 1 and 2, mixed and stirred with a magnetic stirrer for 2 hours, and then further filled with zirconia beads having a diameter of 0.3 mm. The mixture was sufficiently mixed by performing a dispersion treatment in. After stirring for 1 hour, each printing ink composition was obtained by filtering using a 5 μm PTFE membrane filter. Table 1
The values in Table 2 and Table 2 indicate mass%, and pure water (ion-exchanged water) was added so that the mass of each printing ink composition was 100% by mass. In the table, the resin content refers to the resin solid content (mass%).

4.3. Resins used in the printing ink composition Tables 1 and 2 show the resins used in the printing ink compositions used in Examples and Comparative Examples. Takelac WS-6021 is a urethane resin having a polyether skeleton having a self-crosslinkable crosslink group manufactured by Mitsui Chemicals Co., Ltd., and Takelac WS-5100 is a polycarbonate skeleton manufactured by Mitsui Chemicals Co., Ltd. having a self-crosslinkable crosslink group. Elastron E-37 is a urethane resin having a polyester skeleton having a self-crosslinkable cross-linking group manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and Takelac W6110 is a self-cross-linking cross-linking group manufactured by Mitsui Chemicals Co., Ltd. It is a urethane resin (polycarbonate) that does not have. The break point elongation and 100% modulus values of each resin are as follows.

Takelac WS-6021: Break point elongation 750%, modulus 3 MPa
Takelac WS-5100: Break point elongation 180%, modulus 28 MPa
Erastron E-37: Break point elongation 500%, modulus 2 MPa
Takelac W6110: Breaking point elongation 550%
Is.

For the elongation at break point, a film having a thickness of about 60 μm was prepared using an emulsion (dispersion) of each resin, heated at 170 ° C. for 5 minutes, and then a tensile test gauge length of 20 mm and a tensile speed of 100 mm / min. The value obtained by measuring under the conditions of the above was adopted. Further, as the 100% modulus, the value obtained by measuring the tensile stress when the film was stretched 100% with respect to the original length in the tensile test was adopted.
4.4. Other Ingredients In Tables 1 and 2, KF-6011 is a siloxane-based surfactant manufactured by Shin-Etsu Silicone Co., Ltd., and Surfinol 465 is a mixture of AirProductsand Chemicals. Inc. It is an acetylene glycol-based surfactant manufactured by the company. The HLB value of KF-6011 is 14.5, and the HLB value of Surfinol 465 is 13.

The black pigment dispersion is carbon black dispersed by a resin dispersant. Its solid content is 15% by mass. Black pigment dispersions 1 and 2 were prepared as follows.

(Black Pigment Dispersion Solution 1)
40 parts by mass of resin (polymerized at a mass ratio of methacrylic acid / butyl acrylate / styrene / hydroxyethyl acrylate = 25/50/15/10. Weight average molecular weight 12,000), 7 parts by mass of potassium hydroxide, water. 23 parts by mass and 30 parts by mass of triethylene glycol-mono-n-butyl ether were put into a mixed solution and heated at 80 ° C. with stirring to prepare a resin aqueous solution.

3.0 kg of carbon black (CI pigment black 7, average particle size 100 nm) and 10.25 kg of water are mixed with 1.75 kg of the above resin aqueous solution (solid content 43% by mass), and a mixing stirrer is used. The mixture was stirred with and premixed to obtain a mixed solution. The above mixture was dispersed by a multipath method using a horizontal bead mill equipped with a multi-disc impeller having an effective volume of 1.5 liters filled with 85% of 0.5 mm zirconia beads. Specifically, two passes were performed at a bead peripheral speed of 8 m / sec with a discharge rate of 30 liters per hour to obtain a pigment dispersion mixed solution having an average particle diameter of 325 nm. Next, the pigment dispersion mixed solution was circulated and dispersed using a horizontal annular bead mill having an effective volume of 1.5 liters filled with 95% by mass of 0.05 mm zirconia beads. A screen of 0.015 mm was used, and the bead peripheral speed was 10 m / sec, and the pigment dispersion mixture volume of 10 kg was dispersed at a circulation rate of 300 liters / hour for 4 hours. The solid content of the pigment was 15% by mass. An aqueous black pigment dispersion 1 having a resin content of 5% was obtained.

(Black Pigment Dispersion Liquid 2)
MA100 (trade name, manufactured by Mitsubishi Chemical Corporation), which is carbon black as a coloring material; 20 parts are mixed in 250 parts, and the bead filling rate is used with the Eiger motor mill M250 type (trade name, manufactured by Eiger Japan). Grain size dispersion was performed for 1 hour under the conditions of: 70% and rotation speed: 5,000 rpm. The obtained mixed solution of the pigment paste and the solvent was transferred to an evaporator and heated to 120 ° C. while reducing the pressure to 30 mmHg or less to distill off as much water as possible in the system, and then the temperature was controlled to 150 ° C. Next, 25 parts of sulfur trioxide was added and reacted for 6 hours. After the reaction was completed, the reaction was washed with excess sulfolane several times, and then poured into water and filtered to form a sulfinic acid group (SO _2- ) or a sulfonic acid group (SO). _A self-dispersing carbon black pigment slurry was obtained by directly introducing a sulfur-containing dispersibility-imparting group such as _3- ) onto the pigment surface.

Self-dispersing carbon black pigment obtained by the above materials and methods; in 20 parts, surfinol 465 (trade name, Air Products and Chemicals. Inc.), which is an acetylene glycol-based surfactant as a wetting agent; Add 1 part, triethanolamine as a neutralizing agent; 0.2 parts, ion-exchanged water; 77 parts, and use a paint shaker (using glass beads, bead filling rate: 60%, media diameter: 1.7 mm). , The average particle size (secondary particle size) of the pigment is dispersed until it reaches 100 nm, and a sulfur-containing dispersibility-imparting group (hydrophilic group) such as a sulfinic acid group (SO _2- ) or a sulfonic acid group (SO _3- ) is dispersed. ) Was directly introduced onto the surface of the pigment to obtain a dispersed mixture of self-dispersing carbon black pigments. The dispersion time was about 1 hour.

The obtained dispersion mixture was sealed in a polypropylene container, heat-treated in an environment of 80 ° C. for 2 hours, and then naturally cooled to room temperature to obtain a black pigment dispersion liquid 2. The pigment solid content concentration was adjusted to 15.0% by mass. In the examples using the black pigment dispersion liquid 2, the values of the contents of the organic alkaline compound and the surfactant in the table are the total values of those derived from the pigment dispersion liquid and the post-addition amount.

In addition, as the components described by the compound names, those purchased as reagents were used.

4.5. Evaluation test 4.5.1. Creation of imprints Using a printer (SC-F200) manufactured by Seiko Epson Corporation on a fabric (Print Star Heavyweight (white) 5.6 oz), each printing ink composition is applied with a resolution of 1440 dpi x 1440 dpi. Printing was performed at an amount of 200 mg / inch ² . After the printing, heat treatment was performed again in a conveyor oven (hot air drying method) at 165 ° C. for 5 minutes to fix the stamped material.

4.5.2. 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 dry test specified in ISO-105 X12, and wet friction was tested according to the wet test specified in ISO-105 X12, and evaluated using a contaminated gray scale. The evaluation criteria were as follows, and the results are shown in Tables 1 and 2.

Dry friction fastness ◎: Friction fastness is 4th grade or higher ○: Friction fastness is 3rd grade or higher and lower than 4th grade Δ: Friction fastness is 2nd grade or higher and lower than 3rd grade ×: Friction fastness is 2nd grade It is less than the class.

Wet friction fastness ◎: Friction fastness is 3rd grade or higher ○: Friction fastness is 2nd grade or higher and lower than 3rd grade Δ: Friction fastness is 1st grade or higher and lower than 2nd grade ×: Friction fastness is 1 It is less than the class.

4.5.3. Evaluation of color development The OD value of the stamped product of each example was measured with a colorimeter (trade name "Gretag Macbeth Spectrolino", manufactured by X-RITE), and based on the obtained OD value, according to the following evaluation criteria. The color development was evaluated, and the results are shown in Tables 1 and 2.

⊚: OD value is 1.45 or more ◯: OD value is 1.40 or more and less than 1.45 Δ: OD value is 1.30 or more and less than 1.45 ×: OD value is less than 1.30 Is.

4.5.4. Evaluation of the texture of the stamped product The stamped part of the stamped product of each example was directly touched with the palm of the hand, and the feel at that time was judged according to the following criteria. The judgment was made by three people, and the opinion with the most support was taken as the result of the judgment. When the judgment was divided into one person at a time, the opinion in between was used as the judgment result and is shown in Tables 1 and 2.

⊚: The hardness and texture of the stamped part are almost the same as the original fabric and are good. ○: The hardness or texture of the stamped part is slightly different from that of the original fabric, but there is no problem in practical use. The hardness or feel of the stamped part is worse than that of the original fabric, but it is within the permissible range. ×: The stamped part becomes hard, and the usability is poor and it cannot be put into practical use.

4.5.5. Evaluation of redispersibility 5 g of the printing ink composition of each example was placed in a 30 mL glass bottle and left to stand in an environment of 50 ° C. for 3 hours without a lid. 10 g of pure water was added to the ink after being left to stand, and after leaving for 30 minutes, the state change was visually observed, and the redispersibility was evaluated based on the following evaluation criteria. The evaluation results are shown in Tables 1 and 2.

⊚: Ink is immediately redispersed and becomes uniform ○: Ink is redispersed and becomes uniform △: Ink is partially redispersed, but solid matter remains on the wall surface of the bottle ×: Solid matter Remains on the wall surface and hardly redisperses.
XX: Almost solid content remains on the wall surface, and no redispersion is observed.

In Comparative Example 6, since the ink flow path and the like were corroded and a stable evaluation could not be obtained, evaluation results other than redispersibility are not posted, but the frictional fastness was poor.

4.5. Evaluation Results The printing ink compositions of each example containing all of the urethane resin having a crosslinkable group, the inorganic alkaline compound, and the organic alkaline compound were all excellent in friction fastness and redispersibility. ..

On the other hand, in Comparative Example 1 in which a urethane resin having no crosslinkable group was used, the frictional fastness was insufficient. It is considered that this is because the ability of the resin to fix the pigment was insufficient. Further, in Comparative Example 3 in which a urethane-based resin having a crosslinkable group was used and neither an organic alkaline compound nor an inorganic alkaline compound was used, the redispersibility was poor. On the other hand, in Comparative Example 2 in which a urethane resin having no crosslinkable group was used and neither an organic alkaline compound nor an inorganic alkaline compound was used, the friction fastness was insufficient as in Comparative Example 1. However, the redispersibility did not decrease as much as in Comparative Example 3. This indicates that the urethane-based resin having a crosslinkable group tends to have better friction fastness than the urethane-based resin having no crosslinkable group, while the redispersibility tends to be inferior. Further, it can be seen from Comparative Examples 1, 4, 7, and the like that the organic alkaline compound alone cannot obtain sufficient redispersibility. Further, it can be seen that the organic alkali compound maintains better color development when used together with the acetylene glycol-based surfactant than when used together with the silicone-based surfactant. This is because the inclusion of the organic alkaline compound promotes the strike-through of the ink composition and reduces the color development, and the inclusion of the acetylene glycol-based surfactant suppresses the penetration of the ink composition. Conceivable.

Further, from Comparative Example 5, when the inorganic alkaline compound alone is used in a small amount, the redispersibility is poor, and when the inorganic alkali compound alone is used in a large amount, the redispersibility is good, but the pH rises. As a result, the ink flow path and the like were corroded, making it unsuitable for use.

On the other hand, looking at each example, Examples 4-8, 12-14, 16 and 17 using the acetylene glycol-based surfactant were relatively superior in color development. In all examples, the pH was 11.5 or less.

Further, for example, in Examples 1, 9, 15 and the like, when the urethane-based resin having a crosslinkable group is a urethane-based resin having a polyether skeleton, a urethane-based resin having a polycarbonate skeleton or a urethane-based resin having a polyester skeleton is used. It was found that the texture was superior to that of resin. Further, when the urethane resin having a crosslinkable group is a urethane resin having a polycarbonate skeleton, the toughness (particularly wet friction fastness) is higher than that of a urethane resin having a polyether skeleton or a urethane resin having a polyester skeleton. Turned out to be better.

The present invention is not limited to the above-described embodiment, and various modifications are possible. For example, the present invention includes a configuration substantially the same as the configuration described in the embodiment (for example, a configuration having the same function, method and result, or a configuration having 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 (10)

A urethane-based resin dispersion having a crosslinkable group and
Inorganic alkaline compounds and
With organic alkaline compounds
Containing the urethane-based resin have a polycarbonate skeleton, inkjet printing ink composition. In claim 1,
A printing inkjet ink composition further containing a pigment. In claim 2,
A printing inkjet ink composition further containing a resin dispersant. In any one of claims 1 to 3,
A printing inkjet ink composition further containing an acetylene glycol-based surfactant. In claim 4,
A printing inkjet ink composition having an HLB value of 10 or more for the acetylene glycol-based surfactant. In any one of claims 1 to 5,
A printing inkjet ink composition in which the pH of the printing ink composition is 11.5 or less. In any one of claims 1 to 6 ,
The urethane-based resin is a printing inkjet ink composition having a breaking point elongation of 170% or more. In any one of claims 1 to 7,
A printing inkjet ink composition in which the crosslinkable group is an isocyanate group. In claim 8.
A printing inkjet ink composition in which the isocyanate group is chemically protected by a blocking agent. 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.