JP7206293B2 - Water-based ink for inkjet, method for producing printed matter, and ink set - Google Patents

Description

TECHNICAL FIELD Embodiments of the present invention relate to water-based ink jet inks, methods of manufacturing printed matter, and ink sets.

In addition to screen printing and roller printing, methods for printing images such as letters, pictures, and designs on substrates such as woven fabrics, knitted fabrics, and non-woven fabrics, have recently been used to process images on a computer and perform virtually plateless printing. Inkjet methods that can print are of interest.

As a method for inkjetting onto a fabric or the like using water-based ink, Patent Document 1 uses an ink using an emulsion containing at least one resin selected from the group consisting of urethane resin, styrene-acrylic resin, and acrylic resin. discloses a method. Patent Document 2 discloses a method using ink containing at least one selected from urethane-based resins and acrylic-based resins.

The inkjet method is also attracting attention as a method for printing images on impermeable substrates such as plastic substrates.

As a method for inkjetting onto a plastic substrate using an aqueous ink, Patent Document 3 discloses that a structural unit derived from a (meth)acrylate having an alicyclic hydrocarbon group is contained in an amount of 10% by mass or more and less than 50% by mass (meth). ) discloses a method using an ink containing an acrylic resin.

JP 2015-160860 A JP 2014-148563 A JP 2015-24508 A

An object of an embodiment of the present invention is to provide a water-based ink for inkjet, a method for producing a printed matter, and an ink set that can produce a printed matter having excellent wet fastness to rubbing.

According to one embodiment of the present invention, there is provided a water-based inkjet ink containing a colorant, a water-dispersible urethane resin having a film elongation of 600% or more, a water-dispersible polyolefin resin, and water.
According to another embodiment of the present invention, there is provided a method for producing a printed matter, including the step of inkjet printing a substrate using the water-based inkjet ink of the above embodiment.
According to another embodiment of the present invention, there is provided an ink set including the water-based inkjet ink of the above embodiment and a pretreatment liquid containing a coagulant.

According to the water-based inkjet ink of the embodiment of the present invention, it is possible to produce a printed matter having excellent wet rubbing fastness.
According to the method for producing a printed matter according to the embodiment of the present invention, a printed matter having excellent fastness to wet rubbing can be produced.
According to the ink set of the embodiment of the present invention, it is possible to produce printed matter having excellent wet rubbing fastness.

Embodiments of the present invention will be described in detail below, but it goes without saying that the present invention is not limited to these embodiments, and various modifications and changes may be made.

<Water-based ink for inkjet>
The water-based inkjet ink of one embodiment contains a coloring material, a water-dispersible urethane resin having a film elongation of 600% or more, a water-dispersible polyolefin resin, and water.
Hereinafter, the "water-based inkjet ink" may be simply referred to as "ink" or "water-based ink".

With this ink, printed matter having excellent wet rubbing fastness can be produced.
The reason for this is presumed as follows.
By using a water-dispersible urethane resin having a film elongation of 600% or more, it is possible to impart stretchability to the ink film, thereby improving the fixability of the ink to the substrate.
On the other hand, polyolefin resins generally have strong hydrophobicity, tend to be difficult to be compatible with urethane resins, and tend to have a smaller specific gravity than urethane resins. Polyolefin resins generally tend to be relatively hard and have a low coefficient of friction as compared to urethane resins. Therefore, by using a water-dispersible polyolefin resin together with the above-mentioned water-dispersible urethane resin, the polyolefin resin tends to exist on the surface of the ink film on the substrate, and the polyolefin resin on the surface of the ink film allows the ink film to It is presumed that the coefficient of friction of the surface can be reduced to reduce the influence of external friction and prevent the film from coming off.

The ink preferably contains a coloring material.
The coloring material may be either a pigment or a dye, and the pigment or dye may be used alone, or both may be used in combination.

From the viewpoint of weather resistance and water resistance of the printed matter, the ink preferably contains a pigment as a coloring material. Any pigment commonly used in the art can be used.
A non-white pigment, a white pigment, or a combination thereof can be used as the pigment.

Examples of non-white pigments include organic pigments such as azo, phthalocyanine, dye, condensed polycyclic, nitro, and nitroso pigments (Brilliant Carmine 6B, Lake Red C, Watching Red, Disazo Yellow, Hansa Yellow, phthalocyanine blue, phthalocyanine green, alkali blue, aniline black, etc.); metals such as cobalt, iron, chromium, copper, zinc, lead, titanium, vanadium, manganese, nickel, metal oxides and sulfides; Inorganic pigments such as Prussian blue, and carbon blacks such as furnace carbon black, lamp black, acetylene black and channel black can be used. The average particle size of these pigments is preferably 50 nm or more from the viewpoint of color development, and preferably 500 nm or less from the viewpoint of ejection stability. The average particle size of these pigments is, for example, preferably 50 to 500 nm, more preferably 50 to 200 nm.

Examples of white pigments include inorganic pigments such as titanium oxide, zinc white, zinc sulfide, antimony oxide, and zirconium oxide. In addition to inorganic pigments, hollow resin fine particles and polymer fine particles can also be used. Among them, it is preferable to use titanium oxide from the viewpoint of hiding power. The average particle size of titanium oxide is preferably 50 nm or more from the viewpoint of concealability, and preferably 500 nm or less from the viewpoint of ejection stability. When titanium oxide is used, it is preferable to use one surface-treated with alumina or silica in order to suppress the photocatalytic action. The surface treatment amount is preferably about 5 to 20% by mass in the pigment.

The volume-based average particle size of the pigment is preferably 50 to 500 nm, more preferably 50 to 200 nm.

A self-dispersing pigment whose surface is modified with a hydrophilic functional group may also be used. Examples of commercially available self-dispersing pigments include CAB-O-JET series manufactured by Cabot Corporation (“CAB-O-JET200”, “CAB-O-JET300”, “CAB-O-JET250C”, “CAB-O- JET260M", "CAB-O-JET270", etc. (all trade names)), "BONJET BLACK CW-1S", "BONJET BLACK CW-2", "BONJET BLACK CW-3", etc. manufactured by Orient Chemical Industry Co., Ltd. ( All of them are trade names)).
Microencapsulated pigments, which are pigments coated with resin, may also be used.
A pigment dispersion in which the pigment is pre-dispersed with a pigment dispersant may also be used. Examples of commercially available pigment dispersions dispersed with a pigment dispersant include HOSTAJET series (trade name) manufactured by Clariant Co., Ltd., FUJI SP series (trade name) manufactured by Fuji Pigment Co., Ltd., and the like. A pigment dispersion dispersed with a pigment dispersant, which will be described later, may also be used.

One pigment may be used alone, or two or more pigments may be used in combination.
The amount of the pigment to be blended varies depending on the type of pigment used, but from the viewpoint of color development, etc., it is preferably contained in the ink in an amount of about 0.1 to 30% by mass relative to the total amount of the ink, and is preferably about 0.1% by mass. More preferably, it is up to 15% by mass.

The ink may further contain a pigment dispersant to stably disperse the pigment in water.
Examples of pigment dispersants include commercially available TEGO Disperse series (“TEGO Disperse 740W”, “TEGO Disperse 750W”, “TEGO Disperse 755W”, “TEGO Disperse 757W”, “TEGO Disperse 757W”, “TEGO Disperse” manufactured by EVONIK). Disperse 760W" (both trade names)), Solsperse series manufactured by Nippon Lubrizol Co., Ltd. 44000", "Solsperse 46000" (both trade names)), BASF Japan Co., Ltd. Jonkrill series ("Jonkrill 57", "Jonkrill 60", "Jonkrill 62", "Jonkrill 63", " Joncryl 71", "Joncryl 501" (both trade names)), "DISPERBYK-102", "DISPERBYK-185", "DISPERBYK-190", "DISPERBYK-193", "DISPERBYK-193" manufactured by BYK Chemie Japan Co., Ltd. DISPERBYK-199" (both are trade names), Daiichi Kogyo Seiyaku Co., Ltd. "Polyvinylpyrrolidone K-30" and "Polyvinylpyrrolidone K-90" (both trade names).
As the surfactant-type dispersant, for example, Kao Corporation Demoll series (“Demor EP”, “Demor N”, “Demor RN”, “Demor NL”, “Demor RNL”, “Demor T-45” (all trade names)), Emulgen series manufactured by Kao Corporation ("Emulgen A-60", "Emulgen A-90", "Emulgen A-500", "Emulgen B-40", nonionic surfactants such as "Emulgen L-40" and "Emulgen 420" (both trade names).

Pigment dispersants may be used alone or in combination of two or more.
When a pigment dispersant is used, the blending amount in the ink varies depending on the type and is not particularly limited. A range is preferably used.

As the dye, those commonly used in the technical field of printing can be used without particular limitation. Specific examples include basic dyes, acid dyes, direct dyes, soluble vat dyes, acid mordant dyes, mordant dyes, reactive dyes, vat dyes, sulfur dyes, etc. Among these, water-soluble dyes, reduction dyes, etc. Water-soluble substances can be used. More specific examples include azo dyes, rhodamine dyes, methine dyes, azomethine dyes, xanthene dyes, quinone dyes, triphenylmethane dyes, diphenylmethane dyes, and methylene blue. These dyes may be used alone or in combination of two or more.

One type of dye may be used alone, or two or more types may be used in combination.
Although the dye differs depending on the type, from the viewpoint of color development, etc., the solid content is preferably 0.1 to 30% by mass, more preferably 0.5 to 15% by mass, more preferably 1 to 10% by mass, based on the total amount of the aqueous ink. % is more preferred.

The ink preferably contains a water-dispersible urethane resin having a film elongation of 600% or more.
By using a water-dispersible urethane resin having a film elongation of 600% or more, it is possible to impart stretchability to the ink film, thereby improving the fixability of the ink to the substrate. The ink film imparted with elasticity can flexibly follow the expansion and contraction of the base material, for example, when a base material having elasticity such as fabric is used, and can also be applied to non-stretchable materials such as plastic base materials. When a permeable base material is used, even when the base material is rubbed, the vibration generated between the base material and the friction element can be absorbed. In this way, the fixability of the ink to the substrate can be improved.
Hereinafter, a water-dispersible urethane resin having a film elongation of 600% or more may be referred to as a water-dispersible resin A.

The water-dispersible resin A may be a self-emulsifying type into which a hydrophilic component necessary for stable dispersion in water is introduced, or may be water-dispersible by using an external emulsifier.
The water-dispersible resin A can be blended, for example, as an oil-in-water resin emulsion in the production of the ink.

The film elongation of the water-dispersible resin A is preferably 600% or more, more preferably 750% or more, and even more preferably 1000% or more. On the other hand, the film elongation of the water-dispersible resin A is, for example, preferably 2000% or less, more preferably 1800% or less. The film elongation of the water-dispersible resin A is, for example, preferably 600 to 2000%, more preferably 750 to 2000%, even more preferably 1000 to 1800%.

The film elongation of the water-dispersible resin A was measured as follows. First, the water-dispersible resin A was applied to a polytetrafluoroethylene sheet so that the film thickness after drying was 500 μm, dried at 23° C. for 15 hours, further dried at 80° C. for 6 hours, and 120° C. for 20 hours. After drying for minutes, the resin film is produced by peeling from the sheet. Using a tensile tester, the obtained resin film is stretched at a measurement temperature of 20 ° C. and a measurement speed of 200 mm / min, and the length stretched until the resin film breaks is measured, and its ratio to the original length. The value expressed as a percentage is taken as the film elongation. As a tensile tester, a Tensilon universal tester RTC-1225A (manufactured by Orientec Co., Ltd.) can be used.

Examples of water-dispersible urethane resins include polyether-type urethane resins containing ether bonds in the main chain, polyester-type urethane resins containing ester bonds in the main chain, and polycarbonate-type urethane resins containing carbonate bonds in the main chain. can be done.

Commercially available resin emulsions of water-dispersible resin A include "Impranil DLP-R" and "Impranil DL1537" (both trade names) manufactured by Sumika Covestro Urethane Co., Ltd., and ""Superflex300","Superflex740","Superflex500M" (all trade names), and "DAOTAN TW6491" and "DAOTAN TW6495" (all trade names) manufactured by Daicel Corporation.
The water-dispersible resin A may be used alone or in combination of two or more.

The amount of the water-dispersible resin A in the ink is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, and even more preferably 4% by mass or more, relative to the total amount of the ink. . On the other hand, the amount of the water-dispersible resin A in the ink is preferably 20% by mass or less, more preferably 18% by mass or less, still more preferably 15% by mass or less, and even more preferably 12% by mass or less, relative to the total amount of the ink. . The amount of the water-dispersible resin A in the ink is, for example, preferably 0.5 to 20% by mass, more preferably 1 to 18% by mass, even more preferably 2 to 15% by mass, with respect to the total amount of the ink. 12% by mass is more preferred. The amount of the water-dispersible resin is the amount in terms of solid content (that is, the amount of the resin only), and the same applies hereinafter.

The ink preferably contains a water-dispersible polyolefin resin. The water-dispersible polyolefin resin may be referred to as water-dispersible resin B hereinafter.

The water-dispersible resin B may be a self-emulsifying type into which a hydrophilic component necessary for stable dispersion in water is introduced, or may be water-dispersible by using an external emulsifier.
The water-dispersible resin B can be blended, for example, as an oil-in-water resin emulsion when producing the ink.

Examples of the water-dispersible resin B include polyolefin resins such as water-dispersible polypropylene resins and water-dispersible polyethylene resins.
The water-dispersible resin B is preferably a water-dispersible polypropylene resin or a water-dispersible polyethylene resin from the viewpoint of making the surface layer of the ink film harder, lowering the coefficient of friction, and further improving fastness to wet rubbing. A water-dispersible polypropylene resin is more preferred.

The melting point of the water-dispersible polyolefin resin is preferably 100° C. or higher, more preferably 120° C. or higher, from the viewpoint of making the surface layer of the ink film harder, lowering the coefficient of friction, and further improving fastness to wet rubbing. It is more preferable to have

Commercial products of the resin emulsion of the water-dispersible resin B include the Arrow Base series manufactured by Unitika Ltd. (“Arrow Base DB-4010”, “Arrow Base TC-4010”, “Arrow Base SB-1010”, “Arrow Base SE -1010” etc. (all product names)), Toyobo Co., Ltd. Hardren series (“Hardren NZ1004”, “Hardren EW5250”, “Hardren EH801J” etc. (all product names)), BYK Chemie Co., Ltd. AQUACER series (all product names) AQUACER272, AQUACER497, AQUACER531, AQUACER537 (all trade names)) and the like.
The water-dispersible resin B may be used alone or in combination of two or more.

The amount of the water-dispersible resin B in the ink is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and more preferably 1% by mass or more, relative to the total amount of the ink. On the other hand, the amount of the water-dispersible resin B in the ink is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, relative to the total amount of the ink. The amount of the water-dispersible resin A in the ink is, for example, preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and even more preferably 1 to 5% by mass, relative to the total amount of the ink.

The total amount of the water-dispersible resin A and the water-dispersible resin B in the ink is 2% by mass or more with respect to the total amount of the ink, from the viewpoint of improving the friction resistance of the ink film and further improving the wet rubbing fastness. is preferred, 5% by mass or more is more preferred, and 10% by mass or more is even more preferred.
The total amount of water-dispersible resin A and water-dispersible resin B in the ink is preferably 20% by mass or less, more preferably 18% by mass or less, relative to the total amount of ink, from the viewpoint of ejection performance from an inkjet printer head. , 15% by mass or less is more preferable.
The total amount of water-dispersible resin A and water-dispersible resin B in the ink is, for example, preferably 2 to 20% by mass, more preferably 5 to 18% by mass, and more preferably 10 to 15% by mass, relative to the total amount of ink. More preferred.

The mass ratio of the amount of the water-dispersible resin B in the ink to the water-dispersible resin A (water-dispersible resin B/water-dispersible resin A) maintains a balance between the water-dispersible resin A and the water-dispersible resin B. From the viewpoint of further improving the wet rubbing fastness, it is preferably 3.0 or less, more preferably 1.5 or less, and even more preferably 0.8 or less.
The mass ratio of the amount of the water-dispersible resin B in the ink to the water-dispersible resin A (water-dispersible resin B/water-dispersible resin A) maintains a balance between the water-dispersible resin A and the water-dispersible resin B. From the viewpoint of further improving the wet rubbing fastness, it is preferably 0.05 or more, more preferably 0.1 or more, and even more preferably 0.2 or more.
The mass ratio of the amount of the water-dispersible resin B in the ink to the water-dispersible resin A (water-dispersible resin B/water-dispersible resin A) is, for example, preferably 0.05 to 3.0, and 0.1 to 1.5 is more preferred, and 0.2 to 0.8 is even more preferred.

Preferably, the ink mainly contains water as the aqueous solvent. Water is not particularly limited, but water containing as few ionic components as possible is preferable. In particular, from the viewpoint of storage stability of the ink, it is preferable that the content of polyvalent metal ions such as calcium is small. Examples of water include ion-exchanged water, distilled water, and ultrapure water.
From the viewpoint of viscosity adjustment, the water content in the ink is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 70% by mass, relative to the total amount of the ink.

The ink preferably contains a water-soluble organic solvent.
As the water-soluble organic solvent, a water-soluble organic solvent that is liquid at room temperature and soluble in water is preferable from the viewpoint of viscosity adjustment and moisturizing effect. For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, 1,3-propanediol, 1,3-butanediol, 1,2-butanediol, 1,2-pentanediol , 1,2-hexanediol, 2-methyl-2-propanol and other lower alcohols; ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, etc. Glycols; glycerin; acetins (monoacetin, diacetin); diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, Triethylene glycol monobutyl ether, tripropylene glycol monobutyl ether, triethylene glycol monohexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, etc. Glycol derivatives; triethanolamine, 1-methyl-2-pyrrolidone, β-thiodiglycol, sulfolane can be used. Polyethylene glycol having an average molecular weight of 200, 300, 400, 600, etc., having an average molecular weight in the range of 190 to 630, Diol-type polypropylene glycol having an average molecular weight, such as an average molecular weight of 400, in a range of 200 to 600, Average molecular weight of 300, 700, etc. A low molecular weight polyalkylene glycol such as a triol type polypropylene glycol having an average molecular weight in the range of 250 to 800 can also be used.

A water-soluble organic solvent can be used individually by 1 type or in combination of 2 or more types.

The water-soluble organic solvent is preferably contained in the ink in an amount of 1 to 80% by mass, more preferably 1 to 60% by mass, based on the total amount of the ink, from the viewpoint of viscosity adjustment and moisturizing effect. For example, it may be from 1 to 50% by weight, or from 5 to 40% by weight.

The total amount of water and water-soluble organic solvent in the ink (if only one of them is included, the amount) is preferably 50% to 95% by mass, more preferably 70% to 90% by mass, based on the total amount of the ink. more preferred.

The ink may contain other components as appropriate. Other components include dispersing aids, surface tension modifiers (surfactants), antioxidants, preservatives, cross-linking agents, and the like.

Any of anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants may be used as the surface tension modifier (surfactant). As the surfactant, for example, either a polymer surfactant or a low-molecular-weight surfactant may be used. As the surfactant, for example, an acetylene-based surfactant such as an acetylene glycol-based surfactant, a silicone-based surfactant, a fluorine-based surfactant, and the like, which will be described later, are preferable.

Addition of a surfactant is preferable because it makes it easier to stably eject the ink in an inkjet method and makes it easier to appropriately control the dot size. The amount added (the total amount when a surfactant is used as a pigment dispersant) varies depending on the type of surfactant, but the surface tension of the ink and the penetration rate into the substrate such as fabric From the viewpoint of , it is preferably in the range of 0.1 to 10% by mass in the ink.

Specifically, as the anionic surfactant, Kao Corporation Emal series (Emal 0, Emal 10, Emal 2F, Emal 40, Emal 20C), Neoperex series (Neoperex GS, Neoperex G-15, Neopelex G-25, Neopelex G-65), Pelex series (Pelex OT-P, Pelex TR, Pelex CS, Pelex TA, Pelex SS-L, Pelex SS-H), Demol series (Demoll N, Demol NL , demo RN, demo MS).
Cationic surfactants include, for example, Kao Corporation Acetamine series (Acetamine 24, Acetamine 86), Cortamine series (Cortamine 24P, Cortamine 86P, Cortamine 60W, Cortamine 86W), Sanizol series (Sanizol C, Sanizol B-50).

Examples of nonionic surfactants include Surfynol series manufactured by Evonik Industries ("Surfinol 104E", "Surfinol 104H", "Surfinol 420", "Surfinol 440", "Surfinol 465", "Surfinol 485" (all trade names)) and Nissin Chemical Co., Ltd. "OLFINE E1004", "OLFINE E1010", "OLFINE E1020" (all trade names) and other acetylenic surfactants (for example, Acetylene glycol-based surfactants, etc.); Emulgen series manufactured by Kao Corporation (“Emulgen 102KG”, “Emulgen 103”, “Emulgen 104P”, “Emulgen 105”, “Emulgen 106”, “Emulgen 108”, “Emulgen 120” , “Emulgen 147”, “Emulgen 150”, “Emulgen 220”, “Emulgen 350”, “Emulgen 404”, “Emulgen 420”, “Emulgen 705”, “Emulgen 707”, “Emulgen 709”, “Emulgen 1108” , "Emulgen 4085", "Emulgen 2025G", etc.), and the like.

Examples of amphoteric surfactants include the Amphithol series manufactured by Kao Corporation ("Amphitol 20BS", "Amphitol 24B", "Amphitol 86B", "Amphitol 20YB", "Amphitol 20N", etc. (all trade names)), and the like. mentioned.

The ink preferably contains a silicone-based surfactant, a fluorine-based surfactant, or a combination thereof from the viewpoint of improving the wettability to the substrate and thereby obtaining a high dot gain.

Examples of silicone-based surfactants include polyether-modified silicone-based surfactants, alkyl/aralkyl-co-modified silicone-based surfactants, acrylic silicone-based surfactants, and the like.
Examples of commercially available silicone-based surfactants include "Silface SAG002", "Silface SAG016", "Silface SAG005", "Silface SAG008", and "Silface SAG503A" manufactured by Nissin Chemical Industry Co., Ltd. etc. (all product names), BYK-331, BYK-348, BYK-349, BYK-378, BYK-3455 (all product names) manufactured by BYK-Chemie Japan Co., Ltd. is mentioned.

Commercially available fluorosurfactants include, for example, Surflon series manufactured by AGC Seimi Chemical Co., Ltd. S242", "Surflon S243", "Surflon S386", "Surflon S611", "Surflon S647", "Surflon S651", etc. (all trade names)), Neos Co., Ltd.'s Ftergent series ("Ftergent 100", " Futergent 150", "Ftergent 400SW", "Ftergent 251", "Ftergent 212M", "Ftergent 710FL", etc. (all trade names)), Megafac series manufactured by DIC Corporation ("Megafac F410") , "Megafac F477", "Megafac F554", "Megafac F556", "Megafac F565", etc. (all trade names)), Sumitomo 3M Co., Ltd. "FC-4430" (trade name), etc. be done.

From the viewpoint of storage stability of the ink, the pH of the ink is preferably 7.0 to 11.0, more preferably 7.0 to 10.0, even more preferably 7.5 to 10, and 7.5 to 9.0. 0 is more preferred.

The viscosity of the ink can be adjusted as appropriate, but from the viewpoint of ejection properties, the viscosity at 23° C. is preferably 1 to 30 mPa·s.

The method for producing the ink is not particularly limited, and the ink can be produced as appropriate by a known method. For example, it can be prepared by putting all the components together or separately into a stirrer such as a three-one motor, dispersing them, and optionally passing them through a filter such as a membrane filter.

The substrate to be printed with the water-based inkjet ink of the present embodiment is not particularly limited. Examples of the base material include printing paper such as plain paper, coated paper, and special paper, fabric, wood base material, metal base material, glass base material, plastic base material, and the like. In addition, any of a stretchable base material such as cloth, a permeable base material such as cloth, plain paper and coated paper, and an impermeable base material such as plastic base material may be used. .
For example, even when a stretchable base material such as a fabric or a non-permeable base material such as a plastic base material is used, printed matter having excellent wet rubbing fastness can be produced.

The fabric is not particularly limited, but any natural and/or synthetic fiber such as cotton, silk, wool, hemp, nylon, polyester, rayon, acetate, and cupra can be used. Fabrics include woven fabrics, knitted fabrics, non-woven fabrics, and the like. Better wet rubfastness and image quality can be obtained in fabrics comprising polyester.

The plastic substrate is not particularly limited, but examples include polyvinyl chloride, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, nitrocellulose, polyethylene terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, (meth) Examples include acrylic resins.

<Manufacturing method of printed matter>
A method for producing a printed matter according to an embodiment is a method for producing a printed matter, including a step of inkjet printing on a base material using the water-based ink for inkjet described above (hereinafter sometimes referred to as an “inkjet printing step”).
According to this method for producing a printed matter, it is possible to produce a printed matter having excellent wet fastness to rubbing.

The base material is not particularly limited, and for example, the base material described as a base material that can be used for inkjet water-based ink can be used. For example, in one embodiment of this method for producing a printed matter, a printed matter may be produced using a fabric as a substrate.

The inkjet printer used in the inkjet printing process may be of any type, such as a piezo system, an electrostatic system, or a thermal system. The ejected ink droplets can be arranged to land on the substrate.

The amount of the ink applied to the substrate is not particularly limited, but it is preferably 500 g/m ² or less, more preferably 100 g/m ² or less, and 50 g/m ² or less per unit area of the substrate. It is even more preferable to have

From the viewpoint of improving image quality, the method for producing printed matter includes a step of applying a pretreatment liquid containing a flocculant to the substrate (hereinafter sometimes referred to as a "pretreatment liquid applying step") before the inkjet printing step. is preferably included.

When the inkjet printing process is performed after the pretreatment liquid application step of applying a pretreatment liquid containing a flocculant, the dots immediately after the ink has landed on the base material are aggregated, preventing the dots from coalescing and improving the image density. can be improved.
The pretreatment liquid can be selected, for example, according to the substrate. Only one pretreatment liquid may be used, or two or more may be used in combination. Also, the application amount can be selected according to the base material.

The pretreatment liquid can contain a flocculating agent.
Examples of flocculants include metal salts, cationic polymers, organic acids and the like. The pretreatment liquid may contain one of these as a flocculating agent, or two or more of them in combination. These aggregating agents may be appropriately selected, for example, in consideration of the type of substrate.

For impermeable substrates such as plastic substrates, the flocculant preferably comprises a cationic polymer, more preferably a polymer of epichlorohydrin and a nitrogen-containing compound as the cationic polymer. .
For example, for permeable substrates such as fabrics, it is preferable that the cohesive force can be maintained even when the pretreatment liquid permeates the substrate. For permeable substrates such as fabrics, flocculants such as metal salts, cationic polymers, organic acids, etc., or combinations thereof, can be used, but a small amount can exhibit excellent cohesion. It is preferred to include a metal salt, more preferably a polyvalent metal salt, because of its tendency to increase.

For example, from the viewpoint of improving image quality, the content of the flocculant in the pretreatment liquid is preferably 0.5% by mass or more, more preferably 1% by mass or more, and 3% by mass or more, relative to the total amount of the pretreatment liquid. is more preferred. The amount of the coagulant in the pretreatment liquid may be, for example, 5% by mass or more or 8% by mass or more with respect to the total amount of the pretreatment liquid.
On the other hand, the content of the coagulant in the pretreatment liquid is preferably 30% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less, relative to the total amount of the pretreatment liquid.
The amount of the flocculant in the pretreatment liquid is, for example, preferably 0.5 to 30% by mass, more preferably 1 to 30% by mass, and even more preferably 1 to 15% by mass, relative to the total amount of the pretreatment liquid. The amount of the flocculant in the pretreatment liquid may be, for example, 3 to 30% by weight, 5 to 15% by weight, or 8 to 12% by weight with respect to the total amount of the pretreatment liquid.

The content of the flocculant in the pretreatment liquid can also be selected in consideration of the type of base material and flocculant. For example, for non-permeable substrates such as plastic substrates, the amount of the flocculant in the pretreatment liquid is preferably 0.5 to 12% by mass, preferably 0.5% by mass, based on the total amount of the pretreatment liquid. ~10% by mass is more preferred. On the other hand, for permeable substrates such as fabric, the amount of the flocculant in the pretreatment liquid is preferably 1 to 15% by mass, more preferably 3 to 12% by mass, based on the total amount of the pretreatment liquid. more preferred.

As metal salts, polyvalent metal salts are preferred.
A polyvalent metal salt is composed of a polyvalent metal ion having a valence of 2 or more and an anion. Examples of polyvalent metal ions having a valence of 2 or more include Ca ²⁺ , Mg ²⁺ , Cu ²⁺ , Ni ²⁺ , Zn ²⁺ and Ba ²⁺ . Examples of anions include Cl ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , I ⁻ , Br ⁻ and ClO ₃ ⁻ . Specific examples of salts include calcium chloride, calcium nitrate, magnesium nitrate, copper nitrate, calcium acetate, magnesium acetate and the like.

These metal salts may be used individually by 1 type, or may be used in mixture of multiple types.
The concentration of the metal salt in the pretreatment liquid is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, for example, 5% by mass or more. There may be. The concentration of metal salts such as polyvalent metal salts in the pretreatment liquid is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and 15% by mass with respect to the total amount of the pretreatment liquid. The following are more preferable, and 12% by mass or less is even more preferable. The concentration of metal salts such as polyvalent metal salts in the pretreatment liquid is, for example, preferably 0.5 to 30% by mass, more preferably 1 to 25% by mass, and 1 to 20% by mass, relative to the total amount of the pretreatment liquid. % is more preferred, and 1-15% by weight is more preferred, for example, it may be 3-12% by weight, or 5-12% by weight.

The cationic polymer may be either a cationic water-soluble resin or a cationic water-dispersible resin, or a combination thereof.

Cationic polymers include, for example, polyvinylamine, polyallylamine and salts thereof, copolymers of acrylamide, and the like.
Specifically, the cationic polymer is preferably, for example, a polymer of epichlorohydrin and a nitrogen-containing compound, polydiallyldimethylammonium chloride, or the like.

In the polymer of epichlorohydrin and a nitrogen-containing compound, the nitrogen-containing compound is not particularly limited, and examples thereof include amine compounds and ammonia. Only one nitrogen-containing compound may be used, or two or more of them may be used in combination. The amine compound is not particularly limited, and examples thereof include monoalkylamines, dialkylamines, and the like. The nitrogen-containing compound is preferably an amine compound, ammonia, or a combination thereof, and more preferably a dialkylamine such as dimethylamine, ammonia, or a combination thereof.
A polymer of epichlorohydrin and a nitrogen-containing compound may be a polymer having a structure derived from epichlorohydrin, a structure derived from a nitrogen-containing compound, and optionally other structures. The polymer of epichlorohydrin and the nitrogen-containing compound preferably contains one or more structural units having a condensed structure of epichlorohydrin and the nitrogen-containing compound, and if necessary, structural units derived from other compounds, etc. may further contain other structural units.

Specific examples of the polymer of epichlorohydrin and a nitrogen-containing compound include dimethylamine-epichlorohydrin polymer and dimethylamine-ammonia-epichlorohydrin polymer.

Examples of commercially available cationic polymers include Sharoll series manufactured by Daiichi Kogyo Seiyaku Co., Ltd. ("Sharoll DC-303P", "Sharoll DC-902P", etc. (both trade names)), Superflex series (" Super Flex 620", "Super Flex 650", etc. (all product names)), Senka Co., Ltd.'s Unisense series ("Unisense FCA1000L", "Unisense FPA100L", "Unisense KHE100L", "Unisense KHE104L", etc. (all are product names). Product name)), SNF FLOQUAT series (“FLOQUAT FL2250”, “FLOQUAT FL2350”, “FLOQUAT FL2550”, “FLOQUAT FL2650”, “FLOQUAT FL2850” etc. (all product names), Hymo “Himax SC -506” etc., Yokkaichi Gosei Co., Ltd. Catiomaster series (“Catiomaster PD-7”, “Catiomaster PD-30”, “Catiomaster PDT-2) etc. (all trade names)), Osaka Organic Chemical Industry Co., Ltd. HC polymer series ("HC polymer 1S", "HC polymer 1N", "HC polymer 1NS", "HC polymer 2", "HC polymer 2L", etc. (all trade names)), and the like.

Examples of cationic polymers also include cationic water-dispersible resins. The cationic water-dispersible resin is a positively charged resin particle whose surface is positively charged. It is capable of forming an emulsion. The resin may have a cationic functional group present on the particle surface like a self-emulsifying resin, or may be surface-treated such as by attaching a cationic dispersant to the resin particle surface. Cationic functional groups are typically primary, secondary or tertiary amino groups, pyridine groups, imidazole groups, benzimidazole groups, triazole groups, benzotriazole groups, pyrazole groups, benzopyrazole groups, etc. and the cationic dispersant is a primary, secondary, tertiary or quaternary amino group-containing acrylic polymer, polyethyleneimine, cationic polyvinyl alcohol resin, cationic water-soluble multi-branched polyester amide resin, and the like. Examples of cationic water-dispersible resins include ethylene-vinyl chloride copolymer resins, (meth)acrylic resins, styrene-maleic anhydride copolymer resins, urethane resins, vinyl acetate-(meth)acrylic copolymer resins, In vinyl acetate-ethylene copolymer resins and resin emulsions thereof, a cationic functional group is introduced into these resins, or the surface is treated with a cationic dispersant or the like to give a positive surface charge. can be used.

A cationic polymer may be used individually by 1 type, or may be used in mixture of multiple types.
The content of the cationic polymer in the pretreatment liquid is preferably 0.5% by mass or more, more preferably 1% by mass or more, relative to the total amount of the pretreatment liquid. The content of the cationic polymer in the pretreatment liquid is preferably 20% by mass or less, more preferably 12% by mass or less, and even more preferably 10% by mass or less, relative to the total amount of the pretreatment liquid. The content of the cationic polymer in the pretreatment liquid is, for example, preferably 0.5 to 20% by mass, more preferably 0.5 to 12% by mass, and 0.5 to 10% by mass, relative to the total amount of the pretreatment liquid. % is more preferable, and 1 to 10% by mass is more preferable.

Organic acids include formic acid, acetic acid, oxalic acid, citric acid, malic acid, ascorbic acid and the like. Among them, an organic acid that is liquid at 23°C is preferable, and examples of the organic acid that is liquid at 23°C include acetic acid and lactic acid.

From the viewpoint of further improving the wet rubbing fastness, the flocculant is preferably a liquid such as an organic acid. By applying the flocculant to the substrate surface as a liquid, it is possible to reduce the influence of friction. In addition, when the pretreatment liquid is applied by an inkjet method, when a liquid such as an organic acid is used as a coagulant, ejection failure of the inkjet head is unlikely to occur even when used for a long period of time, and good ejection properties can be obtained. tends to be easy.

The organic acid contained in the pretreatment liquid is preferably an organic acid having a boiling point of 120° C. or higher.
In the inkjet printing process, the ink-filled head performs printing while moving over the base material to which the pretreatment liquid has been applied. When an organic acid with a boiling point of 120°C or higher is used, the organic acid is less likely to volatilize from the base material to which the pretreatment liquid has been applied. Hard to happen. For this reason, it is possible to suppress ejection failure of ink from the inkjet head, and it is also possible to reduce the frequency of maintenance of the inkjet head.

An organic acid may be used individually by 1 type, or may be used in mixture of multiple types.
From the viewpoint of improving image quality, the content of the organic acid in the pretreatment liquid is preferably 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, based on the total amount of the pretreatment liquid. % by mass or more is more preferable. On the other hand, the content of the organic acid in the pretreatment liquid is preferably 30% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less, relative to the total amount of the pretreatment liquid. The amount of the organic acid in the pretreatment liquid is, for example, preferably 1 to 30% by mass, preferably 3 to 30% by mass, based on the total amount of the pretreatment liquid, from the viewpoint of forming high image quality even with a substrate having low hydrophilicity. More preferably, 5 to 15% by mass, even more preferably 8 to 12% by mass.

The pretreatment liquid preferably contains water and/or a water-soluble organic solvent.
For example, the pretreatment liquid preferably contains mainly water as an aqueous solvent. Examples of water include, but are not particularly limited to, ion-exchanged water, distilled water, ultrapure water, and the like.
Water is preferably contained in the pretreatment liquid in an amount of, for example, 30% by mass or more, more preferably 40% by mass or more, relative to the total amount of the pretreatment liquid. In one embodiment, the water content in the pretreatment liquid is preferably 50% by mass or more, more preferably 65% by mass or more, relative to the total amount of the pretreatment liquid. The content of water in the pretreatment liquid may be, for example, 95% by mass or less, or may be 90% by mass or less, relative to the total amount of the pretreatment liquid. The amount of water in the pretreatment liquid may be, for example, 30 to 95% by weight, 40 to 95% by weight, 50 to 95% by weight, or 65 to 90% by weight with respect to the total amount of the pretreatment liquid.

The pretreatment liquid preferably contains a water-soluble organic solvent. As the water-soluble organic solvent, for example, one or more of the same solvents as those usable for ink can be selected and used.

The amount of the water-soluble organic solvent in the pretreatment liquid is, for example, preferably 1% by mass or more, more preferably 5% by mass or more, relative to the total amount of the pretreatment liquid. In one embodiment, the amount of the water-soluble organic solvent is, for example, preferably 30% by mass or more, more preferably 40% by mass or more, relative to the total amount of the pretreatment liquid.
The amount of the water-soluble organic solvent in the pretreatment liquid may be, for example, 80% by mass or less, 70% by mass or less, and preferably 60% by mass or less, relative to the total amount of the pretreatment liquid. In one embodiment, the amount of water-soluble organic solvent in the pretreatment liquid may be, for example, 40% by weight or less or 20% by weight or less.
The amount of the water-soluble organic solvent in the pretreatment liquid is, for example, preferably 1 to 80% by mass, more preferably 1 to 70% by mass, and even more preferably 5 to 60% by mass, relative to the total amount of the pretreatment liquid.
In one embodiment, the amount of the water-soluble organic solvent in the pretreatment liquid is, for example, preferably 1 to 40% by mass, more preferably 5 to 20% by mass, relative to the total amount of the pretreatment liquid.
In one embodiment, the amount of the water-soluble organic solvent in the pretreatment liquid is, for example, preferably 30 to 80% by mass, more preferably 40 to 70% by mass, and 40 to 60% by mass, relative to the total amount of the pretreatment liquid. is more preferred.

When the pretreatment liquid contains water and/or a water-soluble organic solvent, the total amount of water and water-soluble organic solvent in the pretreatment liquid 50% by mass or more is preferable, and 70% by mass or more is more preferable with respect to the total amount of the liquid. On the other hand, the total amount of water and water-soluble organic solvent in the pretreatment liquid may be, for example, 99% by mass or less with respect to the total amount of the pretreatment liquid. The total amount of water and water-soluble organic solvent in the pretreatment liquid may be, for example, 50 to 99% by mass or 70 to 99% by mass with respect to the total amount of the pretreatment liquid.

The pretreatment liquid may contain other components such as surfactants, antifoaming agents, pH adjusters, antioxidants, preservatives, etc., if necessary. As for these, one or more of the same substances as those usable for the ink can be selected and used.

As the surfactant, for example, acetylene-based surfactants such as acetylene glycol-based surfactants, silicone-based surfactants, fluorine-based surfactants, and the like are preferable.
From the viewpoint of improving image density, the surfactant more preferably contains a silicone-based surfactant, a fluorine-based surfactant, or a combination thereof. By improving the wettability to the substrate, a high dot gain can be achieved, thereby improving the image density.

The amount of the surfactant in the pretreatment liquid varies depending on the type of surfactant, but from the viewpoint of the surface tension of the pretreatment liquid and the rate of penetration into the substrate, it is 0.1 to 0.1 in the pretreatment liquid. It is preferably in the range of 10% by mass.

The method for producing the pretreatment liquid is not particularly limited, and it can be produced as appropriate by a known method. For example, it can be prepared by putting all the components together or separately into a stirrer such as a three-one motor, dispersing them, and optionally passing them through a filter such as a membrane filter.

The pretreatment liquid is preferably applied to at least the area of the substrate where the ink is printed in the inkjet printing process (hereinafter sometimes referred to as "printing area"), and is applied to the entire surface of the substrate including the printing area. may
The method of applying the pretreatment liquid in the pretreatment liquid application step is not particularly limited, and any method such as a spray method (e.g., an airbrush), an immersion method, a pad method, a coating method, or the like can be used. A printing method, a screen printing method, or the like may be used.
Examples of inkjet printers that can be used in the case of the inkjet method include those described in the above-described inkjet printing process.

The amount of the pretreatment liquid applied to the base material may be, for example, 0.5 g/m ² or more, preferably 2 g/m ² or more, and more preferably 5 g/m ² or more per unit area of the base material. On the other hand, the amount of the pretreatment liquid applied to the substrate is preferably 100 g/m ² or less, more preferably 50 g/m ² or less, for example, 20 g/m ² or less per unit area of the substrate. good too. The amount of the pretreatment liquid applied to the substrate may be, for example, 0.5 to 100 g/m ² , 2 to 50 g/m ² , or 5 to 20 g/m ² per unit area of the substrate.
The amount of the pretreatment liquid to be applied to the base material may be appropriately determined in consideration of the type of the base material. For example, when fabric is used as the substrate, the amount of the pretreatment liquid applied to the substrate is preferably 5 to 100 g/m ² , more preferably 10 to 50 g/m ² per unit area of the substrate. On the other hand, for example, when a non-permeable substrate such as a plastic substrate is used as the substrate, the amount of the pretreatment liquid applied to the substrate is, for example, 1 to 50 g/m ² per unit area of the substrate. is preferred, and 1 to 20 g/m ² is more preferred.

From the viewpoint of further improving the wet rubbing fastness, the method for producing printed matter includes a step of applying a post-treatment liquid containing a resin to the substrate after the inkjet printing process (hereinafter sometimes referred to as a "post-treatment liquid applying step". .) is preferably included. For example, when a non-permeable base material such as a plastic base material is used as the base material, it is preferable to perform the step of applying the post-treatment liquid.

The post-treatment liquid preferably contains a resin from the viewpoint of improving fixability. The resin contained in the post-treatment liquid preferably contains a urethane resin, an olefin resin, or a combination thereof. When the post-treatment liquid contains a urethane resin and/or an olefin resin, which are resins having the same skeleton as the resin contained in the ink, affinity with the ink is improved, and fixing can be facilitated.
Examples of urethane resins include polyether-type urethane resins containing ether bonds in the main chain, polyester-type urethane resins containing ester bonds in the main chain, and polycarbonate-type urethane resins containing carbonate bonds in the main chain.
Examples of olefin resins include polypropylene resins and polyethylene resins.

The resin contained in the post-treatment liquid may be a water-soluble resin, a water-dispersible resin, or a combination thereof, but preferably contains a water-dispersible resin. The water-dispersible resin may be a self-emulsifying type into which a hydrophilic component necessary for stable dispersion in water is introduced, or may be water-dispersible by using an external emulsifier. The water-dispersible resin can be blended, for example, as an oil-in-water resin emulsion when producing the post-treatment liquid.

From the viewpoint of improving wet rubbing fastness, the resin contained in the post-treatment liquid is preferably a resin capable of reacting with the flocculant contained in the pre-treatment liquid. From this point of view, when a pretreatment liquid containing a metal salt, a cationic polymer, an organic acid, or a combination thereof is used, the resin contained in the posttreatment liquid is preferably an anionic resin.

Commercially available examples of resin emulsions of anionic urethane resins include, for example, the Superflex series (“Superflex 210” (trade name), etc.) manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like.

The resin content in the post-treatment liquid is preferably 1% by mass or more, more preferably 3% by mass or more, relative to the total amount of the post-treatment liquid. The content of the resin in the post-treatment liquid is, for example, preferably 30% by mass or less, more preferably 20% by mass or less, relative to the total amount of the post-treatment liquid. The content of the resin in the post-treatment liquid is, for example, preferably 1 to 30% by mass, more preferably 3 to 20% by mass, relative to the total amount of the post-treatment liquid.

The post-treatment liquid preferably contains water and/or a water-soluble organic solvent.
For example, the post-treatment liquid preferably contains mainly water as a solvent. Examples of water include, but are not particularly limited to, ion-exchanged water, distilled water, ultrapure water, and the like.
The water content in the post-treatment liquid is preferably 10% by mass or more, more preferably 30% by mass or more, relative to the total amount of the post-treatment liquid. The content of water in the post-treatment liquid is, for example, preferably 80% by mass or less, more preferably 60% by mass or less, relative to the total amount of the post-treatment liquid. The amount of water in the post-treatment liquid is, for example, preferably 10 to 80% by mass, more preferably 30 to 60% by mass, relative to the total amount of the post-treatment liquid.

The post-treatment liquid preferably contains a water-soluble organic solvent. As the water-soluble organic solvent, for example, one or more of the same solvents as those usable for ink can be selected and used.
The amount of the water-soluble organic solvent in the post-treatment liquid is, for example, preferably 10% by mass or more, more preferably 30% by mass or more, relative to the total amount of the post-treatment liquid. The amount of the water-soluble organic solvent in the post-treatment liquid is, for example, preferably 80% by mass or less, preferably 60% by mass or less, relative to the total amount of the post-treatment liquid. The amount of the water-soluble organic solvent in the post-treatment liquid is, for example, preferably 10 to 80% by mass, more preferably 30 to 60% by mass, relative to the total amount of the post-treatment liquid.

When the post-treatment liquid contains water and/or a water-soluble organic solvent, the total amount of water and water-soluble organic solvent in the post-treatment liquid It is preferably 50% by mass or more, more preferably 70% by mass or more, relative to the total amount of the liquid. On the other hand, the total amount of water and water-soluble organic solvent in the pretreatment liquid may be, for example, 99% by mass or less with respect to the total amount of the pretreatment liquid. The total amount of water and water-soluble organic solvent in the pretreatment liquid may be, for example, 50 to 99% by mass or 70 to 99% by mass with respect to the total amount of the pretreatment liquid.

The post-treatment liquid may contain other components such as surfactants, antifoaming agents, pH adjusters, antioxidants, preservatives, etc., if necessary. As for these, one or more of the same substances as those usable for the ink can be selected and used.

As the surfactant, for example, acetylene-based surfactants such as acetylene glycol-based surfactants, silicone-based surfactants, and fluorine-based surfactants are preferable.
From the viewpoint of improving image density, the surfactant more preferably contains a silicone-based surfactant, a fluorine-based surfactant, or a combination thereof. The image density can be improved by improving the wettability to the substrate.

The amount of the surfactant in the post-treatment liquid varies depending on the type of surfactant, but from the viewpoint of the surface tension of the post-treatment liquid, etc., it should be in the range of 0.1 to 10% by mass in the post-treatment liquid. is preferred.

The method for producing the post-treatment liquid is not particularly limited, and the post-treatment liquid can be produced as appropriate by a known method. For example, it can be prepared by putting all the components together or separately into a stirrer such as a three-one motor, dispersing them, and optionally passing them through a filter such as a membrane filter.

The post-treatment liquid is preferably applied to at least the printed area of the substrate, and may be applied to the entire surface of the substrate including the printed area.
The method of applying the post-treatment liquid in the step of applying the post-treatment liquid is not particularly limited, and can be appropriately selected, for example, from the examples of the method of applying the pre-treatment liquid. The amount of the post-treatment liquid to be applied to the substrate is, for example, preferably 1 to 50 g/m ² , more preferably 5 to 20 g/m ² per unit area of the substrate.

It is preferable that the printed matter manufacturing method includes a step of heating the substrate (hereinafter sometimes referred to as a heating step) after the inkjet printing step. As a result, the ink is dried, and the water-dispersible resin is formed into a film, making it easy to form a strong ink film.
When the method for producing a printed matter includes a post-treatment liquid application step of applying a post-treatment liquid to the substrate after the inkjet printing step, the heating step is preferably performed after the post-treatment liquid application step.

The heating temperature in the heating step for heating the substrate performed after the inkjet printing step is preferably 60° C. or higher, more preferably 80° C. or higher, further preferably 100° C. or higher, from the viewpoint of improving wet fastness to rubbing. °C or more is more preferable. The heating temperature in this heating step may be, for example, 150° C. or higher. On the other hand, the heating temperature in this heating step is preferably 200° C. or less from the viewpoint of improving wet fastness to rubbing. The heating temperature in this heating step is, for example, preferably 60 to 200°C, more preferably 80 to 200°C, still more preferably 100 to 200°C, still more preferably 130 to 200°C, for example, 150 to 200°C. good too. For example, if the heating temperature in this heating step is 150° C. or higher, the leveling of the polyolefin resin proceeds and the area covered by the ink film increases, so that the effect of friction can be further reduced. If the heating temperature in this heating step is 200° C. or less, damage to the substrate due to heating is likely to be alleviated.

The method for producing a printed matter may include a step of drying the pretreatment liquid, such as a step of heating the substrate, between the pretreatment liquid application step and the inkjet printing step. However, in the printed matter manufacturing method of the present embodiment, by using the above-described ink and pretreatment liquid, a pretreatment liquid such as a step of heating the base material is added between the pretreatment liquid application step and the inkjet printing step. Excellent image quality and fastness to wet rubbing can be obtained even when the ink is printed on the base material in which the pretreatment liquid is not yet dried without performing the drying step.
The method of manufacturing printed matter may include other steps, such as other processing steps.

<Ink set>
An ink set of an embodiment includes the above-described water-based inkjet ink and a pretreatment liquid containing a coagulant. The water-based inkjet ink is as described above, and the pretreatment liquid can be the one described as the pretreatment liquid that can be used in the above-described method for producing a printed matter.
The ink set may further include, for example, the post-treatment liquid described above.
The ink set may include, for example, other inks and/or other treatment liquids.

Although the present disclosure includes the following embodiments, the present invention is not limited to the embodiments described below.
<1> A water-based inkjet ink containing a coloring material, a water-dispersible urethane resin having a film elongation of 600% or more, a water-dispersible polyolefin resin, and water.
<2> The aqueous inkjet ink according to <1>, wherein the water-dispersible polyolefin resin contains a water-dispersible polypropylene resin.
<3> The water-based inkjet ink according to <1> or <2>, wherein the water-dispersible polyolefin resin contains a water-dispersible polyolefin resin having a melting point of 100° C. or higher.

<4> A method for producing a printed matter, comprising a step of inkjet printing onto a substrate using the aqueous inkjet ink according to any one of <1> to <3>.
<5> The method for producing a printed matter according to <4>, further comprising the step of applying a pretreatment liquid containing a flocculant to the substrate before the step of inkjet printing.
<6> The method for producing printed matter according to <5>, wherein the flocculant contains an organic acid, a metal salt, a cationic polymer, or a combination thereof.
<7> The method for producing a printed matter according to <6>, wherein the cationic polymer contains a polymer of epichlorohydrin and a nitrogen-containing compound.
<8> The method for producing a printed matter according to any one of <4> to <7>, further comprising applying a resin-containing post-treatment liquid to the substrate after the inkjet printing step.
<9> An ink set comprising the inkjet water-based ink according to any one of <1> to <3> and a pretreatment liquid containing a flocculant.
<10> The ink set according to <9>, further comprising a post-treatment liquid containing a resin.

<A1> A water-based pigment ink for textile inkjet printing, containing a pigment, a water-dispersible urethane resin having a film elongation of 600% or more, a water-dispersible polyolefin resin, and water.
<A2> The water-based pigment ink for textile inkjet printing according to <A1>, wherein the water-dispersible polyolefin resin contains a water-dispersible polypropylene resin.
<A3> The aqueous pigment ink for textile inkjet printing according to <A1> or <A2>, wherein the water-dispersible polyolefin resin contains a water-dispersible polyolefin resin having a melting point of 100° C. or higher.

<A4> A method for producing a printed material, comprising a step of inkjet printing onto a fabric using the water-based pigment ink for textile inkjet printing according to any one of <A1> to <A3>.
<A5> The method for producing a printed material according to <A4>, further including a step of heating the fabric at a temperature of 100° C. or higher after the step of inkjet printing.
<A6> The method for producing a printed material according to <A5>, wherein the fabric is heated at a temperature of 150°C to 200°C in the heating step.
<A7> The method for producing a printed material according to any one of <A4> to <A6>, further comprising a step of applying a pretreatment liquid containing a flocculant to the fabric before the step of inkjet printing. .
<A8> The method for producing a printed material according to <A7>, wherein the flocculant contains an organic acid.
<A9> The method for producing a printed material according to <A8>, wherein the organic acid has a boiling point of 120° C. or higher.
<A10> The method for producing a printed material according to <A8> or <A9>, wherein the content of the organic acid is 3 to 30% by mass with respect to the total amount of the pretreatment liquid.
<A11>
The method for producing a printed material according to any one of <A7> to <A10>, which does not include a step of heating the fabric between the step of applying the pretreatment liquid and the step of inkjet printing. .
<A12> An ink set comprising the aqueous pigment ink for textile inkjet printing according to any one of <A1> to <A3> and a pretreatment liquid containing a flocculant.

The disclosure of Japanese Patent Application No. 2018-205138 is incorporated herein by reference in its entirety.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited only to these examples. "%" means "% by mass" unless otherwise specified. The blending amount of each component in the table is also shown in "% by mass".

<Test piece>
A test piece 1 was obtained by cutting a 100% cotton fabric into a size of 210 mm×74 mm.
A test piece 2 was obtained by cutting a 100% polyester fabric into a size of 210 mm×74 mm.
A test piece 3 was obtained by cutting a polyethylene terephthalate (PET) film (“CF300” manufactured by Sakurai Co., Ltd.) into a size of 210 mm×74 mm.
A test piece 4 was prepared by cutting a polyvinyl chloride sheet (“GIY-11Z5” manufactured by Lintec Co., Ltd.) into a size of 210 mm×74 mm.

<Preparation of inks 1 to 18>
The raw materials listed in Tables 1-5 were mixed and stirred for 1 minute with a three-one motor at a speed of 100 rpm. After stirring, the mixture was filtered through a 0.8 μm membrane filter to obtain inks 1-18. The blending amount of each raw material in Tables 1 to 5 is shown in % by mass. The blending amount of each raw material in Tables 1 to 5 is the amount including the volatile matter for the component containing the volatile matter.

Raw materials listed in Tables 1 to 5 are as follows.
Pigment dispersion: "CAB-O-JET300" (carbon black dispersion manufactured by Cabot Corporation)
Water-dispersible urethane resin 1: “Impranil DLP-R” (water-based resin emulsion of water-dispersible urethane resin, manufactured by Sumika Covestro Urethane Co., Ltd.)
Water-dispersible urethane resin 2: “Impranil DL1537” (water-based resin emulsion of water-dispersible urethane resin, manufactured by Sumika Covestro Urethane Co., Ltd.)
Water-dispersible urethane resin 3: "Superflex 130" (water-based resin emulsion of water-dispersible urethane resin, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Water-dispersible polyolefin resin 1: "Arrowbase DB-4010" (water-based resin emulsion of water-dispersible polypropylene resin, manufactured by Unitika Ltd.)
Water-dispersible polyolefin resin 2: "Arrowbase TC-4010" (water-based resin emulsion of water-dispersible polypropylene resin, manufactured by Unitika Ltd.)
Water-dispersible polyolefin resin 3: "Arrowbase SB-1010" (resin emulsion of water-dispersible polyethylene resin, manufactured by Unitika Ltd.)
Water-dispersible polyolefin resin 4: "Arrowbase SE-1010" (resin emulsion of water-dispersible polyethylene resin, manufactured by Unitika Ltd.)
Water-dispersible polyester resin: "Elitel KT-8803" (water-based resin emulsion of water-dispersible polyester resin, manufactured by Unitika Ltd.)

Cross-linking agent: "Carbodilite SV02" (carbodiimide, manufactured by Nisshinbo Chemical Co., Ltd.)
Surfactant 1: "Surfinol 485" (acetylene glycol-based surfactant, manufactured by Evonik Industries)
Surfactant 2: "Silface SAG002" (silicone-based surfactant, manufactured by Nissin Chemical Industry Co., Ltd.)
Surfactant 3: "Surflon S243" (fluorosurfactant, manufactured by AGC Seimi Chemical Co., Ltd.)
Water-soluble organic solvent 1: Triethylene glycol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Water-soluble organic solvent 2: Glycerin, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Water-soluble organic solvent 3: Diethylene glycol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.

The film elongation of the water-dispersible urethane resin described in the table below is the value obtained as follows.
A water-dispersible urethane resin is applied to a polytetrafluoroethylene sheet so that the film thickness after drying is 500 μm, dried at 23° C. for 15 hours, further dried at 80° C. for 6 hours, and 120° C. for 20 minutes. After drying, the film was peeled off from the sheet to prepare a resin film.
Using a Tensilon universal testing machine RTC-1225A (manufactured by Orientec Co., Ltd.), the obtained resin film is stretched at a measurement temperature of 20 ° C. and a measurement speed of 200 mm / min, and the length stretched until the resin film breaks. It was measured and its ratio to the original length was expressed as the coating elongation in percent.

<Examples 1 to 11 and Comparative Examples 1 to 7>
A. Production of Prints For Examples 1-11 and Comparative Examples 1-7, prints were made as follows.
Examples 1-7 and Comparative Examples 1-4 used the test piece 1, and Examples 8-11 and Comparative Examples 5-7 used the test piece 3. A single-color solid image was printed on the test piece using an ink jet printer MMP813BT-3 manufactured by Mastermind Co., Ltd. using the inks described in Tables 1-5. The ink application amount was about 20 g/m ² .
For Examples 1-7 and Comparative Examples 1-4, after printing, the specimens were heated at 180° C. for 60 seconds using a Hotronix Fusion heat press. In Examples 8-11 and Comparative Examples 5-7, after printing, the test pieces were heated at 110° C. for 120 seconds using a constant temperature bath.
In this manner, prints of Examples 1-11 and Comparative Examples 1-7 were obtained.

B. Evaluation (fastness to wet rubbing)
The wet rubbing fastness of the prints of Examples 1 to 11 and Comparative Examples 1 to 7 prepared as described above was evaluated as follows. The results are shown in Tables 1-5.
For Examples 1 to 7 and Comparative Examples 1 to 4, Gakushin Tester RT-200 (manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.) was used, 100% cotton white cloth Kanakin No. 3 was attached, and test piece 1 ( For the prints of Examples 1 to 7 and Comparative Examples 1 to 4 using the permeable substrate), 100 reciprocating rubbings were performed without weight, and the test piece 3 (non-permeable substrate) Example 8 11 and Comparative Examples 5 to 7 were rubbed back and forth 25 times without a weight. The white cloth was used after being moistened with the same weight of ion-exchanged water as the white cloth.
The discoloration and fading of the printed material after rubbing was evaluated by the grayscale for discoloration and fading specified in JIS L 0849, and the results were evaluated according to the following criteria.
S: Grade 3 or higher A: Grade 2-3 B: Grade 2 C: Grade 1-2 or lower

<Preparation of pretreatment liquid>
The raw materials listed in Tables 6 and 7 were mixed and stirred with a three-one motor at a speed of 100 rpm for 1 minute. After stirring, the mixture was filtered through a 0.8 μm membrane filter to obtain pretreatment solutions 1-7. The blending amount of each raw material in Tables 6 and 7 is shown in % by mass. The blending amount of each raw material in Tables 6 and 7 is the amount including the volatile matter for the components containing the volatile matter.

The raw materials listed in Tables 6 and 7 are as follows.
Organic acid 1: lactic acid, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Organic acid 2: acetic acid, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Metal salt 1: calcium chloride, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Cationic polymer 1: Unisense KHE100L” (dimethylamine-ammonia-epichlorohydrin polymer aqueous solution, manufactured by Senka Co., Ltd.)
Surfactant 3: "Surflon S243" (fluorosurfactant, manufactured by AGC Seimi Chemical Co., Ltd.)
Water-soluble organic solvent 2: Glycerin, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Water-soluble organic solvent 3: Diethylene glycol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.

<Preparation of Inks 19 and 20>
The raw materials listed in Table 8 were mixed and stirred with a three-one motor at a speed of 100 rpm for 1 minute. After stirring, the mixture was filtered through a 0.8 μm membrane filter to obtain Inks 19 and 20. The blending amount of each raw material in Table 8 is shown in % by mass. The blending amount of each raw material in Table 8 is the amount including the volatile matter for the component containing the volatile matter. Inks 1, 19 and 20 listed in Table 8 were used in Examples 12 to 28. Of these, Ink 1 was the ink 1 used in Example 1 listed in Table 1. be.

The details of each raw material listed in Table 8 are the same as those listed in Tables 1-5.

<Production of post-treatment liquid>
The raw materials listed in Table 9 were mixed and stirred with a three-one motor at a speed of 100 rpm for 1 minute. After stirring, the mixture was filtered through a 0.8 μm membrane filter to obtain post-treatment liquid 1. The blending amount of each raw material in Table 9 is shown in % by mass. The blending amount of each raw material in Table 9 is the amount including the volatile matter for the component containing the volatile matter.

The raw materials listed in Table 9 are as follows.
Resin 1: "Superflex 210" (water-based resin emulsion of anionic water-dispersible urethane resin, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Surfactant 1: "Surfinol 485" (acetylene glycol-based surfactant, manufactured by Evonik Industries)
Water-soluble organic solvent 2: Glycerin, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. Water-soluble organic solvent 3: Diethylene glycol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.

<Examples 12 to 28>
A. Preparation of Prints The prints of Examples 12-28 were made as follows.

For Examples 12 to 18, the pretreatment liquids shown in Tables 10 to 11 were uniformly applied to the test pieces shown in Tables 10 to 11 using an airbrush manufactured by Airtex Co., Ltd. For Examples 12 to 18, the application amount of the pretreatment liquid was 20 g/m ² . For Examples 21 to 28, the pretreatment liquids shown in Tables 12 to 13 were uniformly applied to the test pieces shown in Tables 12 to 13 using an inkjet printer MMP813BT-3 manufactured by Mastermind. For Examples 21 to 28, the amount of pretreatment liquid applied was 20 g/m2 for test pieces 1 and 2 (permeable substrate), and 5 g/ ^m2 for test pieces 3 and 4 (non-permeable substrate). ^m2 . This step is referred to as step 1.

Of these, for Examples 12 to 17 and 21 to 28, after step 1, a single-color solid image was printed using the inks shown in Tables 10 to 13 with an inkjet printer MMP813BT-3 manufactured by Mastermind. . The ink application amount was about 20 g/m ² . This step is referred to as step 2.
For Examples 12-17, after printing (ie after step 2), the specimens were heated using a Hotronix Fusion heat press for 60 seconds. The heating temperature was 180° C. for Examples 12 and 14 to 17, and 120° C. for Example 13.
For Examples 21-26 and 28, after printing (ie after step 2), the specimens were heated at 110° C. for 120 seconds using a constant temperature bath.
In Example 27, after printing (that is, after step 2), post-treatment liquid 1 was applied using an inkjet printer MMP813BT-3 manufactured by Mastermind. The application amount of the post-treatment liquid 1 was 10 g/m ² . After applying the post-treatment liquid 1, the test piece was heated at 110° C. for 120 seconds using a constant temperature bath.
Thus, prints of Examples 12-17 and 21-28 were obtained.

For Example 18, after step 1, the specimen is heated at 180° C. for 60 seconds using a Hotronix Fusion heat press to dry the pretreatment liquid before step 2, i.e., Mastermind ink jet printer MMP813BT-3 A single color solid image was printed using the inks listed in the table. The ink application amount was about 20 g/m ² . After printing, the specimens were heated at 180° C. for 60 seconds using a Hotronix Fusion heat press. Thus, a printed matter of Example 18 was obtained.

The printed matter of Example 19 was produced in the same manner as in Example 1.
A printed matter of Example 20 was produced in the same manner as in Example 19, except that Test Piece 2 (100% polyester fabric) was used instead of Test Piece 1 (100% cotton fabric).
Therefore, in Examples 19 and 20 step 1 was not performed.

B. Evaluation (fastness to wet rubbing, image quality, ink jettability)
1. Wet Rubbing Fastness The wet rubbing fastness of the prints of Examples 12-28 prepared as described above was evaluated in the same manner as in Examples 1-11 and Comparative Examples 1-7. As in the evaluation of the wet rubbing fastness in Examples 1 to 11 and Comparative Examples 1 to 7, the printed material using the test piece 1 or 2 (permeable substrate) was rubbed 100 times reciprocatingly without weight. , The printed matter using test piece 3 or 4 (impermeable substrate) was rubbed back and forth 25 times without a weight. The results are shown in Tables 10-13.

2. Image Quality The image quality of the prints of Examples 12 to 28 produced as described above was evaluated as follows. The results are shown in Tables 10-13.
The OD value of the printed matter was measured using a spectrophotometer X-Rite eXact (manufactured by X-Rite) and evaluated according to the following criteria.
S: OD value 1.5 or more A: OD value 1.4 or more and less than 1.5 B: OD value 1.2 or more and less than 1.4 C: OD value 1.1 or more and less than 1.2 D: OD value 1.1. less than 1

3. Ejectability of ink from inkjet head In the production of printed matter in Examples 12 to 18, the test piece to which the pretreatment liquid was applied or the test piece to which heating was performed after the pretreatment liquid was applied (specifically , in Examples 12 to 17, the test piece on which step 1 was performed, and in Example 18, the test piece heated at 180 ° C. for 60 seconds after step 1), 5 A4 size single-color solid images Sheets were printed, and ejection properties from the inkjet head were evaluated according to the following evaluation criteria. The results are shown in Tables 10 and 11 as "Dischargeability".
A: Printing was possible without ejection failure without performing head cleaning in the middle.
B: Printing was possible without ejection failures by performing head cleaning on the way.

As shown in the table, in Examples 1 to 28 using the ink containing the water-dispersible urethane resin and the water-dispersible polyolefin resin having a film elongation of 600% or more, prints having excellent wet rubbing fastness could be produced. rice field. In contrast, in Comparative Examples 1 to 7, the wet rubbing fastness was low.

Further, among Examples 1 to 7, Examples 1 to 5, in which the ink containing the water-dispersible polypropylene resin was used, exhibited even better fastness to wet rubbing. Further, among Examples 8 to 11, Examples 8 to 10, in which the ink containing the water-dispersible polypropylene resin was used, exhibited even better fastness to wet rubbing.

Further, when the pretreatment liquid containing the flocculant was applied (step 1), better image quality was obtained.

Example 12, in which the heating temperature after step 2 was 180°C, was even better in wet rubbing fastness than Example 13, in which the heating temperature after step 2 was 120°C.

Examples 14 and 15, in which the pretreatment liquid containing an organic acid was used, were even better in wet rubbing fastness than Example 16, in which the pretreatment liquid containing a metal salt was used.

Example 14 using the pretreatment liquid containing lactic acid was superior to Example 15 using the pretreatment liquid containing acetic acid with a boiling point of 118° C. in terms of jettability.

Example 12 using a pretreatment liquid having an organic acid content of 10% by mass based on the total amount of the pretreatment liquid is a pretreatment liquid having an organic acid content of 2.5% by mass based on the total amount of the pretreatment liquid. Better image quality was obtained than in Example 14 using the treatment liquid.

Example 12, in which no heating was performed between steps 1 and 2, also exhibited excellent wet rubbing fastness, similar to Example 18, in which heating was performed between steps 1 and 2. .

Claims (12)

Colorant, water-dispersible urethane resin with film elongation of 600% or more, water-dispersible polyolefin resin, and water,
The coloring material contains a pigment,
The water-dispersible polyolefin resin includes a water-dispersible polypropylene resin,
A water-based pigment ink for textile inkjet printing, wherein the water-dispersible polyolefin resin accounts for 2.25% by mass or more of the total amount of the ink . 2. The inkjet printing method according to claim 1, wherein the mass ratio of the water-dispersible polyolefin resin to the water-dispersible urethane resin (water-dispersible polyolefin resin/water-dispersible urethane resin) is 0.2 to 0.8. water-based pigment ink. 3. The aqueous pigment ink for textile inkjet printing according to claim 1, wherein the water-dispersible polyolefin resin contains a water-dispersible polyolefin resin having a melting point of 100[deg.] C. or higher. The water-based pigment ink for textile inkjet printing according to any one of claims 1 to 3, wherein the water-dispersible polyolefin resin accounts for 3.0 mass% or more of the total amount of the ink . The aqueous pigment for textile inkjet printing according to any one of claims 1 to 4, wherein the total amount of the water-dispersible urethane resin and the water-dispersible polyolefin resin is 9.0% by mass or more relative to the total amount of the ink. ink . A method for producing a printed matter, comprising a step of inkjet printing onto a substrate using the water-based pigment ink for textile inkjet printing according to any one of claims 1 to 5 . 7. The method for producing a printed matter according to claim 6 , further comprising the step of applying a pretreatment liquid containing a flocculant to the substrate before the step of inkjet printing. 8. The method of producing printed matter according to claim 7 , wherein the flocculating agent comprises an organic acid, a metal salt, a cationic polymer, or a combination thereof. 9. The method of producing printed matter according to claim 8 , wherein the cationic polymer comprises a polymer of epichlorohydrin and a nitrogen-containing compound. The method for producing a printed matter according to any one of claims 6 to 9 , further comprising a step of applying a resin-containing post-treatment liquid to the substrate after the step of inkjet printing. An ink set comprising the aqueous pigment ink for textile inkjet printing according to any one of claims 1 to 5 and a pretreatment liquid containing a flocculant. 12. The ink set according to claim 11 , further comprising a post-treatment liquid containing a resin.