Aqueous ink composition, aqueous ink, coated object, and use of aqueous ink

Abstract

An aqueous ink composition comprising a pigment (A), water (B), a pigment dispersant (C), a silicone-based resin emulsion (D), and an olefin-based resin emulsion (E), wherein the content of the silicone-based resin emulsion (D) on solid basis is 2 mass% to 40 mass% inclusive with respect to the total mass of the solid components of the aqueous ink composition, the content of the olefin-based resin emulsion (E) on solid basis is 20 mass% to 70 mass% inclusive with respect to the total mass of the solid components of the aqueous ink composition, and the mass ratio ((D) / (E)) on solid basis of the silicone-based resin emulsion (D) to the olefin-based resin emulsion (E) is 0.05 to 1.0 inclusive.

Description

Water-based ink composition, water-based ink, coated article, and use of water-based ink

[0001] The present invention relates to a water-based ink composition capable of forming a coating film excellent in various physical properties such as water resistance or abrasion resistance. Specifically, the present invention relates to a water-based ink composition in which a coating film formed on a plastic, metal, or glass substrate using the water-based ink composition of the present invention is excellent in abrasion resistance or wet rub resistance, and is also excellent in water resistance, dishwasher resistance, or washability.

[0002] Inks include oil-based inks using organic solvents and water-based inks mainly using aqueous solvents. In recent years, there has been an increasing trend to demand more environmentally friendly products and more safe products, so the provision of water-based inks excellent in various physical properties has been eagerly awaited. Also, although it has been mainly water-based pigment inks used for paper substrates, there is an increasing demand for water-based inks that can form a good ink film when forming a coating film on a non-absorbent surface such as polyethylene terephthalate (PET) or polyethylene (PE), as well as the various physical properties required for paper substrates.

[0003] Heretofore, various water-based pigment ink compositions or water-based ink compositions having water resistance that can be used on non-absorbent surfaces such as PET have been proposed. For example, a water-based pigment ink composition having excellent abrasion resistance when written on a non-absorbent surface such as PET has been proposed (Patent Document 1). Also, a water-based ink composition in which the handwriting written on the surface of glass or pottery has water resistance, hot water resistance, and abrasion resistance has been proposed (Patent Document 2).

[0004] Japanese Unexamined Patent Application Publication No. 2019-14769, Japanese Unexamined Patent Application Publication No. 2014-105282

[0005] As described above, various studies have been made to improve various physical properties of water-based inks. However, the water-based ink composition proposed in Patent Document 1 has not been studied for water resistance. Also, although the water-based ink composition proposed in Patent Document 2 has a certain degree of water resistance to water immersion, the present inventors have found a problem that it is not necessarily good in water resistance under various conditions where the water-based ink may be exposed.

[0006] Therefore, the object of the present invention is to provide an aqueous ink composition that not only meets the physical properties required for paper substrates, but also enables the formation of a coating film without repelling even on substrates other than paper, which are usually difficult to coat, and that exhibits excellent line clarity, and that the coating film formed on paper substrates, cloth substrates, etc., or on non-absorbent surfaces such as polypropylene (PP), PET, glass, or metal, exhibits excellent abrasion resistance, water resistance, dishwasher resistance, and especially washability and moisture abrasion resistance for cloth substrates.

[0007] In other words, the present invention provides the following aqueous ink composition, aqueous ink, coated material, and use of aqueous ink: [1] an aqueous ink composition comprising: a pigment (A), water (B), a pigment dispersant (C), a silicone resin emulsion (D), and an olefin resin emulsion (E), wherein the solid content of the silicone resin emulsion (D) is 2% by mass or more and 40% by mass or less with respect to the total mass of the solid content of the ink composition, the solid content of the silicone resin emulsion (D) is 0.3% by mass or more and 10% by mass or less with respect to the total mass of the aqueous ink composition, the solid content of the olefin resin emulsion (E) is 20% by mass or more and 70% by mass or less with respect to the total mass of the solid content of the ink composition, the solid content of the olefin resin emulsion (E) is 5% by mass or more and 20% by mass or less with respect to the total mass of the aqueous ink composition [1] The aqueous ink composition according to [1], wherein the mass ratio ((D) / (E)) of the silicone resin emulsion (D) to the olefin resin emulsion (E) on a solid content basis is 0.05 or more and 1.0 or less. [2] The aqueous ink composition according to [1], wherein the pigment dispersant (C) contains at least one selected from the group consisting of a dispersion resin made of a forming material containing at least one of styrene monomers and (meth)acrylic acid monomers, anionic surfactants, nonionic surfactants, and amphoteric surfactants, and the mass ratio ((C) / (A)) of the pigment dispersant (C) to the pigment (A) on a solid content basis is 0.02 or more and 1.9 or less. [3] The aqueous ink composition according to [1] or [2], further containing a surface modifier (F), wherein the surface modifier (F) is a surfactant, and the solid content of the surface modifier (F) is 0% by mass or more and 40% by mass or less with respect to the total mass of solids of the aqueous ink composition. [4] The aqueous ink composition according to [3], wherein the surface modifier (F) contains at least one of a fluorine-based surfactant and a polyether-modified siloxane-based surfactant. [5] The aqueous ink composition according to any one of [1] to [4], further containing a drying inhibitor. [6] The aqueous ink composition according to any one of [1] to [5], further containing a film-forming aid.[7] Aqueous ink comprising the aqueous ink composition described in any of [1] to [6]. [8] The aqueous ink described in [7] for use in at least one application selected from flexographic ink, gravure ink, and inkjet ink. [9] Use of the aqueous ink described in [7] in any one of a cotton-filled pen, a direct-ink pen, a spray applicator, a stamp ink, and a ballpoint pen.

[10] A coated product using the aqueous ink described in [7] or [8].

[11] A coated product made using any one of the products described in [9].

[0008] According to the present invention, the aqueous ink composition of the present invention can form a coating film without being repelled, not only on paper substrates, which are normally difficult to coat, but also on substrates other than paper, which are required for paper substrates. Furthermore, it can provide an aqueous ink composition that exhibits excellent line clarity, and the coating film formed on paper substrates, cloth substrates, etc., or on non-absorbent surfaces such as PP, PET, glass, or metal, has excellent abrasion resistance, water resistance, dishwasher resistance, and especially on cloth substrates, excellent washability and moisture abrasion resistance.

[0009] The embodiments of the present invention will be described below, but the present invention is not limited to the embodiments described below. The inventors have investigated an aqueous ink composition that not only meets the physical properties required for paper substrates, but also enables the formation of a coating film without repelling even on substrates other than paper, which are usually difficult to coat, and that exhibits excellent line clarity, and that the coating film formed on paper substrates, cloth substrates, etc., or on non-absorbent surfaces such as PP, PET, glass, or metal, exhibits excellent abrasion resistance, water resistance, dishwasher resistance, and especially washability and moisture friction resistance for cloth substrates. As a result, we discovered that when an aqueous ink composition contains a pigment, water, a pigment dispersant, a silicone resin emulsion whose solid content in the aqueous ink composition is within a certain range, and an olefin resin emulsion whose solid content in the aqueous ink composition is within a certain range, and furthermore, when the silicone resin emulsion and the olefin resin emulsion are included in a predetermined solid content mass ratio, the aqueous ink composition of the present invention can form a coating film without being repelled, not only on paper substrates, which are normally difficult to coat, but also on substrates other than paper, and it exhibits excellent line clarity. In addition, we found that the coating film formed on paper substrates, cloth substrates, etc., or on non-absorbent surfaces such as PP, PET, glass, or metal, exhibits excellent abrasion resistance, water resistance, dishwasher resistance, and especially on cloth substrates, excellent washability and moisture friction resistance, resulting in an aqueous ink composition that meets these requirements for paper substrates and cloth substrates.

[0010] In an aqueous ink composition, "aqueous" means including an aqueous medium. "Aqueous medium" means a liquid medium containing water. "Liquid medium" means a volatile liquid such as water or an organic solvent. The aqueous ink composition according to this embodiment contains water as the main liquid medium. "Volatile components" means volatile components such as water or an organic solvent among the components contained in the aqueous ink composition. Specifically, the heat residue obtained by a measurement method compliant with JIS K 5601-1-2:2008 is defined as the solid component (also called the non-volatile component), and the rest is defined as the volatile component. Furthermore, the term "emulsion" used in this embodiment means a liquid (water) in which a liquid (resin) with small particle sizes is dispersed, and also includes what is called an aqueous dispersion (dispersion) of an aqueous polymer (resin). Both types of emulsions may be emulsified using an emulsifier (surfactant) or self-emulsified without the use of an emulsifier (surfactant).

[0011] <<Water-based ink composition>> The water-based ink composition according to this embodiment contains a pigment (A), water (B), a pigment dispersant (C), a silicone resin emulsion (D), and an olefin resin emulsion (E). The solid content of the silicone resin emulsion (D) is 2% by mass or more and 40% by mass or less based on the total mass of the solid content of the water-based ink composition, and is 0.3% by mass or more and 10% by mass or less based on the total mass of the water-based ink composition. The solid content of the olefin resin emulsion (E) is 20% by mass or more and 70% by mass or less based on the total mass of the solid content of the water-based ink composition, and the solid content of the olefin resin emulsion (E) is 5% by mass or more and 20% by mass or less based on the total mass of the water-based ink composition. Furthermore, the mass ratio of the silicone resin emulsion (D) to the olefin resin emulsion (E) in terms of solid content ((D) / (E)) is 0.05 or more and 1.0 or less. The following describes the details of the aqueous ink composition according to this embodiment.

[0012] <Pigments> The pigment (A) constituting the aqueous ink composition according to this embodiment can be a conventionally known resin-dispersible pigment dispersed by a dispersion resin, and is not particularly limited. Examples include inorganic pigments such as carbon black, soluble azo pigments, insoluble azo pigments, high molecular weight azo pigments, phthalocyanine pigments, quinacridone pigments, anthraquinone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, quinophthalone pigments, methine / azomethine pigments, perylene pigments, perinone pigments, isoindolinone pigments, and isoindoline pigments, among other organic pigments.

[0013] In the aqueous ink composition according to this embodiment, the pigment content (pigment concentration) is preferably 0.1% by mass or more and 25% by mass or less of the total amount of the aqueous ink composition, considering the relationship with storage stability and the solubility of other components, and more preferably 2% by mass or more and 18% by mass or less from the viewpoint of particularly improving color development, dispersibility, or storage stability. If the pigment content (pigment concentration) in the aqueous ink composition is less than 0.1% by mass, the color development is poor, while if it exceeds 25% by mass, the dispersibility and storage stability are poor.

[0014] When manufacturing the aqueous ink composition according to this embodiment, it is preferable to use a pigment dispersion liquid in which the pigment and the pigment dispersant described later are dispersed in water, which is the solvent, at a high concentration beforehand. According to the inventors' research, using a pigment dispersion liquid makes it possible to produce an aqueous ink composition that is excellent in terms of color development and storage stability. The pigment concentration in the pigment dispersion liquid used in this embodiment is preferably 5% by mass or more and 55% by mass or less, and more preferably 12% by mass or more and 53% by mass or less from the viewpoint of particularly improving color development, dispersibility, or storage stability. As the pigment dispersant used in this case, those listed in the pigment dispersants described later can be used as appropriate. It is preferable to use ion-exchanged water as the water for preparing the pigment dispersion liquid. If the pigment concentration in the pigment dispersion liquid is less than 5% by mass, the color development is poor, while if it is more than 55% by mass, the dispersibility and storage stability are poor.

[0015] <Pigment Dispersant> The pigment dispersant (C) used in this embodiment is used to disperse the pigment and to improve color development or storage stability. The aqueous ink composition according to this embodiment uses a pigment dispersion liquid in which the pigment described above is dispersed in water, which is the solvent, in advance. The pigment dispersant (C) used in this embodiment may be a dispersion resin or a surfactant.

[0016] Examples of dispersion resins used in this embodiment include dispersion resins comprising a forming material containing at least one of styrene monomers and (meth)acrylic acid monomers. Generally, the structure of a dispersion resin for dispersing pigments consists of a pigment adsorption portion that contributes to pigment adsorption and a solvent affinity portion that contributes to dispersibility by being compatible with the solvent. If the molecular chain of the solvent affinity portion in the structure is long, the steric repulsion between pigments increases, which tends to improve dispersion stability. However, on the other hand, the viscosity of the dispersion resin solution itself tends to increase, resulting in a higher viscosity of the ink composition. Conversely, if the molecular chain of the solvent affinity portion in the structure is short, the viscosity of the dispersion resin solution itself decreases, but the steric repulsion between pigments decreases, which tends to worsen the dispersibility of the pigments. It is preferable to select the dispersion resin used in this embodiment taking these points into consideration.

[0017] The pigment adsorption portion in the structure of the dispersion resin used in this embodiment can be appropriately designed according to the surface properties of the pigment to be dispersed, and is not particularly limited. For example, it is preferable that the monomer of the forming material contains a monomer that contains an acidic group such as methacrylic acid (MAA) or acrylic acid (AAc). Furthermore, in order to disperse the pigment in water, these acidic groups need to be neutralized with a base such as ammonia, potassium hydroxide, or sodium hydroxide.

[0018] The parts of the dispersion resin structure other than the pigment adsorption portion used in this embodiment can be appropriately designed in consideration of the pigment adsorption portion mentioned above, and there are no particular limitations. Examples of monomers for the forming material include methacrylate monomers such as methyl methacrylate (MMA), benzyl methacrylate, hydroxyethyl methacrylate (HEMA), ethyl methacrylate (EMA), and 2-ethylhexyl methacrylate (2ehMA), acrylate monomers such as methyl acrylate, benzyl acrylate, hydroxyethyl acrylate, and ethyl acrylate, and addition polymerizable monomers such as styrene (St).

[0019] The structure of the dispersion resin used in this embodiment is not particularly limited and can be any of various structures, such as random structure, graft structure, block structure, or star structure. Among these, random structure and block structure are preferred.

[0020] In this embodiment, the number-average molecular weight of the dispersion resin used is preferably 5,000 to 25,000 from the viewpoint of improving the fluidity of the pigment dispersion and the stability between pigment particles, and more preferably 7,000 to 22,000 from the viewpoint of particularly excellent fluidity of the pigment dispersion. If the number-average molecular weight is less than 5,000, the steric repulsion between pigments decreases, causing the pigments to aggregate and increasing the viscosity of the pigment dispersion. On the other hand, if the number-average molecular weight exceeds 25,000, the viscosity of the dispersion resin solution itself increases, and the viscosity of the pigment dispersion also increases.

[0021] In this embodiment, a surfactant can be used as the pigment dispersant (C) for the purpose of dispersion. The surfactant is not particularly limited, but for example, conventionally known surfactants can be used. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Other examples of surfactants include acetylene glycol-based surfactants, fluorine-based surfactants, alkylene oxide-based surfactants, hydrocarbon-based surfactants, and polyether-modified siloxane-based surfactants. In this embodiment, one of the above surfactants may be used alone as the pigment dispersant (C), or two or more may be used in combination. Among these, from the viewpoint of superior pigment dispersion, one of anionic surfactants, nonionic surfactants, and amphoteric surfactants is preferred.

[0022] Anionic surfactants include saturated or unsaturated fatty acid salts (e.g., sodium laurate, sodium stearate, sodium oleate, and sodium linolenate), alkyl sulfates, alkylbenzenesulfonic acids (e.g., hexylbenzenesulfonic acid, toctylbenzenesulfonic acid, and dodecylbenzenesulfonic acid) and their salts, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, polyoxyethylene alkyl sulfates, alkyl sulfosuccinates, polyoxyalkylene alkyl sulfosuccinates, polyoxyalkylene alkylphenyl ether sulfates, alkanesulfonates, octyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, Examples include alkyl sulfonates, polyoxyethylene alkylphenyl ether sulfates, polyoxyalkylene alkyl ether acetates, alkyl phosphates, polyoxyalkylene alkyl ether phosphates, acyl glutamates, α-acyl sulfonates, alkyl sulfonates, alkylallyl sulfonates, α-olefin sulfonates, alkylnaphthalene sulfonates, alkanesulfonates, alkyl or alkenyl sulfates, alkylamide sulfates, alkyl or alkenyl phosphates, alkylamide phosphates, alkylylalkyl taurine salts, N-acyl amino acid salts, sulfosuccinates, alkyl ether carboxylates, amide ether carboxylates, α-sulfo fatty acid ester salts, alanine derivatives, glycine derivatives, and arginine derivatives. Examples of salts include alkali metal salts such as sodium salts, alkaline earth metal salts such as magnesium salts, alkanolamine salts such as triethanolamine salts, and ammonium salts.

[0023] Nonionic surfactants include polyoxyalkylene ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene fatty acid diesters, polyoxyalkylene resin acid esters, polyoxyalkylene (hydrogenated) castor oils, polyoxyalkylene alkylphenols, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene phenylphenyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene alkyl esters, sorbitan fatty acid esters, and polyoxyalkylene sorbitan alkyl esters. Examples include polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene glycerin fatty acid esters, polyglycerin alkyl ethers, polyglycerin fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, alkyl glucosides, polyoxyalkylene fatty acid bisphenyl ethers, polypropylene glycol, diethylene glycol, fluorinated surfactants, polyoxyethylene / polyoxypropylene block polymers, and alkyl polyoxyethylene / polyoxypropylene block polymer ethers.

[0024] Examples of amphoteric surfactants include imidazoline type, amidebetaine type, alkylbetaine type, alkylamidebetaine type, alkylsulfobetaine type, amidesulfobetaine type, hydroxysulfobetaine type, carbobetine type, phosphobetaine type, aminocarboxylic acid type, and amideamino acid type. Specifically, these include imidazoline type amphoteric surfactants such as 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium and 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt; alkylbetaine type amphoteric surfactants such as lauryldimethylaminoacetic acid betaine and myristylbetaine; coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine, palm kernel oil fatty acid amidopropyl dimethylaminoacetic acid betaine, beef tallow fatty acid amidopropyl dimethylaminoacetic acid betaine, hydrogenated beef tallow fatty acid amidopropyl dimethylaminoacetic acid betaine, and laurin Amidobetaine-type amphoteric surfactants such as acid amidopropyl dimethylaminoacetic acid betaine, myristate amidopropyl dimethylaminoacetic acid betaine, palmitate amidopropyl dimethylaminoacetic acid betaine, stearate amidopropyl dimethylaminoacetic acid betaine, and oleic acid amidopropyl dimethylaminoacetic acid betaine; alkyl sulfobetaine-type amphoteric surfactants such as coconut oil fatty acid dimethyl sulfopropyl betaine; alkyl hydroxy sulfobetaine-type amphoteric surfactants such as lauryl dimethylamino hydroxy sulfobetaine; phosphobetaine-type amphoteric surfactants such as lauryl hydroxyphosphobetaine; and;N-Lauroyl-N'-Hydroxyethyl-N'-Carboxymethylethylenediamine sodium, N-Oleoyl-N'-Hydroxyethyl-N'-Carboxymethylethylenediamine sodium, N-Cocoyl-N'-Hydroxyethyl-N'-Carboxymethylethylenediamine sodium, N-Lauroyl-N'-Hydroxyethyl-N'-Carboxymethylethylenediamine potassium, N-Oleoyl-N'-Hydroxyethyl-N'-Carboxymethylethylenediamine potassium, N-Lauroyl-N-Hydroxyethyl-N'-Carboxymethylethylenediamine sodium, N-Oleoyl-N-Hydroxyethyl- Examples include amide amino acid type amphoteric surfactants such as N'-carboxymethylethylenediamine sodium, N-cocoyl-N-hydroxyethyl-N'-carboxymethylethylenediamine sodium, N-lauroyl-N-hydroxyethyl-N',N'-dicarboxymethylethylenediamine monosodium, N-oleoyl-N-hydroxyethyl-N',N'-dicarboxymethylethylenediamine monosodium, N-cocoyl-N-hydroxyethyl-N',N'-dicarboxymethylethylenediamine monosodium, N-lauroyl-N-hydroxyethyl-N',N'-dicarboxymethylethylenediamine disodium, N-oleoyl-N-hydroxyethyl-N',N'-dicarboxymethylethylenediamine disodium, and N-cocoyl-N-hydroxyethyl-N',N'-dicarboxymethylethylenediamine disodium.

[0025] The surfactants mentioned above may be synthesized by known methods or may be commercially available products. Examples of commercially available anionic surfactants include Demol N, RN, NL, RNL, T, T-45, MS, P (manufactured by Kao Corporation), SN Wet 970 (manufactured by Sanopco), Ionet D-2, Sunseparar 100 (manufactured by Sanyo Chemical Industries), and Newcol 220-L(20)D (manufactured by Nippon Emulsifier Co., Ltd.). Examples of commercially available nonionic surfactants include Emulgen 103 (manufactured by Kao Corporation), Newcol 610, 1006 (manufactured by Nippon Emulsifier Co., Ltd.), and Surfinol CT151 (manufactured by Nisshin Chemical Industry Co., Ltd.). Examples of commercially available amphoteric surfactants include Levon 2000, 2000L, HC-30W, MY-30W, T-2, Piuceria AMC (manufactured by Sanyo Chemical Industries), and Amhitol 20BS, 24B, 20N, 20HD, 20AB, and 55AB (manufactured by Kao Corporation).

[0026] When preparing the aqueous ink composition according to this embodiment using the pigment dispersion as described above, the dispersion resin solution having the above-described configuration is neutralized with an alkali before use. The alkali used for neutralization is not particularly limited, but examples include ammonia, primary, secondary, or tertiary organic amines (including basic nitrogen-containing heterocyclic compounds), and alkali metal hydroxides. These can be used individually or in combination of two or more.

[0027] The mass ratio of pigment dispersant (C) to pigment (A) on a solid content basis ((C) / (A)) is preferably 0.01 or more and 2.1 or less, more preferably 0.02 or more and 1.9 or less from the viewpoint of particularly improving abrasion resistance, water resistance, washability, moisture friction resistance, dispersibility, storage stability, color development, or viscosity, even more preferably 0.04 or more and 1.6 or less from the viewpoint of particularly improving PP abrasion resistance, water resistance, dishwasher resistance, washability, moisture friction resistance, dispersibility, storage stability, color development, or viscosity, and particularly preferably 0.04 or more and 1.0 or less. By setting the mass ratio of pigment dispersant (C) to pigment (A) on a solid content basis ((C) / (A)) within the above range, excellent abrasion resistance, water resistance, washability, or moisture friction resistance is obtained. If the mass ratio is less than 0.01, the viscosity is poor. If the mass ratio of the pigment dispersant (C) to the pigment (A) on a solid content basis ((C) / (A)) is greater than 2.1, the color development will be poor.

[0028] <Silicone Resin Emulsion> The aqueous ink composition according to this embodiment is characterized by containing the above-mentioned pigment dispersion with a silicone resin emulsion (D) and the olefin resin emulsion (E) described later in a specific ratio. The silicone resin emulsion (D) tends to form a good ink film and improve its abrasion resistance. As used herein, "silicone resin emulsion" means a resin emulsion having a polysiloxane skeleton in its resin backbone.

[0029] The silicone resin emulsion used in this embodiment may be synthesized by known methods, or it may be a commercially available product as listed below. Specifically, for example, NANOFINE KPX-02-04, NANOFINE KPX-02-014, NANOFINE KPX-97-048 and NANOFINE KPX-97-051 (all trade names, Toyo Chem Co., Ltd.), which are acrylic emulsions compounded with oligomers having a polysiloxane skeleton, and 52 Additive, 51 Additive, and IE-4290, which are silicone emulsions having silanol groups. Examples include Dispersion, BY22-055, and BY22-050A (all trade names, manufactured by Toray Dow Corning), as well as X-52-2160, X-52-2127, X-52-2265, X-52-2328, X-52-2162, KM-910, and KM-903 (all trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), TEGO GLIDE 490 (manufactured by EVONIC), and Rheoflo DM S-55 (manufactured by Lion Corporation). These include nonionic emulsions, cationic emulsions, etc.

[0030] The solid content of the silicone resin emulsion (D) constituting the aqueous ink composition according to this embodiment must be 0.3% by mass or more and 10% by mass or less relative to the total mass of the aqueous ink composition. A content of 0.5% by mass or more and 9.0% by mass or less is more preferable from the viewpoint of abrasion resistance, water resistance, washability, or moisture friction resistance. By keeping the content within this range, abrasion resistance or PET water resistance can be improved. If the solid content of the silicone resin emulsion (D) relative to the total mass of the aqueous ink composition is less than 0.3% by mass, abrasion resistance, water resistance, dishwasher resistance, washability, or moisture friction resistance will be poor, while if it exceeds 10% by mass, the clarity of the drawn lines, abrasion resistance, or PET water resistance will be poor.

[0031] In the aqueous ink composition according to this embodiment, the solid content of the silicone resin emulsion (D) must be 2% by mass or more and 40% by mass or less, relative to the total mass of solids in the aqueous ink composition. By setting the solid content of the silicone resin emulsion (D) within the above range, the water resistance of PET can be improved. If the solid content of the silicone resin emulsion (D) is less than 2% by mass, water resistance, washability, and moisture friction resistance are poor. On the other hand, if it exceeds 40% by mass, the clarity of the drawn lines, scratch resistance of PET, metal and glass, and PET water resistance are poor. Furthermore, from the viewpoint of particularly excellent scratch resistance, water resistance, dishwasher resistance, washability, or moisture friction resistance, the solid content of the silicone resin emulsion (D) is more preferably 3% by mass or more and 38% by mass or less.

[0032] <Olefin Resin Emulsion> The olefin resin emulsion (E) used in this embodiment is used for the purpose of improving the abrasion resistance and water resistance of the coating film. The olefin resin emulsion (E) used in this embodiment is not particularly limited, and for example, known polyolefin resins can be used as appropriate. Examples of polyolefin resins include polyethylene (PE), polypropylene (PP), polybutylene, polybutene, hydrogenated polybutene, polyisobutylene, hydrogenated polyisobutylene, and olefin copolymers (excluding ethylene-vinyl acetate copolymers). These may be used individually or in combination of two or more. Examples of polyethylene include low-density polyethylene (LDPE), medium-density polyethylene (MDPE), high-density polyethylene (HDPE), and linear low-density polyethylene (LLDPE). Examples of polypropylene include atactic polypropylene, isotactic polypropylene, syndiotactic polypropylene, oxidized polypropylene, chlorinated polypropylene, crosslinked polypropylene, and modified polypropylene. Examples of olefin copolymers include ethylene-vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, and polypropylene-polyethylene copolymer, as well as other olefin copolymers obtained by copolymerizing two or more of ethylene, propylene, and butylene. Furthermore, the various polyolefin resins listed above may be modified polyolefin resins in which amino groups, carboxyl groups, hydroxyl groups, acryloyl groups, and polymer chains are introduced to the polyolefin chain; oxidized polyolefin resins in which a part of the polyolefin chain is oxidized; or halogenated polyolefin resins in which a part is treated with a halogen.

[0033] The olefin resin emulsion (E) may be an emulsion of resin obtained using raw materials derived from fossil fuels, or an emulsion of resin obtained from biomass-derived raw materials. In addition, the olefin resin emulsion (E) may be manufactured by conventional methods or a commercially available product. Among the above olefin resin emulsions (E), it is preferable that it contains at least one selected from the group consisting of halogenated polyolefin resin emulsion, modified polyolefin resin emulsion, and maleic anhydride-modified chlorinated polyolefin resin emulsion.

[0034] Polypropylene resin emulsion is an emulsion formed by colloidally dispersing polypropylene resin in an aqueous resin composition. In aqueous ink compositions, polypropylene resin emulsion may be used alone, or it may be used in combination with other polyolefin resin emulsions, such as polyethylene resin emulsion and polypropylene-polyethylene copolymer resin emulsion described later.

[0035] Polyethylene resin emulsion is an emulsion formed by colloidally dispersing polyethylene resin in an aqueous resin composition. In aqueous ink compositions, polyethylene resin emulsion may be used alone, or in combination with other polyolefin resin emulsions, such as the polypropylene resin emulsion described above and the polypropylene-polyethylene copolymer resin emulsion described later.

[0036] Polypropylene-polyethylene copolymer resin emulsion is an emulsion formed by colloidally dispersing a polypropylene-polyethylene copolymer resin in an aqueous resin composition. The arrangement of monomer units in the polypropylene-polyethylene copolymer is not particularly limited and may be a block copolymer, an alternating copolymer, a random copolymer, or a graft copolymer. The aqueous ink composition may use the polypropylene-polyethylene copolymer resin emulsion alone, or it may be used in combination with other polyolefin resin emulsions, such as the above-mentioned polypropylene resin emulsion or polyethylene resin emulsion.

[0037] The melting point of the olefin resin is preferably 50°C to 150°C, and more preferably 50°C to 100°C. Using an olefin resin having a melting point within the above range results in good abrasion resistance and water resistance of the coating film.

[0038] The olefin resin emulsion (E) used in this embodiment may be synthesized by a known method or may be a commercially available product. Examples of commercially available products include Arrowbase DA-1010, DC-1010 (both manufactured by Unitika Corporation), Aurolene AE-202, AW-301, Superclon E-480T, and S-4890 (all manufactured by Nippon Paper Industries Co., Ltd.), Hardlen EW-5250 and EW-5303 (both manufactured by Toyobo MC Co., Ltd.), Aptlock BW-5596, and BW-5635 (both manufactured by Mitsubishi Chemical Corporation).

[0039] Furthermore, the solid content of the olefin resin emulsion (E) used in this embodiment must be 5% by mass or more and 20% by mass or less relative to the total mass of the aqueous ink composition. From the viewpoint of particularly improving abrasion resistance, water resistance, washability, or moisture friction resistance, it is even more preferable that it be 6% by mass or more and 18% by mass or less. Setting the solid content of the olefin resin emulsion (E) relative to the total mass of the aqueous ink composition within the above range is preferable from the viewpoint of coating film formation and from the viewpoint of improving the abrasion resistance of PET, metal and glass, or the water resistance of PET. On the other hand, if the solid content of the olefin resin emulsion (E) relative to the total mass of the aqueous ink composition is less than 5% by mass, it becomes difficult to form an ink film. Also, abrasion resistance, water resistance, dishwasher resistance, washability, or moisture friction resistance will be inferior. If it exceeds 20% by mass, the clarity of the drawn lines, the abrasion resistance of PET, metal and glass, or the water resistance of PET will be inferior.

[0040] The solid content of the olefin resin emulsion (E) used in this embodiment needs to be 20% by mass or more and 70% by mass or less with respect to the total solid mass of the aqueous ink composition. By setting the solid content of the olefin resin emulsion (E) within the above range with respect to the total solid mass of the aqueous ink composition, the scratch resistance of metals and glass, the water resistance of PET, or the wet rubbing resistance can be improved. When the solid content of the olefin resin emulsion (E) is less than 20% by mass with respect to the total solid mass of the aqueous ink composition, the scratch resistance, water resistance, dishwasher resistance, washing resistance, and wet rubbing resistance are inferior. When it exceeds 70% by mass, the sharpness of the drawn line, the scratch resistance of metals and glass, the water resistance of PET, or the wet rubbing resistance is inferior. Further, the solid content of the olefin resin emulsion (E) is preferably 23% by mass or more and 68% by mass or less, and more preferably 26% by mass or more and 65% by mass or less from the viewpoint of particularly excellent scratch resistance, water resistance, dishwasher resistance, washing resistance, or wet rubbing resistance.

[0041] The mass ratio ((D) / (E)) of the silicone resin emulsion (D) used in this embodiment to the olefin resin emulsion (E) needs to be 0.05 or more and 1.0 or less. By setting the mass ratio ((D) / (E)) of the silicone resin emulsion (D) to the olefin resin emulsion (E) within the above range, the scratch resistance of metals and glass can be improved. When the mass ratio ((D) / (E)) is less than 0.05, the scratch resistance is inferior. When the mass ratio ((D) / (E)) exceeds 1.0, the scratch resistance, water resistance, washing resistance, and wet rubbing resistance of metals and glass are inferior. Further, the mass ratio ((D) / (E)) is preferably 0.05 or more and 0.95 or less, and more preferably 0.1 or more and 0.90 or less from the viewpoint of particularly improved scratch resistance, water resistance, dishwasher resistance, washing resistance, or wet rubbing resistance.

[0042] The aqueous ink composition according to this embodiment may contain not only the silicone-based resin emulsion (D) and the olefin-based resin emulsion (E), but also other resins as long as they do not affect the present invention. Examples of other resins include styrene-(meth)acrylic resins, acrylic resins other than styrene-(meth)acrylic resins, urethane resins, and vinyl versatic acid ester-based resins.

[0043] <Surface conditioner> The aqueous ink composition according to this embodiment may contain a surface conditioner (F). The surface conditioner is used for the purpose of surface conditioning, and more specifically, for imparting wettability. The surface conditioner (F) may have a dispersing action, and may also have the effect of surface conditioning in addition to the dispersing action.

[0044] As the surface conditioner (F) used in this embodiment, for example, conventionally known surfactants can be used, but it is not particularly limited. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Also, examples of surfactants include acetylene glycol-based surfactants, fluorine-based surfactants, alkylene oxide-based surfactants, hydrocarbon-based, and polyether-modified siloxane-based surfactants. As the surface conditioner (F) used in this embodiment, one of the above surfactants may be used alone, or two or more of them may be used in combination. Among them, it is preferable from the viewpoint of imparting wettability that the surface conditioner (F) contains at least one of a fluorine-based surfactant and a polyether-modified siloxane-based surfactant.

[0045] Examples of fluorine-based surfactants include perfluoroalkyl-based surfactants such as hexafluoropropene-based and tetrafluoroethylene-based, and perfluoroalkenyl-based surfactants.

[0046] Examples of polyether-modified siloxane-based surfactants include polyether-modified siloxane-based surfactants such as dimethylpolysiloxane.

[0047] The surfactants mentioned above may be synthesized by known methods or may be commercially available products. Examples of commercially available fluorine-based surfactants include Florard FC-430 and 431 (all manufactured by 3M Japan), Megafac F-444, 472, 477, 552, 553, 554, 443, 470, 475, 482, 483, 489, and 30 (all manufactured by DIC Corporation), Asahiguard AG710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, and SC-106 (all manufactured by AGC Corporation). Examples of commercially available polyether-modified siloxane surfactants include BYK-345, BYK-346, BYK-347, BYK-348, BYK-3450, and UV3530 (all manufactured by BIC Chemie Japan).

[0048] The solid content of the surface modifier (F) used in this embodiment is preferably 0% to 20% by mass relative to the total mass of the aqueous ink composition, more preferably 0% to 15% by mass, and even more preferably 0% to 8% by mass from the viewpoint of particularly improving the water resistance, corrosion resistance, washing resistance, and moisture friction resistance of the PP. By setting the solid content of the surface modifier (F) relative to the total mass of the aqueous ink composition within the above range, the water resistance, corrosion resistance, washing resistance, or moisture friction resistance of the PP can be improved. If the solid content of the surface modifier (F) relative to the total mass of the aqueous ink composition exceeds 20% by mass, the water resistance, corrosion resistance, washing resistance, or moisture friction resistance of the coating film will be inferior.

[0049] The solid content of the surface modifier (F) used in this embodiment is preferably 0% to 50% by mass relative to the total solid content of the aqueous ink composition, more preferably 0% to 40% by mass, and even more preferably 0% to 25% by mass from the viewpoint of particularly excellent PP water resistance, dishwasher resistance, washability, and moisture friction resistance. By setting the solid content of the surface modifier (F) relative to the total solid content of the aqueous ink composition within the above range, the PP water resistance, dishwasher resistance, washability, or moisture friction resistance can be improved. If the solid content of the surface modifier (F) relative to the total solid content of the aqueous ink composition exceeds 50% by mass, the PP water resistance, dishwasher resistance, washability, or moisture friction resistance of the coating film will be inferior.

[0050] <Other Additives> The aqueous ink composition according to this embodiment may optionally contain additives such as film-forming aids and drying inhibitors, as listed below. However, other additives such as plasticizers, blocking inhibitors, settling inhibitors, leveling agents, defoaming agents, matting agents, pH adjusters, antioxidants, UV absorbers, light stabilizers, preservatives, mold inhibitors, rust inhibitors, flame retardants, color developers, chelating agents, thickening inhibitors, and coupling agents can also be used. These additives may be used individually or in combination of two or more.

[0051] <Film-forming aid> In the aqueous ink composition according to this embodiment, the film-forming ability of the emulsion in the composition can be improved by using a film-forming aid. As mentioned above, it is preferable to use a film-forming aid and design the aqueous ink composition according to this embodiment so that the binder resin forms a film at room temperature, with the MFT being 25°C (room temperature) or lower. In other words, with this configuration, the formed film will have excellent abrasion resistance, and when used in a felt-tip pen, the lines drawn will also have excellent abrasion resistance. Examples of film-forming aids include Solfit (manufactured by Kuraray Co., Ltd.), benzyl alcohol, N-methyl-2-pyrrolidone, 3-methoxy-3-methylbutanol, hexylene glycol, diethylene glycol mono-n-butyl ether, dipropylene glycol dimethyl ether, butyl cellosolve acetate, diethylene glycol mono-ethyl ether, Texanol, butyl carbitol, ethyl cellosolve, carbitol acetate, butyl carbitol acetate, butyl cellosolve, butyl cellosolve acetate, ethylene glycol mono-n-ethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol tert-butyl ether, ethylene glycol methyl ether acetate, polyethylene glycol monomethyl ether, and polypropylene glycol monomethyl ether.

[0052] <Drying Inhibitor> In the aqueous ink composition according to this embodiment, it is preferable to include a hydrophilic solvent as a drying inhibitor. Examples of drying inhibitors that can be used in this case include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, urea, thiourea, ethyleneurea or derivatives thereof, ethylene glycol, polyethylene glycol (PEG200, PEG300, PEG400, and PEG600, etc.), glycerin, propylene glycol, diethylene glycol, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether, and tripropylene glycol monoethyl ether. These can be used individually or in combination of two or more.

[0053] <Applications> The aqueous ink composition according to this embodiment can be suitably used as stationery ink, plastic coating, architectural coating, gravure ink, flexographic ink, and inkjet ink. In particular, it can be suitably used as stationery ink. Lines drawn with stationery using the aqueous ink composition according to this embodiment are not repelled by non-absorbent surfaces such as glass and metal surfaces, as well as plastics such as PP and PET, and can even be written on leather products, polystyrene foam, or paper, and these lines have excellent abrasion resistance and water resistance. Furthermore, coated products using the aqueous ink composition according to this embodiment on plastic products, glass products, or metal products, which are usually difficult to print on with aqueous inks, also have excellent abrasion resistance, water resistance, dishwasher resistance, washability, and moisture friction resistance. The coated product may be a printed product. It is also a preferred embodiment to use the aqueous ink composition according to this embodiment as a flexographic ink or gravure ink.

[0054] The coating method when using the water-based ink composition according to this embodiment as a coating, such as the aforementioned paint for plastics or architectural paint, is not particularly limited. For example, coating methods using a spray, brush, roller, or coater can be used.

[0055] When using the aqueous ink composition according to this embodiment as the above-mentioned stationery ink, it can be suitably used in felt-tip pens, markers, ballpoint pens, brush pens, or stamp inks (where the aqueous ink composition according to this embodiment is absorbed into an ink reservoir such as felt or sponge). A so-called felt-tip pen is a pen that uses a fibrous material for the pen tip and guides ink from an ink reservoir in the pen body to the pen tip by capillary action. There are two types, direct-ink type and cotton-filled type, depending on the structure of the ink reservoir. In the direct-ink type, an ink tank is mounted in the pen body, and the ink is stored directly in this ink tank. On the other hand, in the cotton-filled type, ink is filled into cotton built into the pen body, and a fibrous pen tip is directly attached to the cotton. The ink filled in the cotton is absorbed from the cotton to the pen tip by capillary action for writing.

[0056] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" are based on mass unless otherwise specified.

[0057] In the examples and comparative examples, the dispersion resin was prepared using a polymer having the following monomer composition and molecular weight, and the following solvent, as a solution. Hereinafter, this will be referred to as the "dispersion resin solution."

[0058] (Dispersion resin solution - 1 (Styrene acrylic acid-based dispersion resin)) Random polymer monomer composition: Styrene (St) / Methyl methacrylate (MMA) / Ethyl methacrylate (EMA) / 2-ethylhexyl methacrylate (2EHMA) / Hydroxyethyl methacrylate (HEMA) / Methacrylic acid (MAA) = 20 / 15 / 15 / 20 / 20 / 10, number average molecular weight 18000, molecular weight distribution 2.08 Solvent: Mixed solvent of diethylene glycol mono-n-butyl ether (BDG) / propylene glycol methyl ether (MPG) / water / aqueous ammonia (28%) = 50 / 50 / 70 / 7.7 per 100 parts by mass of polymer pH: 8.7 Solids content: 36% (Dispersion resin solution - 2 (Acrylic acid-based dispersion resin)) • AB block copolymer monomer composition: benzyl methacrylate (BzMA) / cyclohexyl methacrylate (CHMA) (A chain)-b-BzMA / MAA (B chain) = 19.8 / 23.7-b-33.8 / 22.7 Number average molecular weight of A chain 5000, molecular weight distribution 1.20, number average molecular weight of B 5700, number average molecular weight of AB block copolymer 10700, molecular weight distribution 1.31 • Solvent: Mixed solvent of BDG / MPG / water / aqueous ammonia (28%) = 50 / 50 / 182.4 / 17.6 per 100 parts by mass of polymer, pH: 8.9 • Solid content 25.0% (Dispersion resin solution - 3 (acrylic acid-based dispersion resin)) • AB block copolymer monomer composition: CHMA / BzMA (A chain)-b-CHMA / MMA / MAA (B chain) = 39.8 / 16.7-b-10.6 / 12.6 / 20.3 Number average molecular weight of A chain: 4700, molecular weight distribution: 1.31; Number average molecular weight of B chain: 4400; Number average molecular weight of AB block copolymer: 9100, molecular weight distribution: 1.39 • Solvent: Mixed solvent of BDG / water / sodium hydroxide = 100 / 250 / 9.5 per 100 parts by mass of polymer; pH: 9.9 • Solids content: 22.9%

[0059] <Preparation Example 1> 114 parts of the above-mentioned dispersion resin solution-1, 79 parts of carbon black #1000 (trade name, manufactured by Mitsubishi Chemical Corporation), 1.9 parts of 25% aqueous ammonia, and 187 parts of deionized water were dispersed using a horizontal media disperser, DYNO-MILL Type KDL (trade name, manufactured by WAB Corporation). After dispersion, water was added, and coarse particles were removed by centrifugation to obtain the following pigment dispersion-1 with a pigment concentration of 14%. The non-volatile content (N.V. = solids) of this pigment dispersion-1 was 17.5%. The commercially available carbon black #1000 used above had a particle size of 18 nm and a nitrogen adsorption specific surface area of ​​180 m². ２ It is a product with a concentration of 1 / g and a pH of 3.5. • Pigment dispersion-1: Solid content 17.5%, pigment concentration 14%, black pigment (Mitsubishi Chemical Corporation, carbon black #1000)

[0060] <Preparation Examples 2-17> Except for changing the types and amounts of pigments and dispersion resin solutions, and the amounts of ammonia water and ion-exchanged water, the following pigment dispersions-2 to pigment dispersions-17 were prepared in the same manner as in Preparation Example 1. • Pigment dispersion-2: Solid content 19.4%, pigment concentration 15%, black pigment (Printex 80, manufactured by Orion Engineered Carbon, Inc., pigment dispersant (dispersion resin solution-2 above)) • Pigment dispersion-3: Solid content 19.5%, pigment concentration 15%, blue pigment (Chromofine Blue A-220JC, manufactured by Dainichi Seika Kogyo Co., Ltd., pigment dispersant (dispersion resin solution-2 above)) • Pigment dispersion-4: Solid content 32.8%, pigment concentration 24%, red pigment (SEIKAFAST RED 3522, manufactured by Dainichi Seika Kogyo Co., Ltd., pigment dispersant (Emulgen A-90 (nonionic surfactant), manufactured by Kao Corporation) • Pigment dispersion-5: Solid content 52.8%, pigment concentration 50.3%, white pigment (Typake CR-60, manufactured by Ishihara Sangyo Co., Ltd., pigment dispersant (dispersion resin solution-3 above) • Pigment dispersion-6: Solid content 30.3%, pigment concentration 30.0%, white pigment (Ishihara Sangyo Co., Ltd., Typake CR-60), pigment dispersant (Toagosei Co., Ltd., Aron T-50 (acrylic acid-based dispersion resin solution)) • Pigment dispersion-7: Solid content 30.9%, pigment concentration 30.0%, white pigment (Ishihara Sangyo Co., Ltd., Typake CR-60), pigment dispersant (Toagosei Co., Ltd., Aron T-50 (acrylic acid-based dispersion resin solution)) • Pigment dispersion-8: Solid content 24.5%, pigment concentration 17.3%, white pigment (Ishihara Sangyo Co., Ltd., Typake CR-60), pigment dispersant (Toagosei Co., Ltd., Aron T-50 (acrylic acid-based dispersion resin solution)) • Pigment Dispersion-9: Solid content 29.7%, pigment concentration 17.8%, white pigment (Ishihara Sangyo Co., Ltd., Typake CR-60), pigment dispersant (Toagosei Co., Ltd., Aron T-50 (acrylic acid-based dispersion resin solution)) • Pigment Dispersion-10: Solid content 38.1%, pigment concentration 16.2%, white pigment (Ishihara Sangyo Co., Ltd., Typake CR-60), pigment dispersant (Toagosei Co., Ltd., Aron T-50 (acrylic acid-based dispersion resin solution)) • Pigment Dispersion-11: Solid content 40.0%, pigment concentration 16.0%, white pigment (Ishihara Sangyo Co., Ltd., Typake CR-60), pigment dispersant (Toagosei Co., Ltd., Aron T-50 (acrylic acid-based dispersion resin solution))• Pigment Dispersion-12: Solid content 40.5%, pigment concentration 15.0%, white pigment (Typake CR-60, manufactured by Ishihara Sangyo Co., Ltd.), pigment dispersant (Aron T-50 (acrylic acid-based dispersion resin solution), manufactured by Toagosei Co., Ltd.) • Pigment Dispersion-13: Solid content 37.2%, pigment concentration 12.0%, white pigment (Typake CR-60, manufactured by Ishihara Sangyo Co., Ltd.), pigment dispersant (Aron T-50 (acrylic acid-based dispersion resin solution), manufactured by Toagosei Co., Ltd.) • Pigment Dispersion-14: Solid content 36.0%, pigment concentration 32.7%, black pigment (Carbon Black #44B, manufactured by Mitsubishi Chemical Corporation), pigment dispersant (Tamol NN9401 (anionic surfactant), manufactured by BASF Corporation) • Pigment Dispersion-15: Solid content 30.5%, pigment concentration 23.3%, black pigment (Mitsubishi Chemical Corporation, Carbon Black #970), pigment dispersant (Kao Corporation, Emulgen A-90 (nonionic surfactant)) • Pigment Dispersion-16: Solid content 29.7%, pigment concentration 22.0%, black pigment (Mitsubishi Chemical Corporation, Carbon Black #44B), pigment dispersant (Sanyo Chemical Industries, Ltd., Revon 2000 (amphoteric surfactant)) • Pigment Dispersion-17: Solid content 18.2%, pigment concentration 14.0%, black pigment (Mitsubishi Chemical Corporation, Carbon Black #44B), pigment dispersant (Arakawa Chemical Industries, Ltd., Alastor 703S (styrene-maleic acid-based dispersion resin solution))

[0061] <Example 1> To a mixture of 18.9 parts of pigment dispersion-1 and 18.9 parts of pigment dispersion-2 obtained above, 54.2 parts of Aurolene AE-301 (manufactured by Nippon Paper Industries Co., Ltd.) as an olefin resin emulsion, 6 parts of 52 Additive (manufactured by Toray Dow Corning Co., Ltd.) as a silicone resin emulsion, 1 part of BYK-348 (Bic Chemie Japan Co., Ltd.) as a surface modifier, and 1 part of water as a solvent were added to form an aqueous ink composition. Furthermore, this composition was dispersed in a dissolver to obtain an aqueous ink based on the aqueous ink composition. Table 1 shows the composition of the obtained aqueous ink.

[0062] Furthermore, the following values ​​are listed in Table 1. - Pigment content (A) relative to the total mass of water-based ink (hereinafter also referred to as "pigment concentration") - Solid content of olefin resin emulsion (E) relative to the total mass of water-based ink (hereinafter also referred to as "solid content of (E) / total ink mass") - Solid content of silicone resin emulsion (D) relative to the total mass of water-based ink (hereinafter also referred to as "solid content of (D) / total ink mass") - Solid content of olefin resin emulsion (E) relative to the total solid content of water-based ink (hereinafter also referred to as "solid content of (E) / total ink solid content") - Solid content of silicone resin emulsion (D) relative to the total solid content of water-based ink (hereinafter also referred to as "solid content of (D) / total ink solid content") - Mass ratio of silicone resin emulsion (D) to olefin resin emulsion (E) in terms of solid content (hereinafter also referred to as "mass ratio ((D) / (E))") - The mass ratio of the pigment dispersant (C) to the pigment (A) in terms of solid content (hereinafter also referred to as "mass ratio ((C) / (A))") - The solid content of the surface modifier (F) relative to the total mass of the water-based ink (hereinafter also referred to as "solid content of (F) / total ink mass") - The solid content of the surface modifier (F) relative to the total solid content of the water-based ink (hereinafter also referred to as "solid content of (F) / total ink solid content mass")

[0063] <Examples 2-36 and Comparative Examples 1-13> For Examples 2-8, aqueous inks were obtained in the same manner as in Example 1, except that each material was blended according to the composition shown in Table 1. For Examples 9-15, aqueous inks were obtained in the same manner as in Example 1, except that each material was blended according to the composition shown in Table 2. For Comparative Examples 1-13, aqueous inks were obtained in the same manner as in Example 1, except that each material was blended according to the composition shown in Table 3. For Examples 16-21, aqueous inks were obtained in the same manner as in Example 1, except that each material was blended according to the composition shown in Table 4. For Examples 22-29, aqueous inks were obtained in the same manner as in Example 1, except that each material was blended according to the composition shown in Table 5. For Examples 30-36, aqueous inks were obtained in the same manner as in Example 1, except that each material was blended according to the composition shown in Table 6. For Examples 37-48, aqueous inks were obtained in the same manner as in Example 1, except that each material was blended according to the composition shown in Table 7. For Examples 49 to 64, aqueous inks were obtained in the same manner as in Example 1, except that the materials were blended according to the compositions shown in Table 8. For Examples 65 to 82, aqueous inks were obtained in the same manner as in Example 1, except that the materials were blended according to the compositions shown in Table 9. For Examples 83 to 102, aqueous inks were obtained in the same manner as in Example 1, except that the materials were blended according to the compositions shown in Table 10. The raw materials used in each example are as follows.

[0064] [Raw materials used] As the pigment dispersion (a mixture of pigment (A), water (B), and pigment dispersant (C)), pigment dispersions-1 to-17 obtained in Preparation Examples 1 to 17 were used.

[0065] The following compounds were used as the silicone resin emulsion (D).・D-1: 52 Additive (manufactured by Toray Dow Corning, solids content 65% by mass) ・D-2: TEGO GLIDE 490 (manufactured by EVONIC, solids content 65% by mass) ・D-3: 51 Additive (manufactured by Toray Dow Corning, solids content 80% by mass) ・D-4: IE-4290 Dispersion (manufactured by Toray Dow Corning, solids content 68% by mass) ・D-5: NANOFINE KPX-02-014 (manufactured by Toyo Chem, solids content 40% by mass) ・D-6: BY22-055 (manufactured by Toray Dow Corning, solids content 63.5% by mass) ・D-7: X-52-2127 (manufactured by Shin-Etsu Chemical Co., Ltd., solids content 75% by mass) • D-8: X-52-2265 (manufactured by Shin-Etsu Chemical Co., Ltd., solids content 40% by mass) • D-9: X-52-2328 (manufactured by Shin-Etsu Chemical Co., Ltd., solids content 60% by mass) • D-10: X-52-2162 (manufactured by Shin-Etsu Chemical Co., Ltd., solids content 65% by mass) • D-11: KM-910 (manufactured by Shin-Etsu Chemical Co., Ltd., solids content 60% by mass) • D-12: KM-903 (manufactured by Shin-Etsu Chemical Co., Ltd., solids content 60% by mass) • D-13: Leoflow DMS-55 (manufactured by Lion Corporation, solids content 55% by mass)

[0066] The following compounds were used as the olefin resin emulsion (E): • E-1: Aurolene AE-301 (manufactured by Nippon Paper Industries, 30% solids by mass) • E-2: Hardlen EW-5250 (manufactured by Toyobo MC Co., Ltd., 30% solids by mass) • E-3: Aurolene AE-202 (manufactured by Nippon Paper Industries, 30% solids by mass)

[0067] The following compounds were used as surface modifiers (F). • F-1: BYK-348 (manufactured by Big Chemie Japan, 96% solids) • F-2: Megafac F-444 (manufactured by DIC Corporation) • F-3: Florard FC-430 (manufactured by 3M Japan, 100% solids) • F-4: Megafac F-477 (manufactured by DIC Corporation, 100% solids) • F-5: Megafac F-552 (manufactured by DIC Corporation, 100% solids) • F-6: Megafac F-553 (manufactured by DIC Corporation, 100% solids) • F-7: Megafac F-554 (manufactured by DIC Corporation, 100% solids) • F-8: Megafac F-482 (manufactured by DIC Corporation, 20% solids) • F-9: Asahi Guard AG710 (manufactured by AGC Corporation, 19% solids) • F-10: Surflon S-382 (AGC Corporation, 50% solids) ・F-11: Surflon SC-101 (AGC Corporation, 30% solids) ・F-12: Surflon SC-105 (AGC Corporation, 50% solids) ・F-13: BYK-345 (Bic Chemie Japan, 87.5% solids) ・F-14: BYK-346 (Bic Chemie Japan, 45% solids) ・F-15: BYK-347 (Bic Chemie Japan, 85% solids) ・F-16: BYK-3450 (Bic Chemie Japan, 100% solids)

[0068] The following compounds were used as other components (desiccant, film-forming aid, resin emulsion): • Desiccant-1: Propylene glycol • Desiccant-2: Monoethylene glycol • Desiccant-3: Diethylene glycol • Desiccant-4: Glycerin • Desiccant-5: PEG200 • Desiccant-6: PEG300 • Desiccant-7: PEG400 • Desiccant-8: PEG600 • Anti-drying agent - 9: Urea • Anti-drying agent - 10: Polyoxyethylene sorbitan fatty acid ester • Anti-drying agent - 11: Polyoxyethylene sorbitan fatty acid ester • Anti-drying agent - 12: Thiourea • Anti-drying agent - 13: Ethylene urea • Anti-drying agent - 14: Ethylene glycol monophenyl ether • Anti-drying agent - 15: Propylene glycol monophenyl ether • Anti-drying agent - 16: Dipropylene glycol monomethyl ether • Anti-drying agent - 17: Dipropylene glycol monobutyl ether • Anti-drying agent - 18: Tripropylene glycol monoethyl ether • Film-forming aid - 1: Solfit (manufactured by Kuraray Co., Ltd.) Film-forming aid-2: 3-methoxy-3-methylbutanol, Film-forming aid-3: N-methyl-2-pyrrolidone, Film-forming aid-4: Ethylene glycol-tert-butyl ether, Film-forming aid-5: Ethylene glycol methyl ether acetate, Film-forming aid-6: Ethylene glycol-mono-n-ethyl ether, Film-forming aid-7: Ethylene glycol-mono-n-butyl ether, Film-forming aid-8: Carbitol acetate, Film-forming aid-9: Diethylene glycol-mono-n-butyl ether, Film-forming aid-10: Diethylene glycol-mono-ethyl ether Film-forming aid-11: Dipropylene glycol dimethyl ether; Film-forming aid-12: Texanol; Film-forming aid-13: Butyl carbitol acetate; Film-forming aid-14: Butyl cellosolve acetate; Film-forming aid-15: Hexylene glycol; Film-forming aid-16: Benzyl alcohol; Film-forming aid-17: Polyethylene glycol monomethyl ether; Film-forming aid-18: Polypropylene glycol monomethyl ether; Resin emulsion-1: Polyurethane resin emulsion, Bihydrol (registered trademark) UH2606 (manufactured by Covestro)

[0069] <<Evaluation of Water-Based Ink Compositions>> Using the water-based inks of this embodiment, the water-based ink compositions were evaluated (line clarity, repellency, abrasion resistance, water resistance, dishwasher resistance test, washing resistance test, wet friction test) using the following methods. The results obtained are shown in Tables 1 to 6. <Line Clarity> For testing, a specified amount of each water-based ink from the examples and comparative examples was filled into the core (cotton) of a fiber bundle. The ink-filled cotton was attached to a marker pen with a round tip. Lines were drawn on paper using these pens. After drying, the resulting images (lines) were evaluated as evaluation samples. Specifically, the evaluation was performed according to the following criteria. (Evaluation Criteria) A: The lines are clear and easily visible with sufficient density, without any obvious smudging or unevenness. C: The lines have obvious smudging or unevenness, or are too faint to be clearly visible.

[0070] <Ink Repellency> For testing purposes, a specified amount of each water-based ink from the examples and comparative examples was filled into the core (cotton) of a fiber bundle. The ink-filled cotton was attached to a marker pen with a round tip. Lines were drawn on PP film using these pens, and after drying for 5 minutes, the condition of the lines was observed. Specifically, the following criteria were used for evaluation: (Evaluation Criteria) A: No ink repelling in the ink composition B: Slight ink repelling in the ink composition, but at a level that does not pose a practical problem C: Ink repelling in the ink composition, writing is possible, but the lines are not visible or writing is difficult

[0071] <Abrasion Resistance Test> For the test, the specified amount of each water-based ink from the examples and comparative examples was filled into the core (cotton) of a fiber bundle. The ink-filled cotton was attached to a marker pen with a round tip. Using these pens, lines were drawn on the substrate (PP film, PET film, metal plate, or glass plate), and these were dried for 5 minutes. The dried samples were then used as evaluation samples, and the abrasion resistance of the formed images (lines) was evaluated. The test involved wrapping a Kimwipe around the index finger and examining its abrasion resistance. Specifically, the index finger wrapped with the Kimwipe was firmly pressed against the substrate, and a friction motion was performed 30 times back and forth. The degree of scratches and peeling that occurred on the lines was visually observed and evaluated. Specifically, the evaluation was based on the following criteria: 5: 0-5% damage 4: 6-15% damage 3: 16-35% damage 2: 36-60% damage 1: 61-100% damage

[0072] <Water Resistance Test> For the test, the specified amount of each water-based ink from the examples and comparative examples was filled into the core (cotton) of a fiber bundle. The ink-filled cotton was attached to a marker pen with a round tip. Using these pens, lines were drawn on the substrate (PP film or PET film), dried for 5 minutes, and then immersed in tap water for 15 minutes. The immersed samples were then used as evaluation samples, and the water resistance of the formed image (line) was evaluated. Specifically, a dishwashing sponge was placed in close contact with the substrate, and a friction motion was performed 30 times back and forth. The degree of damage and peeling that occurred on the line was visually observed and evaluated. Specifically, the evaluation was performed according to the following criteria: 5: 0-5% defect 4: 6-15% defect 3: 16-35% defect 2: 36-60% defect 1: 61-100% defect

[0073] <Corrosion Washer Resistance Test> For the test, the specified amounts of each water-based ink from the examples and comparative examples were filled into the core (cotton) of a fiber bundle. The ink-filled cotton was attached to a marker pen with a round tip. Using these pens, lines were drawn on PP film or PET film, respectively. After drying for 5 minutes, the film was automatically washed, rinsed, and air-dried using a standard course in a dishwasher SS-M151 (product name, manufactured by Siroca Corporation). The standard course is a course of approximately 1 hour and 30 minutes including washing, rinsing, and air-drying, with hot water of approximately 65°C used only for the final rinse. No detergent was used for washing. The samples after the standard course were used as evaluation samples, and the corrosion washer resistance of the formed images (lines) was evaluated. Specifically, the evaluation was performed according to the following criteria. (Evaluation Criteria) A: No change in the drawn lines B: Reduced visibility of the drawn lines, but at a level that does not pose a practical problem C: The drawn lines have faded or fallen off, and there is a clear deterioration in visibility

[0074] <Wash Resistance Test> For the test, the specified amount of each water-based ink from the examples and comparative examples was filled into the core (filling) of a fiber bundle. The ink-filled filling was attached to a marker pen with a round tip. Using these pens, lines were drawn on cotton cloth, dried for 5 minutes, and then washed in a household washing machine at a water temperature of 40°C or 60°C for 1 hour. The tested samples were then used as evaluation samples, and the resulting images (drawings) were evaluated by determining the discoloration grade by visual inspection according to Clause 10 (Determination of Color Fastness) of JIS L 0801. Specifically, the evaluation was performed according to the following criteria: (Evaluation Criteria) 5: Grade 5 level 4: Grade 4 level 3: Grade 3 level 2: Grade 2 level 1: Grade 1 level

[0075] <Moisture-Resistant Friction Test> For the test, the specified amount of each water-based ink from the examples and comparative examples was filled into the core (cotton) of a fiber bundle. The ink-filled cotton was attached to a marker pen with a round tip. Using these pens, lines were drawn on cotton cloth, and after drying for 5 minutes, each drawing was evaluated according to the wet test specified in JIS L 0849 "Test Method for Color Fastness to Friction" and the following criteria. The test was performed using the JSPS method. The evaluation was performed by visually determining the staining and discoloration grade according to Clause 10 (Determination of Color Fastness) of JIS L 0801, which is cited in JIS L 0849. (Evaluation Criteria) 5: Grade 5 level 4: Grade 4 level 3: Grade 3 level 2: Grade 2 level 1: Grade 1 level

[0076] For Examples 22 to 29, further dispersibility tests, storage stability tests, color development tests, and viscosity tests were performed using the following methods. The results obtained are shown in Table 5. <Dispersibility Test> After preparing the pigment dispersions for Examples 22 to 29, the particle size distribution was measured using the following measuring instrument under the following conditions. Measuring instrument: SZ-100 (manufactured by Horiba, Ltd.), measurement principle: dynamic light scattering method, diluent: ion-exchanged water, measurement temperature: 25°C. Specifically, the evaluation was performed according to the following criteria. (Evaluation Criteria) A: Compared to before dispersion, the particle size distribution is sharper and uniformly finer. B: Compared to before dispersion, it is slightly finer, but the particle size distribution is broad. C: Compared to before dispersion, the particle size distribution has hardly changed.

[0077] <Storage Stability Test> After preparing the pigment dispersions of Examples 22 to 29, they were left to stand at room temperature for one month, and the particle size distribution was measured using the same method as in the dispersibility evaluation test described above. Specifically, the following criteria were used for evaluation: (Evaluation Criteria) A: No change in particle size distribution compared to before standing B: Slight change in particle size distribution compared to before standing C: Significant change in particle size distribution compared to before standing

[0078] <Color Development Test> Color solutions were prepared using the pigment dispersions of Examples 22-29 before and after dispersion treatment, and comparative color development was performed. The difference in concentration was observed visually. Specifically, the following criteria were used for evaluation: (Evaluation Criteria) A: The concentration has increased significantly compared to before dispersion. B: The concentration has increased slightly compared to before dispersion. C: The concentration is almost unchanged or slightly increased compared to before dispersion.

[0079] <Viscosity Test> After preparing the pigment dispersions for Examples 22-29, the dispersions were transferred to poly cups, and the viscosity was visually checked immediately afterward. Specifically, the following criteria were used for evaluation: (Evaluation Criteria) A: Very low viscosity; the liquid flows like water when the poly cup is tilted. B: Medium viscosity; the liquid flows with a slight delay when the poly cup is tilted. C: High viscosity; the liquid does not move easily even when the poly cup is tilted.

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[0090] Furthermore, as a surface modifier (F), BYK-348 (manufactured by Bic Chemie Japan) was replaced with Florard FC-430 (manufactured by 3M Japan), a fluorine-based surfactant, and the evaluation was carried out in the same manner as in Example 1. The aqueous ink composition using Florard FC-430 (manufactured by 3M Japan) also showed excellent evaluation results, similar to Example 1.

[0091] For reference, various commercially available oil-based writing pens were subjected to the same corrosion-resistant washing machine tests as described above and evaluated in the same manner, and compared with the pens of the embodiment of the present invention. (Reference Example 1) Lines were drawn on PP film and PET film using a commercially available oil-based cotton-filled pen called Maki (registered trademark, manufactured by Zebra Co., Ltd.), and a corrosion-resistant washing machine test was performed and evaluated in the same manner as in the embodiment. As a result, under all conditions, the commercially available water-based pen in Reference Example 1 faded.

[0092] As an example of application, the aqueous ink composition according to this embodiment was used in direct-ink marker pens, spray coating agents, stamp inks, or ballpoint pens, and the above-mentioned evaluation tests were performed to evaluate the aqueous ink composition. (Application Example 1) Direct-ink marker pen The aqueous inks of Example 2 and Comparative Example 2 were filled into direct-ink marker pens in which the ink is directly filled into the pen body. Lines were drawn on PP film and PET film using the marker pens and dried for 5 minutes. When these were evaluated as evaluation samples, the lines drawn with the marker pen filled with the aqueous ink used in Example 2 showed particularly excellent abrasion resistance of the PP film and PET film, achieving the objective of the present invention. On the other hand, the lines drawn with the marker pen filled with the aqueous ink used in Comparative Example 2 showed inferior evaluation in the abrasion resistance test of the PP film and PET film, failing to achieve the objective of the present invention.

[0093] (Application Example 2) The aqueous ink of the spray coating agent Example 2 was filled into a small spray gun "W-71-2G" (manufactured by Anest Iwata Co., Ltd.), and the aqueous coating agent was applied to plastic molded products (PP blocks, PET blocks) by spray coating. The coating film was dried at approximately 60°C for several minutes to form. When this was evaluated as an evaluation sample, the abrasion resistance test showed particularly excellent results, achieving the objective of the present invention.

[0094] (Application Example 3) The water-based ink from Stamp Ink Example 2 was applied to a commercially available stamp pad, a medium-sized stamp pad for application (manufactured by Shachihata Co., Ltd.). When a rubber stamp inked with this stamp pad was used to print on PP film and an abrasion resistance test was performed, the results showed significantly superior abrasion resistance compared to PP film printed with a commercially available oil-based pigment stamp pad.

[0095] (Application Example 4) The water-based ink from Ballpoint Pen Example 2 was filled into a ballpoint pen refill to obtain a ballpoint pen with the refill installed. Lines were drawn on a PP film using this pen and a commercially available water-based ballpoint pen called Sarasa (registered trademark, manufactured by Zebra Co., Ltd.), and allowed to dry for 5 minutes. When the resulting handwriting was compared, the ballpoint pen in this embodiment showed particularly superior line clarity. Furthermore, when this evaluation sample was tested for abrasion resistance, it yielded excellent results, thus achieving the objective of the present invention.

[0096] As an example of application, flexographic inks, gravure inks, and inkjet inks were prepared using the aqueous ink composition according to this embodiment, and the above-mentioned evaluation tests were performed using these aqueous inks to evaluate the aqueous ink composition.

[0097] (Application Example 5) 100 parts of the aqueous ink obtained in Flexographic Ink Example 2, 2.4 parts of the product name "Denacol EX-612" (as solid content), 0.08 parts of a thickener (as solid content), 0.04 parts of an antifoaming agent (as solid content), and 0.2 parts of a surfactant were added and thoroughly mixed in a disperser. Then, the mixture was diluted with water in a Zahn cup #4 (manufactured by Rigosha) for 16 seconds (25°C) to obtain a black aqueous flexographic ink. A cell volume of 6.0 cm was applied to a plastic film (uniaxially shrinkable PET film, product name "Toyobo Space Clean S7053", manufactured by Toyobo Co., Ltd., thickness 40 μm). ３ / m ２ A flexo hand proofer equipped with an anilox roll was used as the applicator, and the coating amount after drying was 1.0 g / m². ２ A black ink prepared to achieve the following properties was applied to a plastic film. After application, it was dried at 25°C for 72 hours to obtain a printed material in which a printed layer, a dried film with a thickness of approximately 0.85 μm, was formed on one side of the plastic film. Various evaluation tests were conducted using the printed material, and a printed material with particularly excellent ink repellency and abrasion resistance was obtained.

[0098] (Application Example 6) 372 parts of the aqueous ink obtained in Gravure Ink Example 1 were mixed with 580 parts of IRR-11, 31 parts of deionized water, 4 parts of surfactant (product name "Tegowet 500", manufactured by Evonik), 8 parts of thickener (product name "SN Thickener 623N", manufactured by Sunopco), and 2 parts of defoamer. The mixture was diluted with deionized water so that the viscosity measured with a Zahn cup #4 was 14 seconds at 25°C to obtain an aqueous gravure ink for coating. <Manufacturing of printed materials> Anilox roll (cell volume: 4.5 cm) ３ / m ２ A flexographic hand proofer equipped with a 3D printer was used as an applicator to coat a plastic film (uniaxially shrinkable PET film, product name "Toyobo Space Clean S7053", manufactured by Toyobo Co., Ltd., 40 μm thick) with water-based gravure ink. The film was then dried at 25°C for 48 hours to form a coating on the base film, and test prints were obtained. Various evaluation tests were conducted using the printed materials, and prints with particularly excellent repellency and abrasion resistance were obtained.

[0099] (Application Example 7) The aqueous ink obtained in Inkjet Ink Example 2 was filtered through a 5 μm membrane filter to obtain inkjet ink. This ink was filled into an ink cartridge, and vertical and horizontal lines were printed on inkjet gloss paper PhotoLike QP (manufactured by Konica) using an inkjet printer. The degree of print distortion was observed visually, and no distortion was found. In particular, to check the abrasion resistance of the gloss paper, the printed surface was rubbed with a finger to check for any decrease in gloss, and there was no peeling, indicating a good result.

Claims

1. An aqueous ink composition comprising: a pigment (A), water (B), a pigment dispersant (C), a silicone resin emulsion (D), and an olefin resin emulsion (E), wherein the solid content of the silicone resin emulsion (D) is 2% by mass or more and 40% by mass or less relative to the total mass of the solid content of the ink composition, the solid content of the silicone resin emulsion (D) is 0.3% by mass or more and 10% by mass or less relative to the total mass of the aqueous ink composition, the solid content of the olefin resin emulsion (E) is 20% by mass or more and 70% by mass or less relative to the total mass of the solid content of the ink composition, the solid content of the olefin resin emulsion (E) is 5% by mass or more and 20% by mass or less relative to the total mass of the aqueous ink composition. An aqueous ink composition in which the mass ratio ((D) / (E)) of the silicone resin emulsion (D) to the olefin resin emulsion (E) on a solid content basis is 0.05 or more and 1.0 or less.

2. The aqueous ink composition according to claim 1, wherein the pigment dispersant (C) contains at least one selected from the group consisting of a dispersion resin made of a forming material containing at least one of styrene monomers and (meth)acrylic acid monomers, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant, and the mass ratio of the pigment dispersant (C) to the pigment (A) on a solid content basis ((C) / (A)) is 0.02 or more and 1.9 or less.

3. The aqueous ink composition according to claim 1, further comprising a surface modifier (F), wherein the surface modifier (F) is a surfactant, and the solid content of the surface modifier (F) is 0% by mass or more and 40% by mass or less with respect to the total solid content of the aqueous ink composition.

4. The aqueous ink composition according to claim 3, wherein the surface modifier (F) contains at least one of a fluorine-based surfactant and a polyether-modified siloxane-based surfactant.

5. The aqueous ink composition according to claim 1, further comprising a drying inhibitor.

6. The aqueous ink composition according to claim 1, further comprising a film-forming aid.

7. An aqueous ink comprising the aqueous ink composition according to any one of claims 1 to 6.

8. The aqueous ink according to claim 7, for use in at least one application selected from flexographic inks, gravure inks, and inkjet inks.

9. Use of the aqueous ink described in claim 7 in any one of the following: a cotton-filled pen, a direct-ink pen, a spray coating agent, a stamp ink, and a ballpoint pen.

10. A coated object using the water-based ink described in claim 7.

11. A coated article made using any one of the materials described in claim 9.

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