Aqueous ink composition

Abstract

The problem to be solved by the present invention is to provide an aqueous ink composition having excellent adhesion to at least one of a polyolefin base material, a polyester base material, and a polyamide base material. The problem is solved by using an aqueous ink composition comprising (A) a vinyl chloride-based resin emulsion and / or an acrylic resin emulsion, and at least one selected from the group consisting of (B) a polyolefin-based resin emulsion and (C) an alkali-soluble resin.

Description

Technical Field

[0001] The present invention relates to an aqueous ink composition. Background Art

[0002] Vinyl chloride resins are used in various applications due to their excellent chemical resistance, water resistance, weather resistance, flame retardancy, processability, and coloring. Coatings and inks are known as examples of applications. For example, Patent Document 1 describes a primer ink for inkjet recording, which contains an acrylic-vinyl chloride emulsion, a hydrazine derivative having at least two hydrazine residues, and water.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Publication No. 2018-12219 Summary of the invention

[0006] Problems to be solved by the invention

[0007] However, the substrates on which ink is applied include not only absorbent substrates such as paper but also poorly absorbent substrates such as films. In particular, there are various types of film substrates. However, in the above-mentioned prior art, the adhesion of ink to the substrate is insufficient depending on the type of film substrate, and there is room for improvement.

[0008] An object of one embodiment of the present invention is to provide an aqueous ink composition having excellent adhesion to at least any one of a polyolefin substrate, a polyester substrate, and a polyamide substrate.

[0009] Solutions to the problem

[0010] In order to solve the above problems, an aqueous ink composition according to one embodiment of the present invention contains (A) a vinyl chloride resin emulsion and / or an acrylic resin emulsion, and at least one selected from (B) a polyolefin resin emulsion and (C) an alkali-soluble resin.

[0011] Effects of the Invention

[0012] According to one embodiment of the present invention, there is provided an aqueous ink composition having excellent adhesion to at least one film substrate of a polyolefin substrate, a polyester substrate, and a polyamide substrate. DETAILED DESCRIPTION

[0013] An embodiment of the present invention is described below, but the present invention is not limited to these. The present invention is not limited by the various structures described below, and various changes can be made within the scope shown in the scope of the claims. In addition, embodiments or embodiments obtained by combining the technical means disclosed in different embodiments or embodiments are also included in the technical scope of the present invention. In addition, by combining the technical means disclosed in each embodiment, new technical features can be formed. It should be noted that all academic documents and patent documents recorded in this specification are cited as references in this specification. In addition, in this specification, unless otherwise specified, "A~B" indicating a numerical range means "Above A (including A and larger than A) and below B (including B and smaller than B)". In addition, "(meth)acrylic acid..." is intended to include both "methacrylic acid..." and "acrylic acid..."

[0014] [1. Aqueous ink composition]

[0015] The aqueous ink composition according to one embodiment of the present invention contains (A) a vinyl chloride resin emulsion and / or an acrylic resin emulsion, and at least one selected from (B) a polyolefin resin emulsion and (C) an alkali-soluble resin.

[0016] 〔1-1.(A) Ingredient〕

[0017] The aqueous ink composition according to one embodiment of the present invention contains a vinyl chloride resin emulsion and / or an acrylic resin emulsion as the component (A).

[0018] [1-1-1. Vinyl chloride resin emulsion]

[0019] "Vinyl chloride resin emulsion" refers to an emulsion of "vinyl chloride resin", and "vinyl chloride resin" refers to a resin obtained by polymerizing a monomer mixture containing vinyl chloride monomer. "Vinyl chloride resin" may include any resin obtained by polymerizing a monomer mixture containing vinyl chloride monomer, but when the total amount of the monomer mixture is 100 parts by weight, it is preferably a resin obtained by polymerizing a monomer containing, for example, 30 parts by weight or more, more preferably 40 parts by weight or more, and even more preferably 45 parts by weight or more of vinyl chloride monomer. The upper limit of the amount of vinyl chloride monomer contained in the total amount of the monomer mixture is also not particularly limited, and may be 100 parts by weight or less.

[0020] The above-mentioned "vinyl chloride resin" is not particularly limited, and examples thereof include vinyl chloride resin, vinyl chloride-acrylic acid composite resin, vinyl chloride-acrylic acid copolymer, vinyl chloride-urethane composite resin, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, and vinyl chloride-vinylidene chloride copolymer. Here, in the present specification, "vinyl chloride resin" refers to a resin mainly composed of vinyl chloride, preferably a resin containing more than 90 parts by weight and less than 100 parts by weight of vinyl chloride monomer when the total amount of the monomer mixture is 100 parts by weight. That is, in the present specification, "vinyl chloride resin" means a resin mainly composed of polyvinyl chloride containing only vinyl chloride monomer, and a resin mainly composed of vinyl chloride containing more than 90 parts by weight and less than 100 parts by weight of vinyl chloride monomer. In addition, "acrylic acid resin" refers to a resin mainly composed of acrylic acid, preferably a resin containing 50 to 100 parts by weight of acrylic acid monomer when the total amount of the monomer mixture is 100 parts by weight.

[0021] The above-mentioned "vinyl chloride resin emulsion" is not limited as long as it is an emulsion of "vinyl chloride resin". For example, "vinyl chloride resin emulsion" produced by emulsion polymerization can be used directly. In addition, a vinyl chloride resin produced by another method can be forcibly emulsified in water using a surfactant or the like. In addition, a vinyl chloride resin can be copolymerized with a monomer having a hydrophilic group, and water can be added to the obtained vinyl chloride resin containing a hydrophilic group to make it self-emulsified.

[0022] [1-1-1-1. Vinyl chloride-acrylic acid composite resin emulsion]

[0023] Examples of the vinyl chloride-acrylic acid composite resin emulsion include, for example, a resin emulsion of a resin obtained by polymerizing an acrylic monomer in the presence of a vinyl chloride resin, a resin emulsion of a resin obtained by polymerizing a vinyl chloride monomer in the presence of an acrylic resin, and a resin emulsion of a resin obtained by polymerizing a vinyl chloride monomer in the presence of a styrene / (meth)acrylate oligomer and / or a (meth)acrylate oligomer.

[0024] <Resin emulsion of a composite resin prepared by polymerizing an acrylic monomer in the presence of a vinyl chloride resin>

[0025] Examples of the resin obtained by polymerizing an acrylic monomer in the presence of the vinyl chloride resin include, for example, a resin obtained by polymerizing a monomer mainly composed of a vinyl chloride monomer in the first stage (hereinafter referred to as "step 1") in a multi-stage emulsion polymerization method, and obtaining a vinyl chloride-acrylic acid composite resin by polymerizing a monomer mainly composed of an acrylic monomer after the second stage (hereinafter referred to as "step 2").

[0026] The vinyl chloride-acrylic acid composite resin is, for example, a resin composited as follows: in a multi-stage emulsion polymerization method, as "step 1", a monomer mixture containing more than 90 parts by weight and less than 100 parts by weight of (a1) a vinyl chloride monomer and 0 to less than 10 parts by weight of (a2) an ethylenically unsaturated monomer copolymerizable with the vinyl chloride monomer (herein, the total amount of (a1) and (a2) is 100 parts by weight) is polymerized to obtain a vinyl chloride resin, and as [step 2], in the presence of the vinyl chloride resin, a monomer mixture containing 50 to 100 parts by weight of (b1) an alkyl (meth)acrylate and 0 to 50 parts by weight of (b2) an ethylenically unsaturated monomer copolymerizable with the (b1) (meth)acrylate (herein, the total amount of (b1) and (b2) is 100 parts by weight) is polymerized to obtain a resin composited with an acrylic resin.

[0027] The mechanism is considered to be that the monomers constituting the acrylic resin permeate into the vinyl chloride resin particles obtained in [Step 1] and polymerize inside the vinyl chloride resin particles, whereby the vinyl chloride resin and the acrylic resin do not form a clear core / shell structure inside the particles but are entangled with each other. As a result, composite resin particles having characteristics different from those of the prior art can be obtained.

[0028] (vinyl chloride resin)

[0029] The vinyl chloride resin is obtained by copolymerizing a monomer mixture by emulsion polymerization, wherein the monomer mixture contains more than 90 parts by weight and less than 100 parts by weight of (a1) vinyl chloride monomer and more than 0 and less than 10 parts by weight of (a2) ethylenically unsaturated monomer copolymerizable with the vinyl chloride monomer, and the polymerization is carried out as the first stage of a multi-stage emulsion polymerization. It should be noted that [Step 1] may be carried out once or in multiple stages by changing the composition of the monomer mixture.

[0030] In the vinyl chloride-acrylic acid composite resin, the function is mainly imparted by the acrylic resin obtained in [Step 2] in the multi-stage emulsion polymerization. Therefore, the composition of the vinyl chloride resin in [Step 1] can be relatively simple, and it can also be (a1) vinyl chloride monomer alone. However, copolymerization with other monomers is not denied, and (a2) ethylenically unsaturated monomers copolymerizable with vinyl chloride monomers can be used in combination as needed. The amount of (a2) used is preferably 0 or more and less than 10 parts by weight, and more preferably 0 to 5 parts by weight.

[0031] The ethylenically unsaturated monomer (a2) copolymerizable with the vinyl chloride monomer used in [Step 1] is not particularly limited, and examples thereof include all known monomers copolymerizable with vinyl chloride: for example, olefins such as ethylene, propylene, and butene; vinyl esters such as vinyl acetate, 2-ethylhexanoic acid (Versatic Acid) vinyl ester, vinyl propionate, and vinyl stearate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, octyl vinyl ether, and lauryl vinyl ether; vinylidenes such as vinylidene chloride; unsaturated carboxylic acids and anhydrides thereof such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride; unsaturated carboxylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, monomethyl maleate, dimethyl maleate, and butyl benzyl maleate; aromatic vinyl compounds such as styrene, α-methylstyrene, and divinylbenzene; unsaturated nitriles such as acrylonitrile, and the like. These (a2) ethylenically unsaturated monomers copolymerizable with the vinyl chloride monomer may be used alone or in combination of two or more.

[0032] In [Step 1], for the purpose of crosslinking the vinyl chloride resin and / or introducing a grafting point with the acrylic resin in [Step 2], (F) a compound having at least two non-conjugated double bonds may be used in combination.

[0033] The compound (F) having at least two non-conjugated double bonds used in [Step 1] is not particularly limited, and examples thereof include allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, diallyl fumarate, diallyl maleate, diallyl phthalate, triallyl trimellitate, trimethylolpropane diallyl ether, divinyl adipate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, monoethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, polyethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol diacrylate, polyethylene glycol diacrylate, and bisphenol-modified polyethylene glycol diacrylate.

[0034] In particular, when the purpose is to introduce a grafting point with the acrylic resin in [Step 2], the compound (F) having at least two non-conjugated double bonds is preferably a compound having two or more allyl groups, and particularly preferably triallyl cyanurate (TAC), triallyl isocyanurate, and triallyl trimellitate having three allyl groups. These compounds (F) having at least two non-conjugated double bonds may be used alone or in combination of two or more.

[0035] The amount of the compound having at least two non-conjugated double bonds (F) used is preferably 5 parts by weight or less, more preferably 1 part by weight or less, and further preferably 0.3 parts by weight or less, relative to 100 parts by weight of the total of the vinyl chloride monomer (a1) and the ethylenically unsaturated monomer copolymerizable with the vinyl chloride monomer (a2). When the amount of (F) used is 5 parts by weight or less, the crosslinking degree of the vinyl chloride resin does not become too high, and thus the penetration of the acrylic acid monomer polymerized in [Step 2] is not easily hindered. Therefore, intra-particle compounding is preferably performed.

[0036] In the emulsion polymerization of [Step 1], an ionic or nonionic surfactant generally used in emulsion polymerization can be used.

[0037] Examples of the ionic surfactant used in [Step 1] include anionic surfactants having a polyoxyalkylene chain such as polyoxyethylene nonylphenyl ether sulfate, polyoxyethylene allyl ether sulfate, octylphenoxyethoxyethyl sulfonate, polyoxyethylene tridecyl ether sulfate, and polyoxyethylene polycyclic phenyl ether sulfate; sulfonates such as sodium dodecyl sulfonate, sodium dodecylbenzenesulfonate, and sodium isooctylbenzenesulfonate; ammonium salts such as lauryl imidazoline and ammonium hydroxide; and sulfosuccinic acid-based surfactants such as sodium dilauryl sulfosuccinate.

[0038] Examples of the nonionic surfactant used in the [Step 1] include polyoxyalkylenes such as polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, and polyoxyethylene oxypropylene lauryl ether.

[0039] The surfactant used in the above-mentioned [Step 1] may be used alone or in combination of two or more.

[0040] The amount of the surfactant used in [Step 1] is preferably 10 parts by weight or less, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total amount of the vinyl chloride resin monomer mixture.

[0041] In [Step 1], from the viewpoint of suppressing the generation of new particles during emulsion polymerization and improving the water resistance and weather resistance of the obtained coating film, it is more preferred to use (G) a reactive surfactant having a polymerizable double bond in one molecule as part or all of the surfactants used. In particular, by using a reactive surfactant having a polyoxyalkylene group in the molecule, the mechanical stability of the obtained resin emulsion can be improved.

[0042] Examples of the reactive surfactant (G) having a polymerizable double bond in one molecule used in [Step 1] include, for example, ADEKA REASOAP (registered trademark) ER-10, ER-20, ER-30, ER-40, SR-05, SR-10, SR-20, SR-1025, SR-2025, SR-3025, NE-10, NE-20, NE-30, NE-40, SE-10N manufactured by ADEKA Corporation; Antox (registered trademark) MS-60, RMA-1120, RMA-564, RMA-568, RMA-506 manufactured by Nippon Emulsifier Co., Ltd.; Aqualon (registered trademark) KH-05, KH-10, RN-20, RN-30, RN- 50, RN-2025, HS-10, HS-20, HS-1025, BC05, BC10, BC0515, BC1025, AR-10, AR-20, AR-1025, AR-2020, AN-10, AN-20, AN-30, AN-5065; ELEMINOL (registered trademark) JS-2, JS-20, RS-30, RS-3000 manufactured by Sanyo Chemical Industries, Ltd.; LATEMUL (registered trademark) S-180, S-180A, PD-104, PD-420, PD-430, PD-430S manufactured by Kao Corporation, etc.

[0043] Examples of the polymerization initiator used in [Step 1] include, for example, organic peroxides, azo initiators, peroxodisulfates (also referred to as "persulfates"), aqueous hydrogen peroxide solutions, and the like. Examples of the organic peroxide include, for example, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxyisopropyl carbonate, p-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, and the like. Examples of the azo initiator include, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and the like. Examples of the peroxodisulfates include, for example, ammonium persulfate, potassium persulfate, sodium persulfate, and the like. These polymerization initiators may be used alone or in combination of two or more.

[0044] The polymerization initiator used in [Step 1] may be used in combination with a reducing agent such as sodium sulfite, sodium thiosulfate, sodium hydroxymethanesulfinate, ascorbic acid, sodium ascorbate, Rongalite, Bruggolite (registered trademark) FF-6, thiourea dioxide, etc. as needed. It should be noted that, in consideration of the impact on the environment, the reducing agent is particularly preferably Bruggolite (registered trademark) FF-6 and thiourea dioxide, which do not generate formaldehyde. These reducing agents may be used alone or in combination of two or more.

[0045] The amount of the polymerization initiator used in [Step 1] is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, relative to 100 parts by weight of the total amount of the monomer mixture of (a1) + (a2). When the amount of the polymerization initiator used is 0.01 parts by weight or more, polymerization is easy to proceed; when it is 5 parts by weight or less, heat generation can be appropriately controlled.

[0046] It should be noted that, in particular, from the viewpoint of polymerization stability and water resistance, it is preferred to use an organic peroxide together with a redox catalyst and a reducing agent as a redox polymerization initiator. As the above-mentioned redox catalyst, for example, a transition metal complex generated by combining a transition metal salt and a chelating agent can be used. As the above-mentioned transition metal salt, for example, ferrous sulfate (II), copper sulfate (II), copper chloride, etc. can be mentioned; as a chelating agent, for example, disodium ethylenediaminetetraacetate (EDTA·2Na), tartaric acid, ammonia, etc. can be mentioned. When ferrous sulfate (II) is used as a transition metal salt and disodium ethylenediaminetetraacetate (EDTA·2Na) is used as a chelating agent, Fe-EDTA is generated and functions as a redox catalyst.

[0047] (Acrylic resin)

[0048] The acrylic resin is provided with various functions by polymerizing the acrylic monomer mixture as [Step 2] in the presence of the vinyl chloride resin obtained in [Step 1] and compounding with the vinyl chloride resin.

[0049] The mechanism is considered to be that the monomers constituting the acrylic resin permeate into the vinyl chloride resin particles present in the system and polymerize in the particles, whereby the vinyl chloride resin and the acrylic resin are entangled with each other in the particles.

[0050] According to the above configuration, the presence position of the acrylic resin in the particle can be arbitrarily adjusted by adjusting the monomer composition constituting the acrylic resin to change the balance of hydrophilicity / hydrophobicity. That is, it is believed that when the acrylic resin adopts a composition with higher hydrophobicity than the vinyl chloride resin, it can be placed closer to the inside of the particle, and conversely, when the acrylic resin adopts a composition with higher hydrophilicity than the vinyl chloride resin, it can be placed closer to the outside of the particle. In addition, when the acrylic resin and the vinyl chloride resin are set to the same level of hydrophilicity / hydrophobicity, it is believed that the presence positions of the acrylic resin and the vinyl chloride resin are nearly uniform.

[0051] It should be noted that [Step 2] may be performed once or may be performed in multiple steps by changing the composition of the monomer mixture. The polymerization composition of the acrylic resin in [Step 2] is composed of 50 to 100 parts by weight of (b1) (meth)acrylic acid alkyl ester and 0 to 50 parts by weight of (b2) an ethylenically unsaturated monomer copolymerizable with the (meth)acrylic acid alkyl ester (here, the total amount of (b1) and (b2) is 100 parts by weight).

[0052] Specific examples of the (b1) alkyl (meth)acrylate used in [Step 2] include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, etc. These (b1) alkyl (meth)acrylates may be used alone or in combination of two or more.

[0053] The ethylenically unsaturated monomer (b2) copolymerizable with the (meth)acrylic acid alkyl ester used in [Step 2] is not particularly limited as long as it is copolymerizable with the (meth)acrylic acid alkyl ester (b1). Specific examples of (b2) include: aromatic hydrocarbon vinyl monomers such as styrene, α-methylstyrene, chlorostyrene, 4-hydroxystyrene, and vinyltoluene; vinyl esters such as vinyl acetate, vinyl propionate, and 2-ethylhexanoic acid (versatic acid) vinyl ester; allyl compounds; nitrile-containing vinyl monomers such as (meth)acrylonitrile; macromonomers such as AS-6, AN-6, AA-6, AB-6, and AK-5 manufactured by Toagosei Co., Ltd.; vinyl methyl ether, propylene, butadiene, vinyl chloride, and vinylidene chloride. These (b2) ethylenically unsaturated monomers copolymerizable with the (meth)acrylic acid alkyl ester may be used alone or in combination of two or more.

[0054] As (b2) used in [Step 2] of the present invention, a vinyl monomer further having an acid group may be used. The presence of an acid group can improve the mechanical stability and chemical stability of the obtained resin emulsion and the adhesion to the substrate when used as a coating film.

[0055] Specific examples of the vinyl monomer having an acid group include: unsaturated carboxylic acids and anhydrides thereof such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, etc.; monomers having a sulfonic acid group such as sodium styrene sulfonate, sodium 2-sulfoethyl methacrylate, ammonium 2-sulfoethyl methacrylate, acrylamide tert-butyl sulfonic acid, sodium acrylamide tert-butyl sulfonate, etc. The vinyl monomer having an acid group may be used alone or in combination of two or more thereof.

[0056] When the total amount of the monomer mixture constituting the vinyl chloride resin and the acrylic resin is set to 100 parts by weight, the amount of the vinyl monomer having the acid group is preferably 0.2 to 10 parts by weight, more preferably 0.5 to 10 parts by weight, and further preferably 1 to 5 parts by weight. When the amount of the vinyl monomer having the acid group is 0.2 parts by weight or more, the obtained resin emulsion has excellent mechanical stability and chemical stability; when it is 10 parts by weight or less, a sharp increase in the viscosity of the emulsion and a decrease in water resistance can be prevented.

[0057] As (b2) used in [Step 2], a vinyl monomer having a hydroxyl group may also be further used. Since it has a hydroxyl group, it is preferred from the viewpoint of improving the dispersibility of the pigment and being able to introduce crosslinking points with isocyanate, melamine, etc. Specific examples of vinyl monomers having a hydroxyl group include: for example, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxyethyl vinyl ether, hydroxystyrene; Alonics (registered trademark) 5700 manufactured by Toagosei Co., Ltd.; Placcel (registered trademark) FA-1, FA-4, FM-1, FM-4 manufactured by Daicel Co., Ltd.; HE-10, HE-20, HP-10, HP-20 manufactured by Nippon Shokubai Co., Ltd.; BLEMMER (registered trademark) PEP series, NKH-5050, GLM manufactured by NOF Corporation; hydroxyl-containing vinyl-modified hydroxyalkyl vinyl monomers, etc. The above-mentioned vinyl monomers having a hydroxyl group may be used alone or in combination of two or more.

[0058] When the total amount of the monomer mixture constituting the above-mentioned vinyl chloride resin and the above-mentioned acrylic resin is set to 100 parts by weight, the usage amount of the vinyl monomer having a hydroxyl group is preferably 0.2 to 50 parts by weight, more preferably 1 to 30 parts by weight, and further preferably 2 to 20 parts by weight.

[0059] As (b2) used in [Step 2], a vinyl monomer having a polyoxyalkylene chain may be used. Since the polyoxyalkylene chain is present, the mechanical stability and chemical stability of the obtained resin emulsion can be improved even when a vinyl monomer having an acid group is not used, and this is preferred from this point of view.

[0060] Specific examples of the vinyl monomer having the polyoxyalkylene chain include: for example, BLEMMER (registered trademark) PE-90, PE-200, PE-350, AE-90, AE-200, AE-350, PP-500, PP-800, PP-1000, AP-400, AP-550, AP-800, 700PEP-350B, 10PEP-550B, 55PET-400, 30PET-800, 55PET-800, 800PEP-1000, 800PEP-1000, 800PEP-1000, 800PEP-1000, 800PEP-1000, 800PEP-1000, 800PEP-1000, 800PEP-1000, 800PEP-1000, 800PEP-1000, 800PEP-1000 00, 30PPT-800, 50PPT-800, 70PPT-800, PME-100, PME-200, PME-400, PME-1000, PME-4000, AME-400, 50POEP-800B, 50AOEP-800B, AEP, AET, APT, PLE, ALE, PSE, ASE, PKE, AKE, PNE, ANE, PNP, ANP, PNEP-600; Light Ester (registered trademark) 130MA, 041MA, MTG, LightAcrylate (registered trademark) EC-A, MTG-A, 130A, DPM-A, P-200A, NP-4EA, NP-8EA, EHDG-A; MA-30, MA-50, MA-100, MA-150, RMA-1120, RMA-564, RMA-568, RMA-506, MPG130-MA, Antox MS-60, MPG-130MA, RMA-150M, RMA-300M, RMA-450M, RA-1020, RA-1120, RA-1820 manufactured by Nippon Emulsifier Co., Ltd.; NK-ESTER manufactured by Shin-Nakamura Chemical Industry Co., Ltd. M-20G, M-40G, M-90G, M-230G, AMP-10G, AMP-20G, AMP-60G, AM-90G, LA, etc. The vinyl monomers having the above polyoxyalkylene chains may be used alone or in combination of two or more.

[0061] When the total amount of the monomer mixture constituting the above-mentioned vinyl chloride resin and the above-mentioned acrylic resin is set to 100 parts by weight, the usage-amount of the above-mentioned vinyl monomer having a polyoxyalkylene chain is preferably 0.2 parts by weight to 10 parts by weight, more preferably 1 part by weight to 10 parts by weight, and further preferably 2 parts by weight to 5 parts by weight.

[0062] As (b2) used in [Step 2], a compound (F) having at least two non-conjugated double bonds can be used. In this case, the generated particles have a cross-linked structure inside, and the water resistance of the formed coating film is improved.

[0063] The usage-amount of the compound (F) having at least two non-conjugated double bonds is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 5 parts by weight, and still more preferably 1 to 3 parts by weight, based on 100 parts by weight of the total amount of the monomer mixture constituting the acrylic resin.

[0064] By using a fluorine-containing vinyl monomer as (b2) used in [Step 2], a high degree of water-repellent / oil-repellent function can be imparted.

[0065] Specific examples of the fluorine-containing vinyl monomers include trifluoro(meth)acrylic acid, pentafluoro(meth)acrylic acid, perfluorocyclohexyl(meth)acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, β-(perfluorooctyl)ethyl(meth)acrylate, etc. The fluorine-containing vinyl monomers may be used alone or in combination of two or more. When the total amount of the monomer mixture constituting the vinyl chloride resin and the acrylic resin is 100 parts by weight, the amount of the fluorine-containing vinyl monomer used is preferably 0.1 to 50 parts by weight, more preferably 1 to 40 parts by weight, and even more preferably 2 to 30 parts by weight.

[0066] By using a monomer having an alkoxysilyl group as (b2) used in [Step 2], crosslinking properties can be imparted and adhesion to glass, metal, and the like can be improved.

[0067] Specific examples of the monomer having an alkoxysilyl group include vinyl trimethoxysilane, γ-(meth)acryloxypropyl trimethoxysilane, vinyl triethoxysilane, γ-(meth)acryloxypropyl triethoxysilane, γ-(meth)acryloxypropyl tripropoxysilane, γ-(meth)acryloxypropyl tributoxysilane, vinyl methyl dimethoxysilane, γ-(meth)acryloxypropyl methyl dimethoxysilane, vinyl methyl diethoxysilane, γ-(meth)acryloxypropyl methyl diethoxysilane, γ-(meth)acryloxypropyl methyl dipropoxysilane, γ-(meth)acryloxypropyl methyl dibutoxysilane, etc. The monomer having an alkoxysilyl group may be used alone or in combination of two or more thereof. The amount of the monomer having an alkoxysilyl group used is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, and even more preferably 1 to 10 parts by weight, based on 100 parts by weight of the total amount of the monomer mixture constituting the vinyl chloride resin and the acrylic resin.

[0068] As (b2) used in [Step 2], by using an ethylenically unsaturated monomer having a carbonyl group derived from a ketone group or an aldehyde group, the adhesion to the film can be improved. Specific examples of the above-mentioned ethylenically unsaturated monomer having a carbonyl group derived from a ketone group or an aldehyde group include: for example, acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, styrene, vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), etc. Among them, from the viewpoint of reactivity, availability, and economy, diacetone acrylamide and diacetone methacrylamide are particularly preferred. The above-mentioned ethylenically unsaturated monomer having a carbonyl group derived from a ketone group or an aldehyde group can be used alone or in combination of two or more.

[0069] The amount of the ethylenically unsaturated monomer having a carbonyl group derived from a ketone group or an aldehyde group used is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total monomer mixture constituting the acrylic resin.

[0070] In [Step 2], crosslinking properties may be imparted by using an ethylenically unsaturated monomer having a carbonyl group derived from a ketone group or an aldehyde group as (b2), obtaining an acrylic resin, compounding the acrylic resin with a vinyl chloride resin, and then adding (D) a hydrazine derivative having at least two hydrazine groups or urea amino groups per molecule to the obtained emulsion. This can improve the water resistance, solvent resistance, and adhesion of the obtained coating film, ink, etc.

[0071] Specific examples of the hydrazine derivative having at least two hydrazino groups or ureaamino groups per molecule of (D) include: saturated aliphatic carboxylic acid dihydrazides having 2 to 18 carbon atoms, such as oxalic acid dihydrazide, malonic acid dihydrazide, glutaric acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, etc.; monoolefinic unsaturated dicarboxylic acid dihydrazides, such as maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide, etc.; phthalic acid dihydrazide, terephthalic acid dihydrazide or isophthalic acid dihydrazide, and dihydrazide, trihydrazide or tetrahydrazide of pyromellitic acid; nitrile triacetic acid trihydrazide, citric acid trihydrazide, 1,2,4-benzenetrihydrazide, ethylenediaminetetraacetic acid tetrahydrazide, 1,4,5,8-naphthoic acid tetrahydrazide; oligomers having a carboxylic acid lower alkyl ester group and hydrazide or hydrazine hydrate (hydrazine hydrate) (see Japanese Patent Publication No. 52-22878); dihydrazide carbonate, bis-semicarbazide; polyfunctional semicarbazide obtained by reacting diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate and polyisocyanate compounds derived therefrom with an excess of dihydrazide compounds and / or the above-mentioned dihydrazides; aqueous polyfunctional semicarbazide obtained by reacting the isocyanate groups in the reaction products of the above-mentioned polyisocyanate compounds with active hydrogen compounds containing hydrophilic groups such as polyether polyols and polyethylene glycol monoalkyl ethers with an excess of the above-mentioned dihydrazides; or a mixture of the above-mentioned polyfunctional semicarbazide and the above-mentioned aqueous polyfunctional semicarbazide (see Japanese Patent Publication No. 8-151358 and Japanese Patent Publication No. 8-245878), etc. The above-mentioned (D) hydrazine derivative having at least two hydrazino groups or ureaamino groups per molecule may be used alone or in combination of two or more thereof.

[0072] The amount of the hydrazine derivative having a hydrazine group or ureaamino group (D) to be incorporated is preferably 0.01 to 2 mol, more preferably 0.05 to 1.5 mol, of the total amount of functional groups selected from hydrazide groups, ureaamino groups and hydrazone groups per 1 mol of carbonyl groups in the acrylic resin.

[0073] That is, the vinyl chloride-acrylic acid composite resin emulsion has a carbonyl group derived from a ketone group and an aldehyde group, and more preferably further contains (D) a hydrazine derivative having at least two hydrazine groups or urea amino groups per molecule.

[0074] On the other hand, when the hydrophilicity becomes too high, the acrylic resin in [Step 2] is concentrated near the particle surface, and the interface with the vinyl chloride resin becomes clear, making it difficult to obtain the intended improvement effect, and the emulsion viscosity may increase rapidly.

[0075] Therefore, from the viewpoint of being able to reduce the viscosity of the emulsion, it is more desirable that the hydrophobic monomer having a solubility of less than 5 g / L in water at 20° C. is 60 parts by weight or more, more preferably 80 parts by weight or more, based on 100 parts by weight of the total monomer mixture constituting the acrylic resin. When the ratio of the hydrophobic monomer is 60 parts by weight or more, the acrylic resin is not concentrated near the surface of the particles, so that the properties of the vinyl chloride resin are easily exhibited, the viscosity of the emulsion can be reduced, and productivity and economy are improved.

[0076] Here, in this specification, the solubility of the monomer in water is the value described in the SDS of the manufacturer. The solubility of the main monomers in water (evaluation temperature) is shown below.

[0077] Vinyl chloride: 8.8g / L (25℃)

[0078] Butyl methacrylate: 0.36g / L (20℃)

[0079] Tert-butyl methacrylate: 0.36 g / L (25°C)

[0080] Methyl methacrylate: 15.3g / L (20℃)

[0081] Styrene: 0.32g / L (25℃)

[0082] Butyl acrylate: 1.7g / L (20℃)

[0083] ·2-Ethylhexyl acrylate: 0.025g / L (30℃)

[0084] Methacrylic acid: ∞

[0085] ·Diacetone acrylamide: more than 100g / 100g

[0086] In addition, since the solubility in water decreases when the dissolution temperature decreases, when the evaluation temperature of the SDS value described by the manufacturer is 20° C. or higher, the solubility at 20° C. is regarded as being below the described value.

[0087] In order to improve impact resistance, flexibility and film-forming properties, the glass transition temperature (hereinafter referred to as "Tg") of the acrylic resin is preferably set lower than the Tg of the vinyl chloride resin.

[0088] Therefore, the glass transition temperature (Tg) of the resin obtained by polymerizing the monomer mixture is calculated by the following Fox formula.

[0089] 1 / Tg=Σ(Wn / Tgn) / 100

[0090] In the above formula, Wn represents the weight % of monomer n, and Tgn represents the Tg (absolute temperature) of a homopolymer composed of monomer n.

[0091] The Tg values ​​of the main homopolymers are shown below.

[0092] Vinyl chloride: 80℃

[0093] Butyl methacrylate: 20℃

[0094] Tert-butyl methacrylate: 107°C

[0095] Methyl methacrylate: 105℃

[0096] Styrene: 100℃

[0097] Butyl acrylate: -54℃

[0098] ·2-Ethylhexyl acrylate: -70℃

[0099] Methacrylic acid: 144°C

[0100] Diacetone acrylamide: 77°C.

[0101] As the surfactant and the polymerization initiator used for the polymerization of the acrylic resin in [Step 2], the same ones as those exemplified for the polymerization of the vinyl chloride resin in [Step 1] can be used.

[0102] In addition, similar to the polymerization of the vinyl chloride resin in [Step 1], in [Step 2], from the viewpoints of suppressing the generation of new particles, water resistance and weather resistance, it is preferred to use a reactive surfactant having a polymerizable double bond in the (G)1 molecule as part or all of the surfactant. In particular, when a reactive surfactant having a polyoxyalkylene group in the molecule is used, mechanical stability can be improved.

[0103] As the polymerization initiator used in [Step 2], a redox polymerization initiator in which an organic peroxide, a redox catalyst and a reducing agent are combined is particularly preferred from the viewpoint of polymerization stability and water resistance.

[0104] In the vinyl chloride-acrylic acid composite resin, the weight ratio of the vinyl chloride resin to the acrylic resin is preferably 95:5 to 20:80, more preferably 70:30 to 30:70, from the viewpoint of adhesion, impact resistance, flexibility and film-forming properties.

[0105] In the measurement based on the dynamic light scattering method, the average particle size of the above-mentioned vinyl chloride-acrylic acid composite resin after the completion of [Step 2] is preferably 20nm to 500nm, and more preferably 50nm to 300nm. When the average particle size of the composite resin particles is 20nm or more, the viscosity can be reduced and the stability can be improved, so it is preferred; when it is 500nm or less, the water resistance is excellent, so it is preferred. In addition, when the above-mentioned vinyl chloride-acrylic acid composite resin emulsion is directly used as ink, it is more preferred to adjust the average particle size of the above-mentioned composite resin particles to 60nm to 120nm. As a result, especially the adhesion, water resistance and water whitening resistance become good. It should be noted that the average particle size can be adjusted by the amount of surfactant initially added in [Step 1].

[0106] The composite resin particles obtained by the present invention may be used as they are in the state of an emulsion, or may be dried and used as a powder.

[0107] <Resin emulsion of a resin obtained by polymerizing a vinyl chloride monomer in the presence of an acrylic resin>

[0108] The resin emulsion of a resin obtained by polymerizing a vinyl chloride monomer in the presence of an acrylic resin is not particularly limited, and examples thereof include, for example, an emulsion of a vinyl chloride-acrylic composite resin obtained by polymerizing a monomer mainly composed of an acrylic monomer in the first stage and a monomer mainly composed of a vinyl chloride monomer in the second stage and thereafter in a multi-stage emulsion polymerization method. As the above-mentioned "monomer mainly composed of an acrylic monomer" and "monomer mainly composed of a vinyl chloride monomer", the same monomers as those described in the above-mentioned <Resin emulsion of a resin obtained by polymerizing an acrylic monomer in the presence of a vinyl chloride resin> can be used. In addition, a surfactant, a polymerization initiator, etc. used for emulsion polymerization can be appropriately selected and used.

[0109] Resin emulsions of resins obtained by polymerizing vinyl chloride monomers in the presence of the acrylic resin are well known in the art, and conventionally known resin emulsions can be used as appropriate. A suitable example is the resin emulsion described in Japanese Patent No. 6247317.

[0110] <Resin emulsion of a resin obtained by polymerizing a vinyl chloride monomer in the presence of a styrene / (meth)acrylate oligomer and / or a (meth)acrylate oligomer>

[0111] The resin emulsion of a resin obtained by polymerizing a vinyl chloride monomer in the presence of a styrene / (meth)acrylate oligomer and / or a (meth)acrylate oligomer is not particularly limited, and examples thereof include, for example, an emulsion of a vinyl chloride-acrylic composite resin obtained by polymerizing a monomer mainly composed of a vinyl chloride monomer in a container to which commercially available styrene / (meth)acrylate oligomer and / or a (meth)acrylate oligomer is added. As the above-mentioned "monomer mainly composed of a vinyl chloride monomer", the same monomer as that described in the above-mentioned <Resin emulsion of a resin obtained by polymerizing an acrylic monomer in the presence of a vinyl chloride resin> can be used. In addition, a surfactant, a polymerization initiator, etc. used for emulsion polymerization can be appropriately selected and used.

[0112] Resin emulsions of resins obtained by polymerizing vinyl chloride monomers in the presence of the above-mentioned styrene / (meth)acrylate oligomers and / or (meth)acrylate oligomers are well known in the art, and conventionally known resin emulsions can be used appropriately. As a suitable example, there can be cited: resin emulsions described in, for example, International Publication No. 2010-140647.

[0113] [1-1-1-2. Vinyl chloride resin emulsion]

[0114] The vinyl chloride resin emulsion is not particularly limited, and examples thereof include an emulsion of a vinyl chloride resin obtained by polymerizing a monomer mainly composed of a vinyl chloride monomer in an emulsion polymerization method.

[0115] As the above-mentioned "monomer mainly composed of vinyl chloride monomer", the same monomers as those described in the above-mentioned <Resin emulsion obtained by polymerizing acrylic monomer in the presence of vinyl chloride resin> can be used. In addition, a surfactant, polymerization initiator, etc. used for emulsion polymerization can also be appropriately selected and used.

[0116] [1-1-1-3. Vinyl chloride-acrylic acid copolymer emulsion]

[0117] The vinyl chloride-acrylic acid copolymer emulsion is not particularly limited, and examples thereof include, for example, an emulsion of a vinyl chloride-acrylic acid copolymer obtained by copolymerizing a monomer mainly composed of a vinyl chloride monomer and a monomer mainly composed of an acrylic acid-based monomer in an emulsion polymerization method. As the above-mentioned "monomer mainly composed of an acrylic acid-based monomer" and "monomer mainly composed of a vinyl chloride monomer", the same monomers as those described in the above-mentioned <Resin emulsion of a resin obtained by polymerizing an acrylic acid-based monomer in the presence of a vinyl chloride resin> can be used. In addition, a surfactant, a polymerization initiator, etc. used for emulsion polymerization can be appropriately selected and used.

[0118] The above-mentioned vinyl chloride-acrylic acid copolymer emulsion is well known in the art, and conventionally known resin emulsions can be used appropriately. As a suitable example, there can be mentioned the resin emulsions described in Japanese Unexamined Patent Publication No. 10-176132.

[0119] [1-1-2. Acrylic resin emulsion]

[0120] The acrylic resin emulsion is not particularly limited, and examples thereof include, for example, an acrylic resin emulsion obtained by polymerizing a monomer mainly composed of an acrylic monomer in an emulsion polymerization method. Here, the acrylic resin is a resin obtained by polymerizing a monomer containing no vinyl chloride monomer or only a trace amount (less than 10 parts by weight of the vinyl chloride monomer when the total amount of the monomer mixture is 100 parts by weight).

[0121] As the above-mentioned "monomer mainly composed of acrylic monomers", the same monomers as those described in the above-mentioned <Resin emulsion of a resin obtained by polymerizing acrylic monomers in the presence of a vinyl chloride resin> can be used. In addition, regarding the method of emulsion polymerization and the surfactant, polymerization initiator, etc. used, the method described in [Step 2] of the above-mentioned <Resin emulsion of a resin obtained by polymerizing acrylic monomers in the presence of a vinyl chloride resin> and the surfactant, polymerization initiator, etc. used can be appropriately selected and adopted. Therefore, the emulsion polymerization can be carried out in one step or in multiple steps by changing the composition of the monomer mixture.

[0122] The acrylic resin emulsion is well known in the art, and conventionally known resin emulsions can be used appropriately. As a suitable example, resin emulsions described in, for example, Japanese Patent Application Laid-Open No. 2006-070236 and International Publication No. 2018-088560 can be cited.

[0123] As these acrylic resin emulsions, products commercially available from various companies can be used, and examples thereof include: Bonkote (registered trademark) and Watersol (registered trademark) manufactured by DIC Corporation; Acryset (registered trademark) and UWR (registered trademark) manufactured by Nippon Shokubai Co., Ltd.; Polysol (registered trademark) manufactured by Showa Denko K.K.; Yodosol (registered trademark) and KANEBINOL (registered trademark) manufactured by Henkel Japan; Polytron (registered trademark) and Polydurex (registered trademark) manufactured by Asahi Kasei Chemicals Co., Ltd.; Recabond (registered trademark) and Mowinyl (registered trademark) manufactured by Japan Coating Resin Co., Ltd.; Kaneka Gemlac (registered trademark) manufactured by Kaneka Co., Ltd.; PRIMAL (registered trademark) manufactured by The Dow Chemical Company; Acronal (registered trademark) and Joncryl (registered trademark) manufactured by BASF; NeoCryl (registered trademark) and Bayhydrol (registered trademark) manufactured by Covestro AG, and the like.

[0124] In the description of the above-mentioned vinyl chloride-acrylic composite resin emulsion, it is described that an ethylenically unsaturated monomer having a carbonyl group derived from a ketone group or an aldehyde group is used, and preferably further contains (D) a hydrazine derivative having at least two hydrazine groups or urea amino groups per molecule. For the same reason, the other (A) component also uses an ethylenically unsaturated monomer having a carbonyl group derived from a ketone group or an aldehyde group, and preferably further contains (D) a hydrazine derivative having at least two hydrazine groups or urea amino groups per molecule.

[0125] Among them, from the viewpoint of the balance between film-forming property and film hardness, the vinyl chloride resin emulsion is more preferably a vinyl chloride-acrylic composite resin emulsion, and even more preferably a composite resin emulsion obtained by polymerizing an acrylic monomer in the presence of a vinyl chloride resin.

[0126] [1-2. (B) Component]

[0127] The aqueous ink composition according to one embodiment of the present invention may contain a polyolefin resin emulsion as the component (B).

[0128] The polyolefin resin emulsion is an emulsion of a polyolefin resin. The polyolefin resin is not particularly limited, and examples thereof include polypropylene, ethylene-propylene copolymer, and ethylene-propylene-butene copolymer.

[0129] The polyolefin resin may be subjected to a modification treatment selected from chlorination modification, acrylic acid modification and maleic anhydride modification, and is more preferably a chlorination-modified polyolefin resin emulsion, and particularly preferably a chlorinated polypropylene resin emulsion.

[0130] The polyolefin resin emulsion is well known in the art, and any conventionally known polyolefin resin emulsion can be used appropriately. Suitable examples include resin emulsions described in Japanese Unexamined Patent Application Publication Nos. 2013-193324 and 10-298233.

[0131] The above-mentioned polyolefin resin can use commercially available products on the market. Examples of commercially available products include: Superchlon (registered trademark) series manufactured by Nippon Paper Industries, Ltd. (Superchlon (registered trademark) E-415, E-480T, E-604 (maleic anhydride modified / chlorinated), E-723 (chlorinated), etc.), Auroren (registered trademark) series manufactured by Nippon Paper Industries, Ltd. (chlorine-free polyolefins, Auroren (registered trademark) AE-301, AE-202 (maleic anhydride / acrylic acid modified), S-6375 (maleic anhydride / acrylic acid modified), etc.). Acrylic acid modified), etc.), Hardlen (registered trademark) EH-801J, EW-5515, EW-5303, EW-5250 (maleic anhydride modified / chlorinated), NA-1015, NA-1100, NA-4002, NA-3002, NZ-1001, NZ-1004, NZ-1015, NZ-1029 (maleic anhydride modified), etc. manufactured by Toyobo Co., Ltd., Zaikthene (registered trademark) series (Zaikthene (registered trademark) L, A, NC, N (acrylic acid modified), etc.) manufactured by Sumitomo Seika Chemicals Co., Ltd., etc.

[0132] 〔1-3. (C) Component〕

[0133] The aqueous ink composition according to one embodiment of the present invention may contain an alkali-soluble resin as the component (C).

[0134] Here, "alkali-soluble resin" refers to a resin that is originally insoluble in water but becomes soluble in water by placing it under alkaline conditions. It should be noted that, here, being insoluble in water means that when water with a pH of 7 or less at 25°C is added, it becomes turbid and precipitates. In addition, alkaline conditions mean that the pH exceeds 7.

[0135] Examples of the alkali-soluble resin include, for example, copolymer resins obtained by copolymerizing ethylenically unsaturated carboxylic acids and unsaturated monomers copolymerizable therewith. Specific examples of the alkali-soluble resin include, for example, styrene-(meth)acrylic acid copolymers, styrene-α-methylstyrene-(meth)acrylic acid copolymers, styrene-(meth)acrylate-(meth)acrylic acid copolymers, styrene-maleic anhydride copolymers, vinylnaphthalene-(meth)acrylic acid copolymers, vinylnaphthalene-maleic acid copolymers, isobutylene-maleic anhydride copolymers, (meth)acrylate-(meth)acrylic acid copolymers, and acrylate-methacrylate-(meth)acrylic acid copolymers.

[0136] Examples of the ethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, maleic anhydride, maleic acid monoalkyl esters, citraconic acid, citraconic anhydride, and citraconic acid monoalkyl esters. The ethylenically unsaturated carboxylic acid may be used alone or in combination of two or more thereof. Among them, the ethylenically unsaturated carboxylic acid is more preferably acrylic acid, methacrylic acid, maleic acid, or itaconic acid.

[0137] The component (A) may include an emulsion of a resin obtained by polymerizing a monomer mixture containing the ethylenically unsaturated carboxylic acid. However, the resin is different from the alkali-soluble resin of the component (C) from the viewpoint of being insoluble in water under alkaline conditions.

[0138] When the total amount of the monomer mixture constituting the above-mentioned alkali-soluble resin is set to 100 parts by weight, the usage amount of the above-mentioned ethylenically unsaturated carboxylic acid is preferably 5 to 60 parts by weight, more preferably 7 to 50 parts by weight, further preferably 10 to 40 parts by weight, and particularly preferably 12 to 30 parts by weight. When the usage amount of the above-mentioned ethylenically unsaturated carboxylic acid is 5 parts by weight or more, the above-mentioned alkali-soluble resin is dissolved in water under alkaline conditions, so it is preferred. In addition, when the above-mentioned usage amount is 60 parts by weight or less, it is preferred from the perspective of the stability of the emulsion containing the alkali-soluble resin and the water resistance of the applied ink. In addition, when it exceeds 60 parts by weight, the viscosity after alkali dissolution increases.

[0139] The unsaturated monomer is not particularly limited as long as it is an unsaturated monomer copolymerizable with the ethylenically unsaturated carboxylic acid, and examples thereof include: alkyl esters of acrylic acid or methacrylic acid having 1 to 18 carbon atoms (e.g., methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, tert-butyl (meth)acrylate, etc.); aromatic vinyls (e.g., styrene, 4-methylstyrene, α-methylstyrene, etc.); vinyl aromatics (e.g., styrene, 4-methylstyrene, α-methylstyrene, etc.); saturated carboxylic acid vinyl esters (e.g., vinyl acetate, vinyl propionate, etc.); monoolefinic unsaturated carboxylic acid amides (e.g., acrylamide, methacrylamide, etc.); N-alkyl and / or N-alkyl alcohol derivatives of monoolefinic unsaturated carboxylic acid amides (e.g., N-methylacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylacrylamide, etc.); methacrylamide, etc.); ethylenically unsaturated monomers having a carbonyl group derived from a ketone group or an aldehyde group (for example, acrolein, diacetone acrylamide, diacetone methacrylamide, acetoacetoxyethyl methacrylate, formyl styrene, vinyl alkyl ketones having 4 to 7 carbon atoms (for example, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone), etc.); monoolefinic unsaturated sulfonic acids (for example, vinyl sulfonic acid, methacrylamide propanesulfonic acid) and salts thereof; adducts of polyethylene glycol and methacrylic acid (BLEMMERPE series: trade name, manufactured by NOF Corporation); adducts of polypropylene glycol and methacrylic acid (BLEMMERPP series: trade name, manufactured by NOF Corporation); diolefinic unsaturated monomers (1,4-diacryloxybutane, divinylbenzene, etc.); acrylonitrile; hydroxyethyl acrylate; hydroxyethyl methacrylate; hydroxypropyl acrylate; hydroxypropyl methacrylate; glycidyl methacrylate; vinylidene chloride; vinyl chloride; butadiene, etc. The above unsaturated monomers may be used alone or in combination of two or more.

[0140] By using the above-mentioned ethylenically unsaturated monomer having a carbonyl group derived from a ketone group or an aldehyde group as the above-mentioned unsaturated monomer, the adhesion to the film can be improved. From the viewpoints of reactivity, availability, and economy, among the above-mentioned ethylenically unsaturated monomers having a carbonyl group derived from a ketone group or an aldehyde group, diacetone acrylamide and diacetone methacrylamide are particularly preferred.

[0141] The amount of the ethylenically unsaturated monomer having a carbonyl group derived from a ketone group or an aldehyde group used is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the total monomer mixture constituting the alkali-soluble resin.

[0142] After an alkali-soluble resin is obtained using an ethylenically unsaturated monomer having a carbonyl group derived from a ketone group or an aldehyde group as the above-mentioned unsaturated monomer, the obtained alkali-soluble resin is neutralized with an alkali and then dissolved in water so as to contain (D) a hydrazine derivative having at least two hydrazine groups or urea amino groups per molecule, or when produced by emulsion polymerization, the emulsion contains (D) a hydrazine derivative having at least two hydrazine groups or urea amino groups per molecule, thereby imparting crosslinking properties and improving the water resistance, solvent resistance and adhesion of the obtained coating film, ink, etc.

[0143] Specific examples of the hydrazine derivative (D) having at least two hydrazino groups or ureaamino groups per molecule are as described above for the component (A), and thus their description is omitted here.

[0144] The amount of the hydrazine derivative having a hydrazine group or ureaamino group (D) is preferably 0.01 to 2 mol, more preferably 0.05 to 1.5 mol, of the total amount of functional groups selected from hydrazide groups, ureaamino groups and hydrazone groups per 1 mol of carbonyl groups in the alkali-soluble resin.

[0145] That is, the alkali-soluble resin has a carbonyl group derived from a ketone group or an aldehyde group, and more preferably contains (D) a hydrazine derivative having at least two hydrazine groups or urea amino groups per molecule.

[0146] The weight average molecular weight of the alkali-soluble resin is not limited thereto, and is preferably 1000 to 60000, more preferably 1500 to 30000, and further preferably 2000 to 25000. When the weight average molecular weight of the alkali-soluble resin is 1000 or more, the dispersion stability of the pigment and the scratch resistance of the obtained coating are excellent, so it is preferred. In addition, when the weight average molecular weight of the alkali-soluble resin is 60000 or less, there is no significant increase in viscosity and the workability is excellent, so it is preferred.

[0147] Here, the weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

[0148] From the viewpoint of the hardness of the obtained film, the Tg of the alkali-soluble resin is preferably 50° C. or higher.

[0149] When the alkali-soluble resin is produced by emulsion polymerization, it is water-soluble due to neutralization, so there is no need to consider the particle size in particular. However, when the particle size is too small, the viscosity of the emulsion during polymerization increases, and productivity deteriorates. From this viewpoint, the particle size is preferably set to more than 150 nm.

[0150] The alkali-soluble resin may be produced by any method, such as bulk polymerization, solution polymerization, emulsion polymerization, etc. Among them, the alkali-soluble resin does not require steps such as drying, powdering, solvent removal, and redissolution, and the most preferred method is emulsion polymerization, which is carried out continuously from polymerization to neutralization / water dissolution.

[0151] As a method for producing the emulsion of the alkali-soluble resin, there can be mentioned a method of emulsion-polymerizing an unsaturated monomer mixture consisting of 5 to 60 parts by weight of the ethylenically unsaturated carboxylic acid and 40 to 95 parts by weight of an unsaturated monomer copolymerizable therewith in water in the presence of a surfactant and a chain transfer agent. As the surfactant, the same surfactant as listed in the description of the component (A) can be used.

[0152] Examples of the chain transfer agent include mercaptans such as tert-dodecyl mercaptan and n-dodecyl mercaptan; thioglycolates such as methyl thioglycolate, propyl thioglycolate and 2-ethylhexyl thioglycolate; β-mercaptopropionate esters such as methyl β-mercaptopropionate and octyl β-mercaptopropionate; and α-methylstyrene dimer.

[0153] Moreover, as a polymerization initiator used for emulsion polymerization, the same polymerization initiators as those exemplified in the description of (A) component can be used.

[0154] The alkali-soluble resin can be a commercial product that has already been put on the market. Examples of commercial products include: NeoCryl (registered trademark) B-817 (Tg: 64°C, Mw: 23000), NeoCryl (registered trademark) B-890 (weight average molecular weight Tg: 85°C, Mw: 12500) manufactured by Covestro AG, Germany; Joncryl (registered trademark) 67 (Tg: 73°C, Mw: 12500), Joncryl (registered trademark) 678 (Tg: 85°C, Mw: 8500), Joncryl (registered trademark) 679 (Tg: 85°C, Mw: 8500), Joncryl (registered trademark) 680 (Tg: 85°C, Mw: 8500), and Joncryl (registered trademark) 681 (Tg: 85°C, Mw: 8500) manufactured by BASF, Germany. )690 (Tg: 102°C, Mw: 16500), Joncryl682 (registered trademark) (Tg: 56°C, Mw: 1700), Joncryl (registered trademark) 693 (Tg: 84°C, Mw: 6000), Joncryl (registered trademark) 819 (Tg: 57°C, Mw: 14500), Joncryl (registered trademark) JDX-C3000A (Tg: 65°C, Mw: 10000), Joncryl JDX-C3080 (Tg: 134°C, Mw: 14000), Joncryl (registered trademark) HPD-196 (Tg: 85°C, Mw: 9200), Joncryl (registered trademark) HPD-96J (Tg: 102°C, Mw: 16500), Joncryl (registered trademark) 6610 (Tg: 85°C, Mw: 8500), Joncryl (registered trademark) JDX-6500 (Tg: 65°C, Mw: 10000), etc.

[0155] [1-4. Aqueous ink composition]

[0156] The aqueous ink composition according to one embodiment of the present invention may include the components (A) and (B), (A) and (C), or (A), (B), and (C).

[0157] The aqueous ink composition of one embodiment of the present invention has improved adhesion to a polyolefin substrate by including components (A) and (B). In this case, the mixing ratio of components (A) and (B) is not limited, for example, (A) 50% to 95% by weight, (B) 5% to 50% by weight, more preferably (A) 60% to 90% by weight, (B) 10% to 40% by weight.

[0158] The aqueous ink composition of one embodiment of the present invention has improved adhesion to a polyamide substrate by including components (A) and (C). In this case, the mixing ratio of components (A) and (B) is not limited, for example, (A) 50% to 95% by weight, (C) 5% to 50% by weight, more preferably (A) 60% to 90% by weight, (C) 10% to 40% by weight.

[0159] Among them, the aqueous ink composition of one embodiment of the present invention comprises component (A), component (B) and component (C), and has excellent adhesion to polyolefin substrates, polyester substrates and polyamide substrates. In this case, the mixing ratio of component (A), component (B) and component (C) is not limited, for example, (A) 20% to 90% by weight, (B) 5% to 40% by weight and (C) 5% to 40% by weight, more preferably (A) 35% to 85% by weight, (B) 5% to 30% by weight and (C) 10% to 35% by weight, and further preferably (A) 45% to 85% by weight, (B) 5% to 25% by weight and (C) 10% to 30% by weight.

[0160] The aqueous ink composition according to one embodiment of the present invention preferably further contains (E) a pigment.

[0161] The pigment is not particularly limited, and examples thereof include carbon black, phthalocyanine blue, quinacridone red, monoazo yellow, monoazo red, disazo orange, quinacridone magenta, diazonium blue, and phthalocyanine blue. Azine violet, phthalocyanine green, benzimidazolone, bismuth vanadate, naphthol red, titanium dioxide, calcium carbonate, kaolin, talc, barium sulfate, white carbon black, red oxide, loess, composite oxide, etc.

[0162] In addition, self-dispersible pigments which can be stably dispersed in water by chemically treating the surfaces of these pigments to add hydrophilic functional groups to the surfaces may also be used.

[0163] These pigments may be dispersed when preparing the ink, or commercially available pigment dispersions dispersed in water in advance may be used.

[0164] Generally, when applying water-based ink to a substrate, in order to improve adhesion, a primer as a primer is applied to the substrate before applying the water-based ink composition. However, according to an embodiment of the present invention, the water-based ink composition can achieve sufficient adhesion even without applying a primer. That is, the water-based ink composition of an embodiment of the present invention does not require a primer.

[0165] 〔1-5. Printed materials〕

[0166] One embodiment of the present invention also includes a printed article obtained using the aqueous ink composition of one embodiment of the present invention. The printed article of one embodiment of the present invention is obtained by printing (coating) the aqueous ink composition on a substrate.

[0167] The substrate is not particularly limited, and examples thereof include absorbent substrates such as paper, and poorly absorbent substrates such as resins. In particular, the aqueous ink composition of one embodiment of the present invention has excellent adhesion to at least one film substrate of a polyolefin substrate, a polyester substrate, and a polyamide substrate, and can therefore be suitably used for these substrates.

[0168] There is no limitation on the method for applying the aqueous ink composition to the substrate, and examples thereof include letterpress printing, flexographic printing, gravure printing, screen printing, inkjet printing, etc. The aqueous ink composition can be applied as, for example, flexographic ink, gravure ink, screen ink, inkjet ink, etc. The aqueous ink composition of one embodiment of the present invention is particularly suitable for flexographic ink, gravure ink, and inkjet ink.

[0169] [2. Method for producing aqueous ink composition]

[0170] The method for producing an aqueous ink composition according to one embodiment of the present invention is not particularly limited as long as it is a method for producing an aqueous ink composition comprising (A) a vinyl chloride resin emulsion and / or an acrylic resin emulsion, and at least one selected from (B) a polyolefin resin emulsion and (C) an alkali-soluble resin, and a conventional method for producing aqueous inks can be appropriately adopted. The method for producing an aqueous ink composition according to one embodiment of the present invention includes, for example, a step of blending (A) a vinyl chloride resin emulsion and / or an acrylic resin emulsion, and at least one selected from (B) a polyolefin resin emulsion and (C) an alkali-soluble resin.

[0171] The method for producing an aqueous ink composition according to one embodiment of the present invention may include the step of producing the above-mentioned (A) vinyl chloride resin emulsion by performing the following steps 1 and 2. The following steps 1 and 2 are as described in [1. Aqueous ink composition].

[0172] [Process 1]

[0173] A step of emulsion polymerizing a monomer mixture consisting of more than 90 parts by weight and less than 100 parts by weight of (a1) a vinyl chloride monomer and 0 parts by weight and less than 10 parts by weight of (a2) an ethylenically unsaturated monomer copolymerizable with the vinyl chloride monomer (the total amount of (a1) and (a2) is 100 parts by weight) to obtain a vinyl chloride resin,

[0174] [Process 2]

[0175] A process for obtaining an acrylic resin by emulsion polymerizing a monomer mixture consisting of 50 to 100 parts by weight of (b1) an alkyl (meth)acrylate and 0 to 50 parts by weight of (b2) an ethylenically unsaturated monomer copolymerizable with the alkyl (meth)acrylate (here, the total amount of (b1) and (b2) is 100 parts by weight) in the presence of the above-mentioned vinyl chloride resin.

[0176] For example, an aqueous ink composition can be produced by directly using an emulsion produced by an emulsion polymerization method, adding deionized water, a solvent, a surfactant, a pigment dispersion, etc. so that the total solid content of the (A) component, the (B) component, and the (C) component reaches a desired amount and stirring.

[0177] In addition, in addition to deionized water, solvents, surfactants, pigment dispersions, etc., film-forming aids, colloidal silica, plasticizers, dispersants, wetting agents, preservatives, antifreeze agents, light stabilizers, ultraviolet absorbers, defoaming agents, silane coupling agents, etc., may also be added as additives for coating materials.

[0178] According to the above-mentioned structure, the aqueous ink composition of one embodiment of the present invention can reduce the use of organic solvents and reduce the burden on the environment. Such effects also contribute to the realization of Goal 6 of the Sustainable Development Goals (SDGs) advocated by the United Nations, such as "ensuring the availability and sustainable management of water and sanitation for all".

[0179] <Conclusion>

[0180] One embodiment of the present invention includes the following configurations.

[0181] [1] An aqueous ink composition comprising:

[0182] (A) vinyl chloride resin emulsion and / or acrylic resin emulsion; and

[0183] At least one selected from the group consisting of (B) a polyolefin resin emulsion and (C) an alkali-soluble resin.

[0184] [2] The aqueous ink composition according to [1], comprising all of (A), (B) and (C),

[0185] Wherein, the mixing ratio of (A), (B) and (C) is:

[0186] (A) 20% to 90% by weight,

[0187] (B) 5% to 40% by weight, and

[0188] (C) 5 to 40 wt%.

[0189] [3] The aqueous ink composition according to [1] or [2], wherein

[0190] The (A) has a carbonyl group derived from a keto group or an aldehyde group, and further includes (D) a hydrazine derivative having at least two hydrazine groups or urea amino groups per molecule.

[0191] [4] The aqueous ink composition according to any one of [1] to [3], wherein

[0192] The (C) has a carbonyl group derived from a keto group or an aldehyde group, and further includes (D) a hydrazine derivative having at least two hydrazine groups or urea amino groups per molecule.

[0193] [5] The aqueous ink composition according to any one of [1] to [4], wherein

[0194] The (B) is a chlorinated polypropylene resin emulsion.

[0195] [6] The aqueous ink composition according to any one of [1] to [5], further comprising (E) a pigment.

[0196] [7] The aqueous ink composition according to any one of [1] to [6], wherein

[0197] The (A) vinyl chloride resin emulsion is an emulsion of a composite resin obtained by performing the following steps 1 and 2:

[0198] [Process 1]

[0199] The process of obtaining a vinyl chloride resin by emulsion polymerization of a monomer mixture consisting of the following components:

[0200] (a1) vinyl chloride monomer, more than 90 parts by weight and less than 100 parts by weight;

[0201] (a2) 0 to less than 10 parts by weight of an ethylenically unsaturated monomer copolymerizable with vinyl chloride monomer,

[0202] The total amount of (a1) and (a2) is 100 parts by weight.

[0203] [Process 2]

[0204] A step of obtaining an acrylic resin by emulsion polymerization of a monomer mixture consisting of the following components in the presence of the vinyl chloride resin:

[0205] (b1) alkyl (meth)acrylate, 50 to 100 parts by weight;

[0206] (b2) 0 to 50 parts by weight of an ethylenically unsaturated monomer copolymerizable with an alkyl (meth)acrylate,

[0207] The total amount of (b1) and (b2) is 100 parts by weight.

[0208] [8] The aqueous ink composition according to any one of [1] to [7], wherein

[0209] The (C) is obtained by emulsion polymerization.

[0210] [9] A printed material obtained by printing the aqueous ink composition according to any one of [1] to [8] on a substrate.

[0211]

[10] A method for producing an aqueous ink composition, the aqueous ink composition comprising:

[0212] (A) vinyl chloride resin emulsion and / or acrylic resin emulsion, and

[0213] At least one selected from (B) a polyolefin resin emulsion and (C) an alkali-soluble resin,

[0214] The method comprises:

[0215] A step of blending (A) a vinyl chloride resin emulsion and / or an acrylic resin emulsion, and at least one selected from (B) a polyolefin resin emulsion and (C) an alkali-soluble resin.

[0216]

[11] The method for producing the aqueous ink composition according to

[10] , comprising:

[0217] A process for producing the above-mentioned (A) vinyl chloride resin emulsion by performing the following steps 1 and 2:

[0218] [Process 1]

[0219] The process of obtaining a vinyl chloride resin by emulsion polymerization of a monomer mixture consisting of the following components:

[0220] (a1) vinyl chloride monomer, more than 90 parts by weight and less than 100 parts by weight;

[0221] (a2) 0 to less than 10 parts by weight of an ethylenically unsaturated monomer copolymerizable with vinyl chloride monomer,

[0222] The total amount of (a1) and (a2) is 100 parts by weight.

[0223] [Process 2]

[0224] A step of obtaining an acrylic resin by emulsion polymerization of a monomer mixture consisting of the following components in the presence of the vinyl chloride resin:

[0225] (b1) alkyl (meth)acrylate, 50 to 100 parts by weight;

[0226] (b2) 0 to 50 parts by weight of an ethylenically unsaturated monomer copolymerizable with an alkyl (meth)acrylate,

[0227] The total amount of (b1) and (b2) is 100 parts by weight.

[0228]

[12] The method for producing an aqueous ink composition according to any one of

[10] to

[11] , comprising all of (A), (B) and (C),

[0229] Wherein, the mixing ratio of (A), (B) and (C) is:

[0230] (A) 20% to 90% by weight,

[0231] (B) 5% to 40% by weight, and

[0232] (C) 5 to 40 wt%.

[0233]

[13] The method for producing an aqueous ink composition according to any one of

[10] to

[12] , wherein:

[0234] The (A) has a carbonyl group derived from a keto group or an aldehyde group, and further includes (D) a hydrazine derivative having at least two hydrazine groups or urea amino groups per molecule.

[0235]

[14] The method for producing an aqueous ink composition according to any one of

[10] to

[13] , wherein:

[0236] The (C) has a carbonyl group derived from a keto group or an aldehyde group, and further includes (D) a hydrazine derivative having at least two hydrazine groups or urea amino groups per molecule.

[0237]

[15] The method for producing an aqueous ink composition according to any one of

[10] to

[14] , wherein:

[0238] The (B) is a chlorinated polypropylene resin emulsion.

[0239]

[16] The method for producing an aqueous ink composition according to any one of

[10] to

[15] , further comprising (E) a pigment.

[0240] Example

[0241] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[0242] The methods for measuring the properties of the vinyl chloride resin emulsion, acrylic resin emulsion, and alkali-soluble resin emulsion used in the examples and comparative examples, and the methods for producing and evaluating the aqueous ink compositions obtained in the examples and comparative examples are as follows. In addition, unless otherwise specified, "parts" and "%" are based on weight (parts by weight and % by weight).

[0243] [Methods for determining the properties of vinyl chloride resin emulsions, acrylic resin emulsions, and alkali-soluble resin emulsions]

[0244] (Particle size distribution and average particle size)

[0245] The particle size distribution and average particle size of the resin particles contained in the emulsion were measured using a particle size distribution measuring device using a dynamic light scattering method (Microtrac Bel Co., Ltd., "Nanotrac Wave-EX150"). In the measurement, the emulsion was diluted and adjusted so that the loading index in the sample loading was about 1, and the particle size distribution and average particle size were measured based on the volume.

[0246] (Viscosity)

[0247] The viscosity of the emulsion was measured using a BM type viscometer at a liquid temperature of 25° C. and a rotation speed of 60.

[0248] (Minimum film forming temperature)

[0249] The minimum film forming temperature (hereinafter sometimes referred to as "MFT") of the emulsion was measured using MFT Tester TP-801LT manufactured by Tester Industry Co., Ltd.

[0250] (THF insoluble fraction)

[0251] The emulsion was spread thinly in a polyethylene container and dried in a dryer at 60°C for 16 hours to obtain a solid. The obtained solid was placed in a bag made of a 200-mesh metal mesh whose weight (W1) was measured in advance, and the total weight of the solid and the bag was measured (W2). Thereafter, the bag containing the solid was immersed in tetrahydrofuran (THF) at room temperature for 16 hours. The bag was taken out of THF, dried in a dryer at 120°C for 1 hour, cooled to room temperature in the dryer, and the weight (W3) was measured.

[0252] The THF-insoluble content of the emulsion was calculated by the following formula.

[0253] THF insoluble components (%) = (W3-W1) / (W2-W1)×100

[0254] (Solid content concentration)

[0255] A certain amount of the emulsion was poured into an aluminum container whose weight (w1) was measured in advance, and after the weight (w2) was measured, it was dried in a dryer at 120°C for 1 hour. The weight of the aluminum container including the dried solid content was measured (w3). The solid content concentration was calculated by the following formula.

[0256] Solid content concentration (%) = (w3-w1) / (w2-w1)×100

[0257] (Weight average molecular weight)

[0258] The weight average molecular weight of the alkali-soluble resin is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0259] [Method for producing aqueous ink composition]

[0260] Using the components shown in Tables 4 to 8, deionized water was added and adjusted so that the total solid content of the components (A), (B) and (C) in 100 parts of the final aqueous ink composition was 7 parts, and then the solvent, surfactant and pigment dispersion shown in Table 1 were mixed according to the mixing numbers shown in Table 1, and stirred for 15 minutes using an electromagnetic stirrer to produce an aqueous ink composition.

[0261] [Table 1]

[0262]

[0263] [Evaluation method of aqueous ink composition]

[0264] (Preparation of evaluation samples)

[0265] The prepared aqueous ink composition was applied to various substrates listed in Table 2 using a No. 6 wire bar coater (coating thickness: 13.74 μm), dried in a drier at 60° C. for 10 minutes, and aged at 23° C. for more than 1 day to serve as evaluation samples.

[0266] [Table 2]

[0267]

[0268] (Adhesion Evaluation)

[0269] A 10 cm long transparent tape (18 mm wide) was attached to the surface of the sample coated with the ink composition, and the tape was peeled off from the left end to observe the ink peeling.

[0270] The following criteria were used for the determination. Here, the "peeling area" refers to the area of ​​the portion of the transparent tape that adheres to the ink after peeling. In addition, the ratio (%) of the peeling area refers to the ratio of the "peeling area" to the area of ​​the transparent tape on the evaluation sample.

[0271] ANo peeling at all.

[0272] B The peeling area is less than 30%.

[0273] The C peeling area is 30% or more and less than 70%.

[0274] D The peeling area is 70% or more and less than 100%.

[0275] E completely peeled off.

[0276] [Synthesis example 1]

[0277] [Process 1]: Production of vinyl chloride resin emulsion

[0278] Into a polymerization container equipped with a stirrer were added 120 parts of deionized water, 0.094 parts of sodium formaldehyde sulfoxylate, 0.044 parts of baking soda (sodium bicarbonate), 0.65 parts of sodium lauryl sulfate, 0.00165 parts of ferrous sulfate·7hydrate and 0.00275 parts of disodium ethylenediaminetetraacetate (EDTA·2Na).

[0279] After deoxygenation in the polymerization vessel, 100 parts of vinyl chloride monomer was added, the temperature of the mixture in the polymerization vessel was raised to 60°C, and tert-butyl hydroperoxide aqueous solution (0.1%) was continuously added over 270 minutes to increase the amount of tert-butyl hydroperoxide as a polymerization initiator to 0.012 parts.

[0280] From 45 minutes to 165 minutes after the start of polymerization (the time when the temperature of the mixture in the polymerization container reaches 60°C), ADEKA REASOAP (registered trademark) SR-1025 (manufactured by ADEKA Co., Ltd.: active ingredient 25%) was continuously and uniformly added as a reactive surfactant in the form of an aqueous solution (5%) to make 1.35 parts.

[0281] When the internal pressure in the polymerization vessel dropped to 0.5 MPa or less, the polymerization reaction was stopped and unreacted vinyl chloride was removed to obtain a vinyl chloride resin emulsion (PVC-1).

[0282] The obtained vinyl chloride resin emulsion (PVC-1) had a polymerization conversion rate of 75%, an average particle size of 92 nm, and a solid content concentration of 33%. It should be noted that the average particle size and solid content concentration of the vinyl chloride resin emulsion (PVC-1 and PVC-2 described later) were measured by the same method as the average particle size and solid content concentration of vinyl chloride resin emulsions. In addition, the polymerization conversion rate was calculated by dividing the solid content concentration by the theoretical solid content concentration when all the monomers added were polymerized.

[0283] [Synthesis example 2]

[0284] [Process 1]: Production of vinyl chloride resin emulsion

[0285] In [Step 2], polymerization was carried out in the same manner as in Synthesis Example 1 except that 0.1 part of triallyl cyanurate (TAC) was added and mixed to the aqueous solution of ADEKA REASOAP (registered trademark) SR-1025 for the purpose of introducing a grafting point with an acrylic resin, and unreacted vinyl chloride was removed to obtain a vinyl chloride resin emulsion (PVC-2).

[0286] The polymerization conversion rate of the vinyl chloride resin emulsion (PVC-2) was 74%, the average particle size was 85 nm, and the solid content concentration was 33%. The TAC amount is shown in Table 3. Here, considering the polymerization conversion rate of the vinyl chloride resin, the TAC amount of 0.06 parts shown in Table 3 is the amount (weight parts) contained in 50 parts of the vinyl chloride resin.

[0287] [Production Example 1]

[0288] [Process 2]: Production of composite resin emulsion

[0289] Into a polymerization container equipped with a stirrer, 157 parts of the vinyl chloride resin emulsion (PVC-1) produced in Synthesis Example 1 (equivalent to 50 parts of vinyl chloride resin), 0.6 parts of polyoxyethylene polyoxypropylene lauryl ether (Noigen (registered trademark) LP-180, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 7.5 parts of deionized water were added.

[0290] After deoxygenation in the polymerization vessel, the temperature of the mixture in the polymerization vessel was raised to 50° C., and then 0.028 parts of tert-butyl hydroperoxide as a polymerization initiator and 0.011 parts of Bruggolite (registered trademark) FF-6 (manufactured by Bruggemann Chemical) as a reducing agent were added.

[0291] Furthermore, 0.75 parts of Aqualon (registered trademark) AR-1025 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: active ingredient 25%) as a reactive surfactant, 0.75 parts of Latemul (registered trademark) PD-430S (manufactured by Kao Corporation: active ingredient 25%) as an active ingredient, and 19 parts of deionized water (including the portion carried by the surfactant) were added to 50 parts of the acrylic monomer mixture shown in Preparation Example 1 and Step 2 in Table 3, and emulsified by stirring to obtain a monomer emulsion. The obtained monomer emulsion was continuously added uniformly to the above-mentioned polymerization container over 200 minutes. During the continuous addition of the monomer emulsion, 0.049 parts of tert-butyl hydroperoxide as a polymerization initiator was additionally added to the above-mentioned polymerization container, and 0.030 parts of Bruggolite (registered trademark) FF-6 as a reducing agent were added in 8 portions.

[0292] After the continuous addition of the monomer emulsion was completed, post-polymerization was carried out for 90 minutes. Thereafter, the liquid temperature of the reaction mixture was cooled to below 40°C, neutralized with ammonia, and 0.5 parts of adipic acid dihydrazide (ADH) were added in the form of a 10% aqueous solution relative to 100 parts of the total monomer mixture. Thereafter, the solid content concentration of the reaction mixture was adjusted to 40% with deionized water to obtain a composite resin emulsion (HB-1A).

[0293] The emulsion properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble fraction) of the obtained composite resin emulsion (HB-1A) were measured. The results are shown in Table 3 along with the glass transition temperatures of the vinyl chloride resin polymerized in step 1 and the acrylic resin polymerized in step 2.

[0294] [Production Example 2]

[0295] [Process 2]: Production of composite resin emulsion

[0296] The vinyl chloride resin emulsion (PVC-2) produced in Synthesis Example 2 was used instead of the vinyl chloride resin emulsion (PVC-1), and the acrylic monomer mixture shown in Production Example 2 and Step 2 in Table 3 was used as the acrylic monomer mixture. Instead of adding 0.5 parts of adipic acid dihydrazide (ADH) in the form of a 10% aqueous solution to 100 parts of the total monomer mixture and adjusting the solid content concentration of the reaction mixture to 40% with deionized water, 1.0 parts of adipic acid dihydrazide (ADH) were added in the form of a 10% aqueous solution to 100 parts of the total monomer mixture and the solid content concentration of the reaction mixture was adjusted to 38% with deionized water. The same operations as in Production Example 1 were performed except for the above, to obtain a composite resin emulsion (HB-2A).

[0297] The emulsion properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble fraction) of the obtained composite resin emulsion (HB-2A) were measured. The results are shown in Table 3 along with the glass transition temperatures of the vinyl chloride resin polymerized in step 1 and the acrylic resin polymerized in step 2.

[0298] It can be seen that the particle size distribution of the composite resin emulsions obtained in Preparation Examples 1 and 2 is unimodal, and the average particle size increases accordingly with the amount of additional monomer, so it is speculated that vinyl chloride resin and acrylic resin coexist in the same particle. In other words, it is believed that composite particles of vinyl chloride resin and acrylic resin can be obtained.

[0299] Compared with the acrylic resin emulsions of the later-described Production Examples 3 and 4 obtained by multi-stage polymerization of only acrylic resin, the composite resin emulsions obtained in Production Examples 1 and 2 have lower minimum film-forming temperatures and exhibit good film-forming properties despite the same set Tg in step 1. In addition, when Production Examples 1 and 2 are compared, the THF-insoluble component is further increased by introducing (F) a compound having at least two non-conjugated double bonds into the vinyl chloride resin.

[0300] It can be seen that in Production Examples 1 and 2, since the Tg of the acrylic resin is -20°C or less, the minimum film forming temperature (MFT) is lowered and the film forming property is improved.

[0301] [Table 3]

[0302]

[0303] *The particle size and weight average molecular weight of WS-1 are the values ​​before neutralization (water dissolution).

[0304] VCM Vinyl chloride monomer DAAm Diacetone acrylamide

[0305] TBMA Tert-butyl Methacrylate St Ethylene

[0306] BMA n-Butyl Methacrylate TAC Triallyl Cyanurate

[0307] BA n-Butyl acrylate NDM n-Dodecyl mercaptan

[0308] NMA Methyl Methacrylate MMP Methyl Mercaptopropionate

[0309] MAA methacrylic acid ADH adipic acid dihydrazide

[0310] [Production Example 3]: Production of acrylic resin emulsion (two-stage emulsion polymerization)

[0311] [Process 1]

[0312] Into a polymerization container equipped with a stirrer, 76 parts of deionized water, 0.0125 parts of baking soda (sodium hydrogen carbonate), 0.44 parts of sodium lauryl sulfate, and 1 / 10 of 50 parts of the monomer mixture shown in Preparation Example 3, Step 1 in Table 3 were added.

[0313] After deoxygenation in the polymerization container, the temperature of the mixture in the polymerization container was raised to 50°C, and 0.035 parts of polymerization initiator tert-butyl hydroperoxide, 0.0007 parts of ferrous sulfate·7hydrate, 0.0028 parts of disodium ethylenediaminetetraacetate (EDTA·2Na), and 0.35 parts of reducing agent Bruggolite (registered trademark) FF-6 were added, and stirred for 30 minutes.

[0314] Next, 0.021 parts of polymerization initiator tert-butyl hydroperoxide and 0.01125 parts of reducing agent Bruggolite (registered trademark) FF-6 were added to the above polymerization container. To the remaining 9 / 10 of 50 parts of the monomer mixture shown in Preparation Example 3 and Step 1 in Table 3, 1.8 parts of reactive surfactant ADEKA REASOAP (registered trademark) SR-1025, 0.6 parts of Noigen (registered trademark) LP-180 and 19 parts of ion exchange water (containing surfactant) as active ingredients were added and stirred to emulsify and obtain a monomer emulsion. The obtained monomer emulsion was continuously and uniformly added to the above polymerization container over 180 minutes. During the continuous addition of the monomer emulsion, 0.049 parts of polymerization initiator tert-butyl hydroperoxide and 0.040 parts of reducing agent Bruggolite (registered trademark) FF-6 were added to the above polymerization container in four portions.

[0315] [Process 2]

[0316] Next, 0.028 parts of tert-butyl hydroperoxide as a polymerization initiator and 0.011 parts of Bruggolite (registered trademark) FF-6 as a reducing agent were added to the above polymerization container.

[0317] To 50 parts of the monomer mixture shown in Preparation Example 3, Step 2 in Table 3, 0.75 parts of reactive surfactant Aqualon (registered trademark) AR-1025 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: active ingredient 25%), 0.75 parts of Latemul (registered trademark) PD-430S (manufactured by Kao Corporation: active ingredient 25%), and 19 parts of deionized water (including water introduced by the surfactant) were added and stirred for emulsification to obtain a monomer emulsion. The obtained monomer emulsion was continuously added to the above polymerization vessel uniformly over 200 minutes. During the continuous addition of the monomer emulsion, 0.049 parts of tert-butyl hydroperoxide and 0.030 parts of Bruggolite (registered trademark) FF-6 were added to the above polymerization vessel in 8 portions.

[0318] After the addition of the monomer emulsion was completed, post-polymerization was carried out for 90 minutes. Thereafter, the liquid temperature of the reaction mixture was cooled to below 40°C, neutralized with ammonia, and 0.5 parts of adipic acid dihydrazide (ADH) were added in the form of a 10% aqueous solution relative to 100 parts of the total monomer mixture. Then, the solid content concentration of the reaction mixture was adjusted to 40% with deionized water to obtain an acrylic resin emulsion (AC-1A).

[0319] The emulsion properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble fraction) of the obtained acrylic resin emulsion (AC-1A) were measured. The results are shown in Table 3 along with the glass transition temperatures of the acrylic resin polymerized in step 1 and the acrylic resin polymerized in step 2.

[0320] [Production Example 4]: Production of acrylic resin emulsion (two-stage emulsion polymerization)

[0321] Except having changed the monomer composition of [Step 1] of [Manufacturing Example 3] into the monomer composition shown in Manufacturing Example 4, Step 1 in Table 3, the same operation as in Manufacturing Example 3 was carried out to obtain an acrylic resin emulsion (AC-2A).

[0322] The emulsion properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble content) of the obtained acrylic resin emulsion (AC-2A) were measured. The results are shown in Table 3 along with the glass transition temperatures of the acrylic resin polymerized in step 1 and the acrylic resin polymerized in step 2.

[0323] [Production Example 5]: Production of acrylic resin emulsion (single-stage emulsion polymerization)

[0324] To 100 parts of the monomer mixture shown in Production Example 5, Step 1 in Table 3 (wherein the amount of methacrylic acid used: 3 parts) were added 1.6 parts of ADEKA REASOAP (registered trademark) SR-1025 (manufactured by ADEKA Corporation: active ingredient 25%) as a reactive surfactant and 41 parts of water (including water introduced by the surfactant) and stirred for emulsification to obtain a monomer emulsion.

[0325] 90 parts of deionized water, 0.0125 parts of baking soda, 0.1 parts of sodium lauryl sulfate, and 1 / 20 of the obtained monomer emulsion were added to a polymerization container equipped with a stirrer, and after deoxygenation in the polymerization container, the temperature of the mixture in the polymerization container was raised to 50°C.

[0326] To the polymerization container were added 0.035 parts of tert-butyl hydroperoxide as a polymerization initiator, 0.0007 parts of ferrous sulfate 7-hydrate, 0.0028 parts of disodium ethylenediaminetetraacetate (EDTA·2Na), and 0.035 parts of Bruggolite (registered trademark) as a reducing agent, and the mixture was stirred for 30 minutes.

[0327] Furthermore, the remaining 19 / 20 of the monomer emulsion was added continuously and uniformly to the polymerization vessel over 285 minutes. During the continuous addition of the monomer emulsion, 0.0857 parts of tert-butyl hydroperoxide as a polymerization initiator and 0.050 parts of Bruggolite (registered trademark) FF-6 as a reducing agent were added to the polymerization vessel in 8 portions.

[0328] After the addition of the monomer emulsion was completed, polymerization was carried out for 90 minutes. Thereafter, the reaction mixture was cooled to a temperature below 40°C, neutralized with ammonia, and the solid content concentration of the reaction mixture was adjusted to 38% with deionized water to obtain an acrylic resin emulsion (AC-3).

[0329] The emulsion properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble content) of the obtained acrylic resin emulsion (AC-3) were measured. The results are shown in Table 3 together with the glass transition temperature of AC-3.

[0330] [Production Example 6]: Production of acrylic resin emulsion (single-stage emulsion polymerization)

[0331] 1.0 part of adipic acid dihydrazide (ADH) was added as a 10% aqueous solution to 100 parts of the total monomer mixture of the acrylic resin emulsion (AC-3) obtained in Production Example 5 to obtain an acrylic resin emulsion (AC-3A).

[0332] The emulsion properties (average particle size, particle size distribution, viscosity, MFT, THF insoluble content) of the obtained acrylic resin emulsion (AC-3A) were measured. The results are shown in Table 3 together with the glass transition temperature of AC-3A.

[0333] By setting the Tg to -3°C, it was possible to obtain the same MFT (film-forming property) as that of the composite emulsion (overall average Tg: 19°C).

[0334] [Production Example 7] Production of alkali-soluble resin

[0335] To 100 parts of the monomers shown in Preparation Example 7 and Step 1 in Table 3 (wherein the amount of methacrylic acid used: 18.7 parts) and 4 parts of a chain transfer agent mixture were added 1.56 parts of a reactive surfactant Aqualon (registered trademark) AR-1025 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: active ingredient 25%) as an active ingredient, 1.56 parts of Latemul (registered trademark) PD-430S (manufactured by Kao Corporation: active ingredient 25%) as an active ingredient, and 52.9 parts of deionized water (including water introduced by the surfactant) and stirred for emulsification to obtain a monomer emulsion.

[0336] 97 parts of deionized water, 0.013 parts of baking soda, and 1 / 20 of the obtained monomer emulsion were added to a polymerization container equipped with a stirrer, and after deoxygenation in the polymerization container, the temperature of the mixture in the polymerization container was raised to 50°C.

[0337] To the polymerization container were added 0.36 parts of tert-butyl hydroperoxide as a polymerization initiator, 0.0007 parts of ferrous sulfate 7-hydrate, 0.0028 parts of disodium ethylenediaminetetraacetate (EDTA·2Na), and 0.42 parts of Bruggolite (registered trademark) as a reducing agent, and the mixture was stirred for 30 minutes.

[0338] Furthermore, the remaining 19 / 20 of the monomer emulsion was added continuously and uniformly to the polymerization vessel over 190 minutes. During the continuous addition of the monomer emulsion, 0.65 parts of tert-butyl hydroperoxide as a polymerization initiator and 0.35 parts of Bruggolite (registered trademark) FF-6 as a reducing agent were added to the polymerization vessel in 6 portions.

[0339] After the addition of the monomer emulsion was completed, polymerization was carried out for 90 minutes. Thereafter, the reaction mixture was cooled to below 40°C, neutralized with ammonia, and the solid content concentration of the reaction mixture was adjusted to 28% with deionized water to obtain a transparent alkali-soluble resin (WS-1).

[0340] The properties (average particle size, particle size distribution, weight average molecular weight, viscosity, MFT, THF insoluble fraction) of the obtained alkali-soluble resin (WS-1) were measured. The results and the glass transition temperature of WS-1 are shown in Table 3. However, since the average particle size, particle size distribution, and weight average molecular weight cannot be measured after water dissolution, the substance before ammonia neutralization was measured.

[0341] [Production Example 8] Production of alkali-soluble resin

[0342] 1.0 part of adipic acid dihydrazide (ADH) was added as a 10% aqueous solution to 100 parts of the total monomer mixture of the alkali-soluble resin (WS-1) obtained in Production Example 7 to obtain an alkali-soluble resin (WS-1A).

[0343] The properties (viscosity, THF insoluble content) of the obtained alkali-soluble resin (WS-1A) were measured. The results are shown in Table 3 together with the glass transition temperature of WS-1A.

[0344] [Comparative Examples 1 to 10]

[0345] Aqueous ink compositions were prepared using the components shown in Table 4, respectively, and the adhesion of the obtained aqueous ink compositions was evaluated. The results are shown in Table 4.

[0346]

[0347] In Tables 4 to 8, "XK-190" described as component (A) is NeoCryl (registered trademark) XK-190 (acrylic resin emulsion manufactured by COVESTRO), and E-480T described as component (B) is Superchlon (registered trademark) E-480T (chlorinated polypropylene emulsion manufactured by Nippon Paper Industries). In addition, in Tables 4 to 8, the unit of the amount of each component is "part" (part by weight).

[0348] [Example 1]

[0349] Aqueous ink compositions were prepared according to the compositions shown in Table 5, and the adhesion of the obtained aqueous ink compositions was evaluated. The results are shown in Table 5.

[0350] [Table 5]

[0351]

[0352] As shown in Table 5, the aqueous ink composition of Example 1 containing the vinyl chloride-acrylic acid composite resin emulsion (HB-1A) and the polyolefin resin emulsion has excellent adhesion to OPP compared with the aqueous ink composition of Comparative Example 1 containing only HB-1A.

[0353] [Examples 2-3]

[0354] Aqueous ink compositions were prepared according to the compositions shown in Table 6, and the adhesion of the obtained aqueous ink compositions was evaluated. The results are shown in Table 6.

[0355] [Table 6]

[0356]

[0357] As shown in Table 6, the aqueous ink compositions of Examples 2 and 3 containing the vinyl chloride-acrylic acid composite resin emulsion (HB-1A) and the alkali-soluble resin have excellent adhesion to Ny compared to the aqueous ink composition of Comparative Example 1 containing only HB-1A.

[0358] [Examples 4 to 12]

[0359] Aqueous ink compositions were prepared according to the compositions shown in Table 7, and the adhesion of the obtained aqueous ink compositions was evaluated. The results are shown in Table 7.

[0360]

[0361] As shown in Table 7, the aqueous ink compositions of Examples 4 to 12 containing a vinyl chloride-acrylic acid composite resin emulsion (HB-1A), a polyolefin resin emulsion and an alkali-soluble resin have excellent adhesion to OPP and / or PET, and also have excellent adhesion to Ny, compared to the aqueous ink composition of Comparative Example 1 containing only HB-1A.

[0362] [Examples 13 to 18]

[0363] Aqueous ink compositions were prepared according to the compositions shown in Table 8, and the adhesion of the obtained aqueous ink compositions was evaluated. The results are shown in Table 8.

[0364]

[0365] As shown in Table 8, the aqueous ink compositions of Examples 13 to 18 containing a vinyl chloride-acrylic acid composite resin emulsion (HB-2A) or an acrylic resin emulsion (AC-1A, AC-2A, AC-3, AC-3A, XK-190), a polyolefin resin emulsion and an alkali-soluble resin have improved adhesion to any of OPP, PET and Ny, compared with the aqueous ink compositions of Comparative Examples 2 to 7 containing only HB-2A, AC-1A, AC-2A, AC-3, AC-3A or XK-190.

[0366] In addition, compared with the aqueous ink composition of Example 1 which has the same composition as the vinyl chloride-acrylic acid composite resin emulsion (HB-1A) without TAC and contains a polyolefin resin emulsion and an alkali-soluble resin, the aqueous ink composition of Example 13 which uses the vinyl chloride-acrylic acid composite resin emulsion (HB-2A) with TAC has better adhesion to the substrate, and TAC is a compound having at least two non-conjugated double bonds.

[0367] It should be noted that the aqueous ink compositions of Comparative Example 7 and Example 16 have better adhesion performance than the case of using a vinyl chloride-acrylic acid composite resin emulsion, but are sticky (tacky). This is believed to be due to setting Tg low in order to ensure film-forming properties (lower MFT).

[0368] [Comparative Examples 11 to 13]

[0369] Aqueous ink compositions were prepared according to the compositions shown in Table 8, and the adhesion of the obtained aqueous ink compositions was evaluated. The results are shown in Table 8.

[0370] The aqueous ink composition not containing the component (A) has poor adhesion performance.

[0371] Industrial Applicability

[0372] According to one embodiment of the present invention, an aqueous ink composition having excellent adhesion to at least one of a polyolefin substrate, a polyester substrate, and a polyamide substrate can be provided. Therefore, the aqueous ink composition according to one embodiment of the present invention can be used for various substrates, is very useful as a coating / ink, and can be used in a wide range of industrial fields.

Claims

1. An aqueous ink composition comprising: (A) vinyl chloride resin emulsion and / or acrylic resin emulsion, and At least one selected from the group consisting of (B) a polyolefin resin emulsion and (C) an alkali-soluble resin.

2. The aqueous ink composition according to claim 1, comprising all of (A), (B) and (C), in, The mixing ratio of (A), (B) and (C) is: (A) 20% to 90% by weight, (B) 5% to 40% by weight, and (C) 5 to 40 wt%.

3. The aqueous ink composition according to claim 1, wherein The (A) has a carbonyl group derived from a keto group or an aldehyde group, and further includes (D) a hydrazine derivative having at least two hydrazine groups or urea amino groups per molecule.

4. The aqueous ink composition according to claim 1, wherein The (C) has a carbonyl group derived from a keto group or an aldehyde group, and further includes (D) a hydrazine derivative having at least two hydrazine groups or urea amino groups per molecule.

5. The aqueous ink composition according to claim 1, wherein The (B) is a chlorinated polypropylene resin emulsion. The aqueous ink composition according to claim 1 , further comprising (E) a pigment.

7. The aqueous ink composition according to claim 1, wherein The (A) vinyl chloride resin emulsion is an emulsion of a composite resin obtained by performing the following steps 1 and 2: [Process 1] The process of obtaining a vinyl chloride resin by emulsion polymerization of a monomer mixture consisting of the following components: (a1) vinyl chloride monomer, more than 90 parts by weight and less than 100 parts by weight; (a2) 0 to less than 10 parts by weight of an ethylenically unsaturated monomer copolymerizable with vinyl chloride monomer, The total amount of (a1) and (a2) is 100 parts by weight. [Process 2] A step of obtaining an acrylic resin by emulsion polymerization of a monomer mixture consisting of the following components in the presence of the vinyl chloride resin: (b1) alkyl (meth)acrylate, 50 to 100 parts by weight; (b2) 0 to 50 parts by weight of an ethylenically unsaturated monomer copolymerizable with an alkyl (meth)acrylate, The total amount of (b1) and (b2) is 100 parts by weight.

8. The aqueous ink composition according to claim 1, wherein The (C) is obtained by emulsion polymerization. 9 . A printed matter obtained by printing the aqueous ink composition according to claim 1 on a substrate.

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