Urethane-modified polyether resin, water-based printing ink, water-based inkjet ink, and water-based dispersion

Abstract

To provide an urethane-modified polyether resin which can obtain low viscosity and excellent blocking resistance in an aqueous medium, and blur resistance and dispersion stability of a coloring material or the like.SOLUTION: An urethane-modified polyether resin is obtained by reacting a water-soluble polyether polyol component (A) and a polyisocyanate component (B), wherein the water-soluble polyether polyol component (A) is a polyether polyol component having a valance of 2 to 6, the polyisocyanate component (B) is a polyisocyanate component having an isocyanurate group, a biuret group and / or an allophanate group, and viscosity measured at a shear rate of 1.0 (unit is 1 / sec) when the urethane-modified polyether resin is converted into a water dispersion or an aqueous solution of 40 wt.% concentration is 100-10,000 mPa s and a number average molecular weight thereof is 3,000-100,000.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to urethane-modified polyether resins, aqueous printing inks, aqueous inkjet inks, and aqueous dispersions.

Background Art

[0002] From the viewpoints of environmental protection and operator safety, aqueous printing inks, aqueous inkjet inks, etc. that use an aqueous medium such as water without using an organic solvent have been studied. (Patent Documents 1, 2) In products that use an aqueous medium, water-soluble resins are widely used for the purpose of imparting functions such as adhesiveness, dispersion stability of coloring materials and fillers, and coating film protection. (Non-Patent Documents 1, 2)

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0004]

Non-Patent Document 1

Non-Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] Water-soluble polymers are used in products that utilize aqueous media. However, when high molecular weight polymers are used to ensure adhesion, stable dispersion of colorants, and resin properties, the entanglement of hydrated polymers in the aqueous medium and weak crosslinking due to hydrogen bonding between polymers increase the viscosity of the polymer solution, resulting in stringiness and the Weisenberg effect, which reduces handling and productivity. On the other hand, while lower molecular weight polymers dissolve more easily in aqueous media and improve handling, they suffer from reduced dispersion stability due to decreased resin properties and adsorption capacity to colorants, as well as reduced adhesion to substrates and fillers, making them unsuitable for practical use.

[0006] The object of the present invention is to provide a urethane-modified polyether resin that exhibits low viscosity in an aqueous medium and provides excellent blocking resistance, bleeding prevention, and dispersion stability of colorants and the like. [Means for solving the problem]

[0007] The present inventors have diligently studied to achieve the above objective and have arrived at the present invention. Specifically, the present invention is a urethane-modified polyether resin obtained by reacting a water-soluble polyether polyol component (A) and a polyisocyanate component (B), wherein the water-soluble polyether polyol component (A) is a polyether polyol component with a valency of 2 to 6, and the polyisocyanate component (B) is a polyisocyanate component having isocyanurate groups, biuret groups and / or allophanate groups, and the viscosity measured at a shear rate of 1.0 (unit: 1 / sec) when the urethane-modified polyether resin is a 40% by weight aqueous dispersion or aqueous solution is 100 to 10000 mPa·s, and the number average molecular weight is 3000 to 100000. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a urethane-modified polyether resin that exhibits low viscosity in an aqueous medium and excellent blocking resistance, bleeding prevention, and dispersion stability of colorants and the like. [Modes for carrying out the invention]

[0009] The urethane-modified polyether resin of the present invention is a urethane-modified polyether resin obtained by reacting a water-soluble polyether polyol component (A) with a polyisocyanate component (B).

[0010] The water-soluble polyether polyol component (A) is a polyether polyol component with a valency of 2 to 6. In the present invention, water solubility of the water-soluble polyether polyol component (A) means that 1 g or more of the polyether polyol component dissolves in 100 g of water at 25°C. It is preferable that 10 to 150 g of polyether polyol component (A) dissolves in 100 g of water at 25°C, and more preferably that 50 to 100 g of polyether polyol component (A) dissolves in 100 g of water at 25°C.

[0011] In this invention, the valency of a polyether polyol refers to the number of hydroxyl groups in one molecule of the polyether polyol.

[0012] The valency of the water-soluble polyether polyol component (A) in this invention can be determined from the valency of a compound having two or more hydroxyl groups used to obtain the water-soluble polyether polyol component (A), but it can also be calculated using the following formula (1). Valence of water-soluble polyether polyol component (A) = [Number average molecular weight of water-soluble polyether polyol component (A)] × [Hydroxyl value of water-soluble polyether polyol component (A)] / 56100 (1) The method for measuring the hydroxyl value is not particularly limited, as long as it is a known method capable of measuring the value defined above, but for example, the method specified in JIS K0070 (1995 edition) can be cited. The number-average molecular weight is measured by gel permeation chromatography (GPC) using polyethylene glycol as the standard, as described later.

[0013] In the present invention, the water-soluble polyether polyol component (A) can be an alkylene oxide polymer, for example, an ethylene oxide (hereinafter abbreviated as EO) homopolymer; or an EO / propylene oxide (hereinafter abbreviated as PO) copolymer. From the viewpoint of resin properties, the water-soluble polyether polyol component (A) is preferably an EO homopolymer or an EO / PO copolymer, and from the viewpoint of handling properties, an EO / PO copolymer is more preferred.

[0014] The EO homopolymer may be a polymer obtained by polymerizing EO alone, or a polymer obtained by adding EO to (poly)ethylene glycol. Alternatively, commercially available polyethylene glycol may be used. In this specification, (poly)ethylene glycol means ethylene glycol or polyethylene glycol.

[0015] The EO / PO copolymer may be a block polymer or random polymer of EO and PO, or a polymer obtained by adding EO to (poly)propylene glycol, or by co-adding EO and PO. Alternatively, it may be a polymer obtained by adding PO to (poly)ethylene glycol, or by co-adding EO and PO. In this specification, (poly)propylene glycol means propylene glycol or polypropylene glycol.

[0016] Furthermore, water-soluble polyether polyol components (A) other than EO homopolymers and EO / PO copolymers include compounds obtained by co-adding (poly)ethylene glycol or (poly)propylene glycol with EO and alkylene oxides other than EO or PO [1,2-butylene oxide, tetrahydrofuran, α-olefin oxide, alkylene oxide substituted products (epichlorohydrin, styrene oxide, etc.)], and mixtures of two or more of these.

[0017] In addition, examples of the water-soluble polyether polyol component (A) other than the EO homopolymer and the EO / PO copolymer include compounds obtained by co-adding EO alone or EO and other alkylene oxides [PO, 1,2-butylene oxide, tetrahydrofuran, α-olefin oxide, alkylene oxide substituents (epichlorohydrin, styrene oxide, etc.), etc.] to compounds having two or more hydroxyl groups other than (poly)ethylene glycol or (poly)propylene glycol; and mixtures of two or more of these.

[0018] Examples of compounds having two or more hydroxyl groups other than (poly)ethylene glycol or (poly)propylene glycol include polyhydric alcohols (hexylene glycol, polytetramethylene ether glycol, polybutadiene glycol, polycaprolactone polyol, dimethylolpropionic acid (salt), glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, sucrose, etc.), polyhydric phenols (hydroquinone, catechol, etc.); bisphenols (bisphenol A, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol S, etc.); and water. Among these, from the viewpoints of the viscosity of the aqueous dispersion or aqueous solution of the urethane-modified polyether resin and the physical properties of the resin, polyhydric alcohols are preferred, di- to hexavalent alcohols are more preferred, and divalent alcohols are even more preferred.

[0019] When using other alkylene oxides together with EO, the addition mode may be random addition or block addition, but block addition is desirable from the viewpoint of the viscosity of the aqueous dispersion or aqueous solution of the urethane-modified polyether resin. When the water-soluble polyether polyol component (A) is a polyether polyol component having ethylene oxide units, from the viewpoint of the viscosity of the aqueous dispersion or aqueous solution of the urethane-modified polyether resin, the content of ethylene oxide units is preferably 40 to 100% by weight, more preferably 60 to 100% by weight, still more preferably 70 to 100% by weight or more, and particularly preferably 70 to 90% by weight, based on the weight of the polyether polyol component. When the water-soluble polyether polyol component (A) is an EO homopolymer or an EO / PO copolymer, the proportion of ethylene oxide units in the total weight of ethylene oxide units and propylene oxide units is preferably 50 to 100% by weight, more preferably 60 to 100% by weight, still more preferably 70 to 100% by weight. The content of ethylene oxide units in the water-soluble polyether polyol component (A) may be calculated from the charged composition of the raw materials. The terminal portion of the polyoxyalkylene chain constituting the water-soluble polyether polyol component (A) is preferably a hydroxyethyl group from the viewpoint of reactivity with organic polyisocyanates.

[0020] The number average molecular weight (Mn) of the water-soluble polyether polyol component (A) is preferably 300 or more, more preferably 300 to 50,000, still more preferably 1,000 to 10,000, from the viewpoints of the mechanical properties of the urethane-modified polyether resin and the viscosity of the aqueous dispersion or aqueous solution of the urethane-modified polyether resin. In the present invention, the molecular weight is measured by gel permeation chromatography (GPC) using polyethylene glycol as a standard. However, the Mn of the low molecular polyol is a calculated value from the chemical formula.

[0021] The number average molecular weight (Mn) of the water-soluble polyether polyol component in the present invention can be measured by gel permeation chromatography under, for example, the following conditions. Apparatus: "Waters Alliance 2695" [manufactured by Waters Corporation] Column: "Guardcolumn Super HL" (1 piece), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation) linked together" Sample solution: 0.25% by weight tetrahydrofuran solution Solution injection volume: 10μl Flow rate: 0.6ml / min Measurement temperature: 40℃ Detection device: Refractive index detector Reference substance: Standard polyethylene glycol

[0022] There are no particular restrictions on the method for producing the water-soluble polyether polyol component (A), but the following methods are examples. A compound having two or more hydroxyl groups is charged into a pressurized reaction vessel, and an alkylene oxide is added in the presence of potassium hydroxide as a catalyst. The reaction is carried out under atmospheric pressure or under pressure. The reaction temperature is preferably 50 to 150°C, and the reaction time is preferably 2 to 20 hours. After the addition reaction of the alkylene oxide is complete, the catalyst can be neutralized if necessary and removed and purified by treatment with an adsorbent.

[0023] Polyisocyanate component (B) is a polyisocyanate component having isocyanurate groups, biuret groups and / or allophanate groups. Polyisocyanate components (B) that have been conventionally used in polyurethane production can be used. Specifically, examples include isocyanurate groups, biuret groups and / or allophanate groups-containing modified products of C8-C26 aromatic polyisocyanates (b1) having 2-3 or more isocyanate groups, C4-C22 aliphatic polyisocyanates (b2), C8-C18 alicyclic polyisocyanates (b3), and C10-C18 aromatic aliphatic polyisocyanates (b4).

[0024] Examples of aromatic polyisocyanates (b1) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylenediisocyanate, 2,4- or 2,6-tolylenediisocyanate (hereinafter, tolylenediisocyanate is abbreviated as TDI), crude TDI, 4,4'- or 2,4'-diphenylmethanediisocyanate (hereinafter, diphenylmethanediisocyanate is abbreviated as MDI), crude MDI, polyaryl polyisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylenediisocyanate, 4,4',4"-triphenylmethanetriisocyanate, and m- or p-isocyanatophenylsulfonyl isocyanates.

[0025] Examples of aliphatic polyisocyanates (b2) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

[0026] Examples of alicyclic polyisocyanates (b3) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis(2-isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, and 2,5- or 2,6-norbornane diisocyanate.

[0027] Examples of aromatic aliphatic polyisocyanates (b4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α,α,α',α'-tetramethylxylylene diisocyanate (hereinafter, xylylene diisocyanate will be abbreviated as XDI).

[0028] Examples of modified polyisocyanates containing isocyanurate groups, biuret groups and / or allophanate groups from (b1) to (b4) include biuret-modified HDI, isocyanurate-modified HDI, isocyanurate-modified IPDI and biuret-modified XDI. Modified polyisocyanates containing isocyanurate groups, biuret groups and / or allophanate groups from (b1) to (b4) may have one or more of the following groups: urethane group, carbodiimide group, urea group, uretdione group, uretoimine group and oxazolidone group.

[0029] In the present invention, polyisocyanate component (B) is preferably a polyisocyanate component having isocyanurate groups and / or biuret groups, from the viewpoint of viscosity and resin properties of the aqueous dispersion or aqueous solution of urethane-modified polyether resin, and more preferably biuret-modified HDI, isocyanurate-modified HDI, isocyanurate-modified IPDI, or biuret-modified XDI. Polyisocyanate component (B) may be used alone or in combination of two or more types.

[0030] The average number of functional groups of isocyanate groups in the polyisocyanate component (B) in the present invention is preferably 2.05 to 6, more preferably 2.1 to 4, and even more preferably 2.5 to 4, from the viewpoint of the viscosity of the aqueous dispersion or aqueous solution of the urethane-modified polyether resin. The average number of functional groups of isocyanate groups in the polyisocyanate component (B) can be calculated based on the content of each polyisocyanate and the number of functional groups of isocyanate groups in each polyisocyanate, and the number of functional groups of isocyanate groups in each polyisocyanate component can be determined from the molecular weight and isocyanate group content of the polyisocyanate component.

[0031] The viscosity of the urethane-modified polyether resin in this invention when it is used as an aqueous dispersion or aqueous solution is measured at 25°C using the method described later, from the viewpoint of handling and resin properties, when the aqueous dispersion or aqueous solution is prepared at a concentration of 40 parts by weight of urethane-modified polyether resin per 60 parts by weight of water.

[0032] <Viscosity of aqueous dispersion or aqueous solution of 40% by weight urethane-modified polyether resin> In the present invention, the viscosity of an aqueous dispersion or aqueous solution of 40% by weight urethane-modified polyether resin was measured using the following measuring apparatus and conditions. Equipment: MCR92 (manufactured by Anton Paar) Jig: 50mm cone plate Shear rate: 1.0 (unit: 1 / sec) Measurement temperature: 25℃

[0033] The viscosity of a urethane-modified polyether resin in an aqueous dispersion or aqueous solution with a concentration of 40% by weight is measured at a shear rate of 1.0 (unit: 1 / sec) and is between 100 and 10000 mPa·s, preferably between 100 and 5000 mPa·s, and more preferably between 500 and 3000 mPa·s.

[0034] The viscosity of an aqueous dispersion or aqueous solution of a urethane-modified polyether resin can be adjusted by (i) the valency of the water-soluble polyether polyol component (A), (ii) the addition mode of the water-soluble polyether polyol component (A), (iii) the ethylene oxide unit content of the water-soluble polyether polyol component (A), (iv) the molecular weight of the water-soluble polyether polyol component (A), (v) the number of functional groups of the isocyanate group of the polyisocyanate component (B), and (vi) the molecular weight of the urethane-modified polyether resin. From the viewpoint of resin properties, adjusting by (ii), (iii), or (v) is preferable as it facilitates lower viscosity.

[0035] The molecular weight of the urethane-modified polyether resin in the present invention is 3,000 to 100,000 in number average molecular weight, preferably 10,000 to 50,000, from the viewpoint of the viscosity of the aqueous dispersion or aqueous solution of the urethane-modified polyether resin. The molecular weight is measured by GPC, similar to the polyether polyol component (A) described above.

[0036] In the present invention, the urethane group content in the urethane-modified polyether resin is preferably 0.01 to 1.0 mol / kg, more preferably 0.03 to 0.7 mol / kg, even more preferably 0.04 to 0.7 mol / kg, and particularly preferably 0.05 to 0.5 mol / kg, from the viewpoint of viscosity of the aqueous dispersion or aqueous solution of the urethane-modified polyether resin, ink viscosity, and redispersibility. The urethane group content in the present invention can be calculated from the composition of the raw materials. It can also be measured by the following analytical methods if necessary. <Method for measuring urethane group content> The urethane group content of urethane-modified polyether resin is determined by the nitrogen atom content, which is quantified by a nitrogen analyzer [ANTEK7000 (manufactured by ANTEK)]. 1 The ratio of urethane groups to urea groups quantified by 1H-NMR is used to determine the result. 1 The 1H-NMR measurement will be performed using the method described in "Structural Study of Polyurethane Resins by NMR: Takeda Research Institute Report 34(2), 224-323 (1975)". 1 When using an aliphatic isocyanate, the weight ratio of urea groups to urethane groups is determined by measuring 1H-NMR and the ratio of the integrated hydrogen from urea groups around a chemical shift of 6 ppm to the integrated hydrogen from urethane groups around a chemical shift of 7 ppm. The urethane group concentration and urea group concentration are then calculated from this weight ratio and the nitrogen atom content. When using an aromatic isocyanate, the weight ratio of urea groups to urethane groups is calculated by the ratio of the integrated hydrogen from urea groups around a chemical shift of 8 ppm to the integrated hydrogen from urethane groups around a chemical shift of 9 ppm. The urethane group content is then calculated from this weight ratio and the nitrogen atom content.

[0037] The melting point of the urethane-modified polyether resin in the present invention is preferably 20 to 70°C, more preferably 30 to 60°C, and particularly preferably 35 to 55°C, from the viewpoint of blocking resistance and resolubility. In this invention, the melting point refers to the melting peak temperature measured using a differential scanning calorimeter (DSC) according to the DSC method specified in JIS K7121.

[0038] The hydroxyl value of the urethane-modified polyether resin is preferably 10 to 100 mg KOH / g from the viewpoint of viscosity and blocking resistance of the aqueous dispersion or aqueous solution of the urethane-modified polyether resin. More preferably, it is 10 to 70 mg KOH / g, and particularly preferably, it is 10 to 50 mg KOH / g. The hydroxyl value of the urethane-modified polyether resin is measured by the method specified in JIS K0070 (1995 edition).

[0039] The acid value of the urethane-modified polyether resin is preferably 0 to 49 mg KOH / g, more preferably 0 to 20 mg KOH / g, even more preferably 0 to 10 mg KOH / g, and particularly preferably 0 mg KOH / g, from the viewpoint of stability when mixed with an aqueous medium containing an inorganic salt. The acid value of the urethane-modified polyether resin can be measured by the method described in JIS K0070:1992 (potentiometric titration).

[0040] The acid value of urethane-modified polyether resins can be changed, for example, by adjusting the content of a skeleton derived from a polyol having carboxyl groups and / or carboxylate anion groups (such as dimethylolpropionic acid, an acid group-containing polyol).

[0041] When reacting the above-mentioned water-soluble polyether polyol component with a polyisocyanate component to obtain a urethane-modified polyether resin, chain extenders and reaction inhibitors may be used to control the molecular weight.

[0042] The chain extender is not particularly limited, but examples include water, aliphatic polyamines having 2 to 36 carbon atoms [alkylenediamines such as ethylenediamine and hexamethylenediamine; poly(n=2 to 6)alkylene(2 to 6 carbon atoms) poly(n=3 to 7)amines such as diethylenetriamine, dipropylenetriamine, dihexylentriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine], alicyclic polyamines having 6 to 20 carbon atoms (1,3- or 1,4-diaminocyclohexane, 4,4'- or 2,4'-dicyclohexylmethanediamine and iso Examples include holone diamines, aromatic polyamines having 6 to 20 carbon atoms (such as 1,3- or 1,4-phenylenediamine, 2,4- or 2,6-tolylenediamine, 4,4'- or 2,4'-methylenebisaniline, etc.), heterocyclic polyamines having 3 to 20 carbon atoms (such as 2,4-diamino-1,3,5-triazine, piperazine, and N-aminoethylpiperazine), hydrazine or its derivatives (such as dibasic acid dihydrazides, e.g., adipic acid dihydrazide), and amino alcohols having 2 to 20 carbon atoms (e.g., ethanolamine, diethanolamine, 2-amino-2-methylpropanol, and triethanolamine). The chain extender may be used alone or in combination of two or more types.

[0043] The reaction stopper is not particularly limited, but examples include monoalcohols having 1 to 20 carbon atoms (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol, etc.) and monoamines having 1 to 20 carbon atoms (mono- or dialkylamines such as monomethylamine, monoethylamine, monobutylamine, dibutylamine, and monooctylamine, and mono- or dialkanolamines such as monoethanolamine, diethanolamine, and diisopropanolamine, etc.). The reaction stopper may be used alone or in combination of two or more.

[0044] <Water-based printing ink> The urethane-modified polyether resin of the present invention is preferable for use in aqueous printing inks from the viewpoint of ink viscosity, blocking resistance, resolubility, and stability. The aqueous printing ink (I) of the present invention contains a urethane-modified polyether resin.

[0045] Printing methods using the aqueous printing ink (I) containing the urethane-modified polyether resin of the present invention include conventional printing methods used for printing plastic films, such as special gravure printing, flexographic printing, offset printing, and thermal transfer printing.

[0046] The aqueous printing ink (I) preferably contains, in addition to the urethane-modified polyether resin of the present invention, an aqueous resin dispersion, a colorant such as a pigment, a dispersant, a humectant, a penetrating agent, water, and other additives. Other additives that can be added include one or more types of crosslinking agents, solvents, viscosity modifiers, defoaming agents, preservatives, degradation inhibitors, stabilizers, antifreeze agents, catalysts, leveling agents, etc.

[0047] In the aqueous printing ink (I) containing the urethane-modified polyether resin of the present invention, the urethane-modified polyether resin has little effect on the ink viscosity and exhibits the functions of preventing blocking by being present on the surface of the ink-dried coating film, promoting resolubility by being present between the resins constituting the aqueous resin dispersion dispersed in the ink, and stabilizing the dispersion of pigments by being adsorbed on the surface of the dispersed pigments. From the viewpoint of adhesion, mechanical strength, and handling properties, the content of the urethane-modified polyether resin in the aqueous printing ink (I) is preferably 0.1 to 40% by weight, and more preferably 1 to 30% by weight, based on the weight of the aqueous printing ink (I).

[0048] Examples of aqueous resin dispersions include aqueous resin dispersions containing polyurethane resin. Generally, aqueous resin dispersions used in paint applications can be used. Examples of commercially available products include the Hydran series from DIC Corporation, the Takelac W series and Olestar UD series from Mitsui Chemicals, Inc., the DAOTAN series from Ornex Japan, the U-Coat series and Permarine series from Sanyo Chemical Industries, Ltd., the Superflex series from Daiichi Kogyo Seiyaku Co., Ltd., the NeoRez series from Kusumoto Kasei Co., Ltd., the Adekabon Titer HUX series from ADEKA Corporation, and the Evaphanol series and NeoSticker series from Nikka Chemical Co., Ltd.

[0049] Furthermore, the aqueous resin dispersion may be an aqueous resin dispersion containing an acrylic resin. As the aqueous resin dispersion containing an acrylic resin, an acrylic resin emulsion obtained by copolymerizing (meth)acrylic acid, (meth)acrylic acid ester, and optionally a vinyl monomer, which is generally used for aqueous printing ink applications, can be used.

[0050] Examples of commercially available acrylic resin emulsions include the Almatex E series from Mitsui Chemicals, Inc., the SETAQUA series, AQUAPOL series, UCECRYL series, and VIACRYL VSC series from Ornex Japan Co., Ltd., acrylic emulsions from E-Tech Co., Ltd. (AE872D, AE986B, AE610H, AE981A, AE982, AE337, and AE373D, etc.), the Pegar series from High Pressure Gas Industry Co., Ltd., the Acryset series from Nippon Shokubai Co., Ltd., and the Boncoat series from DIC Corporation.

[0051] Furthermore, the aqueous resin dispersion may be an aqueous resin dispersion containing polyester resin. As the aqueous resin dispersion containing polyester resin, those commonly used for aqueous printing inks can be used. Examples of commercially available products include the RESYDROL series from Ornex Japan, the Byronal series from Toyobo Co., Ltd., the Aronmelt series from Toagosei Co., Ltd., the Pluscoat series from Go-o Chemical Industry Co., Ltd., the Watersol series from DIC Corporation, and Sepolion ES from Sumitomo Seika Co., Ltd.

[0052] Other resins that make up the aqueous resin dispersion include vinyl resins, epoxy resins, polyamide resins, polyimide resins, ionomer resins, polycarbonate resins, nitrocellulose, vinyl acetate resins, styrene-maleic acid copolymer resins, chlorinated polypropylene resins, and rosin resins. Two or more of the above resins, along with polyurethane resins, acrylic resins, and polyester resins, may be used in combination. Preferably, the resin constituting the aqueous resin dispersion is a vinyl resin, polyurethane resin, epoxy resin, polyester resin, or a combination thereof. The amount of aqueous resin dispersion used is preferably 5 to 40% by weight, and more preferably 10 to 30% by weight, based on the weight of the aqueous printing ink (I), as resin solids.

[0053] There are no particular restrictions on the colorants, and preferably inorganic pigments and organic pigments used in water-based printing inks can be used. For example, inorganic pigments with a water solubility of 1 or less (e.g., white pigments, black pigments, gray pigments, red pigments, brown pigments, yellow pigments, green pigments, blue pigments, purple pigments and metallic pigments) and organic pigments (e.g., natural organic pigments, synthetic organic pigments, nitroso pigments, nitro pigments, pigment-type azo pigments, copper phthalocyanine pigments, condensed polycyclic pigments, azo lakes made from water-soluble dyes, azo lakes made from poorly soluble dyes, lakes made from basic dyes, lakes made from acid dyes, xanthan tane lakes, anthraquinone lakes, pigments from vat dyes and phthalocyanine pigments) can be used. The colorant content is preferably 5 to 40% by weight, more preferably 10 to 30% by weight, based on the weight of the water-based printing ink (I). The pigment may be a pigment dispersion in which the pigment is dispersed in an aqueous medium.

[0054] In addition to the urethane-modified polyether resin of the present invention, other dispersants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and other emulsifying dispersants. The amount of these dispersants used is preferably 10% by weight or less, more preferably 5% by weight or less, based on the weight of the aqueous printing ink (I).

[0055] Examples of nonionic surfactants include AO-addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants. Examples of AO-addition type surfactants include EO adducts of aliphatic alcohols having 10 to 20 carbon atoms, EO adducts of phenols, EO adducts of nonylphenols, EO adducts of alkylamines having 8 to 22 carbon atoms, and EO adducts of poly(oxypropylene) glycols. Examples of polyhydric alcohol type surfactants include fatty acid (8 to 24 carbon atoms) esters of polyhydric (3 to 8 or more carbon atoms) alcohols (2 to 30 carbon atoms) (e.g., glycerin monostearate, glycerin monooleate, sorbitan monolaurate, and sorbitan monooleate) and alkyl (4 to 24 carbon atoms) poly(degree of polymerization 1 to 10) glycosides.

[0056] Examples of anionic surfactants include ether carboxylic acids or salts thereof having hydrocarbon groups with 8 to 24 carbon atoms [e.g., sodium lauryl ether acetate and (poly)oxyethylene (1 to 100 added moles) sodium lauryl ether acetate]; sulfate esters or ether sulfate esters having hydrocarbon groups with 8 to 24 carbon atoms and their salts [e.g., sodium lauryl sulfate, (poly)oxyethylene (1 to 100 added moles) sodium lauryl sulfate, (poly)oxyethylene (1 to 100 added moles) triethanolamine lauryl sulfate and (poly)oxyethylene (1 to 100 added moles) coconut oil fatty acid monoethanolamide sulfate sodium]; sulfonates having hydrocarbon groups with 8 to 24 carbon atoms [e.g., sodium dodecylbenzenesulfonate]; hydrocarbons with 8 to 24 carbon atoms Examples include sulfosuccinates having one or two groups; phosphate esters or ether phosphate esters having hydrocarbon groups with 8 to 24 carbon atoms and their salts [e.g., sodium lauryl phosphate and (poly)oxyethylene (1 to 100 moles added) sodium lauryl ether phosphate]; fatty acid salts having hydrocarbon groups with 8 to 24 carbon atoms [e.g., sodium laurate and triethanolamine laurate]; and acylated amino acid salts having hydrocarbon groups with 8 to 24 carbon atoms [e.g., sodium methyl taurate, sodium sarcosinate, triethanolamine sarcosinate, triethanolamine acyl-L-glutamate, sodium acyl-L-glutamate, and sodium lauroylmethyl-β-alanine].

[0057] Examples of cationic surfactants include quaternary ammonium salts [such as stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, and lanolin fatty acid aminopropylethyldimethylammonium ethyl sulfate] and amine salts [such as diethylaminoethylamide lactate stearate, dilaurylamine hydrochloride, and oleylamine lactate].

[0058] Examples of amphoteric surfactants include betaine-type amphoteric surfactants [such as coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryl hydroxysulfobetaine, and lauroylamide ethyl hydroxyethyl carboxymethyl betaine hydroxypropyl sodium phosphate] and amino acid-type amphoteric surfactants [such as β-laurylaminopropionate sodium].

[0059] Other emulsifying dispersants include, for example, polyvinyl alcohol, starch and its derivatives, cellulose derivatives such as carboxymethylcellulose, methylcellulose and hydroxyethylcellulose, carboxyl group-containing (co)polymers such as sodium polyacrylate, and emulsifying dispersants having urethane groups or ester groups as described in U.S. Patent No. 5,906,704 [for example, polycaprolactone polyol and polyetherdiol linked by polyisocyanate].

[0060] Examples of humectants, though not particularly limited, include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, tripropylene glycol, polyethylene glycol with Mn of 2000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, glycerin, mesoerythritol, pentaerythritol, 2-pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. A single humectant may be used, or two or more may be used in combination.

[0061] The penetrating agent is not particularly limited, but examples include glycol ethers (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol monobutyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether and dipropylene glycol monobutyl ether, etc.) and aliphatic diols having 4 to 8 carbon atoms (1,2-pentanediol and 1,2- Organic solvents such as xanediols (1,2-alkyldiols and linear alcohols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol and 1,8-octanediol); acetylene glycol-based surfactants; acetylene alcohol-based surfactants; ether-based surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and polyoxyalkylene alkyl ether; ester-based surfactants such as polyoxyethylene oleic acid, polyoxyethylene oleic acid ester, polyoxyethylene distearate ester, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate and polyoxyethylene stearate; silicone-based surfactants such as dimethylpolysiloxane;Examples of surfactants include fluorinated surfactants such as fluorinated alkyl esters and perfluoroalkyl carboxylates. Penetrating agents may be used individually or in combination of two or more.

[0062] The water used is not particularly limited, but examples include pure water such as ion-exchanged water, ultrafiltered water, reverse osmosis water, and distilled water, as well as ultrapure water, which has had ionic impurities removed as much as possible. Furthermore, using water sterilized by ultraviolet irradiation or the addition of hydrogen peroxide can prevent the growth of bacteria and fungi when water-based printing inks are stored for a long period of time. The amount of water used is preferably 10 to 80% by weight, more preferably 30 to 70% by weight or less, based on the weight of the water-based printing ink (I).

[0063] Examples of crosslinking agents include water-soluble or water-dispersible amino resins, water-soluble or water-dispersible polyepoxides, water-soluble or water-dispersible blocked polyisocyanate compounds, and polyethylene urea. The amount of crosslinking agent added is preferably 30% by weight or less, and more preferably 0.1 to 20% by weight, based on the solid content weight of the aqueous printing ink (I).

[0064] Organic solvents such as ketone solvents (e.g., acetone and methyl ethyl ketone), ester solvents (e.g., ethyl acetate and dibasic acid esters (DBE)), ether solvents (e.g., tetrahydrofuran), amide solvents (e.g., N,N-dimethylformamide and N-methylpyrrolidone), alcohol solvents (e.g., ethanol and isopropyl alcohol), and aromatic hydrocarbon solvents (e.g., toluene) can be used as solvents. From the viewpoint of drying speed and toxicity of the water-based printing ink, alcohol solvents (e.g., ethanol and isopropyl alcohol, etc.) are preferred. The amount of solvent used is preferably 50% by weight or less, more preferably 20% by weight or less, based on the weight of the water-based printing ink (I).

[0065] Examples of viscosity modifiers other than the urethane-modified polyether resin of the present invention include inorganic viscosity modifiers (such as sodium silicate and bentonite), cellulose viscosity modifiers (such as methylcellulose, carboxymethylcellulose, and hydroxymethylcellulose with a Mn of 20,000 or more), protein viscosity modifiers (such as casein, sodium caseinate, and ammonium caseinate), acrylic viscosity modifiers (such as sodium polyacrylate and ammonium polyacrylate with a Mn of 20,000 or more), and vinyl viscosity modifiers (such as polyvinyl alcohol with a Mn of 20,000 or more).

[0066] Examples of antifoaming agents include long-chain alcohols (such as octyl alcohol), sorbitan derivatives (such as sorbitan monooleate), and silicone oils (such as polymethylsiloxane and polyether-modified silicone).

[0067] Examples of preservatives include organic nitrogen sulfur compound-based preservatives and organic sulfur halide-based preservatives. Examples of degradation inhibitors and stabilizers (ultraviolet absorbers and antioxidants, etc.) include hindered phenol-based, hindered amine-based, hydrazine-based, phosphorus-based, benzophenone-based, or benzotriazole-based degradation inhibitors and stabilizers. Examples of antifreeze agents include ethylene glycol and propylene glycol. The content of viscosity modifiers, defoamers, preservatives, degradation inhibitors, stabilizers, and antifreeze agents is preferably 5% by weight or less, and more preferably 3% by weight or less, based on the weight of each composition in the intended use.

[0068] There are no particular restrictions on the method of manufacturing the water-based printing ink (I), and the water-based printing ink (I) can be manufactured using known methods, for example, general-purpose ink manufacturing equipment such as a three-roll mill, ball mill, and sand grinder mill.

[0069] An example of a formulation for water-based printing ink (I) is shown below. Urethane-modified polyether resin: 0.1-40% by weight (preferably 1-30% by weight) Aqueous resin dispersion: 5-40% by weight (preferably 10-30% by weight) Colorants (pigments): 5-40% by weight (preferably 10-30% by weight) Dispersant (pigment dispersant): 0-10% by weight (preferably 0-5% by weight) Solvent: 0-50% by weight (preferably 0-20% by weight) Water: 10-80% (preferably 30-70% by weight)

[0070] Examples of printing substrates used with water-based printing ink (I) include resin substrates such as polycarbonate, rigid polyvinyl chloride, flexible polyvinyl chloride, polystyrene, expanded polystyrene, PMMA, polypropylene, polyethylene, and PET; paper substrates such as fine paper, art paper, coated paper, and cast-coated paper; and metal substrates such as corrugated cardboard, cotton fabric, glass, and stainless steel. From the viewpoint of adhesion, resin substrates or paper substrates are preferred as the substrate for water-based printing ink (I).

[0071] <Water-based inkjet ink> The urethane-modified polyether resin of the present invention can be used for aqueous inkjet inks. Using the urethane-modified polyether resin of the present invention for aqueous inkjet inks is preferable from the viewpoint of suppressing bleeding, preventing blocking, redispersibility when dispersion insufficient in the ink, and the dispersion stability of the colorant. The aqueous inkjet ink (L) of the present invention contains a urethane-modified polyether resin.

[0072] The aqueous inkjet ink (L) containing urethane-modified polyether resin preferably contains a colorant, resin, humectant, penetrant, water, and other additives.

[0073] Examples of colorants include dyes and pigments. While not particularly limited, depending on the media used, reactive dyes, vat dyes, naphthol dyes, sulfur dyes, direct dyes, acid dyes, metal complex dyes, disperse dyes, and cationic dyes can be selected. Examples of pigments include those exemplified in the aqueous printing ink (I) described above.

[0074] Among these colorants, pigments are preferred. One type of colorant may be used alone, or two or more types may be used in combination. The colorant content is preferably 50% by weight or less, more preferably 30% by weight or less, based on the weight of the aqueous inkjet ink (L).

[0075] Examples of resins include the aqueous resin dispersions exemplified in the aqueous printing ink (I) mentioned above.

[0076] Examples of humectants, penetrating agents, and water include the humectants, penetrating agents, and water exemplified in the aqueous printing ink (I).

[0077] Other additives include chelating agents, preservatives, and pH adjusters. Examples of chelating agents include ethylenediaminetetraacetate (EDTA), ethylenediamine nitrilotriacetate, hexametaphosphate, pyrophosphate, or metaphosphate.

[0078] Examples of preservatives include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, and 1,2-dibenzinthiazolin-3-one.

[0079] Examples of pH adjusting agents include potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia, diethanolamine, triethanolamine, triisopropanolamine, potassium carbonate, sodium carbonate, and sodium bicarbonate.

[0080] Examples of printing substrates used with the water-based inkjet ink (L) include the printing substrates exemplified in the water-based printing ink (I).

[0081] <Aqueous dispersion> When the urethane-modified polyether resin of the present invention is used as an aqueous dispersant to form an aqueous dispersion of pigments, dyes, or inorganic particles such as metals and metal oxides, good dispersion stability can be obtained. The aqueous dispersion of the present invention contains a urethane-modified polyether resin as an aqueous dispersant.

[0082] The aqueous dispersion using the urethane-modified polyether resin of the present invention as an aqueous dispersant may contain water and an organic solvent, as long as it does not impair the effects of the present invention. Examples of the organic solvent include xylene, ethyl acetate, toluene, tetrahydrofuran, methyl ethyl ketone, acetone, butyl cellosolve, dimethylformamide, n-propanol, ethanol, dimethyl sulfoxide, n-butanol, and methanol.

[0083] The aqueous dispersion using the urethane-modified polyether resin of the present invention as an aqueous dispersant contains pigments, dyes, or inorganic particles such as metals and metal oxides, and an aqueous medium. The aqueous dispersion may be in the form of a paste. Examples of aqueous media include water, as exemplified in the aqueous printing ink (I) above. The aqueous dispersion using the urethane-modified polyether resin of the present invention as an aqueous dispersant may be a pigment aqueous dispersion (P) containing a pigment. The pigment aqueous dispersion (P) may be in paste form.

[0084] Examples of the aforementioned pigments include those exemplified in the aqueous printing ink (I). Examples of the aforementioned dyes include those exemplified in the water-based inkjet ink (L). Examples of inorganic particles such as metals and metal oxides include at least one metal fine particle and metal oxide particle selected from the group consisting of gold, silver, copper, platinum, nickel, palladium, rhodium, ruthenium, iridium, and osmium.

[0085] From the viewpoint of dispersion stability, the weight percentage of the urethane-modified polyether resin of the present invention in the aqueous pigment dispersion (P) is preferably 1 to 50% by weight, based on the solid content weight of the aqueous pigment dispersion (P). From the viewpoint of handling the aqueous pigment dispersion (P), the weight percentage of the aqueous medium contained in the aqueous pigment dispersion (P) is preferably 50 to 90% by weight, based on the weight of the aqueous pigment dispersion (P).

[0086] Among the methods for producing aqueous dispersions, one method for dispersing pigments, etc., in an aqueous medium is to mix and stir the urethane-modified polyether resin of the present invention, pigments, etc., and water, and optionally an organic solvent. The addition of each component may be carried out by adding them separately, or by mixing the urethane-modified polyether resin of the present invention and pigments, etc., beforehand and then adding them to the aqueous medium. There are no particular restrictions on the method of mixing and stirring, but examples of equipment used for mixing and stirring include sand mills, homogenizers, ball mills, jet mills, paint shakers, and ultrasonic dispersers. Furthermore, heat treatment may be performed before or after the dispersion process.

[0087] This specification discloses the following:

[0088] The present disclosure (1) is a urethane-modified polyether resin obtained by reacting a water-soluble polyether polyol component (A) with a polyisocyanate component (B), The aforementioned water-soluble polyether polyol component (A) is a polyether polyol component with a valency of 2 to 6. The polyisocyanate component (B) is a polyisocyanate component having an isocyanurate group, a biuret group and / or an allophanate group. The viscosity of the urethane-modified polyether resin measured at a shear rate of 1.0 (unit: 1 / sec) when the aforementioned urethane-modified polyether resin is in a 40% by weight aqueous dispersion or aqueous solution is 100 to 10000 mPa·s. This is a urethane-modified polyether resin with a number-average molecular weight of 3,000 to 100,000.

[0089] Disclosure (2) is the urethane-modified polyether resin according to Disclosure (1), wherein the urethane group content of the urethane-modified polyether resin is 0.01 to 1.0 mol / kg.

[0090] Disclosure (3) is a urethane-modified polyether resin according to Disclosure (1) or (2), wherein the water-soluble polyether polyol component (A) is a polyether polyol component having ethylene oxide units, and the content of ethylene oxide units is 40 to 100% by weight based on the weight of the polyether polyol component.

[0091] Disclosure (4) is a urethane-modified polyether resin according to any one of Disclosures (1) to (3), wherein the melting point of the urethane-modified polyether resin is 20 to 70°C.

[0092] Disclosure (5) is a urethane-modified polyether resin according to any one of Disclosures (1) to (4), wherein the urethane-modified polyether resin is for use in aqueous printing inks.

[0093] Disclosure (6) is a urethane-modified polyether resin according to any one of Disclosures (1) to (4), wherein the urethane-modified polyether resin is for use with aqueous inkjet inks.

[0094] Disclosure (7) is a urethane-modified polyether resin according to any one of Disclosures (1) to (4), wherein the urethane-modified polyether resin is an aqueous dispersant.

[0095] Disclosure (8) is an aqueous printing ink containing a urethane-modified polyether resin as described in any one of Disclosures (1) to (5).

[0096] Disclosure (9) is an aqueous inkjet ink comprising a urethane-modified polyether resin as described in any one of Disclosures (1) to (4) and (6).

[0097] Disclosure (10) is an aqueous dispersion containing a urethane-modified polyether resin as described in any one of Disclosures (1) to (4) and (7) as an aqueous dispersant. [Examples]

[0098] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Hereinafter, unless otherwise specified, "parts" refers to parts by weight.

[0099] <Example 1> In a pressurized reactor equipped with a stirrer and temperature control function, 60.0 parts of polypropylene glycol [Sanyo Chemical Industries, Ltd. "Sannix PP-2000 (Mn=2000)"] and 0.2 parts of potassium hydroxide were charged. After nitrogen purging, dehydration was carried out under reduced pressure (20 mmHg) at 120°C for 1 hour. Next, 40.0 parts of EO were added dropwise over 5 hours at a temperature of 120-130°C while adjusting the pressure so as not to exceed 0.5 MPa. After further maturation at the same temperature for 1 hour, the mixture was treated with an adsorbent (synthetic magnesium silicate) and filtered to remove potassium hydroxide, thereby obtaining 100 parts of divalent water-soluble polyether polyol (A-1). 100 parts of the obtained water-soluble polyether polyol and 11.7 parts of the biuret form of xamethylene diisocyanate [Covestro's "Desmodule N100"] as the polyisocyanate component were mixed and stirred at 80°C for 12 hours to carry out a urethane reaction, thereby producing a urethane-modified polyether resin (Q-1).

[0100] <Examples 2-5, Comparative Examples 1 and 2> Urethane-modified polyether resins (Q-2 to Q-5) and (Q'-1, Q'-2) were obtained in the same manner as in Example 1, except that the raw materials and quantities used were changed to those listed in Table 1. The raw materials and quantities used are shown in Table 1.

[0101] The composition of each raw material in Table 1 is as follows: • PEG-10000: Polyethylene glycol [Manufactured by Sanyo Chemical Industries, Mn=10000] • Sannix PP-2000: Polypropylene glycol [Manufactured by Sanyo Chemical Industries, Mn=2000] • Sannix PP-3000: Polypropylene glycol [Manufactured by Sanyo Chemical Industries, Mn=3000] • Sannix PP-4000: Polypropylene glycol [Manufactured by Sanyo Chemical Industries, Mn=4000] • Coronate T-100: Tolylene diisocyanate [Manufactured by Tosoh Corporation] • Death Module N100: Biuret form of hexamethylene diisocyanate [Manufactured by Covestro] • Desmodule Z 4470 BA: Nurate of isophorone diisocyanate [Manufactured by Covestro] • Duranate TPA-100: Nurate of hexamethylene diisocyanate [Manufactured by Asahi Kasei]

[0102] In Table 1, the ethylene oxide unit content in water-soluble polyether polyol component (A) was calculated from the composition of the preparation. In Table 1, the number-average molecular weights of the water-soluble polyether polyol component and the urethane-modified polyether resin were measured by the method described in the specification. In Table 1, the urethane group content of the urethane-modified polyether resin was calculated from the composition of the preparation. In Table 1, the acid value and melting point of the urethane-modified polyether resin were measured by the method described in the specification. In Table 1, the viscosity of a urethane-modified polyether resin in a 40% by weight aqueous dispersion or aqueous solution, measured at a shear rate of 1.0 (unit: 1 / sec), was measured by the method described in the specification.

[0103] [Table 1]

[0104] <Manufacturing of water-based printing inks (I-1) to (I-5), (I'-1, I'-2)> In a polyethylene container, 1.5 parts by weight of the urethane-modified polyether resin obtained in Examples 1-5 and Comparative Examples 1 and 2, 13 parts by weight of deionized water, 9 parts by weight of isopropyl alcohol as a solvent, 60 parts by weight of polyurethane aqueous resin dispersion [Permarine UA-150: manufactured by Sanyo Chemical Industries, Ltd., solid content concentration 30% by weight] as a resin, 15 parts by weight of pigment [Pigment Blue 15:3], 3 parts by weight of dispersant [Caribon L-400: manufactured by Sanyo Chemical Industries, Ltd.], and 100 parts by weight of glass beads [ASGB-100, manufactured by AS ONE] were added and kneaded with paint conditioner [Red Devil Co., Ltd.] for 1 hour. Next, the glass beads were filtered off to obtain aqueous printing inks (I-1) to (I-5) and (I'-1, I'-2).

[0105] <Manufacturing of water-based inkjet inks (L-1) to (L-5), (L'-1, L'-2)> Five parts by weight of the urethane-modified polyether resin obtained in Examples 1-5 and Comparative Examples 1 and 2, 20 parts by weight of polyurethane aqueous resin dispersion [Permarin UA-150 (manufactured by Sanyo Chemical Industries), solid content concentration 30% by weight] as the resin, 25 parts by weight of pigment dispersion [carbon black aqueous dispersion {Aqua-Black 162 (manufactured by Tokai Carbon), solid content concentration 20% by weight}], 10 parts by weight of glycerin as a humectant, 1 part by weight of triethylene glycol, 1 part by weight of 1,2-hexanediol as a penetrating agent, and 20 parts by weight of ion-exchanged water were placed in a container and mixed for 10 minutes to obtain aqueous inkjet inks (L-1) to (L-5) and (L'-1, L'-2).

[0106] <Manufacturing of aqueous pigment dispersions (P-1) to (P-5), (P'-1, P'-2)> In the vessel of a pigment disperser (TSU-6U, manufactured by AIMEX), 10 parts by weight of urethane-modified polyether resin obtained in Examples 1-5 and Comparative Examples 1 and 2, and 20 parts by weight of deionized water were stirred until uniformly dissolved. Next, 70 parts by weight of cyanide pigment [BASF Heliogen Blue D7088] and 200 parts by weight of glass beads [ASGB-320, manufactured by AS ONE] were added, and the mixture was dispersed for 4 hours while cooling water at 4°C was passed through the jacket. The obtained dispersion slurry was stirred at 200 rpm, and 100 parts by weight of deionized water was added under stirring. Next, the glass beads were filtered off to obtain aqueous pigment dispersions (P-1) to (P-5) and (P'-1, P'-2).

[0107] The water-based printing inks (I-1) to (I-5) and (I'-1) and (I'-2) were evaluated using the following method.

[0108] <Viscosity of water-based printing inks> Viscosity was measured at 20°C using a BL-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd.) with rotors No. 1, No. 2, or No. 3. The evaluation results are shown in Table 2.

[0109] <Blocking resistance of water-based printing inks> A PET film [Toyobo Co., Ltd.'s "Espet E-5102" (thickness 12 μm)] with corona treatment on one side was coated with printing ink using a bar coater so that the thickness after drying was 1 μm. After drying at 90°C for 10 minutes, it was cut into a 4 cm x 8 cm piece. The printed side of this sample was placed on the uncoated side of an unprinted film of the same size, and a pressure of 7 kg / cm² was applied at 50°C for 24 hours. The degree of peeling and resistance of the printed side when the film was peeled off was observed. The evaluation criteria are shown below. 5 points: No ink peeling was observed at all from the printed material, and there was no resistance when peeling it off. 4 points: No ink peeling was observed from the printed material, but there was resistance when peeling it off. 3 points: Some ink peeling was observed on the printed material, but it covered less than 10% of the total printed area. 2. Ink peeling occurred on more than 10% but less than 50% of the total printed area of ​​the printed material. 1. Ink peeling occurred on more than 50% of the printed area of ​​the material.

[0110] <Resolubility of water-based printing inks> Table 2 shows the amount of ink remaining in the cells (by volume %) after printing 100m of water-based printing ink onto OPP film at a speed of 10m / min using a gravure printing test machine (TS-1 type printing machine; manufactured by Higashitani Iron Works Co., Ltd.) with a gravure plate with a depth of 35μm, and then lightly washing off the excess ink adhering to the gravure plate with water.

[0111] The water-based inkjet inks (L-1) to (L-5) and (L'-1) and (L'-2) were evaluated using the following method. The evaluation results are shown in Table 2.

[0112] <Viscosity of water-based inkjet ink> The viscosity of the water-based inkjet ink was measured using the following measuring device and conditions. Equipment: MCR92 (manufactured by Anton Paar) Jig: 50mm cone plate Shear rate: 200 (unit: 1 / s) Measurement temperature: 25℃

[0113] <Bleeding properties of water-based inkjet ink> Water-based inkjet ink was used with an inkjet printer PX-105 (manufactured by Seiko Epson Corporation) to print text in 5-point and 8-point fonts on the surface of PET film [Toyobo Co., Ltd.'s "Espet E-5102" (thickness 12 μm)]. The evaluation criteria are as follows. 4 points: The text was printed clearly without any blurring. 3 points: There is some blurring of the letters, but they are still legible. Points 2: There is some blurring of the text, and some characters are illegible. 1 point: The text is generally blurred and illegible.

[0114] <Blocking resistance of water-based inkjet inks> Water-based inkjet ink was used with an inkjet printer PX-105 (Seiko Epson Corporation) to print across the entire surface of a PET film [Toyobo Co., Ltd. "Espet E-5102" (thickness 12 μm)] that had been corona-treated on one side. After drying at 90°C for 10 minutes, the sample was cut to 4 cm x 8 cm. The printed side of this sample was then placed on the un-corona-treated side of an unprinted film of the same size, and subjected to a pressure of 7 kg / cm² at 50°C for 24 hours. The degree of peeling and resistance of the printed surface when the film was peeled off was observed. The evaluation criteria are shown below. 5 points: No ink peeling was observed at all from the printed material, and there was no resistance when peeling it off. 4 points: No ink peeling was observed from the printed material, but there was resistance when peeling it off. 3 points: Some ink peeling was observed on the printed material, but it covered less than 10% of the total printed area. 2. Ink peeling occurred on more than 10% but less than 50% of the total printed area of ​​the printed material. 1. Ink peeling occurred on more than 50% of the printed area of ​​the material.

[0115] <Redispersibility of water-based inkjet inks> 10g of water-based inkjet ink was placed in a 70mL mayonnaise jar and left uncovered for 3 hours in an environment of 50% humidity and 50°C. After standing, 10g of pure water was added to the ink, and the change in state after 30 minutes was visually observed. The redispersibility was evaluated based on the following evaluation criteria. 5 points: The ink immediately redisperses and becomes uniform. 4 points: The ink redisperses and becomes uniform. 3. The ink partially redisperses, but a dried film of ink remains on the bottle walls. Two points: A significant amount of the dried ink film remains on the wall surface and hardly redisperses. 1 point: The dried ink film remained almost entirely on the wall surface, and no redispersion was observed.

[0116] The aqueous pigment dispersions (P-1) to (P-5) and (P'-1) and (P'-2) were evaluated using the following method. The evaluation results are shown in Table 2.

[0117] <Viscosity of aqueous pigment dispersions> The viscosity was measured using the same apparatus conditions as the viscosity measurement method for the aqueous inkjet ink described above.

[0118] <Dispersion stability of aqueous pigment dispersions> The viscosity change rate of the aqueous pigment dispersion was measured after storage at 70°C for 7 days, and the dispersion stability was evaluated according to the evaluation criteria shown below. The evaluation results are shown in Table 2. The viscosity change rate was calculated according to the following formula. Viscosity change rate (%) = {(Viscosity after 7 days) / (Initial viscosity) - 1} × 100 Evaluation Criteria 4 points: Viscosity after storage is lower than the initial state, with a change rate of less than 10%. 3 points: Viscosity is higher after storage than in the initial state, with a change rate of less than 10%. 2 points: Viscosity after storage is lower than the initial state, with a change rate of 10% or more. 1 point: The viscosity after storage is higher than the initial state, with a change rate of 10% or more.

[0119] [Table 2]

[0120] The results in Table 2 show that the aqueous printing ink containing the urethane-modified polyether resin of the present invention has low viscosity and excellent blocking resistance and redissolution properties. Furthermore, the aqueous inkjet ink containing the urethane-modified polyether resin of the present invention has low viscosity and excellent bleeding resistance, blocking resistance, and redispersibility properties. In addition, the aqueous pigment dispersion containing the urethane-modified polyether resin of the present invention has low viscosity and excellent dispersion stability. [Industrial applicability]

[0121] The urethane-modified polyether resin of the present invention can be suitably used in aqueous printing inks, aqueous inkjet inks, aqueous paint compositions, aqueous adhesive compositions, aqueous textile processing agent compositions (such as pigment printing binder compositions, nonwoven fabric binder compositions, reinforcing fiber sizing agent compositions, ceramic binder compositions, antibacterial agent binder compositions, and raw material compositions for artificial leather and synthetic leather), aqueous coating compositions (such as waterproof coating compositions, water-repellent coating compositions, and antifouling coating compositions), aqueous paper processing agent compositions, and aqueous ink compositions.

Claims

1. A water-based printing ink containing a urethane-modified polyether resin obtained by reacting a water-soluble polyether polyol component (A) with a polyisocyanate component (B), The water-soluble polyether polyol component (A) is a polyether polyol component with a valency of 2 to 6, and the polyisocyanate component (B) is a polyisocyanate component having isocyanurate groups, biuret groups and / or allophanate groups, and the viscosity measured at a shear rate of 1.0 (unit: 1 / sec) when the urethane-modified polyether resin is an aqueous dispersion or aqueous solution with a concentration of 40% by weight is 100 to 10000 mPa·s, and the number average molecular weight is 3000 to 100000, wherein the aqueous printing ink is an aqueous ink.

2. The aqueous printing ink according to claim 1, wherein the urethane group content of the urethane-modified polyether resin is 0.01 to 1.0 mol / kg.

3. The aqueous printing ink according to claim 1, wherein the water-soluble polyether polyol component (A) is a polyether polyol component having ethylene oxide units, and the content of ethylene oxide units is 40 to 100% by weight based on the weight of the polyether polyol component.

4. The aqueous printing ink according to claim 1, wherein the melting point of the urethane-modified polyether resin is 20 to 70°C.

5. An aqueous inkjet ink comprising a urethane-modified polyether resin obtained by reacting a water-soluble polyether polyol component (A) and a polyisocyanate component (B), The aqueous inkjet ink is an aqueous inkjet ink in which the water-soluble polyether polyol component (A) is a polyether polyol component with a valency of 2 to 6, the polyisocyanate component (B) is a polyisocyanate component having an isocyanurate group, a biuret group and / or an allophanate group, and the viscosity measured at a shear rate of 1.0 (unit: 1 / sec) when the urethane-modified polyether resin is an aqueous dispersion or aqueous solution with a concentration of 40% by weight is 100 to 10000 mPa·s, and the number average molecular weight is 3000 to 100000.

6. The aqueous inkjet ink according to claim 5, wherein the urethane group content of the urethane-modified polyether resin is 0.01 to 1.0 mol / kg.

7. The aqueous inkjet ink according to claim 5, wherein the water-soluble polyether polyol component (A) is a polyether polyol component having ethylene oxide units, and the content of ethylene oxide units is 40 to 100% by weight based on the weight of the polyether polyol component.

8. The aqueous inkjet ink according to claim 5, wherein the melting point of the urethane-modified polyether resin is 20 to 70°C.

9. An aqueous dispersion comprising a urethane-modified polyether resin obtained by reacting a water-soluble polyether polyol component (A) and a polyisocyanate component (B) as an aqueous dispersant, The water-soluble polyether polyol component (A) is a polyether polyol component with a valency of 2 to 6, and the polyisocyanate component (B) is a polyisocyanate component having an isocyanurate group, a biuret group and / or an allophanate group, and the aqueous dispersion of the urethane-modified polyether resin has a viscosity of 100 to 10000 mPa·s when measured at a shear rate of 1.0 (unit: 1 / sec) when the aqueous dispersion or aqueous solution of the urethane-modified polyether resin is concentrated at a concentration of 40% by weight, and has a number-average molecular weight of 3000 to 100000.

10. The aqueous dispersion according to claim 9, wherein the urethane group content of the urethane-modified polyether resin is 0.01 to 1.0 mol / kg.

11. The aqueous dispersion according to claim 9, wherein the water-soluble polyether polyol component (A) is a polyether polyol component having ethylene oxide units, and the content of ethylene oxide units is 40 to 100% by weight based on the weight of the polyether polyol component.

12. The aqueous dispersion according to claim 9, wherein the urethane-modified polyether resin has a melting point of 20 to 70°C.

Images