Polyurethane resin dispersion composition, thickening inhibitor, and method for improving wetting properties of polyurethane resin dispersion composition

Abstract

The present invention relates to: a first polyurethane resin dispersion composition that includes a polyurethane resin (A), an anionic surfactant (B), a polyhydroxy compound (C) that has at least one triple bond, and an aqueous medium (D); a thickening inhibitor for a second polyurethane resin dispersion composition that includes the polyurethane resin (A) and the aqueous medium (D), the thickening inhibitor using a combination of the anionic surfactant (B) and the polyhydroxy compound (C); and a method for improving the wetting properties of the second polyurethane resin dispersion composition that uses the abovementioned combination. The first polyurethane resin dispersion composition contributes to the achievement of Goal 7 and the like of the Sustainable Development Goals (SDGs).

Description

Polyurethane resin dispersion composition, thickening inhibitor, and method for improving wettability of polyurethane resin dispersion composition

[0001] The present invention relates to a polyurethane resin dispersion composition, a thickening inhibitor, and a method for improving the wettability of a polyurethane resin dispersion composition.

[0002] Inks are broadly divided into water-based inks and solvent-based inks. Water-based inks use water as the main solvent and emit less volatile organic compounds, making them an environmentally friendly material that is increasingly replacing solvent-based inks.

[0003] Various recording methods using aqueous inks have been proposed, and inkjet recording in particular has become extremely popular due to its advantages of being easy to produce full color and inexpensive. However, there are problems with poor wettability of aqueous inks to substrates, such as poor image quality, and high viscosity aqueous inks that are prone to nozzle clogging.

[0004] Various studies have been conducted to improve the wettability of aqueous inks to substrates, and for example, Patent Document 1 discloses a method of using a pretreatment liquid in an inkjet recording method in which an aqueous ink containing crosslinked polymer particles containing a pigment is used to record on a low-water-absorbent recording medium. Also, Patent Document 2 discloses a method of using a surfactant in an inkjet ink composition containing a polyurethane resin.

[0005] JP 2018-108651 A JP 2022-146031 A

[0006] In Patent Document 1, when used in inkjet applications, a specific process must be carried out, and there is a problem that it is difficult to apply to various inkjet inks and devices. Patent Document 2 studies the viscosity of an ink composition containing a nonionic surfactant and a polyurethane resin, but further improvement in the viscosity change rate is required to prevent nozzle clogging during ejection.

[0007] An object of the present invention is to solve the problems of the prior art described above and to provide a polyurethane resin dispersion composition that has excellent wettability and a small rate of viscosity change. Another object of the present invention is to provide a thickening inhibitor that exhibits a small rate of viscosity change when added to a polyurethane resin dispersion composition. Another object of the present invention is to provide a method for improving the wettability of a polyurethane resin dispersion composition.

[0008] The present inventors have conducted various investigations to overcome the above-mentioned problems of the prior art, and have arrived at the present invention.

[0009] The present invention has the following features. [1] A polyurethane resin dispersion composition comprising a polyurethane resin (A), an anionic surfactant (B), a polyhydroxy compound (C) having at least one triple bond, and an aqueous medium (D). [2] The polyurethane resin dispersion composition according to [1], wherein the polyurethane resin (A) has a structure derived from an acidic group-free polyol (a), a structure derived from a polyisocyanate (b), and a structure derived from an acidic group-containing polyol (c). [3] The polyurethane resin dispersion composition according to [2], wherein the acidic group-free polyol (a) is at least one selected from the group consisting of polycarbonate polyols, polyester polyols, and polyether polyols. [4] The polyurethane resin dispersion composition according to [3], wherein the polyurethane resin (A) further has a structure derived from a compound (d) having two or more groups in total selected from the group consisting of hydroxyl groups and amino groups (provided that the compound is not a polycarbonate polyol, polyester polyol, polyether polyol, or acidic group-containing polyol (c)). [5] The polyurethane resin dispersion composition according to any one of [2] to [4], wherein the polyisocyanate (b) is an alicyclic polyisocyanate compound. [6] The polyurethane resin dispersion composition according to any one of [1] to [5], wherein the polyhydroxy compound (C) having at least one triple bond is at least partially emulsified by at least a portion of the anionic surfactant (B). [7] The polyurethane resin dispersion composition according to any one of [1] to [6], wherein the anionic surfactant (B) is at least one selected from the group consisting of ether carboxylic acids, salts of ether carboxylic acids, sulfate esters, salts of sulfate esters, ether sulfate esters, salts of ether sulfate esters, sulfonates, sulfosuccinates, phosphate esters, salts of phosphoric acid esters, ether phosphoric acid esters, salts of ether phosphoric acid esters, fatty acid salts, and acylated amino acid salts. [8] The polyurethane resin dispersion composition according to any one of [1] to [7], wherein the polyhydroxy compound (C) having at least one triple bond is represented by the following formula (1): (In the formula, R １are independently a linear alkyl group having 1 to 6 carbon atoms or a branched or cyclic alkyl group having 3 to 6 carbon atoms; R ２ are independently a linear alkyl group having 1 to 12 carbon atoms or a branched or cyclic alkyl group having 3 to 12 carbon atoms; R ３ are independently a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, and n and m are the same or different and are an integer of 0 or 1 or greater, provided that the total value of n and m is 0 to 100.) [9] The polyurethane resin dispersion composition according to any one of [1] to [8], wherein the mass ratio (A:(B+C)) of the solids content of the polyurethane resin (A) to the total of the anionic surfactant (B) and the polyhydroxy compound (C) having at least one triple bond is 30:0.1 to 30:6.0.

[10] The polyurethane resin dispersion composition according to any one of [1] to [9], which is a binder for an aqueous ink used in inkjet printing.

[11] An aqueous ink comprising the polyurethane resin dispersion composition according to any one of [1] to [9].

[12] A thickening inhibitor for a polyurethane resin dispersion composition comprising a polyurethane resin (A) and an aqueous medium (D), the thickening inhibitor comprising an anionic surfactant (B) and a polyhydroxy compound (C) having at least one triple bond.

[13] A method for improving the wettability of a polyurethane resin dispersion composition containing a polyurethane resin (A) and an aqueous medium (D), the method comprising adding an anionic surfactant (B) and a polyhydroxy compound (C) having at least one triple bond to the polyurethane resin dispersion composition.

[0010] The present invention provides a polyurethane resin dispersion composition having excellent wettability and a small rate of viscosity change. The present invention also provides a thickening inhibitor that exhibits a small rate of viscosity change when added to a polyurethane resin dispersion composition. The present invention also provides a method for improving the wettability of a polyurethane resin dispersion composition.

[0011] As used herein, the term "acidic group" refers to a carboxy group, a sulfonic acid group, a phosphate group, or a phenolic hydroxyl group, and does not include hydroxyl groups other than phenolic hydroxyl groups. In this specification, a numerical range indicated using "to" indicates a range that includes the numerical values ​​before and after "to" as the minimum and maximum values, respectively. Furthermore, when a composition contains multiple substances corresponding to each component, the amount of each component in the composition refers to the total amount of the multiple substances present in the composition, unless otherwise specified. As used herein, the term "process" does not only include independent processes, but also includes processes that cannot be clearly distinguished from other processes, as long as the intended purpose of the process is achieved.

[0012] [Polyurethane Resin Dispersion Composition] The polyurethane resin dispersion composition (hereinafter, may be referred to as "first polyurethane resin dispersion composition") contains a polyurethane resin (A), an anionic surfactant (B), a polyhydroxy compound having at least one triple bond (C), and an aqueous medium (D).

[0013] In the polyurethane resin dispersion composition, the polyurethane resin (A) is dispersed in at least the aqueous medium (D). Specifically, in the polyurethane resin dispersion composition, the polyurethane resin (A) is dispersed in the aqueous medium (D).

[0014] The polyurethane resin dispersion composition has excellent wettability and a small viscosity change rate. Furthermore, by using the polyurethane resin aqueous dispersion in an aqueous ink, the amount of solvent used in the ink can be reduced, which can contribute to the achievement of Goal 7 of the Sustainable Development Goals (SDGs).

[0015] (Viscosity Change Rate) In this specification, the "viscosity change rate" refers to the change in viscosity of a polyurethane resin dispersion composition before and after the addition of a surfactant and a polyhydroxy compound (C) having at least one triple bond. Specifically, it is as follows. The viscosity was measured after 5 minutes at 25°C using an 18 mL liquid volume of the polyurethane resin dispersion composition at a rotation speed of 30 rpm. This viscosity was designated as viscosity (2) (i.e., the viscosity when the composition contains a surfactant and a polyhydroxy compound (C) having at least one triple bond). Under similar conditions, a polyurethane resin dispersion composition was prepared without the addition of a surfactant and a polyhydroxy compound (C) having at least one triple bond, and its viscosity was measured. This viscosity was designated as viscosity (1). The viscosity change rate (also referred to as thickening rate) was calculated using the following formula: Viscosity change rate (%) = 100 × (viscosity (2) - viscosity (1)) / viscosity (1)

[0016] The viscosity change rate of the polyurethane resin dispersion composition is preferably less than 10.0%, more preferably 7.0% or less, and particularly preferably 5.0% or less. When the viscosity change rate is within the above range, the viscosity change is small even when differences in the concentration of the anionic surfactant (B) in the polyurethane resin dispersion composition occur. This allows the composition to be used as a paint, adhesive, ink, or various coating agent, which can suppress the occurrence of color unevenness when applied to various substrates. Specifically, when the aqueous polyurethane resin dispersion composition and an aqueous ink containing the composition are used for painting, dyeing, etc., the error in the amount of ink or paint applied at a constant application pressure can be reduced. As a result, variations in color tone, coating thickness, etc., and the occurrence of unevenness during painting can be suppressed.

[0017] <Polyurethane Resin (A)> The polyurethane resin (A) is not particularly limited as long as it is a resin having a urethane bond. Examples of structures contained in the polyurethane resin (A) include a structure derived from an acidic group-free polyol (a), a structure derived from a polyisocyanate (b), and a structure derived from an acidic group-containing polyol (c). The polyurethane resin (A) may also contain a structure other than the structures derived from (a) to (c). Examples of such additional structures include a structure derived from a compound (d) having a total of two or more groups selected from the group consisting of hydroxyl groups and amino groups (but not the acidic group-free polyol (a) or the acidic group-containing polyol (c)), a structure derived from a neutralizing agent (e), and a structure derived from another compound (f).

[0018] (Acidic Group-Free Polyol (a)) As the acidic group-free polyol (a), known polyols can be used. For example, polymer polyols such as polycarbonate polyols, polyester polyols, polyether polyols, polyester polyether polyols, polyurethane polyols, polyesteramide polyols, and acrylic polyols (all of which have terminal hydroxyl groups), and low molecular weight polyols such as ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, trimethylolpropane, and glycerin can be used. Among these, from the viewpoint of further reducing the viscosity and viscosity change rate of the aqueous polyurethane resin dispersion, at least one selected from the group consisting of polycarbonate polyols, polyester polyols, and polyether polyols is preferred, and polycarbonate polyols are more preferred. The acidic group-free polyol (a) may be used alone or in combination of two or more types.

[0019] Polycarbonate polyols can be obtained by reacting one or more polyol components with a carbonate ester or phosgene. From the viewpoints of safety and handling of reagents, etc., polycarbonate polyols obtained by reacting one or more polyol monomers with a carbonate ester are preferred because they are easy to produce and do not produce terminal chlorinated products as by-products.

[0020] Known polyol monomers can be used as polyol monomers constituting the polycarbonate polyol. For example, aliphatic polyols such as linear aliphatic diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and 1,9-nonanediol, and branched aliphatic diols such as 2-methyl-1,3-propanediol, 1,5-hexanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, and neopentyl glycol; trifunctional or higher polyhydric alcohols such as trimethylolpropane and pentaerythritol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, and 2,5-bis(hydroxymethyl)methyl Examples of suitable polyols include alicyclic polyols such as diols having an alicyclic structure in the main chain, such as (ethyl)-1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, and 1,4-bis(hydroxyethoxy)cyclohexane; aromatic diols such as 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4'-naphthalenedimethanol, and 3,4'-naphthalenedimethanol; polyester polyols of hydroxycarboxylic acids and diols, such as polyester polyols of 6-hydroxycaproic acid and hexanediol; polyester polyols of dicarboxylic acids and diols, such as polyester polyols of adipic acid and hexanediol; and polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Among these, alicyclic polyols and / or aliphatic polyols are preferred from the viewpoint of further reducing the viscosity and viscosity change rate of the polyurethane resin aqueous dispersion. The polyol monomers may be used alone or in combination. As the alicyclic polyol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanediol are more preferred.As the aliphatic polyol, a linear aliphatic diol is more preferred, and 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are even more preferred.

[0021] The carbonate ester is not particularly limited, and examples thereof include aliphatic carbonate esters such as dimethyl carbonate and diethyl carbonate; aromatic carbonate esters such as diphenyl carbonate; and cyclic carbonate esters such as ethylene carbonate. In addition, phosgene or the like capable of producing polycarbonate polyol can also be used. Among these, aliphatic carbonate esters are preferred, and dimethyl carbonate is more preferred, in view of the ease of producing polycarbonate polyol.

[0022] Known polyester polyols can be used. Examples include polyester polyols obtained by esterifying a polyol (e.g., a polyol having a molecular weight of 50 to 500) with a polycarboxylic acid; polyester polyols obtained by ring-opening polymerization of a cyclic ester compound such as ε-caprolactone; and copolymer polyester polyols thereof. Specific examples of polyester polyols include polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, poly(neopentyl glycol terephthalate) diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, polybutylene sebacate diol, poly-ε-caprolactone diol, poly(3-methyl-1,5-pentylene adipate) diol, and polyester diols such as polycondensates of 1,6-hexanediol and dimer acid.

[0023] As the polyol, for example, the polyol monomers described above can be used. The low-molecular-weight polyols can be used alone or in combination. In addition, polyether polyols, which will be described later, can also be used as the polyol.

[0024] Examples of polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid; and anhydrides of the aliphatic polycarboxylic acids and aromatic polycarboxylic acids. The polycarboxylic acids may be used alone or in combination.

[0025] Known polyether polyols can be used. Examples include polyethylene glycol, poly(1,2-propylene glycol), poly(1,3-propylene glycol), poly(1,3-tetramethylene glycol), poly(1,4-tetramethylene glycol), poly(1,6-hexamethylene glycol), polyoxyethylene triol, polyoxypropylene triol, polyoxyethylene polyoxypropylene triol, random copolymers or block copolymers of ethylene oxide and propylene oxide, random copolymers or block copolymers of ethylene oxide and butylene oxide, and random copolymers or block copolymers of propylene oxide and butylene oxide. Poly(1,4-tetramethylene glycol) is preferred from the viewpoint of further reducing the viscosity and viscosity change rate of the aqueous polyurethane resin dispersion.

[0026] The polyester polyether polyol can be obtained by reacting the polyester polyol with the polyether polyol.

[0027] The acidic group-free polyol (a) preferably has a number average molecular weight (Mn) of 100 to 5,000. When Mn is 100 or more, the performance as a soft segment is good and cracks are less likely to occur in printed matter. When Mn is 5,000 or less, the reactivity of the acidic group-free polyol (a) with the polyisocyanate (b) is not reduced, and problems such as the urethane prepolymer production process taking a long time, the reaction not proceeding sufficiently, and the viscosity of the polycarbonate polyol becoming high and making it difficult to handle do not occur. In this specification, Mn is defined as the hydroxyl value and １The value is calculated by H-NMR or calculated from the quantitative value of the polyol by gas chromatography after alkaline hydrolysis.

[0028] The acidic group-free polyol (a) preferably has a hydroxyl value of 20 to 1,200 mgKOH / g, more preferably 30 to 300 mgKOH / g. When the hydroxyl value is within the above range, the viscosity of the aqueous polyurethane resin dispersion can be further reduced. In this specification, the hydroxyl value is the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl groups in 1 g of sample, and can be measured by Method A of JIS K 1557.

[0029] (Polyisocyanate (b)) As the polyisocyanate (b), known compounds can be used. For example, aromatic polyisocyanate compounds such as 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, and 4,4'-diphenylmethane diisocyanate (MDI) can be used; and aliphatic polyisocyanates such as ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), and hexamethylene diisocyanate (HDI) can be used. alicyclic polyisocyanate compounds such as isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-dicyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, and 2,6-norbornane diisocyanate. The polyisocyanate (b) may have a structure whose entirety or part has been derivatized by isocyanuration, carbodiimidization, biuretization, or the like.

[0030] Among the polyisocyanates (b), from the viewpoint of controlling reactivity, etc., an aliphatic polyisocyanate compound and / or an alicyclic polyisocyanate compound is preferred, and from the viewpoint of further reducing the viscosity and viscosity change rate of the polyurethane resin aqueous dispersion, an alicyclic polyisocyanate compound is more preferred, and at least one selected from the group consisting of isophorone diisocyanate (IPDI), 4,4'-diphenylmethane diisocyanate (MDI), and 4,4'-dicyclohexylmethane diisocyanate (H12MDI) is particularly preferred. The polyisocyanates (b) may be used alone or in combination of two or more types.

[0031] (Blocked isocyanate structure) When the polyurethane resin (A) has a structure derived from the polyisocyanate (b), the polyurethane resin (A) may have a blocked isocyanate structure. The blocked isocyanate structure refers to a structure in which a blocking agent is added to an isocyanate group. The blocked isocyanate structure in the polyurethane resin is a structure in which a blocking agent is added to an isocyanate group in a part of the structure derived from the polyisocyanate (b), and is usually present at the terminal of the polyurethane resin (A).

[0032] The blocking agent refers to a compound that can react with an isocyanate group to convert the isocyanate group to another group, and that can reversibly convert the other group to an isocyanate group by heat treatment. The heat treatment temperature is not particularly limited, but is preferably 80 to 180°C.

[0033] Examples of the blocking agent include phenol-based blocking agents such as phenol, aliphatic alcohol-based blocking agents such as methanol, active methylene-based blocking agents such as dimethyl malonate, mercaptan-based blocking agents such as butyl mercaptan, acid amide-based blocking agents such as acetanilide, lactam-based blocking agents such as ε-caprolactam, acid imide-based blocking agents such as succinimide, oxime-based blocking agents such as acetaldoxime, acetoneoxime, methyl ethyl ketoxime, and amine-based blocking agents such as diphenylaniline, aniline, ethyleneimine, dimethylpyrazole, etc. The blocking agents may be used alone or in combination.

[0034] (Acidic Group-Containing Polyol (c)) The acidic group-containing polyol (c) is a polyol containing two or more hydroxyl groups and one or more acidic groups in one molecule. The acidic group-containing polyol (c) may be used alone or in combination of two or more kinds.

[0035] Known acidic group-containing polyols can be used as the acidic group-containing polyol (c). Examples include dimethylolalkanoic acids such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid; N,N-bishydroxyethylglycine, N,N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, and 3,6-dihydroxy-2-toluenesulfonic acid. Among these, from the viewpoint of availability, dimethylolalkanoic acids having 4 to 12 carbon atoms and two methylol groups are preferred, and among dimethylolalkanoic acids, 2,2-dimethylolpropionic acid is more preferred.

[0036] (Compound (d) Having a Total of Two or More Groups Selected from the Group Consisting of Hydroxyl Groups and Amino Groups (However, This Is Not the Case of the Non-Acidic Group-Containing Polyol (a) and the Acidic Group-Containing Polyol (c))) Compound (d) Having a Total of Two or More Groups Selected from the Group Consisting of Hydroxyl Groups and Amino Groups (However, This Is Not the Case of the Non-Acidic Group-Containing Polyol (a) and the Acidic Group-Containing Polyol (c)) (hereinafter also referred to as "Compound (d)")) is a component that increases the molecular weight of polyurethane resin (A). Compound (d) is a compound that is reactive with the isocyanato group of polyurethane prepolymer, which is a synthetic intermediate in the production of polyurethane resin (A). Compounds that are reactive with the isocyanato group of polyurethane prepolymer, which is a synthetic intermediate of polyurethane resin (A), are called chain extenders, and compound (d) is a type of chain extender. Note that examples of chain extenders other than compound (d) include water. Here, the "amino group" in compound (d) refers to a primary amino group or a secondary amino group.

[0037] The compound (d) may vary depending on the range of the acidic group-free polyol (a). For example, when the acidic group-free polyol (a) is at least one selected from the group consisting of polycarbonate polyol, polyester polyol, and polyether polyol, the compound (d) is not a polycarbonate polyol, polyester polyol, polyether polyol, or acidic group-containing polyol (c).

[0038] Examples of the compound (d) include polyamine compounds (i.e., compounds having two or more amino groups in one molecule and no hydroxyl groups), polyol compounds (i.e., compounds having two or more hydroxyl groups in one molecule and no amino groups), and aminoalcohol compounds (i.e., compounds having one or more hydroxyl groups in one molecule and one or more amino groups in one molecule).

[0039] As the compound (d), known compounds can be used, and they may be used alone or in combination of two or more kinds.

[0040] Examples of the polyamine compound include diamine compounds having only primary amino groups, such as hydrazine, ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis(aminomethyl)cyclohexane, and xylylenediamine; diamine compounds having only secondary amino groups, such as piperazine and 2,5-dimethylpiperazine; polyamines having a total of three or more amino groups and imino groups in one molecule, such as adipodihydrazide, diethylenetriamine, and triethylenetetramine; and other polyamine compounds, such as polyetheramines.

[0041] The polyol compound is as described above in connection with the acidic group-free polyol (a), and the compounds exemplified as low-molecular-weight polyol compounds are preferred.

[0042] Examples of the amino alcohol compound include ethanolamine, butanolamine, and hexanolamine.

[0043] The compound (d) is preferably at least one selected from the group consisting of polyamine compounds and aminoalcohol compounds, and is particularly preferably a polyamine compound.

[0044] The number average molecular weight (Mn) of the compound (d) is preferably not more than 300. When the Mn of the compound (d) is not more than 300, the cohesive strength of the polyurethane resin (A) can be increased.

[0045] (Neutralizing agent (e)) When the polyurethane resin (A) has a structure derived from the acidic group-containing polyol (c), the polyurethane resin (A) has an acidic group. In this case, the polyurethane resin (A) may have a structure derived from a neutralizing agent (e) in order to neutralize the acidic group. The neutralizing agent (e) may be used alone or in combination of two or more types.

[0046] Known neutralizing agents can be used as the neutralizing agent (e), including, for example, organic amines such as trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-phenyldiethanolamine, 2-dimethylaminoethanol, 2-(dimethylamino)-2-methyl-1-propanol, diethylethanolamine, N-methylmorpholine, and pyridine; inorganic alkalis such as sodium hydroxide and potassium hydroxide; and ammonia.

[0047] The neutralizing agent (e) preferably has a boiling point of 200° C. or lower, more preferably in the range of −50 to 180° C., because when a resin film is formed from the aqueous dispersion composition, the neutralizing agent (e) volatilizes and disappears from the printed matter at the temperature (usually 40 to 200° C.) used when drying the aqueous medium (D), thereby providing even better adhesive strength. When a printed matter is obtained at a low temperature of 100° C. or lower in a short time of several seconds to 1 hour, the boiling point is preferably 130° C. or lower, more preferably 110° C. or lower.

[0048] (Other Compounds (f)) Examples of the other compounds (f) include monoalcohols and monoamines. When the other compounds (f) are monoalcohols or monoamines, a polyurethane resin (A) having non-reactive molecular terminals is obtained. Examples of monoalcohols include ethanol, n-propanol, isopropanol, n-butanol, hexanol, and octanol. Examples of monoamines include ethylamine, n-propylamine, isopropylamine, n-butylamine, and n-hexylamine. The other compounds (f) may be used alone or in combination.

[0049] (Hydroxyl equivalents of the acidic group-free polyol (a), the acidic group-containing polyol (c), and the other compounds (f)) In the polyurethane resin (A), the total hydroxyl equivalents of the acidic group-free polyol (a), the acidic group-containing polyol (c), and the polyols contained in the other compounds (f) is preferably 50 to 4,000. If the hydroxyl equivalents are within this range, production of an aqueous dispersion of the polyurethane resin (A) containing the obtained polyurethane resin (A) is easy. From the viewpoint of storage stability of the obtained aqueous dispersion of the polyurethane resin (A), the hydroxyl equivalents are preferably 100 to 3,500, more preferably 120 to 2,000, and particularly preferably 130 to 1,500.

[0050] The hydroxyl equivalent number can be calculated by the following formulas (1) and (2): Hydroxyl equivalent number of each polyol component = Molecular weight of each polyol component / Number of hydroxyl groups in each polyol component (1) Total hydroxyl equivalent number of polyol components = M / Total number of moles of polyol components (2) In formula (2), M represents [[Hydroxyl equivalent number of acidic group-free polyol component × Number of moles of acidic group-free polyol component] + [Hydroxyl equivalent number of acidic group-containing polyol × Number of moles of acidic group-containing polyol] + [Hydroxyl equivalent number of polyol contained in other compound (f) × Number of moles of that polyol]].

[0051] (Preferred Structure of Polyurethane Resin (A)) The polyurethane resin (A) preferably has a structure derived from the acidic group-free polyol (a), a structure derived from the polyisocyanate (b), and a structure derived from the acidic group-containing polyol (c). The polyurethane resin (A) more preferably has a structure derived from the acidic group-free polyol (a), a structure derived from the polyisocyanate (b), and a structure derived from the acidic group-containing polyol (c) in its main chain. Here, the main chain refers to a chain connected by two or more urethane bonds, and the carbon chain with the largest number of carbon atoms among multiple carbon chains connecting carbons in adjacent urethane bonds with the smallest number of carbon atoms. For example, when the carbon chain contains a 1,3-cyclohexanediyl group, the number of carbon atoms in the main chain in this group is 5. When the polyurethane resin (A) has a structure derived from the acidic group-free polyol (a), the acidic group-free polyol (a) is preferably at least one selected from the group consisting of polycarbonate polyols, polyester polyols, and polyether polyols. Here, it is more preferable that the polyurethane resin (A) further has a structure derived from a compound (d) having a total of two or more groups selected from the group consisting of hydroxyl groups and amino groups (however, this is not a polycarbonate polyol, polyester polyol, polyether polyol, or acidic group-containing polyol (c)). When the polyurethane resin (A) has a structure derived from the polyisocyanate (b), the polyisocyanate (b) is preferably an alicyclic polyisocyanate compound.

[0052] (Characteristics of Polyurethane Resin (A)) [Urethane Bond and Urea Bond] In the polyurethane resin (A), the total content of urethane bonds and urea bonds is preferably 7.0 to 25.0 mass %, and particularly preferably 8.0 to 22.0 mass %, based on the solid content of the polyurethane resin (A).

[0053] By setting the total content of the urethane bond and the urea bond to 7.0% by mass or more, stickiness on the surface of a printed material may be reduced in some cases. Furthermore, by setting the content of the urethane bond and the urea bond to 25.0% by mass or less, when the polyurethane resin dispersion composition is used in an aqueous ink, the ink may have improved adhesion to a substrate.

[0054] From the viewpoint of further reducing the viscosity of the aqueous polyurethane resin dispersion, the content of urethane bonds in the polyurethane resin (A) is preferably 3.0 to 20.0 mass%, more preferably 4.0 to 16.0 mass%, even more preferably 5.0 to 14.0 mass%, and particularly preferably 6.0 to 13.0 mass%, based on the solid content.

[0055] From the viewpoint of further reducing the viscosity of the aqueous polyurethane resin dispersion, the content of urea bonds in the polyurethane resin (A) is preferably 0.6 to 10.0 mass%, more preferably 0.8 to 8.5 mass%, even more preferably 1.0 to 7.0 mass%, and particularly preferably 1.2 to 6.0 mass%, based on the solid content.

[0056] The content ratio of urethane bonds and the content ratio of urea bonds in the polyurethane resin (A) can be controlled by the molecular weight of each of the acidic group-free polyol (a), the polyisocyanate (b), the acidic group-containing polyol (c), and the compound (d), the number of hydroxyl groups, isocyanato groups, and amino groups in one molecule, and the usage ratio of each raw material on a solids basis in the aqueous dispersion of the polyurethane resin (A).

[0057] The content of urethane bonds, urea bonds, etc. in the polyurethane resin (A) can be roughly calculated from the charged amounts, molecular weights of each raw material, and molecular weights or mole numbers of portions corresponding to each structure.

[0058] [Alicyclic Structure Content] From the viewpoint of improving flexibility, the alicyclic structure content in the polyurethane resin (A) is preferably 5 to 50 mass%, particularly preferably 15 to 50 mass%. In this specification, the alicyclic structure content in the polyurethane resin (A) can be measured by 1H-NMR.

[0059] [Weight-Average Molecular Weight] The weight-average molecular weight (Mw) of the polyurethane resin (A) is preferably 100,000 to 10,000,000, more preferably 200,000 to 5,000,000, and particularly preferably 300,000 to 2,000,000. The weight-average molecular weight is measured by gel permeation chromatography (GPC), and a converted value obtained from a previously prepared calibration curve of standard polystyrene can be used. By setting the weight-average molecular weight to 100,000 or more, good printed matter tends to be obtained. By setting the weight-average molecular weight to 10,000,000 or less, the drying properties of the ink tend to be improved.

[0060] [Acid Value] The acid value of the polyurethane resin (A) is preferably 5 to 40 mgKOH / g, more preferably 8 to 35 mgKOH / g, and particularly preferably 10 to 30 mgKOH / g. Setting the acid value of the polyurethane resin in the range of 5 to 40 mgKOH / g tends to improve storage stability. The acid value can be measured in accordance with the indicator titration method of JIS K 1557. When the polyurethane resin (A) contains a structure derived from a neutralizer (e), the measurement is performed after removing the neutralizer (e) used to neutralize the acidic groups. For example, when an organic amine is used as the neutralizer (e), an aqueous dispersion of the polyurethane resin (A) is applied to a glass plate, and the coating film obtained by drying at a temperature of 60°C and under a reduced pressure of 20 mmHg for 24 hours is dissolved in N-methylpyrrolidone (NMP), and the acid value can be measured in accordance with the indicator titration method of JIS K 1557. The acid value of the polyurethane resin (A) can be controlled by the content of the acidic group-containing polyol (c).

[0061] (Composition of polyurethane resin (A)) The content ratio of each structure in the polyurethane resin (A) is preferably as follows. In this specification, the content ratio of each component in the polyurethane resin (A) is a value calculated from the charged amount. The charged amount indicates the amount of each component used when producing the polyurethane resin (A). In the production of the polyurethane resin (A), each component is almost completely reacted, so the charged amount is taken as the content ratio in the polyurethane resin (A).

[0062] The content of the structure derived from the acidic group-free polyol (a) in the polyurethane resin (A) is preferably 35.0 to 85.0 mass %, particularly preferably 40.0 to 80.0 mass %.

[0063] The content of the structure derived from polyisocyanate (b) in the polyurethane resin (A) is preferably 10.0 to 60.0 mass %, particularly preferably 15.0 to 50.0 mass %.

[0064] The content of the structure derived from the acidic group-containing polyol (c) in the polyurethane resin (A) is preferably from 0.5 to 20.0 mass %, particularly preferably from 1.0 to 15.0 mass %.

[0065] The content of the structure derived from polyisocyanate (b) is preferably an amount such that the molar ratio of isocyanate groups in polyisocyanate (b) to hydroxyl groups in the acidic group-free polyol (a) and the acidic group-containing polyol (c) (isocyanate groups / hydroxyl groups) is in the range of 0.5 to 3.0, and particularly preferably in the range of 1.2 to 2.0. When polyurethane resin (A) has a blocked isocyanate structure, the content of the structure derived from polyisocyanate (Ab) includes the content of the blocked isocyanate structure.

[0066] When the polyurethane resin (A) has a structure derived from the compound (d), the content of the structure derived from the compound (d) in the polyurethane resin (A) is preferably 0 to 15.5 mass%, and particularly preferably 1.0 to 8.0 mass%.

[0067] The content of the structure derived from compound (d) is preferably an amount equal to or less than the equivalent of the isocyanato group that serves as the chain extension initiation point in the polyurethane prepolymer, which is a synthetic intermediate for polyurethane resin (A), and particularly preferably an amount equal to 0.70 to 0.99 equivalents of the isocyanato group in the polyurethane prepolymer. Adding compound (d) in an amount equal to or less than the equivalent of the isocyanato group in the polyurethane prepolymer tends to improve solvent resistance without reducing the molecular weight of the chain-extended polyurethane resin (A).

[0068] When the polyurethane resin (A) has a structure derived from the neutralizer (e), the content ratio of the structure derived from the neutralizer (e) is preferably in the range of 0.8 to 1.2 times the number of moles of acidic groups contained in the polyurethane resin (A). When the content ratio of the structure derived from the neutralizer (e) is 0.8 times or more the number of moles of the acidic groups, the stability of the polyurethane resin (A) in the aqueous dispersion is high. When the content ratio of the structure derived from the neutralizer (e) is 1.2 times or less the number of moles of the acidic groups, a printed material with high substrate adhesion can be obtained in a short time of several seconds to 1 hour under low-temperature drying at 100°C or less. Note that when a coating film (cured layer) of the aqueous dispersion composition is obtained by applying the aqueous dispersion composition to a substrate and drying and curing the aqueous dispersion composition, the neutralizer (e) may volatilize during drying, and the polyurethane resin (A) in the coating film may not contain a structure derived from the neutralizer (e).

[0069] When the polyurethane resin (A) has a structure derived from the other compound (f), the content of the structure derived from the other compound (f) in the polyurethane resin (A) is preferably less than 2 mass%, and particularly preferably less than 1 mass%.

[0070] <Method for producing polyurethane resin (A)> The polyurethane resin (A) can be produced by any method as long as the desired polyurethane resin (A) is obtained. For example, the polyurethane resin (A) can be produced by a production method including a step of reacting an acidic group-free polyol (a) and a polyisocyanate (b). In addition, the polyurethane resin (A) is preferably a polyurethane resin (A) produced by the following method for producing an aqueous dispersion of the polyurethane resin (A).

[0071] (Aqueous Dispersion of Polyurethane Resin (A)) The aqueous dispersion of polyurethane resin (A) is one in which polyurethane resin (A) is dispersed in aqueous medium (D). The content (solid content) of polyurethane resin (A) in the aqueous dispersion of polyurethane resin (A) is preferably 5 to 60 mass %, particularly preferably 20 to 50 mass %. Here, the content of polyurethane resin (A) in the aqueous dispersion of polyurethane resin (A) refers to the content of polyurethane resin (A) relative to the total amount of the aqueous dispersion including polyurethane resin (A), aqueous medium (D), and optional additives. In the aqueous dispersion of polyurethane resin (A), the amount of hydrophilic organic solvent in the aqueous medium (D) is preferably 0 to 20 mass %. The pH of the aqueous dispersion of polyurethane resin (A) is preferably 5.0 to 9.0.

[0072] (Method for Producing Aqueous Dispersion of Polyurethane Resin (A)) The method for producing the aqueous dispersion of polyurethane resin (A) preferably includes the following steps: (I) a step of reacting the acidic group-free polyol (a), the polyisocyanate (b), the acidic group-containing polyol (c), and optionally other compounds (f) in the presence of an organic solvent to obtain a polyurethane prepolymer, (II) a step of mixing the polyurethane prepolymer with water, and (III) a step of reacting the polyurethane prepolymer with compound (d) or other chain extender.

[0073] Furthermore, when a neutralizing agent (e) is used, a step of neutralizing the acidic groups of the polyurethane prepolymer with the neutralizing agent (e) may be included after step (I).In addition, a step of removing the organic solvent may be included as step (IV).

[0074] When the polyurethane resin (A) does not contain a structure derived from the compound (d), the polyurethane prepolymer obtained in step (I) or step (II) can be used as the polyurethane resin (A).

[0075] The aqueous dispersion of polyurethane resin (A) can be produced by a known method described in known literature (for example, WO 2016 / 039396, WO 2016 / 163394, etc.).

[0076] In the step (I), the polyurethane prepolymer is obtained by reacting an acidic group-free polyol (a), a polyisocyanate (b), an acidic group-containing polyol (c), and optionally other compounds (f). Thus, the polyurethane prepolymer has a structure derived from the acidic group-free polyol (a), a structure derived from the polyisocyanate (b), a structure derived from the acidic group-containing polyol (c), and optionally a structure derived from other compounds (f).

[0077] The polyurethane prepolymer is preferably selected so that the content of free isocyanato groups is in the range of 0.5 to 5.0 mass % based on the solid content of the polyurethane prepolymer, in terms of improving dispersibility in water.

[0078] The acid value (AV) of the polyurethane prepolymer is preferably 4 to 40 mgKOH / g, more preferably 6 to 38 mgKOH / g, and particularly preferably 8 to 35 mgKOH / g. By making the acid value of the polyurethane prepolymer 4 mgKOH / g or more, it tends to be possible to improve dispersibility in an aqueous medium and storage stability. Furthermore, by making the acid value of the polyurethane prepolymer 40 mgKOH / g or less, it tends to be possible to increase the flexibility of printed matter. It also tends to be possible to improve the drying properties of the ink when it is dried.

[0079] The "acid value of the polyurethane prepolymer" refers to the acid value of the so-called solid content, excluding the solvent used in producing the polyurethane prepolymer and the neutralizing agent used to disperse the polyurethane prepolymer in an aqueous medium.

[0080] Specifically, the acid value of the polyurethane prepolymer can be calculated by the following formula (3).

[0081] [Acid value of polyurethane prepolymer]=[(number of millimoles of acidic group-containing polyol)×(number of acidic groups in one molecule of acidic group-containing polyol)]×56.1 / [total mass of polyisocyanate, acidic group-containing polyol, optional blocking agent, and acidic group-free polyol] (3)

[0082] In this way, the acid value of the polyurethane prepolymer is adjusted by the content ratio of the acidic group-containing polyol (c) in all polyols that form the polyurethane prepolymer.

[0083]

[0033] In the step (III), the polyurethane prepolymer is reacted with the compound (d) or another chain extender to bond the polyurethane prepolymers together, thereby adjusting the molecular weight of the polyurethane resin to a desired range. In the step (I), when the acidic group-free polyol (a) is at least one selected from the group consisting of polycarbonate polyols, polyester polyols, and polyether polyols, it is preferable that the compound (d) used in the step (III) is not a polycarbonate polyol, polyester polyol, polyether polyol, or acidic group-containing polyol (c).

[0084] The step (III) may be carried out slowly under cooling, or in some cases, the reaction may be accelerated under heating conditions of 90° C. or less. The reaction time under cooling may be, for example, 0.5 to 24 hours, and the reaction time under heating conditions of 90° C. or less may be, for example, 0.1 to 6 hours.

[0085] <Anionic Surfactant (B)> Known anionic surfactants can be used as the anionic surfactant (B). Examples include ether carboxylic acids or salts thereof, such as sodium lauryl ether acetate and sodium polyoxyethylene lauryl ether acetate; sulfate esters or ether sulfate esters and salts thereof, such as sodium lauryl sulfate, sodium polyoxyethylene lauryl sulfate, polyoxyethylene triethanolamine lauryl sulfate, and polyoxyethylene coconut oil fatty acid monoethanolamide sodium sulfate; sulfonates, such as sodium dodecylbenzenesulfonate; sulfosuccinates; phosphate esters or ether phosphate esters and salts thereof, such as sodium lauryl phosphate and sodium polyoxyethylene lauryl ether phosphate; fatty acid salts, such as sodium laurate and triethanolamine laurate; and acylated amino acid salts, such as sodium coconut oil fatty acid methyl taurate, sodium coconut oil fatty acid sarcosine, triethanolamine coconut oil fatty acid sarcosine, triethanolamine N-coconut oil fatty acid acyl-L-glutamate, sodium N-coconut oil fatty acid acyl-L-glutamate, and sodium lauroylmethyl-β-alanine. The anionic surfactant (B) may be used alone or in combination of two or more kinds.

[0086] <Polyhydroxy Compound (C) Having At Least One Triple Bond> In the polyhydroxy compound (C) having at least one triple bond (also simply referred to as "polyhydroxy compound (C)" in this specification), the polyhydroxy compound is a compound having two or more hydroxy groups. The polyhydroxy compound (C) having at least one triple bond is preferably a dihydroxy compound having a carbon-carbon triple bond in its main chain. Here, "main chain" refers to a carbon chain connecting two hydroxy groups with the shortest number of carbon atoms. Note that when the main chain contains a cyclic group, multiple carbon chains may be present. In this case, the carbon chain having the greatest number of carbon atoms among the carbon chains connecting two hydroxy groups with the shortest number of carbon atoms refers to the carbon chain having the greatest number of carbon atoms.

[0087] The polyhydroxy compound (C) is not particularly limited, and is preferably a dihydroxy compound, and examples thereof include a diol compound having an acetylene group and a compound obtained by adding ethylene oxide to the above compound. Examples of the diol compound having an acetylene group include a compound having a 2-butyne-1,4-diol skeleton. Here, the methylene groups (-CH) at the 1st and 4th positions in 2-butyne-1,4-diol are ２ -) can be unsubstituted or substituted with one or two hydrocarbon groups (e.g., alkyl groups) or poly(alkyleneoxy) groups. Additionally, the hydroxy groups in 2-butyne-1,4-diol may be replaced with alkylpoly(alkyleneoxy) groups.

[0088] The polyhydroxy compound (C) is preferably a compound represented by the following formula (1):

[0089] (In the formula, R １ are independently a linear alkyl group having 1 to 6 carbon atoms or a branched or cyclic alkyl group having 3 to 6 carbon atoms; R ２ are independently a linear alkyl group having 1 to 12 carbon atoms or a branched or cyclic alkyl group having 3 to 12 carbon atoms; R ３ are independently a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, and n and m are the same or different and are integers of 0 or 1 or more, with the sum of n and m being 0 to 100.

[0090] Examples of the linear alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, and an n-dodecyl group.

[0091] Examples of branched alkyl groups having 3 to 12 carbon atoms include an i-propyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a neohexyl group, an isohexyl group, a sec-hexyl group, and a tert-hexyl group.

[0092] Examples of cyclic alkyl groups having 3 to 12 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, cyclododecyl, adamantyl, and norbornyl groups.

[0093] The linear alkyl group having 1 to 6 carbon atoms, the branched alkyl group having 3 to 6 carbon atoms, or the cyclic alkyl group having 3 to 6 carbon atoms can be appropriately selected from the above groups depending on the number of carbon atoms.

[0094] n and m may be the same or different and are preferably 0 or an integer of 1 to 50.

[0095] The total value of n and m is preferably 0 to 100, and particularly preferably 2 to 80.

[0096] Examples of the polyhydroxy compound (C) in which n and m are 0 include Surfynol (registered trademark) 104 series (manufactured by Evonik).

[0097] Examples of the polyhydroxy compound (C) in which at least one of n and m is 1 or greater include Surfynol (registered trademark) 400 series (manufactured by Evonik).

[0098] The polyhydroxy compound (C) having at least one triple bond can be produced, for example, by the method described in JP 2014-108417 A. The polyhydroxy compound (C) having at least one triple bond may be used alone or in combination of two or more types. The polyhydroxy compound (C) having at least one triple bond may react with the polyurethane resin (A) when the polyurethane resin (A) contains unreacted isocyanate groups or the like. Therefore, the polyurethane resin dispersion composition may contain a product (partial reaction product) in which a portion of the polyurethane resin (A) and a portion of the polyhydroxy compound (C) have reacted.

[0099] <Preferred Aspects of Anionic Surfactant (B) and Polyhydroxy Compound (C) Having at Least One Triple Bond> In the polyurethane resin dispersion composition, the anionic surfactant (B) and the polyhydroxy compound (C) having at least one triple bond may be present independently or together. However, it is preferred that at least a portion of the polyhydroxy compound (C) having at least one triple bond is emulsified by at least a portion of the anionic surfactant (B). A commercially available product can be used as the combination of the anionic surfactant (B) and the polyhydroxy compound (C) having at least one triple bond. Examples of such commercially available products include Olfine (registered trademark) WE-003, PD-201, PD-301, PD-301A, PD-611, and PD-631 (manufactured by Nissin Chemical Industry Co., Ltd.), Surfynol (registered trademark) SE, and Surfynol (registered trademark) SE-F (manufactured by Evonik).

[0100] <Aqueous Medium (D)> The aqueous medium (D) is water or a mixed medium of water and a hydrophilic organic solvent. Examples of water include tap water, ion-exchanged water, distilled water, and ultrapure water. Examples of hydrophilic organic solvents include ketones such as acetone; pyrrolidones such as N-methylpyrrolidone and N-ethylpyrrolidone; ethers such as diethyl ether and dipropylene glycol dimethyl ether; alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, diethylene glycol, and glycerin; polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; amides such as β-alkoxypropionamide, typified by "KJCMPA(R)-100" manufactured by KJ Chemical Co.; and hydroxyl group-containing tertiary amines such as 2-(dimethylamino)-2-methyl-1-propanol (DMAP). The aqueous medium (D) may be used alone or in combination of two or more kinds.

[0101] <Additional Components> The polyurethane resin dispersion composition may contain other resins and / or other additives as necessary.

[0102] Examples of the other resins include polyester resins, acrylic resins, polyether resins, polycarbonate resins, epoxy resins, alkyd resins, polyolefin resins, vinyl chloride resins, etc. The other resins may be used alone or in combination of two or more.

[0103] Polyester resins can usually be produced by an esterification reaction or transesterification reaction between an acid component and an alcohol component. The acid component can be a compound that is usually used as an acid component in the production of polyester resins. Examples of the acid component that can be used include aliphatic polybasic acids, alicyclic polybasic acids, and aromatic polybasic acids.

[0104] Acrylic resins are compounds having polymerization units derived from "(meth)acrylic monomers" having one or more "(meth)acryloyl groups" in the molecule. Acrylic resins are usually obtained by polymerizing one or more (meth)acrylic monomers. "(Meth)acryloyl group" refers to "methacryloyl group" and "acryloyl group". "(Meth)acrylic monomer" refers to "methacrylic monomer" and "acrylic monomer".

[0105] Examples of polyether resins include polymers or copolymers having an ether bond, such as polyoxyethylene-based polyethers, polyoxypropylene-based polyethers, polyoxybutylene-based polyethers, and polyethers derived from aromatic polyhydroxy compounds such as bisphenol A or bisphenol F.

[0106] Examples of polycarbonate resins include polymers produced from bisphenol compounds, such as bisphenol A polycarbonate.

[0107] Examples of epoxy resins include resins obtained by reacting a bisphenol compound with epichlorohydrin. Examples of bisphenol compounds include bisphenol A and bisphenol F.

[0108] Examples of alkyd resins include alkyd resins obtained by reacting a polybasic acid such as phthalic acid, terephthalic acid, succinic acid, or the like with a polyhydric alcohol and a modifier such as fats and oils / fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, or the like) or natural resins (rosin, amber, or the like).

[0109] Examples of polyolefin resins include those obtained by polymerizing or copolymerizing an olefinic monomer with other monomers according to a conventional polymerization method, dispersing the resulting polyolefin resin in water using an emulsifier, or those obtained by emulsion polymerizing an olefinic monomer with other monomers. In some cases, so-called chlorinated polyolefin-modified resins obtained by chlorinating the above-mentioned polyolefin resins may also be used.

[0110] Examples of olefin-based monomers include α-olefins such as ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-hexene, 1-decene, and 1-dodecene; and conjugated or non-conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene, and 1,5-hexadiene. These monomers may be used alone or in combination.

[0111] Examples of other monomers copolymerizable with the olefin-based monomer include styrene, vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, and itaconic anhydride. These monomers may be used alone or in combination.

[0112] Examples of the other additives that can be used include surfactants other than the anionic surfactant (B), curing agents, surface conditioners, emulsifiers, thickeners, urethanization catalysts, fillers, foaming agents, oil repellents, pigments, dyes, film-forming aids, hollow foams, flame retardants, antifoaming agents, leveling agents, antiblocking agents, UV absorbers, light stabilizers, plasticizers, antisettling agents, polymerization inhibitors, dispersants, penetration promoters, moisturizing agents, fixing agents, preservatives, antioxidants, antifungal agents, chelating agents, sensitizers, pH adjusters, wetting agents, etc. These additives may be used alone or in combination.

[0113] The surfactant other than the anionic surfactant (B) may be a nonionic surfactant, and known surfactants may be used. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, oxyethylene-oxypropylene block polymer, silicone surfactant, and fluorine surfactant. A small amount of the nonionic surfactant may be used as long as it does not affect the viscosity change rate.

[0114] Known curing agents can be used, such as polyisocyanate compounds, polycarbodiimide compounds, amino resins, epoxy group-containing compounds, and aziridine compounds.

[0115] The coalescing agent is generally a hydrophilic compound that promotes film formation. Examples of the coalescing agent include pyrrolidone-based compounds such as N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-isopropylpyrrolidone, N-butylpyrrolidone, N-cyclohexylpyrrolidone, N-octylpyrrolidone, N-phenylpyrrolidone, and vinylpyrrolidone; alcohol-based compounds such as methanol, ethanol, isopropanol, n-butanol, and n-hexanol; and glycol-based compounds such as propylene glycol, diethylene glycol, propylene glycol, triethylene glycol, and polyethylene glycol, with pyrrolidone-based compounds being preferred. The coalescing agent can also serve as the aqueous medium in which the polyurethane resin is dispersed.

[0116] As the polymerization initiator, known initiators can be used, for example, persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis(2,4-dimethylvaleronitrile), and peroxides such as hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, and lauroyl peroxide.

[0117] (Composition of Polyurethane Resin Dispersion Composition) The content ratio of each component relative to the total amount of the polyurethane resin dispersion composition is as follows.

[0118] The content (solid content) of the polyurethane resin (A) in the polyurethane resin dispersion composition is preferably from 5 to 60% by mass, particularly preferably from 20 to 50% by mass.

[0119] In the polyurethane resin dispersion composition, the total content (solid content) of the anionic surfactant (B) and the polyhydroxy compound (C) having at least one triple bond is preferably 0.1 to 3.0 mass%, and particularly preferably 0.2 to 2.8 mass%, relative to the total amount of the ink composition, from the viewpoints of wettability and the rate of change in viscosity of the polyurethane resin dispersion composition.

[0120] In the polyurethane resin dispersion composition, the content (solid content) of the anionic surfactant (B) is preferably 0.05 to 3.0 mass%, particularly preferably 0.1 to 2.0 mass%, from the viewpoints of wettability and the viscosity of the polyurethane resin dispersion composition.

[0121] In the polyurethane resin dispersion composition, the content (solid content) of the polyhydroxy compound (C) having at least one triple bond is preferably 0.05 to 3.0 mass%, particularly preferably 0.1 to 2.5 mass%, from the viewpoints of wettability and the viscosity of the polyurethane resin dispersion composition.

[0122] In the polyurethane resin dispersion composition, the mass ratio (A:(B+C)) of the polyurethane resin (A) to the total solid content of the anionic surfactant (B) and the polyhydroxy compound (C) having at least one triple bond is preferably 30:0.1 to 30:6.0. This mass ratio is the ratio of the content (solid content) of the polyurethane resin (A) in the polyurethane resin dispersion composition (% by mass) to the sum of the content (solid content) of the anionic surfactant (B) and the content (solid content) of the polyhydroxy compound (C) having at least one triple bond in the polyurethane resin dispersion composition (% by mass).

[0123] In the polyurethane resin dispersion composition, the content of the aqueous medium (D) is preferably from 10 to 90% by mass, particularly preferably from 20 to 80% by mass, from the viewpoint of the drying properties of the ink.

[0124] In the polyurethane resin dispersion composition, the content of the hydrophilic organic solvent in the aqueous medium (D) is preferably 0 to 20% by mass.

[0125] In the polyurethane resin dispersion composition, the total content of the polyurethane resin (A), the anionic surfactant (B), the polyhydroxy compound having at least one triple bond (C), and the aqueous medium (D) is preferably 20 to 100% by mass, particularly preferably 30 to 99% by mass, with the remainder being the content of other resins and other additives.

[0126] The pH of the polyurethane resin dispersion composition is preferably 5.0 to 9.0.

[0127] <Method for Producing Polyurethane Resin Dispersion Composition> The method for producing the polyurethane resin dispersion composition is not particularly limited as long as it can disperse the polyurethane resin (A) in the anionic surfactant (B), the polyhydroxy compound (C) having at least one triple bond, and the aqueous medium (D). The method for producing the polyurethane resin dispersion composition preferably includes the steps of producing an aqueous dispersion of the polyurethane resin (A) and mixing the aqueous dispersion of the polyurethane resin (A), the anionic surfactant (B), and the polyhydroxy compound (C) having at least one triple bond. Alternatively, the polyurethane resin dispersion composition may be produced, for example, by dispersing a polyurethane prepolymer in the aqueous medium (D) and reacting the polyurethane prepolymer with the compound (d) in the presence of the anionic surfactant (B) and the polyhydroxy compound (C) having at least one triple bond. In the method for producing the polyurethane resin dispersion composition, additives may be added at any step.

[0128] <Uses of Polyurethane Resin Dispersion Composition> The polyurethane resin dispersion composition can be used as a raw material for aqueous inks. The polyurethane resin dispersion composition can also be used to form a cured product layer (a cured film of the polyurethane resin dispersion composition) using the polyurethane resin dispersion composition on various substrates.

[0129] The polyurethane resin dispersion composition is preferably a binder for aqueous inks, particularly preferably a binder for aqueous inks used in inkjet printing. Because aqueous inks containing the polyurethane resin dispersion composition have low viscosity, they are less likely to clog nozzles during ejection, even when used in inkjet printing. The aqueous ink binder is a component added to aqueous inks to impart adhesion between pigments.

[0130] <Water-based ink> The water-based ink contains a polyurethane resin dispersion composition. Specifically, the water-based ink contains a polyurethane resin dispersion composition and a pigment.

[0131] The pigment may be an inorganic pigment or an organic pigment. These may be used alone or in combination. Mixed crystals may also be used.

[0132] Examples of pigments that can be used include black pigments, yellow pigments, magenta pigments, cyan pigments, white pigments, green pigments, orange pigments, glossy pigments such as gold and silver pigments, and metallic pigments.

[0133] Examples of inorganic pigments that can be used include titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chrome yellow, as well as carbon black produced by known methods such as the contact method, furnace method, and thermal method.

[0134] Examples of organic pigments include polycyclic pigments such as phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments, dye chelates, nitro pigments, nitroso pigments, azo pigments, aniline black, resin hollow particles, and inorganic hollow particles.

[0135] In the aqueous ink, the content ratio of the pigment and the polyurethane resin dispersion composition is not particularly limited and can be appropriately selected depending on the purpose. The content ratio of the aqueous medium (D) in the aqueous ink is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of the drying property of the ink, it is preferably 10% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 80% by mass or less.

[0136] The viscosity of the aqueous ink at 25°C is not particularly limited, but from the viewpoint of workability, it is preferably 2.0 cP to 8.5 cP, and more preferably 3.0 to 7.5 cP. The viscosity can be measured using, for example, a Brookfield LVDV2T type B viscometer. The measurement conditions are 25°C, 30 rpm, and 5 minutes.

[0137] <Method for producing aqueous ink> The method for producing the aqueous ink is not particularly limited, and known production methods can be used. Generally, the method for producing the aqueous ink includes a step of mixing the polyurethane resin dispersion composition with the pigment described above. Note that, in order to adjust the viscosity of the ink according to the application method, the method for producing the ink may further include a step of adding the aqueous medium (D) and / or other components contained in the polyurethane resin dispersion composition.

[0138] <Method of Using Water-Based Ink> Examples of methods for applying water-based ink include bell coating, spray coating, roll coating, shower coating, dip coating, inkjet printing, flexographic printing, thermal transfer printing, gravure printing, reverse offset printing, sheet-fed screen printing, rotary screen printing, air spray coating, and electrostatic coating, with inkjet printing being preferred.

[0139] As a pass method for inkjet printing, either a single-pass method in which ink is ejected onto a substrate only once, or a serial method in which ink is ejected while a short shuttle head is scanned back and forth in a direction perpendicular to the substrate transport direction, may be employed. However, with a serial method, it is necessary to adjust the ejection timing taking into account the movement of the inkjet head, which can easily result in deviations in the landing position. Therefore, the pass method for inkjet printing using the aqueous ink of the present invention is preferably a single-pass method.

[0140] There are no particular limitations on the method for ejecting the aqueous ink, and known methods can be used, such as a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezoelectric element, or a thermal inkjet method that heats the aqueous ink to form bubbles and uses the resulting pressure.

[0141] The amount of droplets of aqueous ink ejected from the inkjet head is preferably 0.2 to 30 pL, and more preferably 1 to 20 pL, from the viewpoints of greatly reducing the drying load and improving color reproducibility and image quality.

[0142] <Substrate> Examples of substrates onto which the aqueous ink can be applied include wallpaper, flooring, building materials such as tiles, clothing fabrics such as T-shirts, textiles, leather, metals, plastics, inorganic materials, and wood.

[0143] <Printed matter obtained using aqueous ink> A printed matter (textile print) obtained using aqueous ink can be produced by applying the aqueous ink to a substrate. The printed matter can be the second laminate described below.

[0144] <First Laminate> When the polyurethane resin dispersion composition is used to form a cured film of the polyurethane resin dispersion composition on various substrates, a laminate (hereinafter also referred to as a "first laminate") is obtained. The first laminate comprises the cured film of the polyurethane resin dispersion composition described above and a substrate. The cured film of the polyurethane resin dispersion composition is a resin film adhered to the substrate, and may also be called a coated film of the polyurethane resin dispersion composition, a dried film of the polyurethane resin dispersion composition, a coating layer of the polyurethane resin dispersion composition, etc.

[0145] The method for producing a cured film of the polyurethane resin dispersion composition is not particularly limited, and examples thereof include a method comprising the steps of applying the polyurethane resin dispersion composition to a substrate and drying the polyurethane resin dispersion composition to form a cured film of the polyurethane resin dispersion composition. The substrate and the method for applying the polyurethane resin dispersion composition are not particularly limited, and examples thereof include the methods described above as methods for applying an aqueous ink to a substrate.

[0146] The thickness of the polyurethane resin dispersion composition to be applied is not particularly limited, but is preferably a thickness that corresponds to the thickness of a cured layer of the polyurethane resin dispersion composition described below.

[0147] A coating film (cured layer) of the polyurethane resin dispersion composition can be obtained by applying the polyurethane resin dispersion composition to a substrate, drying the composition, and curing the polyurethane resin dispersion composition. To improve adhesion to the substrate, the polyurethane resin dispersion composition may be applied to the substrate and then dried by heating or other means to cure the polyurethane resin dispersion composition. Examples of the heating method include a heating method using the heat of reaction itself and a heating method that combines the heat of reaction with active heating of the mold. Examples of active heating of the mold include a method in which the mold is placed in a hot air oven, electric furnace, or infrared induction heating furnace for heating.

[0148] The heating temperature is preferably 10 to 200° C., and more preferably 60 to 160° C. By heating at such a temperature, drying can be carried out more efficiently.

[0149] The heating time is preferably 0.0001 to 20 hours, more preferably 1 to 10 hours. By using such a heating time, a laminate having a cured material layer with higher hardness can be obtained. The thickness of the cured material layer of the polyurethane resin dispersion composition is not particularly limited, but is preferably 0.1 to 100 μm, and particularly preferably 1 to 90 μm.

[0150] <Second Laminate> The second laminate comprises the cured film of the aqueous ink described above and a substrate. That is, in the first laminate, the cured film of the polyurethane resin dispersion composition may further contain the pigment described above in the aqueous ink. In the second laminate, the substrate, the cured film of the aqueous ink, and the production method are as described above for the aqueous ink and the cured film of the polyurethane resin dispersion composition in the first laminate.

[0151] [Uses of the Anionic Surfactant (B) and the Polyhydroxy Compound (C)] The combination of the anionic surfactant (B) and the polyhydroxy compound (C) can be used as a thickening inhibitor for a polyurethane resin dispersion composition containing a polyurethane resin (A) and an aqueous medium (D). The combination can also be used in a method for improving the wettability of a polyurethane resin dispersion composition containing a polyurethane resin (A) and an aqueous medium (D). The "polyurethane resin dispersion composition containing a polyurethane resin (A) and an aqueous medium (D)" is also referred to as a "second polyurethane resin dispersion composition."

[0152] [Thickening inhibitor] The thickening inhibitor includes an anionic surfactant (B) and a polyhydroxy compound (C) having at least one triple bond. The thickening inhibitor is a thickening inhibitor for a polyurethane resin dispersion composition containing a polyurethane resin (A) and an aqueous medium (D).

[0153] In the thickening inhibitor, the polyurethane resin (A), the anionic surfactant (B), the polyhydroxy compound having at least one triple bond (C), and the aqueous medium (D) are as described above in the first polyurethane resin dispersion composition.

[0154] In the thickening inhibitor, the contents of the anionic surfactant (B) and the polyhydroxy compound (C) having at least one triple bond are as described above for the contents of the anionic surfactant (B) and the polyhydroxy compound (C) having at least one triple bond in the first polyurethane resin dispersion composition.

[0155] The second polyurethane resin dispersion composition to which the thickening inhibitor is applied may contain components other than the polyurethane resin (A) and the aqueous medium (D). Such components are components other than the anionic surfactant (B) and the polyhydroxy compound (C) having at least one triple bond, and examples of such components include the components described above. The second polyurethane resin dispersion composition may contain the anionic surfactant (B) and the polyhydroxy compound (C) having at least one triple bond, as long as the effects of the present invention are achieved.

[0156] In the second polyurethane resin dispersion composition to which the thickening inhibitor is applied, the contents of the polyurethane resin (A), the aqueous medium (D), and the further component are as described above for the contents of the polyurethane resin (A), the aqueous medium (D), and the further component in the first polyurethane resin dispersion composition.

[0157] [Method for Improving Wettability] A further aspect of the present invention relates to a method for improving the wettability of a polyurethane resin dispersion composition containing a polyurethane resin (A) and an aqueous medium (D), comprising adding an anionic surfactant (B) and a polyhydroxy compound (C) having at least one triple bond to the polyurethane resin dispersion composition, wherein the combination of the anionic surfactant (B) and the polyhydroxy compound (C) is used as a wettability improver for the second polyurethane resin dispersion composition.

[0158] In the above method, the polyurethane resin (A), the anionic surfactant (B), the polyhydroxy compound (C) having at least one triple bond, and the aqueous medium (D) are as described above. The amounts of the anionic surfactant (B) and the polyhydroxy compound (C) having at least one triple bond used are as described above for the contents of the anionic surfactant (B) and the polyhydroxy compound (C) having at least one triple bond in the first polyurethane resin dispersion composition. In the above method, the second polyurethane resin dispersion composition is as described above for the thickening inhibitor.

[0159] The above method improves the wettability of the second polyurethane resin dispersion composition, i.e., improves the wettability to such an extent that when the polyurethane resin dispersion composition is poured onto a slide glass, no repelling is visually observed.

[0160] Next, 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.

[0161] [Production Example 1] Polyurethane Resin Aqueous Dispersion (U1) Polycarbonate polyol (product name "UH200" manufactured by UBE Corporation; number average molecular weight 2,000; hydroxyl value 57 mgKOH / g; reaction product of 1,6-hexanediol and dimethyl carbonate, 270 g), 2,2-dimethylolpropionic acid (DMPA, 13.7 g), and isophorone diisocyanate (IPDI, 73.7 g) were heated in dipropylene glycol dimethyl ether (DMM, 117 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80 to 95°C for 5 hours. The reaction mixture was cooled to 80°C, and triethylamine (10.4 g) was added and mixed. 330 g of the mixture was added to water (480 g) with vigorous stirring. Next, a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 0.34 g) was added, and the mixture was heated at 70 to 80° C. for 3 hours to obtain an aqueous polyurethane resin dispersion (U1). The solid content was 30% by mass.

[0162] [Production Example 2] Polyurethane Resin Aqueous Dispersion (U2) Polycarbonate polyol (product name "UH200" manufactured by UBE Corporation, 270 g), 2,2-dimethylolpropionic acid (DMPA, 14.1 g), and isophorone diisocyanate (IPDI, 74.8 g) were heated in dipropylene glycol dimethyl ether (DMM, 118 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80 to 95°C for 5 hours. The reaction mixture was cooled to 80°C, and triethylamine (10.7 g) was added and mixed. 330 g of the mixture was added to water (484 g) with vigorous stirring. Next, a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 21.6 g) was added to obtain a polyurethane resin aqueous dispersion (U2). The solids content was 30% by mass.

[0163] [Production Example 3] Polyurethane Resin Aqueous Dispersion (U3) Polycarbonate polyol (product name "UH200" manufactured by UBE Corporation, 270 g), 2,2-dimethylolpropionic acid (DMPA, 14.1 g), and isophorone diisocyanate (IPDI, 74.8 g) were heated in N-ethylpyrrolidone (NEP, 118 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80 to 95°C for 5 hours. The reaction mixture was cooled to 80°C, and triethylamine (10.7 g) was added and mixed. 330 g of the mixture was added to water (484 g) with vigorous stirring. Next, a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 21.6 g) was added to obtain a polyurethane resin aqueous dispersion (U3). The solids content was 30% by mass.

[0164] [Production Example 4] Polyurethane Resin Aqueous Dispersion (U4) Polyester polyol (product name "Placcel (registered trademark) 220N" manufactured by Daicel Corporation; number average molecular weight 2,000; hydroxyl value 57 mgKOH / g; polycaprolactone diol, 270 g), 2,2-dimethylolpropionic acid (DMPA, 13.7 g), and isophorone diisocyanate (IPDI, 73.7 g) were heated in dipropylene glycol dimethyl ether (DMM, 117 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80 to 95°C for 5 hours. The reaction mixture was cooled to 80°C, and triethylamine (10.4 g) was added and mixed. 330 g of the mixture was added to water (480 g) with vigorous stirring. Next, a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 0.34 g) was added, and the mixture was heated at 70 to 80° C. for 3 hours to obtain an aqueous polyurethane resin dispersion (U4). The solid content was 30% by mass.

[0165] Production Example 5 Polyurethane Resin Aqueous Dispersion (U5) Polycarbonate polyol (product name "UM90 (3 / 1)" manufactured by UBE Corporation; number average molecular weight 900; hydroxyl value 125 mgKOH / g; 190 g of a reaction product of a polyol mixture in a molar ratio of 1,4-cyclohexanedimethanol:1,6-hexanediol=3:1 and dimethyl carbonate), 2,2-dimethylolpropionic acid (DMPA, 27.5 g), and dicyclohexylmethane 4,4'-diisocyanate (H12MDI, 180 g) were heated in dipropylene glycol dimethyl ether (DMM, 138 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80 to 95°C for 5 hours. The reaction mixture was cooled to 80°C, and triethylamine (20.8 g) was added and mixed thereto. 330 g of the mixture was then added to water (466 g) with strong stirring. Subsequently, a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 53.3 g) was added to obtain an aqueous polyurethane resin dispersion (U5). The solid content was 30% by mass.

[0166] Production Example 6 Polyurethane Resin Aqueous Dispersion (U6) Polycarbonate polyol (product name "UH200" manufactured by UBE Corporation, 270 g), 2,2-dimethylolpropionic acid (DMPA, 13.7 g), and isophorone diisocyanate (IPDI, 73.7 g) were heated in the presence of dibutyltin dilaurate (0.3 g) in a hydrophobic organic solvent, ethyl methyl ketone (MEK, 117 g), at 80 to 95°C for 5 hours under a nitrogen atmosphere. The reaction mixture was cooled to 80°C, and triethylamine (10.4 g) was added and mixed. 330 g of the mixture was then added to water (561 g) with vigorous stirring. Next, a 35% by mass aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 0.34 g) was added, and the mixture was heated at 70 to 80°C for 3 hours, and then heated at 10 KPa and 50 to 60°C for 3 hours to distill off the MEK, thereby obtaining an aqueous polyurethane resin dispersion (U6). The solid content was 30% by mass. The aqueous polyurethane resin dispersion (U6) did not contain a hydrophilic organic solvent.

[0167] [Mixture of Anionic Surfactant (B) and Polyhydroxy Compound (C), and Nonionic Surfactant and Polyhydroxy Compound (C)] The following Components A1 to A2 were used as the anionic surfactant (B) and the polyhydroxy compound (C) having at least one triple bond. The following Components A3 to A8 were used as the nonionic surfactant and the polyhydroxy compound having at least one triple bond. Components A1 to A8 are obtained by emulsifying at least a portion of the polyhydroxy compound (C) having at least one triple bond with at least a portion of the surfactant. The "mass %" in the "active ingredient" section indicates the total content (solids content) of the anionic surfactant (B) or nonionic surfactant and the polyhydroxy compound (C) in the product. Abbreviations in Table 1 are as follows. Note that, in Formula (1), all of Components A1 to A8 contain a group represented by R １ are identical and are methyl groups, and R ２ are identical and are i-butyl groups, and R ３ are the same and are hydrogen atoms, and contain a polyhydroxy compound (C). A1: Olfine (registered trademark) PD-301A (anionic surfactant, active ingredient 30% by mass) manufactured by Nissin Chemical Industry Co., Ltd. A2: Olfine (registered trademark) PD-611 (anionic surfactant, active ingredient 100% by mass) manufactured by Nissin Chemical Industry Co., Ltd. A3: Olfine (registered trademark) PD-002W (nonionic surfactant, active ingredient 83% by mass) manufactured by Nissin Chemical Industry Co., Ltd. A4: Olfine (registered trademark) EXP. 4200 (nonionic surfactant, active ingredient 75% by mass) manufactured by Nissin Chemical Industry Co., Ltd. A5: Olfine (registered trademark) EXP. 4300 (nonionic surfactant, active ingredient 60% by mass) A6: Olfine (registered trademark) PD-001 (nonionic surfactant, active ingredient 83% by mass) manufactured by Nissin Chemical Industry Co., Ltd. A7: Olfine (registered trademark) PD-003 (nonionic surfactant, active ingredient 71% by mass) manufactured by Nissin Chemical Industry Co., Ltd. A8: Olfine (registered trademark) PD-005 (nonionic surfactant, active ingredient 83% by mass) manufactured by Nissin Chemical Industry Co., Ltd.

[0168] Example 1 A polyurethane resin dispersion composition was produced by blending 4.0 parts by mass of component A1, 140 parts by mass of purified water, and 60 parts by mass of glycerin with 100 parts by mass of polyurethane resin aqueous dispersion U1.

[0169] Example 2 A polyurethane resin dispersion composition was produced by blending 1.2 parts by mass of component A2, 140 parts by mass of purified water, and 60 parts by mass of glycerin with 100 parts by mass of polyurethane resin aqueous dispersion U1.

[0170] Example 3 A polyurethane resin dispersion composition was produced by blending 4.0 parts by mass of component A1, 140 parts by mass of purified water, and 60 parts by mass of glycerin with 100 parts by mass of polyurethane resin aqueous dispersion U2.

[0171] Example 4 A polyurethane resin dispersion composition was produced by blending 4.0 parts by mass of Component A1, 140 parts by mass of purified water, and 60 parts by mass of glycerin with 100 parts by mass of the aqueous polyurethane resin dispersion U3.

[0172] Example 5 A polyurethane resin dispersion composition was produced by blending 4.0 parts by mass of Component A1, 140 parts by mass of purified water, and 60 parts by mass of glycerin with 100 parts by mass of the polyurethane resin aqueous dispersion U4.

[0173] Example 6 A polyurethane resin dispersion composition was produced by blending 4.0 parts by mass of Component A1, 140 parts by mass of purified water, and 60 parts by mass of glycerin with 100 parts by mass of the aqueous polyurethane resin dispersion U5.

[0174] Example 7 A polyurethane resin dispersion composition was produced by blending 4.0 parts by mass of Component A1, 140 parts by mass of purified water, and 60 parts by mass of glycerin with 100 parts by mass of the polyurethane resin aqueous dispersion U6.

[0175] Comparative Example 1 A polyurethane resin dispersion composition was produced by blending 140 parts by mass of purified water and 60 parts by mass of glycerin with 100 parts by mass of the aqueous polyurethane resin dispersion U1.

[0176] Comparative Example 2 A polyurethane resin dispersion composition was produced by blending 1.4 parts by mass of component A3, 140 parts by mass of purified water, and 60 parts by mass of glycerin with 100 parts by mass of polyurethane resin aqueous dispersion U1.

[0177] Comparative Example 3 A polyurethane resin dispersion composition was produced by blending 1.6 parts by mass of component A4, 140 parts by mass of purified water, and 60 parts by mass of glycerin with 100 parts by mass of polyurethane resin aqueous dispersion U1.

[0178] Comparative Example 4 A polyurethane resin dispersion composition was produced by blending 2.0 parts by mass of component A5, 140 parts by mass of purified water, and 60 parts by mass of glycerin with 100 parts by mass of polyurethane resin aqueous dispersion U1.

[0179] Comparative Example 5 A polyurethane resin dispersion composition was produced by blending 1.4 parts by mass of component A6, 140 parts by mass of purified water, and 60 parts by mass of glycerin with 100 parts by mass of polyurethane resin aqueous dispersion U1.

[0180] Comparative Example 6 A polyurethane resin dispersion composition was produced by blending 1.7 parts by mass of component A7, 140 parts by mass of purified water, and 60 parts by mass of glycerin with 100 parts by mass of polyurethane resin aqueous dispersion U1.

[0181] Comparative Example 7 A polyurethane resin dispersion composition was produced by blending 1.4 parts by mass of component A8, 140 parts by mass of purified water, and 60 parts by mass of glycerin with 100 parts by mass of polyurethane resin aqueous dispersion U1.

[0182] Comparative Example 8 A polyurethane resin dispersion composition was produced by blending 1.4 parts by mass of Component A3, 140 parts by mass of purified water, and 60 parts by mass of glycerin with 100 parts by mass of the polyurethane resin aqueous dispersion U3.

[0183] [Viscosity Evaluation] The viscosity of the polyurethane resin dispersion compositions obtained in Examples 1 to 7 and Comparative Examples 2 to 8 was measured using a Brookfield viscometer (LVDV2T, manufactured by Brookfield, combined with a low-viscosity adapter UL-EZY). The measurement conditions were 25°C, 18 mL sample volume, 30 rpm, and 5 minutes. This was designated "viscosity (2)" (i.e., the viscosity when an anionic surfactant (B) and a polyhydroxy compound (C) were contained; in Comparative Examples 2 to 8, the viscosity when a nonionic surfactant and a polyhydroxy compound (C) were contained). Similarly, polyurethane resin dispersion compositions without the addition of Components A1 and A2 were prepared in Examples 1 to 7, and the viscosity was measured. Furthermore, polyurethane resin dispersion compositions without the addition of Components A3 to A8 were prepared in Comparative Examples 1 to 8, and the viscosity was measured. This was designated as "viscosity (1)" (i.e., the viscosity when the anionic surfactant (B) and the polyhydroxy compound (C) were not contained. In Comparative Examples 1 to 8, the viscosity was the viscosity when the nonionic surfactant and the polyhydroxy compound (C) were not contained). The viscosity change rate (thickening rate) was calculated using the following formula: Viscosity change rate (thickening rate) (%) = 100 × (viscosity (2) - viscosity (1)) / viscosity (1)

[0184] [Wettability Evaluation] 2 mL of each of the polyurethane resin dispersion compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 8 was poured onto a slide glass (S2215 manufactured by Matsunami Glass Industry Co., Ltd.) The case where no cissing of the polyurethane resin dispersion composition was visually confirmed was marked with a circle, and the case where cissing was visually confirmed was marked with an ×.

[0185] The results are summarized in the following Tables 1 and 2. Here, "mass ratio (A:(B+C))" means the mass ratio of the solid content of the polyurethane resin (A) to the sum of the solid content of the anionic surfactant (B) and the solid content of the polyhydroxy compound having at least one triple bond (C).

[0186]

[0187]

[0188] The abbreviations used in Tables 1 and 2 are as follows: Here, the number average molecular weights and hydroxyl values ​​of the polycarbonate polyols and polyester polyols are catalog values. UH200: Product name "UH200" manufactured by UBE Corporation; number average molecular weight 2,000; hydroxyl value 57 mg KOH / g; polycarbonate polyol obtained by reacting 1,6-hexanediol with dimethyl carbonate. 220N: Product name "Placcel 220N" manufactured by Daicel Corporation; number average molecular weight 2,000; hydroxyl value 57 mg KOH / g; polycaprolactone diol. UM90 (3 / 1): Product name "UM90 (3 / 1)" manufactured by UBE Corporation; number average molecular weight 900; hydroxyl value 125 mg KOH / g; polycarbonate polyol obtained by reacting a polyol mixture in a molar ratio of 1,4-cyclohexanedimethanol:1,6-hexanediol = 3:1 with dimethyl carbonate. IPDI: isophorone diisocyanate. H12MDI: dicyclohexylmethane 4,4'-diisocyanate. DMM: Dipropylene glycol dimethyl ether NEP: N-ethylpyrrolidone

[0189] As can be seen from the results in Table 1, the viscosity increase rates of Examples 1 to 7 were all 10.0% or less, indicating that the polyurethane resin dispersion compositions of the Examples had a small viscosity change rate. Furthermore, the combination of anionic surfactant (B) and polyhydroxy compound (C) in Examples 1 to 7 functioned as a thickening inhibitor for the second polyurethane resin dispersion composition. Specifically, as shown in Examples 1 and 2, polyurethane resin dispersion compositions with a small viscosity change rate were obtained even when the types of anionic surfactant (B) and polyhydroxy compound (C) were changed. Furthermore, as shown in Examples 1, 3, 5, and 6, polyurethane resin dispersion compositions with a small viscosity change rate were obtained even when the composition of polyurethane resin (A) was changed. Furthermore, as shown in Examples 1, 4, and 7, the viscosity change rate of the resulting polyurethane resin dispersion compositions was small even when the type of hydrophilic organic solvent in the aqueous dispersion of polyurethane resin (A) was changed.

[0190] Furthermore, the wettability evaluations of Examples 1 to 7 were all rated as "good," indicating that the wettability of the Examples was good. Thus, the addition of the anionic surfactant (B) and the polyhydroxy compound (C) in Examples 1 to 7 improved the wettability of the second polyurethane resin dispersion composition.

[0191] On the other hand, in Comparative Examples 2 to 8, when a nonionic surfactant was used instead of the anionic surfactant (B), the polyurethane resin dispersion composition was thickened. Also, in Comparative Example 1, when the anionic surfactant (B) and the polyhydroxy compound (C) were not used, the wettability was poor.

[0192] The polyurethane resin dispersion composition of the present invention has excellent wettability and a small rate of change in viscosity, and therefore can be applied to various printing methods including inkjet printing.

Claims

1. A polyurethane resin dispersion composition comprising a polyurethane resin (A), an anionic surfactant (B), a polyhydroxy compound having at least one triple bond (C), and an aqueous medium (D).

2. The polyurethane resin dispersion composition according to claim 1, wherein the polyurethane resin (A) has a structure derived from the acidic group-free polyol (a), a structure derived from the polyisocyanate (b), and a structure derived from the acidic group-containing polyol (c).

3. The polyurethane resin dispersion composition according to claim 2, wherein the acidic group-free polyol (a) is at least one member selected from the group consisting of polycarbonate polyols, polyester polyols and polyether polyols.

4. The polyurethane resin dispersion composition according to claim 3, wherein the polyurethane resin (A) further has a structure derived from a compound (d) having a total of two or more groups selected from the group consisting of hydroxyl groups and amino groups (provided that the compound (d) is not a polycarbonate polyol, a polyester polyol, a polyether polyol, or an acidic group-containing polyol (c)).

5. The polyurethane resin dispersion composition according to claim 2, wherein the polyisocyanate (b) is an alicyclic polyisocyanate compound.

6. The polyurethane resin dispersion composition according to claim 1, wherein at least a portion of the polyhydroxy compound (C) having at least one triple bond is emulsified by at least a portion of the anionic surfactant (B).

7. The polyurethane resin dispersion composition according to claim 1, wherein the anionic surfactant (B) is at least one selected from the group consisting of ether carboxylic acids, salts of ether carboxylic acids, sulfate esters, salts of sulfate esters, ether sulfate esters, salts of ether sulfate esters, sulfonates, sulfosuccinates, phosphate esters, salts of phosphoric esters, ether phosphate esters, salts of ether phosphate esters, fatty acid salts and acylated amino acid salts.

8. The polyurethane resin dispersion composition according to claim 1, wherein the polyhydroxy compound (C) having at least one triple bond is represented by the following formula (1): (In the formula, R １ are independently a linear alkyl group having 1 to 6 carbon atoms, or a branched or cyclic alkyl group having 3 to 6 carbon atoms; R ２ are independently a linear alkyl group having 1 to 12 carbon atoms, or a branched or cyclic alkyl group having 3 to 12 carbon atoms; R ３ are independently a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms, n and m are the same or different and are integers of 0 or 1 or more, with the sum of n and m being 0 to 100.

9. The polyurethane resin dispersion composition according to claim 1, wherein the solids mass ratio (A:(B+C)) of the polyurethane resin (A) to the total of the anionic surfactant (B) and the polyhydroxy compound (C) having at least one triple bond is 30:0.1 to 30:6.

0.

10. The polyurethane resin dispersion composition according to any one of claims 1 to 9, which is a binder for aqueous inks used in ink-jet printing.

11. An aqueous ink comprising the polyurethane resin dispersion composition according to any one of claims 1 to 9.

12. A thickening inhibitor for a polyurethane resin dispersion composition comprising a polyurethane resin (A) and an aqueous medium (D), the thickening inhibitor comprising an anionic surfactant (B) and a polyhydroxy compound (C) having at least one triple bond.

13. A method for improving the wettability of a polyurethane resin dispersion composition containing a polyurethane resin (A) and an aqueous medium (D), comprising adding an anionic surfactant (B) and a polyhydroxy compound (C) having at least one triple bond to the polyurethane resin dispersion composition.

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