Composition, fabric, apparel, layered product, and vehicle

Abstract

Provided is a composition able to form a good coating film. Provided is a composition that contains: an aqueous polyurethane dispersion (PUD) containing a polyurethane resin (U) having a structure derived from an acidic group-containing polyol (B), a structure derived from a hydrophobic substituent group-containing ethylene glycol (C), a structure derived from an acidic group-free polyol (A) (excluding the hydrophobic substituent group-containing ethylene glycol (C)) and a structure derived from a polyisocyanate (D); a functional additive (E); and a pigment (F).

Description

Composition, cloth, clothing, laminate, and vehicle

[0001] The present invention relates to a composition containing an aqueous dispersion of a polyurethane resin, cloth, clothing, a laminate, and a vehicle.

[0002] The aqueous dispersion of polyurethane resin is widely used as coatings, paints, adhesives, fiber processing agents, paper processing agents, inks, etc. Since it can reduce volatile organic compounds compared to conventional solvent-based polyurethanes, it is a material that is being increasingly replaced from solvent-based polyurethanes as an environmentally friendly material.

[0003] Since the solvent-based polyurethane has the urethane resin dissolved in the solvent, it has good film-forming properties regardless of the heating temperature. In contrast, the aqueous dispersion of polyurethane resin has a particle shape and forms a film by the fusion of particles. Therefore, compared to solvent-based polyurethanes, there is a problem that it is difficult to form a good coating film.

[0004] For example, in Patent Documents 1 and 2, a composition containing a structure derived from glycerin monofatty acid ester is disclosed as an aqueous dispersion of polyurethane resin.

[0005] Various studies have been made to form a good coating film from an aqueous dispersion of polyurethane resin. For example, Patent Document 3 discloses a method of using a resin emulsion particle and an oxazoline group-containing compound in combination. Patent Document 4 discloses a method of using a pretreatment agent containing an ethylene-vinyl acetate resin and an aqueous ink containing a specific water-soluble organic solvent in combination. Patent Document 5 discloses a method of using a urethane (meth)acrylate and a reactive surfactant in combination. Patent Document 6 discloses a method of using a curable resin composition and a specific adhesion-imparting agent in combination.

[0006] JP-A-2006-52294, JP-A-2006-56973, JP-A-2023-156338, JP-A-2022-86441, JP-A-2023-39945, JP-A-2024-44176

[0007] The coating films obtained using the compositions disclosed in Patent Documents 1 to 6 have room for improvement in terms of frictional fastness and adhesion, and there was a need for a technology that could form a better coating film.

[0008] Furthermore, in Patent Document 2, the synthesis process of polyurethane resin and the polymerization process of acrylic monomer are essential, and a reduction in the burden of the manufacturing process of aqueous dispersions was desired. In Patent Document 3, since an oxazoline group-containing compound is used, an extension of the pot life of the aqueous ink was desired. In Patent Document 4, since a pretreatment agent is essential, a reduction in the burden of the printing process was desired. In Patent Document 5, since the resin has ethylenically unsaturated groups, an extension of the pot life of the coating composition was desired. In Patent Document 6, the synthesis process of both the resin composition and the adhesion imparter is required, and a reduction in the burden of the manufacturing process of aqueous dispersions was desired.

[0009] The object of the present invention is to solve the problems of the prior art described above and to provide a composition that can form a good coating film.

[0010] The inventors of this invention arrived at the present invention as a result of various studies conducted to overcome the problems of the prior art described above.

[0011] The present invention has the following configuration: [1] A composition comprising a polyurethane resin aqueous dispersion (PUD) containing a polyurethane resin (U) having a structure derived from an acidic group-containing polyol (B), a structure derived from a hydrophobic substituent-containing ethylene glycol (C), a structure derived from an acidic group-free polyol (A) (excluding the hydrophobic substituent-containing ethylene glycol (C)), and a structure derived from a polyisocyanate (D), a functional additive (E), and a pigment (F). [2] The composition according to [1], wherein the functional additive (E) is a humectant (E1). [3] The composition according to [1] or [2], wherein the composition is an ink composition. [4] The composition according to any one of [1] to [3], wherein the functional additive (E) is a film-forming aid (E2). [5] The composition according to any one of [1] to [4], wherein the composition is a coating composition. [6] The composition according to any one of [1] to [5], wherein the molar ratio of hydrophobic substituents (excluding terminals) to acidic groups in the polyurethane resin (U) is hydrophobic substituent / acidic group = 0.05 to 2.00. [7] The composition according to any one of [1] to [6], wherein the acidic group-free polyol (A) comprises a polycarbonate polyol. [8] The composition according to any one of [1] to [7], wherein the acidic group-containing polyol (B) comprises a carboxyl group-containing polyol. [9] The composition according to any one of [1] to [8], wherein the hydrophobic substituent-containing ethylene glycol (C) comprises a glycerin monofatty acid ester.

[10] The composition according to any one of [1] to [9], wherein the polyisocyanate (D) comprises an alicyclic polyisocyanate compound.

[11] The composition according to any one of [1] to

[10] , wherein the mass ratio of the functional additive (E) in the composition is 0.010 or more and 0.60 or less.

[12] The composition according to any one of [1] to

[11] , wherein the humectant (E1) comprises a polyhydric alcohol.

[13] The composition according to any one of [1] to

[12] , wherein the mass ratio of the pigment (F) in the composition is 0.001 to 0.400.

[14] The composition according to any one of [1] to

[13] , wherein the value of the color transfer brightness measured in accordance with the wetting test of JIS L 0849:2013 for a test piece obtained by forming the composition on a polyethylene terephthalate substrate at 160°C for 5 minutes is 3 or less.

[15] A composition according to any one of [1] to

[14] used in inkjet printing.

[16] A fabric coated with the composition according to any one of [1] to

[15] .

[17] Clothing comprising the fabric according to any one of [1] to

[16] .

[18] A composition according to any one of [1] to

[17] , wherein when a test piece obtained by forming the composition on a polymethyl methacrylate substrate at 90°C for 30 minutes is subjected to a grid peel test (100 squares) in accordance with JIS K 5400, the number of remaining pieces after one tape peel is 100 and the number of remaining pieces after two tape peels is 95 or more.

[19] A laminate formed by laminating a substrate and a coating film made of the composition according to any one of [1] to

[18] .

[20] A vehicle comprising the laminate according to any one of [1] to

[19] .

[0012] The present invention provides a composition that can form a good coating film.

[0013] In this specification, "acidic group" refers to a carboxyl 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, "hydrophobic substituent" refers to an alkyl chain having 5 or more carbon atoms. In this specification, numerical ranges indicated using "~" indicate a range that includes the numbers before and after "~" as the minimum and maximum values, respectively. Furthermore, the amount of each component in a composition means the total amount of multiple substances present in the composition, unless otherwise specified, if there are multiple substances corresponding to each component in the composition. In this specification, the term "process" does not only include independent processes, but also includes processes that are not clearly distinguishable from other processes, as long as their intended purpose is achieved.

[0014] <Polyurethane resin (U)> Polyurethane resin (U) has structures derived from acidic group-containing polyol (B), hydrophobic substituent-containing ethylene glycol (C), acidic group-free polyol (A) (excluding hydrophobic substituent-containing ethylene glycol (C)), and polyisocyanate (D). Furthermore, polyurethane resin (U) may also contain structures other than those derived from (A) to (D). Such further structures include structures derived from compounds (G) having a total of two or more groups selected from the group consisting of hydroxyl groups and amino groups (however, not acidic group-free polyol (A), acidic group-containing polyol (B), and hydrophobic substituent-containing ethylene glycol (C)), structures derived from neutralizing agents (H), and structures derived from other compounds (I).

[0015] (Polyols without acidic groups (A)) Polyols without acidic groups (A) (excluding ethylene glycols containing hydrophobic substituents (C)) are compounds that contain two or more alcoholic hydroxyl groups in one molecule and do not contain acidic groups, and are different from ethylene glycols containing hydrophobic substituents (C).

[0016] As the acid-free polyol (A), known polyols can be used. For example, high-molecular-weight polyols such as polycarbonate polyol, polyester polyol, polyether polyol, polyester polyether polyol, polyurethane polyol, polyesteramide polyol, and acrylic polyol (however, all of which have hydroxyl groups at least two terminals), or 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 the composition forming an even better coating film, it is preferable that at least one is selected from the group consisting of polycarbonate polyol, polyester polyol, and polyether polyol, and polycarbonate polyol is more preferable. The acid-free polyol (A) may be used alone or in combination of multiple types.

[0017] Polycarbonate polyols are obtained by reacting one or more polyol components with a carbonate ester or phosgene. From the viewpoint of safety and ease of handling of reagents, and because there is no by-production of terminal chlorinated products, polycarbonate polyols obtained by reacting one or more polyol monomers with a carbonate ester are preferred.

[0018] Known polyol monomers can be used to form polycarbonate polyols. For example, aliphatic polyols such as linear aliphatic diols like 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, and 1,9-nonanediol; branched aliphatic diols like 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; polyhydric alcohols with three or more functions 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 Examples include alicyclic polyols such as diols having an alicyclic structure in the main chain, such as 1,4-dioxane, 2,7-norbornanediol, tetrahydrofrangimethanol, 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 polyol of 6-hydroxycaproic acid and hexanediol; polyester polyols of dicarboxylic acids and diols, such as polyester polyol 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 that the composition forms an even better coating film. Polyol monomers may be used alone or in combination of multiple types. As alicyclic polyols, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanediol are more preferred.As the aliphatic polyol, linear aliphatic diols are more preferred, and 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol are even more preferred.

[0019] The carbonate ester is not particularly limited, but examples 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, which can produce polycarbonate polyols, can also be used. Among these, aliphatic carbonate esters are preferred due to the ease of producing polycarbonate polyols, and dimethyl carbonate is more preferred.

[0020] Known polyester polyols can be used. Examples include polyester polyols obtained by esterifying a polyol (for example, a polyol with a molecular weight of 50 to 500) with a polycarboxylic acid; polyester polyols obtained by ring-opening polymerization of cyclic ester compounds such as ε-caprolactone; and copolymer polyester polyols of these. Specifically, 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.

[0021] As the polyol, for example, the aforementioned polyol monomer can be used. Low molecular weight polyols may be used alone or in combination of multiple types. In addition, polyether polyols, which will be described later, may be used as the polyol.

[0022] 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 and aromatic polycarboxylic acids. Polycarboxylic acids may be used individually or in combination of multiple types.

[0023] 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 and block copolymers of ethylene oxide and propylene oxide, random copolymers and block copolymers of ethylene oxide and butylene oxide, and random copolymers and block copolymers of propylene oxide and butylene oxide.

[0024] Polyester polyether polyol is obtained by reacting the polyester polyol with the polyether polyol.

[0025] The acid-free polyol (A) preferably has a number-average molecular weight (Mn) of 100 to 5,000. If Mn is 100 or more, it has good performance as a soft segment and is less prone to cracking in the coating film. If Mn is 5,000 or less, the reactivity between the acid-free polyol (A) and the polyisocyanate (D) does not decrease, and problems such as the manufacturing process of the urethane prepolymer taking a long time or the reaction not proceeding sufficiently do not occur, nor does the viscosity of the acid-free polyol (A) become high and difficult to handle occur. In this specification, Mn is defined as having a hydroxyl value and １ These values ​​are calculated using either 1H-NMR or from the quantitative analysis of polyols by gas chromatography after alkaline hydrolysis.

[0026] The acid-free polyol (A) preferably has a hydroxyl value of 20 to 1,200 mgKOH / g, and more preferably 30 to 300 mgKOH / g. When the hydroxyl value is within the above range, the urethane prepolymer is easy to handle. In this specification, the hydroxyl value is the number of milligrams (mg) of potassium hydroxide equivalent to the number of hydroxyl groups in 1 g of the sample, and can be measured by Method A of JIS K 1557.

[0027] (Acidic group-containing polyol (B)) Acidic group-containing polyol (B) is a polyol containing two or more alcoholic hydroxyl groups and one or more acidic groups in one molecule. Acidic group-containing polyol (B) may be used alone or in combination of multiple types.

[0028] Known polyols can be used as the acidic group-containing polyol (B). For example, dimethylolalkanoates 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 are examples. Among these, carboxyl group-containing polyols are preferred from the viewpoint that the composition forms an even better coating film, and dimethylolalkanoates having 4 to 12 carbon atoms are preferred from the viewpoint of ease of availability, and among dimethylolalkanoates, 2,2-dimethylolpropionic acid is more preferred.

[0029] (Hydrophobic substituent-containing ethylene glycol (C)) Hydrophobic substituent-containing ethylene glycol (C) is an ethylene glycol compound having a hydrophobic substituent. Hydrophobic substituent-containing ethylene glycol (C) can be used to introduce a hydrophobic substituent as a side chain into polyurethane resin (U). Hydrophobic substituent-containing ethylene glycol (C) may be used alone or in combination of multiple types.

[0030] Known ethylene glycols containing hydrophobic substituents (C) can be used. Examples of hydrophobic substituent-containing ethylene glycols (C) include compounds represented by the following general formula (c1).

[0031] HO-CH(-R)-CH ２ -OH (c1) (In the general formula (c1), R represents a hydrophobic substituent.)

[0032] In general formula (c1), the hydrophobic substituent represented by R is preferably a hydrocarbon group which may contain an ester bond, and more preferably an alkyl group which may contain an ester bond, from the viewpoint of the composition forming an even better coating film. Furthermore, if a coating film with extremely excellent friction fastness in a dry state is required, the hydrophobic substituent represented by R is even more preferably an alkyl group which contains an ester bond. In addition, the number of carbon atoms in the hydrophobic substituent represented by R is preferably 5 to 30, and more preferably 10 to 20.

[0033] Examples of hydrophobic substituent-containing ethylene glycol (C) include glycerin monofatty acid esters such as glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, and glycerin monooleate (limited to those represented by general formula (c1)); and 1,2-alkyldiols such as 1,2-heptanediol, 1,2-octanediol, 1,2-nonanediol, 1,2-decanediol, 1,2-undecanediol, 1,2-dodecanediol, 1,2-tridecanediol, 1,2-tetradecanediol, 1,2-pentadecanediol, 1,2-hexadecanediol, 1,2-heptadecanediol, 1,2-octadecanediol, and 1,2-nonadecanediol. In particular, from the viewpoint of the composition forming an even better coating film, compound (c1) represented by general formula (c1) is preferred. Furthermore, when a coating film with extremely excellent frictional fastness in a dry state is required, glycerin mono fatty acid esters are more preferred, and glycerin monopalmitate, glycerin monostearate, and glycerin monooleate are even more preferred.

[0034] (Polyisocyanates (D)) Polyisocyanates (D) are those that contain two or more -N=C=O structures in one molecule. Known polyisocyanates (D) can be used. For example, aromatic polyisocyanate compounds such as 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 2,4-tolylenediisocyanate (TDI), 2,6-tolylenediisocyanate, and 4,4'-diphenylmethanediisocyanate (MDI); and aliphatic polyisocyanates such as ethylenediisocyanate, tetramethylenediisocyanate, pentamethylenediisocyanate (PDI), and hexamethylenediisocyanate (HDI). Examples of polyisocyanate compounds include isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-diclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, and 2,6-norbornane diisocyanate. Polyisocyanate (D) may have part or all of its structure derivatized by isocyanuration, carbodiimide, or biuretization.

[0035] Among the polyisocyanates (D) mentioned above, aliphatic polyisocyanate compounds and / or alicyclic polyisocyanate compounds are preferred from the viewpoint of controlling reactivity, and alicyclic polyisocyanate compounds are more preferred from the viewpoint of the composition forming an even better coating film, with isophorone diisocyanate (IPDI) and 4,4'-dicyclohexylmethane diisocyanate (H12MDI) being particularly preferred. Polyisocyanate (D) may be used alone or in combination of multiple types.

[0036] (Blocked Isocyanate Structure) The polyurethane resin (U) may have a blocked isocyanate structure. A blocked isocyanate structure is a structure in which a blocking agent is attached to an isocyanate group. In polyurethane resins, the blocked isocyanate structure is formed by attaching a blocking agent to some of the isocyanate groups of a structure derived from polyisocyanate (D), and is usually located at the ends of the polyurethane resin (U).

[0037] A blocking agent is a compound that reacts with an isocyanate group to convert the isocyanate group into another group, and which can be reversibly converted back into an isocyanate group by heat treatment. The heat treatment temperature is not particularly limited, but 80 to 180°C is preferred.

[0038] Examples of blocking agents include phenolic blocking agents such as phenol; aliphatic alcohol blocking agents such as methanol; active methylene blocking agents such as dimethyl malonate; mercaptan blocking agents such as butyl mercaptan; acid amide blocking agents such as acetanilide; lactam blocking agents such as ε-caprolactam; acid imide blocking agents such as succinimide; oxime blocking agents such as acetaldehyde oxime, acetone oxime, and methyl ethyl ketoxime; and amine blocking agents such as diphenylaniline, aniline, ethyleneimine, and dimethylpyrazole. Blocking agents may be used individually or in combination of multiple types.

[0039] Compound (G), which has a total of two or more groups selected from the group consisting of hydroxyl groups and amino groups (however, it is not an acidic group-free polyol (A), an acidic group-containing polyol (B), or a hydrophobic substituent-containing ethylene glycol (C)) (hereinafter also referred to as "compound (G)") is a component that increases the molecular weight of polyurethane resin (U). Compound (G) is a compound that reacts with the isocyanate group of the polyurethane prepolymer, which is a synthetic intermediate in the production of polyurethane resin (U). Compounds that react with the isocyanate group of the polyurethane prepolymer, which is a synthetic intermediate of polyurethane resin (U), are called chain extenders, and compound (G) is a type of chain extender. Other chain extenders besides compound (G) include water. Furthermore, polyols without acidic groups (A), polyols containing acidic groups (B), and ethylene glycols containing hydrophobic substituents (C) can also be used as chain extenders. Here, "amino group" in compound (G) refers to a primary amino group or a secondary amino group.

[0040] Compound (G) may vary depending on the range of acid-free polyols (A), acid-containing polyols (B), and hydrophobic substituent-containing ethylene glycols (C). For example, if the acid-free polyol (A) is at least one selected from the group consisting of polycarbonate polyols, polyester polyols, and polyether polyols, then compound (G) is not a polycarbonate polyol, polyester polyol, polyether polyol, acid-containing polyol (B), or hydrophobic substituent-containing ethylene glycol (C).

[0041] As the compound (G), there can be mentioned polyamine compounds (that is, compounds having two or more amino groups in one molecule and no hydroxyl group), polyol compounds (that is, compounds having two or more hydroxyl groups in one molecule and no amino group) (however, excluding the polyol without acidic group (A), the polyol with acidic group (B), and the ethylene glycol with hydrophobic substituent (C)), amino alcohol compounds (that is, compounds having one or more hydroxyl groups in one molecule and one or more amino groups in one molecule), and the like.

[0042] As the compound (G), known compounds can be used, and they may be used alone or in combination of two or more kinds.

[0043] As the polyamine compounds, there can be mentioned diamine compounds having only primary amino groups such as hydrazine, ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-diaminopentane, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis(aminomethyl)cyclohexane, xylylenediamine; diamine compounds having only secondary amino groups such as piperazine, 2,5-dimethylpiperazine; polyamines having three or more amino groups and imino groups in total in one molecule such as adipodihydrazide, diethylenetriamine, triethylenetetramine; and other polyamine compounds such as polyetheramine.

[0044] The polyol compound as the compound (G) can vary depending on the ranges of the polyol without acidic group (A), the polyol with acidic group (B), and the ethylene glycol with hydrophobic substituent (C). Depending on the above ranges, the polyol compound as the compound (G) may not exist. On the other hand, for example, when the polyol without acidic group (A) is a polycarbonate polyol, among the above-mentioned polyol compounds in the polyol without acidic group (A), compounds other than the polycarbonate polyol can be used as the polyol compound as the compound (G). The polyol compound as the compound (G) is preferably a compound exemplified as a low molecular weight polyol compound.

[0045] Examples of the amino alcohol compound include ethanolamine, butanolamine, hexanolamine, and the like.

[0046] Compound (G) is preferably at least one selected from the group consisting of a polyamine compound and an amino alcohol compound, and particularly preferably a polyamine compound.

[0047] The number average molecular weight (Mn) of compound (G) is preferably 300 or less. When the Mn of compound (G) is 300 or less, the cohesive force of the polyurethane resin (U) can be increased.

[0048] (Neutralizing agent (H)) The polyurethane resin (U) or the polyurethane prepolymer, which is a synthetic intermediate in the production of the polyurethane resin (U), has an acidic group. The polyurethane resin (U) may have a structure derived from the neutralizing agent (H) in order to neutralize the above acidic group. The neutralizing agent (H) may be used alone or in combination of multiple types.

[0049] As the neutralizing agent (H), known ones can be used. 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, pyridine; inorganic alkalis such as sodium hydroxide, potassium hydroxide, ammonia, etc. can be used.

[0050] As the neutralizing agent (H), when forming a coating film from the composition, it volatilizes at the temperature (usually 40 to 200 degrees) when drying the aqueous medium and disappears from the coating film. From the point of obtaining better adhesion strength, its boiling point is preferably 200 degrees or less, and more preferably in the range of -50 to 180 degrees. When obtaining a coating film in a short time of several seconds to 1 hour at a low temperature of 100 °C or less, its boiling point is preferably 130 °C or less, and more preferably 110 °C or less.

[0051] (Other Compounds (I)) When reacting an acid-free polyol (A), an acid-containing polyol (B), a hydrophobic substituent-containing ethylene glycol (C), and a polyisocyanate (D) during the production of polyurethane resin (U), the following other compounds (I) may be reacted together with the above components (A) to (D). Examples of other compounds (I) include monoalcohols, hydroxyalkanoic acids, esters of hydroxyalkanoic acids, and monoamines. When other compounds (I) are monoalcohols or monoamines, polyurethane resin (U) with unreactive molecular ends is obtained. Examples of monoalcohols include ethanol, n-propanol, isopropanol, n-butanol, hexanol, and octanol. Examples of hydroxyalkanoic acids include 3-hydroxypivalic acid, 2-hydroxyacetic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 10-hydroxydecanoic acid, 12-hydroxydodecanoic acid, 16-hydroxyhexadecanoic acid, 2-hydroxyoctanoic acid, 3-hydroxyundecanoic acid, and 12-hydroxystearic acid. Examples of monoamines include ethylamine, n-propylamine, isopropylamine, n-butylamine, and n-hexylamine. Other compounds (I) may be used alone or in combination of multiple types.

[0052] (Number of hydroxyl groups in polyols (A) that do not contain acidic groups, polyols (B) that contain acidic groups, ethylene glycol (C) that contains hydrophobic substituents, and other compounds (I)) In polyurethane resin (U), the total number of hydroxyl groups in polyols contained in polyols (A) that do not contain acidic groups, polyols (B) that contain acidic groups, ethylene glycol (C) that contains hydrophobic substituents, and other compounds (I) is preferably 100 to 2,000. If the number of hydroxyl groups is within this range, it is easy to manufacture an aqueous dispersion of polyurethane resin containing the obtained polyurethane resin (U). From the viewpoint of storage stability of the obtained aqueous dispersion of polyurethane resin, the number of hydroxyl groups is preferably 150 to 1,500, more preferably 200 to 1,300, and particularly preferably 250 to 1,000.

[0053] The number of hydroxyl groups can be calculated using the following formulas (1) and (2): Number of hydroxyl groups for each polyol component = Molecular weight of each polyol component / Number of hydroxyl groups in each polyol component ... (1) Total number of hydroxyl groups for all polyol components = M / Total number of moles of polyol components ... (2) In formula (2), M represents [[Number of hydroxyl groups for polyol components without acidic groups × Number of moles of polyol components without acidic groups] + [Number of hydroxyl groups for polyols containing acidic groups × Number of moles of polyols containing acidic groups] + [Number of hydroxyl groups for ethylene glycol containing hydrophobic substituents × Number of moles of ethylene glycol containing hydrophobic substituents] + [Number of hydroxyl groups for polyols contained in other compounds (I) × Number of moles of those polyols]].

[0054] (Properties of Polyurethane Resin (U)) In polyurethane resin (U), the total content of urethane bonds and urea bonds is preferably 7.0 to 20.0% by mass, and particularly preferably 8.0 to 18.0% by mass, based on the solid content of polyurethane resin (U).

[0055] By setting the total content of the urethane and urea bonds to 7.0% by mass or more, it may be possible to reduce the stickiness of the coating surface. Furthermore, by setting the content of the urethane and urea bonds to 20.0% by mass or less, it may be possible to improve the adhesion of the coating.

[0056] From the viewpoint of ensuring that the composition forms an even better coating film, the content of urethane bonds in the polyurethane resin (U) is preferably 3.0 to 18.0% by mass, more preferably 4.0 to 16.0% by mass, even more preferably 5.0 to 14.0% by mass, and particularly preferably 6.0 to 13.0% by mass, based on solid content.

[0057] From the viewpoint of the composition forming an even better coating film, the content of urea bonds in the polyurethane resin (U) is preferably 0.5 to 10.0% by mass, more preferably 0.8 to 8.0% by mass, even more preferably 1.0 to 6.0% by mass, and particularly preferably 1.2 to 5.0% by mass, based on solid content.

[0058] The content of urethane bonds and urea bonds in the polyurethane resin (U) can be controlled by the molecular weight, the number of hydroxyl groups, isocyanate groups, and amino groups in one molecule of each of the acid-free polyol (A), acid-containing polyol (B), hydrophobic substituent-containing ethylene glycol (C), polyisocyanate (D), compound (G), and other compounds (I), as well as the usage ratio of each raw material on a solid content basis in the aqueous dispersion of the polyurethane resin (U).

[0059] Furthermore, the proportion of urethane bonds, urea bonds, etc., in polyurethane resin (U) can be roughly calculated based on the amount used, the molecular weight of each raw material, and the molecular weight or number of moles of the portion corresponding to each structure.

[0060] From the viewpoint of the composition forming an even better coating film, the content of alicyclic structures in the polyurethane resin (U) is preferably 3 to 50% by mass, and particularly preferably 5 to 30% by mass. In this specification, the content of alicyclic structures in the polyurethane resin (U) can be measured by 1H-NMR.

[0061] From the viewpoint of ensuring that the composition forms an even better coating film, the molar ratio of hydrophobic substituents (excluding terminals) to acidic groups in the polyurethane resin (U) is preferably hydrophobic substituent / acidic group = 0.05 to 2.00, and more preferably 0.10 to 1.50. When a coating film with extremely excellent friction resistance and adhesion is required, the above molar ratio is particularly preferably hydrophobic substituent / acidic group = 0.50 to 1.20. Hydrophobic substituents exclude those located at the ends of the molecular main chain. Furthermore, the hydrophobic substituents are structures derived from one of the following: an acidic group-free polyol (A), an acidic group-containing polyol (B), a hydrophobic substituent-containing ethylene glycol (C), a polyisocyanate (D), and a compound (G).

[0062] The weight-average molecular weight (Mw) of the polyurethane resin (U) 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 conversion value obtained from a pre-prepared calibration curve of standard polystyrene can be used. A weight-average molecular weight of 100,000 or more tends to yield a better coating film. A weight-average molecular weight of 10,000,000 or less tends to yield a higher drying rate for the coating film.

[0063] The acid value of the polyurethane resin (U) is preferably 5 to 40 mg KOH / g, more preferably 8 to 35 mg KOH / g, and particularly preferably 10 to 30 mg KOH / g. Setting the acid value of the polyurethane resin within the range of 5 to 40 mg KOH / g tends to improve storage stability. The acid value can be measured in accordance with the indicator titration method of JIS K 1557. If the polyurethane resin (U) contains a structure derived from a neutralizing agent (H), the neutralizing agent (H) used to neutralize the acidic group is removed before measurement. For example, when organic amines are used as the neutralizing agent (H), an aqueous dispersion of the polyurethane resin (U) is applied to a glass plate, dried at 60°C under reduced pressure of 20 mmHg for 24 hours, and the resulting coating is dissolved in N-methylpyrrolidone (NMP). The acid value can then be measured in accordance with the indicator titration method of JIS K 1557. The acid value of polyurethane resin (U) can be controlled by the proportion of acidic group-containing polyol (B) it contains.

[0064] (Composition of Polyurethane Resin (U)) The content ratio of each structure in the polyurethane resin (U) is preferably as follows. In this specification, the content ratio of each component in the polyurethane resin (U) is a value calculated based on the amount used. The amount used refers to the amount of each component used when manufacturing the polyurethane resin (U). Since all of the components react almost completely in the manufacturing of the polyurethane resin (U), the amount used is considered to be the content ratio in the polyurethane resin (U).

[0065] The content of the structure derived from the acid-free polyol (A) is preferably 35.0 to 85.0% by mass, and particularly preferably 40.0 to 80.0% by mass, in the polyurethane resin (U).

[0066] The content of the structure derived from the acidic group-containing polyol (B) is preferably 1.0 to 15.0% by mass, and particularly preferably 1.5 to 10.0% by mass, in the polyurethane resin (U).

[0067] The content of the hydrophobic substituent-containing ethylene glycol (C)-derived structure is preferably 0.3 to 30.0% by mass, and more preferably 0.5 to 25.0% by mass, in the polyurethane resin (U). Furthermore, when a coating film with extremely excellent frictional fastness and adhesion is required, the content of the hydrophobic substituent-containing ethylene glycol (C)-derived structure is particularly preferably 1.0% by mass or more, especially preferably 2.0% by mass or more, and most preferably 4.0% by mass or more, in the polyurethane resin (U).

[0068] The content of the polyisocyanate (D)-derived structure is preferably 10.0 to 50.0% by mass, and particularly preferably 15.0 to 40.0% by mass, in the polyurethane resin (U).

[0069] Furthermore, the content of the structure derived from polyisocyanate (D) is preferably such that the molar ratio (isocyanate group / hydroxyl group) of the isocyanate groups of polyisocyanate (D) to the hydroxyl groups of the acidic group-free polyol (A), acidic group-containing polyol (B), and hydrophobic substituent-containing ethylene glycol (C) is in the range of 0.5 to 3.0, and is particularly preferably in the range of 1.2 to 2.0. Note that if the polyurethane resin (U) has a blocked isocyanate structure, the content of the structure derived from polyisocyanate (D) shall include the content of the blocked isocyanate structure.

[0070] When the polyurethane resin (U) has a structure derived from compound (G), the content of the structure derived from compound (G) is preferably 0.1 to 10.0% by mass, and particularly preferably 0.5 to 8.0% by mass, in the polyurethane resin (U).

[0071] Furthermore, the content of the structure derived from compound (G) is preferably less than or equal to the equivalent amount of the isocyanate group that serves as the starting point for chain extension in the polyurethane prepolymer, which is a synthesis intermediate for the polyurethane resin (U). It is particularly preferable that the content is 0.70 to 0.99 equivalents of the isocyanate group in the polyurethane prepolymer. By adding compound (G) in an amount less than or equal to the equivalent amount of the isocyanate group in the polyurethane prepolymer, the molecular weight of the chain-extended polyurethane resin (U) is not reduced, and the composition tends to be able to form an even better coating film.

[0072] When the polyurethane resin (U) has a structure derived from the neutralizing agent (H), the content of the structure derived from the neutralizing agent (H) is preferably in the range of 0.8 to 1.2 times the number of moles of acidic groups contained in the polyurethane resin (U). If the content of the structure derived from the neutralizing agent (H) is 0.8 times or more the number of moles of acidic groups, the stability of the polyurethane resin (U) in the aqueous dispersion is high, and if it is 1.2 times or less, a coating film with high adhesion to the substrate can be obtained in a short time of a few seconds to 1 hour under low temperature drying at 100°C or below. Note that when a coating film (cured layer) is obtained by drying the composition after applying it to a substrate, the neutralizing agent (H) may volatilize during drying, and the polyurethane resin (U) in the coating film may not contain the structure derived from the neutralizing agent (H).

[0073] If the polyurethane resin (U) has a structure derived from other compound (I), the content of the structure derived from other compound (I) is preferably less than 2% by mass, and particularly preferably less than 1% by mass, of the polyurethane resin (U).

[0074] <Method for producing polyurethane resin (U)> Polyurethane resin (U) can be obtained using any method within the range in which the desired polyurethane resin (U) can be obtained. For example, polyurethane resin (U) can be obtained by a manufacturing method that includes a step of reacting an acid group-free polyol (A) and a polyisocyanate (D). Furthermore, it is preferable that the polyurethane resin (U) is obtained by the following method for producing an aqueous dispersion of polyurethane resin (U).

[0075] (Aqueous dispersion (PUD) of polyurethane resin (U)) An aqueous dispersion (emulsion) of polyurethane resin (U) is a dispersion of polyurethane resin (U) in an aqueous medium. The content (solids) of polyurethane resin (U) in the aqueous dispersion of polyurethane resin (U) is preferably 5 to 60% by mass, and particularly preferably 20 to 50% by mass. Here, the content of polyurethane resin (U) in the aqueous dispersion of polyurethane resin (U) refers to the content of polyurethane resin (U) relative to the total amount of the aqueous dispersion, which includes polyurethane resin (U), the aqueous medium, and optional additives. In the aqueous dispersion of polyurethane resin (U), the amount of hydrophilic organic solvent in the aqueous medium is preferably 0 to 20% by mass. The pH of the aqueous dispersion of polyurethane resin (U) is preferably 5.0 to 9.0.

[0076] (Method for producing an aqueous dispersion of polyurethane resin (U)) The method for producing an aqueous dispersion of polyurethane resin (U) preferably includes the following steps: (I) a step of reacting the acid group-free polyol (A), the acid group-containing polyol (B), the hydrophobic substituent-containing ethylene glycol (C), the polyisocyanate (D), and optionally other compounds (I) 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 a chain extender (compound (G) or other chain extender).

[0077] Furthermore, if a neutralizing agent (H) is used, a step of neutralizing the acidic groups of the polyurethane prepolymer with the neutralizing agent (H) may be included after step (I). In addition, a step of removing the organic solvent may be included as step (IV).

[0078] If the polyurethane resin (U) does not contain a structure derived from compound (G), the polyurethane prepolymer obtained in step (I) or step (II) may be used as the polyurethane resin (U).

[0079] Aqueous dispersions of polyurethane resin (U) can be produced by known methods described in known literature (e.g., International Publication No. 2016 / 039396, International Publication No. 2016 / 163394, etc.).

[0080] In step (I) described above, the polyurethane prepolymer is obtained by reacting an acid-free polyol (A), an acid-containing polyol (B), a hydrophobic substituent-containing ethylene glycol (C), a polyisocyanate (D), and optionally other compounds (I). Therefore, the polyurethane prepolymer has a structure derived from the acid-free polyol (A), a structure derived from the acid-containing polyol (B), a structure derived from the hydrophobic substituent-containing ethylene glycol (C), a structure derived from the polyisocyanate (D), and optionally other compounds (I).

[0081] The polyurethane prepolymer is preferable if it is selected within a range where the content of free isocyanate groups is 0.5 to 5.0% by mass, based on the solid content of the polyurethane prepolymer, as this results in good dispersibility in water.

[0082] The acid value (AV) of the polyurethane prepolymer is preferably 4 to 40 mg KOH / g, more preferably 6 to 38 mg KOH / g, and particularly preferably 8 to 35 mg KOH / g. Setting the acid value of the polyurethane prepolymer to 4 mg KOH / g or higher tends to improve dispersibility in aqueous media and storage stability. Furthermore, setting the acid value of the polyurethane prepolymer to 40 mg KOH / g or lower tends to result in a composition that forms a coating film with extremely excellent flexibility and adhesion. It also tends to improve the drying properties of the composition during drying.

[0083] Furthermore, the "acid value of polyurethane prepolymer" refers to the acid value of the so-called solid content, excluding the solvent used in the manufacture of the polyurethane prepolymer and the neutralizing agent used to disperse the polyurethane prepolymer in an aqueous medium.

[0084] Specifically, the acid value of a polyurethane prepolymer can be derived using the following formula (3).

[0085] [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, any blocking agent, acidic group-free polyol, and hydrophobic substituent-containing ethylene glycol] ... (3)

[0086] Thus, the acid value of the polyurethane prepolymer is adjusted by the proportion of acidic group-containing polyol (B) in the total polyols forming the polyurethane prepolymer.

[0087] Step (III), in which the polyurethane prepolymer is reacted with compound (G) or other chain extender, is a step to bond the polyurethane prepolymers together and adjust the molecular weight of the polyurethane resin to a desired range. In step (I), if the acid group-free polyol (A) is at least one selected from the group consisting of polycarbonate polyol, polyester polyol, and polyether polyol, it is preferable that the chain extender used in step (III) is not polycarbonate polyol, polyester polyol, polyether polyol, acid group-containing polyol (B), or hydrophobic substituent-containing ethylene glycol (C).

[0088] Step (III) may be carried out slowly under cooling conditions, or, in some cases, the reaction may be accelerated under heating conditions of 90°C or below. The reaction time under cooling conditions can be, for example, 0.5 to 24 hours, and the reaction time under heating conditions of 90°C or below can be, for example, 0.1 to 6 hours.

[0089] An aqueous medium is water or a mixture of water and a hydrophilic organic solvent. Examples of water include tap water, deionized water, distilled water, and ultrapure water. Examples of hydrophilic organic solvents include ketones such as acetone and methyl ethyl ketone; 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 (glycol 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, propylene glycol monoethyl ether, and dipropylene glycol-n-butyl ether; amides such as β-alkoxypropionamide, represented by "KJCMPA(R)-100" manufactured by KJ Chemical Co., Ltd.; and hydroxyl-containing tertiary amines such as 2-(dimethylamino)-2-methyl-1-propanol (DMAP).

[0090] <Further Components> The aqueous dispersion of polyurethane resin (U) may optionally contain other resins and / or other additives.

[0091] Examples of other resins include polyester resin, acrylic resin, polyether resin, polycarbonate resin, epoxy resin, alkyd resin, polyolefin resin, and vinyl chloride resin. These other resins may be used individually or in combination of multiple types.

[0092] Polyester resins can usually be produced by an esterification or transesterification reaction between an acid component and an alcohol component. As the acid component, compounds commonly used as acid components in the production of polyester resins can be used. Examples of acid components include aliphatic polybasic acids, alicyclic polybasic acids, and aromatic polybasic acids.

[0093] Acrylic resins are compounds having polymerization units derived from (meth)acrylic monomers that have one or more types of (meth)acryloyl groups in their molecules. Acrylic resins are usually obtained by polymerizing one or more types of (meth)acrylic monomers. "(meth)acryloyl group" refers to both "methacryloyl group" and "acryloyl group". "(meth)acrylic monomer" refers to both "methacrylic monomer" and "acrylic monomer".

[0094] Examples of polyether resins include polymers or copolymers having ether bonds, 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.

[0095] Examples of polycarbonate resins include polymers produced from bisphenol compounds, such as bisphenol A polycarbonate.

[0096] Examples of epoxy resins include resins obtained by the reaction of bisphenol compounds with epichlorohydrin. Examples of bisphenol compounds include bisphenol A and bisphenol F.

[0097] Examples of alkyd resins include those obtained by reacting polybasic acids such as phthalic acid, terephthalic acid, and succinic acid with polyhydric alcohols, and further reacting with modifiers such as oils and fats, fatty acids (soybean oil, linseed oil, coconut oil, stearic acid, etc.), and natural resins (rosin, succin, etc.).

[0098] Examples of polyolefin resins include those obtained by polymerizing or copolymerizing olefin monomers with other monomers according to conventional polymerization methods, and then dispersing the resulting polyolefin resin in water using an emulsifier, or by emulsion polymerization of olefin monomers with other monomers. In some cases, a so-called chlorinated polyolefin-modified resin, in which the above-mentioned polyolefin resin has been chlorinated, may also be used.

[0099] Examples of olefin 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 unconjugated dienes such as butadiene, ethylidenenorbornene, dicyclopentadiene, and 1,5-hexadiene. These monomers may be used individually or in combination of multiple types.

[0100] Other monomers copolymerizable with olefin monomers include, for example, styrene, vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, and itaconic anhydride. These monomers may be used individually or in combination of multiple types.

[0101] Other additives that can be used include, for example, surfactants, curing agents, surface modifiers, emulsifiers, thickeners, urethane catalysts, fillers, foaming agents, oil repellents, pigments, dyes, film-forming aids, hollow foams, flame retardants, defoaming agents, leveling agents, blocking inhibitors, UV absorbers, light stabilizers, plasticizers, settling inhibitors, polymerization inhibitors, dispersants, penetration enhancers, humectants, fixing agents, preservatives, antioxidants, fungicides, chelating agents, sensitizers, pH adjusters, wetting agents, etc. These additives may be used individually or in combination of multiple types.

[0102] As the surfactant, any known surfactant can be used. Examples include acetylenediol-based surfactants, silicone-based surfactants, and fluorine-based surfactants.

[0103] Known curing agents can be used. Examples include polyisocyanate compounds, polycarbodiimide compounds, oxazoline compounds, amino resins, epoxy group-containing compounds, and aziridine compounds.

[0104] Film-forming aids are generally hydrophilic compounds that promote film formation. Examples of film-forming aids include pyrrolidone compounds such as N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-isopropylpyrrolidone, N-butylpyrrolidone, N-cyclohexylpyrrolidone, N-octylpyrrolidone, N-phenylpyrrolidone, and vinylpyrrolidone; alcohol compounds such as methanol, ethanol, isopropanol, n-butanol, and n-hexanol; glycol compounds such as propylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol; and glycol ether compounds such as ethylene glycol monobutyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, triethylene glycol monobutyl ether, polyethylene glycol monobutyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether. Among these, pyrrolidone compounds and glycol ether compounds are preferred.

[0105] Known polymerization initiators can be used. Examples include 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.

[0106] <Functional Additives (E)> Functional additives (E) are additives added to the composition according to the present invention in order to form a good coating film. Examples of functional additives (E) include humectants (E1) and film-forming aids (E2). When a humectant (E1) is used as the functional additive (E), the composition will be able to form a coating film with particularly excellent friction resistance. When a film-forming aid (E2) is used as the functional additive (E), the composition will be able to form a coating film with particularly excellent adhesion.

[0107] The humectant (E1) is a water-soluble compound with low volatility and high water retention capacity. Known compounds can be used as the humectant (E1). Examples include glycerols such as glycerin, diglycerin, triglycerin, trimethylolethane, and trimethylolpropane (polyols having a glycerin-derived skeleton); and glycols such as ethylene glycol, propanediol, butanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butylene glycol, thioglycol, and polyethylene glycol. Among these, polyhydric alcohols are preferred from the viewpoint of suppressing drying of the composition, glycerols are more preferred, and glycerin is particularly preferred.

[0108] The moisturizer (E1) may be used alone or in combination of multiple types.

[0109] Film-forming aids (E2) are generally hydrophilic compounds that promote film formation. Known substances can be used as film-forming aids (E2). Examples include pyrrolidone compounds such as N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-isopropylpyrrolidone, N-butylpyrrolidone, N-cyclohexylpyrrolidone, N-octylpyrrolidone, N-phenylpyrrolidone, and vinylpyrrolidone; alcohol compounds such as methanol, ethanol, isopropanol, n-butanol, and n-hexanol; glycol compounds such as propylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol; and glycol ether compounds such as ethylene glycol monobutyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, triethylene glycol monobutyl ether, polyethylene glycol monobutyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol n-butyl ether. From the viewpoint of improving the quick-drying properties of the composition and the adhesion of the resulting coating film, glycol ether compounds and pyrrolidone compounds are preferred.

[0110] The film-forming aid (E2) may be used alone or in combination of multiple types.

[0111] <Pigment (F)> As pigment (F), inorganic pigments or organic pigments can be used. These may be used individually or in combination of multiple types. Mixed crystals may also be used.

[0112] Examples of pigments that can be used include black pigment, yellow pigment, magenta pigment, cyan pigment, white pigment, green pigment, orange pigment, and glossy pigments such as gold and silver, as well as metallic pigments.

[0113] As inorganic pigments, for example, titanium dioxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, and chromium yellow can be used, as well as carbon black produced by known methods such as the contact method, furnace method, and thermal method.

[0114] 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, as well as dye chelates, nitro pigments, nitroso pigments, azo pigments, aniline black, resin hollow particles, and inorganic hollow particles.

[0115] <Composition> The composition according to the present invention comprises an aqueous dispersion of polyurethane resin (U), a functional additive (E), and a pigment (F).

[0116] The mass ratio of polyurethane resin (U) in the composition is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of the composition forming an even better coating film, it is preferably 0.01 or higher, more preferably 0.02 or higher, even more preferably 0.05 or higher, particularly preferably 0.10 or higher, preferably 0.45 or lower, more preferably 0.40 or lower, even more preferably 0.30 or lower, and particularly preferably 0.25 or lower.

[0117] When a humectant (E1) is used as a functional additive (E), the mass ratio of polyurethane resin (U) is preferably 0.01 to 0.30, and more preferably 0.02 to 0.25, from the viewpoint of the frictional fastness of the resulting coating film. On the other hand, when a film-forming aid (E2) is used as a functional additive (E), the mass ratio of polyurethane resin (U) is preferably 0.05 to 0.45, and more preferably 0.10 to 0.40, from the viewpoint of improving the adhesion of the resulting coating film.

[0118] The mass ratio of the functional additive (E) in the composition is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of the composition forming an even better coating film, it is preferably 0.010 or more, more preferably 0.030 or more, even more preferably 0.05 or more, particularly preferably 0.10 or more, preferably 0.60 or less, more preferably 0.50 or less, even more preferably 0.200 or less, and particularly preferably 0.100 or less. The content of the functional additive (E) in the composition is preferably 2 parts by mass or more, more preferably 5 parts by mass or more, preferably 500 parts by mass or less, and more preferably 400 parts by mass or less, per 100 parts by mass of polyurethane resin (U) in the composition.

[0119] When a humectant (E1) is used as a functional additive (E), the mass ratio of the humectant (E1) in the composition is preferably 0.05 to 0.60, and more preferably 0.10 to 0.50, from the viewpoint of the drying properties of the composition. The content of the humectant (E1) in the composition is preferably 50 to 500 parts by mass, and more preferably 100 to 400 parts by mass, per 100 parts by mass of polyurethane resin (U) in the composition.

[0120] On the other hand, when a film-forming aid (E2) is used as a functional additive (E), the mass ratio of the film-forming aid (E2) in the composition is preferably 0.010 to 0.200, and more preferably 0.030 to 0.100, from the viewpoint of the quick-drying properties of the composition. The content of the film-forming aid (E2) in the composition is preferably 2 to 200 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of polyurethane resin (U) in the composition.

[0121] The mass ratio of pigment (F) in the composition is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of the color development of the resulting coating film, it is preferably 0.001 or more, more preferably 0.003 or more, even more preferably 0.005 or more, particularly preferably 0.007 or more, preferably 0.400 or less, and even more preferably 0.300 or less. The pigment (F) content is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 5 parts by mass or more, particularly preferably 7 parts by mass or more, preferably 400 parts by mass or less, more preferably 200 parts by mass or less, and even more preferably 100 parts by mass or less per 100 parts by mass of polyurethane resin (U) in the composition.

[0122] When a humectant (E1) is used as a functional additive (E), the mass ratio of pigment (F) in the composition is preferably 0.003 to 0.400, more preferably 0.005 to 0.400, and even more preferably 0.007 to 0.300, from the viewpoint of the color development of the resulting coating film. Furthermore, when a humectant (E1) is used as a functional additive (E), the pigment (F) content is preferably 5 to 400 parts by mass, and more preferably 7 to 200 parts by mass, per 100 parts by mass of polyurethane resin (U) in the composition.

[0123] On the other hand, when a film-forming aid (E2) is used as a functional additive (E), the mass ratio of pigment (F) in the composition is preferably 0.001 to 0.400, and more preferably 0.003 to 0.300, from the viewpoint of the color development of the resulting coating film. Furthermore, when a film-forming aid (E2) is used as a functional additive (E), the pigment (F) content is preferably 1 to 200 parts by mass, and more preferably 2 to 50 parts by mass, per 100 parts by mass of polyurethane resin (U) in the composition.

[0124] The viscosity of the composition 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 2.5 to 7.5 cP. The viscosity can be measured, for example, using a Type B viscometer TV10 (manufactured by Toki Sangyo Co., Ltd.) under the conditions of 20°C, spindle M1, sample volume 300 mL, rotation speed 100 rpm, and 5 minutes. In particular, when a humectant (E1) is used as a functional additive (E), it is preferable that the viscosity is within the above range.

[0125] It is preferable that the value of the color transfer brightness measured in accordance with the wet test of JIS L 0849:2013 for test pieces in which the composition was deposited on a polyethylene terephthalate substrate at 160°C for 5 minutes is 3 or less. In particular, it is preferable that the value of the color transfer brightness is within the above range when a humectant (E1) is used as the functional additive (E).

[0126] In this specification, the brightness of color transfer is calculated by scanning a wafer after a friction fastness test conducted in accordance with JIS L 0849:2013 to create image data, and then using the image processing software ImageJ.

[0127] When a test specimen prepared by depositing the composition onto a polymethyl methacrylate substrate at 90°C for 30 minutes is subjected to a grid peel test (100 squares) in accordance with JIS K 5400, it is preferable that the number of remaining particles after one tape peel is 100, and the number of remaining particles after two peels is 95 or more. In particular, when a film-forming aid (E2) is used as the functional additive (E), it is preferable that the number of remaining particles be within the above range.

[0128] <Method for Manufacturing the Composition> The method for manufacturing the composition according to the present invention is not particularly limited, but known manufacturing methods can be used. Generally, the method for manufacturing the composition includes the step of mixing a polyurethane resin (U) aqueous dispersion, a functional additive (E), and a pigment (F).

[0129] <Applications> The composition according to the present invention can be suitably used in applications that form coating films, such as inks and coatings. For example, when a humectant (E1) is used as a functional additive (E), the composition according to the present invention can be suitably used as an ink composition for printing on various substrates such as fabrics. Furthermore, when a film-forming aid (E2) is used as a functional additive (E), the composition according to the present invention can be suitably used as a coating composition for manufacturing laminates formed by coating various substrates. When the composition according to the present invention is used as a coating composition, examples of applications include vehicles, ships, aircraft, buildings, civil engineering structures, electrical products, resin molded products, paper processing, film processing, etc., with vehicles being particularly preferred.

[0130] <Method of using the ink composition> When using the composition of the present invention as an ink composition, examples of application methods for the ink composition include bell coating, spray coating, roll coating, shower coating, dipping coating, inkjet printing, flexographic printing, thermal transfer printing, gravure printing, reverse offset printing, sheet-fed screen printing, rotary screen printing, air spray coating method, electrostatic coating, etc., but inkjet printing is preferred.

[0131] In inkjet printing, either a single-pass method, in which ink is ejected to the substrate only once, or a serial method, in which a short shuttle head is scanned back and forth in a direction perpendicular to the substrate transport direction while ejecting ink, may be used as the pass method. However, in the case of the serial method, it is necessary to adjust the ejection timing taking into account the movement of the inkjet head, which can easily lead to misalignment of the landing position. Therefore, in inkjet printing using an ink composition, a single-pass method is preferred.

[0132] There are no particular restrictions on the method of ejecting the ink composition; known methods such as the drop-on-demand method (pressure pulse method) that utilizes the vibration pressure of a piezoelectric element, and the thermal inkjet method that heats the ink composition to form bubbles and utilizes the resulting pressure can be used.

[0133] The amount of ink composition droplets ejected from the inkjet head is preferably 0.2 to 30 pL, and more preferably 1 to 20 pL, in terms of significantly reducing the drying load and improving color reproducibility and image quality.

[0134] <Substrate> Examples of substrates to which the ink composition is applied include building materials such as wallpaper, flooring, and tiles, as well as fabrics, leather, metals, plastics, inorganic materials, and wood, with fabric being the most preferred. By applying the ink composition to the above substrate to form a coating (printed surface), printed materials with excellent friction fastness of the printed surface can be obtained in both dry and wet conditions. Furthermore, since the ink composition has excellent penetration into porous substrates, it exhibits excellent applicability to porous substrates. In particular, when fabric is used as the substrate, the penetration and applicability of the ink composition are excellent, allowing for the production of printed materials with excellent friction fastness of the printed surface with high productivity.

[0135] <Apparel> Apparel includes fabrics to which an ink composition has been applied. Fabrics include woven fabrics, knitted fabrics, and nonwoven fabrics made from natural fibers such as cotton, silk, and wool, as well as synthetic fibers such as nylon, and composite fibers that are mixtures thereof. This includes both long rolls of fabric and fabrics cut to predetermined lengths.

[0136] Clothing items include T-shirts, handkerchiefs, scarves, towels, tote bags, cloth bags, furniture such as curtains, sheets, and bedspreads, as well as fabrics before and after cutting that exist as parts before sewing.

[0137] <Method of using the coating composition> When using the composition of the present invention as a coating composition, examples of application methods for the coating composition include bell coating, spray coating, roll coating, shower coating, dipping coating, electrostatic coating, etc.

[0138] A coating film can be obtained by drying or curing the coating composition after application. Preferably, the coating film is obtained by drying or curing the composition by heating after applying it to the substrate.

[0139] Examples of the aforementioned heating methods include heating by the heat of the reaction itself, and heating methods that actively heat the coating composition and the substrate. Active heating methods include heating the coating composition and the substrate by placing them in a hot air oven, electric furnace, or infrared induction heating furnace.

[0140] <Laminate> The present invention also relates to a laminate formed by laminating a substrate and a coating film made of the coating composition according to the present invention. Examples of substrates include building materials such as wallpaper, flooring, and tiles, as well as fabrics, leather, metals, plastics, inorganic materials, and wood, with metals and plastics being preferred. By using the composition according to the present invention as a coating composition, a coating film with excellent adhesion to the substrate can be formed. Furthermore, the coating composition has excellent quick-drying properties, is less prone to dripping, and can uniformly form a coating film with a beautiful appearance on the substrate. In particular, even when using substrates with low affinity to urethane resin, such as plastic substrates like acrylic substrates or metal substrates, it is possible to uniformly form a coating film with a beautiful appearance that is less prone to dripping.

[0141] 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.

[0142] [Synthesis Example 1] Aqueous polyurethane resin dispersion (PUD1) Polycarbonate polyol (Polyol without acidic groups (A), product name "UH200", manufactured by UBE Corporation; number average molecular weight 2,000; hydroxyl value 57 mg KOH / g; reaction product of 1,6-hexanediol and dimethyl carbonate, 300 g), 2,2-dimethylolpropionic acid (Polyol containing acidic groups (B), DMPA, 16.1 g), and glycerin monopalmitate (Ethylene glycol containing hydrophobic substituents (C), product name "Almax-1600", ILSHIN Wells (4.4 g) and isophorone diisocyanate (polyisocyanate (D), IPDI, 88.2 g) were heated in methyl ethyl ketone (MEK, 117 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80-85°C for 5 hours. The reaction mixture was cooled to 80°C, and triethylamine (neutralizing agent (H), 12.2 g) was added and mixed. 390 g of this mixture was then added to water (600 g) under vigorous stirring. Next, a 35% by mass aqueous solution of 2-methyl-1,5-diaminopentane (compound (G), MPMD, 24.5 g) was added to obtain an aqueous polyurethane resin dispersion (PUD1). The solid content was 30% by mass.

[0143] [Synthesis Example 2] Aqueous polyurethane resin dispersion (PUD2) Polycarbonate polyol (product name "UH200", manufactured by UBE Corporation, 290 g), 2,2-dimethylolpropionic acid (DMPA, 16.3 g), glycerin monopalmitate (product name "Almax-1600", manufactured by ILSHIN WELLS, 13.0 g), and isophorone diisocyanate (IPDI, 95.2 g) were heated in methyl ethyl ketone (MEK, 119 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80-85°C for 5 hours. The reaction mixture was cooled to 80°C, and triethylamine (12.4 g) was added and mixed. 390 g of this mixture was then added to water (602 g) under vigorous stirring. Next, a polyurethane resin aqueous dispersion (PUD2) was obtained by adding 35% by mass of an aqueous solution of 2-methyl-1,5-diaminopentane (MPMD, 26.1 g). The solid content was 30% by mass.

[0144] [Synthesis Example 3] Aqueous polyurethane resin dispersion (PUD3) Polycarbonate polyol (product name "UH200", manufactured by UBE Corporation, 240 g), 2,2-dimethylolpropionic acid (DMPA, 16.5 g), glycerin monopalmitate (product name "Almax-1600", manufactured by ILSHIN WELLS, 43.1 g), and isophorone diisocyanate (IPDI, 116 g) were heated in methyl ethyl ketone (MEK, 119 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80-85°C for 5 hours. The reaction mixture was cooled to 80°C, and triethylamine (12.5 g) was added and mixed. 390 g of this mixture was then added to water (602 g) under vigorous stirring. Next, a polyurethane resin aqueous dispersion (PUD3) was obtained by adding a 35% by mass aqueous solution of 2-methyl-1,5-diaminopentane (MPMD, 31.7 g). The solid content was 30% by mass.

[0145] [Synthesis Example 4] Aqueous polyurethane resin dispersion (PUD4) Polycarbonate polyol (product name "UH200", manufactured by UBE Corporation, 290 g), 2,2-dimethylolpropionic acid (DMPA, 17.5 g), 1,2-hexadecanediol (ethylene glycol (C) containing hydrophobic substituent, 21.9 g), and isophorone diisocyanate (IPDI, 112 g) were heated in methyl ethyl ketone (MEK, 128 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80-85°C for 5 hours. The reaction mixture was cooled to 80°C, and triethylamine (13.2 g) was added and mixed. 420 g of this mixture was then added to water (646 g) under vigorous stirring. Next, a polyurethane resin aqueous dispersion (PUD4) was obtained by adding a 35% by mass aqueous solution of 2-methyl-1,5-diaminopentane (MPMD, 31.0 g). The solid content was 30% by mass.

[0146] [Synthesis Example 5] Aqueous polyurethane resin dispersion (PUD5) Aqueous polyurethane resin dispersion (PUD5) was obtained by the same method as in Synthesis Example 3.

[0147] [Synthesis Example 6] Aqueous polyurethane resin dispersion (PUD6) Polycarbonate polyol (product name "UH200", manufactured by UBE Corporation, 280 g), 2,2-dimethylolpropionic acid (DMPA, 14.6 g), and isophorone diisocyanate (IPDI, 77.5 g) were heated in methyl ethyl ketone (MEK, 104 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80-85°C for 5 hours. The reaction mixture was cooled to 80°C, and triethylamine (11.1 g) was added and mixed. 350 g of this mixture was then added to water (544 g) under strong stirring. Next, a 35% by mass aqueous solution of 2-methyl-1,5-diaminopentane (MPMD, 21.4 g) was added to obtain an aqueous polyurethane resin dispersion (PUD6). The solid content was 30% by mass.

[0148] [Synthesis Example 7] Aqueous dispersion of polyurethane resin (PUD7) Polycarbonate polyol (product name "UH200", manufactured by UBE Corporation, 280 g), 2,2-dimethylolpropionic acid (DMPA, 8.30 g), 12-hydroxystearic acid (Other Compounds (I), HSA, 37.7 g), and isophorone diisocyanate (IPDI, 78.9 g) were heated in methyl ethyl ketone (MEK, 162 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80-85°C for 5 hours. The reaction mixture was cooled to 80°C, and triethylamine (19.5 g) was added and mixed. 430 g of this mixture was then added to water (564 g) under vigorous stirring. Next, a polyurethane resin aqueous dispersion (PUD7) was obtained by adding a 35% by mass aqueous solution of diethylenetriamine (neutralizing agent (H), DETA, 9.30 g) and a 35% by mass aqueous solution of polyetheramine (compound (G), product name "JEFFAMINE® D-400", manufactured by HUNTSMAN Corporation, 17.1 g). The solid content was 30% by mass.

[0149] [Synthesis Example 8] Aqueous polyurethane resin dispersion (PUD8) Polycarbonate polyol (product name "UH200", manufactured by UBE Corporation, 360 g), 2,2-dimethylolpropionic acid (DMPA, 19.0 g), isophorone diisocyanate (IPDI, 98.5 g), and aliphatic diisocyanate Tolonate (polyisocyanate (D), registered trademark) X FLO 100 (manufactured by Vencorex; weight percentage of isocyanate group 12.4%; reaction product of 1,6-diisocyanatohexane, ethoxylated alcohol (C=12-18), and polyethylene polypropylene glycol, 4.9 g) were heated in methyl ethyl ketone (MEK, 138 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80-85°C for 5 hours. The reaction mixture was cooled to 80°C, and 470g of the mixture, to which triethylamine (14.4g) was added and mixed, was added to water (726g) under vigorous stirring. Then, a 35% by mass aqueous solution of 2-methyl-1,5-diaminopentane (MPMD, 28.5g) was added to obtain an aqueous polyurethane resin dispersion (PUD8). The solid content was 30% by mass.

[0150] [Synthesis Example 9] Aqueous polyurethane resin dispersion (PUD9) Aqueous polyurethane resin dispersion (PUD9) was obtained by the same method as in Synthesis Example 1.

[0151] [Example A1] A composition was prepared by mixing 100 parts by mass of polyurethane resin aqueous dispersion PUD1 with 20 parts by mass of pigment aqueous dispersion (product name "EMFPINK2B-1", manufactured by Toyo Color Co., Ltd., pigment component 15% by mass), 180 parts by mass of purified water, 65 parts by mass of glycerin (humectant (E1)), and 5.0 parts by mass of surface modifier (product name "BYK-345", manufactured by BYK-Chemie). The mass ratio of glycerin in the composition was 0.18, the mass ratio of pigment was 0.008, and the mass ratio of polyurethane resin (U) was 0.08.

[0152] [Example A2] A composition was prepared in the same manner as in Example A1, except that polyurethane resin aqueous dispersion PUD2 was used instead of polyurethane resin aqueous dispersion PUD1.

[0153] [Example A3] A composition was prepared in the same manner as in Example A1, except that polyurethane resin aqueous dispersion PUD3 was used instead of polyurethane resin aqueous dispersion PUD1.

[0154] [Example A4] A composition was prepared in the same manner as in Example A1, except that polyurethane resin aqueous dispersion PUD4 was used instead of polyurethane resin aqueous dispersion PUD1.

[0155] [Example A5] A composition was prepared by mixing 100 parts by mass of polyurethane resin aqueous dispersion PUD5 with 20 parts by mass of pigment aqueous dispersion (product name "EMFPINK2B-1", manufactured by Toyo Color Co., Ltd., pigment component 15% by mass), 180 parts by mass of purified water, 65 parts by mass of 1,3-propanediol (humectant (E1)), and 5.0 parts by mass of surface modifier (product name "BYK-345", manufactured by BYK-Chemie). The mass ratio of 1,3-propanediol in the composition was 0.18, the mass ratio of pigment was 0.008, and the mass ratio of polyurethane resin (U) was 0.08.

[0156] [Comparative Example A1] A composition was prepared in the same manner as in Example A1, except that polyurethane resin aqueous dispersion PUD6 was used instead of polyurethane resin aqueous dispersion PUD1.

[0157] [Comparative Example A2] A composition was prepared in the same manner as in Example A1, except that polyurethane resin aqueous dispersion PUD7 was used instead of polyurethane resin aqueous dispersion PUD1.

[0158] [Comparative Example A3] A composition was prepared in the same manner as in Example A1, except that polyurethane resin aqueous dispersion PUD8 was used instead of polyurethane resin aqueous dispersion PUD1.

[0159] [Comparative Example A4] A composition was prepared by mixing 100 parts by mass of polyurethane resin aqueous dispersion PUD9 with 20 parts by mass of pigment aqueous dispersion (product name "EMFPINK2B-1", manufactured by Toyo Color Co., Ltd.), 245 parts by mass of purified water, and 5.0 parts by mass of surface modifier (product name "BYK-345", manufactured by BYK-Chemie).

[0160] [Method for Manufacturing Test Samples for Friction Robustness Evaluation] Test specimens were prepared for the evaluation tests described later using the method shown below. A polyethylene terephthalate plate (70 mm x 150 mm, 2.0 mm thick, manufactured by Engineering Test Service Co., Ltd.) was attached to a SUS304 plate (70 mm x 150 mm, 1.0 mm thick, manufactured by Engineering Test Service Co., Ltd.) with double-sided tape to create an evaluation substrate. Each of the compositions from Examples A1 to 5 and Comparative Examples A1 to 4 was applied to the polyethylene terephthalate surface of the evaluation substrate using a #18 bar coater, and a test sample was obtained in which a coating film was formed on the polyethylene terephthalate plate by heating at 160°C for 5 minutes.

[0161] If no repulsion was observed in the coating film formed on the test sample, it was evaluated as having "good coatability." If repulsion was observed, it was evaluated as having "poor coatability."

[0162] [Friction Fastness Evaluation] The friction fastness of the coating film was evaluated in accordance with JIS L 0849:2013 (dry test and wet test). In the dry evaluation, a 900g load was applied to a wafer and the coating film of the test sample was rubbed back and forth 10 times. In the wet evaluation, a 900g load was applied to a wafer impregnated with pure water and the coating film of the test sample was rubbed back and forth 10 times. Next, the wafer was scanned to create image data. After performing color inversion processing (invert) on the acquired image data using image processing software (ImageJ), the brightness of the areas where color transfer occurred on the wafer was quantified (Measure). A smaller numerical value indicates higher friction fastness of the resulting coating film. In both the dry and wet tests, if the friction fastness evaluation result was 3 or less, it was evaluated as "good friction fastness".

[0163]

[0164] As is clear from the results in Table 1, the brightness of color transfer in Examples A1 to A5 was 3 or less in all cases, indicating that the compositions of the examples were able to provide a coating with excellent friction fastness. Specifically, as shown in Examples A1 to A3, a coating with excellent friction fastness was obtained even when the content of hydrophobic substituent-containing ethylene glycol (C) was changed. Furthermore, the higher the content of hydrophobic substituent-containing ethylene glycol (C), the better the friction fastness of the coating. Also, as shown in Example A4, a coating with good friction fastness was obtained even when the type of hydrophobic substituent-containing ethylene glycol (C) was changed. Moreover, as shown in Example A5, a coating with excellent friction fastness was obtained even when the type of humectant (E1) was changed.

[0165] On the other hand, as is clear from Comparative Example A1, when the hydrophobic substituent-containing ethylene glycol (C) was not included, the frictional fastness of the resulting coating film was poor. Also, as is clear from Comparative Example A2, when the hydrophobic substituent-containing ethylene glycol (C) was not included but a hydrophobic long-chain alkyl group was present at the terminal, the frictional fastness of the resulting coating film was poor. Furthermore, as is clear from Comparative Example A3, when the hydrophobic substituent-containing ethylene glycol (C) was not included but a hydrophobic substituent was present, the frictional fastness of the resulting coating film was poor. In addition, as is clear from Comparative Example A4, when the humectant (E1) was not included, the frictional fastness of the resulting coating film decreased.

[0166] [Example B1] A composition was prepared by blending 4.5 parts by mass of a pigment aqueous dispersion (product name "EMFPINK2B-1", manufactured by Toyo Color Co., Ltd., pigment component 15% by mass) with 100 parts by mass of polyurethane resin aqueous dispersion PUD1, 5.0 parts by mass of dipropylene glycol n-butyl ether (film-forming aid (E2)), and 0.6 parts by mass of a surface modifier (product name "BYK-345", manufactured by BYK-Chemie). The mass ratio of dipropylene glycol n-butyl ether in the composition was 0.045, the mass ratio of pigment was 0.006, and the mass ratio of polyurethane resin (U) was 0.272.

[0167] [Example B2] A composition was prepared in the same manner as in Example B1, except that polyurethane resin aqueous dispersion PUD2 was used instead of polyurethane resin aqueous dispersion PUD1.

[0168] [Example B3] A composition was prepared in the same manner as in Example B1, except that polyurethane resin aqueous dispersion PUD3 was used instead of polyurethane resin aqueous dispersion PUD1.

[0169] [Example B4] A composition was prepared in the same manner as in Example B1, except that polyurethane resin aqueous dispersion PUD4 was used instead of polyurethane resin aqueous dispersion PUD1.

[0170] [Example B5] A composition was prepared by blending 4.5 parts by mass of a pigment aqueous dispersion (product name "EMFPINK2B-1", manufactured by Toyo Color Co., Ltd., pigment component 15% by mass) with 100 parts by mass of polyurethane resin aqueous dispersion PUD5, 5.0 parts by mass of N-ethylpyrrolidone (film-forming aid (E2)), and 0.6 parts by mass of a surface modifier (product name "BYK-345", manufactured by BYK-Chemie). The mass ratio of N-ethylpyrrolidone in the composition was 0.045, the mass ratio of the pigment was 0.006, and the mass ratio of polyurethane resin (U) was 0.272.

[0171] [Comparative Example B1] A composition was prepared in the same manner as in Example B1, except that polyurethane resin aqueous dispersion PUD6 was used instead of polyurethane resin aqueous dispersion PUD1.

[0172] [Comparative Example B2] A composition was prepared in the same manner as in Example B1, except that polyurethane resin aqueous dispersion PUD7 was used instead of polyurethane resin aqueous dispersion PUD1.

[0173] [Comparative Example B3] A composition was prepared in the same manner as in Example B1, except that polyurethane resin aqueous dispersion PUD8 was used instead of polyurethane resin aqueous dispersion PUD1.

[0174] [Comparative Example B4] A composition was prepared by mixing 4.5 parts by mass of a pigment aqueous dispersion (product name "EMFPINK2B-1", manufactured by Toyo Color Co., Ltd.) and 0.6 parts by mass of a surface modifier (product name "BYK-345", manufactured by BYK-Chemie) with 100 parts by mass of a polyurethane resin aqueous dispersion PUD9.

[0175] [Method for Manufacturing Test Samples] Test specimens were prepared for the evaluation tests described later using the method shown below. Each of the compositions from Examples B1 to 5 and Comparative Examples B1 to 4 was applied to a PMMA board (70 mm x 150 mm, 2.0 mm thick, manufactured by Engineering Test Service Co., Ltd.) using a #18 bar coater, and the board was heated at 90°C for 30 minutes to obtain test samples in which a coating film was formed on the PMMA board.

[0176] [Evaluation of quick-drying properties] The coating film formed on the test sample was visually inspected. If the coating film was not cracked, it was evaluated as having "good quick-drying properties." If the coating film was cracked, it was evaluated as having "poor quick-drying properties."

[0177] [Adhesion Evaluation] The adhesion of the coating film was evaluated in accordance with JIS K 5400. Cuts were made in the coating film at 2 mm intervals vertically and horizontally over an area of ​​20 mm x 20 mm. After applying adhesive tape, the number of squares remaining on the PMMA board after peeling was visually counted and evaluated. This was repeated twice. If 15 out of 100 squares remained in the first peel test, it was recorded as 15 / 100 (1). If no peeling occurred in the first test and 85 out of 100 squares remained in the second test, it was recorded as 85 / 100 (2). If no peeling occurred at all, it was recorded as 100 / 100 (2). If the adhesion evaluation result was 95 / 100 (2) or higher, it was evaluated as "good adhesion".

[0178]

[0179] As is clear from the results in Table 2, the adhesion of Examples B1 to B5 was 95 / 100(2) or higher in all cases, indicating that the compositions of the examples can provide a coating film with excellent adhesion. Specifically, as shown in Examples B1 to B3, a coating film with excellent adhesion was obtained even when the content of hydrophobic substituent-containing ethylene glycol (C) was changed. Furthermore, the higher the content of hydrophobic substituent-containing ethylene glycol (C), the better the adhesion of the coating film. Also, as shown in Example B4, a coating film with good adhesion was obtained even when the type of hydrophobic substituent-containing ethylene glycol (C) was changed. Moreover, as shown in Example B5, a coating film with excellent adhesion was obtained even when the type of film-forming aid (E2) was changed.

[0180] On the other hand, as is clear from Comparative Example B1, when the hydrophobic substituent-containing ethylene glycol (C) was not included, the adhesion of the resulting coating film was poor. Also, as is clear from Comparative Example B2, when the hydrophobic substituent-containing ethylene glycol (C) was not included but a hydrophobic long-chain alkyl group was present at the terminal, the adhesion of the resulting coating film was poor. Furthermore, as is clear from Comparative Example B3, when the hydrophobic substituent-containing ethylene glycol (C) was not included but a hydrophobic substituent was present, the adhesion of the resulting coating film was poor. In addition, as is clear from Comparative Example B4, when the film-forming aid (E2) was not included, the adhesion of the resulting coating film decreased.

[0181] The composition of the present invention can form a good coating film and can therefore be applied to a variety of applications, such as inks for printing on clothing and the like, and in the manufacture of laminates made by coating various substrates, such as vehicle parts.

Claims

1. A composition comprising a polyurethane resin aqueous dispersion (PUD) containing a polyurethane resin (U) having a structure derived from an acidic group-containing polyol (B), a structure derived from a hydrophobic substituent-containing ethylene glycol (C), a structure derived from an acidic group-free polyol (A) (excluding the hydrophobic substituent-containing ethylene glycol (C)), and a structure derived from a polyisocyanate (D), a functional additive (E), and a pigment (F).

2. The composition according to claim 1, wherein the functional additive (E) is a humectant (E1).

3. The composition according to claim 2, wherein the composition is an ink composition.

4. The composition according to claim 1, wherein the functional additive (E) is a film-forming aid (E2).

5. The composition according to claim 4, wherein the composition is a coating composition.

6. The composition according to claim 1, wherein the molar ratio of hydrophobic substituents (excluding terminals) to acidic groups in the polyurethane resin (U) is hydrophobic substituent / acidic group = 0.05 to 2.

00.

7. The composition according to claim 1, wherein the acidic group-free polyol (A) includes a polycarbonate polyol.

8. The composition according to claim 1, wherein the acidic group-containing polyol (B) includes a carboxyl group-containing polyol.

9. The composition according to claim 1, wherein the hydrophobic substituent-containing ethylene glycol (C) comprises a glycerin monofatty acid ester.

10. The composition according to claim 1, wherein the polyisocyanate (D) comprises an alicyclic polyisocyanate compound.

11. The composition according to any one of claims 1 to 10, wherein the mass ratio of the functional additive (E) in the composition is 0.010 or more and 0.60 or less.

12. The composition according to claim 2 or 3, wherein the humectant (E1) comprises a polyhydric alcohol.

13. The composition according to any one of claims 1 to 12, wherein the mass ratio of the pigment (F) in the composition is 0.001 or more and 0.400 or less.

14. The composition according to claim 2, 3, or 12, wherein the value of the color transfer brightness measured in accordance with the wet test of JIS L 0849:2013 for a test piece obtained by depositing the composition on a polyethylene terephthalate substrate at 160°C for 5 minutes is 3 or less.

15. The composition according to claim 2, 3, 12, or 14, used in inkjet printing.

16. A fabric coated with the composition according to claim 2, 3, 12, 14, or 15.

17. Clothing comprising the fabric described in claim 16.

18. The composition according to claim 4 or 5, wherein when a test piece prepared by depositing the composition onto a polymethyl methacrylate substrate at 90°C for 30 minutes is subjected to a grid peel test (100 squares) in accordance with JIS K 5400, the number of remaining pieces after one tape peel is 100, and the number of remaining pieces after two tape peels is 95 or more.

19. A laminate comprising a substrate and a coating film made of the composition described in claim 4, 5, or 18.

20. A vehicle comprising the laminate described in claim 19.

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