Emulsion composition

Abstract

To provide an emulsion composition which is excellent in soft feeling property, tack-free property and friction fastness.SOLUTION: An emulsion composition is provided, including a polyurethane resin (A), an acrylic resin (B) and an aqueous medium (C), wherein elastic modulus of a film with thickness of 90 μm of the polyurethane resin (A) is 200 MPa or more, the acrylic resin (B) has a glass transition temperature of -15°C or lower, and a solid content ratio (A / B) of the polyurethane resin (A) to the acrylic resin (B) is 0.02 to 0.23. Amount of a solvent used in ink can be reduced by using the emulsion composition as a binder of aqueous ink, and accordingly the emulsion composition can contribute to achievement of Goal 7 and the like of SDGs (Sustainable Development Goals).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an emulsion composition.

Background Art

[0002] Inks are roughly classified into aqueous inks and solvent-based inks. Since the main solvent of aqueous inks is water and the generation of volatile organic compounds is small, they are materials that are being replaced from solvent-based inks as environmentally friendly materials.

[0003] The properties of inks are greatly affected by the binder resin (i.e., the resin used as a binder for inks) to be blended, and thus the development of binder resins suitable for inks has been carried out. For example, Patent Document 1 describes a binder resin containing an acrylic resin and a polyurethane resin having a structure derived from a polyethylene oxide chain-containing polyol. Patent Document 2 describes a binder resin containing a polyurethane resin and a silicone compound. Patent Document 3 describes a composition containing a polyurethane resin and an oxazoline-crosslinked acrylic resin. Patent Document 4 describes a vinyl resin obtained by polymerizing a specific vinyl monomer. Patent Document 5 describes a composite resin aqueous dispersion produced by emulsion polymerization of an ethylenically unsaturated monomer in the presence of a polyurethane resin aqueous dispersion.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0005] Generally, when trying to improve the soft feel property of a binder resin, there is a problem that the tack-free property and the friction fastness decrease, and it is difficult to simultaneously exhibit the soft feel property, the tack-free property, and the friction fastness.

[0006] In Patent Documents 1 and 4, the constitution of a binder resin that simultaneously exhibits soft feel property, tack-free property, and friction fastness has not been studied. In Patent Document 2, the binder resin is relatively hard, and further improvement in soft feel property is required. In Patent Document 3, the composition is hard, and it is difficult to apply it to ink applications. In Patent Document 5, a two-stage emulsion polymerization process is required, and reduction of the process load is desired.

[0007] An object of the present invention is to solve the problems in the above-mentioned prior art and provide an emulsion composition excellent in soft feel property, tack-free property, and friction fastness.

Means for Solving the Problems

[0008] As a result of various studies to overcome the problems of the above-mentioned prior art, the present inventors have arrived at the present invention.

[0009] The present invention has the following constitution. [1] An emulsion composition containing a polyurethane resin (A), an acrylic resin (B), and an aqueous medium (C), wherein the elastic modulus of a film of the polyurethane resin (A) having a film thickness of 90 μm is 200 MPa or more, the acrylic resin (B) has a glass transition temperature of -15°C or lower, An emulsion composition in which the solid content ratio (A / B) of the polyurethane resin (A) and the acrylic resin (B) is 0.02 to 0.23. [2] The emulsion composition according to [1], wherein the polyurethane resin (A) has a structure derived from an acid group-free polyol (a), a structure derived from a polyisocyanate (b), and a structure derived from an acid group-containing polyol (c). [3] The emulsion composition according to [2], wherein the acid group-free polyol (a) is at least one selected from the group consisting of a polycarbonate polyol, a polyester polyol, and a polyether polyol. [4] The emulsion composition according to [3], wherein the polyurethane resin (A) further has a structure derived from a compound (d) (provided that it is not a polycarbonate polyol, a polyester polyol, a polyether polyol, or the acid group-containing polyol (c)) having a total of two or more groups selected from the group consisting of a hydroxyl group and an amino group. [5] The emulsion composition according to any one of [2] to [4], wherein the polyisocyanate (b) is an alicyclic polyisocyanate compound. [6] The emulsion composition according to any one of [1] to [5], wherein the total content ratio of the urethane bond and the urea bond in the polyurethane resin (A) is 10.0 to 25.0% by mass based on the solid content of the polyurethane resin (A). [7] The emulsion composition according to any one of [1] to [6], wherein the content ratio of the alicyclic structure in the polyurethane resin (A) is 15 to 50% by mass based on the solid content of the polyurethane resin (A). [8] The film having a film thickness of 90 μm of the polyurethane resin (A) is a film obtained by heating an emulsion of the polyurethane resin (A) at 60°C for 2 hours and then at 120°C for 2 hours. The emulsion composition according to any one of [1] to [7]. [9] The emulsion composition according to any one of [1] to [8], wherein the breaking point strength of the film having a film thickness of 90 μm of the emulsion composition is 5 MPa or more. The emulsion composition according to any one of [1] to [9], which is a binder for aqueous ink used in inkjet printing.

[11] A method for producing an emulsion composition according to any one of [1] to [9], the method including a step of producing an emulsion of a polyurethane resin (A), a step of producing an emulsion of an acrylic resin (B), and a step of mixing the emulsion of the polyurethane resin (A) and the emulsion of the acrylic resin (B).

[12] An aqueous ink containing the emulsion composition according to any one of [1] to [9].

[13] A laminate including a cured film of the emulsion composition according to any one of [1] to [9] and a substrate.

[14] A laminate including a cured film of the aqueous ink according to

[12] and a substrate.

[15] A film containing a polyurethane resin (A) and an acrylic resin (B), wherein an elastic modulus of a film having a film thickness of 90 μm of the polyurethane resin (A) is 200 MPa or more, the acrylic resin (B) has a glass transition temperature of -15°C or lower, and a content ratio (A / B) of the polyurethane resin (A) and the acrylic resin (B) is 0.02 to 0.23. [Advantages of the Invention]

[0010] According to the present invention, an emulsion composition excellent in soft feel property, tack-free property, and friction fastness is provided. [Modes for Carrying Out the Invention]

[0011] [Explanation of Terms] In the present specification, the "acidic group" means a carboxy group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and does not include hydroxyl groups other than the phenolic hydroxyl group.

[0012] In this specification, a numerical range indicated using "~" indicates a range that includes the numerical values described before and after "~" as the minimum value and the maximum value, respectively. Also, the amount of each component in the composition means the total amount of the plurality of substances corresponding to each component in the composition when there are a plurality of substances corresponding to each component in the composition, unless otherwise specified.

[0013] In this specification, the term "process" includes not only independent processes, but also, even if it cannot be clearly distinguished from other processes, it shall be included in this term if the intended purpose of the process is achieved. Hereinafter, the present invention will be described in detail.

[0014] [Emulsion Composition] The emulsion composition contains a polyurethane resin (A), an acrylic resin (B), and an aqueous medium (C). The elastic modulus of a film with a film thickness of 90 μm of the polyurethane resin (A) is 200 MPa or more. The acrylic resin (B) has a glass transition temperature of -15°C or lower. The solid content ratio (A / B) of the polyurethane resin (A) and the acrylic resin (B) is 0.02 to 0.23.

[0015] In the emulsion composition, the polyurethane resin (A) and the acrylic resin (B) are dispersed in the aqueous medium (C).

[0016] By using the emulsion composition as a binder for aqueous ink, the amount of solvent used in the ink can be reduced, so it can contribute to the achievement of SDGs (Sustainable Development Goals) such as Goal 7.

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

[0018] (acid group-free polyol (a)) As the acid group-free polyol (a), known ones can be used. For example, polymer polyols such as polycarbonate polyol, polyester polyol, polyether polyol, polyester polyether polyol, polyurethane polyol, polyester amide polyol, acrylic polyol (all having a hydroxyl group at the terminal), and low molecular weight polyols such as ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, trimethylolpropane, and glycerin can be used. Among them, from the viewpoint of improving rubbing fastness, it is preferably at least one selected from the group consisting of polycarbonate polyol, polyester polyol, and polyether polyol, and more preferably polycarbonate polyol. The acid group-free polyol (a) may be used alone or in combination of two or more.

[0019] The polycarbonate polyol can be obtained by reacting one or more polyol components with a carbonic acid ester or phosgene. From the viewpoints of easy production in terms of safety and handling of reagents, and no by-production of terminal chlorinated products, a polycarbonate polyol obtained by reacting one or more polyol monomers with a carbonic acid ester is preferred.

[0020] As the polyol monomers constituting the polycarbonate polyol, known ones can be used. For example, linear aliphatic diols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol; branched aliphatic diols such as 2-methyl-1,3-propanediol, 1,5-hexanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, neopentyl glycol and the like, that is, aliphatic polyols; polyhydric alcohols having three or more functional groups such as trimethylolpropane and pentaerythritol; alicyclic polyols such as diols having an alicyclic structure in the main chain, such as 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, 2,5-bis(hydroxymethyl)-1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis(hydroxyethoxy)cyclohexane; aromatic diols such as 1,4-benzenedimethanol, 1,3-benzenedimethanol, 1,2-benzenedimethanol, 4,4'-naphthalenedimethanol, 3,4'-naphthalenedimethanol; polyester polyols of hydroxycarboxylic acid and diol such as polyester polyol of 6-hydroxycaproic acid and hexanediol; polyester polyols of dicarboxylic acid and diol such as polyester polyol of adipic acid and hexanediol; polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol. Among them, from the viewpoint of improving rubbing fastness, alicyclic polyols and / or aliphatic polyols are preferred. As the alicyclic polyol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol are more preferred. As the aliphatic polyol, linear aliphatic diols are more preferred, and 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol are even more preferred.The polyol monomer may be used alone or in combination of two or more kinds.

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

[0022] As the polyester polyol, known ones can be used. For example, a polyester polyol obtained by subjecting a polyol (for example, a polyol having a molecular weight of 50 or more and 500 or less) and a polycarboxylic acid to an esterification reaction; a polyester polyol obtained by subjecting a cyclic ester compound such as ε-caprolactone to a ring-opening polymerization reaction; these copolymer polyester polyols and the like. Specifically, examples of the polyester polyol 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 a polycondensate of 1,6-hexanediol and dimer acid.

[0023] As the polyol, for example, the above polyol monomer and the like can be used. The low molecular weight polyol may be used alone or in combination of two or more kinds. Further, the polyether polyol described later may be used as the polyol.

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

[0025] As the polyether polyol, known ones can be used. For example, polyethylene glycol, poly(1,2-propylene glycol), poly(1,3-propylene glycol), poly(1,3-tetramethylene glycol), poly(1,4-tetramethylene glycol), poly(1,6-hexamethylene glycol), polyoxyethylene triol, polyoxypropylene triol, polyoxyethylene polyoxypropylene triol, random copolymers or block copolymers of ethylene oxide and propylene oxide, random copolymers or block copolymers of ethylene oxide and butylene oxide, random copolymers or block copolymers of propylene oxide and butylene oxide, etc. are mentioned. Poly(1,4-tetramethylene glycol) is preferable in terms of improving the soft feel property of the obtained coating film.

[0026] The polyester polyether polyol is obtained by reacting the polyester polyol and the polyether polyol.

[0027] The acid group-free polyol (a) preferably has a number average molecular weight (Mn) of 100 to 5,000. When Mn is 100 or more, the performance as a soft segment is good and cracks are less likely to occur in the printed matter. When Mn is 5,000 or less, there are no problems such as a decrease in the reactivity between the acid group-free polyol (a) and the polyisocyanate (b), which causes the production process of the urethane prepolymer to take time or the reaction not to proceed sufficiently, or the viscosity of the polycarbonate polyol to increase and handling to become difficult. In this specification, Mn is the hydroxyl value and 1It is a value calculated from the value calculated by 1H-NMR or the quantitative value of the polyol by gas chromatography after alkali hydrolysis.

[0028] The acid group-free polyol (a) preferably has a hydroxyl value of 20 to 1,200 mgKOH / g, more preferably 30 to 1,000 mgKOH / g. When the hydroxyl value is within the above range, it is preferable in terms of improving flexibility. In this specification, the hydroxyl value is the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl groups in 1 g of the sample, and can be measured by Method A of JIS K 1557.

[0029] (Polyisocyanate (b)) As the polyisocyanate (b), known ones can be used. For example, aromatic polyisocyanate compounds such as 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI); aliphatic polyisocyanate compounds such as ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI); alicyclic polyisocyanate compounds such as isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-dicyclohexene-1,2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate. Part or all of the structure of the polyisocyanate (b) may be derivatized such as isocyanuration, carbodiimidization, or biuretization.

[0030] Among the polyisocyanates (b), from the viewpoint of controlling reactivity and the like, it is preferably an aliphatic polyisocyanate compound and / or an alicyclic polyisocyanate compound, and from the viewpoint of improving rubbing fastness, it is more preferably an alicyclic polyisocyanate compound, and it is particularly preferably at least one selected from the group consisting of isophorone diisocyanate (IPDI), 4,4'-diphenylmethane diisocyanate (MDI), and 4,4'-dicyclohexylmethane diisocyanate (H12MDI). The polyisocyanate (b) may be used alone or in combination of two or more.

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

[0032] The blocking agent is a compound capable of reacting with the isocyanate group to convert the isocyanate group into another group, and means a compound capable of reversibly converting another group into the isocyanate group by heat treatment. The heat treatment temperature is not particularly limited, but 80 to 180 °C is preferable.

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

[0034] (Polyol (c) containing an acidic group) The polyol (c) containing an acidic group contains two or more hydroxyl groups and one or more acidic groups in one molecule. The polyol (c) containing an acidic group may be used alone or in combination of two or more kinds.

[0035] As the polyol (c) containing an acidic group, known ones can be used. For example, dimethylolalkanoic acids such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid; N,N-bishydroxyethylglycine, N,N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, etc. are mentioned. Among them, from the viewpoint of easy availability, dimethylolalkanoic acids having 4 to 12 carbon atoms containing two methylol groups are preferable, and among the dimethylolalkanoic acids, 2,2-dimethylolpropionic acid is more preferable.

[0036] (Compound (d) having a total of two or more groups selected from the group consisting of a hydroxyl group and an amino group (however, it is not the acidic group-free polyol (a) and the acidic group-containing polyol (c))) A compound (d) having in total two or more groups selected from the group consisting of a hydroxyl group and an amino group (provided that it is not the non-acidic-group-containing polyol (a) or the acidic-group-containing polyol (c)) (hereinafter also referred to as "compound (d)") is a component for increasing the molecular weight of the polyurethane resin (A). Compound (d) is a compound having reactivity with the isocyanato group of the polyurethane prepolymer which is a synthetic intermediate in the production of the polyurethane resin (A). A compound having reactivity with the isocyanato group of the polyurethane prepolymer which is a synthetic intermediate of the polyurethane resin (A) is called a chain extender, and compound (d) is a kind of chain extender. Here, water can be mentioned as another chain extender other than compound (d). Here, the "amino group" in compound (d) means a primary amino group or a secondary amino group.

[0037] Note that compound (d) can vary according to the range of the non-acidic-group-containing polyol (a). For example, when the non-acidic-group-containing polyol (a) is at least one selected from the group consisting of a polycarbonate polyol, a polyester polyol, and a polyether polyol, compound (d) is not a polycarbonate polyol, a polyester polyol, a polyether polyol, or the acidic-group-containing polyol (c).

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

[0039] Known compounds can be used as compound (d), and it may be used alone or in combination of two or more kinds.

[0040] Examples of the polyamine compound include diamine compounds having only primary amino groups such as hydrazine, ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylenediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis(aminomethyl)cyclohexane, 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.

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

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

[0043] Compound (d) 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.

[0044] The number average molecular weight (Mn) of compound (d) is preferably 300 or less. When the Mn of compound (d) is 300 or less, the cohesive force of the polyurethane resin (A) can be increased.

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

[0046] As the neutralizing agent (e), 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.

[0047] The boiling point of the neutralizing agent (e) is preferably 200°C or lower, and particularly preferably in the range of -50 to 180°C. When the boiling point of the neutralizing agent (e) is within the above range, when forming a resin film from the emulsion composition, it volatilizes at the temperature (usually 40 to 200°C) when drying the aqueous medium (C) and disappears from the printed matter, and more excellent adhesive strength can be obtained. When obtaining a printed matter at a low temperature of 100°C or lower for a short time of several seconds to 1 hour, the boiling point of the neutralizing agent (e) is preferably 130°C or lower, and particularly preferably 110°C or lower.

[0048] (Other compound (f)) Examples of other compound (f) include monoalcohol and monoamine. When other compound (f) is monoalcohol or monoamine, a polyurethane resin (A) with a non-reactive molecular end can be obtained. Examples of monoalcohol include ethanol, n-propanol, isopropanol, n-butanol, hexanol, octanol, etc. Examples of monoamine include ethylamine, n-propylamine, isopropylamine, n-butylamine, n-hexylamine, etc. Other compound (f) may be used alone or in combination of multiple types.

[0049] (Hydroxyl equivalent numbers of acid group-free polyol (a), acid group-containing polyol (c) and other compound (f)) In the polyurethane resin (A), the total number of hydroxyl equivalent moles of the non-acidic group-containing polyol (a), the acidic group-containing polyol (c), and the polyol contained in the other compound (f) is preferably 50 to 4,000. If the number of hydroxyl equivalent moles is within this range, it is easy to produce an emulsion of the polyurethane resin (A) containing the obtained polyurethane resin (A). From the viewpoint of the storage stability of the obtained emulsion of the polyurethane resin (A), the number of hydroxyl equivalent moles is preferably 100 to 3,500, more preferably 120 to 3,000, and particularly preferably 130 to 2,500.

[0050] The number of hydroxyl equivalent moles can be calculated by the following formulas (1) and (2). The number of hydroxyl equivalent moles of each polyol component = the molecular weight of each polyol component / the number of hydroxyl groups of each polyol component ··· (1) The total number of hydroxyl equivalent moles of the polyol components = M / the total number of moles of the polyol components ·· (2) In formula (2), M represents [〔the number of hydroxyl equivalent moles of the non-acidic group-containing polyol component × the number of moles of the non-acidic group-containing polyol component〕+〔the number of hydroxyl equivalent moles of the acidic group-containing polyol × the number of moles of the acidic group-containing polyol〕+〔the number of hydroxyl equivalent moles of the polyol contained in the other compound (f) × the number of moles of that polyol〕].

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

[0052] (Properties of the polyurethane resin (A)) ·Urethane bond and urea bond In the polyurethane resin (A), the total content ratio of the urethane bond and the urea bond is preferably 10.0 to 25.0% by mass, more preferably 10.0 to 22.0% by mass, and particularly preferably 12.0 to 20.0% by mass based on the solid content of the polyurethane resin (A).

[0053] By setting the total content ratio of the urethane bond and the urea bond to 10.0% by mass or more, it may be possible to reduce the stickiness on the surface of the printed matter. Also, by setting the content ratio of the urethane bond and the urea bond to 25.0% by mass or less, the adhesion of the ink to the substrate may be increased.

[0054] From the viewpoint of improving soft feel and tack-free property, the content ratio of the urethane bond in the polyurethane resin (A) is preferably 3.0 to 20.0% by mass, more preferably 4.0 to 15.0% by mass, still more preferably 5.0 to 14.0% by mass, and particularly preferably 6.0 to 13.0% by mass based on the solid content.

[0055] From the viewpoint of improving softness and tack - free property, the content ratio of urea bonds in the polyurethane resin (A) is preferably 3.0 to 10.0% by mass, more preferably 3.5 to 9.5% by mass, still more preferably 3.8 to 9.2% by mass, and particularly preferably 4.0 to 9.0% by mass on a solid - content basis.

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

[0057] Also, the content ratio of urethane bonds, urea bonds, etc. in the polyurethane resin (A) can be approximately calculated based on the charged amounts, the molecular weights of each raw material, and the molecular weights or molar numbers of the parts corresponding to each structure.

[0058] · Content ratio of alicyclic structure From the viewpoint of efficiently making the elastic modulus of the film with a film thickness of 90 μm of the polyurethane resin (A) 200 MPa or more, the content ratio of the alicyclic structure in the polyurethane resin (A) is preferably 10 to 50% by mass, and particularly preferably 15 to 50% by mass. In this specification, the content ratio of the alicyclic structure in the polyurethane resin (A) can be measured by 1H - NMR.

[0059] · Weight - average molecular weight The weight average molecular weight (Mw) of the polyurethane resin (A) is preferably from 100,000 to 10,000,000, more preferably from 200,000 to 5,000,000, and particularly preferably from 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 calibration curve of a pre-prepared standard polystyrene can be used. By setting the weight average molecular weight to 100,000 or more, there is a tendency to obtain a good printed matter. By setting the weight average molecular weight to 10,000,000 or less, there is a tendency to make the drying property of the ink higher.

[0060] The acid value of the polyurethane resin (A) is preferably from 5 to 40 mgKOH / g, more preferably from 8 to 35 mgKOH / g, and particularly preferably from 10 to 30 mgKOH / g. By setting the acid value of the polyurethane resin in the range of 5 to 40 mgKOH / g, the storage stability tends to be improved. The acid value can be measured in accordance with the indicator titration method of JIS K 1557. When the polyurethane resin (A) contains a structure derived from the neutralizing agent (e), in the measurement, the neutralizing agent (e) used to neutralize the acidic group is removed for measurement. For example, when organic amines are used as the neutralizing agent (e), an emulsion of the polyurethane resin (A) is applied on a glass plate, and the coating film obtained by drying at 60 °C under a reduced pressure of 20 mmHg for 24 hours is dissolved in N-methylpyrrolidone (NMP), and the acid value can be measured in accordance with the indicator titration method of JIS K 1557. The acid value of the polyurethane resin (A) can be controlled by the content ratio of the acid group-containing polyol (c).

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

[0062] The content ratio of the structure derived from the acid group-free polyol (a) is preferably 35 to 85% by mass, particularly preferably 40 to 80% by mass in the polyurethane resin (A).

[0063] The content ratio of the structure derived from the polyisocyanate (b) is preferably 10 to 60% by mass, particularly preferably 20 to 50% by mass in the polyurethane resin (A).

[0064] The content ratio of the structure derived from the acid group-containing polyol (c) is preferably 0.5 to 20% by mass, particularly preferably 1.0 to 10% by mass in the polyurethane resin (A).

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

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

[0067] Also, the content ratio of the structure derived from the compound (d) is preferably an amount such that it is equal to or less than the equivalent amount of the isocyanato group that serves as the chain extension starting point in the polyurethane prepolymer, which is an intermediate in the synthesis of the polyurethane resin (A), and particularly preferably an amount such that it is 0.70 to 0.99 equivalents of the isocyanato group in the polyurethane prepolymer. By adding the compound (d) in an amount equal to or less than the equivalent amount of the isocyanato group in the polyurethane prepolymer, there is a tendency to not lower the molecular weight of the chain-extended polyurethane resin (A) and to improve the solvent resistance.

[0068] When the polyurethane resin (A) has a structure derived from the neutralizing agent (e), the content ratio of the structure derived from the neutralizing agent (e) is preferably in the range of 0.8 to 1.2 times the number of moles of the acidic groups contained in the polyurethane resin (A). When the content ratio of the structure derived from the neutralizing agent (e) is 0.8 times or more the number of moles of the acidic groups, the stability of the polyurethane resin (A) in the emulsion is high, and when it is 1.2 times or less, a printed matter with high substrate adhesion can be obtained in a short time of several seconds to 1 hour under low-temperature drying at 100°C or lower. Incidentally, when the emulsion composition is applied to a substrate and then dried to cure the emulsion composition, a coating film (also called a cured product layer or cured film) of the emulsion composition is obtained. During drying, the neutralizing agent (e) may volatilize, and the structure derived from the neutralizing agent (e) may not be contained in the polyurethane resin (A) in the coating film.

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

[0070] <Method for Producing Polyurethane Resin (A)> The polyurethane resin (A) can be obtained by any method within the range where the desired polyurethane resin (A) can be obtained. For example, the polyurethane resin (A) can be obtained by a production method including a step of reacting an acid group-free polyol (a) and a polyisocyanate (b). Further, the polyurethane resin (A) is preferably a polyurethane resin (A) obtained by the following method for producing an emulsion of the polyurethane resin (A).

[0071] (Emulsion of polyurethane resin (A)) The emulsion (aqueous dispersion) of the polyurethane resin (A) is one in which the polyurethane resin (A) is dispersed in an aqueous medium (C). The content ratio (solid content) of the polyurethane resin (A) in the emulsion of the polyurethane resin (A) is preferably 5 to 60% by mass, and particularly preferably 20 to 50% by mass. Here, the content ratio of the polyurethane resin (A) in the emulsion of the polyurethane resin (A) means the content ratio of the polyurethane resin (A) with respect to the total amount of the emulsion containing the polyurethane resin (A), the aqueous medium (C), and an additive which is an optional component. In the emulsion of the polyurethane resin (A), the amount of the hydrophilic organic solvent in the aqueous medium (C) is preferably 0 to 20% by mass. The pH of the emulsion of the polyurethane resin (A) is preferably 5.0 to 9.0.

[0072] (Method for producing emulsion of polyurethane resin (A)) The method for producing the emulsion of the polyurethane resin (A) preferably includes the following steps. (I) A step of reacting the acid group-free polyol (a), the polyisocyanate (b), the acid group-containing polyol (c), and optionally another compound (f) in the presence of an organic solvent to obtain a polyurethane prepolymer. (II) A step of mixing the polyurethane prepolymer with water, and (III) A step of reacting the polyurethane prepolymer with a compound (d) or another chain extender.

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

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

[0075] The emulsion of the polyurethane resin (A) can be produced by a known method described in known literature (for example, International Publication No. 2016 / 039396, International Publication No. 2016 / 163394, etc.).

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

[0077] When the polyurethane prepolymer is selected within the range where the content ratio of the free isocyanato group is 0.5 to 5.0% by mass based on the solid content of the polyurethane prepolymer, it is preferable in terms of good dispersibility in water.

[0078] The acid value (AV) of the polyurethane prepolymer is preferably from 4 to 40 mg KOH / g, more preferably from 6 to 38 mg KOH / g, and particularly preferably from 8 to 35 mg KOH / g. By setting the acid value of the polyurethane prepolymer to 4 mg KOH / g or more, the dispersibility in an aqueous medium and the storage stability tend to be improved. Further, by setting the acid value of the polyurethane prepolymer to 40 mg KOH / g or less, the flexibility of the printed matter tends to be increased. Also, the drying property during ink drying tends to be improved.

[0079] Note that the "acid value of the polyurethane prepolymer" is the acid value of the so-called solid content excluding the solvent used in producing the polyurethane prepolymer and the neutralizing agent for dispersing the polyurethane prepolymer in an aqueous medium.

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

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

[0082] Thus, the acid value of the polyurethane prepolymer is adjusted by the content ratio of the acid group-containing polyol (c) in all the polyols forming the polyurethane prepolymer.

[0083] Step (III) of reacting the polyurethane prepolymer with compound (d) or other chain extender is a step of bonding polyurethane prepolymers together and adjusting the molecular weight of the polyurethane resin to the target range. In step (I), when 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 compound (d) used in step (III) is not polycarbonate polyol, polyester polyol, polyether polyol, or acid group-containing polyol (c).

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

[0085] <Film with a film thickness of 90 μm of polyurethane resin (A)> The elastic modulus of a film with a film thickness of 90 μm of polyurethane resin (A) (hereinafter, also referred to as "the film of polyurethane resin (A)") (hereinafter, also referred to as "the elastic modulus of polyurethane resin (A)") is 200 MPa or more and 1,500 MPa or less. From the viewpoint of further improving the friction fastness, the elastic modulus of polyurethane resin (A) is preferably 230 MPa or more, and particularly preferably 250 MPa or more. From the viewpoint of further improving the soft feel property, the elastic modulus of polyurethane resin (A) is preferably 1,400 MPa or less, and particularly preferably 1,300 MPa or less. In this specification, the elastic modulus of polyurethane resin (A) is measured by the tensile test defined in JIS K7311. The elastic modulus of polyurethane resin (A) can be adjusted by making the content ratio of the alicyclic structure in polyurethane resin (A) within the above-mentioned range, making the total content ratio of urethane bonds and urea bonds within the above-mentioned range, and the like.

[0086] The film of the polyurethane resin (A) is a film composed only of the polyurethane resin (A), or a film containing only the polyurethane resin (A) and one or more components selected from the group consisting of a wetting agent, a film-forming aid, and a polymerization initiator as optional components. Here, the wetting agent, the film-forming aid, and the polymerization initiator are as described below as other additives. Therefore, the film of the polyurethane resin (A) is different from the film containing the polyurethane resin (A) and the acrylic resin (B) described below in that it does not contain the acrylic resin (B).

[0087] The method for producing the film of the polyurethane resin (A) is not particularly limited. Examples of the method for producing the film of the polyurethane resin (A) include a step of applying the polyurethane resin (A) or a composition containing the polyurethane resin (A) to a substrate to obtain a substrate coated with the polyurethane resin (A) or the composition containing the polyurethane resin (A), a step of drying the substrate coated with the polyurethane resin (A) or the composition containing the polyurethane resin (A) to obtain a coating film of the polyurethane resin (A), and a step of separating the coating film of the polyurethane resin (A) from the substrate to obtain a film of the polyurethane resin (A).

[0088] The drying conditions for producing the film are not particularly limited. For example, a method of heating the substrate coated with the polyurethane resin (A) or the composition containing the polyurethane resin (A) at 60°C for 2 hours and then at 120°C for 2 hours can be mentioned. In this case, the temperature conditions are to raise the temperature from room temperature (25°C) to 60°C in 20 minutes, hold at 60°C for 2 hours, raise the temperature from 60°C to 120°C in 20 minutes, hold at 120°C for 2 hours, and lower the temperature from 120°C to room temperature in 40 minutes. The film for measuring the elastic modulus of the polyurethane resin (A) is preferably a film obtained by heating an emulsion of the polyurethane resin (A) at 60°C for 2 hours and then at 120°C for 2 hours.

[0089] As a method for applying the polyurethane resin (A) or a composition containing the polyurethane resin (A), for example, dipping method, roll coating method, reverse roll coating method, gravure roll coating method, screen coating method, spray coating method, knife coating method, air knife coating method, bar coating method, spin coating method and the like can be mentioned.

[0090] In the method for producing a film of the polyurethane resin (A), the substrate is not particularly limited. The substrate may be an inorganic substrate such as glass or an elastomer substrate.

[0091] <Acrylic resin (B)> The acrylic resin (B) is a compound having a polymerization unit derived from one or more kinds of “(meth)acryloyl group”-containing “(meth)acrylic monomers” in the molecule. The “(meth)acryloyl group” means at least one of “methacryloyl group” and “acryloyl group”. The “(meth)acrylic monomer” means at least one of “methacrylic monomer” and “acrylic monomer”. The acrylic resin (B) preferably contains a polymer composed of repeating units containing at least one selected from the group consisting of acrylic esters, methacrylic esters, acrylic acid and methacrylic acid. Specific examples of the acrylic resin include styrene·(meth)acrylate copolymer, (meth)acrylate copolymer, (meth)acrylate·(meth)acrylic acid copolymer, vinyl acetate copolymer, ethylene·vinyl acetate copolymer and the like. From the viewpoint of high soft feel, the acrylic resin is preferably a styrene·(meth)acrylate copolymer. In addition, the “(meth)acrylate ester” in the acrylic resin may exist as a combination of an acrylic ester, a methacrylic ester, and an acrylic ester and a methacrylic ester. The acrylic resin is usually obtained by polymerizing one or more (meth)acrylic monomers. Here, the (meth)acrylic monomer is arbitrary as long as it is a monomer constituting the above copolymer, and can be appropriately used from components known to those skilled in the art.

[0092] The Tg (glass transition temperature) of the acrylic resin (B) is -15°C or lower. When the Tg of the acrylic resin is -15°C or lower, the soft feel property of the emulsion composition is improved. The Tg is preferably -65°C to -15°C, more preferably -50°C to -17°C, and particularly preferably -30°C to -17°C.

[0093] The MFT (minimum film-forming temperature) of the acrylic resin (B) is not particularly limited, but is preferably -40°C or higher and 40°C or lower. When the MFT of the acrylic resin (B) is -40°C or higher, the rubbing fastness is improved. When the MFT of the acrylic resin (B) is 40°C or lower, the soft feel property is improved. Further, the MFT is preferably -35°C or higher, more preferably -30°C or higher. Also, the MFT is preferably 35°C or lower, more preferably 30°C or lower. Note that the MFT (minimum film-forming temperature) indicates the lowest temperature at which a continuous film can be formed, and can be measured, for example, by the method based on JIS K6828-2, the method described in ISO standard 2115, etc.

[0094] Commercially available products can be used as the acrylic resin (B). Also, as the acrylic resin, the acrylic resin contained in the emulsion of the acrylic resin (B) can be used.

[0095] (Emulsion of acrylic resin (B)) The emulsion of the acrylic resin (B) is one in which the acrylic resin (B) is dispersed in the aqueous medium (C). From the viewpoint of the dispersibility of the acrylic resin (B) in the emulsion, the content ratio (solid content) of the acrylic resin (B) in the emulsion of the acrylic resin (B) is preferably 30 to 70% by mass, and particularly preferably 40 to 65% by mass. Here, the content ratio of the acrylic resin (B) in the emulsion of the acrylic resin (B) means the content ratio of the acrylic resin (B) with respect to the total amount of the emulsion containing the acrylic resin (B), the aqueous medium (C), and the additive which is an optional component.

[0096] As the emulsion of the acrylic resin (B), commercially available products can be used. Examples of commercially available products of the emulsion of the acrylic resin (B) include the following. Note that the Tg and MFT in parentheses are the Tg and MFT of the acrylic resin (B) contained in the emulsion of the acrylic resin (B). Manufactured by Takasago Kogyo Co., Ltd.: Pegarl 718 (Tg: -64°C, MFT: 0°C), 781 (Tg: -20°C, MFT: 0°C), 783 (Tg: -20°C, MFT: 2°C), 804 (Tg: -20°C), 806 (Tg: -35°C, MFT: 0°C), 809 (Tg: -16°C, MFT: 0°C), 852 (Tg: -28°C, MFT: 0°C), 860 (Tg: -18°C, MFT: 0°C), 892 (Tg: -45°C, MFT: 0°C); Manufactured by Nippon Carbide Industries Co., Ltd.: Nikazol FX-2555A (Tg: -17°C), FX-3750 (Tg: -33°C), FX-2138Y (Tg: -17°C); Manufactured by Parachem Japan Co., Ltd.: Parabond G-60 (Tg: -30°C).

[0097] The acrylic resin (B) may be used alone or in combination of two or more kinds.

[0098] <aqueous medium (C)> The aqueous medium (C) is water or a mixed medium of water and a hydrophilic organic solvent. Examples of water include tap water, ion-exchanged water, distilled water, ultrapure water, etc. Examples of the hydrophilic organic solvent include ketones such as acetone and ethyl methyl 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 such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and propylene glycol monoethyl ether; amides such as β-alkoxypropionamide represented by "KJCMPA(R)-100" manufactured by KJ Chemical Co., Ltd.; and hydroxyl group-containing tertiary amines such as 2-(dimethylamino)-2-methyl-1-propanol (DMAP). The aqueous medium (C) may be used alone or in combination of two or more kinds thereof.

[0099] <Additional Component> The emulsion composition may contain other resins and / or other additives as necessary.

[0100] Examples of the other resins include polyester resins, acrylic resins other than the acrylic resin (B), polyether resins, polycarbonate resins, polyurethane resins other than the polyurethane resin (A), epoxy resins, alkyd resins, polyolefin resins, vinyl chloride resins, etc. The other resins may be used alone or in combination of two or more kinds thereof.

[0101] The polyester resin can usually be produced by an esterification reaction or a transesterification reaction between an acid component and an alcohol component. As the acid component, a compound usually used as an acid component in the production of polyester resins can be used. Examples of the acid component include aliphatic polybasic acids, alicyclic polybasic acids, aromatic polybasic acids, etc.

[0102] Examples of acrylic resins other than the acrylic resin (B) include acrylic resins having a Tg exceeding -15°C.

[0103] Examples of the polyether resin include polymers or copolymers having an ether bond, such as polyoxyethylene-based polyethers, polyoxypropylene-based polyethers, polyoxybutylene-based polyethers, and polyethers derived from aromatic polyhydroxy compounds such as bisphenol A or bisphenol F.

[0104] Examples of the polycarbonate resin include polymers produced from bisphenol compounds, such as bisphenol A polycarbonate.

[0105] Examples of the polyurethane resin other than the polyurethane resin (A) include polyurethane resins in which the elastic modulus of a film with a thickness of 90 μm is less than 200 MPa.

[0106] Examples of the epoxy resin include resins obtained by reacting bisphenol compounds with epichlorohydrin. Examples of the bisphenol compounds include bisphenol A and bisphenol F.

[0107] Examples of the alkyd resin include alkyd resins 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 of oils and fats (such as soybean oil, linseed oil, coconut oil, and stearic acid), and natural resins (such as rosin and copal).

[0108] Examples of the polyolefin resin include polyolefin resins obtained by polymerizing or copolymerizing olefin monomers with other monomers as appropriate according to a normal polymerization method, and then dispersing them in water using an emulsifier, or resins obtained by emulsion polymerization of olefin monomers with other monomers as appropriate. In some cases, a so-called chlorinated polyolefin modified resin obtained by chlorinating the above polyolefin resin may also be used.

[0109] 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, 1-dodecene, etc.; conjugated dienes or non-conjugated dienes such as butadiene, ethylidene norbornene, dicyclopentadiene, 1,5-hexadiene, etc. These monomers may be used alone or in combination of two or more.

[0110] Examples of other monomers copolymerizable with olefin monomers include styrene, vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride. These monomers may be used alone or in combination of two or more.

[0111] Examples of the other additives include curing agents, wetting agents, surface conditioners, surfactants, emulsifiers, thickeners, urethanization catalysts, fillers, foaming agents, oil repellents, pigments, dyes, film-forming aids, hollow foams, flame retardants, defoamers, leveling agents, anti-blocking agents, ultraviolet absorbers, light stabilizers, plasticizers, anti-settling agents, polymerization initiators, polymerization inhibitors, dispersants, penetration promoters, moisturizers, fixing agents, preservatives, antioxidants, fungicides, chelating agents, sensitizers, pH adjusters, etc. These additives may be used alone or in combination of two or more.

[0112] Known curing agents can be used. For example, polyisocyanate compounds, polycarbodiimide compounds, amino resins, epoxy group-containing compounds, aziridine compounds, etc. can be mentioned.

[0113] As the wetting agent, known ones can be used. For example, anionic surfactants such as sulfates of higher alcohols, salts of sulfates of higher alcohols, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates; nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, oxyethylene-oxypropylene block polymers; silicone-based surfactants, etc. can be mentioned.

[0114] The film-forming aid is generally a hydrophilic compound having an action of promoting film formation. Examples of the film-forming aid include pyrrolidone-based compounds such as N-methylpyrrolidone, N-ethylpyrrolidone, N-propylpyrrolidone, N-isopropylpyrrolidone, N-butylpyrrolidone, N-cyclohexylpyrrolidone, N-octylpyrrolidone, N-phenylpyrrolidone, vinylpyrrolidone; alcohol-based compounds such as methanol, ethanol, isopropanol, n-butanol, n-hexanol; glycol-based compounds such as propylene glycol, diethylene glycol, propylene glycol, triethylene glycol, polyethylene glycol, etc. Among them, pyrrolidone-based compounds are preferred. The film-forming aid can also serve as an aqueous medium in which the polyurethane resin is dispersed.

[0115] As the polymerization initiator, known ones can be used. For example, persulfates such as ammonium persulfate, potassium persulfate, sodium persulfate; azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile); peroxides such as hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, lauroyl peroxide, etc. can be mentioned.

[0116] (Composition of the emulsion composition) In the emulsion composition, the solid content ratio (A / B) of the polyurethane resin (A) and the acrylic resin (B) is 0.02 to 0.23. When the solid content ratio is within this range, the soft feel, tack-free property, and rubbing fastness of the emulsion composition are improved. The solid content ratio is particularly preferably 0.04 to 0.20. The solid content ratio (A / B) of the polyurethane resin (A) and the acrylic resin (B) indicates the ratio of the mass of the solid content of the polyurethane resin (A) to the mass of the solid content of the acrylic resin (B).

[0117] In the emulsion composition, the total content ratio (solid content) of the polyurethane resin (A) and the acrylic resin (B) is preferably 5 to 70% by mass, and particularly preferably 10 to 60% by mass.

[0118] In the emulsion composition, the content ratio of the aqueous medium (C) is preferably 10 to 90% by mass, and particularly preferably 20 to 70% by mass. In the emulsion composition, the content ratio of the hydrophilic organic solvent in the aqueous medium (C) is preferably 0 to 20% by mass. In the emulsion composition, the total content ratio of the polyurethane resin (A), the acrylic resin (B), and the aqueous medium (C) is preferably 20 to 100% by mass, and particularly preferably 30 to 99% by mass. The remainder is the content ratio of other resins and other additives. The pH of the emulsion composition is preferably 5.0 to 9.0.

[0119] <Method for producing emulsion composition> The method for producing the emulsion composition is not particularly limited as long as it can disperse the polyurethane resin (A) and the acrylic resin (B) in the aqueous medium (C). The method for producing the emulsion composition preferably includes a step of producing an emulsion of the polyurethane resin (A), a step of producing an emulsion of the acrylic resin (B), and a step of mixing the emulsion of the polyurethane resin (A) and the emulsion of the acrylic resin (B). Further, the emulsion composition may be produced, for example, by dispersing a polyurethane prepolymer and the acrylic resin (B) in the aqueous medium (C) and reacting the polyurethane prepolymer with the compound (d) in the presence of the acrylic resin (B). Further, the emulsion composition may be produced, for example, by mixing the polyurethane resin (A), the (meth)acrylic monomer, and the aqueous medium (C) and then polymerizing the (meth)acrylic monomer by a polymerization initiator, light, or a combination thereof to form the acrylic resin (B). In the method for producing the emulsion composition, the additive may be added in any step. Further, the method for producing the emulsion composition may include a step of adding an additive after the step of mixing the emulsion of the polyurethane resin (A) and the emulsion of the acrylic resin (B).

[0120] The method for producing the emulsion of the acrylic resin (B) is not particularly limited as long as it can obtain an emulsion of the acrylic resin (B) in which the acrylic resin (B) is dispersed in the aqueous medium (C), and it can be produced by a known method. Further, as the emulsion of the acrylic resin (B), the commercially available products described above for the acrylic resin (B) can be used.

[0121] <Film with a film thickness of 90 μm of the emulsion composition> The film with a film thickness of 90 μm of the emulsion composition (hereinafter also referred to as "the film of the emulsion composition") is a film with a film thickness of 90 μm produced from the emulsion composition. The breaking point strength of the film of the emulsion composition (hereinafter also referred to as "the breaking point strength of the emulsion composition") is preferably 5 MPa or more. From the viewpoint of further improving the friction fastness, the breaking point strength of the emulsion composition is preferably 8 MPa or more, and particularly preferably 10 MPa or more. Further, the elongation at break of the film of the emulsion composition (hereinafter also referred to as "the elongation at break of the emulsion composition") is preferably 800% or more. From the viewpoint of further improving the soft feel property, the elongation at break of the emulsion composition is preferably 850% or more, and particularly preferably 900% or more. In this specification, the breaking point strength and the elongation at break of the emulsion composition are measured by the tensile test defined in JIS K7311. The breaking point strength and the elongation at break of the emulsion composition can be adjusted by making the content ratio of the alicyclic structure in the polyurethane resin (A) within the above-mentioned range, making the total content ratio of the urethane bond and the urea bond within the above-mentioned range, and the like.

[0122] The method for producing the film of the emulsion composition is not particularly limited. Examples of the method for producing the film of the emulsion composition include a step of applying the emulsion composition to a substrate to obtain a substrate coated with the emulsion composition, a step of drying the substrate coated with the emulsion composition to obtain a coating film of the emulsion composition, and a step of separating the coating film of the emulsion composition from the substrate to obtain a film of the emulsion composition.

[0123] The drying conditions when producing the film are not particularly limited. For example, there is a method of heating the substrate coated with the emulsion composition at 60 °C for 2 hours and then at 120 °C for 2 hours. In this case, the temperature conditions are as follows: the temperature is raised from room temperature (25 °C) to 60 °C in 20 minutes, held at 60 °C for 2 hours, raised from 60 °C to 120 °C in 20 minutes, held at 120 °C for 2 hours, and then lowered from 120 °C to room temperature in 40 minutes.

[0124] The coating method of the emulsion composition and the substrate are not particularly limited, and are as described above in the case of the polyurethane resin film.

[0125] <Use of the emulsion composition> The emulsion composition can be used as a raw material for paints, inks, adhesives, coating agents, and surface treatment agents for various substrates. Further, the emulsion composition can be used to form a cured product layer (cured film of the emulsion composition) using the emulsion composition on various substrates.

[0126] The emulsion composition is preferably a binder for aqueous ink, and particularly preferably a binder for aqueous ink used in inkjet printing. Here, the binder for aqueous ink is a component added to aqueous ink to impart adhesiveness between pigments.

[0127] <Aqueous ink> The aqueous ink contains the emulsion composition. Specifically, the aqueous ink contains the emulsion composition and a pigment.

[0128] As the pigment, an inorganic pigment or an organic pigment can be used. These may be used alone or in combination of multiple types. Further, mixed crystals may be used.

[0129] As the pigment, for example, black pigment, yellow pigment, magenta pigment, cyan pigment, white pigment, green pigment, orange pigment, metallic pigments such as gold and silver, and metallic pigments can be used.

[0130] As the inorganic pigment, for example, titanium oxide, iron oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, cadmium red, chrome yellow, and carbon black produced by known methods such as the contact method, furnace method, and thermal method can be used.

[0131] 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, quinophthalone pigments, etc., dye chelates, nitro pigments, nitroso pigments, azo pigments, aniline black, resin hollow particles, inorganic hollow particles, and the like.

[0132] In order to obtain an ink by dispersing a pigment, methods such as introducing a hydrophilic functional group into the pigment to make a self-dispersing pigment, coating the surface of the pigment with a resin for dispersion, and using a dispersant for dispersion can be mentioned.

[0133] In the aqueous ink, the content ratios of the pigment and the emulsion composition are not particularly limited and can be appropriately selected according to the purpose. The content ratio of the aqueous medium (C) in the aqueous ink is not particularly limited and can be appropriately selected according to the purpose. However, from the viewpoint of the drying property of the ink, it is preferably 10% by mass or more and 90% by mass or less, and more preferably 20% by mass or more and 80% by mass or less.

[0134] The viscosity of the ink at 25°C is preferably 2.0 cP to 8.5 cP, and more preferably 3.0 to 7.5 cP from the viewpoint of workability. The viscosity can be measured, for example, using a B-type viscometer LVDV2T (manufactured by BROOKFIELD). As the measurement conditions, it can be measured at 25°C, a rotation speed of 30 rpm, and for 5 minutes.

[0135] <Method for producing aqueous ink> The method for producing the aqueous ink is not particularly limited, and known production methods can be used. Generally, the method for producing the aqueous ink includes a step of mixing the emulsion composition and the above-described pigment. In addition, in order to adjust the viscosity of the ink according to the application method, the method for producing the ink may further include a step of adding the aqueous medium (C) and / or other components contained in the emulsion composition.

[0136] <Method for using aqueous ink> As methods for applying the aqueous ink, for example, bell coating, spray coating, roll coating, shower coating, dip coating, inkjet printing, flexographic printing, thermal transfer printing, gravure printing, reverse offset printing, sheet-fed screen printing, rotary screen printing, air spray coating method, electrostatic coating, etc. can be mentioned, and inkjet printing is preferred.

[0137] As the pass method in inkjet printing, either a single pass method in which ink is ejected only once onto the substrate or a serial method in which a short shuttle head is reciprocally scanned in a direction perpendicular to the conveyance direction of the substrate while ejecting can be adopted. However, in the case of the serial method, it is necessary to adjust the ejection timing in consideration of the movement of the inkjet head, and deviation of the landing position is likely to occur. Therefore, the pass method in the inkjet printing using the aqueous ink of the present invention is preferably the single pass method.

[0138] There is also no particular limitation on the method of ejecting the aqueous ink, and known methods such as a drop-on-demand method (pressure pulse method) that utilizes the vibration pressure of a piezo element and a thermal inkjet method that heats the aqueous ink to form bubbles and utilizes the generated pressure can be used.

[0139] The droplet volume of the aqueous ink ejected from the inkjet head is preferably 0.2 to 30 pL, more preferably 1 to 20 pL, from the viewpoint of a large effect of reducing the drying load and improving color reproducibility and image quality.

[0140] <Substrate> Examples of the substrate on which the aqueous ink is applied include building materials such as wallpaper, floor materials, and tiles, clothing fabrics such as T-shirts, textiles, leather, metal, plastic, inorganic substances, and wood.

[0141] <Printed matter obtained using aqueous ink> The printed matter (dyed matter) obtained using the aqueous ink can be manufactured by applying the aqueous ink to a substrate. Note that the printed matter can be the second laminate described later.

[0142] <The first laminate> When the emulsion composition is used to form a cured film of the emulsion composition on various substrates, a laminate (hereinafter, also referred to as "the first laminate") is obtained. The first laminate includes the cured film of the emulsion composition described above and a substrate. The cured film of the emulsion composition is a resin film adhered to the substrate, and may also be referred to as a coating film of the emulsion composition, a dried film of the emulsion composition, a coating layer of the emulsion composition, etc.

[0143] The method for producing the cured film of the emulsion composition is not particularly limited, and examples thereof include a method including a step of applying the emulsion composition onto a substrate and a step of drying the emulsion composition to form a cured film of the emulsion composition. The substrate and the method for applying the emulsion composition are not particularly limited, and the methods described above can be mentioned as the method for applying the aqueous ink onto the substrate.

[0144] The coating thickness of the emulsion composition is not particularly limited, and it is preferably a thickness such that it becomes the thickness of the cured product layer of the emulsion composition described later.

[0145] After applying the emulsion composition onto the substrate and drying it to cure the emulsion composition, a coating film (cured product layer) of the emulsion composition is obtained. In order to improve the adhesion to the substrate, after applying the emulsion composition onto the substrate, it may be dried by means such as heating to cure the emulsion composition. Examples of the heating method include a heating method using its own reaction heat and a heating method using a combination of the reaction heat and active heating of the mold. Active heating of the mold includes a method of heating the entire mold in a hot air oven, an electric furnace, or an infrared induction heating furnace.

[0146] The heating temperature is preferably 10 to 200 °C, more preferably 60 to 160 °C. By heating at such a temperature, drying can be performed more efficiently.

[0147] The heating time is preferably from 0.0001 to 20 hours, more preferably from 1 to 10 hours. By setting the heating time in this way, a laminate having a cured product layer with higher hardness can be obtained. The thickness of the cured product layer of the emulsion composition is not particularly limited, but is preferably from 0.1 to 100 μm, and particularly preferably from 1 to 90 μm.

[0148] <Second laminate> The second laminate includes the cured film of the aqueous ink described above and a substrate. That is, in the first laminate, the cured film of the emulsion composition may further contain the pigment described above with the aqueous ink. In the second laminate, the substrate, the cured film of the aqueous ink, the production method, etc. are as described above for the aqueous ink and the cured film of the emulsion composition in the first laminate.

[0149] <Film containing polyurethane resin (A) and acrylic resin (B)> The film containing polyurethane resin (A) and acrylic resin (B) has an elastic modulus of 200 MPa or more for a film with a film thickness of 90 μm of the polyurethane resin (A), the acrylic resin (B) has a glass transition temperature of -15°C or lower, and the content ratio (A / B) of the polyurethane resin (A) and the acrylic resin (B) is from 0.02 to 0.23. The content ratio (A / B) of the polyurethane resin (A) and the acrylic resin (B) is the value obtained by dividing the mass of the solid content of the polyurethane resin (A) by the mass of the solid content of the acrylic resin (B), and represents the ratio of the mass of the solid content of the polyurethane resin (A) to the mass of the solid content of the acrylic resin (B). In the film, the polyurethane resin (A), the acrylic resin (B), and the elastic modulus of the film with a film thickness of 90 μm of the polyurethane resin (A) are as described above. Further, as the production method of the film, the method described above can be mentioned as the production method of the cured film of the emulsion composition in the first laminate. The uses of the film include release films; packaging of foods, fibers, sundries, etc.; decoration, protection, advertising, etc. of the surface of the base material.

Example

[0150] Next, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited thereto.

[0151] [Production Example 1] Emulsion of polyurethane resin (U1) Polycarbonate polyol (product name "UM90(1 / 3)", manufactured by UBE Industries, Ltd.; number average molecular weight 900; hydroxyl value 125 mgKOH / g; a reaction product of a polyol mixture of 1,4-cyclohexanedimethanol:1,6-hexanediol = 1:3 molar ratio and dimethyl carbonate, 190 g), 2,2-dimethylolpropionic acid (DMPA, 27.8 g), and dicyclohexylmethane 4,4'-diisocyanate (H12MDI, 181 g) were heated in dipropylene glycol dimethyl ether (DMM, 138 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80 to 95 °C for 5 hours. The reaction mixture was cooled to 80 °C, and 330 g of the mixture obtained by adding and mixing triethylamine (21.0 g) thereto was added to water (465 g) under strong stirring. Then, an aqueous solution of 35 mass% 2-methyl-1,5-pentanediamine (MPMD, 53.4 g) was added to obtain an emulsion of polyurethane resin (U1). The solid content was 30 mass%. Also, the elastic modulus of the film with a film thickness of 90 μm was 640 MPa.

[0152] [Production Example 2] Emulsion of polyurethane resin (U2) Polycarbonate polyol (product name "UM90(3 / 1)", manufactured by UBE Industries, Ltd.; number average molecular weight 900; hydroxyl value 125 mgKOH / g; a reaction product of a polyol mixture of 1,4-cyclohexanedimethanol:1,6-hexanediol = 3:1 molar ratio and dimethyl carbonate, 190 g), 2,2-dimethylolpropionic acid (DMPA, 27.8 g), and dicyclohexylmethane 4,4'-diisocyanate (H12MDI, 181 g) were heated at 80 to 95 °C for 5 hours in dipropylene glycol dimethyl ether (DMM, 138 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere. The reaction mixture was cooled to 80 °C, and 330 g of the mixture obtained by adding and mixing triethylamine (21.0 g) thereto was added to water (465 g) with strong stirring. Subsequently, an aqueous solution of 35 mass% 2-methyl-1,5-pentanediamine (MPMD, 53.4 g) was added to obtain an emulsion (U2) of a polyurethane resin. The solid content was 30 mass%. Also, the elastic modulus of a film with a thickness of 90 μm was 1200 MPa.

[0153] [Production Example 3] Emulsion (U3) of polyurethane resin Polycarbonate polyol (product name "UM180(1 / 3)", manufactured by UBE Industries, Ltd.; number average molecular weight 1,800; hydroxyl value 62 mgKOH / g; a reaction product of a polyol mixture of 1,4-cyclohexanedimethanol:1,6-hexanediol = 1:3 molar ratio and dimethyl carbonate, 250 g), 2,2-dimethylolpropionic acid (DMPA, 17.9 g), and isophorone diisocyanate (IPDI, 90.8 g) were heated in dipropylene glycol dimethyl ether (DMM, 124 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80 - 95 °C for 5 hours. The reaction mixture was cooled to 80 °C, and 330 g of the mixture obtained by adding and mixing triethylamine (13.6 g) thereto was added to water (470 g) with strong stirring. Subsequently, a 35 mass% aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 30.0 g) was added to obtain an emulsion (U3) of a polyurethane resin. The solid content was 30 mass%. Also, the elastic modulus of a film with a thickness of 90 μm was 280 MPa.

[0154] [Production Example 4] Emulsion (U4) of polyurethane resin Polycarbonate polyol (product name "UH100", manufactured by UBE Industries, Ltd.; number average molecular weight 1,000; hydroxyl value 112 mgKOH / g; a reaction product of 1,6-hexanediol and dimethyl carbonate, 180 g), 2,2-dimethylolpropionic acid (DMPA, 24.0 g), and dicyclohexylmethane 4,4'-diisocyanate (H12MDI, 155 g) were heated in dipropylene glycol dimethyl ether (DMM, 125 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80 - 95 °C for 5 hours. The reaction mixture was cooled to 80 °C, and 330 g of the mixture obtained by adding and mixing triethylamine (18.2 g) thereto was added to water (465 g) with strong stirring. Subsequently, a 35 mass% aqueous solution of 2-methyl-1,5-pentanediamine (MPMD, 50.9 g) was added to obtain an emulsion (U4) of a polyurethane resin. The solid content was 30 mass%. Also, the elastic modulus of a film with a thickness of 90 μm was 530 MPa.

[0155] [Production Example 5] Emulsion of polyurethane resin (U5) A polyester polyol (product name "HS 2F-136P", manufactured by Toyo Kosan Co., Ltd.; number average molecular weight 1,000; hydroxyl value 112 mgKOH / g; reaction product of neopentyl glycol and terephthalic acid, 102 g), a polyether polyol (product name "PTMG2000", manufactured by Mitsubishi Chemical Corporation; number average molecular weight 2,000; hydroxyl value 57 mgKOH / g; polytetramethylene ether glycol, 68.0 g), 2,2-dimethylolpropionic acid (DMPA, 24.6 g), and dicyclohexylmethane 4,4'-diisocyanate (H12MDI, 155 g) were heated at 80 to 95 °C for 5 hours in dipropylene glycol dimethyl ether (DMM, 122 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere. The reaction mixture was cooled to 80 °C, and 330 g of the mixture obtained by adding and mixing triethylamine (18.7 g) thereto was added to water (465 g) with strong stirring. Subsequently, an aqueous solution of 35 mass% 2-methyl-1,5-pentanediamine (MPMD, 60.7 g) was added to obtain an emulsion of polyurethane resin (U5). The solid content was 30 mass%. Also, the elastic modulus of a film with a thickness of 90 μm was 1500 MPa.

[0156] [Production Example 6] Emulsion of polyurethane resin (U6) Polycarbonate polyol (product name "UH200", manufactured by UBE Industries, Ltd.; number average molecular weight 2,000; hydroxyl value 57 mgKOH / g; reaction product of 1,6 - hexanediol and dimethyl carbonate, 270 g), 2,2 - dimethylolpropionic acid (DMPA, 17.6 g), and dicyclohexylmethane 4,4'-diisocyanate (H12MDI, 104.7 g) were heated in dipropylene glycol dimethyl ether (DMM, 129 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80 - 95°C for 5 hours. The reaction mixture was cooled to 80°C, and 330 g of the mixture obtained by adding and mixing triethylamine (13.3 g) thereto was added to water (482 g) with strong stirring. Subsequently, a 35 mass% aqueous solution of 2 - methyl - 1,5 - pentanediamine (MPMD, 27.3 g) was added to obtain an emulsion (U6) of a polyurethane resin. The solid content was 30 mass%. Also, the elastic modulus of a film with a thickness of 90 μm was 140 MPa.

[0157] [Production Example 7] Emulsion (U7) of polyurethane resin Polycarbonate polyol (product name "UH200", manufactured by UBE Industries, Ltd., 270 g), 2,2 - dimethylolpropionic acid (DMPA, 13.7 g), and isophorone diisocyanate (IPDI, 73.7 g) were heated in dipropylene glycol dimethyl ether (DMM, 117 g) in the presence of dibutyltin dilaurate (0.3 g) under a nitrogen atmosphere at 80 - 95°C for 5 hours. The reaction mixture was cooled to 80°C, and 330 g of the mixture obtained by adding and mixing triethylamine (10.4 g) thereto was added to water (480 g) with strong stirring. Subsequently, a 35 mass% aqueous solution of 2 - methyl - 1,5 - pentanediamine (MPMD, 0.34 g) was added and heated at 70 - 80°C for 3 hours to obtain an emulsion (U7) of a polyurethane resin. The solid content was 30 mass%. Also, the elastic modulus of a film with a thickness of 90 μm was 20 MPa.

[0158] The number average molecular weight and hydroxyl value of polycarbonate polyol, polyester polyol, and polyether polyol are catalog values.

[0159] [Emulsion of acrylic resin (B)] As the emulsion of acrylic resin (B), the following were used. The abbreviations in Tables 1 to 2 are as follows. A1: Nikazole FX-2138Y manufactured by Nippon Carbide Industries Co., Ltd. ((meth)acrylate copolymer, solid content 59% by mass, Tg: -17°C) A2: Pegarl 804 manufactured by High Pressure Gas Industry Co., Ltd. (styrene·(meth)acrylate copolymer, solid content 57% by mass, Tg: -20°C) A3: Pegarl 865 manufactured by High Pressure Gas Industry Co., Ltd. (styrene·(meth)acrylate copolymer, solid content 48% by mass, Tg: -12°C) A4: Pegarl 861 manufactured by High Pressure Gas Industry Co., Ltd. (styrene·(meth)acrylate copolymer, solid content 55% by mass, Tg: 0°C)

[0160] The Tg of the acrylic resin is the catalog value.

[0161] [Example 1] To 100 parts by mass of the emulsion U1 of the polyurethane resin, 373 parts by mass of the emulsion A1 of the acrylic resin and 360 parts by mass of purified water were blended to produce an emulsion composition.

[0162] [Example 2] To 100 parts by mass of the emulsion U2 of the polyurethane resin, 373 parts by mass of the emulsion A1 of the acrylic resin and 360 parts by mass of purified water were blended to produce an emulsion composition.

[0163] [Example 3] To 100 parts by mass of the emulsion U2 of the polyurethane resin, 386 parts by mass of the emulsion A2 of the acrylic resin and 347 parts by mass of purified water were blended to produce an emulsion composition.

[0164] [Example 4] To 100 parts by mass of the emulsion U3 of the polyurethane resin, 386 parts by mass of the emulsion A2 of the acrylic resin and 347 parts by mass of purified water were blended to produce an emulsion composition.

[0165] [Example 5] To 100 parts by mass of the emulsion U4 of the polyurethane resin, 386 parts by mass of the emulsion A2 of the acrylic resin and 347 parts by mass of purified water were blended to produce an emulsion composition.

[0166] [Example 6] To 100 parts by mass of the emulsion U1 of the polyurethane resin, 585 parts by mass of the emulsion A1 of the acrylic resin and 565 parts by mass of purified water were blended to produce an emulsion composition.

[0167] [Example 7] To 100 parts by mass of the emulsion U1 of the polyurethane resin, 1,220 parts by mass of the emulsion A1 of the acrylic resin and 1,180 parts by mass of purified water were blended to produce an emulsion composition.

[0168] [Example 8] To 100 parts by mass of the emulsion U5 of the polyurethane resin, 386 parts by mass of the emulsion A2 of the acrylic resin and 347 parts by mass of purified water were blended to produce an emulsion composition.

[0169] [Comparative Example 1] The emulsion U2 of the polyurethane resin was used as the emulsion composition.

[0170] [Comparative Example 2] To 100 parts by mass of the emulsion A1 of the acrylic resin, 97 parts by mass of purified water were blended to produce an emulsion composition.

[0171] [Comparative Example 3] To 100 parts by mass of the emulsion U1 of the polyurethane resin, 5,034 parts by mass of the emulsion A1 of the acrylic resin and 4,866 parts by mass of purified water were blended to produce an emulsion composition.

[0172] [Comparative Example 4] To 100 parts by mass of the emulsion U1 of the polyurethane resin, 203 parts by mass of the emulsion A1 of the acrylic resin and 197 parts by mass of purified water were blended to produce an emulsion composition.

[0173] [Comparative Example 5] To 100 parts by mass of the emulsion U6 of the polyurethane resin, 386 parts by mass of the emulsion A2 of the acrylic resin and 347 parts by mass of purified water were blended to produce an emulsion composition.

[0174] [Comparative Example 6] To 100 parts by mass of the emulsion U7 of the polyurethane resin, 386 parts by mass of the emulsion A2 of the acrylic resin and 347 parts by mass of purified water were blended to produce an emulsion composition.

[0175] [Comparative Example 7] To 100 parts by mass of the emulsion U2 of the polyurethane resin, 458 parts by mass of the emulsion A3 of the acrylic resin and 275 parts by mass of purified water were blended to produce an emulsion composition.

[0176] [Comparative Example 8] To 100 parts by mass of the emulsion U2 of the polyurethane resin, 400 parts by mass of the emulsion A4 of the acrylic resin and 333 parts by mass of purified water were blended to produce an emulsion composition.

[0177] [Tensile Test (Breaking Point Strength and Elongation at Break of the Film of the Emulsion Composition)] The emulsion compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 8 were applied onto a glass plate and heated at 60°C for 2 hours and then at 120°C for 2 hours to obtain a film of the emulsion composition with a film thickness of 90 μm. Using a Super Dumbbell (registered trademark) cutter (SDK-300) of Dumbell Co., Ltd., punched test pieces were prepared from the obtained film of the emulsion composition. The obtained test pieces were subjected to a tensile test in accordance with the method specified in JIS K 7311 using a universal testing machine 5982 of Instron Corporation, and the breaking point strength and elongation at break were measured. The measurement conditions were at 23°C and 50% humidity, using a 500 N load cell and a tensile speed of 100 mm / min.

[0178] [Tensile Test (Elastic Modulus of Polyurethane Resin Film)] The emulsions of the polyurethane resin (A) used in Examples 1 to 8 and Comparative Examples 1 to 8 were applied onto a glass plate and heated at 60°C for 2 hours and then at 120°C for 2 hours to obtain a film of the polyurethane resin (A) with a film thickness of 90 μm. Using a Super Dumbbell (registered trademark) cutter (SDK-300) of Dumbell Co., Ltd., punched test pieces were prepared from the obtained film of the polyurethane resin (A). The obtained test pieces were subjected to a tensile test in accordance with the method specified in JIS K 7311 using a universal testing machine 5982 of Instron Corporation, and the elastic modulus was measured. The measurement conditions were at 23°C and 50% humidity, using a 500 N load cell and a tensile speed of 100 mm / min.

[0179] [Resist Dyeing Evaluation] (Preparation of Test Pieces) To 100 parts by weight of the emulsion compositions obtained in Examples 1 to 8 and Comparative Examples 1 to 8, 80 parts by weight of a titanium paste (aqueous paste with a titanium oxide powder content of 60%), 20 parts by weight of a pigment aqueous dispersion (manufactured by Toyo Color Co., Ltd.: EMFPINK2B-1), 2.0 parts by weight of 25% aqueous ammonia (manufactured by Wako Pure Chemical Industries, Ltd.), and 10 parts by weight of an alkali thickener (manufactured by Toagosei Co., Ltd.: Aron B-500) were mixed to obtain an aqueous ink. Subsequently, using a 150-mesh screen and a urethane rubber squeegee, the aqueous ink was printed twice onto a white cotton knitted fabric. The printed material was dried under the condition of 160°C for 3 minutes to obtain test pieces.

[0180] (Tactile evaluation (soft feel property)) The surface of the test piece was traced with a finger. Those that felt a soft feeling on the coating film surface were marked as ○, and those that did not feel a soft feeling on the coating film surface were marked as ×. When the result of the tactile evaluation was ○, it was evaluated that "the soft feel property is good".

[0181] (Tack evaluation (tack-free property)) The test piece was folded back so that the printed surfaces faced each other inward, and pressed with a fingertip for 3 seconds. After removing the load, those in which the printed surfaces spontaneously peeled off within 1 second were marked as ◎, those in which the printed surfaces spontaneously peeled off within more than 1 second and within 5 seconds were marked as ○, and those in which there was no spontaneous peeling within 5 seconds were marked as ×. When the result of the tack evaluation was ◎ or ○, it was evaluated that "the tack-free property is good".

[0182] (Friction fastness evaluation) A 900 g load was applied to a wafer sheet impregnated with pure water, and the printed surface of the test piece was rubbed back and forth 25 times. Next, the wafer sheet was scanned to obtain image data. After performing color inversion processing (invert) on the obtained image data using image processing software (ImageJ), the luminance of the portion where color transfer occurred on the wafer sheet was quantified (Measure). The smaller the numerical value, the higher the friction fastness. When the result of the friction fastness evaluation was 25 or less, it was evaluated that "the friction fastness is good".

[0183] [Table 1]

[0184] [Table 2]

[0185] [Table 3]

[0186] The abbreviations described in Tables 1 to 2 are as follows. UM90(1 / 3): Product name "UM90(1 / 3)", manufactured by UBE Industries, Ltd.; number average molecular weight 900; hydroxyl value 125 mgKOH / g; polycarbonate polyol obtained by reacting a polyol mixture having a molar ratio of 1,4-cyclohexanedimethanol:1,6-hexanediol = 1:3 with dimethyl carbonate UM90(3 / 1): Product name "UM90(3 / 1)", manufactured by UBE Industries, Ltd.; number average molecular weight 900; hydroxyl value 125 mgKOH / g; polycarbonate polyol obtained by reacting a polyol mixture having a molar ratio of 1,4-cyclohexanedimethanol:1,6-hexanediol = 3:1 with dimethyl carbonate UM180(1 / 3): Product name "UM180(1 / 3)", manufactured by UBE Industries, Ltd.; number average molecular weight 1,800; hydroxyl value 62 mgKOH / g; polycarbonate polyol obtained by reacting a polyol mixture having a molar ratio of 1,4-cyclohexanedimethanol:1,6-hexanediol = 1:3 with dimethyl carbonate UH100: Product name "UH100", manufactured by UBE Industries, Ltd.; number average molecular weight 1,000; hydroxyl value 112 mgKOH / g; polycarbonate polyol obtained by reacting 1,6-hexanediol with dimethyl carbonate HS 2F-136P: Product name "HS 2F-136P", manufactured by Toyo Oil Co., Ltd.; number average molecular weight 1,000; hydroxyl value 112 mgKOH / g; polyester polyol obtained by reacting neopentyl glycol with terephthalic acid PTMG2000: Product name "PTMG2000", manufactured by Mitsubishi Chemical Corporation; number average molecular weight 2,000; hydroxyl value 57 mgKOH / g; polytetramethylene ether glycol UH200: Product name "UH200", manufactured by UBE Industries, Ltd.; number average molecular weight 2,000; hydroxyl value 57 mgKOH / g; polycarbonate polyol obtained by reacting 1,6-hexanediol with dimethyl carbonate H12MDI: Dicyclohexylmethane 4,4'-diisocyanate IPDI: Isophorone diisocyanate

[0187] From the results in Table 1, it can be seen that the emulsion compositions of all examples have good soft feel, tack-free property, and rubbing fastness. Specifically, even when the elastic modulus of the polyurethane resin (A) or the Tg of the acrylic resin (B) was changed within the ranges of Examples 1 to 5, they had good soft feel, tack-free property, and rubbing fastness. Also, even when the solid content ratio of the polyurethane resin (A) and the acrylic resin (B) was changed within the ranges of Examples 1, 6, and 7, they had good soft feel, tack-free property, and rubbing fastness. In addition, as in Examples 1 and 8, even when the type of the acid group-free polyol (a) was changed, they had good soft feel, tack-free property, and rubbing fastness. Further, from the results in Table 3, it can be seen that the emulsion compositions of the examples have good elongation at break and breaking point strength.

[0188] On the other hand, from Comparative Example 1, when the emulsion composition did not contain the acrylic resin (B), the soft feel decreased as compared with the examples. Also, from Comparative Example 2, when the emulsion composition did not contain the polyurethane resin (A), the tack-free property and rubbing fastness decreased as compared with the examples. Further, from Comparative Example 3, when the solid content ratio (A / B) of the polyurethane resin (A) and the acrylic resin (B) in the emulsion composition was less than 0.02, the tack-free property and rubbing fastness decreased as compared with the examples. In addition, from Comparative Example 4, when the solid content ratio of the polyurethane resin (A) and the acrylic resin (B) exceeded 0.23, the soft feel decreased as compared with the examples. Also, from Comparative Examples 5 and 6, when the elastic modulus of the film of the polyurethane resin (A) with a film thickness of 90 μm was less than 200 MPa, the tack-free property decreased as compared with the examples. In addition, from Comparative Examples 7 and 8, when the Tg of the acrylic resin (B) exceeded -15°C, the soft feel decreased as compared with the examples.

Industrial Applicability

[0189] Since the emulsion composition is excellent in soft feel, tack-free property, and rubbing fastness, it can be applied to various uses including clothing as an aqueous ink binder to be blended in aqueous inks.

Claims

1. An emulsion composition comprising a polyurethane resin (A), an acrylic resin (B), and an aqueous medium (C), wherein the elastic modulus of a 90-μm-thick film of the polyurethane resin (A) is 200 MPa or more, the acrylic resin (B) has a glass transition temperature of -15°C or lower, and the solid content ratio (A / B) of the polyurethane resin (A) and the acrylic resin (B) is 0.02 to 0.

23.

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

3. The emulsion composition according to claim 2, wherein the acid group-free polyol (a) is at least one selected from the group consisting of a polycarbonate polyol, a polyester polyol, and a polyether polyol.

4. The emulsion composition according to claim 3, wherein the polyurethane resin (A) further has a structure derived from a compound (d) (excluding polycarbonate polyol, polyester polyol, polyether polyol, and acid group-containing polyol (c)) having a total of two or more groups selected from the group consisting of a hydroxyl group and an amino group.

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

6. The emulsion composition according to claim 1, wherein the total content ratio of the urethane bond and the urea bond in the polyurethane resin (A) is 10.0 to 25.0% by mass based on the solid content of the polyurethane resin (A).

7. The emulsion composition according to claim 1, wherein the content ratio of the alicyclic structure in the polyurethane resin (A) is 15 to 50% by mass based on the solid content of the polyurethane resin (A).

8. The emulsion composition according to claim 1, wherein the 90-μm-thick film of the polyurethane resin (A) is a film obtained by heating an emulsion of the polyurethane resin (A) at 60°C for 2 hours and then at 120°C for 2 hours.

9. The emulsion composition according to claim 1, wherein the breaking point strength of a 90-μm-thick film of the emulsion composition is 5 MPa or more.

10. The emulsion composition according to any one of claims 1 to 9, which is an aqueous ink binder used for inkjet printing.

11. A method for producing an emulsion composition according to any one of Claims 1 to 9, comprising a step of producing an emulsion of a polyurethane resin (A), a step of producing an emulsion of an acrylic resin (B), and a step of mixing the emulsion of the polyurethane resin (A) and the emulsion of the acrylic resin (B).

12. An aqueous ink comprising the emulsion composition according to any one of Claims 1 to 9.

13. A laminate comprising a cured film of the emulsion composition according to any one of Claims 1 to 9 and a substrate.

14. A laminate comprising a cured film of the aqueous ink according to Claim 12 and a substrate.

15. A film containing a polyurethane resin (A) and an acrylic resin (B), wherein the elastic modulus of a film having a film thickness of 90 μm of the polyurethane resin (A) is 200 MPa or more, the acrylic resin (B) has a glass transition temperature of -15°C or lower, and the content ratio (A / B) of the polyurethane resin (A) and the acrylic resin (B) is 0.02 to 0.23.

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