Polyurethane Dispersion

Abstract

To provide a polyurethane dispersion which is excellent in color development property and adhesion, when a fabric is printed.SOLUTION: A polyurethane dispersion is obtained by water dispersion of a polyurethane resin. The polyurethane resin is a reaction product of an isocyanate group-terminated prepolymer, monoamine, and a chain extender. The isocyanate group-terminated prepolymer is a reaction product of a polyisocyanate component, and a polyol component containing macropolyol and a hydrophilic group-containing active hydrogen compound. The acid value of the polyurethane resin is 10.5 mgKOH / g or more and 24.0 mgKOH / g or less. The total of urethane group concentration and urea group concentration of the polyurethane resin is 14 mass% or more and 22 mass% or less. The content of the monoamine in the polyurethane resin is 0.200 mmol / g or more and 0.257 mmol / g or less.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a polyurethane dispersion. [Background technology]

[0002] It is known that ink jet printing is performed on fabric by ejecting droplets of an ink composition from a nozzle using an ink jet method. The ink composition contains, for example, a colorant and a resin in which the colorant is dispersed.

[0003] As such a resin, for example, a polyurethane resin has been proposed which is obtained by reacting hydrogenated xylylene diisocyanate, polytetramethylene ether glycol, and dimethylolpropionic acid, and then blending and reacting triisopropanolamine and a methyl ethyl ketone hydrazone composition (a methyl ethyl ketone hydrazone composition containing methyl ethyl ketone hydrazone and hydrazine hydrate) (see, for example, Example 3 of Patent Document 1 below). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 09-255751 Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, when printing fabrics (especially synthetic fibers), the fabrics may be pretreated in order to improve the interaction between the fabric and the ink composition.

[0006] If the fabric is pretreated, the ink composition aggregates on the surface of the fabric due to the interaction between the fabric and the ink composition, thereby suppressing penetration of the ink composition into the fabric. This increases the color density on the surface of the fabric (improves color development). On the other hand, if penetration of the ink composition into the fabric is suppressed, the adhesion between the fabric and the ink composition decreases. In other words, color development and adhesion are in a trade-off relationship.

[0007] The present invention aims to provide a polyurethane dispersion that is excellent in color development and adhesion when used to print fabrics. [Means for solving the problem]

[0008] The present invention [1] is a polyurethane dispersion in which a polyurethane resin is dispersed in water, the polyurethane resin being a reaction product of an isocyanate-terminated prepolymer, a monoamine, and a chain extender, the isocyanate-terminated prepolymer being a reaction product of a polyisocyanate component and a polyol component containing a macropolyol and a hydrophilic-group-containing active hydrogen compound, the acid value of the polyurethane resin being 10.5 mgKOH / g or more and 24.0 mgKOH / g or less, the sum of the urethane group concentration and the urea group concentration of the polyurethane resin being 14% by mass or more and 22% by mass or less, and the content of the monoamine in the polyurethane resin being 0.200 mmol / g or more and 0.257 mmol / g or less.

[0009] The present invention [2] includes the polyurethane dispersion according to the above [1], in which the polyisocyanate component includes an alicyclic polyisocyanate.

[0010] The present invention [3] includes the polyurethane dispersion according to the above [1] or [2], in which the hydrophilic group-containing active hydrogen compound is an anionic group-containing active hydrogen compound.

[0011] The present invention [4] includes the polyurethane dispersion according to any one of claims 1 to 3, wherein the monoamine includes a ketimine. [Effects of the Invention]

[0012] In the polyurethane dispersion of the present invention, the polyurethane resin has an acid value of 10.5 mgKOH / g or more and 24.0 mgKOH / g or less. When the acid value is 10.5 mgKOH / g or more, excellent color development is achieved when textile printing is performed on fabrics. When the acid value is 24.0 mgKOH / g or less, excellent adhesion is achieved when textile printing is performed on fabrics.

[0013] In this polyurethane dispersion, the total concentration of urethane groups and urea groups in the polyurethane resin is 14% by mass or more and 22% by mass or less. If the total concentration of urethane groups and urea groups is 14% by mass or more, excellent color development is achieved when textile printing is performed on fabrics. If the total concentration of urethane groups and urea groups is 22% by mass or less, excellent adhesion is achieved when textile printing is performed on fabrics.

[0014] In this polyurethane dispersion, the content of monoamine in the polyurethane resin is 0.200 mmol / g or more and 0.257 mmol / g or less. When the content of monoamine is 0.200 mmol / g or more, excellent adhesion is achieved when textile printing is performed on fabrics. When the content of monoamine is 0.257 mmol / g or less, excellent color development is achieved when textile printing is performed on fabrics. [Brief explanation of the drawings]

[0015] [Figure 1] 1A to 1C are schematic diagrams of printed fabrics (printed items). FIG. 1A shows a printed item with excellent color development but poor adhesion. FIG. 1B shows a printed item with excellent adhesion but poor color development. FIG. 1C shows a printed item that achieves both excellent color development and good adhesion. DETAILED DESCRIPTION OF THE INVENTION

[0016] The polyurethane dispersion is prepared by dispersing a polyurethane resin in water.

[0017] Polyurethane resins are reaction products of isocyanate-terminated prepolymers, monoamines, and chain extenders.

[0018] <Isocyanate-terminated prepolymer> The isocyanate-terminated prepolymer is a reaction product of a polyisocyanate component and a polyol component containing a macropolyol and a hydrophilic group-containing active hydrogen compound.

[0019] [Polyisocyanate component] The polyisocyanate component includes polyisocyanate and / or a derivative of polyisocyanate.

[0020] (Polyisocyanate) Examples of polyisocyanates include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.

[0021] Examples of aliphatic polyisocyanates include aliphatic diisocyanates. Examples of aliphatic diisocyanates include 1,6-hexamethylene diisocyanate (1,6-HDI), 1,5-pentamethylene diisocyanate (1,5-PDI), tetramethylene diisocyanate, trimethylene diisocyanate, 1,2-, 2,3-, or 1,3-butylene diisocyanate, and 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate. Preferred examples of aliphatic polyisocyanates include 1,6-HDI and 1,5-PDI.

[0022] Examples of alicyclic polyisocyanates include alicyclic diisocyanates. Examples of alicyclic diisocyanates include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), 4,4'-, 2,4'-, or 2,2'-methylenebis(cyclohexyl isocyanate), or mixtures thereof (H 12 Examples of the alicyclic polyisocyanate include IPDI, 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof (H6XDI), bis(isocyanatomethyl)norbornane (NBDI), 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, and methyl-2,6-cyclohexane diisocyanate. 12 Examples include MDI and H6XDI. From the viewpoint of improving texture, H6XDI is more preferred. 1,3-H6XDI is even more preferred.

[0023] Examples of aromatic polyisocyanates include aromatic diisocyanates, such as 4,4'-, 2,4'-, or 2,2'-diphenylmethane diisocyanate or a mixture thereof (MDI), 2,4- or 2,6-tolylene diisocyanate or a mixture thereof (TDI), o-tolidine diisocyanate, 1,5-naphthalene diisocyanate (NDI), m- or p-phenylene diisocyanate or a mixture thereof, 4,4'-diphenyl diisocyanate, and 4,4'-diphenyl ether diisocyanate.

[0024] Examples of araliphatic polyisocyanates include araliphatic diisocyanates. Examples of araliphatic diisocyanates include xylylene diisocyanate (1,2-, 1,3-, or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), and ω,ω'-diisocyanato-1,4-diethylbenzene. XDI is preferably used as the araliphatic polyisocyanate.

[0025] The polyisocyanate is preferably an aliphatic polyisocyanate, an alicyclic polyisocyanate, or an araliphatic polyisocyanate. From the viewpoint of improving color development and mechanical stability, the polyisocyanate is more preferably an alicyclic polyisocyanate. The polyisocyanate is even more preferably an alicyclic polyisocyanate.

[0026] The polyisocyanates can be used alone or in combination of two or more kinds.

[0027] (Polyisocyanate derivatives) Examples of the polyisocyanate derivatives include the above-mentioned polyisocyanate polymers, allophanate derivatives, polyol derivatives, biuret derivatives, urea derivatives, oxadiazinetrione derivatives, carbodiimide derivatives, uretdione derivatives, and uretonimine derivatives.

[0028] The polyisocyanate derivatives can be used alone or in combination of two or more kinds.

[0029] The polyisocyanate component preferably does not contain a derivative of polyisocyanate and is composed of polyisocyanate, and more preferably is composed of alicyclic polyisocyanate.

[0030] [Polyol component] The polyol component includes a macropolyol and a hydrophilic group-containing active hydrogen compound.

[0031] (macropolyol) The macropolyol is a compound having two or more hydroxyl groups at the molecular terminals and having a number average molecular weight of 400 or more, preferably 500 or more, and 10,000 or less, preferably 5,000 or less, more preferably 3,000 or less.

[0032] The average functionality of the macropolyol is, for example, 2 or more, and for example, 3 or less, and preferably 2.

[0033] Examples of the macropolyol include polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, polyolefin polyol, acrylic polyol, silicone polyol, fluorine polyol, and vinyl monomer-modified polyol. Preferably, the macropolyol is polyether polyol.

[0034] Examples of polyether polyols include polyoxyalkylene (having 2 to 3 carbon atoms) polyols and polytetramethylene ether polyols.

[0035] Examples of polyoxyalkylene (C2-3) polyols include low-molecular-weight polyols described below and addition polymers of alkylene oxides having C2-3 using known low-molecular-weight polyamines as initiators.

[0036] Examples of alkylene oxides having 2 to 3 carbon atoms include propylene oxide and ethylene oxide. These alkylene oxides can be used alone or in combination of two or more.

[0037] Specific examples of polyoxyalkylene (carbon number 2 to 3) polyols include polyoxyethylene glycol, polyoxypropylene glycol, and random and / or block copolymers of propylene oxide and ethylene oxide.

[0038] Furthermore, the polyoxyalkylene (carbon number 2 to 3) polyol also includes polytrimethylene ether glycol.

[0039] An example of polytrimethylene ether glycol is a glycol obtained by polycondensation reaction of 1,3-propanediol derived from plant components.

[0040] Examples of polytetramethylene ether polyols include ring-opening polymers (crystalline polytetramethylene ether glycols) obtained by cationic polymerization of tetrahydrofuran, and amorphous (non-crystalline) polytetramethylene ether glycols obtained by copolymerizing alkyl-substituted tetrahydrofuran or the above-mentioned dihydric alcohols with polymerization units of tetrahydrofuran, etc. Examples include:

[0041] As the polyether polyol, preferably, polytetramethylene ether polyol is used, and more preferably, polytetramethylene ether glycol is used.

[0042] The macropolyols can be used alone or in combination of two or more kinds.

[0043] The blending ratio of the macropolyol is, for example, 70 parts by mass or more, preferably 80 parts by mass or more, more preferably 85 parts by mass or more, and even more preferably 90 parts by mass or more, and for example, 98 parts by mass or less, per 100 parts by mass of the total amount of the polyol components.

[0044] (Hydrophilic group-containing active hydrogen compound) The hydrophilic group-containing active hydrogen compound is a compound containing a hydrophilic group and two or more active hydrogen groups, such as hydroxyl groups and amino groups.

[0045] Examples of the hydrophilic group include a nonionic group and an ionic group. More specific examples of the hydrophilic group-containing active hydrogen compound include an active hydrogen group-containing compound containing a nonionic group and an active hydrogen group-containing compound containing an ionic group.

[0046] The active hydrogen group-containing compound containing a nonionic group is a compound having one or more nonionic groups and two or more active hydrogen groups.The nonionic group can be, for example, a polyoxyethylene group.The active hydrogen group-containing compound containing a nonionic group can be, for example, polyoxyethylene glycol, one-end-blocked polyoxyethylene glycol, and polyol containing a polyoxyethylene side chain.

[0047] Examples of active hydrogen group-containing compounds containing an ionic group include active hydrogen group-containing compounds containing an anionic group and active hydrogen group-containing compounds containing a cationic group.

[0048] The active hydrogen group-containing compound containing an anionic group is a compound having both one or more anionic groups and two or more active hydrogen groups. Examples of the anionic group include a carboxy group (carboxylic acid group) and a sulfo group (sulfonic acid group), and preferably a carboxy group. In addition, in the active hydrogen group-containing compound containing an anionic group, examples of the active hydrogen group include a hydroxyl group and an amino group, and preferably a hydroxyl group. That is, the active hydrogen group-containing compound containing an anionic group is preferably an organic compound having both a carboxy group and two hydroxyl groups.

[0049] Examples of organic compounds having both a carboxy group and two hydroxyl groups include carboxy group-containing polyols. Examples of carboxy group-containing polyols include polyhydroxyalkanoic acids. Examples of polyhydroxyalkanoic acids include 2,2-dimethylolacetic acid, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid (also known as dimethylolpropionic acid), 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolvaleric acid. A preferred example of an organic compound having both a carboxy group and two hydroxyl groups is 2,2-dimethylolpropionic acid.

[0050] The active hydrogen group-containing compound containing a cationic group is a compound that has one or more cationic groups and two or more active hydrogen groups. Examples of the cationic group include a tertiary amino group (a tertiary amine that can form a tertiary ammonium salt). In addition, in the active hydrogen group-containing compound containing a cationic group, examples of the active hydrogen group include a hydroxyl group and an amino group, and preferably a hydroxyl group. That is, the active hydrogen group-containing compound containing a cationic group is preferably an organic compound that has both a tertiary amino group and two hydroxyl groups.

[0051] Examples of organic compounds having both a tertiary amino group and two hydroxyl groups include N-alkyldialkanolamines, such as N-methyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine, and N-methyldipropanolamine.

[0052] The hydrophilic group-containing active hydrogen compound is preferably an active hydrogen group-containing compound containing an ionic group, and more preferably an active hydrogen group-containing compound containing an anionic group, from the viewpoint of adjusting the acid value of the polyurethane resin described below to a predetermined range.

[0053] The hydrophilic group-containing active hydrogen compounds can be used alone or in combination of two or more.

[0054] The blending ratio of the hydrophilic group-containing active hydrogen compound relative to 100 parts by mass of the total amount of the polyol components is, for example, 1 part by mass or more, preferably 3 parts by mass or more, more preferably 4 parts by mass or more, and for example, 10 parts by mass or less, preferably 5 parts by mass or less.

[0055] In particular, when the hydrophilic group-containing active hydrogen compound is an active hydrogen group-containing compound containing an anionic group (preferably a carboxy group), by setting the blending ratio within the above range, the acid value of the polyurethane resin described below can be set within a predetermined range.

[0056] (Low molecular weight polyol) The polyol component may also contain a low molecular weight polyol (a low molecular weight polyol excluding a hydrophilic group-containing active hydrogen compound).

[0057] The low-molecular-weight polyol is a compound having a number-average molecular weight of 40 or more and less than 400, preferably 300 or less.

[0058] The functionality of the low molecular weight polyol is, for example, 2 or more, and, for example, 3 or less. The functionality of the low molecular weight polyol is preferably 2.

[0059] Examples of low molecular weight polyols include diols having 2 to 6 carbon atoms and other low molecular weight polyols (excluding diols having 2 to 6 carbon atoms).

[0060] The diol having 2 to 6 carbon atoms has a number average molecular weight of 40 or more but less than 400, preferably 300 or less, and is a compound having 2 to 6 carbon atoms and two hydroxyl groups. Examples of the diol include an alkanediol having 2 to 6 carbon atoms (an alkylene glycol having 2 to 6 carbon atoms), an etherdiol having 2 to 6 carbon atoms, and an alkenediol having 2 to 6 carbon atoms.

[0061] Examples of alkanediols having 2 to 6 carbon atoms include ethylene glycol, propylene glycol (1,2- or 1,3-propanediol or a mixture thereof), butylene glycol (1,2-, 1,3-, or 1,4-butanediol or a mixture thereof), 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 1,3- or 1,4-cyclohexanediol.

[0062] Examples of the ether diol having 2 to 6 carbon atoms include diethylene glycol, triethylene glycol, and dipropylene glycol, and preferably triethylene glycol. Examples of the ether diol having 2 to 6 carbon atoms include triethylene glycol.

[0063] An example of the alkenediol having 2 to 6 carbon atoms is 1,4-dihydroxy-2-butene.

[0064] As the diol having 2 to 6 carbon atoms, preferably, an ether diol having 2 to 6 carbon atoms is used.

[0065] The other low-molecular-weight polyols are compounds having a number-average molecular weight of 40 or more but less than 400, preferably 300 or less, and having two or more hydroxyl groups in one molecule, such as diols (dihydric alcohols) having 7 or more carbon atoms and low-molecular-weight polyols having 3 or more hydric atoms.

[0066] The diol (dihydric alcohol) having 7 or more carbon atoms is a compound having a number average molecular weight of 40 or more but less than 400, preferably 300 or less, and having two hydroxyl groups per molecule and having 7 or more carbon atoms, and examples thereof include alkane-1,2-diols having 7 to 20 carbon atoms, 2,6-dimethyl-1-octene-3,8-diol, 1,3- or 1,4-cyclohexanedimethanol, and mixtures thereof, hydrogenated bisphenol A, and bisphenol A.

[0067] Examples of diols (dihydric alcohols) having 7 or more carbon atoms include dihydric polyalkylene oxides having a number-average molecular weight of less than 400, preferably 300 or less. Such polyalkylene oxides can be obtained, for example, by addition reaction of alkylene oxides such as ethylene oxide and / or propylene oxide with the above-mentioned dihydric alcohols as an initiator, to give polyethylene glycols (polyoxyethylene ether glycols), polypropylene glycols (polyoxypropylene ether glycols), polyethylenepolypropylene glycols (random or block copolymers), etc. Further examples include polytetramethylene ether glycols having a number-average molecular weight of less than 400, preferably 300 or less, obtained by ring-opening polymerization of tetrahydrofuran, for example.

[0068] The trihydric or higher low-molecular-weight polyol has a number-average molecular weight of 40 or more but less than 400, preferably 300 or less, and is a compound having three or more hydroxyl groups per molecule. Examples of the trihydric alcohol include trihydric alcohol (low-molecular-weight triol), tetrahydric alcohol, pentahydric alcohol, hexahydric alcohol, heptahydric alcohol, and octahydric alcohol. Examples of the trihydric alcohol include glycerin, 2-methyl-2-hydroxymethyl-1,3-propanediol, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexanetriol, trimethylolpropane, and 2,2-bis(hydroxymethyl)-3-butanol. Examples of the tetrahydric alcohol include tetramethylolmethane (pentaerythritol) and diglycerin. Examples of the pentahydric alcohol include xylitol. Examples of hexahydric alcohols include sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, and dipentaerythritol. Examples of heptahydric alcohols include perseitol. Examples of octahydric alcohols include sucrose.

[0069] Examples of the trivalent or higher low-molecular-weight polyol also include trivalent or higher polyalkylene oxides having a number average molecular weight of 40 or more but less than 400, preferably 300 or less. Such polyalkylene oxides can be obtained as polyethylene polyols, polypropylene polyols, and polyethylene-polypropylene polyols (random or block copolymers) by addition reaction of alkylene oxides such as ethylene oxide and / or propylene oxide with the above-mentioned trivalent or higher low-molecular-weight polyols or known polyamines as an initiator.

[0070] The low molecular weight polyol is preferably a diol having 2 to 6 carbon atoms.

[0071] The low molecular weight polyols can be used alone or in combination of two or more kinds.

[0072] The mixing ratio of the low-molecular-weight polyol relative to 100 parts by mass of the total amount of the polyol components is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and for example, 15 parts by mass or less.

[0073] The polyol component preferably does not contain a low-molecular-weight polyol, and is composed of a macropolyol and a hydrophilic group-containing active hydrogen compound.

[0074] [Preparation of isocyanate-terminated prepolymer] The isocyanate-terminated prepolymer can be obtained by reacting a polyisocyanate component with a polyol component.

[0075] As a method for reacting the polyisocyanate component and the polyol component, a known polymerization method (e.g., bulk polymerization or solution polymerization) is selected, and preferably, solution polymerization is selected from the viewpoint of easier adjustment of reactivity and viscosity.

[0076] In solution polymerization, for example, the above components are mixed in an organic solvent (solvent) under a nitrogen atmosphere and reacted.

[0077] In this reaction, the equivalent ratio (isocyanate group / active hydrogen group) of the isocyanate group in the polyisocyanate component to the active hydrogen groups (hydroxyl groups and / or amino groups) in the polyol component exceeds 1, for example, 1.2 or more, preferably 1.3 or more, for example, 3.0 or less, preferably 2.5 or less. In such a case, the terminal functional group of the resulting reaction product is an isocyanate group. In other words, an isocyanate-terminated prepolymer is obtained.

[0078] As for reaction conditions, the reaction temperature is, for example, 20° C. or higher and, for example, 80° C. or lower, and the reaction time is, for example, 1 hour or longer and, for example, 20 hours or shorter.

[0079] Examples of the organic solvent include those which are inert to isocyanate groups and highly hydrophilic, such as acetone, methyl ethyl ketone, ethyl acetate, tetrahydrofuran, acetonitrile, and N-methylpyrrolidone. Ethyl acetate is preferred.

[0080] In the polymerization, a reaction catalyst (for example, an amine-based, tin-based, or lead-based catalyst) may be added as needed.

[0081] In the above reaction, unreacted polyisocyanate components and / or unreacted polyol components can be removed by known methods such as distillation or extraction.

[0082] This produces an isocyanate-terminated prepolymer, which is a reaction product of the polyisocyanate component and the polyol component.

[0083] When the polyisocyanate component and the polyol component are reacted by solution polymerization, the isocyanate-terminated prepolymer is obtained as a reaction liquid containing the isocyanate-terminated prepolymer and an organic solvent.

[0084] The isocyanate-terminated prepolymer is a polyurethane prepolymer having at least one (preferably multiple, more preferably two) free isocyanate group at its molecular end. The isocyanate group content (isocyanate group content calculated as solid content excluding solvent, i.e., isocyanate group concentration) is, for example, 2% by mass or more, preferably 2.5% by mass or more, more preferably 3% by mass or more, and for example, 5% by mass or less, preferably 4% by mass or less.

[0085] Furthermore, when the reaction product contains an ionic group, it is preferable to neutralize it by adding a neutralizing agent to form a salt of the ionic group.

[0086] As the neutralizing agent, when the ionic group is an anionic group, a conventional base (e.g., triethylamine) is used, and when the ionic group is a cationic group, a conventional acid (e.g., acetic acid) is used.

[0087] In particular, when the ionic group is an anionic group (preferably a carboxy group), the neutralizing agent is added in a proportion of 0.6 equivalents or more, preferably 0.8 equivalents or more, per equivalent of the anionic group, and for example, 1.2 equivalents or less, preferably 1.1 equivalents or less.

[0088] <Monoamine> Monoamines are compounds that contain one amino group. Because they contain one amino group, they are reaction terminators in the chain extension reaction described below.

[0089] Examples of monoamines include alkylamines and dialkylamines. Examples of alkylamines include 2-ethylhexylamine and cyclohexylamine. Examples of dialkylamines include diethylamine, dipropylamine, and dibutylamine.

[0090] As the monoamine, preferably, dialkylamine is used, and more preferably, diethylamine is used.

[0091] Monoamines also include ketimines.

[0092] Ketimines are compounds in which the oxygen of the carbonyl group of a ketone is replaced with an imino group.

[0093] Examples of ketimines include hydrazones obtained by reacting hydrazine or a derivative thereof (e.g., hydrazine monohydrate, described below) with a ketiminizing agent (a ketone (e.g., acetone, methyl ethyl ketone)). Examples of hydrazones include aliphatic ketone hydrazones and aromatic ketone hydrazones. Examples of aliphatic ketone hydrazones include acetone hydrazone, methyl ethyl ketone hydrazone, and methyl isobutyl ketone hydrazone. Examples of aromatic ketone hydrazones include acetophenone hydrazone and benzophenone hydrazone. Preferred examples of ketimines include aliphatic ketone hydrazones. More preferred examples of ketimines include methyl ethyl ketone hydrazone and acetone hydrazone. Even more preferred examples of ketimines include methyl ethyl ketone hydrazone.

[0094] As described above, hydrazone is obtained by reacting hydrazine or its derivative with a ketiminizing agent. In the reaction, by adding an excess equivalent of hydrazine to the ketiminizing agent, the unreacted hydrazine or its derivative can be used as it is as a chain extender, which will be described later.

[0095] The monoamine preferably comprises a ketimine.

[0096] When the monoamine contains ketimine, the molecular weight distribution broadens, making it easier to achieve a balance between color development and adhesion.

[0097] The monoamines more preferably include dialkylamines and ketimines.

[0098] When the monoamine includes a dialkylamine and a ketimine, the dialkylamine and ketimine are blended into the polyurethane resin described below so that the dialkylamine content is, relative to 100 moles of the total amount of the dialkylamine and the ketimine, for example, 4 mole% or more, preferably 8 mole% or more, and for example, 30 mole% or less, preferably 20 mole% or less, more preferably 15 mole% or less, and particularly preferably 12 mole% or less, and the ketimine content is, relative to 100 moles of the total amount of the dialkylamine and the ketimine, for example, 70 mole% or more, preferably 80 mole% or more, more preferably 85 mole% or more, even more preferably 88 mole% or more, and for example, 96 mole% or less, preferably 92 mole% or less.

[0099] When the dialkylamine content and the ketimine content are within the above ranges, color development and adhesion can be further improved.

[0100] The monoamines more preferably comprise dialkylamines and ketimines.

[0101] <Chain extender> Examples of the chain extender include the above-mentioned low molecular weight polyols and amino group-containing compounds.

[0102] Examples of the amino group-containing compound include aromatic polyamines, araliphatic polyamines, alicyclic polyamines, aliphatic polyamines, amino alcohols, polyoxyethylene group-containing polyamines, alkoxysilyl compounds having a primary amino group or a primary amino group and a secondary amino group, and hydrazine or a derivative thereof.

[0103] Examples of aromatic polyamines include 4,4'-diphenylmethanediamine and tolylenediamine.

[0104] Araliphatic polyamines include, for example, 1,3- or 1,4-xylylenediamine or mixtures thereof.

[0105] Examples of alicyclic polyamines include 3-aminomethyl-3,5,5-trimethylcyclohexylamine (also known as isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,4-cyclohexanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis-(4-aminocyclohexyl)methane, diaminocyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, 1,3- and 1,4-bis(aminomethyl)cyclohexane, and mixtures thereof.

[0106] Examples of aliphatic polyamines include ethylenediamine, propylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 1,2-diaminoethane, 1,2-diaminopropane, and 1,3-diaminopentane.

[0107] Examples of amino alcohols include 2-((2-aminoethyl)amino)ethanol (also known as N-(2-aminoethyl)ethanolamine) and 2-((2-aminoethyl)amino)-1-methylpropanol (also known as N-(2-aminoethyl)isopropanolamine), and preferably 2-((2-aminoethyl)amino)ethanol (also known as N-(2-aminoethyl)ethanolamine).

[0108] Examples of polyoxyethylene group-containing polyamines include polyoxyalkylene ether diamines such as polyoxyethylene ether diamine, more specifically PEG#1000 diamine manufactured by NOF Corporation, and Jeffamine ED-2003, EDR-148, and XTJ-512 manufactured by Huntsman.

[0109] Examples of alkoxysilyl compounds having a primary amino group or a primary amino group and a secondary amino group include alkoxysilyl compounds having a primary amino group and alkoxysilyl compounds having a primary amino group and a secondary amino group. Examples of alkoxysilyl compounds having a primary amino group include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane. Examples of alkoxysilyl compounds having a primary amino group and a secondary amino group include N-β(aminoethyl)γ-aminopropyltrimethoxysilane (also known as N-2-(aminoethyl)-3-aminopropyltrimethoxysilane), N-β(aminoethyl)γ-aminopropyltriethoxysilane (also known as N-2-(aminoethyl)-3-aminopropyltriethoxysilane), N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane (also known as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane), and N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane (also known as N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane). Preferred examples of alkoxysilyl compounds having a primary amino group or a primary amino group and a secondary amino group include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane.

[0110] Examples of hydrazine or its derivatives include hydrazine (including hydrazine monohydrate), succinic acid dihydrazide, and adipic acid dihydrazide.Preferably, hydrazine or its derivatives is hydrazine monohydrate.

[0111] Furthermore, as described above, when preparing chemitin (specifically, hydrazone), unreacted hydrazine or its derivative can be used as it is as a chain extender.

[0112] In such a case, for example, a ketiminizing agent and an excess equivalent of hydrazine or its derivative are mixed with water to prepare an aqueous ketimine-containing chain extender solution containing ketimine (hydrazone) and unreacted hydrazine or its derivative (chain extender).

[0113] If necessary, the aqueous solution of the ketimine-containing chain extender may further contain the above-mentioned monoamine and / or the above-mentioned chain extender (excluding unreacted hydrazine or a derivative thereof).

[0114] The chain extender is preferably hydrazine or a derivative thereof, or an alkoxysilyl compound having a primary amino group or a primary amino group and a secondary amino group, and more preferably hydrazine or a derivative thereof.

[0115] The chain extender can also be prepared, for example, as an aqueous solution (aqueous chain extender solution).

[0116] The chain extenders can be used alone or in combination of two or more.

[0117] <Preparation of polyurethane resin> The polyurethane resin is obtained by reacting an isocyanate-terminated prepolymer, a monoamine, and a chain extender.

[0118] Specifically, an isocyanate-terminated prepolymer, a monoamine, and a chain extender are reacted in, for example, water to obtain a polyurethane resin (polyurethane dispersion).

[0119] To react an isocyanate-terminated prepolymer, a monoamine, and a chain extender in water, for example, first, the isocyanate-terminated prepolymer is added to water to disperse the isocyanate-terminated prepolymer in water, and then, a monoamine and a chain extender are added thereto to extend the chain of the isocyanate-terminated prepolymer with the chain extender.

[0120] To disperse the isocyanate-terminated prepolymer in water, the isocyanate-terminated prepolymer is added to 100 parts by mass of isocyanate-terminated prepolymer in 50 to 1000 parts by mass of water (sometimes referred to as water dispersion water) while stirring the water.

[0121] Thereafter, the chain extender is added dropwise to the water in which the isocyanate group-terminated prepolymer has been dispersed, while stirring, so that the equivalent ratio (active hydrogen groups / isocyanate groups) of the active hydrogen groups (amino groups and hydroxyl groups) of the chain extender to the isocyanate groups of the isocyanate group-terminated prepolymer is, for example, 0.8 or more and 1.2 or less.

[0122] In this method, a monoamine is added together with the chain extender. As described above, the monoamine is a reaction terminator in the chain extension reaction. Therefore, the molecular weight of the polyurethane resin can be adjusted depending on the blending ratio of the monoamine.

[0123] When the above-mentioned aqueous solution of a ketimine-containing chain extender is added, the monoamine and the chain extender are added simultaneously.

[0124] After the dropwise addition of the monoamine and chain extender is completed, the reaction is continued with stirring, for example, at room temperature, to complete the reaction. The reaction time until the reaction is completed is, for example, 0.1 hours or more and, for example, 10 hours or less.

[0125] Conversely to the above, water can be added to the isocyanate group-terminated prepolymer to disperse the isocyanate group-terminated prepolymer in water, and then a monoamine and a chain extender can be added thereto to extend the chains of the isocyanate group-terminated prepolymer with the chain extender.

[0126] In this method, the organic solvent and water can be removed as needed, and further, water can be added to adjust the solid content concentration.

[0127] This allows the chain of the isocyanate-terminated prepolymer to be extended by the chain extender, thereby obtaining a polyurethane resin prepared as an aqueous dispersion (polyurethane dispersion).

[0128] The acid value of the polyurethane resin is 10.5 mgKOH / g or more, preferably 11.0 mgKOH / g or more, and 24.0 mgKOH / g or less, preferably 19.0 mgKOH / g or less, more preferably 15.0 mgKOH / g or less, and even more preferably 12.0 mgKOH / g or less.

[0129] The acid value can be adjusted to fall within the above range, for example, by adjusting the blending ratio of the active hydrogen group-containing compound that contains an anionic group (preferably a carboxy group).

[0130] If the acid value is equal to or greater than the lower limit, color development is improved when a fabric (described later) is printed (that is, color density is increased on the surface of the fabric (described later)).

[0131] On the other hand, if the acid value is less than the lower limit, color development will be reduced when printing fabrics (described later), and the polyurethane resin will not be able to be dispersed in water.

[0132] Furthermore, if the acid value is equal to or less than the upper limit, adhesion is improved when printing fabrics (described later).

[0133] On the other hand, if the acid value exceeds the upper limit, adhesion decreases when printing fabrics (described later).

[0134] The acid value can be calculated from the ratio of the components charged.

[0135] The total concentration of urethane groups and urea groups in the polyurethane resin is 14% by mass or more, preferably 16% by mass or more, more preferably 18% by mass or more, and 22% by mass or less, preferably 20% by mass or less, more preferably 19% by mass or less.

[0136] If the total concentration of the urethane group and the urea group is equal to or higher than the lower limit, color development is improved when printing a fabric (described later), and mechanical stability is also improved.

[0137] On the other hand, if the total concentration of urethane groups and urea groups is less than the above lower limit, color development will be poor when printing fabrics (described later), and mechanical stability will also be poor.

[0138] Furthermore, if the total concentration of the urethane group and the urea group is not more than the above upper limit, when printing a fabric (described later), the adhesion is improved and the feel is also improved.

[0139] On the other hand, if the total concentration of urethane groups and urea groups exceeds the upper limit, adhesion will decrease when printing fabrics (described later), and the texture will also deteriorate.

[0140] The total of the urethane group concentration and the urea group concentration can be calculated from the charge ratio of the raw material components.

[0141] The content of monoamine in the polyurethane resin is 0.200 mmol / g or more, preferably 0.210 mmol / g or more, and 0.257 mmol / g or less, preferably 0.239 mmol / g or less.

[0142] When the content of the monoamine is equal to or greater than the lower limit, adhesion is improved when printing a fabric (described later), and the texture is also improved.

[0143] On the other hand, if the content of the monoamine is less than the lower limit, the adhesion is reduced when printing a fabric (described later), and the texture is also reduced.

[0144] Furthermore, if the content of the monoamine is equal to or less than the upper limit, color development is improved when printing fabric (described later).

[0145] On the other hand, if the content of the monoamine is less than the lower limit, color development will be reduced when printing fabric (described later).

[0146] The content of the monoamine can be calculated from the ratio of the raw material components.

[0147] The solids concentration of the polyurethane dispersion is, for example, 10% by mass or more, preferably 20% by mass or more, and for example, 50% by mass or less, preferably 40% by mass or less.

[0148] <Use of polyurethane dispersion> The polyurethane dispersion is suitably used as a resin for dispersing coloring materials in the ink composition.

[0149] The ink composition is a raw material for printing fabrics.

[0150] Examples of fabrics include natural fibers and chemical fibers. Examples of natural fibers include cotton, silk, wool, and hemp. Examples of chemical fibers include polypropylene fibers, polyester fibers, and polyamide fibers.

[0151] The ink composition contains a colorant and the polyurethane dispersion.

[0152] The coloring material is not particularly limited, and known coloring materials can be used.

[0153] The polyurethane dispersion is a component that disperses the coloring material in the ink composition.

[0154] The mixing ratio of the polyurethane dispersion relative to 100 parts by mass of the colorant is, for example, 500 parts by mass or more, and for example, 1000 parts by mass or less, preferably 700 parts by mass or less.

[0155] The ink composition is then prepared by mixing the colorant and the polyurethane dispersion.

[0156] In addition, if necessary, known additives (for example, humectants, penetrants, chelating agents, preservatives, and pH adjusters) can also be blended into the ink composition. That is, the ink composition contains known additives as needed. The humectants, penetrants, chelating agents, preservatives, and pH adjusters described in JP 2021-165353 A can be used.

[0157] The ink composition can also be diluted with water and / or an organic solvent (eg, ethylene glycol).

[0158] Next, a method for printing fabric using this ink composition will be described in detail.

[0159] When printing a fabric using an ink composition, the fabric is first pretreated. If the fabric is not pretreated, the interaction between the fabric and the ink composition is weak, and the ink composition penetrates into the fabric, resulting in a decrease in color development. In particular, when the fabric is made of chemical fibers, the above-mentioned interaction is weaker than that of natural fibers, and the above-mentioned decrease in color development becomes more pronounced.

[0160] On the other hand, if the fabric is pretreated, the ink composition aggregates on the surface of the fabric due to the interaction between the fabric and the ink composition, thereby suppressing the ink composition from penetrating into the fabric, thereby improving color development.

[0161] To pretreat the fabric, the fabric is treated with a pretreatment agent.

[0162] Examples of pretreatment agents include organic acids and their salts (e.g., formic acid, sodium formate, acetic acid, and sodium acetate), polyvalent metal salts, and cationic compounds. Preferable pretreatment agents include organic acids. More preferably, acetic acid and sodium acetate are used. The pretreatment agent can also be prepared as an aqueous solution.

[0163] To treat a fabric with a pretreatment agent, the pretreatment agent is applied to the fabric. A known method (for example, a spray method) is selected as the method for applying the pretreatment agent to the fabric.

[0164] Next, the ink composition is applied to the fabric. A known method (for example, a spray method or an inkjet method) is selected as the method for applying the ink composition to the fabric. In this way, the ink composition is applied to the fabric.

[0165] Next, the fabric (the fabric to which the ink composition has been applied) is heated.

[0166] The heating temperature is, for example, 80° C. or higher, preferably 100° C. or higher, and for example, 120° C. or lower. The heating time is, for example, 1 minute or longer, preferably 5 minutes or longer, and for example, 60 minutes or shorter, preferably 30 minutes or shorter, more preferably 15 minutes or shorter.

[0167] This results in printing of the fabric (i.e., obtaining a printed product).

[0168] Since the ink composition contains the polyurethane dispersion described above, it is possible to produce printed items that are excellent in color development and adhesion.

[0169] <Action and effect> In the polyurethane dispersion, the acid value of the polyurethane resin, the total concentration of the urethane group and the urea group in the polyurethane resin, and the content of the monoamine in the polyurethane resin are all within a predetermined range, so that the polyurethane dispersion exhibits excellent color development and adhesion when used for textile printing.

[0170] On the other hand, color development and adhesion have a trade-off relationship.

[0171] 1A, when a fabric 1 is printed, if most of the polyurethane dispersion 2 (specifically, the ink composition containing the polyurethane dispersion 2) remains on the surface 3 of the fabric 1, the color density at the surface 3 of the fabric 1 increases, improving color development. On the other hand, in such a case, the polyurethane dispersion 2 (specifically, the ink composition containing the polyurethane dispersion 2) hardly penetrates into the fabric 1, and therefore the adhesion between the fabric 1 and the polyurethane dispersion 2 (specifically, the ink composition containing the polyurethane dispersion 2) decreases.

[0172] 1B, adhesion improves when most of the polyurethane dispersion 2 (specifically, the ink composition containing the polyurethane dispersion 2) penetrates into the fabric 1. On the other hand, in this case, almost no polyurethane dispersion 2 (specifically, the ink composition containing the polyurethane dispersion 2) is present on the surface 3 of the fabric 1, and color development deteriorates.

[0173] Therefore, in order to achieve both color development and adhesion, it is considered to adjust the polyurethane dispersion 2 (specifically, the ink composition containing the polyurethane dispersion 2) that remains on the surface 3 of the fabric 1 and the polyurethane dispersion 2 (specifically, the ink composition containing the polyurethane dispersion 2) that soaks into the fabric 1. Specifically, as shown in Fig. 1C, the polyurethane dispersion 2 (specifically, the ink composition containing the polyurethane dispersion 2) is adjusted to an extent that it remains on the surface 3 of the fabric 1 and soaks into the surface 3 of the fabric 1.

[0174] In this polyurethane dispersion, the acid value of the polyurethane resin, the total concentration of urethane groups and urea groups in the polyurethane resin, and the content of monoamine in the polyurethane resin can be adjusted within predetermined ranges to achieve the adjustment shown in Figure 1C. As a result, it is possible to achieve both color development and adhesion.

[0175] Specifically, when the acid value of the polyurethane resin is high, the polyurethane dispersion (specifically, the ink composition containing the polyurethane dispersion) tends to aggregate on the surface of the fabric due to interaction with the pretreatment agent (preferably organic acid ions) in the fabric. This can improve color development, but tends to reduce adhesion.

[0176] On the other hand, when the acid value of the polyurethane resin is low, the polyurethane dispersion (specifically, the ink composition containing the polyurethane dispersion) is less likely to aggregate due to interaction with the pretreatment agent (preferably formate ions) in the fabric. As a result, the polyurethane dispersion (specifically, the ink composition containing the polyurethane dispersion) is more likely to penetrate into the fabric. This can improve adhesion, but tends to reduce color development.

[0177] In addition, since the acid value of this polyurethane dispersion is adjusted to fall within a predetermined range, it is possible to achieve both color development and adhesion.

[0178] Furthermore, when the total concentration of urethane groups and urea groups in the polyurethane resin increases, the polyurethane dispersion (specifically, the ink composition containing the polyurethane dispersion) tends to aggregate. As a result, the polyurethane dispersion (specifically, the ink composition containing the polyurethane dispersion) tends to remain on the surface of the fabric. While this improves color development, it also tends to reduce adhesion.

[0179] On the other hand, when the total concentration of urethane groups and urea groups in the polyurethane resin is low, the polyurethane dispersion (specifically, the ink composition containing the polyurethane dispersion) is less likely to aggregate. As a result, the polyurethane dispersion (specifically, the ink composition containing the polyurethane dispersion) is more likely to penetrate into the fabric. This can improve adhesion, but tends to reduce color development.

[0180] In this polyurethane dispersion, the total concentration of urethane groups and urea groups in the polyurethane resin is adjusted to fall within a predetermined range, so that both color development and adhesion can be achieved.

[0181] Furthermore, as the content of monoamine in the polyurethane resin increases, the molecular weight of the polyurethane dispersion decreases. A small molecular weight makes the polyurethane resin more susceptible to softening upon heating, which makes it easier for the polyurethane dispersion (specifically, the ink composition containing the polyurethane dispersion) to penetrate into the fabric. While this improves adhesion, it also tends to reduce color development.

[0182] On the other hand, as the content of monoamine in the polyurethane resin decreases, the molecular weight of the polyurethane dispersion increases. A high molecular weight makes the polyurethane resin less likely to soften when heated. As a result, the polyurethane dispersion (specifically, the ink composition containing the polyurethane dispersion) tends to remain on the surface of the fabric. While this improves color development, it also tends to reduce adhesion.

[0183] In this polyurethane dispersion, the content of monoamine in the polyurethane resin is adjusted to fall within a predetermined range, so that both color development and adhesion can be achieved.

[0184] As described above, in this polyurethane dispersion, by adjusting the acid value of the polyurethane resin, the total of the urethane group concentration and urea group concentration of the polyurethane resin, and the monoamine content in the polyurethane resin within predetermined ranges, it is possible to achieve both color development and adhesion. [Example]

[0185] Specific numerical values ​​of blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the corresponding upper limit values ​​(numeric values ​​defined as "not more than" or "less than") or lower limit values ​​(numeric values ​​defined as "not less than" or "exceeding") of blending ratios (content ratios), physical property values, parameters, etc. described in the above "Description of the Invention." Furthermore, unless otherwise specified in the following description, "parts" and "%" are based on mass.

[0186] <Ingredient details> H6XDI: 1,3-bis(isocyanatomethyl)cyclohexane, trade name "Takenate 600," manufactured by Mitsui Chemicals, Inc. IPDI: Isophorone diisocyanate, Vestanat IPDI, manufactured by Evonik H 12 MDI: Methylenebis(cyclohexyl isocyanate), trade name "Vestanat H12 MDI" manufactured by Evonik XDI: 1,3-xylylene diisocyanate, product name "Takenate 500", Mitsui Chemicals HDI: Hexamethylene diisocyanate, product name "Takenate 700", manufactured by Mitsui Chemicals, Inc. PDI: 1,5-pentamethylene diisocyanate, trade name "Stabio PDI", manufactured by Mitsui Chemicals PTG2000SN: Polytetramethylene ether glycol (number average molecular weight: 2000), manufactured by Hodogaya Chemical Co., Ltd. PTG1000SN: Polytetramethylene ether glycol (number average molecular weight: 1000), manufactured by Hodogaya Chemical Co., Ltd. PTG650SN: Polytetramethylene ether glycol (number average molecular weight: 650), manufactured by Hodogaya Chemical Co., Ltd. DMPA: 2,2-dimethylolpropionic acid TEG: Triethylene glycol TIPA: Triisopropanolamine TEA: Triethylamine MEK: Methyl ethyl ketone KBM602: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.

[0187] <Preparation of polyurethane dispersion> Example 1 A four-neck flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube was charged with 184.49 parts by mass of PTG650SN (macropolyol), 8.49 parts by mass of DMPA (hydrophilic group-containing active hydrogen compound), and 71.89 parts by mass of ethyl acetate. Next, 94.58 parts by mass of H6XDI (polyisocyanate component) was added, and a urethane reaction was carried out at 70 ° C until the NCO concentration reached 3.47% by mass, yielding an isocyanate-terminated prepolymer (a reaction solution containing an isocyanate-terminated prepolymer).

[0188] Next, 82.95 parts by mass of acetonitrile was added to this reaction liquid, and after cooling to 30° C., 5.12 parts by mass of TEA (neutralizing agent) was added.

[0189] Next, 695.76 parts by mass of ion-exchanged water (aqueous dispersion) was gradually added while continuing stirring to disperse the isocyanate-terminated prepolymer in water, thereby preparing an aqueous dispersion of the isocyanate-terminated prepolymer.

[0190] Next, a ketimine-containing chain extender aqueous solution was prepared. Specifically, 6.82 parts by mass of hydrazine monohydrate, 4.20 parts by mass of MEK (ketiminizing agent), and 0.50 parts by mass of diethylamine (monoamine) were added to 103.70 parts by mass of ion-exchanged water to prepare the ketimine-containing chain extender aqueous solution. Furthermore, since an excess of hydrazine monohydrate was blended relative to MEK, unreacted hydrazine monohydrate was used as the chain extender. In other words, this ketimine-containing chain extender aqueous solution contains diethylamine (monoamine), ketimine (methyl ethyl ketone hydrazone obtained by reacting hydrazine monohydrate with MEK), and unreacted hydrazine monohydrate (chain extender).

[0191] Then, the aqueous solution of the ketimine-containing chain extender was added to the aqueous dispersion of the isocyanate-terminated prepolymer.

[0192] Next, ethyl acetate was distilled off under reduced pressure at 50°C, and then ion-exchanged water was added to prepare a polyurethane dispersion (solid content 30% by mass).

[0193] Examples 2 to 13 and Comparative Examples 1 to 6 A polyurethane dispersion (solid content 30% by mass) was prepared according to the same procedure as in Example 1, except that the blending recipe was changed according to Tables 1 and 2. In Comparative Example 3, the polyurethane dispersion was not dispersed in water.

[0194] <Evaluation> [Acid value] The acid value of the polyurethane dispersion of each example and comparative example was calculated from the ratio of the raw material components used, and the results are shown in Tables 1 and 2.

[0195] [Mechanical stability] 100 parts by mass of the polyurethane dispersion of each Example and Comparative Example was compounded in a test container, and the solid content was adjusted with water to 20% by mass.

[0196] Next, this polyurethane dispersion was rotated at 1000 rpm for 15 minutes under a load of 15 kg using a Maron-type mechanical stability tester A-802 (Tester Sangyo Co., Ltd.). The aggregates in the test container were then filtered through a 100-mesh stainless steel wire mesh, and the residue remaining on the stainless steel wire mesh was dried at 150°C for 30 minutes, after which the mass (residue amount) was measured. The mass (%) of the aggregates was then calculated based on the following formula (1). The results are shown in Table 1. Mass of aggregate (%) = Residue (g) / [100 (g) × 20 (%) ÷ 100] × 100 (1)

[0197] The mechanical stability was evaluated according to the following criteria, and the results are shown in Tables 1 and 2. (standard) Good: The mass of aggregates was less than 0.5%. △: The mass of aggregates was 0.5% or more and less than 2%. ×: The mass of the aggregates was 2% or more.

[0198] [Color development] Kanakin No. 3 (100% cotton) fabric was cut into 30 mm x 210 mm pieces and prepared as fabric.

[0199] Next, 7.5 g of acetic acid, 10.3 g of sodium acetate, and 82.3 g of water were mixed together to prepare a pretreatment agent.

[0200] Next, 40.0 g of the polyurethane dispersion (solid content concentration 30% by mass) of each Example and Comparative Example, 8.0 g of a colorant (Dystone X Color Blue MX, manufactured by Matsui Pigment Chemical Industry Co., Ltd., active ingredient 25% by mass), 20.0 g of ethylene glycol, and 32.0 g of water were mixed to prepare an ink composition.

[0201] Next, about 1.2 g of the pretreatment agent was applied to the fabric using a spray, and then about 2 g of the ink composition was applied to the fabric using a spray.

[0202] Thereafter, the fabric was heat treated at 110° C. for 10 minutes, thereby obtaining a printed item.

[0203] The color development of the printed textile was visually observed. The color development was evaluated according to the following criteria. The results are shown in Tables 1 and 2. (standard) ◯: A film was formed on the fabric, with almost no unevenness. △: There was some discoloration and uneven coloring. ×: The dye penetrated into the fabric and the color was clearly lighter.

[0204] [Adhesion] The printed textiles obtained in the color development test were subjected to loads (scratching and stretching) and checked for lifting, cracking, and peeling of the coating film (dried ink composition). Adhesion was evaluated according to the following criteria. The results are shown in Tables 1 and 2. (standard) Good: No lifting, cracking or peeling occurred even when a load was applied. △: Floating, cracking, or peeling occurred due to the load. ×: Lifting, cracking, or peeling occurred.

[0205] [Texture] The printed textiles obtained in the color development test were observed with a hand. The texture was evaluated according to the following criteria. The results are shown in Tables 1 and 2. (standard) 〇: It was flexible. △: Somewhat hard. ×: It was hard.

[0206] [Table 1]

[0207] [Table 2]

Claims

1. A polyurethane dispersion obtained by dispersing a polyurethane resin in water, the polyurethane resin is a reaction product of an isocyanate group-terminated prepolymer, a monoamine as a reaction terminator, and a chain extender; The isocyanate group-terminated prepolymer is a reaction product of a polyisocyanate component with a polyol component containing a macropolyol and a hydrophilic group-containing active hydrogen compound, the acid value of the polyurethane resin is 10.5 mgKOH / g or more and 24.0 mgKOH / g or less; the sum of the urethane group concentration and the urea group concentration of the polyurethane resin is 14% by mass or more and 22% by mass or less; the content of the monoamine in the polyurethane resin is 0.200 mmol / g or more and 0.257 mmol / g or less, The polyurethane dispersion, wherein the monoamine is at least one selected from the group consisting of alkylamines, dialkylamines, and ketimines.

2. The polyurethane dispersion according to claim 1 , wherein the polyisocyanate component comprises an alicyclic polyisocyanate.

3. 3. The polyurethane dispersion according to claim 1, wherein the hydrophilic group-containing active hydrogen compound is an anionic group-containing active hydrogen compound.

4. The polyurethane dispersion according to any one of claims 1 to 3, wherein the monoamine comprises a ketimine.

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