Water-dispersible blocked isocyanate, fiber treatment agent, water repellent agent, coating composition, and adhesive

Abstract

The invention relates to a water-dispersible blocked isocyanate, a fiber treatment agent, a water repellent agent, a coating composition and an adhesive. The blocked isocyanate is obtained by blocking an isocyanate group of a polyisocyanate compound with a blocking agent including a first blocking agent represented by general formula (1). At least a portion of the first blocking agent is neutralized with an acid. (In the formula, each of R1-R5 represents a hydrocarbon group having 1-12 carbon atoms or a hydrogen atom. In addition, R1 and R3 may be bonded to each other to form a heterocyclic ring. In addition, R4 and R1 may be bonded to each other to form a heterocyclic ring, and R5 and R3 may be bonded to each other to form a heterocyclic ring. > # imgabs0 #

Description

[0001] This application is a divisional application of Chinese Patent Application No. 202180054738.4 (PCT application number: PCT / JP2021 / 034284), with the filing date of September 17, 2021 and the invention title of "Water-dispersible blocked isocyanate, fiber treatment agent, water repellent, coating composition and adhesive". Technical Field

[0002] The present invention relates to a water-dispersible blocked isocyanate, a fiber treatment agent, a water repellent, a coating composition and an adhesive. Background Art

[0003] Conventionally, blocked isocyanates in which the isocyanate group is blocked by a blocking agent have been known. The blocked isocyanate is, for example, mixed with a compound having an active hydrogen group and then heated in the production of a resin. Then, the blocking agent dissociates from the isocyanate group, thereby regenerating the isocyanate group. As a result, the isocyanate group reacts with the compound having an active hydrogen group.

[0004] In addition, in order to reduce the use of organic solvents, water-dispersible blocked isocyanates dispersed in water have been studied to replace the blocked isocyanates used by dissolving them in organic solvents.

[0005] For example, a blocked polyisocyanate having both an isocyanate group blocked by a pyrazole compound and a cationic group introduced by dimethylethanolamine in the same molecule has been proposed (see, for example, Patent Document 1 (Example 1)).

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2010-59089 Summary of the Invention

[0009] Problems to be Solved by the Invention

[0010] In recent years, from the viewpoints of low energy consumption and low cost, a decrease in the temperature at which the blocking agent dissociates from the isocyanate group, that is, low-temperature curability of the blocked isocyanate, has been desired.

[0011] However, with respect to the blocked polyisocyanate described in Patent Document 1, low-temperature curability cannot be sufficiently ensured. In addition, it is required that the water-dispersible blocked isocyanate can be stably stored in a state of being dispersed in water.

[0012] The present invention provides a water-dispersible blocked isocyanate, a fiber treatment agent, a water repellent, a coating composition and an adhesive having excellent low-temperature curability and storage stability.

[0013] Means for Solving the Problems

[0014] The present invention [1] includes a water-dispersible blocked isocyanate, which is a blocked isocyanate obtained by blocking the isocyanate groups of a polyisocyanate compound with a blocking agent. The aforementioned blocking agent contains a first blocking agent represented by the following general formula (1), and at least a part of the aforementioned first blocking agent is neutralized with an acid.

[0015] [Chemical formula 1]

[0016] Chemical formula 1

[0017]

[0018] (In the formula, R 1 ~R 5 represents a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom. In addition, R 1 and R 3 may be bonded to each other to form a heterocyclic ring. In addition, it may be that R 4 and R 1 are bonded to each other to form a heterocyclic ring, and R 5 and R 3 are bonded to each other to form a heterocyclic ring.)

[0019] The present invention [2] includes the water-dispersible blocked isocyanate described in the above [1], wherein, in the aforementioned general formula (1), R 1 ~R 5 represents a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom.

[0020] The present invention [3] includes the water-dispersible blocked isocyanate described in the above [1] or [2], wherein the aforementioned blocking agent further contains a second blocking agent having a smaller catalytic effect on activating the isocyanate group than the aforementioned first blocking agent.

[0021] The present invention [4] includes the water-dispersible blocked isocyanate described in the above [3], wherein the content ratio of the aforementioned first blocking agent in the aforementioned blocking agent is higher than 2 mol% and lower than 80 mol%.

[0022] The present invention [5] includes the water-dispersible blocked isocyanate described in any one of the above [1] to [4], wherein the aforementioned acid includes an organic acid.

[0023] The present invention [6] includes the water-dispersible blocked isocyanate described in the above [5], wherein the aforementioned acid includes at least one organic acid selected from the group consisting of acetic acid, propionic acid, and lactic acid.

[0024] The present invention [7] includes the water-dispersible blocked isocyanate described in any one of the above [1] to [6], wherein the aforementioned polyisocyanate compound includes an aromatic polyisocyanate derivative and / or an araliphatic polyisocyanate derivative.

[0025] The present invention [8] includes a fiber treating agent, which contains the water-dispersible blocked isocyanate described in any one of [1] to [7] above.

[0026] The present invention [9] includes a water repellent, which contains the water-dispersible blocked isocyanate described in any one of [1] to [7] above.

[0027] The present invention

[10] includes a coating composition, which contains the water-dispersible blocked isocyanate described in any one of [1] to [7] above.

[0028] The present invention

[11] includes an adhesive, which contains the water-dispersible blocked isocyanate described in any one of [1] to [7] above.

[0029] Advantages of the Invention

[0030] In the water-dispersible blocked isocyanate of the present invention, at least a part of the first blocking agent represented by the above general formula (1) is neutralized by an acid. Therefore, the water-dispersible blocked isocyanate can be smoothly dispersed in water and can maintain the state of being dispersed in water for a long time. In addition, in the water-dispersible blocked isocyanate, at least a part of the first blocking agent dissociates from the isocyanate group at a relatively low temperature.

[0031] Therefore, the water-dispersible blocked isocyanate is excellent in low-temperature curability and storage stability.

[0032] The fiber treating agent, water repellent, coating composition and adhesive of the present invention contain the above water-dispersible blocked isocyanate. Therefore, the fiber treating agent, water repellent, coating composition and adhesive are excellent in low-temperature curability and storage stability. Detailed Embodiments

[0033] The water-dispersible blocked isocyanate is a blocked isocyanate obtained by blocking the isocyanate group of a polyisocyanate compound. In the water-dispersible blocked isocyanate, at least a part of the blocking agent that has blocked the isocyanate group is neutralized by an acid. The water-dispersible blocked isocyanate is used, for example, by being dispersed in water.

[0034] Hereinafter, when the blocking agent is not neutralized by an acid, it is simply referred to as "blocked isocyanate" to distinguish it from "water-dispersible blocked isocyanate".

[0035] The blocked isocyanate is a reaction product of a polyisocyanate compound and a blocking agent.

[0036] (1) Polyisocyanate Compound

[0037] Examples of the polyisocyanate compound include, for example, polyisocyanate monomers and polyisocyanate derivatives.

[0038] As the polyisocyanate monomer, for example, aliphatic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates can be cited.

[0039] As the aliphatic polyisocyanates, for example, ethylene diisocyanate, trimethylene diisocyanate, 1,4-butylene diisocyanate, 1,5-pentylene diisocyanate, 1,6-hexylene diisocyanate, trimethylhexamethylene diisocyanate, and 2,6-diisocyanatomethyl hexanoate can be cited.

[0040] In addition, as the aliphatic polyisocyanate monomer, alicyclic polyisocyanate monomers can also be cited.

[0041] As the alicyclic polyisocyanate monomers, for example, 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, methylene bis(cyclohexyl isocyanate), 2,4-cyclohexane diisocyanate methyl ester, 2,6-cyclohexane diisocyanate methyl ester, norbornane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and 1,4-bis(isocyanatomethyl)cyclohexane can be cited.

[0042] As the aromatic polyisocyanates, for example, toluene diisocyanate, benzene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, and 4,4'-diphenyl ether diisocyanate can be cited.

[0043] As the araliphatic polyisocyanates, for example, xylylene diisocyanate, tetramethylxylylene diisocyanate, and ω,ω'-diisocyanato-1,4-diethylbenzene can be cited.

[0044] The polyisocyanate derivatives are derived from the above polyisocyanate monomers. As the polyisocyanate derivatives, for example, isocyanurate-modified products, iminooxadiazinedione-modified products, triol adducts, urethane-modified products, biuret-modified products, urea-modified products, oxadiazinetrione-modified products, carbodiimide-modified products, uretdione-modified products, and uretonimine-modified products can be cited.

[0045] The polyisocyanate compound preferably contains polyisocyanate derivatives, and more preferably consists of polyisocyanate derivatives.

[0046] As the polyisocyanate derivative, preferably, there may be mentioned aliphatic polyisocyanate derivatives derived from aliphatic polyisocyanates, aromatic polyisocyanate derivatives derived from aromatic polyisocyanates, and araliphatic polyisocyanate derivatives derived from araliphatic polyisocyanates. More preferably, there may be mentioned aromatic polyisocyanate derivatives and araliphatic polyisocyanate derivatives. Further preferably, there may be mentioned araliphatic polyisocyanate derivatives.

[0047] As the aliphatic polyisocyanate derivative, further preferably, there may be mentioned isocyanurate-modified products of aliphatic polyisocyanates. Particularly preferably, there may be mentioned isocyanurate-modified products of 1,6-hexamethylene diisocyanate.

[0048] In addition, as the aromatic polyisocyanate derivative, further preferably, there may be mentioned isocyanurate-modified products of aromatic polyisocyanates. Particularly preferably, there may be mentioned isocyanurate-modified products of toluene diisocyanate.

[0049] In addition, as the araliphatic polyisocyanate derivative, further preferably, there may be mentioned isocyanurate-modified products of araliphatic polyisocyanates. Particularly preferably, there may be mentioned isocyanurate-modified products of xylylene diisocyanate.

[0050] In addition, the polyisocyanate compound may be modified with a hydrophilic compound containing an active hydrogen group, or a cationic hydrophilic group and a nonionic hydrophilic group may be used in combination.

[0051] The hydrophilic compound has an active hydrogen group and a hydrophilic group. As the hydrophilic compound, for example, nonionic hydrophilic compounds may be mentioned. Preferably, polyoxyethylene compounds may be mentioned. The polyoxyethylene compound has at least 3 consecutive oxyethylene groups.

[0052] As the polyoxyethylene compound, for example, polyols containing polyoxyethylene groups, polyamines containing polyoxyethylene groups, mono-terminally blocked polyoxyethylene diols, and mono-terminally blocked polyoxyethylene diamines may be mentioned.

[0053] The polyoxyethylene compound may be used alone or in combination of 2 or more.

[0054] The polyoxyethylene compound preferably contains mono-terminally blocked polyoxyethylene diols, and more preferably contains mono-alkoxy polyoxyethylene diols.

[0055] One end of the mono-alkoxy polyoxyethylene diol is blocked with an alkyl group having 1 to 20 carbon atoms, for example. The hydroxyl group is located at the other end of the mono-alkoxy polyoxyethylene diol.

[0056] As the mono-alkoxy polyoxyethylene diol, for example, methoxy polyoxyethylene diol and ethoxy polyoxyethylene diol may be mentioned. Preferably, methoxy polyoxyethylene diol may be mentioned.

[0057] The number average molecular weight of the polyoxyethylene compound is, for example, 200 or more, preferably 400 or more, and, for example, 2000 or less, preferably 1500 or less. It should be noted that the number average molecular weight of the polyoxyethylene compound can be measured by gel permeation chromatography.

[0058] When the polyisocyanate compound is modified with a hydrophilic compound, for example, the above-mentioned polyisocyanate monomer and / or polyisocyanate derivative and the above-mentioned hydrophilic compound are reacted in a proportion in which free isocyanate groups remain.

[0059] With respect to 100 moles of the isocyanate groups of the polyisocyanate compound before modification, the proportion of the active hydrogen groups of the hydrophilic compound is, for example, 0.5 mole or more, preferably 1 mole or more, and, for example, 10 moles or less, preferably 5 moles or less.

[0060] Such polyisocyanate compounds can be used alone or in combination of two or more.

[0061] The average number of functional groups of the isocyanate groups in the polyisocyanate compound is, for example, 2 or more, preferably 2.5 or more, and, for example, 4 or less, preferably 3.5 or less.

[0062] The content (NCO%) of the isocyanate groups in the polyisocyanate compound is, for example, 5% by mass or more, preferably 7% by mass or more, and, for example, 30% by mass or less, preferably 25% by mass or less.

[0063] (2) Blocking agent

[0064] The blocking agent contains at least a first blocking agent. Therefore, the blocked isocyanate contains at least a first latent isocyanate group formed by blocking the isocyanate group with the first blocking agent.

[0065] (2-1) First blocking agent

[0066] The first blocking agent blocks the isocyanate group to deactivate it. On the other hand, in the state where the isocyanate group has been blocked and the state where it has been deblocked, it has a catalytic action of activating the isocyanate group. The catalytic action will be described later.

[0067] The first blocking agent is represented by the following general formula (1). The first blocking agent is a guanidine compound having a guanidine skeleton.

[0068] [Chemical formula 2]

[0069] Chemical formula 2

[0070]

[0071] (In the formula, R1 ~R 5 represents a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom. Further, R 1 and R 3 may be bonded to each other to form a heterocyclic ring. Further, it may also be that R 4 and R 1 are bonded to each other to form a heterocyclic ring, and R 5 and R 3 are bonded to each other to form a heterocyclic ring.)

[0072] In the above general formula (1), R 1 ~R 5 may be the same as or different from each other. R 1 ~R 5 represents a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom. At least any one of R 1 ~R 5 preferably represents a hydrogen atom.

[0073] As the hydrocarbon group having 1 to 12 carbon atoms represented by R 1 ~R 5 , examples thereof include an alkyl group having 1 to 12 carbon atoms and an aryl group having 6 to 12 carbon atoms.

[0074] As the alkyl group having 1 to 12 carbon atoms, examples thereof include a linear alkyl group having 1 to 12 carbon atoms and a cyclic alkyl group having 3 to 12 carbon atoms.

[0075] As the linear alkyl group having 1 to 12 carbon atoms, examples of the linear or branched linear alkyl group having 1 to 12 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, isononyl, decyl, undecyl, and dodecyl.

[0076] As the cyclic alkyl group having 3 to 12 carbon atoms, examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and cyclododecyl.

[0077] As the aryl group having 6 to 12 carbon atoms, examples thereof include phenyl, tolyl, xylyl, naphthyl, azulenyl, and biphenyl.

[0078] The hydrocarbon groups having 1 to 12 carbon atoms in R 1 ~R 5 may be the same as or different from each other.

[0079] Further, R 1 and R 3 may be bonded to each other to form a heterocyclic ring.

[0080] R 1 and R3 The heterocycle formed by bonding with each other is a nitrogen-containing heterocycle having an -N=C-N- structure. Examples thereof include heterocycles having 3 to 20 members, preferably 3 to 10 members, more preferably 3 to 8 members, and still more preferably 5 to 7 members. In addition, the heterocycle may be, for example, monocyclic or polycyclic in which a plurality of monocycles share one side. In addition, the heterocycle may also be a conjugated heterocycle.

[0081] In addition, it may be R 4 and R 1 bond with each other to form a heterocycle, and R 5 and R 3 bond with each other to form a heterocycle.

[0082] In addition, the heterocycle formed by R 1 , R 3 , R 4 and R 5 may also be polycyclic in which a plurality of monocycles share one side. In this case, the formed heterocycle is a nitrogen-containing heterocycle having an -N=C-N- structure. Examples thereof include heterocycles having 6 to 20 members, preferably 6 to 15 members, more preferably 6 to 12 members, and still more preferably 10 to 12 members. In addition, the heterocycle may also be a conjugated heterocycle. It should be noted that when R 1 , R 3 , R 4 and R 5 form a heterocycle, R 2 preferably represents a hydrogen atom. As such a heterocyclic structure, specifically, a triazabicyclic ring structure can be cited.

[0083] In the above general formula (1), R 1 to R 5 preferably represent a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom, more preferably an alkyl group having 1 to 12 carbon atoms or a hydrogen atom, and still more preferably a linear alkyl group having 1 to 12 carbon atoms or a hydrogen atom. Particularly preferably, in the above general formula (1), R 1 , R 2 , R 4 and R 5 represent a linear alkyl group having 1 to 12 carbon atoms, and R 3 represents a hydrogen atom.

[0084] The first capping agent represented by the above general formula (1) can be used alone or in combination of two or more.

[0085] Specific examples of the first capping agent represented by the above general formula (1) include 3,3-dialkylguanidine, 1,1,3,3-tetraalkylguanidine, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0086] The first capping agent represented by the above general formula (1) preferably contains 1,1,3,3-tetraalkylguanidine, more preferably contains 1,1,3,3-tetramethylguanidine, and further preferably consists of 1,1,3,3-tetramethylguanidine.

[0087] If the first capping agent contains 1,1,3,3-tetraalkylguanidine, the low-temperature curability of the water-dispersible blocked isocyanate can be reliably ensured.

[0088] In addition, the dissociation temperature of the first capping agent is, for example, 60 °C or higher, preferably 80 °C or higher, for example, 150 °C or lower, preferably 130 °C or lower.

[0089] It should be noted that the dissociation temperature of the capping agent can be measured by the following method (the same applies hereinafter).

[0090] The blocked isocyanate is coated on a silicon wafer, and the temperature at which the isocyanate group regenerates is observed by IR measurement while heating. It should be noted that in the case where the catalytic ability of the capping agent is high and the regenerated isocyanate group cannot be observed, it can be mixed with a polyol, the mixture is coated on a silicon wafer, and the temperature at which the hydroxyl group of the polyol compound reacts is observed by IR measurement while heating, thereby measuring the dissociation temperature of the capping agent. The catalytic ability of the capping agent will be described later.

[0091] The content ratio of the first capping agent in the capping agent is, for example, 1 mol% or more, preferably higher than 2 mol%, more preferably 4 mol% or more, further preferably 6 mol% or more. In addition, for example, it is 100 mol% or less, preferably 90 mol% or less, more preferably less than 80 mol%, further preferably 70 mol% or less, and particularly preferably 25 mol% or less.

[0092] If the content ratio of the first capping agent is within the above range, the water dispersibility of the water-dispersible blocked isocyanate can be stably ensured, and the storage stability of the aqueous dispersion of the water-dispersible blocked isocyanate can be improved.

[0093] (2-2) The second capping agent

[0094] The capping agent preferably contains a second capping agent in addition to the above-mentioned first capping agent. The capping agent more preferably consists of the first capping agent and the second capping agent. Therefore, the blocked isocyanate preferably contains, in addition to the first latent isocyanate group, a second latent isocyanate group in which the isocyanate group is blocked by the second capping agent.

[0095] If the capping agent contains the second capping agent, the low-temperature curability of the water-dispersible blocked isocyanate can be more reliably ensured.

[0096] The second capping agent is a capping agent that caps and inactivates the isocyanate group and, on the other hand, regenerates the isocyanate group in the uncapped state. In addition, it is the following capping agent: it does not have a catalytic action to the extent of activating the regenerated isocyanate group, or even if it has a catalytic action to the extent of activating the regenerated isocyanate group, its catalytic action is smaller than that of the above-mentioned first capping agent.

[0097] It should be noted that the catalytic action of the first capping agent and the catalytic action of the second capping agent can be compared by the method described in paragraphs

[0242] to

[0247] of Japanese Patent Laid-Open No. 2017-82208.

[0098] Examples of the second capping agent include imidazole-based compounds, alcohol-based compounds, phenol-based compounds, active methylene-based compounds, amine-based compounds, imine-based compounds, oxime-based compounds, carbamic acid-based compounds, urea-based compounds, amide-based compounds, imide-based compounds, triazole-based compounds, pyrazole-based compounds, thiol-based compounds, bisulfites, imidazoline-based compounds, and pyrimidine-based compounds.

[0099] Examples of the imidazole-based compounds include imidazole, benzimidazole, 2-methylimidazole, 4-methylimidazole, 2-ethylimidazole, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, and 2-aminoimidazole.

[0100] Examples of the alcohol-based compounds include methanol, ethanol, 2-propanol, n-butanol, sec-butanol, 2-ethylhexanol, 1-octanol, 2-octanol, cyclohexanol, ethylene glycol, benzyl alcohol, 2,2,2-trifluoroethanol, 2,2,2-trichloroethanol, 2-(hydroxymethyl)furan, 2-methoxyethanol, methoxypropanol, 2-ethoxyethanol, n-propoxyethanol, 2-butoxyethanol, 2-ethoxyethoxyethanol, 2-ethoxybutoxyethanol, butoxyethoxyethanol, 2-butoxyethyl ethanol, 2-butoxyethoxyethanol, N,N-dibutyl-2-hydroxyacetamide, N-hydroxysuccinimide, N-morpholineethanol, 2,2-dimethyl-1,3-dioxolane-4-methanol, 3-oxazolidineethanol, 2-hydroxymethylpyridine, furfuryl alcohol, 12-hydroxystearic acid, triphenylsilanol, and 2-hydroxyethyl methacrylate.

[0101] Examples of phenolic compounds include phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, n-butylphenol, sec-butylphenol, tert-butylphenol, n-hexylphenol, 2-ethylhexylphenol, n-octylphenol, n-nonylphenol, di-n-propylphenol, diisopropylphenol, isopropylcresol, di-n-butylphenol, di-sec-butylphenol, di-tert-butylphenol, di-n-octylphenol, di-2-ethylhexylphenol, di-nonylphenol, nitrophenol, bromophenol, chlorophenol, fluorophenol, dimethylphenol, styrenated phenol, methyl salicylate, methyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 2-ethylhexyl 4-hydroxybenzoate, 4-[(dimethylamino)methyl]phenol, 4-[(dimethylamino)methyl]nonylphenol, bis(4-hydroxyphenyl)acetic acid, 2-hydroxypyridine, 2-hydroxyquinoline, 8-hydroxyquinoline, 2-chloro-3-pyridinol, and pyridine-2-thiol.

[0102] Examples of active methylene compounds include Meldrum's acid, dialkyl malonates, alkyl acetoacetates, 2-acetoxyethyl methacrylate, acetylacetone, and ethyl cyanoacetate. Examples of dialkyl malonates include dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-tert-butyl malonate, di-2-ethylhexyl malonate, methyl n-butyl malonate, ethyl n-butyl malonate, methyl sec-butyl malonate, ethyl sec-butyl malonate, methyl tert-butyl malonate, ethyl tert-butyl malonate, diethyl methylmalonate, dibenzyl malonate, diphenyl malonate, benzyl methyl malonate, ethyl phenyl malonate, tert-butyl phenyl malonate, and isopropylidene malonate. Examples of alkyl acetoacetates include methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, tert-butyl acetoacetate, benzyl acetoacetate, and phenyl acetoacetate.

[0103] Examples of amine compounds include dibutylamine, diphenylamine, aniline, N-methylaniline, carbazole, bis(2,2,6,6-tetramethylpiperidyl)amine, di-n-propylamine, diisopropylamine, isopropylethylamine, 2,2,4-trimethylhexamethylenediamine, 2,2,5-trimethylhexamethylenediamine, N-isopropylcyclohexylamine, dicyclohexylamine, bis(3,5,5-trimethylcyclohexyl)amine, piperidine, 2,6-dimethylpiperidine, tert-butylmethylamine, tert-butylethylamine, tert-butylpropylamine, tert-butylbutylamine, tert-butylbenzylamine, tert-butylphenylamine, 2,2,6-trimethylpiperidine, 2,2,6,6-tetramethylpiperidine, (dimethylamino)-2,2,6,6-tetramethylpiperidine, 2,2,6,6-tetramethyl-4-piperidine, 6-methyl-2-piperidine, and 6-aminocaproic acid.

[0104] Examples of imine compounds include, for example, ethyleneimine, polyethyleneimine, and 1,4,5,6-tetrahydropyrimidine.

[0105] Examples of oxime compounds include, for example, formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, cyclohexanone oxime, diacetyl monoxime, benzophenone oxime, 2,2,6,6-tetramethylcyclohexanone oxime, diisopropyl ketone oxime, methyl tert-butyl ketone oxime, diisobutyl ketone oxime, methyl isobutyl ketone oxime, methyl isopropyl ketone oxime, methyl 2,4-dimethylpentyl ketone oxime, methyl 3-ethylheptyl ketone oxime, methyl isoamyl ketone oxime, n-pentyl ketone oxime, 2,2,4,4-tetramethyl-1,3-cyclobutanedione monoxime, 4,4'-dimethoxybenzophenone oxime, and 2-heptanone oxime.

[0106] Examples of carbamic acid compounds include, for example, phenyl N-phenylcarbamate.

[0107] Examples of urea compounds include, for example, urea, thiourea, and ethyleneurea.

[0108] In other words, amide compounds are lactam compounds. Examples of amide compounds include, for example, acetanilide, N-methylacetamide, acetamide, ε-caprolactam, δ-valerolactam, γ-butyrolactam, pyrrolidone, 2,5-piperazinedione, and laurolactam, etc.

[0109] Examples of imide compounds include, for example, succinimide, maleimide, and phthalimide.

[0110] Examples of triazole compounds include, for example, 1,2,4-triazole and benzotriazole.

[0111] Examples of pyrazole compounds include, for example, pyrazole, 3-methylpyrazole, 3-methyl-5-phenylpyrazole, 3,5-diphenylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, and 3,5-dialkylpyrazole. 3,5-Dialkylpyrazole does not have a substituent at the 4-position of the pyrazole ring. Examples of 3,5-dialkylpyrazole include, for example, 3,5-dimethylpyrazole, 3,5-diisopropylpyrazole, and 3,5-di-tert-butylpyrazole.

[0112] Examples of thiol compounds include, for example, butyl mercaptan, dodecyl mercaptan, and hexyl mercaptan.

[0113] Examples of bisulfites include, for example, sodium bisulfite.

[0114] Examples of imidazoline compounds include, for example, 2-methylimidazoline and 2-phenylimidazoline.

[0115] As a pyrimidine compound, for example, 2-methyl-1,4,5,6-tetrahydropyrimidine can be cited.

[0116] In addition, the second capping agent is not limited to the above compounds. As the second capping agent, for example, benzoxazolone, isatoic acid anhydride, and tetrabutylphosphonium acetate can also be cited.

[0117] Such a second capping agent can be used alone or in combination of two or more.

[0118] The second capping agent preferably contains a pyrazole compound, and more preferably consists of a pyrazole compound. As the pyrazole compound, 3,5-diphenylpyrazole and 3,5-dialkylpyrazole are preferably cited, 3,5-dialkylpyrazole is more preferably cited, and 3,5-dimethylpyrazole is further preferably cited.

[0119] The dissociation temperature of the second capping agent is, for example, 150 °C or lower, preferably 140 °C or lower, more preferably 130 °C or lower, and, for example, 60 °C or higher.

[0120] The content ratio of the second capping agent in the capping agent is, for example, 0 mol% or more, preferably 10 mol% or more, more preferably higher than 20 mol%, further preferably 30 mol% or more, particularly preferably 75 mol% or more. In addition, for example, it is 99 mol% or less, preferably less than 98 mol%, more preferably 96 mol% or less, and further preferably 94 mol% or less.

[0121] (3) Preparation of blocked isocyanate

[0122] Next, the preparation of blocked isocyanate will be described.

[0123] To prepare blocked isocyanate, a capping agent is reacted with a polyisocyanate compound.

[0124] When the capping agent contains only the first capping agent, the polyisocyanate compound is reacted with the first capping agent.

[0125] The equivalent ratio (active group / isocyanate group) of the active group capable of reacting with the isocyanate group in the first capping agent to the isocyanate group of the polyisocyanate compound is, for example, 1.0 or more, and, for example, 1.5 or less, preferably 1.2 or less, and more preferably 1.1 or less.

[0126] In addition, the reaction of the polyisocyanate compound with the first capping agent is, for example, carried out in an inert gas atmosphere. As the inert gas, for example, nitrogen and argon can be cited.

[0127] The reaction temperature is, for example, 0 °C or higher, preferably 20 °C or higher, and, for example, 80 °C or lower, preferably 60 °C or lower. The reaction pressure is, for example, atmospheric pressure. The reaction time is, for example, 0.5 hours or longer, preferably 1.0 hour or longer, and, for example, 24 hours or shorter, preferably 12 hours or shorter.

[0128] Thereby, the isocyanate group reacts with the first capping agent to form a first latent isocyanate group.

[0129] In addition, when the capping agent contains the first capping agent and the second capping agent, the above-mentioned polyisocyanate compound is reacted with the above-mentioned first capping agent and the above-mentioned second capping agent.

[0130] There is no particular limitation on the reaction order of the polyisocyanate compound with the first capping agent and the second capping agent. For example, after reacting the polyisocyanate compound with the second capping agent in a proportion where free isocyanate groups remain, the capped isocyanate having free isocyanate groups is reacted with the first capping agent.

[0131] The equivalent ratio (active group / isocyanate group) of the active group capable of reacting with the isocyanate group in the second capping agent relative to the isocyanate group of the polyisocyanate compound is, for example, 0.1 or higher, preferably higher than 0.2, more preferably 0.3 or higher, further preferably 0.75 or higher, and, for example, lower than 0.99, preferably 0.98 or lower, more preferably 0.94 or lower.

[0132] Thereby, the second capping agent blocks a part of the isocyanate groups of the polyisocyanate compound to form a second latent isocyanate group, and the remaining part of the isocyanate groups of the polyisocyanate compound remains in a free state.

[0133] Next, the capped isocyanate having free isocyanate groups remaining is reacted with the first capping agent.

[0134] The equivalent ratio (active group / isocyanate group) of the active group capable of reacting with the isocyanate group in the first capping agent relative to the free isocyanate group of the capped isocyanate is, for example, 0.01 or higher, preferably 0.05 or higher, for example, 1.3 or lower, preferably 1.2 or lower, further preferably 1.1 or lower.

[0135] It should be noted that the reaction conditions of the polyisocyanate compound with the first capping agent and the second capping agent are the same as the reaction conditions of the above-mentioned polyisocyanate compound with the first capping agent.

[0136] In addition, the end of the reaction can be judged, for example, by confirming the disappearance or reduction of the isocyanate group by using infrared spectroscopy or the like.

[0137] Accordingly, the isocyanate groups remaining in the blocked isocyanate in a free state react with the first blocking agent to form the first latent isocyanate groups.

[0138] In addition, for each of the above reactions, it can be carried out without a solvent, or for example, in the presence of an organic solvent.

[0139] Examples of the organic solvent include ketones, nitriles, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, glycol ether esters, ethers, halogenated aliphatic hydrocarbons, and polar aprotics. The organic solvent can be used alone or in combination of two or more.

[0140] By the above method, a blocked isocyanate can be prepared.

[0141] The blocked isocyanate has at least the first latent isocyanate groups formed by blocking the isocyanate groups with the first blocking agent. The blocked isocyanate preferably has both the first latent isocyanate groups and the second latent isocyanate groups formed by blocking the isocyanate groups with the second blocking agent in one molecule.

[0142] The content ratio range of the first latent isocyanate groups in the blocked isocyanate is the same as the content ratio range of the first blocking agent in the above-mentioned blocking agent.

[0143] In addition, the content ratio range of the second latent isocyanate groups in the blocked isocyanate is the same as the content ratio range of the second blocking agent in the above-mentioned blocking agent.

[0144] It should be noted that the preparation method of the blocked isocyanate is not limited to the above method.

[0145] For example, after reacting the polyisocyanate compound with the first blocking agent in a proportion where free isocyanate groups remain, the blocked isocyanate having free isocyanate groups can be reacted with the second blocking agent. In addition, the polyisocyanate compound can be reacted with the first blocking agent and the second blocking agent simultaneously.

[0146] In addition, a polyisocyanate compound blocked only with the first blocking agent and a polyisocyanate compound blocked only with the second blocking agent can be separately prepared and mixed. In this case, the blocked isocyanate contains molecules having the first latent isocyanate groups and molecules having the second latent isocyanate groups, respectively.

[0147] (3) Acid

[0148] In the water-dispersible blocked isocyanate, at least a part of the first blocking agent that has blocked the isocyanate group is neutralized with an acid. As a result, the amino group possessed by the first blocking agent forms an ammonium salt as a cationic group. It should be noted that when the blocking agent contains a second blocking agent, the acid can neutralize a part of the second blocking agent.

[0149] Examples of the acid include organic acids and inorganic acids.

[0150] The acid preferably contains an organic acid, and more preferably consists of an organic acid.

[0151] If the acid contains an organic acid, the low-temperature curability and storage stability of the water-dispersible blocked isocyanate can be ensured more stably.

[0152] Examples of the organic acid include carboxylic acids having 2 or 3 carbon atoms and carboxylic acids having 4 or more carbon atoms. Preferred examples include carboxylic acids having 2 or 3 carbon atoms.

[0153] Examples of the carboxylic acid having 2 or 3 carbon atoms include acetic acid, propionic acid, and lactic acid. In other words, the acid is more preferably composed of at least one organic acid selected from the group consisting of acetic acid, propionic acid, and lactic acid.

[0154] The acid can be used alone or in combination of two or more.

[0155] In order to neutralize at least a part of the first blocking agent with an acid, for example, the above-mentioned blocked isocyanate and the above-mentioned acid are reacted.

[0156] The equivalent ratio of the acid to the first blocking agent that has blocked the isocyanate group (acid / first blocking agent) is, for example, 0.1 or more, preferably 0.5 or more, more preferably 0.8 or more. In addition, for example, it is 5.0 or less, preferably 3.0 or less, more preferably 2.0 or less.

[0157] In addition, the reaction of the blocked isocyanate and the acid is not particularly limited. For example, it is carried out in the atmosphere or in an inert gas atmosphere. Examples of the inert gas include nitrogen and argon.

[0158] The reaction temperature is, for example, 0°C or more, preferably 20°C or more. In addition, for example, it is 80°C or less, preferably 60°C or less. As the conditions of the reaction pressure, there is no particular limitation. For example, pressurized conditions and atmospheric pressure conditions can be cited, and atmospheric pressure conditions are preferably cited. The reaction time is, for example, 0.1 hour or more, preferably 0.5 hour or more. In addition, for example, it is 24 hours or less, preferably 12 hours or less.

[0159] In addition, the above reaction is preferably carried out in the presence of the above organic solvent.

[0160] As a result, the amino group of the first blocking agent having the isocyanate group blocked is neutralized with an acid to form an ammonium salt as a cationic group.

[0161] In the above manner, water-dispersible blocked isocyanate can be produced.

[0162] When an organic solvent is used in the reaction of the blocked isocyanate with an acid, the water-dispersible blocked isocyanate is dissolved in the reaction solution containing the organic solvent.

[0163] In this case, water is added to the reaction solution containing the water-dispersible blocked isocyanate, and the reaction solution and water are emulsified using a stirrer. Then, for example, the emulsion is heated under reduced pressure to volatilize and remove the organic solvent.

[0164] As a result, an aqueous dispersion of water-dispersible blocked isocyanate can be produced.

[0165] The solid content concentration of the aqueous dispersion of water-dispersible blocked isocyanate is, for example, 1% by mass or more, preferably 10% by mass or more, and, for example, 80% by mass or less, preferably 50% by mass or less.

[0166] The viscosity of the aqueous dispersion of water-dispersible blocked isocyanate is, for example, 1 mPa·s or more, preferably 3 mPa·s or more, and, for example, 800 mPa·s or less, preferably 500 mPa·s or less. It should be noted that the viscosity of the aqueous dispersion can be measured according to the method described in the examples below (the same applies hereinafter).

[0167] The pH of the aqueous dispersion of water-dispersible blocked isocyanate is, for example, 3.0 or more, preferably 4.0 or more, and, for example, 9.0 or less, preferably 8.0 or less. It should be noted that the pH of the aqueous dispersion can be measured according to the method described in the examples below (the same applies hereinafter).

[0168] The particle size in the aqueous dispersion of water-dispersible blocked isocyanate is, for example, 5 nm or more, preferably 10 nm or more, and, for example, 500 nm or less, preferably 300 nm or less. It should be noted that the particle size of the aqueous dispersion can be measured according to the method described in the examples below (the same applies hereinafter).

[0169] <Function and effect>

[0170] In the above water-dispersible blocked isocyanate, at least a part of the first blocking agent represented by the above general formula (1) is neutralized with an acid. Therefore, the water-dispersible blocked isocyanate can be smoothly dispersed in water and can maintain the state of being dispersed in water for a long time. In addition, in the water-dispersible blocked isocyanate, at least a part of the first blocking agent dissociates from the isocyanate group at a relatively low temperature, specifically 120°C or lower.

[0171] Therefore, the water-dispersible blocked isocyanate has excellent low-temperature curability and storage stability.

[0172] In addition, if at least a part of the first blocking agent represented by the above general formula (1) is neutralized with an acid, the above water-dispersible blocked isocyanate contains a cationic salt of a tertiary ammonium formed by the above neutralization. Therefore, the water-dispersible blocked isocyanate can exhibit excellent antibacterial properties derived from the cationic salt of the tertiary ammonium.

[0173] <Resin raw material>

[0174] The resin raw material contains the above water-dispersible blocked isocyanate and, if necessary, a polyol compound. Examples of the resin raw material include a two-component polyurethane resin raw material, a one-component polyurethane resin raw material, and a blocked isocyanate-binder resin composition.

[0175] The two-component polyurethane resin raw material is a polyurethane resin raw material in which a curing agent containing the above water-dispersible blocked isocyanate and a main agent containing a polyol compound are separately prepared and mixed just before use.

[0176] The one-component polyurethane resin raw material is a polyurethane resin raw material obtained by previously mixing a curing agent containing the above water-dispersible blocked isocyanate and a main agent containing a polyol compound.

[0177] The blocked isocyanate-binder resin composition is a composition obtained by previously mixing the above water-dispersible blocked isocyanate and a binder resin liquid containing a binder resin. It should be noted that the binder resin liquid does not contain a polyol compound.

[0178] Examples of the polyol compound include low molecular weight polyols and high molecular weight polyols.

[0179] The number average molecular weight of the low molecular weight polyol is, for example, less than 300, preferably less than 400. The low molecular weight polyol has two or more hydroxyl groups.

[0180] Examples of the low molecular weight polyol include diols, triols, tetraols, pentaols, hexaols, heptaols, and octaols.

[0181] As the dihydric alcohol, examples thereof include ethylene glycol, propylene glycol, 1,3 - propanediol, 1,4 - butanediol, 1,3 - butanediol, 1,2 - butanediol, 1,5 - pentanediol, 1,6 - hexanediol, neopentyl glycol, 3 - methyl - 1,5 - pentanediol, 2,2,2 - trimethylpentanediol, 3,3 - bis(hydroxymethyl)heptane, alkane (C7 - 20) diol, 1,3 - cyclohexanedimethanol, 1,4 - cyclohexanedimethanol, 1,3 - cyclohexanediol, 1,4 - cyclohexanediol, hydrogenated bisphenol A, 1,4 - dihydroxy - 2 - butene, 2,6 - dimethyl - 1 - octene - 3,8 - diol, bisphenol A, diethylene glycol, triethylene glycol, and dipropylene glycol.

[0182] As the trihydric alcohol, examples thereof include glycerin, trimethylolpropane, and triisopropanolamine.

[0183] As the tetrahydric alcohol, examples thereof include tetramethylolmethane (pentaerythritol), and diglycerol.

[0184] As the pentahydric alcohol, examples thereof include xylitol.

[0185] As the hexahydric alcohol, examples thereof include sorbitol, mannitol, allitol, iditol, dulcitol, adonitol, inositol, and dipentaerythritol.

[0186] As the heptahydric alcohol, examples thereof include perseitol.

[0187] As the octahydric alcohol, examples thereof include sucrose.

[0188] Such low - molecular - weight polyhydric alcohols can be used alone or in combination of two or more.

[0189] The number - average molecular weight of the high - molecular - weight polyhydric alcohol is, for example, 300 or more, preferably 400 or more, and more preferably 500 or more. The high - molecular - weight polyhydric alcohol has two or more hydroxyl groups.

[0190] As the high - molecular - weight polyhydric alcohol, examples thereof include polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy - group polyol, vegetable - oil polyol, polyolefin polyol, acrylic polyol, vinyl - monomer - modified polyol, and fluorine - containing polyol.

[0191] As the polyether polyol, examples thereof include polyoxyalkylene (C2 - 3) polyol, and polytetramethylene ether glycol.

[0192] As the polyester polyol, examples thereof include adipic - acid - based polyester polyol, phthalic - acid - based polyester polyol, and lactone - based polyester polyol.

[0193] As the polycarbonate polyol, for example, a ring-opening polymer of ethylene carbonate using the above-mentioned low molecular weight polyol as an initiator, and an amorphous polycarbonate polyol obtained by copolymerizing the above-mentioned diol and the ring-opening polymer can be cited.

[0194] As the polyurethane polyol, for example, polyester polyurethane polyol, polyether polyurethane polyol, polycarbonate polyurethane polyol, and polyester polyether polyurethane polyol can be cited.

[0195] As the epoxy group polyol, for example, an epoxy group polyol obtained by the reaction of the above-mentioned low molecular weight polyol and a polyfunctional haloalcohol can be cited.

[0196] As the vegetable oil polyol, for example, castor oil, coconut oil, and ester-modified castor oil polyol can be cited.

[0197] As the polyolefin polyol, for example, polybutadiene polyol and a partially saponified ethylene-vinyl acetate copolymer can be cited.

[0198] As the acrylic polyol, for example, a copolymer of a hydroxy-containing acrylate and a copolymerizable vinyl monomer capable of copolymerizing with the hydroxy-containing acrylate can be cited.

[0199] The vinyl monomer-modified polyol is obtained by the reaction of the above-mentioned high molecular weight polyol and a vinyl monomer.

[0200] As the fluorine-containing polyol, for example, an acrylic polyol obtained by incorporating a fluorine compound as a copolymerizable vinyl monomer in the copolymerization of the above-mentioned acrylic polyol can be cited.

[0201] These high molecular weight polyols can be used alone or in combination of two or more.

[0202] Such polyol compounds can be used alone or in combination of two or more.

[0203] Among the polyol compounds, high molecular weight polyols are preferably cited, and polyurethane polyols and acrylic polyols are more preferably cited.

[0204] As the binder resin, in addition to the above-mentioned polyol compounds, for example, high molecular compounds without a hydroxy group can be cited, and urethane resins and acrylic resins are preferably cited.

[0205] In addition, according to requirements, additives can be appropriately incorporated into any one or all of the water-dispersible blocked isocyanate, polyol compound, and binder resin. Examples of additives include reaction solvents, catalysts, epoxy resins, coating property improvers, leveling agents, defoamers, antioxidants, ultraviolet absorbers, thickeners, anti-settling agents, plasticizers, surfactants, pigments, fillers, organic fine particles, inorganic fine particles, and mildew-proof agents. The blending amount of the additives can be appropriately determined according to their purposes and uses.

[0206] In the blending of the water-dispersible blocked isocyanate and the polyol compound, the equivalent ratio of the latent isocyanate groups of the water-dispersible blocked isocyanate to the hydroxyl groups of the polyol compound (latent isocyanate groups / hydroxyl groups) is, for example, 0.1 or more, preferably 0.5 or more, and, for example, 5 or less, preferably 3 or less.

[0207] Moreover, a treatment agent containing any one of the water-dispersible blocked isocyanate, polyol compound, and binder resin, or a mixture thereof, is applied to an object by a known coating method and dried, thereby forming a coating film. Then, the coating film is heated and, if necessary, cured.

[0208] The heating temperature is, for example, 60°C or higher, preferably 80°C or higher, and, for example, 180°C or lower, preferably 150°C or lower, more preferably 130°C or lower, further preferably 120°C or lower, and particularly preferably 110°C or lower.

[0209] In the case of a high heating temperature, as the low-temperature curable curing of the present invention, the curing time can be shortened.

[0210] Examples of uses of such resin raw materials include fiber treatment agents, water repellents, coating compositions, adhesives, antistatic agents, paper-making treatment agents, paper wet strength agents, receiving layers of recording media, electrodeposition coating compositions, antibacterial and antiviral compositions, encapsulated compositions, optical members, and latex compositions.

[0211] Among the uses of such resin raw materials, fiber treatment agents, water repellents, coating compositions, and adhesives are preferably cited, and fiber treatment agents and water repellents are more preferably cited.

[0212] <Fiber treatment agent>

[0213] The fiber treatment agent is used for printing ink on a cloth-like fiber product to form an image by printing. Examples of printing include, for example, analog printing and digital printing. Examples of analog printing include, for example, printing based on screen printing. Examples of digital printing include, for example, printing based on inkjet printing.

[0214] When printing ink on a fibrous fabric article without using a fiber treatment agent, the rubbing fastness of the dyed article may sometimes not be sufficiently ensured.

[0215] The fibrous fabric article is composed of fibers. Examples of the form of the fibrous fabric article include, for example, woven fabric, knitted fabric, non-woven fabric, and flannelette. The fibrous fabric article may also have parts other than fibers.

[0216] Examples of the fibers of the fibrous fabric article include, for example, natural fibers, regenerated fibers, synthetic fibers, semi-synthetic fibers, and inorganic fibers.

[0217] Examples of the natural fibers include, for example, cotton, kapok, flax, ramie, jute, abaca, sisal, cashmere, mohair, alpaca hair, camel hair, silk, wool, and feathers.

[0218] Examples of the regenerated fibers include, for example, rayon, polynosic fiber, cuprammonium fiber, and Tencel.

[0219] Examples of the synthetic fibers include, for example, polyamide fiber, polyester fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber, polyurethane fiber, polyoxymethylene fiber, polytetrafluoroethylene fiber, benzoate fiber, poly(p-phenylene benzobisthiazole) fiber, poly(p-phenylene benzobisoxazole) fiber, polyimide fiber, and lactic acid fiber.

[0220] Examples of the semi-synthetic fibers include, for example, acetate and promix.

[0221] Examples of the inorganic fibers include, for example, asbestos, glass fiber, carbon fiber, alumina fiber, silicon carbide fiber, boron fiber, Tyranno fiber, inorganic whiskers, rock fiber, and slag fiber glass fiber.

[0222] The fibers can be used alone or in combination of two or more.

[0223] Specifically, examples of the fibrous fabric article include clothing, personal items, and other articles. Examples of the clothing include, for example, shirts, training clothes, sportswear, shorts, dresses, blouses, hats, and socks. Examples of the personal items include, for example, handkerchiefs, neckties, and cloth belts. Examples of the other articles include, for example, shoes, bedding, sheets, curtains, car seats, bags, and flags.

[0224] In addition, the color of the fibrous fabric article is not particularly limited. The fibrous fabric article can be white or colored other than white.

[0225] The surface of such a fibrous fabric article has an anionic property.

[0226] The ink contains, for example, an anionic resin, a pigment, and water.

[0227] Examples of the anionic resin include a resin having an anionic group and a resin surface-treated with an anionic dispersant.

[0228] Examples of the resin include a urethane resin, a (meth)acrylic resin, an olefin resin, a vinyl resin, and a cellulose resin. It should be noted that examples of (meth)acrylic acid include methacrylic acid and acrylic acid (the same applies hereinafter).

[0229] Examples of the anionic group include a carboxyl group and a sulfo group. The anionic group is located in the main chain or side chain of the resin.

[0230] Examples of the anionic dispersant include an anionic surfactant.

[0231] The anionic resin can be used alone or in combination of two or more.

[0232] Examples of the pigment include known organic pigments and known inorganic pigments.

[0233] In addition, the ink can contain the above-mentioned low molecular weight polyol as needed.

[0234] The fiber treatment agent is applied to the fabric-like fiber product as a pretreatment and / or post-treatment for printing the ink on the fabric-like fiber product in dyeing. The fiber treatment agent can impart excellent rubbing fastness to the dyed product.

[0235] The fiber treatment agent contains at least the above-mentioned water-dispersible blocked isocyanate. Therefore, the fiber treatment agent has excellent low-temperature curability and storage stability. In addition, the fiber treatment agent preferably further contains the above-mentioned high molecular weight polyol.

[0236] The fiber treatment agent can further contain a nonionic resin and / or a cationic resin.

[0237] Examples of the nonionic resin include a resin having a nonionic group and a resin surface-treated with a nonionic dispersant.

[0238] Examples of the resin as the nonionic resin include the above-mentioned resins.

[0239] Examples of the nonionic group include at least three consecutive oxyethylene groups (polyoxyethylene groups). The nonionic group is located in the main chain or side chain of the resin.

[0240] Examples of the nonionic dispersant include polyoxyethylene alkyl phenyl ethers and polyoxyethylene alkyl ethers. The nonionic dispersant may be used alone or in combination of two or more.

[0241] Examples of the cationic resin include a resin having a cationic group and a resin surface-treated with a cationic dispersant.

[0242] Examples of the resin as the cationic resin include the above resins.

[0243] Examples of the cationic group include an amino group, a pyridyl group, an imidazolyl group, a benzimidazolyl group, a triazolyl group, a benzotriazolyl group, a pyrazolyl group, and a benzopyrazolyl group. The cationic group is located in the main chain or side chain of the resin.

[0244] Examples of the cationic dispersant include an acrylic polymer containing an amino group, polyethyleneimine, a cationic polyvinyl alcohol resin, and a cationic water-soluble multi-branched polyester amide resin. The cationic dispersant may be used alone or in combination of two or more.

[0245] The cationic resin may be used alone or in combination of two or more.

[0246] Such a fiber treatment agent is, for example, a polyurethane resin, a polyester resin, or an acrylic resin, and preferably a polyurethane resin raw material.

[0247] When the fiber treatment agent is a polyurethane resin raw material, the fiber treatment agent is, for example, a mixed dispersion obtained by previously mixing a water dispersion of a water-dispersible blocked isocyanate as a curing agent and a water dispersion of a high molecular weight polyol as a main agent in the above ratio.

[0248] More specifically, when the fiber treatment agent is used for the pretreatment of printing, first, the water-dispersible blocked isocyanate and the high molecular weight polyol are mixed so that the equivalent ratio of the latent isocyanate group to the hydroxyl group falls within the above range, and a pretreatment liquid as an example of the fiber treatment agent is prepared.

[0249] In addition, water and / or alcohol is added to the pretreatment liquid as needed to adjust the solid content concentration of the pretreatment liquid. The solid content concentration of the pretreatment liquid is, for example, 1% by mass or more, and for example, 20% by mass or less, preferably 10% by mass or less.

[0250] Next, the pretreatment liquid is applied to the above-mentioned cloth-like fiber product. Examples of the method for applying the pretreatment liquid include a padding method, a dipping method, a spraying method, a coating method, and a printing method, and the dipping method is preferably used. Specifically, after the cloth-like fiber product is immersed in the pretreatment liquid, the cloth-like fiber product is lifted from the pretreatment liquid and dried as needed.

[0251] Thus, a coating film of the pretreatment liquid is formed on the surface of the fabric-like fiber product. Then, the coating film of the pretreatment liquid is heated to the above-mentioned heating temperature.

[0252] At this time, the above-mentioned first blocking agent dissociates from the above-mentioned polyisocyanate compound. Therefore, the polyisocyanate compound reacts with the high molecular weight polyol to form a polyurethane resin. Thus, the coating film of the pretreatment liquid is cured.

[0253] The cured coating film of the pretreatment liquid contains the first blocking agent in a de-blocked state, and at least a part of the first blocking agent is neutralized by an acid to form an ammonium salt. Therefore, the cured coating film of the pretreatment liquid has cationicity. The cured coating film of the pretreatment liquid having cationicity forms an ionic bond with the surface of the fabric-like fiber product having anionicity. As a result, the cured coating film of the pretreatment liquid can be stably fixed to the surface of the fabric-like fiber product.

[0254] Next, the above-mentioned ink is printed on the cured coating film of the pretreatment liquid to form an ink layer. Additionally, the ink layer is dried as needed. The ink layer contains an anionic resin. Therefore, the ink layer has anionicity. The ink layer having anionicity forms an ionic bond with the cured coating film of the pretreatment liquid having cationicity. Therefore, the ink layer can be stably fixed to the cured coating film of the pretreatment liquid.

[0255] In addition, when a fiber treatment agent is used for post-treatment of printing, a post-treatment liquid as an example of the fiber treatment agent is prepared in the same manner as the pretreatment liquid. Then, the post-treatment liquid is coated so as to cover the ink layer. Then, the coating film of the post-treatment liquid is heated to the above-mentioned heating temperature to cure it. The cured coating film of the post-treatment liquid has cationicity in the same manner as the cured coating film of the pretreatment liquid. The cured coating film of the post-treatment liquid having cationicity forms an ionic bond with the ink layer having anionicity. Therefore, the cured coating film of the post-treatment liquid can be stably fixed to the ink layer.

[0256] In the above manner, a dyed fabric obtained by forming an image on a fabric-like fiber product can be prepared.

[0257] The dyed fabric sequentially includes a fabric-like fiber product having anionicity, a cured coating film of a pretreatment liquid having cationicity, an ink layer having anionicity, and a cured coating film of a post-treatment liquid having cationicity as needed in the thickness direction of the fabric-like fiber product.

[0258] In such a dyed fabric, an ionic bond is formed between the fabric-like fiber product and the cured coating film of the pretreatment liquid, and an ionic bond is formed between the cured coating film of the pretreatment liquid and the ink layer. As needed, an ionic bond is formed between the ink layer and the cured coating film of the post-treatment liquid. Therefore, excellent rubbing fastness can be imparted to the dyed fabric.

[0259] <Hydrophobic agent>

[0260] The hydrophobic agent imparts hydrophobicity that inhibits water adhesion to the above-described cloth-like fiber product.

[0261] The cloth-like fiber product is usually washed and reused repeatedly. Therefore, wash durability is desired, that is, even if the cloth-like fiber product treated with the hydrophobic agent is washed multiple times, excellent hydrophobicity can be maintained.

[0262] The hydrophobic agent contains at least the above-described water-dispersible blocked isocyanate. Therefore, the hydrophobic agent has excellent low-temperature curability and storage stability. In addition, the hydrophobic agent preferably further contains a fluororesin.

[0263] The fluororesin is a polymer of a fluorine-containing (meth)acrylate monomer. As the fluorine-containing (meth)acrylate monomer, for example, a (meth)acrylate having 3 to 6 carbon atoms in the perfluoroalkyl group can be mentioned.

[0264] The fluororesin may also be a copolymer of a fluorine-containing (meth)acrylate monomer and other monomers.

[0265] As the other monomers, for example, (meth)acrylates, (meth)acrylamides, alkyl maleates, olefins, vinyl carboxylates, styrenes, and vinyl ethers can be mentioned.

[0266] As the (meth)acrylates, for example, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, glycidyl (meth)acrylate, aziridinyl (meth)acrylate, hydroxyalkyl (meth)acrylate, 3-chloro-2-hydroxypropyl methacrylate, and alkylene glycol acrylate can be mentioned.

[0267] As the (meth)acrylamides, for example, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, diacetone (meth)acrylamide, and hydroxymethylated diacetone acrylamide can be mentioned.

[0268] As the alkyl maleates, for example, dibutyl maleate can be mentioned.

[0269] As the olefins, for example, ethylene, propylene, butadiene, isoprene, vinyl chloride, vinyl fluoride, vinylidene chloride, vinylidene fluoride, and chloroprene can be mentioned.

[0270] As the vinyl carboxylates, for example, vinyl acetate can be mentioned.

[0271] As the styrenes, for example, styrene, α-methylstyrene, and β-methylstyrene can be mentioned.

[0272] Examples of the vinyl ether include ethyl vinyl ether, cyclohexyl vinyl ether, and haloalkyl vinyl ether.

[0273] These other monomers may be used alone or in combination of two or more.

[0274] Regarding the polymerization ratio of the fluorine-containing (meth)acrylate monomer, it is, for example, 40% by mass or more, preferably 50% by mass or more, and, for example, 100% by mass or less, preferably 80% by mass or less, based on all the monomers used in the copolymerization.

[0275] Regarding the content ratio of such a fluororesin, it is, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, and, for example, 95% by mass or less, based on 100% by mass of the total of the fluororesin and the water-dispersible blocked isocyanate.

[0276] In addition, the water repellent may further contain a nonionic compound and / or a cationic compound.

[0277] Examples of the nonionic compound include an ether-type nonionic compound, an ester-type nonionic compound, and an alkanolamide-type nonionic compound.

[0278] Examples of the ether-type nonionic compound include a compound obtained by adding ethylene oxide to an alcohol having 10 to 18 carbon atoms, a compound obtained by adding ethylene oxide to an alkylphenol, a compound obtained by adding ethylene oxide to polypropylene alcohol, and a compound obtained by adding ethylene oxide to a fatty acid ester of a polyol.

[0279] Examples of the ester-type nonionic compound include glycerol fatty acid ester and sorbitan fatty acid ester.

[0280] Examples of the alkanolamide-type nonionic compound include a reaction product of a fatty acid and diethanolamine.

[0281] These nonionic compounds may be used alone or in combination of two or more.

[0282] Examples of the cationic compound include a quaternary ammonium salt and an alkylamine salt.

[0283] These cationic compounds may be used alone or in combination of two or more.

[0284] Such a water repellent is, for example, a blocked isocyanate-binder resin composition.

[0285] When the water repellent is a blocked isocyanate - binder resin composition, the water repellent is, for example, a mixed liquid obtained by mixing an aqueous dispersion of a water - dispersible blocked isocyanate and a fluororesin as a binder resin in the above - mentioned ratio.

[0286] The solid - component concentration of the water repellent can be adjusted by adding water to the water repellent. The solid - component concentration of the water repellent is, for example, 0.5 mass% or more, and, for example, 10 mass% or less, preferably 5 mass% or less.

[0287] When treating a cloth - like fiber product with such a water repellent, the water repellent is applied to the above - mentioned cloth - like fiber product. As a method for applying the water repellent, for example, the same method as the method for applying a pretreatment agent can be cited, and the dipping method is preferably cited. Specifically, after immersing the cloth - like fiber product in the water repellent, the cloth - like fiber product is lifted from the water repellent and dried as needed.

[0288] Thereby, a water - repellent coating film is formed on the surface of the cloth - like fiber product. Then, the water - repellent coating film is heated to the above - mentioned heating temperature. At this time, the above - mentioned first blocking agent dissociates from the above - mentioned polyisocyanate compound.

[0289] Therefore, the water - repellent coating film contains the first blocking agent in a de - blocked state, and at least a part of the first blocking agent is neutralized by an acid to form an ammonium salt. Thus, the water - repellent coating film has cationicity. The water - repellent coating film having cationicity forms an ionic bond with the surface of the cloth - like fiber product having anionicity.

[0290] As a result, the water - repellent coating film can be stably fixed to the surface of the cloth - like fiber product, and excellent washing durability can be imparted to the cloth - like fiber product treated with the water repellent.

[0291] <Coating composition>

[0292] The coating composition contains at least the above - mentioned water - dispersible blocked isocyanate. Therefore, the coating composition has excellent low - temperature curability and storage stability. In addition, the coating composition preferably further contains the above - mentioned high - molecular - weight polyol.

[0293] Such a coating composition is, for example, a polyurethane resin, a polyester resin, an acrylic resin, and preferably a polyurethane resin raw material.

[0294] When the coating composition is a polyurethane resin raw material, the coating composition is, for example, a mixed dispersion obtained by premixing an aqueous dispersion of a water - dispersible blocked isocyanate as a curing agent and an aqueous dispersion of a high - molecular - weight polyol as a main agent in the above - mentioned ratio.

[0295] In addition, water is added to the coating composition as needed to adjust the solid content concentration of the coating composition. The solid content concentration of the coating composition is, for example, 1% by mass or more, and, for example, 40% by mass or less, preferably 30% by mass or less.

[0296] Moreover, the coating composition is applied to the object to be coated by a known coating method.

[0297] Examples of the coating method include spray coating, dip coating, spin coating, rotary atomization coating, and curtain coating.

[0298] Examples of the object to be coated include inorganic substances and organic substances. Examples of inorganic substances include concrete, natural stone, glass, and metal. Examples of organic substances include plastic, rubber, adhesive, and wood.

[0299] Then, the coating film of the coating composition is heated to the above-mentioned heating temperature.

[0300] At this time, the above-mentioned first blocking agent dissociates from the above-mentioned polyisocyanate compound. Then, the polyisocyanate compound reacts with the high molecular weight polyol to form a polyurethane resin. Thereby, the coating film of the coating composition is cured.

[0301] The cured coating film of such a coating composition has excellent adhesion to the object to be coated.

[0302] <Adhesive>

[0303] The adhesive at least contains the above-mentioned water-dispersible blocked isocyanate. Therefore, the adhesive has excellent low-temperature curability and storage stability. In addition, the adhesive preferably further contains the above-mentioned high molecular weight polyol.

[0304] Such an adhesive is, for example, a polyurethane resin, a polyester resin, or an acrylic resin, and preferably a polyurethane resin raw material.

[0305] When the adhesive is a polyurethane resin raw material, the adhesive is, for example, a mixed dispersion obtained by pre-mixing a water dispersion of a water-dispersible blocked isocyanate as a curing agent and a water dispersion of a high molecular weight polyol as a main agent in the above-mentioned ratio.

[0306] In addition, water is added to the adhesive as needed to adjust the solid content concentration of the adhesive. The range of the solid content concentration of the adhesive is, for example, the same as the range of the solid content concentration of the coating composition.

[0307] Then, the adhesive is applied to a specified position for bonding the adherends by the above-mentioned coating method.

[0308] Examples of adherends include, for example, packaging materials and civil engineering materials. Examples of packaging materials include, for example, plastic films, metal foils, and metal vapor deposition films. Examples of civil engineering materials include, for example, FRP and steel materials.

[0309] Then, while bringing the adherend into contact with the adhesive, the adhesive is heated to the above-mentioned heating temperature. Thereby, the adhesive cures. The cured product of such an adhesive has excellent adhesiveness to the adherend.

[0310] <Other uses>

[0311] Regarding the above-mentioned water-dispersible blocked isocyanate, in addition to fiber treating agents, water repellents, coating compositions, and adhesives, it can be suitably used in various industrial fields. In particular, the above-mentioned water-dispersible blocked isocyanate can exhibit excellent antibacterial properties derived from the cationic salt of tertiary ammonium, and thus can be suitably used as an antibacterial agent.

[0312] Examples

[0313] Examples are shown below to more specifically illustrate the present invention, but the present invention is not limited thereto. The specific numerical values of the compounding ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the upper limit values (values defined in the form of "below" and "less than") or lower limit values (values defined in the form of "above" and "more than") of the corresponding compounding ratios (content ratios), physical property values, parameters, etc. described in the above-mentioned "Detailed Description". It should be noted that unless otherwise specified, "parts" and "%" are based on mass.

[0314] <Preparation of water-dispersible blocked isocyanate>

[0315] Examples 1 to 11

[0316] At room temperature (25 °C), 200 parts by mass of an isocyanurate derivative of hexamethylene diisocyanate (HDI) (polyisocyanate compound, trade name: TAKENATE (registered trademark) D-170N, solid content: 100% by mass, isocyanate group content: 20.7%, manufactured by Mitsui Chemicals, Inc.) and ethyl acetate (solvent) were charged into a 2-L reactor equipped with a stirrer, a thermometer, a condenser, and a nitrogen inlet tube.

[0317] Next, 3,5-dimethylpyrazole (DMP, the second blocking agent) was added to the reactor. The addition ratio of DMP was the number of moles shown in Table 1 per 100 moles of the isocyanate group of the isocyanurate derivative of HDI. Then, the isocyanurate derivative of HDI was reacted with DMP.

[0318] Next, 1,1,3,3 - tetramethylguanidine (TMG, the first capping agent) was added to the reactor. The addition ratio of TMG was the number of moles shown in Table 1 relative to 100 moles of the isocyanate groups of the isocyanurate derivative of HDI. Then, the isocyanurate derivative of HDI was reacted with TMG.

[0319] Then, by measuring the FT - IR spectrum, it was confirmed that the isocyanate groups had been blocked. Thus, a reaction solution containing blocked isocyanate was obtained.

[0320] Next, acetic acid was added to the reaction solution and stirred. The addition ratio of acetic acid was the number of moles shown in Table 1 relative to 1 mole of the first capping agent (TMG) used. At this time, the temperature of the reaction solution was 28 °C. The stirring time was 0.5 hours.

[0321] Thus, the amino group of the first capping agent was neutralized by acetic acid, and ammonium acetate salt as a cationic group was formed. Thus, a reaction solution containing water - dispersible blocked isocyanate was obtained.

[0322] Then, 220 parts by mass of water was added to 120 parts by mass of the reaction solution containing water - dispersible blocked isocyanate. Then, the reaction solution and water were stirred with a homogenizer to emulsify them.

[0323] Next, under reduced pressure, ethyl acetate (the solvent) was distilled off from the emulsion, and at the same time, a part of the water was distilled off.

[0324] In this way, an aqueous dispersion of water - dispersible blocked isocyanate was prepared. The solid - component concentration of the aqueous dispersion of water - dispersible blocked isocyanate was 30% by mass.

[0325] Example 12

[0326] An aqueous dispersion of water - dispersible blocked isocyanate was prepared in the same manner as in Example 1.

[0327] It should be noted that in Example 12, as shown in Table 2, the second capping agent was not used. For the isocyanurate derivative of hexamethylene diisocyanate (HDI), only TMG was added as the capping agent. The addition ratio of TMG was 100 moles relative to 100 moles of the isocyanate groups of the isocyanurate derivative of HDI.

[0328] Example 13

[0329] An aqueous dispersion of water - dispersible blocked isocyanate was prepared in the same manner as in Example 5.

[0330] It should be noted that in Example 13, as shown in Table 2, propionic acid was used instead of acetic acid.

[0331] Example 14

[0332] A water dispersion of a water-dispersible blocked isocyanate was prepared in the same manner as in Example 5.

[0333] It should be noted that in Example 14, as shown in Table 2, lactic acid was used instead of acetic acid.

[0334] Examples 15 to 17

[0335] At room temperature (25 °C), 600 parts by mass of an isocyanurate derivative of hexamethylene diisocyanate (HDI) (polyisocyanate compound, trade name: TAKENATE (registered trademark) D-170N, solid content: 100% by mass, isocyanate group content: 20.7%, manufactured by Mitsui Chemicals, Inc.) and ethyl acetate (solvent) were charged into a 2-L reactor equipped with a stirrer, a thermometer, a condenser, and a nitrogen inlet tube.

[0336] Next, poly(oxyethylene) methyl ether (methoxypolyethylene glycol, methoxy PEG1000, hydrophilic compound) was added to the reactor. The addition ratio of poly(oxyethylene) methyl ether was the number of moles shown in Table 2 relative to 100 moles of the isocyanate groups of the isocyanurate derivative of HDI. Then, the isocyanurate derivative of HDI was reacted with poly(oxyethylene) methyl ether.

[0337] Thereby, a reaction solution containing a blocked isocyanate having an oxyethylene group was obtained.

[0338] Next, DMP (the second blocking agent) was added to the reaction solution containing the blocked isocyanate having an oxyethylene group. The addition ratio of DMP was the number of moles shown in Table 2 relative to 100 moles of the isocyanate groups of the isocyanurate derivative of HDI. Then, the isocyanurate derivative of HDI was reacted with DMP.

[0339] Next, TMG (the first blocking agent) was added to the reaction solution. The addition ratio of TMG was the number of moles shown in Table 2 relative to 100 moles of the isocyanate groups of the isocyanurate derivative of HDI. Then, the isocyanurate derivative of HDI was reacted with TMG.

[0340] Then, by measuring the FT-IR spectrum, it was confirmed that the isocyanate groups had been blocked. Thereby, a reaction solution containing a blocked isocyanate was obtained.

[0341] Next, acetic acid was added to the reaction solution and stirred. The addition ratio of acetic acid was 2 moles relative to 1 mole of the first blocking agent (TMG) used. At this time, the temperature of the reaction solution was 34 °C. The stirring time was 0.5 hour.

[0342] As a result, the amino group of the first capping agent was neutralized by acetic acid to form an ammonium acetate salt. As a result, a reaction solution containing a water-dispersible blocked isocyanate was obtained.

[0343] Then, 220 parts by mass of water was added to 120 parts by mass of the reaction solution containing the water-dispersible blocked isocyanate. Then, the reaction solution and water were stirred with a homogenizer to emulsify them.

[0344] Next, under reduced pressure, ethyl acetate (solvent) was distilled off from the emulsion, and at the same time, a part of the water was distilled off.

[0345] In this way, an aqueous dispersion (polyisocyanate component) of the water-dispersible blocked isocyanate was prepared. The solid content concentration of this aqueous dispersion was 30% by mass.

[0346] Example 18

[0347] An aqueous dispersion of a water-dispersible blocked isocyanate was prepared in the same manner as in Example 5.

[0348] It should be noted that in Example 18, as shown in Table 2, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TABD) was used as the first capping agent instead of TMG.

[0349] Examples 19 to 30

[0350] An aqueous dispersion of a water-dispersible blocked isocyanate was prepared in the same manner as in Example 2.

[0351] It should be noted that, as shown in Tables 4 to 5, the following polyisocyanate derivatives were used as the polyisocyanate compound. The trade name, isocyanate type, and modification form are shown in the table.

[0352] Trimethylolpropane (TMP) adduct of HDI (triol adduct) (polyisocyanate compound, trade name: TAKENATE (registered trademark) D-160N, solid content 75% by mass, isocyanate group content 12.6%, manufactured by Mitsui Chemicals, Inc.)

[0353] Biuret of HDI (polyisocyanate compound, trade name: TAKENATE (registered trademark) D-165N, solid content 100% by mass, isocyanate group content 23.3%, manufactured by Mitsui Chemicals, Inc.)

[0354] Urethane of HDI (polyisocyanate compound, trade name: TAKENATE (registered trademark) D-178NL, solid content 100% by mass, isocyanate group content 19.2%, manufactured by Mitsui Chemicals, Inc.)

[0355] 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H 6 XDI) TMP adduct (polyisocyanate compound, trade name: TAKENATE® D-120N, solid content 75% by mass, isocyanate group content 11.0%, manufactured by Mitsui Chemicals, Inc.)

[0356] 1,3-H 6 Isocyanurate of 1,3-H

[0357] TMP adduct of xylylene diisocyanate (XDI) (polyisocyanate compound, trade name: TAKENATE® D-110N, solid content 75% by mass, isocyanate group content 11.5%, manufactured by Mitsui Chemicals, Inc.)

[0358] Isocyanurate of XDI (polyisocyanate compound, trade name: TAKENATE® D-131N, solid content 75% by mass, isocyanate group content 13.7%, manufactured by Mitsui Chemicals, Inc.)

[0359] TMP adduct of tolylene diisocyanate (TDI) (polyisocyanate compound, trade name: TAKENATE® D-103H, solid content 75% by mass, isocyanate group content 13.0%, manufactured by Mitsui Chemicals, Inc.)

[0360] Isocyanurate of TDI (polyisocyanate compound, trade name: TAKENATE® D-204, solid content 50% by mass, isocyanate group content 7.5%, manufactured by Mitsui Chemicals, Inc.)

[0361] Isocyanurate of PDI (polyisocyanate compound, trade name: STABiO® D-370N, solid content 100% by mass, isocyanate group content 25%, manufactured by Mitsui Chemicals, Inc.)

[0362] Comparative Example 1

[0363] A water dispersion of a water-dispersible blocked isocyanate was prepared in the same manner as in Example 5.

[0364] It should be noted that in Comparative Example 1, as shown in Table 3, dimethylaminoethanol (DMAE) was used as the first blocking agent instead of TMG.

[0365] Comparative Example 2

[0366] A water dispersion of a water-dispersible blocked isocyanate was prepared in the same manner as in Example 5.

[0367] It should be noted that in Comparative Example 2, as shown in Table 3, N-methylpiperazine (MPZ) was used as the first blocking agent instead of TMG.

[0368] Comparative Example 3

[0369] A water dispersion of a water-dispersible blocked isocyanate was prepared in the same manner as in Example 5.

[0370] It should be noted that in Comparative Example 3, as shown in Table 3, N-methylhomopiperazine (MHPZ) was used as the first blocking agent instead of TMG.

[0371] Comparative Example 4

[0372] A water-dispersible blocked isocyanate was prepared in the same manner as in Example 5. The water-dispersible blocked isocyanate was not dispersed in water.

[0373] It should be noted that in Comparative Example 4, as shown in Table 3, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) was used as the first blocking agent instead of TMG.

[0374] Comparative Example 5

[0375] A water dispersion of a water-dispersible blocked isocyanate was prepared in the same manner as in Example 5.

[0376] It should be noted that in Comparative Example 5, as shown in Table 3, N,N,N'-trimethylethylenediamine (TMEDA) was used as the first blocking agent instead of TMG.

[0377] Comparative Example 6

[0378] A water-dispersible blocked isocyanate was prepared in the same manner as in Example 5. The water-dispersible blocked isocyanate was not dispersed in water.

[0379] It should be noted that in Comparative Example 6, as shown in Table 3, the first blocking agent was not used. For the isocyanurate derivative of hexamethylene diisocyanate (HDI), only DMP was added as a blocking agent. The addition ratio of DMP was 100 moles per 100 moles of the isocyanate groups of the isocyanurate derivative of HDI.

[0380] Comparative Example 7

[0381] A water dispersion of a water-dispersible blocked isocyanate was prepared in the same manner as in Example 15.

[0382] It should be noted that in Comparative Example 7, as shown in Table 3, the first blocking agent and acid were not used.

[0383] For the isocyanurate derivative of HDI, only DMP was added as a capping agent.

[0384] The addition ratio of DMP was 98 moles relative to 100 moles of the isocyanate groups in the isocyanurate derivative of HDI.

[0385] <Synthesis of Polyurethane Resin>

[0386] Synthesis Example 1

[0387] At room temperature (25 °C), 703.3 parts by mass of polytetramethylene ether glycol (trade name: PTG-2000SN, manufactured by Hodogaya Chemical Co., Ltd.), 52.8 parts by mass of triethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.), 144.6 parts by mass of N-methyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 293.3 parts by mass of acetonitrile were charged into a 3 L reactor equipped with a stirrer, a thermometer, a condenser, and a nitrogen inlet tube, and they were stirred at a liquid temperature of 40 °C or lower for 30 minutes.

[0388] Next, 346.1 parts by mass of 1,3-bis(isocyanatomethyl)cyclohexane (trade name: TAKENATE (registered trademark) 600, manufactured by Mitsui Chemicals, Inc.) was added to the reactor. Then, 1,3-bis(isocyanatomethyl)cyclohexane, polytetramethylene ether glycol, triethylene glycol, and N-methyldiethanolamine were reacted for 30 minutes.

[0389] Then, 0.4 part by mass of stannous octoate (trade name: STANOCT, manufactured by Mitsubishi Chemical Corporation) was added to the reactor, and the reactor was heated to a liquid temperature of 75 °C. Then, 1,3-bis(isocyanatomethyl)cyclohexane, polytetramethylene ether glycol, triethylene glycol, and N-methyldiethanolamine were reacted at a liquid temperature of 75 °C for 3 hours. Then, by measuring the FT-IR spectrum, it was confirmed that the isocyanate groups had reacted. Thus, polyurethane resin 1 was produced.

[0390] Then, the reaction solution containing polyurethane resin 1 was cooled to room temperature (25 °C), 72.9 parts by mass of acetic acid and 586.7 parts by mass of acetonitrile were added to the reaction solution, and it was stirred for 1 hour. In this way, an acetonitrile solution of polyurethane resin 1 was obtained.

[0391] Next, 4431.8 parts by mass of water cooled to 15 °C to 25 °C was charged into a 20 L SUS container, and while stirring with a homogenizer, 2083.3 parts by mass of the acetonitrile solution of polyurethane resin 1 was added to the water to emulsify it.

[0392] Next, under reduced pressure, acetonitrile (the solvent) was distilled off from the emulsion, and at the same time, a part of the water was distilled off.

[0393] In the above manner, an aqueous dispersion of polyurethane resin 1 was prepared. The solid content concentration of the aqueous dispersion of polyurethane resin 1 was 26.2% by mass.

[0394] Synthesis Example 2

[0395] At room temperature (25 °C), 291.1 parts by mass of polycarbonate diol (trade name: DURANOL T-6002, manufactured by Asahi Kasei Corporation), 15.5 parts by mass of N-methyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 54.5 parts by mass of acetonitrile were charged into a 1-L reactor equipped with a stirrer, a thermometer, a condenser, and a nitrogen inlet tube, and they were stirred at a liquid temperature of 60 °C for 1 hour.

[0396] Next, 74.8 parts by mass of 1,3-bis(isocyanatomethyl)cyclohexane (trade name: TAKENATE® 600, manufactured by Mitsui Chemicals, Inc.) was added to the reactor, and the reactor was heated until the liquid temperature reached 80 °C. Thus, 1,3-bis(isocyanatomethyl)cyclohexane, polycarbonate diol, and N-methyldiethanolamine were reacted to form polyurethane resin 2. Then, the amine equivalent was measured every 1 hour to measure the reaction rate of the isocyanate group.

[0397] Then, when the reaction rate reached 99.5% or more, the reaction solution was cooled to room temperature (25 °C). Next, 27.3 parts by mass of acetic acid and 217.9 parts by mass of acetonitrile were added to the reaction solution, and they were stirred for 1 hour. In the above manner, an acetonitrile solution of polyurethane resin 2 was obtained.

[0398] Then, 970 parts by weight of water cooled to 15 °C to 25 °C was added to the reactor, and it was stirred to emulsify it.

[0399] Next, under reduced pressure, acetonitrile (the solvent) was distilled off from the emulsion, and at the same time, a part of the water was distilled off.

[0400] In the above manner, an aqueous dispersion of polyurethane resin 2 was prepared. The solid content concentration of the aqueous dispersion of polyurethane resin 2 was 32.5% by mass.

[0401] <Evaluation>

[0402] 1. Water dispersibility of the water-dispersible blocked isocyanate

[0403] As described in the above embodiments and comparative examples, water was added to the reaction solution containing the water-dispersible blocked isocyanate, and the reaction solution and water were stirred using a homogenizer to emulsify them. The dispersibility of the reaction solution in water at this time was regarded as the water dispersibility of the water-dispersible blocked isocyanate and evaluated based on the following criteria. The results are shown in Tables 1 to 5.

[0404] 〇: The reaction solution containing the water-dispersible blocked isocyanate was rapidly dispersed in water.

[0405] △: The reaction solution containing the water-dispersible blocked isocyanate was dispersed in water by stirring for a long time (more than 0.5 hour).

[0406] ×: The reaction solution containing the water-dispersible blocked isocyanate was not dispersed in water. Precipitation occurred.

[0407] 2. Viscosity of the aqueous dispersion of the water-dispersible blocked isocyanate

[0408] After bringing the aqueous dispersion of the water-dispersible blocked isocyanate prepared in each of the examples and comparative examples to 25 °C using a constant temperature water bath, the viscosity of the aqueous dispersion was measured using a rotational viscometer RB-85 (manufactured by Toki Sangyo Co., Ltd.). The results are shown in Tables 1 to 5.

[0409] 3. pH of the aqueous dispersion of the water-dispersible blocked isocyanate

[0410] The pH of the aqueous dispersion of the water-dispersible blocked isocyanate prepared in each of the examples and comparative examples was measured using a pH meter (manufactured by Horiba, Ltd.). The results are shown in Tables 1 to 5.

[0411] 4. Particle size in the aqueous dispersion of the water-dispersible blocked isocyanate

[0412] The particle size in the aqueous dispersion of the water-dispersible blocked isocyanate prepared in each of the examples and comparative examples was measured using a thick particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.). The results are shown in Tables 1 to 5.

[0413] 5. Storage stability of the aqueous dispersion of the water-dispersible blocked isocyanate

[0414] The aqueous dispersions of the water-dispersible blocked isocyanate prepared in each of the examples and comparative examples were placed in containers. Then, the aqueous dispersions of the water-dispersible blocked isocyanate were allowed to stand at 40 °C for 7 days. Then, the storage stability of the aqueous dispersions was evaluated in five grades based on the following criteria by visual inspection. The results are shown in Tables 1 to 5.

[0415] In addition, in Examples 2 to 3 and Examples 19 to 29, using the above method, the aqueous dispersion of the water-dispersible blocked isocyanate was allowed to stand at 40°C for 30 days. Then, visually, the storage stability of the aqueous dispersion was evaluated in five grades according to the following criteria. The results are shown in Tables 4 to 5. It should be noted that in the following evaluations, the grades become better in the order from 1 to 5.

[0416] 5: No precipitation in the aqueous dispersion and no attachment on the container wall surface.

[0417] 4: No precipitation in the aqueous dispersion, but there is a small amount of attachment on the container wall surface.

[0418] 3: No precipitation in the aqueous dispersion, but there is attachment on the container wall surface.

[0419] 2: There is a small amount of precipitation in the aqueous dispersion and there is attachment on the container wall surface.

[0420] 1: There is precipitation in the aqueous dispersion and there is attachment on the container wall surface.

[0421] 6. Curing property of water-dispersible blocked isocyanate

[0422] The aqueous dispersion of the water-dispersible blocked isocyanate (polyisocyanate component) prepared in each Example and each Comparative Example was mixed with the aqueous dispersion of polyurethane resin 1 synthesized in Synthesis Example 1 (polyol component). The ratio of the mass of the solid component of the aqueous dispersion of the water-dispersible blocked isocyanate to the mass of the solid component of the aqueous dispersion of polyurethane resin 1 was 1 / 6.

[0423] Then, water was added to the mixed dispersion of the aqueous dispersion of the water-dispersible blocked isocyanate and the aqueous dispersion of polyurethane resin 1 to adjust the final solid component concentration to 20% by mass.

[0424] Furthermore, a leveling agent (trade name: BYK-348, manufactured by BYK JAPAN KK) was added to the mixed dispersion and stirred for 30 minutes. The addition ratio of the leveling agent was 0.5 parts by mass relative to 100 parts by mass of the mixed dispersion.

[0425] Thus, a curing property evaluation liquid was prepared.

[0426] Next, the curing property evaluation liquid was coated on a polypropylene substrate. Then, the coating film of the curing property evaluation liquid was cured at 110°C or 120°C for 30 minutes. After measuring the mass of the cured coating film, it was immersed in a mixed solvent of acetone:methanol with a mass ratio of 1:1 for 24 hours.

[0427] Then, after taking out the gel component by filtration, it was dried at 110 °C for 3 hours, and the mass of the film after impregnation was measured. Then, the gel fraction was calculated from the following formula. Note that the mass of the film before curing and before impregnation with the mixed solvent is designated as mass A, and the mass of the film after impregnation with the mixed solvent is designated as mass B.

[0428] Gel fraction (%) = 100 × mass B / mass A

[0429] Then, the curability of the water-dispersible blocked isocyanate when the curing temperature of the film was 110 °C and the curability of the water-dispersible blocked isocyanate when the curing temperature of the film was 120 °C were evaluated in five grades according to the following criteria. The results are shown in Tables 1 to 5.

[0430] 5: The gel fraction is 60% or more.

[0431] 4: The gel fraction is 45% or more and less than 60%.

[0432] 3: The gel fraction is 30% or more and less than 45%.

[0433] 2: The gel fraction is 15% or more and less than 30%.

[0434] 1: The gel fraction is 0% or more and less than 15%.

[0435] 7. Friction fastness of the film

[0436] (1) Pretreatment

[0437] The aqueous dispersion of the water-dispersible blocked isocyanate prepared in each of the examples and comparative examples, the aqueous dispersion of the polyurethane resin 2 prepared in Synthesis Example 2, and isopropyl alcohol were mixed. The solid content contained in the aqueous dispersion of the water-dispersible blocked isocyanate was 0.835 parts by mass. The solid content contained in the aqueous dispersion of the polyurethane resin 2 was 4.165 parts by mass. The addition amount of isopropyl alcohol was 5 parts by mass.

[0438] Then, water was added to the mixed dispersion of the aqueous dispersion of the water-dispersible blocked isocyanate, the aqueous dispersion of the polyurethane resin 2, and isopropyl alcohol to adjust the final solid content concentration to 5% by mass. Then, the mixed dispersion was stirred for 30 minutes to prepare a pretreatment liquid.

[0439] Next, a cotton cloth cut to a length of 25 cm and a width of 3 cm (No. 3 bleached cotton cloth (cannequin) according to JIS L0803) was immersed in the pretreatment liquid. Then, the cotton cloth was lifted from the pretreatment liquid and squeezed thoroughly, and then dried in the dark at room temperature (25 °C) for 24 hours.

[0440] The cotton cloth obtained by drying the dried cotton cloth in a heating furnace at 110°C for 1 minute was used as the pre-treated cotton cloth 1. The cotton cloth obtained by drying the dried cotton cloth in a heating furnace at 150°C for 5 minutes was used as the pre-treated cotton cloth 2.

[0441] In addition, an aqueous dispersion of water-based polyurethane resin (trade name: TAKELAC W-6110, manufactured by Mitsui Chemicals, Inc.), water-based ink (X Color Blue MX, manufactured by Matsui Pigment Chemical Industry Co., Ltd.), and ethylene glycol were mixed. The solid content contained in the aqueous dispersion of water-based polyurethane resin was 12 parts by mass. The solid content contained in the water-based ink was 2 parts by mass. The mixing amount of ethylene glycol was 20 parts by mass.

[0442] Then, water was added to the mixture of the aqueous dispersion of water-based polyurethane resin, water-based ink, and ethylene glycol, and the final solid content concentration was adjusted to 14% by mass. The mixture was stirred for 30 minutes to prepare an ink solution.

[0443] Next, the pre-treated cotton cloth 1 was immersed in the ink solution. Then, the pre-treated cotton cloth 1 was lifted from the ink solution and squeezed thoroughly, and then dried in the dark at room temperature (25°C) for 24 hours. Further, the cotton cloth was dried in a heating furnace at 110°C for 1 minute to prepare the evaluation cotton cloth 1.

[0444] In addition, the pre-treated cotton cloth 2 was immersed in the ink solution. Then, the pre-treated cotton cloth 2 was lifted from the ink solution and squeezed thoroughly, and then dried in the dark at room temperature (25°C) for 24 hours. Further, the cotton cloth was dried in a heating furnace at 150°C for 5 minutes to prepare the evaluation cotton cloth 2.

[0445] The evaluation cotton cloth 1 or the evaluation cotton cloth 2 was set on a rubbing fastness tester, and a moistened rubbing cotton cloth (No. 3 bleached cotton cloth according to JIS L0803) was installed on the rubbing fastness tester, and the rubbing fastness test under moist conditions was carried out according to JIS L0849.

[0446] The rubbing cotton cloth was taken out and dried in the dark at room temperature (25°C) for 24 hours. At this time, the rubbing cotton cloth obtained by rubbing the evaluation cotton cloth 1 was used as the contaminated cotton cloth 1, and the rubbing cotton cloth obtained by rubbing the evaluation cotton cloth 2 was used as the contaminated cotton cloth 2.

[0447] Regarding the coloring degree of the contaminated cotton cloth, the L ＊ value was measured and quantified using a spectrophotometric color difference meter (model: SE-2000, manufactured by Nippon Denshoku Industries Co., Ltd.). Using the L of the contaminated cotton cloth 1 ＊The friction fastness 1 of the coating film was evaluated in five levels according to the following criteria. The evaluation of the friction fastness 1 is higher in the order from 1 to 5. The results are shown in Tables 1 to 5.

[0448] 5:86 and above.

[0449] 4: Above 84 and below 86.

[0450] 3: Above 82 and below 84.

[0451] 2: Above 80 and below 82.

[0452] 1: Below 80.

[0453] In addition, using the L of the contaminated cotton cloth 2 ＊ The friction fastness 2 of the coating film was evaluated in five levels according to the following criteria. The evaluation of the friction fastness 2 was higher in the order of 1 to 5. The results are shown in Tables 1 to 5.

[0454] 5:92 and above.

[0455] 4: Above 91 and below 92.

[0456] 3: Above 90 and below 91.

[0457] 2: Above 89 and below 90.

[0458] 1: Below 89.

[0459] (2) Post-processing

[0460] Untreated cotton cloth (No. 3 bleached cotton cloth) was immersed in the ink solution, then the cotton cloth was pulled out of the ink solution, fully squeezed, and then dried in a dark place at room temperature (25° C.) for 24 hours.

[0461] Next, the aqueous dispersion of the water-dispersible blocked isocyanate of Example 1 or Comparative Example 7 was applied to the cotton cloth by spraying. The coating amount was 0.2 g / m 2 .

[0462] Then, the cotton cloth was heat-treated to obtain cotton cloths 3 to 5 for evaluation.

[0463] More specifically, a cotton cloth subjected to heat treatment at a temperature of 90° C. and for a period of 5 minutes was designated as cotton cloth 3 for evaluation.

[0464] The cotton cloth obtained by heat-treating at a temperature of 110° C. and a heat-treating time of 5 minutes was referred to as cotton cloth 4 for evaluation.

[0465] Use the cotton cloth obtained by subjecting it to a heat treatment temperature of 150 °C and a heat treatment time of 5 minutes as the evaluation cotton cloth 5.

[0466] Then, place the evaluation cotton cloths 3 to 5 on a rubbing fastness testing machine, install the wetted rubbing cotton cloth (No. 3 bleached cotton cloth in accordance with JIS L0803) on the rubbing fastness testing machine, and conduct a rubbing fastness test under wet conditions in accordance with JIS L0849.

[0467] Take out the rubbing cotton cloth and dry it in the dark at room temperature (25 °C) for 24 hours. At this time, use the rubbing cotton cloth obtained by rubbing the evaluation cotton cloth 3 as the contaminated cotton cloth 3, the rubbing cotton cloth obtained by rubbing the evaluation cotton cloth 4 as the contaminated cotton cloth 4, and the rubbing cotton cloth obtained by rubbing the evaluation cotton cloth 5 as the contaminated cotton cloth 5.

[0468] Regarding the coloring degree of the contaminated cotton cloth, use a spectrophotometric color difference meter (model: SE-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) to measure the L ＊ value and digitize it. Use the L ＊ value of the contaminated cotton cloth 3 to evaluate the rubbing fastness 3 of the coating film in five grades according to the following criteria. It should be noted that the evaluation of the rubbing fastness 3 increases in order from 1 to 5. The results are shown in Table 6.

[0469] 5: 86 or more.

[0470] 4: 84 or more and less than 86.

[0471] 3: 82 or more and less than 84.

[0472] 2: 80 or more and less than 82.

[0473] 1: Less than 80.

[0474] In addition, use the L ＊ value of the contaminated cotton cloth 4 to evaluate the rubbing fastness 4 of the coating film in five grades according to the following criteria. It should be noted that the evaluation of the rubbing fastness 4 increases in order from 1 to 5. The results are shown in Table 6.

[0475] 5: 86 or more.

[0476] 4: 84 or more and less than 86.

[0477] 3: 82 or more and less than 84.

[0478] 2: 80 or more and less than 82.

[0479] 1: Less than 80.

[0480] In addition, use the L of the contaminated cotton cloth 5＊ The value is used to evaluate the rubbing fastness 5 of the coating film in five grades according to the following criteria. It should be noted that the evaluation of the rubbing fastness 5 becomes higher in the order from 1 to 5. The results are shown in Table 6.

[0481] 5: 92 or more.

[0482] 4: 91 or more and less than 92.

[0483] 3: 90 or more and less than 91.

[0484] 2: 89 or more and less than 90.

[0485] 1: Less than 89.

[0486] 8. Hydrophobicity

[0487] A fluorine-based water and oil repellent (fluororesin, trade name: AsahiGuard AG-E061, manufactured by AGC Inc.) is mixed with the aqueous dispersion (polyisocyanate component) of the blocked isocyanate prepared in each example and each comparative example. The mass ratio of the solid content of the aqueous dispersion of the blocked isocyanate to the fluorine-based water and oil repellent is 1 / 9.

[0488] Then, water is added to the mixture of the fluorine-based water and oil repellent and the aqueous dispersion of the blocked isocyanate, and stirring is carried out to adjust the final solid content concentration to 1% by mass. Thus, a hydrophobicity evaluation liquid is prepared.

[0489] A cotton cloth (No. 3 bleached cotton cloth according to JIS L0803) is immersed in the hydrophobicity evaluation liquid. Then, the cotton cloth is lifted from the hydrophobicity evaluation liquid and squeezed thoroughly, and then dried in the dark at room temperature (25°C) for 24 hours. Then, the dried cotton cloth is dried in a heating furnace at 110°C for 1 minute and washed 10 times using a fully automatic washing machine according to JIS L0217. At this time, 30 g of a powder detergent (trade name: Attack Highly-Active Bio-EX, manufactured by Kao Corporation) is added to 37 L of the washing water. The washed cotton cloth is dried in the dark at room temperature (25°C) for 24 hours to prepare a test cloth.

[0490] Then, 20 μL of a mixed liquid of water and isopropyl alcohol is dropped onto the test cloth, and the state of the liquid drop after 3 minutes is observed. The mass ratio of water to isopropyl alcohol in the mixed liquid is 9 / 1.

[0491] Then, the hydrophobicity is evaluated in five grades by visual inspection according to the following criteria. The results are shown in Tables 1 to 5.

[0492] 5: The liquid drop forms a spherical shape and no infiltration trace remains.

[0493] 4: The droplets form spheres, with a little infiltration trace remaining.

[0494] 3: The droplets form spheres, with infiltration traces clearly remaining.

[0495] 2: The droplets form spheres, the infiltration traces are larger than the diameter of the droplets and clearly remain.

[0496] 1: The droplets completely infiltrate into the test cloth.

[0497] 9. Adhesiveness

[0498] The aqueous dispersion of the water-dispersible blocked isocyanate prepared in Example 5 was mixed with the aqueous dispersion of the polyurethane resin 1 prepared in Synthesis Example 1. The mass ratio of the solid content contained in the aqueous dispersion of the water-dispersible blocked isocyanate to the solid content contained in the aqueous dispersion of the polyurethane resin 1 was 1 / 6.

[0499] Then, water was added to the mixed dispersion of the aqueous dispersion of the water-dispersible blocked isocyanate and the aqueous dispersion of the polyurethane resin 1, and stirred for 30 minutes to adjust the final solid content concentration to 20% by mass. Thus, a polyurethane adhesive composition was prepared.

[0500] Next, the polyurethane adhesive composition was coated on an ABS substrate formed of acrylonitrile-butadiene-styrene copolymer. Then, the coating film of the polyurethane adhesive composition was cured at 130 °C for 30 minutes.

[0501] Next, based on JIS K5600-5-6, the adhesion of the cured product of the coating film was evaluated by a checkerboard test. For the cured product of the above coating film, in the tape peeling, all 25 grids were not peeled off from the ABS substrate and adhered (the number of adhered parts / the number of all parts = 25 / 25).

[0502] Therefore, it was confirmed that excellent adhesiveness was achieved when using the aqueous dispersion of the water-dispersible blocked isocyanate of Example 5 as a curing agent.

[0503] 10. Antibacterial property

[0504] The antibacterial properties of the water-dispersible blocked isocyanates of Examples 2, 11 to 12 and Comparative Example 7 were evaluated by the following method. The results are shown in Table 7.

[0505] <A: Minimum inhibitory concentration (MIC test)>

[0506] (1) Pre-culture

[0507] (Test bacteria species)

[0508] I. Escherichia coli (E. coli, NBRC - 3972, distributed by National Institute of Technology and Evaluation, Escherichia coli)

[0509] II. Staphylococcus aureus (S. aureus, NBRC - 12732, distributed by National Institute of Technology and Evaluation, Staphylococcus aureus)

[0510] The bacteria in I and II above were test strains obtained by culturing in a liquid medium (LB medium, BD Difco (trade name) LB Broth Miller, Becton, Dickinson and Company) that had been autoclaved at 121°C for 20 minutes, at 35 ± 1°C for 20 ± 4 hours.

[0511] (2) Bacterial suspension preparation

[0512] The test strains cultured in (1) above were suspended in LB medium that had been autoclaved at 121°C for 20 minutes, and then the O.D. (Optical Density) of the bacterial suspension was measured and adjusted to be less than 2.0.

[0513] (3) Sample preparation

[0514] A dimethyl sulfoxide solution (sample) containing 3% water - dispersible blocked isocyanate was prepared, and the sample was added to LB medium that had been autoclaved at 121°C for 20 minutes to obtain a mixed solution. It should be noted that the maximum concentration of the water - dispersible blocked isocyanate was set at 1000 ppm, and a two - fold dilution series of 8 levels was made.

[0515] (4) MIC determination test

[0516] The bacterial suspension prepared in (2) was inoculated into each dilution series in (3) and cultured at 35°C for 24 ± 2 hours. Then, the growth of the bacteria was visually confirmed, and the maximum dilution concentration at which no growth occurred was taken as the MIC value.

[0517] <B: Membrane test>

[0518] (Test strains)

[0519] Escherichia Coli (E. coli, NBRC - 3972, distributed by National Institute of Technology and Evaluation, Escherichia coli)

[0520] With reference to "Antibacterial processed products - Antibacterial test method and antibacterial effect" specified in JIS Z 2801:2010, the antibacterial property against Staphylococcus aureus was evaluated as described below. (1)

[0522] 1.8 parts by mass (based on solid content) of a water-dispersible blocked isocyanate, 88.2 parts by mass (based on solid content) of TAKELAC W-6355 (trade name, aqueous polyurethane resin, manufactured by Mitsui Chemicals, Inc.), and 10.0 parts by mass of isopropyl alcohol were mixed to obtain a mixed solution. Further, water was added to the mixed solution to adjust the solid content concentration of the mixed solution to 10% by mass.

[0523] Next, the above-mentioned mixed solution was applied onto a polyethylene terephthalate film (trade name Lumirror S10, manufactured by Toray Industries, Inc.) using a bar coater and heated under the curing conditions (temperature / time) described in Table 7 to cure it. Thus, a film with a thickness of 0.1 to 2.0 μm was obtained. (2)

[0525] The film was cut into squares with a side length of 50 ± 2 mm as test pieces. The test pieces were placed in a sterilized plastic petri dish and inoculated with 0.4 mL of a test bacterial solution (the number of bacteria was 2.5×10 5 ~10×10 5 CFU / mL). It should be noted that the test bacterial solution was prepared by the following method.

[0526] That is, in an incubator, at a temperature of 35 ± 1°C, the cultured bacteria were pre-cultured (first solution) for 20 ± 4 hours using an LB medium (BD Difco (trade name) LB Broth Miller, Becton, Dickinson and Company).

[0527] Next, the first solution was further inoculated onto a slant medium (ordinary agar medium, Nutrient agar, manufactured by Merck & Co., Inc.) and pre-cultured (second solution) for 20 ± 4 hours at a temperature of 35 ± 1°C in an incubator.

[0528] Then, the second solution was appropriately adjusted in concentration (third solution) using separately prepared 1 / 500 strength ordinary broth medium (Nutrient broth, manufactured by Merck & Co., Inc.). (3)

[0530] On the other hand, as a control specimen, a polyethylene terephthalate film with a size of 50 ± 2 mm square (trade name: Lumirror S10, manufactured by Toray Industries, Inc.) was prepared, and the test bacterial solution was inoculated in the same manner as the test piece. (4)

[0532] Next, a biaxially oriented polypropylene (OPP) film with a size of 40 ± 2 mm square was placed over the inoculated test bacterial solution, so that the test bacterial solution was evenly inoculated over the entire film. Then, the culture was carried out for 20 ± 4 hours under the conditions of a temperature of 35 ± 1°C and a relative humidity of 85 ± 5%. (5)

[0534] Immediately after inoculating the test bacterial solution or after the culture in (4) above, 10 mL of SCDLP medium (SCDLP medium DAIGO (trade name), manufactured by Nippon Pharmaceutical Co., Ltd.) was added, and the test bacterial solution on the test piece was washed 4 times or more to completely recover the bacterial solution. In addition, the recovered liquid (eluate) was quickly supplied to the next process to measure the viable cell count. (6)

[0536] Using the liquid (eluate) recovered in (5) above and phosphate buffered saline, a 10-fold dilution series was prepared.

[0537] Then, each dilution series was mixed with a standard agar medium (standard agar medium DAIGO (trade name), manufactured by Nippon Pharmaceutical Co., Ltd.) to prepare a culture medium. Then, the culture medium was cultured at a temperature of 35 ± 1°C for 20 ± 4 hours, and then the number of colonies was measured. It should be noted that the culture dishes of the dilution series with 30 to 300 colonies were used as the counting objects. (7)

[0539] Based on the measurement results, the viable cell count was calculated using the following formula.

[0540] N = C × D × V / A

[0541] N: Viable cell count (per 1 cm 2 test piece)

[0542] C: Number of colonies

[0543] D: Dilution ratio (dilution multiple of each dilution in the culture dish used)

[0544] V: Volume of SCDLP medium used for elution (mL)

[0545] A: Surface area of the coated film (cm 2 ) (8)

[0547] The antibacterial activity value is calculated using the following formula. When R is 2.0 or more, it is recorded as having antibacterial activity (○). When R is less than 2.0, it is recorded as having no antibacterial activity (×).

[0548] R = (Ut - U0) - (At - U0) = Ut - At

[0549] R: Antibacterial activity value

[0550] U0: Average value of the logarithm of the viable bacteria count immediately after inoculation of the unprocessed test piece

[0551] Ut: Average value of the logarithm of the viable bacteria count 24 hours after inoculation of the unprocessed test piece

[0552] At: Average value of the logarithm of the viable bacteria count 24 hours after inoculation of the antibacterial processed test piece

[0553] [Table 1]

[0554] Table 1

[0555]

[0556] [Table 2]

[0557] Table 2

[0558]

[0559] [Table 3]

[0560] Table 3

[0561]

[0562] [Table 4]

[0563] Table 4

[0564]

[0565] [Table 5]

[0566] Table 5

[0567]

[0568] [Table 6]

[0569] Table 6

[0570]

[0571] [Table 7]

[0572] Table 7

[0573]

[0574] It should be noted that the details of the abbreviations in the following tables are described below.

[0575] TAKENATE D-170N: HDI isocyanurate: an isocyanurate derivative of hexamethylene diisocyanate, trade name TAKENATE (registered trademark) D-170N, isocyanate group content is 20.7%, manufactured by Mitsui Chemicals,

[0576] TAKENATE D-160N: A trimethylolpropane (TMP) adduct derivative of HDI, a polyisocyanate compound, trade name TAKENATE (registered trademark) D-160N, solid content is 75% by mass, isocyanate group content is 12.6%, manufactured by Mitsui Chemicals,

[0577] TAKENATE D-165N: A biuret derivative of HDI, a polyisocyanate compound, trade name TAKENATE (registered trademark) D-165N, solid content is 100% by mass, isocyanate group content is 23.3%, manufactured by Mitsui Chemicals,

[0578] TAKENATE D-178NL: A urethane derivative of HDI, a polyisocyanate compound, trade name TAKENATE (registered trademark) D-178NL, solid content is 100% by mass, isocyanate group content is 19.2%, manufactured by Mitsui Chemicals,

[0579] TAKENATE D-120N: A TMP adduct derivative of 1,3-bis(isocyanatomethyl)cyclohexane (1,3-H 6 XDI), a polyisocyanate compound, trade name: TAKENATE (registered trademark) D-120N, solid content is 75% by mass, isocyanate group content is 11.0%, manufactured by Mitsui Chemicals,

[0580] TAKENATE D-127N: 1,3-H 6 XDI isocyanurate derivative, a polyisocyanate compound, trade name TAKENATE (registered trademark) D-127N, solid content is 75% by mass, isocyanate group content is 13.5%, manufactured by Mitsui Chemicals,

[0581] TAKENATE D-110N: A TMP adduct derivative of xylylene diisocyanate (XDI), a polyisocyanate compound, trade name TAKENATE (registered trademark) D-110N, solid content is 75% by mass, isocyanate group content is 11.5%, manufactured by Mitsui Chemicals,

[0582] TAKENATE D-131N: An isocyanurate derivative of XDI, a polyisocyanate compound, trade name TAKENATE (registered trademark) D-131N, solid content 75% by mass, isocyanate group content 13.7%, manufactured by Mitsui Chemicals, Inc.,

[0583] TAKENATE D-103H: A TMP adduct derivative of toluene diisocyanate (TDI), a polyisocyanate compound, trade name TAKENATE (registered trademark) D-103H, solid content 75% by mass, isocyanate group content 13.0%, manufactured by Mitsui Chemicals, Inc.,

[0584] TAKENATE D-204: An isocyanurate derivative of TDI, a polyisocyanate compound, trade name: TAKENATE (registered trademark) D-204, solid content 50% by mass, isocyanate group content 7.5%, manufactured by Mitsui Chemicals, Inc.,

[0585] STABiO D-370N: An isocyanurate of PDI, a polyisocyanate compound, trade name STABiO (registered trademark) D-370N, solid content 100% by mass, isocyanate group content 25%, manufactured by Mitsui Chemicals, Inc.,

[0586] TMG: 1,1,3,3 - tetramethylguanidine,

[0587] TABD: 1,5,7 - triazabicyclo[4.4.0]dec - 5 - ene,

[0588] DMAE: Dimethylaminoethanol,

[0589] MPZ: N - methylpiperazine,

[0590] MHPZ: N - methylhomopiperazine,

[0591] DBU: 1,8 - diazabicyclo[5.4.0]-7 - undecene,

[0592] TMEDA: N,N,N’ - trimethylethylenediamine,

[0593] Methoxy PEG1000: Methoxy PEG #1000, number - average molecular weight 1000, manufactured by Toho Chemical Industry Co., Ltd.

[0594] It should be noted that the above - mentioned inventions are provided as exemplary embodiments of the present invention, but they are merely examples and should not be construed in a limiting sense. Variations of the present invention that are apparent to those skilled in the art are included in the appended claims.

[0595] Industrial Applicability

[0596] The water-dispersible blocked isocyanate of the present invention can be suitably used in the fields of fiber treating agents, water repellents, coating compositions, adhesives, and antibacterial agents.

Claims

1. A water-dispersible blocked isocyanate, which is a blocked isocyanate obtained by blocking the isocyanate groups of a polyisocyanate compound with a blocking agent, wherein the blocking agent contains a first blocking agent represented by the following general formula (1), and at least a part of the amino groups of the first blocking agent is neutralized with an acid, [Chemical formula 1] Chemical formula 1 In formula (1), R 1 ~R 5 represent a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom; in addition, R 1 and R 3 may be bonded to each other to form a heterocycle; in addition, it may also be that R 4 and R 1 are bonded to each other to form a heterocycle, and R 5 and R 3 are bonded to each other to form a heterocycle.

2. The water-dispersible blocked isocyanate according to claim 1, wherein, In the general formula (1), R 1 ~R 5 represents a hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom.

3. The water-dispersible blocked isocyanate according to claim 1, wherein, the blocking agent further contains a second blocking agent having a smaller catalytic effect on activating the isocyanate group than the first blocking agent.

4. The water-dispersible blocked isocyanate according to claim 3, wherein, the content ratio of the first blocking agent in the blocking agent is higher than 2 mol% and lower than 80 mol%.

5. The water-dispersible blocked isocyanate according to claim 1, wherein, the acid contains an organic acid.

6. The water-dispersible blocked isocyanate according to claim 5, wherein, the acid contains at least one organic acid selected from the group consisting of acetic acid, propionic acid, and lactic acid.

7. The water-dispersible blocked isocyanate according to claim 1, wherein, the polyisocyanate compound contains an aromatic polyisocyanate derivative and / or an araliphatic polyisocyanate derivative.

8. A fiber treating agent, which contains the water-dispersible blocked isocyanate according to claim 1.

9. A water repellent, which contains the water-dispersible blocked isocyanate according to claim 1.

10. A coating composition, which contains the water-dispersible blocked isocyanate according to claim 1.

11. An adhesive, which contains the water-dispersible blocked isocyanate according to claim 1.

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