urethane compound

Abstract

The present invention provides a urethane compound capable of obtaining a crosslinking agent that provides high water and oil repellency. The urethane compound (A) is composed of an isocyanate (A1) and a long-chain alcohol (A2) represented by the formula: HO-Z(Y-R) n [wherein each R is independently -O-, -NH-, -O-C(=O)-, -NH-C(=O)-, -C(=O)-NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -NH-S(=O)2-, -S(=O)2-NH-, -NH-(CH2) m -NH-S(=O)2- or -NH-(CH2) m -S(=O)2-NH-, etc. (where m is an integer of 1 to 5), Z is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1 or 2].

Description

Technical Field

[0001] The present invention relates to a urethane compound and an aqueous urethane composition containing the urethane compound. Background Art

[0002] In repellents such as fluorine-containing repellents and non-fluorine-containing repellents, high performance is demanded. As an additive for assisting water repellency, a crosslinking agent can be cited. The main crosslinking agent is an isocyanate-based crosslinking agent, for example, an isocyanate crosslinking agent having a characteristic blocking agent.

[0003] Patent Document 1 (International Publication No. 2006 / 038466) discloses an aqueous polyurethane composition containing, as an essential component, a polyisocyanate represented by a specific chemical formula.

[0004] Patent Document 2 (Japanese Patent Laid-Open No. 2014-210882) discloses a blocked polyisocyanate composition having a polyisocyanate unit, a polyethylene oxide unit having a single terminal hydroxyl group, and a blocking agent unit, and a urethane group / isocyanurate group number ratio of 30 / 100 to 200 / 100.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: International Publication No. 2006 / 038466

[0008] Patent Document 2: Japanese Patent Laid-Open No. 2014-210882 Summary of the Invention

[0009] Technical Problem to be Solved by the Invention

[0010] With existing crosslinking agents, it may not be possible to sufficiently assist water and oil repellency, and there is a need for a crosslinking agent with higher performance for assisting washing durability.

[0011] Technical Means for Solving the Technical Problem

[0012] The present invention provides a urethane compound formed from a long-chain alcohol having a hydrocarbon group with 7 to 40 carbon atoms.

[0013] Preferred embodiments of the present invention are as follows.

[0014] Embodiment 1:

[0015] A urethane compound (A) containing a unit formed from an isocyanate (A1) and a long-chain alcohol (A2) represented by the formula: HO-Z(Y-R) n shown.

[0016] [In the formula, each R is independently a hydrocarbon group having 7 to 40 carbon atoms,

[0017] Y is independently selected from -O-, -NH-, -NH-C(=O)-, -C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -C6H4-, -NH-(CH2) m -NH-, -NH-(CH2) m -O-, -O-C(=O)-, -C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-C(=O)-NH-, -O-C6H4-, -NH-S(=O)2-, -S(=O)2-NH-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4-, -NH-(CH2) m -NH-S(=O)2- or -NH-(CH2) m -S(=O)2-NH- (wherein, m is an integer from 1 to 5),

[0018] Z is a direct bond, or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms,

[0019] n is 1 or 2.]

[0020] Mode 2:

[0021] The urethane compound as described in Mode 1, further comprising a unit formed from at least one selected from a capping agent (A3) and an alcohol compound (A4).

[0022] Mode 3:

[0023] The urethane compound as described in Method 1 or 2, wherein the isocyanate (A1) is at least one selected from toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), MDI oligomer, naphthalene-1,5-diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, isophorone diisocyanate (IPDI), adduct of diisocyanate, urethane-modified product, biuret-modified product, isocyanurate-modified product, carbodiimide-modified product, and urethane prepolymer.

[0024] Method 4:

[0025] The urethane compound as described in any one of Methods 1 to 3, wherein

[0026] The long-chain alcohol (A2) is at least one selected from the following formulas:

[0027] HO-(CH2) m -NH-C(=O)-R,

[0028] HO-(CH2) m -C(=O)-NH-R,

[0029] HO-(CH2) m -O-C(=O)-R,

[0030] HO-(CH2) m -C(=O)-O-R,

[0031] HO-(CH2) m -NH-C(=O)-O-R,

[0032] HO-(CH2) m -O-C(=O)-NH-R,

[0033] HO-(CH2) m -NH-C(=O)-NH-R,

[0034] HO-(CH2) m -NH-S(=O)2-R, and

[0035] HO-(CH2) m -S(=O)2-NH-R.

[0036] [In the formula, R is a hydrocarbon group having 12 to 30 carbon atoms,

[0037] and m is an integer from 1 to 5].

[0038] Method 5:

[0039] The urethane compound according to any one of Modes 2 to 4, wherein the capping agent (A3) is at least one selected from oxime, phenol, alcohol, thiol, amide, imide, imidazole, urea, amine, imine, pyrazole, and active methylene compounds.

[0040] Mode 6:

[0041] The urethane compound according to any one of Modes 2 to 5, wherein

[0042] the alcohol compound (A4) is a mono-ol or a polyol,

[0043] the mono-ol is a compound formed by adding C2 or C3 alkylene oxide to a starting mono alcohol having 1 to 10 carbon atoms,

[0044] the polyol is a diol and a polyol having 3 or more hydroxyl groups, and is at least one selected from low molecular weight polyols, polyether polyols, polyester polyols, polyester polycarbonate polyols, crystalline or amorphous polycarbonate polyols.

[0045] Mode 7:

[0046] A urethane mixture containing the urethane compound according to any one of Modes 1 to 6, and at least one selected from polyisocyanate (A1), long-chain alcohol (A2), capping agent (A3), and alcohol compound (A4).

[0047] Mode 8:

[0048] An aqueous urethane composition containing: the urethane compound (A) according to any one of Modes 1 to 6; and water (B).

[0049] Mode 9:

[0050] The aqueous urethane composition according to Mode 8, wherein the aqueous urethane composition is an aqueous dispersion.

[0051] Mode 10:

[0052] The aqueous urethane composition according to Mode 8 or 9, wherein the aqueous urethane composition is a crosslinking agent or an auxiliary agent.

[0053] Mode 11:

[0054] A method for producing the aqueous urethane composition according to any one of Modes 8 to 10, wherein isocyanate (A1) and long-chain alcohol (A2) are mixed and reacted in an organic solvent, and then mixed with water.

[0055] Mode 12:

[0056] A method for treating a substrate, comprising: a step of treating a substrate with a surface treatment composition containing a urethane compound according to any one of Mode 1 to Mode 6.

[0057] Mode 13:

[0058] A treated fiber product, wherein the urethane compound according to any one of Mode 1 to Mode 6 is attached to the object to be treated in the form of a crosslinked product.

[0059] Advantages of the Invention

[0060] According to the present invention, a urethane compound that functions as an adjuvant for improving the performance of surface treatment agents such as water and oil repellents can be obtained. The urethane compound assists the surface treatment agent to provide high water and oil repellency. Based on the urethane compound, high washing durability can be obtained, and in particular, high washing durability for water repellency can be provided. Detailed Embodiments

[0061] The present invention relates to an aqueous urethane composition containing a urethane compound (A) and water (B).

[0062] The urethane compound (A) is formed from a polyisocyanate (A1) and a long-chain alcohol (A2) represented by the formula: HO-Z(Y-R) n as shown.

[0063] [In the formula, each R is independently a hydrocarbon group having 7 to 40 carbon atoms,

[0064] each Y is independently -O-, -NH-, -NH-C(=O)-, -C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -C6H4-, -NH-(CH2) m -NH-, -NH-(CH2) m -O-, -O-C(=O)-, -C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-C(=O)-NH-, -O-C6H4-, -NH-S(=O)2-, -S(=O)2-NH-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m-O-C6H4-, -NH-(CH2) m -NH-C6H4-, -NH-(CH2) m -NH-S(=O)2-, or -NH-(CH2) m -S(=O)2-NH-(wherein m is an integer from 1 to 5),

[0065] Z is a direct bond, or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms,

[0066] n is 1 or 2.]

[0067] That is, the urethane compound (A) has a unit formed from the polyisocyanate (A1) and a unit formed from the long-chain alcohol (A2).

[0068] The urethane compound (A) may further have a unit formed from at least one selected from the blocking agent (A3) and the alcohol compound (A4). The urethane compound (A) preferably has both a unit formed from the blocking agent (A3) and a unit formed from the alcohol compound (A4).

[0069] The urethane compound (A) can be formed from the following components.

[0070] Component (A1) + Component (A2)

[0071] Component (A1) + Component (A2) + Component (A3)

[0072] Component (A1) + Component (A2) + Component (A4)

[0073] Or Component (A1) + Component (A2) + Component (A3) + Component (A4)

[0074] In the present invention, any of the polyisocyanate (A1), the long-chain alcohol (A2), the blocking agent (A3), and the alcohol compound (A4) may be at least partially unreacted. Accordingly, the present invention provides a urethane mixture containing at least one selected from the polyisocyanate (A1), the long-chain alcohol (A2), the blocking agent (A3), and the alcohol compound (A4), and the urethane compound (A).

[0075] Examples of the polyisocyanate (A1) include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), MDI oligomers, naphthalene-1,5-diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, isophorone diisocyanate (IPDI), adducts of diisocyanates, urethane-modified products, biuret-modified products, isocyanurate-modified products or carbodiimide-modified products, and urethane prepolymers.

[0076] The polyisocyanate (A1) is preferably a diisocyanate. The polyisocyanate (A1) is preferably a compound represented by the following formula.

[0077] O=C=N-R 0 -N=C=O

[0078] [In the formula, R 0 is a divalent organic group. ]

[0079] R 0 is the group obtained by removing the isocyanate group from the polyisocyanate. R 0 may be, for example, a hydrocarbon group having 3 to 30 carbon atoms, for example 4 to 20 or 5 to 15 carbon atoms.

[0080] In the long-chain alcohol (A2), R is preferably a linear or branched hydrocarbon group. The hydrocarbon group may particularly be a linear hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly preferably a saturated aliphatic hydrocarbon group, and particularly preferably an alkyl group. The number of carbon atoms of the hydrocarbon group is preferably 12 to 30, more preferably 16 to 22.

[0081] In the long-chain alcohol (A2), Y may be -O-, -NH-, -NH-C(=O)-, -C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -C6H4-, -NH-(CH2) m -NH-, -NH-(CH2) m -O-, -O-C(=O)-, -C(=O)-O-, -NH-(CH2) m -O-C(=O)-, -NH-(CH2) m -C(=O)-O-, -O-C(=O)-NH-, -O-C6H4-, -NH-S(=O)2-, -S(=O)2-NH-, -NH-(CH2) m -O-C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-O-, -NH-(CH2) m -C(=O)-NH-, -NH-(CH2) m -NH-C(=O)-, -NH-(CH2) m -NH-C(=O)-NH-, -NH-(CH2) m -O-C6H4-, -NH-(CH2) m -NH-C6H4-, -NH-(CH2) m -NH-S(=O)2-, or -NH-(CH2) m -S(=O)2-NH-.

[0082] [In the formula, m is an integer from 1 to 5, especially 2 or 4.]

[0083] Y is preferably -O-, -NH-, -O-C(=O)-, -NH-C(=O)-, -C(=O)-NH-, -O-C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -NH-S(=O)2-, -S(=O)2-NH-, -NH-(CH2) m -NH-S(=O)2-, or -NH-(CH2) m -S(=O)2-NH-.

[0084] [In the formula, m is an integer from 1 to 5, especially 2 or 4.]

[0085] Y is more preferably -NH-C(=O)-, -C(=O)-NH-.

[0086] In the long-chain alcohol (A2), Z is a direct bond, or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, which may have a straight-chain structure or a branched structure. The number of carbon atoms of Z is preferably 2 to 4, particularly preferably 2. Specific examples of Z are: direct bond, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH= with a branched structure, -CH2(CH-)CH2- with a branched structure, -CH2CH2CH= with a branched structure, -CH2CH2CH2CH2CH= with a branched structure, -CH2CH2(CH-)CH2- with a branched structure, -CH2CH2CH2CH= with a branched structure. Z is preferably -CH2CH2-, -CH2CH2CH2- or -CH2CH2CH2CH2-.

[0087] Z is preferably not a direct bond.

[0088] Preferred specific examples of the long-chain alcohol (A2) are as follows.

[0089] HO-(CH2) m -NH-C(=O)-R

[0090] HO-(CH2) m -C(=O)-NH-R

[0091] HO-(CH2) m -O-C(=O)-R

[0092] HO-(CH2) m -C(=O)-O-R

[0093] HO-(CH2)m -NH-C(=O)-O-R

[0094] HO-(CH2) m -O-C(=O)-NH-R

[0095] HO-(CH2) m -NH-C(=O)-NH-R

[0096] HO-(CH2) m -NH-S(=O)2-R

[0097] HO-(CH2) m -S(=O)2-NH-R

[0098] [In the formula, R is a hydrocarbon group having 7 to 40 carbon atoms,

[0099] and m is an integer of 1 to 5.]

[0100] The blocking agent (A3) is a compound that masks the isocyanate group of the polyisocyanate and thus inhibits the reaction of the isocyanate group. Examples of the blocking agent (A3) include oxime, phenol, alcohol, thiol, amide, imide, imidazole, urea, amine, imine, pyrazole, and active methylene compounds. Other examples of the blocking agent (A3) include pyridinol, thiophenol, diketone, and ester. The blocked polyisocyanate (blocked isocyanate compound) can be modified with a compound having a hydrophilic group. As the blocking agent (A3), oxime, pyrazole, and active methylene compounds are preferred because of the improved water repellency and oil repellency.

[0101] The water repellency washing durability is improved by the presence of the blocking agent.

[0102] Examples of the oxime include carbamoyl oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, and cyclohexanone oxime.

[0103] Examples of the phenol include phenol which may have at least 1 (preferably 1 or 2) C 1－10 alkyl groups according to circumstances. Specific examples of the phenol include: phenol; monoalkylphenols (such as cresol, ethylphenol, propylphenol, butylphenol, hexylphenol, 2-ethylhexylphenol, and octylphenol); and dialkylphenols (such as diethylphenol, dipropylphenol, dipropylcresol, dibutylphenol, di-2-ethylhexylphenol, dioctylphenol, and dinonylphenol).

[0104] Additional specific examples of the phenol include styrenated phenol and hydroxybenzoate.

[0105] Examples of the alcohol include those having C1-C 30Alkyl (preferably monohydric) alcohols (especially alkanols).

[0106] Specific examples of the alcohol include methanol, ethanol, propanol, 1-butanol, sec-butanol, 2-ethyl-1-hexanol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxy-1-propanol, and 3-methyl-2-pentene-4-yn-1-ol.

[0107] Specific examples of the thiol include butanethiol and dodecyl mercaptan.

[0108] Specific examples of the amide (preferably acidic amide) include acetanilide, acetamide, β-propiolactam, γ-butyrolactam, δ-valerolactam, ε-caprolactam, laurolactam, stearolactam, N-methyl-ε-caprolactam, and pyrrolidone.

[0109] Specific examples of the imide include acid imides such as maleimide and succinimide.

[0110] Specific examples of the imidazole include imidazole and 2-methylimidazole.

[0111] Specific examples of the urea include urea, thiourea, and ethyleneurea.

[0112] Specific examples of the amine include diphenylamine, aniline, carbazole, diethylamine, dipropylamine, and propylethylamine.

[0113] Specific examples of the imine include ethyleneimine and polyethyleneimine.

[0114] Specific examples of the pyrazole include 2-methylpyrazole, 3-methylpyrazole, 4-methylpyrazole, 2,4-dimethylpyrazole, 2,5-dimethylpyrazole, 3,4-dimethylpyrazole, 3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, and 4-bromo-3,5-dimethylpyrazole.

[0115] Examples of the active methylene compound include malonic esters (e.g., C 1－30 -alkyl malonic esters), acetoacetic esters (e.g., C 1－30 -alkyl acetoacetic esters), and acetylacetone.

[0116] The capping agent for forming the capped isocyanate compound is preferably a pyrazole compound or a malonic ester compound, particularly preferably a pyrazole compound.

[0117] The pyrazole compound can be a compound represented by the following formula.

[0118]

[0119] [In the formula, each R 11identical or different, and is an alkyl group, alkenyl group, aralkyl group, N-substituted carbamoyl group, phenyl group, NO2, halogen atom or -C(=O)OR 12 group (R 12 is an alkyl group having 1 to 4 carbon atoms),

[0120] n is 0, 1, 2 or 3.]

[0121] As specific examples of the pyrazole compound, 2-methylpyrazole, 3-methylpyrazole, 4-methylpyrazole, 2,4-dimethylpyrazole, 2,5-dimethylpyrazole, 3,4-dimethylpyrazole, 3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole can be cited.

[0122] The malonic ester compound is a reaction product of malonic acid and an alcohol (e.g., a monohydric alcohol) (monoester or diester (preferably diester)). Usually, the alcohol has a hydrocarbon group having 1 to 30 carbon atoms bonded to the hydroxyl group. The hydrocarbon group is preferably an alkyl group, particularly preferably an alkyl group having 1 to 4 carbon atoms.

[0123] As specific examples of the malonic ester, dimethyl malonate, diethyl malonate, dipropyl malonate, dibutyl malonate, methyl malonate, ethyl malonate, propyl malonate and butyl malonate can be cited. Diesters are preferred. As preferred specific examples of the malonic ester, dimethyl malonate, diethyl malonate, dipropyl malonate and dibutyl malonate can be cited.

[0124] The alcohol compound (A4) can be a monohydric alcohol or a polyhydric alcohol.

[0125] The monohydric alcohol is preferably a compound formed by adding C2 or C3 alkylene oxide to a starting monohydric alcohol (such as methanol) having 1 to 10 carbon atoms.

[0126] The polyhydric alcohol can be a dihydric alcohol and a polyhydric alcohol having 3 or more hydroxyl groups. The polyhydric alcohol can be a low molecular weight polyhydric alcohol, a polyether polyhydric alcohol, a polyester polyhydric alcohol, a polyester polycarbonate polyhydric alcohol, or a crystalline or amorphous polycarbonate polyhydric alcohol.

[0127] The alcohol compound (A4) preferably has a hydrophilic group in addition to the hydroxyl group. The hydrophilic group is not consumed by the urethane reaction. Examples of the hydrophilic group include a C2 or C3 alkylene oxide group, an amino group, etc.

[0128] Since the molecular weight of the urethane compound increases due to crosslinking, the alcohol compound (A4) can be composed only of monohydric alcohols.

[0129] The urethane compound preferably has an R 0 group derived from the polyisocyanate (A1) and a -Z(Y-R) nThe base also has a group derived from the blocking agent (A3) and a group derived from the alcohol compound (A4).

[0130] Regarding the total amount of the long-chain alcohol (A2) and the alcohol compound (A4), it can be an amount such that the isocyanate index [the equivalent ratio of the isocyanate group in the polyisocyanate to the active hydrogen group in the alcohol] reaches 2 to 0.5, preferably 1.5 to 0.8, particularly 1.2 to 0.9. The molar ratio of the long-chain alcohol (A2) to the alcohol compound (A4) can be 10:90 to 100:0, 10:90 to 90:10, for example 20:80 to 80:20, particularly 30:70 to 70:30.

[0131] The amount (equivalent ratio) of the blocking agent (A3) relative to the equivalent of the isocyanate group in the polyisocyanate can be 1 to 50 equivalent%, for example 2 to 30 equivalent%, particularly 3 to 20 equivalent%.

[0132] The aqueous urethane composition contains a urethane compound (A) and water (B). Regarding the amount of water (B), it can be an amount such that the amount of the urethane compound (A) reaches 0.1 to 70% by weight, for example 1 to 50% by weight, relative to the aqueous urethane composition. The aqueous urethane composition may also contain an organic solvent, and the amount of the organic solvent can be 200 parts by weight or less, for example 1 to 50 parts by weight, relative to 100 parts by weight of water (B).

[0133] The aqueous urethane composition is preferably an aqueous dispersion. The aqueous urethane composition is preferably self-emulsifying. The aqueous urethane composition may contain (in an amount of 0.1 to 10 parts by weight relative to 100 parts by weight of the urethane compound (A)) an emulsifier, but preferably does not contain an emulsifier.

[0134] The urethane compound (A) can be produced by reacting the long-chain alcohol (A2) and, if necessary, the alcohol compound (A4) with the polyisocyanate (A1), and, if necessary, reacting with the blocking agent (A3).

[0135] The aqueous urethane composition can be produced by mixing and reacting the polyisocyanate (A1) and the long-chain alcohol (A2) in an organic solvent and then adding water. Alternatively, the aqueous urethane composition can also be produced by mixing and reacting the polyisocyanate (A1), the long-chain alcohol (A2) and the alcohol compound (A4) in an organic solvent, then reacting with the blocking agent (A3), and then adding water. After adding water, the organic solvent can be removed.

[0136] The temperature and time for reacting the long-chain alcohol (A2) and the alcohol compound (A4) with the polyisocyanate (A1) can be 0 to 60°C, 1 minute to 24 hours. The temperature and time for reacting the blocking agent (A3) can be 30 to 120°C, 1 minute to 24 hours.

[0137] The urethane compound (A) (and the aqueous urethane composition) can function as a crosslinking agent or an auxiliary agent. "Auxiliary agent" refers to an agent that aids the performance of a surface treatment agent (an agent that improves water / oil repellency, stain resistance, detergency, peelability, and / or mold release properties, especially an agent that improves water / oil repellency), an agent that modifies the object to be treated (especially an agent that modifies fiber products, such as an agent that improves the feel of fiber products), or an agent that aids in stable processing during surface treatment agent treatment.

[0138] By mixing the aqueous urethane composition with a surface treatment agent, a surface treatment composition can be obtained.

[0139] The surface treatment agent mixed with the urethane compound (A) can be any substance, and can be fluorine-based, silicon-based, urethane-based, acrylic-based, etc. The surface treatment agent can be in the form of a solution, an emulsion (especially an aqueous dispersion) or an aerosol, but is preferably an aqueous dispersion. Examples of the active ingredient of the surface treatment agent include fluorine-containing polymers, silicon-containing polymers, polyurethanes, non-fluorine non-silicon polymers, etc. In the surface treatment composition, the amount of the urethane compound (A) can be 1 to 100 parts by weight, especially 5 to 50 parts by weight, relative to 100 parts by weight of the active ingredient of the surface treatment agent.

[0140] The surface treatment composition can be used as a water repellent, an oil repellent, a stain repellent, a detergent, a release agent and a mold release agent.

[0141] The surface treatment composition can be applied to the object to be treated by known methods. Usually, the following method is adopted: the treatment agent is dispersed in water (and / or an organic solvent) for dilution, and is attached to the surface of the object to be treated by known methods such as dip coating, spray coating, foam coating, etc., and then dried. Curing is preferably carried out. The curing temperature can be 60 to 250 °C, especially 100 to 200 °C, and the curing time can be 1 second to 10 minutes, especially 10 seconds to 3 minutes. An insect repellent, a softening agent, an antibacterial agent, a flame retardant, an antistatic agent, a fixing agent, an anti-wrinkle agent, etc. can also be added and used in the surface treatment composition. The concentration of the urethane fluorine-containing polymer in the treatment liquid in contact with the substrate can be 0.01 to 10% by weight (especially during dip coating), for example, 0.05 to 10% by weight.

[0142] Examples of the object to be treated with a surface treatment composition (such as a water and oil repellent) include fiber products, stones, filters (such as electrostatic filters), dust covers, components of fuel cells (such as gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, coatings, and plasters. As for fiber products, various examples can be cited. For example, animal and plant natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, semi-synthetic fibers such as rayon and acetate fiber, inorganic fibers such as glass fiber, carbon fiber, and asbestos fiber, or their mixed fibers can be mentioned.

[0143] The fiber product can be in any form such as fibers or cloth.

[0144] The surface treatment composition can impart the desired peelability to the surface of the substrate. Therefore, it is possible to easily peel the surface of the substrate from other surfaces (other surfaces of the same substrate or surfaces of other substrates).

[0145] Examples of the substrate to which the surface treatment composition is applied include fiber products (such as non-woven fabrics and woven fabrics), paper, stones, leather, resins, glass, metals, etc. The substrate is preferably cloth or paper.

[0146] The surface treatment composition can be used for peeling between the same substrates (such as cloth and cloth, paper and paper) or different substrates (such as cloth and resin, cloth and metal, paper and cloth, paper and glass). The surface treatment composition can be used for the manufacture of adhesive sheets, protective materials for the adhesive surface of adhesive tapes, release films, release papers, sticky notes, etc.

[0147] The surface treatment composition can also be used as an internal release agent or an external release agent.

[0148] The fluoropolymer can be applied to a fibrous substrate (such as a fiber product) by any known method for treating a fiber product with a liquid. When the fiber product is cloth, the cloth can be immersed in a solution, or the solution can be attached to the cloth or sprayed onto the cloth. For the treated fiber product, in order to exhibit oil repellency, it can be dried, preferably heated at 100°C to 200°C, for example.

[0149] Alternatively, the fluoropolymer can be applied to the fiber product by a cleaning method, for example, it can be a washing application or an application in a dry cleaning method, etc., to the fiber product.

[0150] The fibrous article to be treated is typically cloth, which includes woven fabric, knitted fabric, non-woven fabric, cloth in the form of clothing, and carpets. It can also be fibers, filaments, or intermediate fibrous articles (such as slivers or rovings). The material of the fibrous article can be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or lyocell), or synthetic fibers (such as polyester, polyamide, or acrylic fibers), or it can also be a mixture of fibers (such as a mixture of natural fibers and synthetic fibers). The fluoropolymer of the present invention is particularly effective in imparting oil repellency and water repellency to cellulose-based fibers (such as cotton or rayon). In addition, the method of the present invention generally imparts hydrophobicity and water repellency to the fibrous article.

[0151] Alternatively, the fibrous substrate can also be leather. In order to impart hydrophobicity and oil repellency to leather, the fluoropolymer can be applied to the leather from an aqueous solution or an aqueous emulsion at various stages of leather processing, such as during the wet processing of leather or during the finishing of leather.

[0152] Alternatively, the fibrous substrate can also be paper. The fluoropolymer can be applied to pre-formed paper, or it can also be applied at various stages of papermaking, such as during the drying of paper.

[0153] "Treatment" means applying a treatment agent (surface treatment composition) to the object to be treated by means of dipping, spraying, coating, etc. Through treatment, the polymer, which is the active ingredient of the treatment agent, penetrates into the interior of the object to be treated and / or adheres to the surface of the object to be treated.

[0154] The cross-linked product of the urethane compound (the reaction product of the active ingredient of the surface treatment agent and the urethane compound) adheres to the object to be treated.

[0155] Examples

[0156] Hereinafter, examples and comparative examples will be listed to specifically illustrate the present invention, but these illustrations do not limit the present invention.

[0157] Hereinafter, unless otherwise specified, parts, %, or ratios represent parts by weight, % by weight, or weight ratio.

[0158] The test methods used hereinafter are as follows.

[0159] Spray water repellency test

[0160] The spray water repellency test was carried out in accordance with AATCC Test Method 22-2010.

[0161] Use a glass funnel with a volume of at least 250 ml and a nozzle that can spray 250 ml of water within 20 to 30 seconds. The test piece holder is a metal holder with a diameter of 15 cm. Prepare 3 test pieces with dimensions of approximately 20 cm × 20 cm, fix the sheet to the test piece holding holder so that the sheet has no wrinkles. Place the center of the spray at the center of the sheet. Pour water at room temperature (250 mL) into the glass funnel and spray the test piece (for 25 to 30 seconds). Remove the holding holder from the pedestal, hold one end of the holding holder so that the front surface faces down, and gently strike the opposite end with a hard object. Then rotate the holding holder 180° and repeat the same steps to let the excess water droplets fall. Compare the wet test piece with the wet control standard and rate it as 0, 50, 70, 80, 90, and 100 points (water repellency No.) in the order from poor to good water repellency. The result is obtained from the average value of three measurements. The mark “+” after the number indicates that the evaluation is higher than this number, and the mark “-” indicates that the evaluation is lower than this number.

[0162] Oil repellency test

[0163] Conduct the oil repellency test according to AATCC Test Method 118 - 1992.

[0164] Store the treated test cloth in a thermo-hygrostat at a temperature of 21 °C and a humidity of 65% for more than 4 hours. Also use the test liquid stored at a temperature of 21 °C for the test liquid. The test is conducted in a thermo-hygrostatic chamber at a temperature of 21 °C and a humidity of 65%. Quietly drop 0.05 ml of the test liquid on the test cloth. After 30 seconds, if the liquid droplet remains on the test cloth, it is evaluated as passing this test liquid. The oil repellency is set as the highest score of the test liquid passed, and it is evaluated as nine grades: unqualified, 1, 2, 3, 4, 5, 6, 7, and 8 in the order from poor to good oil repellency. The mark “+” after the number indicates that the evaluation is higher than this number, and the mark “-” indicates that the evaluation is lower than this number.

[0165] Oil repellency test liquid

[0166]

[0167] Washing durability of water and oil repellency

[0168] According to JIS L - 0217 - 103 method, wash it repeatedly 5 times, 10 times, or 15 times, and evaluate the subsequent water and oil repellency (HL5, HL10, or HL15). HL0 is the initial water and oil repellency without washing.

[0169] Synthesis Example 1

[0170] In a 300 mL flask, 32.5 g of the allophanate of 1,6 - hexamethylene diisocyanate (NCO content 21.8%), 30 g of dipropylene glycol dimethyl ether, and 4.85 g of stearamide ethanol were added. Under a nitrogen atmosphere and with stirring, the internal temperature was raised from room temperature to 85°C. 0.020 g of dibutyltin dilaurate was added and stirred for 2 hours. Then, 5 g of polyethylene glycol monomethyl ether (molecular weight 1000) was added and stirred for 3 hours. Next, 14.3 g of dimethylpyrazole was added and stirred for 2 hours. The disappearance of the NCO group was confirmed by IR, and it was cooled to room temperature. After cooling, water at 40°C was added under strong stirring and stirred for 10 minutes to prepare an aqueous dispersion with a solid content of 20%.

[0171] Comparative Synthesis Example 1

[0172] In a 300 mL flask, 32.5 g of diphenyl diisocyanate (NCO content 21.8%) and 30 g of dipropylene glycol dimethyl ether were added. Under a nitrogen atmosphere and with stirring, the internal temperature was raised from room temperature to 85°C. 0.020 g of dibutyltin dilaurate was added and stirred for 2 hours. Then, 5 g of polyethylene glycol monomethyl ether (molecular weight 1000) was added and stirred for 3 hours. Next, 14.3 g of methyl ethyl ketoxime was added and stirred for 2 hours. The disappearance of the NCO group was confirmed by IR, and it was cooled to room temperature. After cooling, water at 40°C was added under strong stirring and stirred for 10 minutes to prepare an aqueous dispersion with a solid content of 20%.

[0173] Comparative Synthesis Example 2

[0174] In a 300 mL flask, 32.5 g of the allophanate of 1,6 - hexamethylene diisocyanate (NCO content 21.8%), 30 g of dipropylene glycol dimethyl ether, and 4.05 g of stearyl alcohol were added. Under a nitrogen atmosphere and with stirring, the internal temperature was raised from room temperature to 85°C. 0.020 g of dibutyltin dilaurate was added and stirred for 2 hours. Then, 5 g of polyethylene glycol monomethyl ether (molecular weight 1000) was added and stirred for 3 hours. Next, 14.3 g of dimethylpyrazole was added and stirred for 2 hours. The disappearance of the NCO group was confirmed by IR, and it was cooled to room temperature. After cooling, water at 40°C was added under strong stirring and stirred for 10 minutes to prepare an aqueous dispersion with a solid content of 20%.

[0175] Synthesis Example 2

[0176] In a 1000 mL autoclave, CF3CF2-(CF2CF2) n -CH2CH2OCOC(Cl)=CH2 (n = 2.0) (13FClA) 65.1 g, CF3CF2-(CF2CF2) n-CH2CH2OCOCH=CH2 (n = 2.0) (13FA) 65.1 g, stearyl acrylate 30.9 g, pure water 400 g, water-soluble glycol-based solvent 56 g, alkyldimethylammonium chloride 1.56 g, polyoxyethylene alkyl ether 16.1 g, and under stirring, ultrasonic emulsification and dispersion were carried out at 60 °C for 15 minutes. After nitrogen replacement in the flask, 61.2 g of vinyl chloride (VCM) was pressed in, 0.4 g of a water-soluble azo-based initiator was added, and the reaction was carried out at 60 °C for 20 hours to obtain an aqueous dispersion of a fluoropolymer (fluorine-based water and oil repellent). The composition of the polymer was substantially the same as the composition of the charged monomers.

[0177] Synthesis Example 3

[0178] In a 500 mL autoclave, 45 g of stearyl acrylate, 5 g of isobornyl methacrylate, 145 g of pure water, 15 g of tripropylene glycol, 1.5 g of sorbitan monooleate, 2 g of polyoxyethylene (EO: 18) secondary alkyl (C12-14) ether, and 1.5 g of di(octadecyl)dimethylammonium chloride were added. Under stirring, ultrasonic emulsification and dispersion were carried out at 60 °C for 15 minutes. After nitrogen replacement in the autoclave, 0.5 g of 2,2-azobis(2-amidinopropane) dihydrochloride was added, and the reaction was carried out at 60 °C for 3 hours to obtain an aqueous dispersion of a non-fluoropolymer. Then, the solid content concentration was adjusted to 30% with pure water. The monomer composition of the generated polymer was substantially the same as the monomer charging composition.

[0179] Example 1

[0180] The fluorine-based water and oil repellent obtained in Synthesis Example 2 (a water and oil repellent with a fluorinated acrylic polymer having a C6 perfluoroalkyl group as an active ingredient) was diluted with water to 4%, and the aqueous dispersion obtained in Synthesis Example 1 was added to make it 1%, and it was stirred evenly. Ten pieces of nylon fabric (500 mm × 200 mm) and cotton fabric (500 mm × 200 mm) were continuously immersed in this test solution, passed through a padding machine, and treated at 170 °C for 1 minute using a pin tenter. Then, for each of the nylon fabric and cotton fabric, a water repellency test, an oil repellency test, and a washing durability test were carried out. The results are shown in Table A.

[0181] Comparative Examples 1 and 2

[0182] Instead of the aqueous dispersion obtained in Synthesis Example 1, the aqueous dispersions obtained in Comparative Synthesis Example 1 (Comparative Example 1) or Comparative Synthesis Example 2 (Comparative Example 2) were used, and otherwise, the same steps as in Example 1 were repeated. The results are shown in Table A.

[0183] Example 2

[0184] Instead of the aqueous dispersion of the fluoropolymer obtained in Synthesis Example 2, the aqueous dispersion of the non-fluoropolymer obtained in Synthesis Example 3 was used, and other than that, the same procedure as in Example 1 was repeated. The results are shown in Table A.

[0185] Comparative Examples 3 and 4

[0186] Instead of the aqueous dispersion obtained in Synthesis Example 1, the aqueous dispersion obtained in Comparative Synthesis Example 1 (Comparative Example 3) or Comparative Synthesis Example 2 (Comparative Example 4) was used, and other than that, the same procedure as in Example 2 was repeated. The results are shown in Table A.

[0187]

[0188] Industrial Applicability

[0189] The urethane composition of the present invention can be used as a crosslinking agent or an auxiliary agent. The urethane composition of the present invention can be used together with a surface treatment agent, and can improve the efficacy of the surface treatment agent and the durability of the efficacy (especially washing durability).

Claims

1. An aqueous urethane composition, characterized in that, Containing: urethane compound (A); and water (B), The urethane compound (A) contains a unit formed from an isocyanate (A1) as a polyisocyanate and a unit formed from a long-chain alcohol (A2) represented by the formula: HO-Z(Y-R) n shown wherein R is independently an aliphatic hydrocarbon group having 7 to 40 carbon atoms, Y is independently -NH-C(=O)-, -C(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH-, -O-C(=O)-NH-, -NH-S(=O)2- or -S(=O)2-NH-, Z is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- or -CH2CH2CH2CH2CH2-, n is 1, The urethane bond is formed by the reaction of isocyanate (A1) and long-chain alcohol (A2).

2. The aqueous urethane composition according to claim 1, characterized in that: The urethane compound (A) further contains units formed from at least one selected from a blocking agent (A3) and an alcohol compound (A4).

3. The aqueous urethane composition according to claim 1 or 2, characterized in that: The isocyanate (A1) is at least one selected from toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), MDI oligomer, naphthalene-1,5-diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate (HDI), 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, isophorone diisocyanate (IPDI), an adduct of diisocyanate, a urethane-modified product, a biuret-modified product, an isocyanurate-modified product or a carbodiimide-modified product, and a urethane prepolymer.

4. The aqueous urethane composition according to claim 1 or 2, characterized in that: The long-chain alcohol (A2) is at least one selected from the following formula, HO-(CH2) m -NH-C(=O)-R、 HO-(CH2) m -C(=O)-NH-R、 HO-(CH2) m -NH-C(=O)-O-R、 HO-(CH2) m -O-C(=O)-NH-R、 HO-(CH2) m -NH-C(=O)-NH-R、 HO-(CH2) m -NH-S(=O)2-R, and HO-(CH2) m -S(=O)2-NH-R, wherein R is an aliphatic hydrocarbon group having 12 to 30 carbon atoms, m is an integer of 1 to 5.

5. The aqueous urethane composition according to claim 2, characterized in that: The blocking agent (A3) is at least one selected from oxime, phenol, alcohol, thiol, amide, imide, imidazole, urea, amine, imine, pyrazole and active methylene compounds.

6. The aqueous urethane composition according to claim 2, characterized in that: The alcohol compound (A4) is a monoalcohol or a polyol, The monoalcohol is a compound formed by the addition of C2 or C3 alkylene oxide to a starting monohydric alcohol having 1 to 10 carbon atoms, The polyol is a diol and a polyol having three or more hydroxyl groups, and is at least one selected from low molecular weight polyols, polyether polyols, polyester polyols, polyester polycarbonate polyols, crystalline or amorphous polycarbonate polyols.

7. The aqueous urethane composition according to claim 1 or 2, characterized in that: It further contains at least one selected from polyisocyanate (A1), long-chain alcohol (A2), blocking agent (A3) and alcohol compound (A4).

8. The aqueous urethane composition according to claim 1 or 2, characterized in that: The aqueous urethane composition is an aqueous dispersion.

9. The aqueous urethane composition according to claim 1 or 2, wherein: The aqueous urethane composition is a crosslinking agent or an auxiliary agent.

10. A method for producing the aqueous urethane composition according to any one of claims 1 to 9, wherein: The isocyanate (A1) and the long-chain alcohol (A2) are mixed and reacted in an organic solvent, and then mixed with water.

11. A method for treating a substrate, wherein, Including: The step of treating a substrate with the aqueous urethane composition according to any one of claims 1 to 9.

12. A treated fiber product, wherein: The urethane compound in the aqueous urethane composition according to any one of claims 1 to 9 adheres to the object to be treated in the form of a crosslinked product.

Images