Hydrophobically modified polyether urethane polymer, viscosity modifier, and aqueous composition

Abstract

To provide a hydrophobically modified polyether urethane polymer having a superior thickening effect and a favorable thixotropy-modifying effect.SOLUTION: The present invention provides a hydrophobically modified polyether urethane polymer represented by formula (1), a viscosity modifier composed of the polymer, and an aqueous composition containing the polymer and water. (In the formula, R1 and R9 independently represent a saturated aliphatic hydrocarbon group having 6 to 30 carbon atoms or an unsaturated aliphatic hydrocarbon group having 6 to 30 carbon atoms; R2, R3, R10, and R11 independently represent an alkyl group having 6 to 24 carbon atoms or an alkenyl group having 6 to 24 carbon atoms; R4, R6, and R8 independently represent an alkylene group having 2 to 4 carbon atoms; R5 and R7 independently represent a divalent hydrocarbon group having 6 to 16 carbon atoms; a and d independently represent a number of 0 or 1; b and c independently represent a number of 0 or 1; l and n independently represent a number from 0 to 200; x represents a number from 0 to 10; and m represents a number from 20 to 500).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a hydrophobically modified polyetherurethane polymer having an excellent thickening effect and a good thixotropy adjusting effect.

Background Art

[0002] In paints, adhesives, adhesives, inks, cosmetics, etc., in order to achieve a viscosity and thixotropy suitable for use, natural viscosity modifiers such as carboxymethyl cellulose and hydroxyethyl cellulose, and types of alkali-thickening viscosity modifiers that thicken with alkali such as polyacrylic acid and polyacrylic acid-containing copolymers, and various viscosity modifiers such as urethane-type viscosity modifiers such as urethane-modified polyethers are used. Among these, urethane-type viscosity modifiers with various structures have been developed and used because it is easy to achieve the desired thixotropy and leveling properties, and the water resistance of the resulting paint is also good (see, for example, Patent Documents 1 to 3).

[0003] However, even these urethane-type viscosity modifiers do not have a sufficient thickening effect and thixotropy adjusting effect, and there is still a demand in the market for a viscosity modifier having an excellent thickening effect and a good thixotropy adjusting effect.

Prior Art Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] ​Accordingly, an object of the present invention is to provide a hydrophobically modified polyetherurethane polymer having an excellent thickening effect and a good thixotropy adjusting effect.

Means for Solving the Problems

[0006] Therefore, the present inventors have conducted intensive studies and found that a specific hydrophobically modified polyetherurethane polymer has an excellent thickening effect and a good thixotropy adjusting effect, thereby completing the present invention. That is, the present invention is a hydrophobically modified polyetherurethane polymer represented by the following general formula (1).

[0007]

Chemical formula

[0008] (In the formula, R 1 , R 9 each independently represents a saturated aliphatic hydrocarbon group having 6 to 30 carbon atoms or an unsaturated aliphatic hydrocarbon group having 6 to 30 carbon atoms, and R 2 , R 3 , R 10 , R 11 each independently represents an alkyl group having 6 to 24 carbon atoms or an alkenyl group having 6 to 24 carbon atoms, and R 4 , R 6 , R 8 each independently represents an alkylene group having 2 to 4 carbon atoms, and R 5 , R 7 each independently represents a divalent hydrocarbon group having 6 to 16 carbon atoms, a and d each independently represent a number of 0 or 1, b and c each independently represent a number of 0 or 1, l and n each independently represent a number of 0 to 200, x represents a number of 0 to 10, and m represents a number of 20 to 500.)

Effects of the Invention

[0009] The hydrophobically modified polyetherurethane polymer of the present invention exhibits an excellent thickening effect and a good thixotropy adjusting effect.

Modes for Carrying Out the Invention

[0010] The hydrophobic modified polyetherurethane polymer of the present invention is a hydrophobic modified polyetherurethane polymer represented by the following general formula (1).

[0011] [Chemical formula]

[0012] (In the formula, R 1 , R 9 each independently represents a saturated aliphatic hydrocarbon group having 6 to 30 carbon atoms or an unsaturated aliphatic hydrocarbon group having 6 to 30 carbon atoms, and R 2 , R 3 , R 10 , R 11 each independently represents an alkyl group having 6 to 24 carbon atoms or an alkenyl group having 6 to 24 carbon atoms, and R 4 , R 6 , R 8 each independently represents an alkylene group having 2 to 4 carbon atoms, and R 5 , R 7 each independently represents a divalent hydrocarbon group having 6 to 16 carbon atoms, a and d each independently represent a number of 0 or 1, b and c each independently represent a number of 0 or 1, l and n each independently represent a number from 0 to 200, x represents a number from 0 to 10, and m represents a number from 20 to 500.)

[0013] R 1 , R 9Each independently represents a saturated aliphatic hydrocarbon group having 6 to 30 carbon atoms or an unsaturated aliphatic hydrocarbon group having 6 to 30 carbon atoms. Examples of such groups include a linear alkyl group having 6 carbon atoms, a branched alkyl group having 6 carbon atoms, a linear alkyl group having 8 carbon atoms, a branched alkyl group having 8 carbon atoms, a linear alkyl group having 9 carbon atoms, a branched alkyl group having 9 carbon atoms, a linear alkyl group having 10 carbon atoms, a branched alkyl group having 10 carbon atoms, a linear alkyl group having 12 carbon atoms, a branched alkyl group having 12 carbon atoms, a linear alkyl group having 14 carbon atoms, a branched alkyl group having 14 carbon atoms, a linear alkyl group having 16 carbon atoms, a branched alkyl group having 16 carbon atoms, a linear alkyl group having 18 carbon atoms, a branched alkyl group having 18 carbon atoms, a linear alkyl group having 20 carbon atoms, a branched alkyl group having 20 carbon atoms, a linear alkyl group having 22 carbon atoms, a branched alkyl group having 22 carbon atoms, a linear alkyl group having 24 carbon atoms, a branched alkyl group having 24 carbon atoms, a linear alkyl group having 26 carbon atoms, a branched alkyl group having 26 carbon atoms, a linear alkyl group having 28 carbon atoms, a branched alkyl group having 28 carbon atoms, a linear alkyl group having 30 carbon atoms, a branched alkyl group having 30 carbon atoms, a linear alkenyl group having 6 carbon atoms, a branched alkenyl group having 6 carbon atoms, a linear alkenyl group having 8 carbon atoms, a branched alkenyl group having 8 carbon atoms, a linear alkenyl group having 10 carbon atoms, a branched alkenyl group having 10 carbon atoms, a linear alkenyl group having 12 carbon atoms, a branched alkenyl group having 12 carbon atoms, a linear alkenyl group having 14 carbon atoms, a branched alkenyl group having 14 carbon atoms, a linear alkenyl group having 16 carbon atoms, a branched alkenyl group having 16 carbon atoms, a linear alkenyl group having 18 carbon atoms, a branched alkenyl group having 18 carbon atoms, a linear alkenyl group having 20 carbon atoms, a branched alkenyl group having 20 carbon atoms, a linear alkenyl group having 22 carbon atoms, a branched alkenyl group having 22 carbon atoms, a linear alkenyl group having 24 carbon atoms, a branched alkenyl group having 24 carbon atoms, a linear alkenyl group having 26 carbon atoms, a branched alkenyl group having 26 carbon atoms, a linear alkenyl group having 28 carbon atoms, a branched alkenyl group having 28 carbon atoms, a linear alkenyl group having 30 carbon atoms, a branched alkenyl group having 30 carbon atoms, and the like.In the present invention, from the viewpoint of the thickening effect and thixotropy adjusting effect of the resulting hydrophobically modified polyether urethane polymer, among these, R. 1 and R 9 are each independently preferably a saturated aliphatic hydrocarbon group having 6 to 24 carbon atoms or an unsaturated aliphatic hydrocarbon group having 6 to 24 carbon atoms, more preferably a saturated aliphatic hydrocarbon group having 6 to 16 carbon atoms or an unsaturated aliphatic hydrocarbon group having 6 to 16 carbon atoms, and still more preferably a saturated aliphatic hydrocarbon group having 8 to 14 carbon atoms.

[0014] R in the general formula (1) 2 and R 3 and R 10 and R 11Each independently represents an alkyl group having 6 to 24 carbon atoms or an alkenyl group having 6 to 24 carbon atoms. Examples of such groups include a linear alkyl group having 6 carbon atoms, a branched alkyl group having 6 carbon atoms, a linear alkyl group having 8 carbon atoms, a branched alkyl group having 8 carbon atoms, a linear alkyl group having 10 carbon atoms, a branched alkyl group having 10 carbon atoms, a linear alkyl group having 12 carbon atoms, a branched alkyl group having 12 carbon atoms, a linear alkyl group having 14 carbon atoms, a branched alkyl group having 14 carbon atoms, a linear alkyl group having 16 carbon atoms, a branched alkyl group having 16 carbon atoms, a linear alkyl group having 18 carbon atoms, a branched alkyl group having 18 carbon atoms, a linear alkyl group having 20 carbon atoms, a branched alkyl group having 20 carbon atoms, a linear alkyl group having 22 carbon atoms, a branched alkyl group having 22 carbon atoms, a linear alkyl group having 24 carbon atoms, a branched alkyl group having 24 carbon atoms, a linear alkenyl group having 6 carbon atoms, a branched alkenyl group having 6 carbon atoms, a linear alkenyl group having 8 carbon atoms, a branched alkenyl group having 8 carbon atoms, a linear alkenyl group having 10 carbon atoms, a branched alkenyl group having 10 carbon atoms, a linear alkenyl group having 12 carbon atoms, a branched alkenyl group having 12 carbon atoms, a linear alkenyl group having 14 carbon atoms, a branched alkenyl group having 14 carbon atoms, a linear alkenyl group having 16 carbon atoms, a branched alkenyl group having 16 carbon atoms, a linear alkenyl group having 18 carbon atoms, a branched alkenyl group having 18 carbon atoms, a linear alkenyl group having 20 carbon atoms, a branched alkenyl group having 20 carbon atoms, a linear alkenyl group having 22 carbon atoms, a branched alkenyl group having 22 carbon atoms, a linear alkenyl group having 24 carbon atoms, a branched alkenyl group having 24 carbon atoms, and the like. In the present invention, from the viewpoints of the thickening effect and the thixotropy adjusting effect of the obtained hydrophobically modified polyetherurethane polymer, among these, R 2 、R 3 、R 10 、R 11 Each independently is preferably an alkyl group having 8 to 18 carbon atoms or an alkenyl group having 8 to 18 carbon atoms, and more preferably an alkyl group having 8 to 16 carbon atoms.

[0015] R in the general formula (1) 4 、R 6, R 8 each independently represents an alkylene group having 2 to 4 carbon atoms. Examples of such groups include an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, and the like. In the present invention, from the viewpoints of the thickening effect and the thixotropy adjusting effect of the obtained hydrophobically modified polyetherurethane polymer, among these, R 4 , R 6 , R 8 are each independently preferably an ethylene group or a propylene group, and more preferably an ethylene group.

[0016] R in the general formula (1) 5 , R 7 each independently represents a divalent hydrocarbon group having 6 to 16 carbon atoms. Examples of such groups include an alkylene group having 6 to 16 carbon atoms, a divalent unsaturated aliphatic hydrocarbon group having 6 to 16 carbon atoms, a divalent alicyclic hydrocarbon group having 6 to 16 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 16 carbon atoms, and the like. In the present invention, from the viewpoints of the thickening effect and the thixotropy adjusting effect of the obtained hydrophobically modified polyetherurethane polymer, among these, R 5 , R 7 are each independently preferably an alkylene group having 6 to 16 carbon atoms or a divalent alicyclic hydrocarbon group having 6 to 16 carbon atoms, more preferably an alkylene group having 6 to 10 carbon atoms or a divalent alicyclic hydrocarbon group having 8 to 16 carbon atoms, and even more preferably a residue obtained by removing two isocyanate groups from hexamethylene diisocyanate, isophorone diisocyanate, or 4,4-methylenebis(cyclohexyl isocyanate).

[0017] a and d in the general formula (1) each independently represent a number of 0 or 1. In the present invention, from the viewpoints of the thickening effect and the thixotropy adjusting effect of the obtained hydrophobically modified polyetherurethane polymer, it is preferable that a and d are each 0.

[0018] In the general formula (1), b and c each independently represent a number of 0 or 1. In the present invention, from the viewpoints of the thickening effect and the thixotropy adjusting effect of the obtained hydrophobically modified polyether urethane polymer, it is preferable that b and c are each 1.

[0019] In the general formula (1), l and n each independently represent a number from 0 to 200. In the present invention, from the viewpoints of the thickening effect and the thixotropy adjusting effect of the obtained hydrophobically modified polyether urethane polymer, among these, it is preferable that l and n are each independently from 0 to 150, more preferably from 0 to 120, and even more preferably from 0 to 60. At this time, the average value of l and n is not particularly limited, but from the viewpoints of the thickening effect and the thixotropy adjusting effect of the obtained hydrophobically modified polyether urethane polymer, the average value of l and n is preferably each independently from 0 to 150, more preferably from 0 to 120, even more preferably from 0 to 60, and still more preferably from 0 to 40. In the present invention, the values and average values of l and n are each calculated from the measurement results of gel permeation chromatography (GPC), proton nuclear magnetic resonance spectrum (1H-NMR), gas chromatography-mass spectrometry (GC-MS), and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOFMS) of the hydrophobically modified polyether urethane polymer hydrolyzed with alkali as needed.

[0020] In the general formula (1), x represents a number from 0 to 10. In the present invention, from the viewpoints of the thickening effect and the thixotropy adjusting effect of the obtained hydrophobic modified polyether urethane polymer, among these, x is preferably from 0 to 8. At this time, the average value of x is not particularly limited, but from the viewpoints of the thickening effect and the thixotropy adjusting effect of the obtained hydrophobic modified polyether urethane polymer, the average value of x is preferably from 0.1 to 3.0, more preferably from 0.2 to 2.0, and even more preferably from 0.5 to 1.5. In the present invention, the value and the average value of x are calculated from the measurement results of gel permeation chromatography (GPC), proton nuclear magnetic resonance spectrum (1H-NMR), gas chromatography mass spectrometry (GC-MS), and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOFMS) of the alkali-hydrolyzed hydrophobic modified polyether urethane polymer as necessary.

[0021] In the general formula (1), m represents a number from 20 to 500. In the present invention, from the viewpoints of the thickening effect and the thixotropy adjusting effect of the obtained hydrophobic modified polyether urethane polymer, among these, m is preferably from 50 to 400, and more preferably from 100 to 350. At this time, the average value of m is not particularly limited, but from the viewpoints of the thickening effect and the thixotropy adjusting effect of the obtained hydrophobic modified polyether urethane polymer, the average value of m is preferably from 50 to 400, and more preferably from 100 to 350. In the present invention, the value and the average value of m are calculated from the measurement results of gel permeation chromatography (GPC), proton nuclear magnetic resonance spectrum (1H-NMR), gas chromatography mass spectrometry (GC-MS), and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOFMS) of the alkali-hydrolyzed hydrophobic modified polyether urethane polymer as necessary.

[0022] The method for producing the hydrophobic modified polyether urethane polymer of the present invention can be produced, for example, by reacting a secondary amine having an alkyl group with 6 to 24 carbon atoms or an alkenyl group with 6 to 24 carbon atoms, and a glycidyl ether having a saturated aliphatic hydrocarbon group with 6 to 30 carbon atoms, an unsaturated aliphatic hydrocarbon group with 6 to 30 carbon atoms, or an aromatic hydrocarbon group with 6 to 30 carbon atoms, or an α-olefin oxide with 6 to 30 carbon atoms, or a compound obtained by further adding 1 to 200 moles of an alkylene group with 2 to 4 carbon atoms to this compound as a reaction intermediate, and reacting this reaction intermediate with a polyether polyol and a polyisocyanate.

[0023] A compound obtained by reacting a secondary amine having an alkyl group having 6 to 24 carbon atoms or an alkenyl group having 6 to 24 carbon atoms, which can be used as a reaction intermediate in the present invention, with a glycidyl ether having a saturated aliphatic hydrocarbon group having 6 to 30 carbon atoms, an unsaturated aliphatic hydrocarbon group having 6 to 30 carbon atoms, or an aromatic hydrocarbon group having 12 to 36 carbon atoms is a reaction intermediate having a structure in which the epoxy group in the glycidyl group of the glycidyl ether used in the reaction is ring-opened and bonded to the amino group of the secondary amine. At this time, as the secondary amine to be used, from the viewpoints of the thickening effect and thixotropy adjusting effect of the obtained hydrophobically modified polyether urethane polymer, a dialkylamine having the same alkyl group having 6 to 24 carbon atoms or a dialkenylamine having the same alkenyl group having 6 to 24 carbon atoms is preferable, it is more preferable to use a dialkylamine having the same alkyl group having 6 to 24 carbon atoms, and it is even more preferable to use a dialkylamine having the same alkyl group having 8 to 16 carbon atoms. Among these, examples of the dialkylamine having the same alkyl group having 6 to 24 carbon atoms include di-hexylamine, di-heptylamine, di-octylamine, di-ethylhexylamine, di-nonylamine, di-decylamine, di-undecylamine, di-dodecylamine, di-tridecylamine, di-isotridecylamine, di-tetradecylamine, di-hexadecylamine, di-octadecylamine, di-icosylamine, di-docosylamine, di-tetracosylamine and the like.

[0024] In addition, as the glycidyl ether to be used, from the viewpoints of the thickening effect and thixotropy adjusting effect of the resulting hydrophobically modified polyether urethane polymer, a glycidyl ether having a monovalent saturated aliphatic hydrocarbon group with 6 to 30 carbon atoms, a glycidyl ether having a monovalent unsaturated aliphatic hydrocarbon group with 6 to 30 carbon atoms, or a glycidyl ether having a monovalent aromatic hydrocarbon group with 12 to 36 carbon atoms is preferable, a glycidyl ether having an alkyl group with 6 to 24 carbon atoms or a glycidyl ether having a monovalent aromatic hydrocarbon group with 12 to 24 carbon atoms is more preferable, and a glycidyl ether having an alkyl group with 6 to 24 carbon atoms is even more preferable. Among these, examples of the glycidyl ether having an alkyl group with 6 to 24 carbon atoms include hexyl glycidyl ether, octyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, dodecyl glycidyl ether, tetradecyl glycidyl ether, hexadecyl glycidyl ether, octadecyl glycidyl ether, eicosyl glycidyl ether, docosyl glycidyl ether, tetracosyl glycidyl ether and the like. Among these, from the viewpoints of the thickening effect and thixotropy adjusting effect of the resulting hydrophobically modified polyether urethane polymer, it is particularly preferable to use a compound obtained by reacting a dialkylamine having the same alkyl group with 8 to 16 carbon atoms and a glycidyl ether having an alkyl group with 6 to 24 carbon atoms.

[0025] The compound obtained by reacting a secondary amine having an alkyl group with 6 to 24 carbon atoms or an alkenyl group with 6 to 24 carbon atoms, which can be used as a reaction intermediate in the present invention, with a glycidyl ether can be obtained by reacting the above-mentioned secondary amine and glycidyl ether by a known method. For example, the secondary amine and glycidyl ether are mixed in an amount of 1:0.5 to 1:2 in a molar ratio and reacted for 10 minutes to 240 hours in a temperature environment of room temperature to 180°C under a reduced pressure to normal pressure to pressurized environment.

[0026] In the present invention, as the reaction intermediate, a compound obtained by adding 1 to 200 moles of an alkylene oxide having 2 to 4 carbon atoms to the reaction product of the above-mentioned secondary amine and glycidyl ether can also be used. At this time, the method of adding 1 to 200 moles of an alkylene oxide having 2 to 4 carbon atoms is not particularly limited and can be obtained by a known method. For example, an alkylene oxide having 2 to 4 carbon atoms is added to the reaction product of the above-mentioned secondary amine and glycidyl ether in an amount of 1 to 200 moles per mole of the reaction product of the above-mentioned secondary amine and glycidyl ether. It can be obtained by reacting. At this time, the reaction method of the reaction product of the secondary amine and glycidyl ether and the alkylene oxide having 2 to 4 carbon atoms is not particularly limited, and a known method can be used. For example, an alkylene oxide having 2 to 4 carbon atoms is added to the reaction product of the above-mentioned secondary amine and glycidyl ether in an amount of 1 to 200 moles per mole of the reaction product of the above-mentioned secondary amine and glycidyl ether, and is contacted once or divided into a plurality of times. It can be obtained by reacting for 10 minutes to 24 hours in a temperature environment of room temperature to 180°C under a reduced pressure to normal pressure to pressurized environment. In the present invention, when using, as the reaction intermediate, a compound obtained by adding 1 to 200 moles of an alkylene oxide having 2 to 4 carbon atoms to the reaction product of the above-mentioned secondary amine and glycidyl ether, from the viewpoint of the thickening effect and thixotropy adjusting effect of the obtained hydrophobically modified polyether urethane polymer, the number of moles of alkylene oxide added is preferably 1 to 150 moles per mole of the reaction product of the secondary amine and glycidyl ether, more preferably 1 to 120 moles, and even more preferably 1 to 60 moles.

[0027] A compound obtained by reacting a secondary amine having an alkyl group having 6 to 24 carbon atoms or an alkenyl group having 6 to 24 carbon atoms, which can be used as a reaction intermediate in the present invention, with an α-olefin oxide having 6 to 30 carbon atoms is a reaction intermediate having a structure in which the epoxy group of the α-olefin oxide used in the reaction is ring-opened and bonded to the amino group of the secondary amine. At this time, as the secondary amine to be used, from the viewpoints of the thickening effect and the thixotropy adjusting effect of the obtained hydrophobically modified polyether urethane polymer, it is preferably a dialkylamine having the same alkyl group having 6 to 24 carbon atoms or a dialkenylamine having the same alkenyl group having 6 to 24 carbon atoms, more preferably a dialkylamine having the same alkyl group having 6 to 24 carbon atoms, and even more preferably a dialkylamine having the same alkyl group having 8 to 16 carbon atoms. Among these, examples of the dialkylamine having the same alkyl group having 6 to 24 carbon atoms include di-hexylamine, di-heptylamine, di-octylamine, di-ethylhexylamine, di-nonylamine, di-decylamine, di-undecylamine, di-dodecylamine, di-tridecylamine, di-isotridecylamine, di-tetradecylamine, di-hexadecylamine, di-octadecylamine, di-icosylamine, di-docosylamine, di-tetracosylamine, and the like.

[0028] In addition, examples of the α-olefin oxide having 6 to 30 carbon atoms include α-olefin oxide having 6 carbon atoms, α-olefin oxide having 8 carbon atoms, α-olefin oxide having 10 carbon atoms, α-olefin oxide having 12 carbon atoms, α-olefin oxide having 14 carbon atoms, α-olefin oxide having 16 carbon atoms, α-olefin oxide having 18 carbon atoms, α-olefin oxide having 20 carbon atoms, α-olefin oxide having 22 carbon atoms, α-olefin oxide having 24 carbon atoms, α-olefin oxide having 26 carbon atoms, α-olefin oxide having 28 carbon atoms, α-olefin oxide having 30 carbon atoms, and the like. Among these, from the viewpoints of the thickening effect and the thixotropy adjusting effect of the obtained hydrophobically modified polyether urethane polymer, it is preferable to use an α-olefin oxide having 8 to 24 carbon atoms, and more preferably to use an α-olefin oxide having 10 to 20 carbon atoms. Among these, from the viewpoints of the thickening effect and the thixotropy adjusting effect of the obtained hydrophobically modified polyether urethane polymer, it is particularly preferable to use a compound obtained by reacting a dialkylamine having the same alkyl group having 8 to 16 carbon atoms with an α-olefin oxide having 10 to 20 carbon atoms. Note that the "α-olefin oxide having 6 to 30 carbon atoms" means that the total number of carbon atoms in the whole compound containing a glycidyl group in the α-olefin oxide is 6 to 30.

[0029] The compound obtained by reacting a secondary amine with an α-olefin oxide, which can be used as a reaction intermediate in the present invention, can be obtained by reacting the above-mentioned secondary amine with an α-olefin oxide by a known method. For example, the secondary amine and the α-olefin oxide are mixed in an amount of 1:0.5 to 1:2 in a molar ratio and reacted for 10 minutes to 240 hours in a temperature environment of room temperature to 180°C under a reduced pressure to normal pressure to pressurized environment.

[0030] In the present invention, as the reaction intermediate, a compound obtained by adding 1 to 200 moles of an alkylene oxide having 2 to 4 carbon atoms to the reaction product of the above-described secondary amine and α-olefin oxide can also be used. At this time, the method of adding 1 to 200 moles of an alkylene oxide having 2 to 4 carbon atoms is not particularly limited and can be obtained by a known method. For example, to the reaction product of the above-described secondary amine and α-olefin oxide, an alkylene oxide having 2 to 4 carbon atoms is reacted in an amount of 1 to 200 moles per mole of the reaction product of the above-described secondary amine and α-olefin oxide to obtain it. At this time, the reaction method of the reaction product of the secondary amine and α-olefin oxide and the alkylene oxide having 2 to 4 carbon atoms is not particularly limited, and a known method can be used. For example, to the reaction product of the above-described secondary amine and α-olefin oxide, an alkylene oxide having 2 to 4 carbon atoms is contacted in an amount of 1 to 200 moles per mole of the reaction product of the above-described secondary amine and α-olefin oxide, either once or in multiple portions, and reacted under a reduced pressure to normal pressure to pressurized environment and at a temperature environment of room temperature to 180 ° C for 10 minutes to 24 hours to obtain it. In the present invention, when using, as the reaction intermediate, a compound obtained by adding 1 to 200 moles of an alkylene oxide having 2 to 4 carbon atoms to the reaction product of the above-described secondary amine and α-olefin oxide, from the viewpoint of the thickening effect and thixotropy adjusting effect of the resulting hydrophobic modified polyether urethane polymer, the number of moles of the added alkylene oxide is preferably 1 to 150 moles per mole of the reaction product of the secondary amine and α-olefin oxide, more preferably 1 to 120 moles, and even more preferably 1 to 60 moles.

[0031] In the present invention, from the viewpoints of the thickening effect and the thixotropy adjusting effect of the obtained hydrophobically modified polyether urethane polymer, as reaction intermediates, a dialkylamine having the same alkyl group with 8 to 16 carbon atoms, a compound obtained by reacting a glycidyl ether having an alkyl group with 6 to 24 carbon atoms, a compound obtained by reacting a dialkylamine having the same alkyl group with 8 to 16 carbon atoms and an α-olefin oxide with 10 to 20 carbon atoms, and a compound obtained by adding 1 to 60 moles of an alkylene oxide with 2 to 4 carbon atoms to a compound obtained by reacting a dialkylamine having the same alkyl group with 8 to 16 carbon atoms and a glycidyl ether having an alkyl group with 6 to 24 carbon atoms. It is preferable to produce the hydrophobically modified polyether urethane polymer using one or more reaction intermediates selected from the group consisting of the compounds thus obtained.

[0032] In the production of the reaction intermediate used in the present invention, a catalyst may be used if necessary. Examples of the catalyst include imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, dimethyloctylamine, dimethyldecylamine, dimethyldodecylamine, triallylamine, triethylamine, 3-(dibutylamino)propylamine, tri-n-octylamine, triethanolamine, methyldiethanolamine, boron trifluoride ethyl ether, boron trifluoride phenol, boron trifluoride piperidine, boron trifluoride monoethylamine, boron trifluoride triethanolamine, boron trifluoride monoethanolamine, and the like.

[0033] Examples of the polyether polyol used in the production of the hydrophobic modified polyether urethane polymer of the present invention include polymers of alkylene glycols having 2 to 4 carbon atoms and a degree of polymerization of 20 to 500. Examples of such polymers include homopolymers of ethylene glycol with a degree of polymerization of 20 to 500, homopolymers of propylene glycol with a degree of polymerization of 20 to 500, homopolymers of butylene glycol with a degree of polymerization of 20 to 500, copolymers of ethylene glycol and propylene glycol with a total degree of polymerization of 20 to 500, copolymers of ethylene glycol and butylene glycol with a total degree of polymerization of 20 to 500, copolymers of propylene glycol and butylene glycol with a total degree of polymerization of 20 to 500, copolymers of ethylene glycol, propylene glycol, and butylene glycol with a total degree of polymerization of 20 to 500, and the like. Among these, from the viewpoints of the thickening effect and the thixotropy adjusting effect of the resulting hydrophobic modified polyether urethane polymer, it is preferable to use a homopolymer of ethylene glycol with a degree of polymerization of 20 to 500 or a homopolymer of propylene glycol with a degree of polymerization of 20 to 500 as the polyether polyol. It is more preferable to use a homopolymer of ethylene glycol with a degree of polymerization of 20 to 500, and even more preferable to use a homopolymer of ethylene glycol with a degree of polymerization of 50 to 400. Also, the average value of the degree of polymerization is not particularly limited, but from the viewpoints of the thickening effect and the thixotropy adjusting effect of the resulting hydrophobic modified polyether urethane polymer, the average value of the degree of polymerization is preferably 50 to 400, and more preferably 100 to 350.

[0034] As the polyisocyanate used in the production of the hydrophobic modified polyetherurethane polymer of the present invention, any compound having two or more isocyanate groups in the molecule can be used without particular limitation. For example, aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, trans-1,4-cyclohexane diisocyanate, cis-1,4-cyclohexane diisocyanate, and norbornene diisocyanate; aromatic diisocyanates such as toluylene diisocyanate, diphenylmethane-4,4'-diisocyanate, p-phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, and tetramethylxylylene diisocyanate; polyfunctional isocyanates having three or more functional groups such as triphenylmethane triisocyanate, 1-methylbenzene-2,4,6-triisocyanate, and dimethyltriphenylmethane tetraisocyanate; carbodiimide-modified products, isocyanurate-modified products, and biuret-modified products of these polyfunctional isocyanates having three or more functional groups; blocked isocyanates obtained by blocking these modified products with various blocking agents; isocyanurate trimers and biuret trimers of the above-mentioned diisocyanates, etc. In the present invention, from the viewpoint of the thickening effect and thixotropy adjustment effect of the obtained hydrophobic modified polyetherurethane polymer, as the polyisocyanate, one or more selected from the group consisting of aliphatic diisocyanates having 6 to 16 carbon atoms other than the isocyanate group and alicyclic diisocyanates having 6 to 16 carbon atoms other than the isocyanate group are preferably used, and one or more selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, and 4,4-methylenebis(cyclohexyl isocyanate) are more preferably used.

[0035] In the method for producing the hydrophobic modified polyether urethane polymer of the present invention, the ratio of the reaction intermediate, polyether polyol, and polyisocyanate used is not particularly limited and can be appropriately adjusted according to the purpose. From the viewpoints of the thickening effect and thixotropy adjustment effect of the obtained hydrophobic modified polyether urethane polymer, the equivalent ratio of the reaction intermediate to the polyether polyol used is preferably 1:0.1 to 2, and more preferably 1:0.2 to 1.5. Also, from the viewpoints of the thickening effect and thixotropy adjustment effect of the obtained hydrophobic modified polyether urethane polymer, the equivalent ratio of the reaction intermediate to the polyisocyanate used is preferably 1:0.5 to 5, and more preferably 1:1 to 3. Further, from the viewpoints of the thickening effect and thixotropy adjustment effect of the obtained hydrophobic modified polyether urethane polymer, the equivalent ratio of the polyether polyol to the polyisocyanate used is preferably 1:0.5 to 5, and more preferably 1:1 to 3. Additionally, from the viewpoints of the thickening effect and thixotropy adjustment effect of the obtained hydrophobic modified polyether urethane polymer, the ratio of the total amount of the reactive intermediate and polyether polyether to the amount of polyisocyanate is preferably 1:0.5 to 2 in terms of equivalent ratio, and more preferably 1:0.8 to 1.5.

[0036] In the method for producing the hydrophobic modified polyether urethane polymer of the present invention, the reaction method of the reaction intermediate, polyether polyol, and polyisocyanate is not particularly limited and can be reacted by a known method. For example, each raw material can be mixed once or in multiple portions, and can be obtained by reacting under a reduced pressure to normal pressure to pressurized environment at a temperature environment of room temperature to 180°C for 10 minutes to 24 hours.

[0037] In the method for producing a hydrophobically modified polyetherurethane polymer of the present invention, a catalyst, a solvent, etc. may be used as necessary. Examples of the catalyst include metal halides such as titanium tetrachloride, hafnium chloride, zirconium chloride, aluminum chloride, gallium chloride, indium chloride, iron chloride, tin chloride, boron fluoride; hydroxides, alcoholates, carbonates of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium carbonate; organometallic compounds such as tetraisopropyl titanate, dibutyltin dichloride, dibutyltin oxide, dibutyltin bis(2-ethylhexyl thioglycolate); sodium octylate, potassium octylate, sodium laurate, potassium laurate, etc. Examples of the solvent include acetone, methyl ethyl ketone, dioxane, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, ethylene glycol ethyl methyl ether, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, dipropylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, polyethylene glycol dimethyl ether, 2-methyltetrahydrofuran, tetrahydrofuran, ethyl acetate, butyl acetate, etc.

[0038] The hydrophobic modified polyether urethane polymer of the present invention can be used in various products where urethane polymers are used, such as paints, coating agents, adhesives, binders, inks, fiber treatment agents, sizing agents, binders, paper treatment agents, cosmetics, quasi-drugs, pharmaceuticals, artificial leather, synthetic leather, foams, etc. From the viewpoints of the thickening effect and thixotropy adjusting effect of the hydrophobic modified polyether urethane polymer, it is preferably used as a viscosity modifier, and more preferably used as a viscosity modifier for products selected from paints, coating agents, adhesives, binders, and inks. Further, since the hydrophobic modified polyether urethane polymer of the present invention exhibits an excellent thickening effect and a good thixotropy adjusting effect in an aqueous composition, it is preferably blended and used in an aqueous composition containing water.

[0039] The aqueous composition of the present invention is an aqueous composition containing the hydrophobic modified polyether urethane polymer represented by the general formula (1) described above and water. By containing the hydrophobic modified polyether urethane polymer represented by the general formula (1), the aqueous composition of the present invention has excellent viscosity and thixotropy. The content of the hydrophobic modified polyether urethane polymer represented by the general formula (1) in the aqueous composition of the present invention is not particularly limited, but from the viewpoints of the viscosity and thixotropy of the aqueous composition, it is preferably 0.001 to 20 parts by mass, more preferably 0.005 to 10 parts by mass, and even more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of water.

[0040] The water content in the aqueous composition of the present invention is not particularly limited, but from the viewpoints of the viscosity and thixotropy of the aqueous composition, the water content in the aqueous composition is preferably 10 to 99.9% by mass, more preferably 20 to 99% by mass, and even more preferably 30 to 98% by mass.

[0041] The aqueous composition of the present invention may contain, depending on the purpose, resin particles, other viscosity modifiers excluding the hydrophobic modified polyether urethane polymer represented by the general formula (1), pigments, colorants, pearlescent agents, preservatives, fragrances, plasticizers, defoamers, fillers, antioxidants, ultraviolet absorbers, heat insulating agents, curing agents, catalysts, flame retardants, antistatic agents, emulsifiers, heat stabilizers, pH adjusters, design agents, antifreezing agents, wetting agents, dispersants, anti-skinning agents, drying accelerators, etc.

[0042] The resin particles that can be used in the present invention are not particularly limited as long as they are known resin particles. For example, epoxy resin particles, vinyl resin particles, acrylic resin particles with an acid value of 0 to 100 mgKOH / g, styrene resin particles, styrene-butadiene rubber particles, acrylonitrile-butadiene rubber particles, acrylonitrile-butadiene-styrene rubber particles, butadiene rubber particles, and isoprene rubber particles, etc. can be mentioned, and one or more of these can be used.

[0043] Examples of the epoxy resin particles include resin particles obtained by polymerizing monomers containing epoxy monomers such as mono- or polyglycidyl ether-based monomers, mono- or polyglycidyl ester-based monomers, mono- or polyglycidyl acrylate-based monomers, and mono- or polyglycidyl amino-based monomers, and particles of various aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. having various structures.

[0044] Examples of the vinyl resin particles include resin particles obtained by polymerizing monomers containing vinyl monomers such as vinyl acetate, vinyl acetate ester, vinyl chloride, vinyl chloride ester, vinyl ether, etc. More specifically, vinyl acetate homopolymer, vinyl acetate / vinyl chloride copolymer, vinyl acetate / acrylonitrile copolymer, vinyl acetate / maleic acid (ester) copolymer, vinyl acetate / fumaric acid (ester) copolymer, vinyl acetate / ethylene copolymer, vinyl acetate / propylene copolymer, vinyl acetate / isobutylene copolymer, vinyl acetate / vinylidene chloride copolymer, vinyl acetate / cyclopentadiene copolymer, vinyl acetate / crotonic acid copolymer, vinyl acetate / acrolein copolymer, vinyl acetate / alkyl vinyl ether copolymer, vinyl chloride homopolymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ether copolymers, and the like.

[0045] Examples of acrylic resin particles with an acid value of 0 to 100 mg KOH / g include particles of a resin having an acid value of 0 to 100 mg KOH / g obtained by polymerizing a monomer containing an acrylic monomer such as acrylic acid, methacrylic acid, an acrylic acid ester, a methacrylic acid ester, etc. More specifically, (meth)acrylic acid (ester) homopolymer, (meth)acrylic acid (ester) / styrene copolymer, (meth)acrylic acid (ester) / vinyl acetate copolymer, (meth)acrylic acid (ester) / acrylonitrile copolymer, (meth)acrylic acid (ester) / butadiene copolymer, (meth)acrylic acid (ester) / vinylidene chloride copolymer, (meth)acrylic acid (ester) / allylamine copolymer, (meth)acrylic acid (ester) / vinyl pyridine copolymer, (meth)acrylic acid (ester) / alkylolamide copolymer, (meth)acrylic acid (ester) / N,N-dimethylaminoethyl ester copolymer, (meth)acrylic acid (ester) / N,N-diethylaminoethyl vinyl ether copolymer, etc. Particles with an acid value of 0 to 100 mg KOH / g can be mentioned.

[0046] Examples of styrene resin particles include resin particles obtained by polymerizing a monomer containing styrene. More specifically, styrene homopolymer, styrene / acrylonitrile copolymer, styrene / butadiene copolymer, styrene / fumaronitrile copolymer, styrene / maleinonitrile copolymer, styrene / cyanoacrylate copolymer, styrene / phenyl vinyl acetate copolymer, styrene / chloromethylstyrene copolymer, styrene / dichlorostyrene copolymer, styrene / vinyl carbazole copolymer, styrene / N,N-diphenylacrylamide copolymer, styrene / methylstyrene copolymer, acrylonitrile / butadiene / styrene copolymer, styrene / acrylonitrile / methylstyrene copolymer, styrene / acrylonitrile / vinyl carbazole copolymer, styrene / maleic acid copolymer, etc. Particles can be mentioned.

[0047] When the aqueous composition of the present invention contains resin particles, the content of the resin particles in the aqueous composition is not particularly limited. However, from the viewpoints of the viscosity characteristics and thixotropic properties of the aqueous composition, it is preferable to contain 1.0 to 50% by mass of resin particles with respect to the total amount of the aqueous composition, more preferably 2.0 to 45% by mass, and even more preferably 5.0 to 40% by mass. In the present invention, when producing the aqueous composition, as the resin particles, at least one resin particle selected from the group consisting of epoxy resin particles, vinyl resin particles, acrylic resin particles having an acid value of 0 to 100 mgKOH / g, styrene resin particles, styrene-butadiene rubber particles, acrylonitrile-butadiene rubber particles, acrylonitrile-butadiene-styrene rubber particles, butadiene rubber particles, and isoprene rubber particles is preferably used to produce a resin emulsion dispersed in water.

[0048] Other viscosity modifiers that can be used in the present invention are not particularly limited as long as they are known viscosity modifiers (excluding the hydrophobic modified polyether urethane polymer represented by the general formula (1)). For example, cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose, polysaccharides such as xanthan gum or guar gum, clay minerals such as clay, bentonite, or hectorite, polyester type viscosity modifiers, acrylic type viscosity modifiers, urethane type viscosity modifiers (excluding the hydrophobic modified polyether urethane polymer represented by the general formula (1)), and the like can be mentioned, and one or more of these can be used. Among these, examples of the urethane type viscosity modifier include a viscosity modifier represented by the following general formula (2).

[0049]

Chemical formula

[0050] (In the formula, R 12 , R 18represents a saturated aliphatic hydrocarbon group having 6 to 40 carbon atoms or an unsaturated aliphatic hydrocarbon group having 6 to 40 carbon atoms, each of which may independently have a substituent, and R 13 , R 15 , R 17 each independently represents an alkylene group having 2 to 4 carbon atoms, R 14 , R 16 each independently represents a divalent hydrocarbon group having 6 to 16 carbon atoms, p and r each independently represent a number from 0 to 200, y represents a number from 0 to 10, and q represents a number from 0 to 500.)

[0051] R in the general formula (2) 12 , R 18each independently represents a saturated aliphatic hydrocarbon group having 6 to 40 carbon atoms or an unsaturated aliphatic hydrocarbon group having 6 to 40 carbon atoms. Among these, examples of the saturated aliphatic hydrocarbon group having 6 to 40 carbon atoms include a linear alkyl group having 6 carbon atoms, a branched alkyl group having 6 carbon atoms, a linear alkyl group having 8 carbon atoms, a branched alkyl group having 8 carbon atoms, a linear alkyl group having 10 carbon atoms, a branched alkyl group having 10 carbon atoms, a linear alkyl group having 12 carbon atoms, a branched alkyl group having 12 carbon atoms, a linear alkyl group having 14 carbon atoms, a branched alkyl group having 14 carbon atoms, a linear alkyl group having 16 carbon atoms, a branched alkyl group having 16 carbon atoms, a linear alkyl group having 18 carbon atoms, a branched alkyl group having 18 carbon atoms, a linear alkyl group having 20 carbon atoms, a branched alkyl group having 20 carbon atoms, a linear alkyl group having 22 carbon atoms, a branched alkyl group having 22 carbon atoms, a linear alkyl group having 24 carbon atoms, a branched alkyl group having 24 carbon atoms, a linear alkyl group having 28 carbon atoms, a branched alkyl group having 28 carbon atoms, a linear alkyl group having 32 carbon atoms, a branched alkyl group having 32 carbon atoms, a linear alkyl group having 36 carbon atoms, a branched alkyl group having 36 carbon atoms, a linear alkyl group having 40 carbon atoms, a branched alkyl group having 40 carbon atoms, and the like. Further, examples of the unsaturated aliphatic hydrocarbon group having 16 to 40 carbon atoms include a linear alkenyl group having 16 carbon atoms, a branched alkenyl group having 16 carbon atoms, a linear alkenyl group having 18 carbon atoms, a branched alkenyl group having 18 carbon atoms, a linear alkenyl group having 20 carbon atoms, a branched alkenyl group having 20 carbon atoms, a linear alkenyl group having 22 carbon atoms, a branched alkenyl group having 22 carbon atoms, a linear alkenyl group having 24 carbon atoms, a branched alkenyl group having 24 carbon atoms, a linear alkenyl group having 28 carbon atoms, a branched alkenyl group having 28 carbon atoms, a linear alkenyl group having 32 carbon atoms, a branched alkenyl group having 32 carbon atoms, a linear alkenyl group having 36 carbon atoms, a branched alkenyl group having 36 carbon atoms, a linear alkenyl group having 40 carbon atoms, a branched alkenyl group having 40 carbon atoms, and the like. Among these, R 12 and R 18is preferably an aliphatic hydrocarbon group having 12 to 36 carbon atoms or an unsaturated aliphatic hydrocarbon group having 12 to 36 carbon atoms, more preferably an aliphatic hydrocarbon group having 16 to 32 carbon atoms or an unsaturated aliphatic hydrocarbon group having 16 to 32 carbon atoms, respectively and independently.

[0052] R in the general formula (2) 13 , R 15 , R 17 each independently represents an alkylene group having 2 to 4 carbon atoms. Examples of such groups include an ethylene group, a propylene group, an isopropylene group, a butylene group, an isobutylene group, etc. Among these, R 13 , R 15 , R 17 are each independently preferably an ethylene group or a propylene group, more preferably an ethylene group.

[0053] R in the general formula (2) 14 , R 16 each independently represents a divalent hydrocarbon group having 6 to 16 carbon atoms. Examples of such groups include an alkylene group having 6 to 16 carbon atoms, a divalent unsaturated aliphatic hydrocarbon group having 6 to 16 carbon atoms, a divalent alicyclic hydrocarbon group having 6 to 16 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 16 carbon atoms, etc. Among these, R 14 , R 16 are each independently preferably an alkylene group having 6 to 16 carbon atoms or a divalent alicyclic hydrocarbon group having 6 to 16 carbon atoms, more preferably an alkylene group having 6 to 10 carbon atoms or a divalent alicyclic hydrocarbon group having 8 to 16 carbon atoms, and even more preferably a residue obtained by removing two isocyanate groups from hexamethylene diisocyanate, isophorone diisocyanate, or 4,4'-methylenebis(cyclohexyl isocyanate).

[0054] In the general formula (2), p and r each independently represent a number from 0 to 200. Among these, p and r are preferably from 0 to 150, and more preferably from 0 to 120. At this time, the average value of p and r is not particularly limited, but the average value of p and r is preferably from 0 to 150, and more preferably from 0 to 120. In the present invention, the values and average values of p and r are respectively calculated from the measurement results of gel permeation chromatography (GPC), proton nuclear magnetic resonance spectrum (1H-NMR), gas chromatography-mass spectrometry (GC-MS), and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOFMS) of the viscosity modifier represented by the general formula (2) that has been alkali-hydrolyzed as necessary.

[0055] In the general formula (2), y represents a number from 0 to 10. Among these, y is preferably from 0 to 8. At this time, the average value of y is not particularly limited, but the average value of y is preferably from 0.1 to 3.0, more preferably from 0.2 to 2.0, and even more preferably from 0.5 to 1.5. In the present invention, the values and average values of y are calculated from the measurement results of gel permeation chromatography (GPC), proton nuclear magnetic resonance spectrum (1H-NMR), gas chromatography-mass spectrometry (GC-MS), and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOFMS) of the viscosity modifier represented by the general formula (2) that has been alkali-hydrolyzed as necessary.

[0056] In the general formula (2), q represents a number from 0 to 500. Among these, q is preferably from 0 to 400, and more preferably from 0 to 350. At this time, the average value of q is not particularly limited, but the average value of q is preferably from 0 to 400, and more preferably from 0 to 350. In the present invention, the values and average values of q are calculated from the measurement results of gel permeation chromatography (GPC), proton nuclear magnetic resonance spectrum (1H-NMR), gas chromatography-mass spectrometry (GC-MS), and matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOFMS) of the viscosity modifier represented by the general formula (2) that has been alkali-hydrolyzed as necessary.

[0057] The aqueous composition of the present invention can be used as a paint, coating agent, adhesive, binder, ink, fiber treatment agent, sizing agent, binder, paper treatment agent, cosmetics, etc. Among these, it is preferably used as a paint, coating agent, adhesive, binder, or ink. When the aqueous composition of the present invention is used as a paint, specific applications and usage methods can be used without particular limitation. For example, in the fields of machinery, ships, vehicles, aircraft, civil engineering, construction, heavy anti-corrosion, ink, and other general industrial fields, it can be applied to various base materials such as metals, woods, plastics, papers, stones, slates, concretes, and mortars.

Examples

[0058] Hereinafter, the present invention will be described more specifically by way of examples. In the following examples, % is based on mass unless otherwise specified.

[0059] <Example 1> Into a flask equipped with a stirrer, thermometer, nitrogen tube, and reflux condenser, 0.25 mol of di-2-ethylhexylamine, 0.25 mol of 2-ethylhexyl glycidyl ether, and 0.1 g of boron trifluoride monoethylamine were charged. While stirring, the reaction was carried out under a normal pressure nitrogen atmosphere at 90 to 110 °C for 24 hours for reflux aging to react di-2-ethylhexylamine with 2-ethylhexyl glycidyl ether. Then, under a pressure environment of 100 to 110 °C and less than 10 hPa, unreacted raw materials were distilled off under reduced pressure to obtain a reaction intermediate having a structure in which the epoxy group in the glycidyl group of 2-ethylhexyl glycidyl ether was ring-opened and bonded to the amino group of di-2-ethylhexylamine.

[0060] Subsequently, 0.15 mol of the reaction intermediate obtained in another flask and 0.075 mol of polyethylene glycol with a weight average molecular weight of 11,000 were charged, and dehydration was carried out at 90 - 100 °C under 10 hPa or less for 2 hours to reduce the water content in the reaction system to 0.03 mass% or less. Next, after returning to normal pressure by introducing nitrogen, 100 g of butyl acetate was added as a solvent, the temperature was adjusted to 80 °C, and then 0.15 mol of hexamethylene diisocyanate was added, and the reaction was carried out at 80 - 90 °C for 2 hours under a nitrogen stream. After confirming that the isocyanate content was 0% with an infrared spectrometer, the solvent was distilled off under reduced pressure at 100 - 110 °C under a pressure environment of less than 10 hPa to obtain a hydrophobic modified polyether urethane polymer 1 in the form of a white solid at room temperature. The obtained hydrophobic modified polyether urethane polymer 1, in the general formula (1), R 1 、R 9 are each a 2-ethylhexyl group, R 2 、R 3 、R 10 、R 11 are each a 2-ethylhexyl group, R 6 is an ethylene group, R 5 、R 7 are each a hexylene group, a and d are each 0, b and c are each 1, l and n are each 0, x is a number from 0 to 8 (average value is 1.0), and the value of m is 200 - 300 (average value is 250), which is a hydrophobic modified polyether urethane. Furthermore, by mixing the hydrophobic modified polyether urethane polymer 1 with water at 80 °C, a viscous aqueous solution containing 10 mass% of the hydrophobic modified polyether urethane polymer 1 was obtained.

[0061] <Example 2> As a reaction intermediate, an aqueous solution containing 10 mass% of a hydrophobic modified polyether urethane polymer 2 was obtained in the same manner as in Example 1, except that 0.15 mol of the reaction intermediate obtained by using 0.25 mol of di-n-octylamine instead of di-2-ethylhexylamine in Example 1 was used. The hydrophobic modified polyether urethane polymer 2, in the general formula (1), R 1 、R 9 are each a 2-ethylhexyl group, R 2, R 3 , R 10 , R 11 are each an octyl group, R 6 is an ethylene group, R 5 , R 7 are each a hexylene group, a and d are each 0, b and c are each 1, l and n are each 0, x is a number from 0 to 8 (average value is 1.0), and the value of m is from 200 to 300 (average value is 250), and it was a hydrophobic modified polyether urethane.

[0062] <Example 3> As a reaction intermediate, an aqueous solution containing 10% by mass of a hydrophobic modified polyether urethane polymer 3 was obtained in the same manner as in Example 1, except that 0.15 mol of the reaction intermediate obtained by using 0.25 mol of di-isotridecylamine instead of di-2-ethylhexylamine in Example 1 was used. The hydrophobic modified polyether urethane polymer 3, in the general formula (1), R 1 , R 9 are each a 2-ethylhexyl group, R 2 , R 3 , R 10 , R 11 are each a branched alkyl group having 13 carbon atoms, R 6 is an ethylene group, R 5 , R 7 are each a hexylene group, a and d are each 0, b and c are each 1, l and n are each 0, x is a number from 0 to 8 (average value is 1.0), and the value of m is from 200 to 300 (average value is 250), and it was a hydrophobic modified polyether urethane.

[0063] <Example 4> As a reaction intermediate, an aqueous solution containing 10% by mass of a hydrophobically modified polyether urethane polymer 4 was obtained in the same manner as in Example 1, except that 0.15 mol of a reaction intermediate obtained by using 0.25 mol of di-isotridecylamine instead of di-2-ethylhexylamine and 0.25 mol of a cardanol group-containing glycidyl ether (LITE 513E manufactured by Cardolite) instead of 2-ethylhexyl glycidyl ether in Example 1 was used. The hydrophobically modified polyether urethane polymer 4 has, in the general formula (1), R 1 , R 9 being each an unsaturated aliphatic hydrocarbon group having 15 carbon atoms, R 2 , R 3 , R 10 , R 11 being each a branched alkyl group having 13 carbon atoms, R 6 being an ethylene group, R 5 , R 7 being each a hexylene group, a and d being each 1, b and c being each 1, l and n being each 0, x being a number from 0 to 8 (average value is 1.0), and the value of m being from 200 to 300 (average value is 250), and it was a hydrophobically modified polyether urethane.

[0064] <Example 5> As a reaction intermediate, an aqueous solution containing 10% by mass of a hydrophobically modified polyether urethane polymer 5 was obtained in the same manner as in Example 1, except that 0.15 mol of a reaction intermediate obtained by using 0.25 mol of di-isotridecylamine instead of di-2-ethylhexylamine and 0.25 mol of an α-olefin oxide having 16 carbon atoms instead of 2-ethylhexyl glycidyl ether in Example 1 was used. The hydrophobically modified polyether urethane polymer 5 has, in the general formula (1), R 1 , R 9 being each a tetradecyl group, R 2 , R 3 , R 10 , R 11 being each a branched alkyl group having 13 carbon atoms, R 6 being an ethylene group, R 5 , R 7Each of them is a hexylene group, a and d are each 0, b and c are each 0, l and n are each 0, x is a number from 0 to 8 (average value is 1.0), and the value of m is from 200 to 300 (average value is 250). It was a hydrophobic modified polyether urethane.

[0065] <Example 6> As a reaction intermediate, an aqueous solution containing 10% by mass of a hydrophobic modified polyether urethane polymer 6 was obtained in the same manner as in Example 1, except that 0.15 mol of a reaction intermediate obtained by adding an average of 20 mol of ethylene oxide per mol of the reaction intermediate obtained in Example 1 was used. The hydrophobic modified polyether urethane polymer 6 has, in the general formula (1), R 1 , R 9 are each a 2-ethylhexyl group, R 2 , R 3 , R 10 , R 11 are each a branched alkyl group having 13 carbon atoms, R 4 , R 6 , R 8 are each an ethylene group, R 5 , R 7 are each a hexylene group, a and d are each 0, b and c are each 1, the values of l and n are each from 15 to 25 (average value is 20 each), x is a number from 0 to 8 (average value is 1.0), and the value of m is from 200 to 300 (average value is 250). It was a hydrophobic modified polyether urethane.

[0066] <Example 7> As a reaction intermediate, 0.15 mol of a reaction intermediate obtained by using 0.25 mol of di-isotridecylamine instead of di-2-ethylhexylamine in Example 1 was used, and 0.15 mol of 4,4-methylenebis(cyclohexyl isocyanate) was used instead of hexamethylene diisocyanate. An aqueous solution containing 10% by mass of a hydrophobic modified polyether urethane polymer 7 was obtained in the same manner as in Example 1. The hydrophobic modified polyether urethane polymer 7 has, in the general formula (1), R 1 , R 9are each 2-ethylhexyl groups, and R 2 , R 3 , R 10 , R 11 are each branched alkyl groups having 13 carbon atoms, R 6 is an ethylene group, R 5 , R 7 are each the residues obtained by removing two isocyanate groups from 4,4-methylenebis(cyclohexyl isocyanate), a and d are each 0, b and c are each 1, l and n are each 0, x is a number from 0 to 8 (average value is 1.0), and the value of m is from 200 to 300 (average value is 250). It was a hydrophobic modified polyether urethane.

[0067] <Example 8> As a reaction intermediate, 0.15 mol of the reaction intermediate obtained in Example 1 using 0.25 mol of di-isotridecylamine instead of di-2-ethylhexylamine was used, and 0.15 mol of isophorone diisocyanate was used instead of hexamethylene diisocyanate. An aqueous solution containing 10% by mass of the hydrophobic modified polyether urethane polymer 8 was obtained in the same manner as in Example 1. The hydrophobic modified polyether urethane polymer 8 has, in the general formula (1), R 1 , R 9 are each 2-ethylhexyl groups, R 2 , R 3 , R 10 , R 11 are each branched alkyl groups having 13 carbon atoms, R 6 is an ethylene group, R 5 , R 7 are each the residues obtained by removing two isocyanate groups from isophorone diisocyanate, a and d are each 0, b and c are each 1, l and n are each 0, x is a number from 0 to 8 (average value is 1.0), and the value of m is from 200 to 300 (average value is 250). It was a hydrophobic modified polyether urethane.

[0068] <Comparative Example 1> In Example 1, an aqueous solution containing 10% by mass of a hydrophobically modified polyether urethane polymer 9 was obtained in the same manner as in Example 1, except that 0.15 mol of an ethylene oxide 20 - mol adduct of 2 - decyl - 1 - tetradecanol was used instead of the reaction intermediate. The hydrophobically modified polyether urethane polymer 9, in the general formula (2), where R 12 , R 18 are each a 2 - decyl - 1 - tetradecyl group having 24 carbon atoms, R 13 , R 15 , R 17 are each an ethylene group, R 14 , R 16 are each a hexylene group, the values of p and r are each 15 - 25 (average value is 20 each), y is a number from 0 to 8 (average value is 1.0), and the value of q is 200 - 300 (average value is 250), was a hydrophobically modified polyether urethane.

[0069] <Comparative Example 2> An aqueous solution containing 10% by mass of a hydrophobically modified polyether urethane polymer 10 was obtained in the same manner as in Example 1, except that 0.15 mol of a reaction intermediate obtained by using 0.25 mol of dibenzylamine instead of di - 2 - ethylhexylamine in Example 1 was used as the reaction intermediate. The hydrophobically modified polyether urethane polymer 10, in the general formula (1), where R 1 , R 9 are each a 2 - ethylhexyl group, R 2 , R 3 , R 10 , R 11 are each a benzyl group, R 6 is an ethylene group, R 5 , R 7 are each a hexylene group, a and d are each 0, b and c are each 1, l and n are each 0, x is a number from 0 to 8 (average value is 1.0), and the value of m is 200 - 300 (average value is 250), was a hydrophobically modified polyether urethane.

[0070] <Comparative Example 3> As a reaction intermediate, an aqueous solution containing 10% by mass of the hydrophobically modified polyether urethane polymer 11 was obtained in the same manner as in Example 1, except that 0.15 mol of the reaction intermediate obtained by using 0.25 mol of di-n-butylamine instead of di-2-ethylhexylamine in Example 1 was used. The hydrophobically modified polyether urethane polymer 11 has, in the general formula (1), R 1 , R 9 being 2-ethylhexyl groups respectively, R 2 , R 3 , R 10 , R 11 being butyl groups respectively, R 6 being an ethylene group, R 5 , R 7 being hexylene groups respectively, a and d being 0 respectively, b and c being 1 respectively, l and n being 0 respectively, x being a number from 0 to 8 (average value is 1.0), and the value of m being from 200 to 300 (average value is 250), and it was a hydrophobically modified polyether urethane.

[0071] <Comparative Example 4> In Example 1, an aqueous solution containing 10% by mass of the hydrophobically modified polyether urethane polymer 12 was obtained in the same manner as in Example 1, except that 0.15 mol of an adduct of 12 moles of ethylene oxide with a secondary alkyl alcohol having 12 to 14 carbon atoms was used instead of the reaction intermediate. The hydrophobically modified polyether urethane polymer 12 has, in the general formula (2), R 12 , R 18 being secondary alkyl groups having 12 to 14 carbon atoms respectively, R 13 , R 15 , R 17 being ethylene groups respectively, R 14 , R 16 being hexylene groups respectively, the average values of p and r being 12 respectively, y being a number from 0 to 8 (average value is 1.0), and the value of q being from 200 to 300 (average value is 250), and it was a hydrophobically modified polyether urethane.

[0072] <Comparative Example 5> In Example 1, 0.15 mol of 2-hexyl-1-decanol was used instead of the reaction intermediate, 0.075 mol of polyethylene glycol with a weight-average molecular weight of 8000 was used instead of polyethylene glycol with a weight-average molecular weight of 11000, and 0.15 mol of 4,4-methylenebis(cyclohexyl isocyanate) was used instead of hexamethylene diisocyanate. An aqueous solution containing 10% by mass of the hydrophobically modified polyether urethane polymer 13 was obtained in the same manner as in Example 1. The hydrophobically modified polyether urethane polymer 13 has, in the general formula (2), R 12 , R 18 being 2-hexyl-1-decyl groups respectively, R 13 , R 15 , R 17 being ethylene groups respectively, R 14 , R 16 being the residues obtained by removing two isocyanate groups from 4,4-methylenebis(cyclohexyl isocyanate) respectively, p and r being 0 respectively, y being a number from 0 to 8 (average value is 1.0), and the value of q being from 150 to 210 (average value is 180), and it was a hydrophobically modified polyether urethane.

[0073] <Comparative Example 6> In Example 1, an aqueous solution containing 10% by mass of the hydrophobically modified polyether urethane polymer 14 was obtained in the same manner as in Example 1, except that 0.15 mol of bis(2-ethylhexyl)aminoethanol was used instead of the reaction intermediate. The hydrophobically modified polyether urethane polymer 14 has, in the general formula (2), R 12 , R 18 being the residues obtained by removing the hydroxyl group from bis(2-ethylhexyl)aminoethanol respectively, R 15 being an ethylene group, R 14 , R 16 being hexylene groups respectively, p and r being 0 respectively, y being a number from 0 to 8 (average value is 1.0), and the value of q being from 200 to 300 (average value is 250), and it was a hydrophobically modified polyether urethane.

[0074] <Comparative Example 7> As a reaction intermediate, an aqueous solution containing 10% by mass of a hydrophobically modified polyether urethane polymer 15 was obtained in the same manner as in Example 1, except that 0.25 mol of dibenzylamine was used instead of di-2-ethylhexylamine and 0.15 mol of a reaction intermediate obtained using phenyl glycidyl ether instead of 2-ethylhexyl glycidyl ether were used. The hydrophobically modified polyether urethane polymer 15 has, in the general formula (1), R 1 , R 9 being hydrogen atoms respectively, R 2 , R 3 , R 10 , R 11 being benzyl groups respectively, R 6 being an ethylene group, R 5 , R 7 being hexylene groups respectively, a and d being 1 respectively, b and c being 1 respectively, l and n being 0 respectively, x being a number from 0 to 8 (average value is 1.0), and the value of m being from 200 to 300 (average value is 250), and it was a hydrophobically modified polyether urethane.

[0075] <Preparation of Aqueous Compositions> Using the obtained aqueous solutions of the hydrophobically modified polyether urethane polymers 1 to 15 and the components shown below, the components were mixed at the compounding ratios shown in Tables 1 to 4 to prepare aqueous compositions 1 to 36. Among these, aqueous compositions 19 to 28 are aqueous compositions as comparative examples.

[0076] Acrylic resin emulsion 1: 50% aqueous dispersion of an acrylic resin (acid value 18 mgKOH / g) (Mobinyl (registered trademark) 727 manufactured by Nippon Coating Resin Co., Ltd., viscosity at 10 rpm: 1070 mPa·s) Acrylic resin emulsion 2: 30% aqueous dispersion of an acrylic resin (acid value 16 mgKOH / g) (water-diluted product of Mobinyl (registered trademark) 1711 manufactured by Nippon Coating Resin Co., Ltd., viscosity at 10 rpm: less than 10 mPa·s) Organic solvent 1: Butyl cellosolve Defoaming agent 1: Adekanate B-943 (mineral oil-based defoaming agent) Other thickener 1: 10% by mass aqueous dispersion of methacrylic acid / ethyl acrylate copolymer (acid value: 336 mg KOH / g)

[0077] <Viscosity and TI value measurement> For each of the prepared aqueous compositions, using a B-type rotational viscometer (manufactured by Toki Sangyo Co., Ltd., TVB-10H), the viscosities at 25 °C were measured at rotational speeds of 6 rpm, 10 rpm, and 60 rpm, respectively. Also, using the measured viscosity values at rotational speeds of 6 rpm and 60 rpm, the TI values were calculated based on the calculation formula "TI value = [viscosity at 6 rpm (mPa·s)] / [viscosity at 60 rpm (mPa·s)]". The viscosity measurement results at 10 rpm and the calculated TI values are shown in Tables 1 to 4. In the present invention, if the TI value of the aqueous composition is 3.5 to 10, it can be said that the aqueous composition has excellent thixotropic properties.

[0078]

Table 1

[0079]

Table 2

[0080]

Table 3

[0081]

Table 4

[0082] From the above results, it can be seen that the hydrophobic modified polyetherurethane polymer of the present invention exhibits an excellent thickening effect and a good thixotropy adjusting effect on the aqueous composition.

Claims

1. A hydrophobic modified polyetherurethane polymer represented by the following general formula (1). 【Chemical 1】 (wherein, R １ , R ９ each independently represents a saturated aliphatic hydrocarbon group having 6 to 30 carbon atoms or an unsaturated aliphatic hydrocarbon group having 6 to 30 carbon atoms, R ２ , R ３ , R １０ , R １１ each independently represents an alkyl group having 6 to 24 carbon atoms or an alkenyl group having 6 to 24 carbon atoms, R ４ , R ６ , R ８ each independently represents an alkylene group having 2 to 4 carbon atoms, R ５ , R ７ each independently represents a divalent hydrocarbon group having 6 to 16 carbon atoms, a and d each independently represent a number of 0 or 1, b and c each independently represent a number of 0 or 1, l and n each independently represent a number of 0 to 200, x represents a number of 0 to 10, and m represents a number of 20 to 500.)

2. R of the general formula (1) ５ , R ７ is a residue obtained by removing two isocyanate groups from hexamethylene diisocyanate, isophorone diisocyanate, or 4,4'-methylenebis(cyclohexyl isocyanate), respectively, and the hydrophobic modified polyether urethane polymer according to claim 1.

3. A viscosity modifier comprising the hydrophobic modified polyetherurethane polymer according to Claim 1 or 2.

4. An aqueous composition containing the hydrophobic modified polyetherurethane polymer according to Claim 1 or 2 and water.

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