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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/43—Thickening agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
  • C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
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  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D187/00—Coating compositions based on unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
  • C09D187/005—Block or graft polymers not provided for in groups C09D101/00 - C09D185/04
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
  • C08G69/34—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/40—Polyamides containing oxygen in the form of ether groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/06—Polyurethanes from polyesters
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
  • C09D177/06—Polyamides derived from polyamines and polycarboxylic acids
  • C09D177/08—Polyamides derived from polyamines and polycarboxylic acids from polyamines and polymerised unsaturated fatty acids
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/10—Block or graft copolymers containing polysiloxane sequences
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D201/00—Coating compositions based on unspecified macromolecular compounds
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  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/36—Pearl essence, e.g. coatings containing platelet-like pigments for pearl lustre
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  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
  • C09K23/42—Ethers, e.g. polyglycol ethers of alcohols or phenols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
  • C09K23/52—Natural or synthetic resins or their salts
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
  • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/54—Aqueous solutions or dispersions

Definitions

• the present invention relates to aqueous compositions, diluted compositions, and aqueous coating compositions.
• Water-based paints are environmentally friendly paints, so water-based paints are being used in a variety of fields, including automotive paints. Many types of viscosity modifiers are used in these water-based paints, such as preventing pigment settling and hard caking during storage, preventing paint from sagging during painting, and adjusting the leveling of the painted surface. is used for the purpose of
• Patent Document 1 discloses that a polyamide obtained by reacting a diamine with an excess of dicarboxylic acid or the like relative to the diamine is neutralized using a neutralizing base (such as an amine).
• a neutralizing base such as an amine
• An anti-settling agent for water-based paints is disclosed, which is dispersed in a water-based medium after hydration.
• Patent Document 2 discloses the use of a composition consisting of a hydrocarbon-polyether-polyamide-polyether-hydrocarbon block copolymer and a specific solvent as a gelling agent for urethane/acrylic paints. There is.
• the anti-settling agent described in Patent Document 1 lacks the hydrophilicity of polyamide because only the terminal carboxylic acid becomes a hydrophilic part, and a large amount of co-solvent is required to exert the viscosity imparting effect. is often required.
• the gel described in Patent Document 2 may have poor compatibility with water, making it difficult to disperse in water-based formulations. It has a weak viscosity imparting effect on other water-based formulations and often does not have sufficient viscosity.
• the present invention has been made in view of the above circumstances, and is capable of imparting viscosity to water, and is capable of imparting sufficient viscosity even when conventional compositions have difficulty in exerting the viscosity imparting effect.
• the object of the present invention is to provide an aqueous composition capable of exhibiting a viscosity-imparting effect, as well as a diluted composition and a water-based coating composition containing this aqueous composition.
• the present inventors have developed a block copolymer with a specific structure that has a carboxyl group at the molecular end and has a polyamide block and a polyether block, and a water-containing block copolymer.
• a water-based composition as a viscosity modifier, it is possible to impart viscosity to water, and even in formulations where conventional compositions are difficult to exert viscosity imparting effects, sufficient viscosity imparting effects can be achieved.
• the present invention was completed based on this knowledge.
• the present invention includes a block copolymer (A1) represented by the following general formula (1) and water, and all of the block copolymer (A1) represented by the above formula (1) Among X, X, which is Y, is 5 mol% or more, and the mass ratio of the block copolymer (A1) to water, A1/water, is 5/95 to 50/50. It is an aqueous composition.
• X is each independently a carboxyl group or a salt thereof, or Y, Y is R 3 -(OR 4 ) n -Z-, and R 1 is each independently a carbon number of 2 to 52 is a divalent and/or trivalent hydrocarbon group, R 2 is a divalent hydrocarbon group having 2 to 36 carbon atoms, and R 3 is a hydrocarbon group having 1 to 22 carbon atoms.
• R 4 is a divalent hydrocarbon group having 2 to 4 carbon atoms
• W 1 and W 2 are secondary amide bonds
• Z is an ester bond or amide bond
• a is 1 to 11 carbon atoms.
• b is an integer
• b is 1 or 2
• c is 1 or 2
• m is an integer from 0 to 10
• n is an integer from 2 to 100
• p is an integer from 1 to 11.
• the aqueous composition may include the block copolymer (A1) in which at least some of the Xs in formula (1) are carboxyl groups or salts thereof.
• the amount of X which is a carboxyl group or a salt thereof, may be 30 mol% or more based on the total amount of X in the block copolymer (A1) contained in the aqueous composition.
• the mass remaining after removing the Y portion from all the block copolymers (A1) contained in the aqueous composition is based on the mass of the entire block copolymer (A1), It may be 50% by mass or more and 90% by mass or less.
• the block copolymer (A1) may have an acid value of 15 or more and 80 or less.
• 50 mol% or more of either or both of R 1 and R 2 in the formula (1) may be a divalent hydrocarbon group having 34 or more carbon atoms.
• At least a part of It may be 5% by mass or more and 45% by mass or less based on the total mass of (A1).
• the aqueous composition further includes a polyether (B1) having a boiling point of 230° C. or higher and represented by the following general formula (2), and at least a part of X in the formula (1) is Y, and the number of carbon atoms in R 4 in the block copolymer (A1) is 2 (OR 4 ) n site, and the number of carbon atoms in R 6 in the polyether (B1) is 2 (OR 6 )
• the total mass with the q site may be 5% by mass or more and 50% by mass or less with respect to the total mass of the block copolymer (A1) and the polyether (B1).
• R 5 -(OR 6 ) q -OR 7 ...(2) (In the above formula (2), R 5 is a hydrocarbon group having 1 to 22 carbon atoms, R 6 is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R 7 is a hydrogen atom or a carbon number It is a hydrocarbon group of 1 to 4, and q is an integer of 2 to 100.)
• the aqueous composition further includes a polyether (B1) having a boiling point of 230° C. or higher and represented by the following general formula (2), and at least a part of X in the formula (1) is Y, and the number of carbon atoms in R 4 in the block copolymer (A1) is 2 (OR 4 ) n site, and the number of carbon atoms in R 6 in the polyether (B1) is 2 (OR 6 )
• the total mass including the q site may be 5% by mass or more and 50% by mass or less based on the total mass of nonvolatile components in the aqueous composition.
• R 5 -(OR 6 ) q -OR 7 ...(2) (In the above formula (2), R 5 is a hydrocarbon group having 1 to 22 carbon atoms, R 6 is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R 7 is a hydrogen atom or a carbon number It is a hydrocarbon group of 1 to 4, and q is an integer of 2 to 100.)
• the aqueous composition may include the block copolymer (A1) in which all Xs in the formula (1) are Y.
• 80 mol% or more of X in the block copolymer (A1) represented by formula (1) may be Y.
• the aqueous composition further includes a polyether (B1) having a boiling point of 230° C. or higher represented by the following general formula (2), and the block copolymer (A1) and the polyether
• the acid value of the mixture (B1) may be 10 or less.
• R 5 -(OR 6 ) q -OR 7 ...(2) (In the above formula (2), R 5 is a hydrocarbon group having 1 to 22 carbon atoms, R 6 is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R 7 is a hydrogen atom or a carbon number It is a hydrocarbon group of 1 to 4, and q is an integer of 2 to 100.)
• R 3 in formula (1) may have 1 to 4 carbon atoms.
• the content may be 50% by mass or less.
• the aqueous composition further includes a polyether (B1) having a boiling point of 230° C. or higher and represented by the following general formula (2), and at least a part of X in the formula (1) is Y, and the number of carbon atoms in R 4 in the block copolymer (A1) is 2 (OR 4 ) n site, and the number of carbon atoms in R 6 in the polyether (B1) is 2 (OR 6 )
• the total mass with the q site may be 50% by mass or more and 90% by mass or less with respect to the total mass of the block copolymer (A1) and the polyether (B1).
• R 5 -(OR 6 ) q -OR 7 ...(2) (In the above formula (2), R 5 is a hydrocarbon group having 1 to 22 carbon atoms, R 6 is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R 7 is a hydrogen atom or a carbon number It is a hydrocarbon group of 1 to 4, and q is an integer of 2 to 100.)
• the aqueous composition further includes a polyether (B1) having a boiling point of 230° C. or higher and represented by the following general formula (2), and at least a part of X in the formula (1) is Y, and the number of carbon atoms in R 4 in the block copolymer (A1) is 2 (OR 4 ) n site, and the number of carbon atoms in R 6 in the polyether (B1) is 2 (OR 6 )
• the total mass including the q site may be 50% by mass or more and 90% by mass or less based on the total mass of nonvolatile components in the aqueous composition.
• R 5 -(OR 6 ) q -OR 7 ...(2) (In the above formula (2), R 5 is a hydrocarbon group having 1 to 22 carbon atoms, R 6 is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R 7 is a hydrogen atom or a carbon number It is a hydrocarbon group of 1 to 4, and q is an integer of 2 to 100.)
• the present invention also provides a diluted composition obtained by diluting the above-mentioned aqueous composition, wherein the mass ratio of the block copolymer (A1) to water, A1/water, is 0.01/99.99 to 5. /95.
• the diluted composition is different from the block copolymer (A1) and contains a urethane-based viscosity modifier, an acrylic-based viscosity modifier, a cellulose-based modified viscosity modifier, a polysaccharide-based viscosity modifier, and an amide-based viscosity modifier. It may further contain at least one viscosity modifier selected from the group consisting of modifiers, polyamide viscosity modifiers, urea viscosity modifiers, cellulose nanofibers, and inorganic viscosity modifiers.
• the present invention is a water-based paint composition characterized by containing the above-described aqueous composition and a glitter pigment.
• the water-based coating composition differs from the block copolymer (A1) and contains a urethane-based viscosity modifier, an acrylic-based viscosity modifier, a cellulose-based modified viscosity modifier, a polysaccharide-based viscosity modifier, and an amide-based viscosity modifier. It may further contain at least one viscosity modifier selected from the group consisting of viscosity modifiers, polyamide viscosity modifiers, urea viscosity modifiers, cellulose nanofibers, and inorganic viscosity modifiers.
• an aqueous composition containing water and a block copolymer having a specific structure having a carboxyl group at the molecular end and having a polyamide block and a polyether block it is possible to impart viscosity to the composition, and it is possible to exhibit a sufficient viscosity imparting effect even if the composition is difficult to exhibit a viscosity imparting effect in conventional compositions.
• by adjusting the formulation when synthesizing the block copolymer it is also possible to exhibit the effect of dispersing pigments and the like in water-based paints.
• the aqueous composition according to the present invention is an additive used in a water-based coating composition, and contains a block copolymer (A1) represented by the following general formula (1) and water.
• A1 represented by the following general formula (1) and water.
• each X is independently a carboxyl group, a salt thereof, or Y.
• Y is R 3 -(OR 4 ) n -Z-.
• R 1 is each independently a divalent and/or trivalent hydrocarbon group having 2 to 52 carbon atoms.
• R 2 is a divalent hydrocarbon group having 2 to 36 carbon atoms.
• R 3 is a hydrocarbon group having 1 to 22 carbon atoms.
• R 4 is a divalent hydrocarbon group having 2 to 4 carbon atoms.
• W 1 and W 2 are secondary amide bonds.
• Z is an ester bond or an amide bond.
• a is an integer from 1 to 11.
• b is 1 or 2.
• c is 1 or 2.
• m is an integer from 0 to 10.
• n is an integer from 2 to 100.
• p is an integer from 1 to 11.
• R 1 's in [R 1 (-W 1 -R 2 -W 2 ) b ] m in formula (1) there are m R 1 's in [R 1 (-W 1 -R 2 -W 2 ) b ] m in formula (1), and each of them can be divalent or trivalent. Also, one of R 1 in [R 1 (-W 1 -R 2 -W 2 ) b ] m is outside of [R 1 (-W 1 -R 2 -W 2 ) b ] m . One is a bond with an atom, and the other is a bond with W 1 . If R 1 is trivalent, there are two possibilities: either it is further bonded to X, or it is bonded to W 1 .
• the number of a in formula (1) is maximum when all R 1 in [R 1 (-W 1 -R 2 -W 2 ) b ] m are trivalent hydrocarbon groups, And when R 1 is combined with the leftmost X as much as possible, X is [R 1 (-W 1 - R 2 - W 2 ) b ] Number of R 1 in m : 1 for m The number is the sum of the individual parts. Therefore, when m is 10, which is the maximum, a is 11, which is the maximum.
• c in formula (1) is 1 when R 1 in ( -R 1 (-X) c ) p is a divalent hydrocarbon group ;
• R 1 is a trivalent hydrocarbon group, it is 2.
• This block copolymer (A1) is a polyamide-polyether consisting of a polyether block corresponding to the Y portion when X in formula (1) is Y, and a polyamide block corresponding to the portion excluding Y. It is a block copolymer.
• aqueous composition containing water and a block copolymer (A1) having a polyamide block and a polyether block having a specific structure it is possible to impart viscosity to water, and It becomes possible to exhibit a sufficient viscosity-imparting effect even with a formulation that is difficult to exhibit a viscosity-imparting effect in conventional compositions.
• the viscosity imparting effect in the present invention refers to the effect of increasing the viscosity (thickening) of the water-based paint to which the aqueous composition is added.
• the dispersion effect in the present invention refers to the effect of uniformly dispersing pigments, carbon nanotubes (CNTs), other fillers, etc. in a water-based paint containing an aqueous composition.
• CNTs carbon nanotubes
• the block copolymer (A1) is a polyamide-polyether block copolymer obtained by a dehydration reaction of polyamide and polyether.
• R 1 in formula (1) is a hydrocarbon group derived from dicarboxylic acid or tricarboxylic acid when synthesizing polyamide as a raw material. That is, R 1 is a divalent hydrocarbon group obtained by removing two carboxyl groups from the above dicarboxylic acid, or a trivalent hydrocarbon group obtained by removing three carboxyl groups from the above tricarboxylic acid. Note that the carboxyl group in the dicarboxylic acid and tricarboxylic acid remains as an unreacted portion or is used to form an amide bond or an ester bond during the synthesis of the block copolymer (A1).
• dicarboxylic acid at least one carboxylic acid selected from dicarboxylic acids having 4 to 54 carbon atoms can be used.
• dicarboxylic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, Examples include dimer acid.
• Dimer acid is a polymerized fatty acid obtained by polymerizing (dimerizing) unsaturated fatty acids (for example, unsaturated fatty acids having 18 or 22 carbon atoms) obtained from vegetable oils such as soybean oil, tall oil, linseed oil, and cottonseed oil. Generally, dimer acids having 36 or 44 carbon atoms and those obtained by hydrogenating the unsaturated sites of these dimer acids are commercially available.
• unsaturated fatty acids for example, unsaturated fatty acids having 18 or 22 carbon atoms
• vegetable oils such as soybean oil, tall oil, linseed oil, and cottonseed oil.
• dimer acids having 36 or 44 carbon atoms and those obtained by hydrogenating the unsaturated sites of these dimer acids are commercially available.
• dimer acids examples include Pripol 1013, Pripol 1017, Pripol 1004 (manufactured by Croda Japan Co., Ltd.), Haridimer 200, Haridimer 250, Haridimer 270S (manufactured by Harima Kasei Co., Ltd.), Tsunodimer ( (registered trademark) 205, Tsuno Dime 228, and Tsuno Dime 395 (all manufactured by Tsukino Foods Co., Ltd.).
• Some commercially available dimer acids contain monomer acids and trimer acids in addition to dimer acids.
• Halidimer 250 contains about 10 to 20% by mass of trimer acid, but there is also a high-purity type such as Tsunodimer 395 in which components other than dimer acid are reduced as much as possible.
• high-purity types containing trimer acid can be used, those containing a small amount of monomer acid are preferred.
• tricarboxylic acid at least one carboxylic acid selected from tricarboxylic acids having 4 to 54 carbon atoms can be used.
• tricarboxylic acids include trimer acid and trimesic acid.
• Trimer acid is a polymerized fatty acid that is based on dimer acid and has a higher trimer acid content through distillation and purification, and trimer acids having 54 carbon atoms are generally commercially available.
• dimer acids include Pripol 1040 (manufactured by Croda Japan Co., Ltd.), Tsunodimu (registered trademark) 346 (manufactured by Tsukino Foods Co., Ltd.), and the like.
• Commercially available trimer acids contain monomer acids and dimer acids in addition to trimer acids, but those with a low monomer acid content are preferred.
• monocarboxylic acids may be used in combination with the above-mentioned dicarboxylic acids and/or tricarboxylic acids as long as the effects of the aqueous composition according to the present invention are not impaired.
• monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and arachidic acid.
• saturated aliphatic monocarboxylic acids such as behenic acid, oleic acid, linoleic acid, ricinoleic acid, linolenic acid, eicosenoic acid, erucic acid, mixed fatty acids obtained from natural oils and fats (tall oil fatty acid, rice bran unsaturated aliphatic monocarboxylic acids such as fatty acids, soybean oil fatty acids, beef tallow fatty acids, etc.).
• a monocarboxylic acid having a hydroxyl group such as 12-hydroxystearic acid may be used.
• dicarboxylic acids and tricarboxylic acids described above may be used alone or in combination of two or more.
• R 2 in formula (1) is a hydrocarbon group derived from the diamine used in synthesizing the polyamide that is the raw material for the block copolymer (A1). That is, R 2 is a divalent hydrocarbon group obtained by removing two amino groups from the above diamine. Note that the amino group in the diamine is used to form an amide bond during the synthesis of the block copolymer (A1).
• the diamine at least one amine selected from the group consisting of diamines having 2 to 36 carbon atoms can be used.
• diamines include ethylene diamine (EDA), propylene diamine (PDA), tetramethylene diamine (TMDA), pentamethylene diamine (PMDA), hexamethylene diamine (HMDA), octamethylene diamine (OMDA), and dodecamethylene.
• Aliphatic diamines such as diamine (DMDA) and trimethylhexamethylene diamine, aromatic diamines such as orthoxylene diamine, metaxylene diamine (MXDA), paraxylene diamine (PXDA), diaminodiphenylmethane, and alicyclic diamines such as isophorone diamine. Can be mentioned.
• DMDA diamine
• MXDA metaxylene diamine
• PXDA paraxylene diamine
• diaminodiphenylmethane diaminodiphenylmethane
• alicyclic diamines such as isophorone diamine.
• a diamine derived from a polymerized fatty acid which is a polymerized fatty acid derivative
• polymerized fatty acid derivatives include dimer diamine (DDA), which is a dimer acid derivative.
• DDA dimer diamine
• the dimer diamine is a dimer acid derivative in which two terminal carboxyl groups of a dimer acid are substituted with a primary aminomethyl group or an amino group, and generally commercially available products can be used.
• Examples of such commercially available dimer diamines include Priamine 1075, Priamine 1074 (manufactured by Croda Japan Co., Ltd.), and Versamine 551 (manufactured by BASF Japan Co., Ltd.).
• monoamines may be used in combination with the above-mentioned diamines as long as the effects of the aqueous composition according to the present invention are not impaired.
• examples of such monoamines include ethylamine, monoethanolamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, decylamine, laurylamine, myristylamine, cetylamine, stearylamine, behenylamine, and the like.
• the above-mentioned diamines may be used alone or in combination of two or more.
• the acid/amine ratio 3.8
• the acid/amine ratio 2.4
• the acid/amine ratio 1.7
• each X in formula (1) is independently a carboxyl group or a salt thereof, or Y:R 3 -(OR 4 ) n -Z-.
• the salt of a carboxyl group include a neutralization salt of a carboxyl group and the following neutralizing base.
• neutralizing bases include alkali metal element hydroxides such as sodium hydroxide and potassium hydroxide, ammonia as inorganic amines, alkylamines such as ethylamine and diethylamine, and 2,2',2''-nitrilotritridine.
• Amino alcohols such as ethanol, 2,2'-iminodiethanol, 2-(dimethylamino)ethanol, 2-(diethylamino)ethanol, 2-amino-2-methyl-1-propanol, Jeffamine (registered trademark) M- 1000, Jeffamine M-2070 (manufactured by Huntsman), and other polyether amines.
• the polyether used as a raw material for synthesizing the block copolymer (A1) has the formula: R 3 -(OR 4 ) n -Z T (wherein R 3 is a hydrocarbon group having 1 to 22 carbon atoms; , R 4 is a divalent hydrocarbon group having 2 to 4 carbon atoms, and Z T is an amino group, a hydroxyl group or a carboxyl group, of which an amino group or a hydroxyl group is preferable. n is an integer of 2 to 100; , preferably 2 to 50, more preferably 5 to 50). Z T becomes Z (that is, an ester bond or an amide bond) by the dehydration reaction between the polyamide and polyether described above.
• R 3 is not particularly limited as long as it is a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms or an aromatic hydrocarbon group, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be a linear However, it may be branched or cyclic.
• Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, a cycloalkynyl group, and the like.
• the alkyl group, alkenyl group, and alkynyl group may be linear or branched.
• the cycloalkyl group, cycloalkenyl group, and cycloalkynyl group may be monocyclic or polycyclic.
• alkyl groups include methyl, ethyl, propyl, hexyl and 2-ethylhexyl, dodecyl, tetradecyl, hexadecyl, octadecyl, docosyl, and the like.
• cycloalkyl groups include cyclohexyl and norbornyl groups.
• aromatic hydrocarbon groups include aryl groups.
• Aromatic hydrocarbons may be monocyclic or polycyclic. Examples of monocyclic aryl groups include phenyl groups, and examples of polycyclic aryl groups include naphthyl groups.
• R 3 may be a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
• hydrocarbon groups include arylalkylene groups such as benzyl, alkylarylene groups such as tolyl, and dialkylarylene groups such as xylyl.
• R 3 may be a combination of two or more aromatic hydrocarbon groups. Examples of such hydrocarbon groups include arylarylene groups such as biphenyl groups, and arylalkylenearylene groups such as styrenated phenyl groups.
• R 4 is not particularly limited as long as it is a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be linear, branched, or cyclic. However, saturated linear hydrocarbon groups and saturated branched hydrocarbon groups are particularly preferred. Moreover, among them, those having 2 to 3 carbon atoms are preferable, and those having 2 carbon atoms are more preferable. Further, they may contain different numbers of carbon atoms or different shapes. Even when different carbon numbers are included, it is preferable that the carbon atoms contain 2 to 3 carbon atoms, and more preferably 2 carbon atoms.
• the component having 2 carbon atoms is contained in an amount of 50 mol% or more, more preferably 75 mol% or more.
• the component with 2 carbon atoms in 50 mol% is contained in an amount of 50 mol% or more, more preferably 75 mol% or more.
• Examples of the aliphatic hydrocarbon group include an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, and a cycloalkenylene group.
• the alkylene group, alkenylene group, and alkynylene group may be linear or branched.
• Examples of alkylene groups include ethylene and propylene groups.
• ⁇ Suitable structural example of block copolymer (A1)> In the aqueous composition of the present invention, among all the Xs in the block copolymer (A1) represented by the formula (1), the amount of X that is Y is 5 mol% or more. If this amount is less than 5 mol%, the viscosity imparting effect and dispersion effect required by the present invention cannot be exhibited.
• the mol% of the Y moiety can be controlled by adjusting the polyamide/polyether ratio when synthesizing the block copolymer (A1), but if the reaction yield is not 100%, it is necessary to consider the reaction yield. . It is also possible to analyze by 1 H-NMR.
• the aqueous composition of the present invention may contain a block copolymer (A1) in which at least some of the Xs in formula (1) are carboxyl groups or salts thereof.
• the amount of X which is a carboxyl group or a salt thereof, is preferably 30 mol% or more, more preferably 40 mol%, based on the total amount of X in the block copolymer (A1) contained in the aqueous composition.
• the content is preferably 50 mol% or more, and more preferably 50 mol% or more.
• the amount in which X is a carboxyl group or its salt can be controlled by adjusting the polyamide/polyether ratio when synthesizing the block copolymer (A1), but if the reaction yield is not 100%, the reaction yield may be need to be considered. It is also possible to analyze by 1 H-NMR.
• the remaining mass after removing the Y portion from all the block copolymers (A1) contained in the aqueous composition is equal to the mass of the entire block copolymer (A1). On the other hand, it is preferably 50% by mass or more and 90% by mass or less.
• the mass remaining after removing the Y portion from the block copolymer (A1) can be controlled by adjusting the amount of polyamide charged/the amount of polyether charged when synthesizing the block copolymer (A1), but the When the yield is not 100%, it is necessary to consider the reaction yield. It is also possible to analyze by 1 H-NMR using an internal standard.
• the acid value of the block copolymer (A1) is preferably 15 or more and 80 or less, more preferably 15 or more and 60 or less, and 15 or more and 50 or less. It is more preferable that If the acid value of the block copolymer (A1) is less than 15, the acid-base interaction of the block copolymer (A1) will be too small, which may reduce the thickening effect, and if the acid value exceeds 80. Then, the molecular weight of the block copolymer (A1) is too small and the thickening effect is reduced. Note that the high acid value of the block copolymer (A1) means that the polyamide part has a low molecular weight and the amount of the polyether part is small.
• the acid value in this specification can be measured according to JIS K0070-1992.
• the acid value refers to the number of mg of potassium hydroxide required to neutralize free fatty acids and the like contained in 1 g of a sample.
• methods for measuring acid value include neutralization titration and potentiometric titration, and the acid value in this specification is a value measured by neutralization titration.
• the reaction yield can be determined by using the acid value measured by this method, and the reaction yield is assumed to be 0% for the acid value of the polyamide/polyether mixture before the reaction, and the theoretical acid value is calculated as the reaction yield. Treated as 100%.
• 50 mol% or more of either or both of R 1 and R 2 in formula (1) is a divalent hydrocarbon group having 34 or more carbon atoms. It is preferable that there be.
• At least a part of X in formula (1) is Y, and the number of carbon atoms in R 4 is 2 (OR 4 ). It is preferably 5% by mass or more and 45% by mass or less based on the total mass of the copolymer (A1).
• the mass of the above (OR 4 ) n site is calculated by calculating the mass of (OR 4 ) n in which the number of carbon atoms in R 4 is 2 among the polyether raw materials to be charged, and then calculating the mass of (OR 4 ) n and calculating the amount of polyamide and the amount of polyether to be charged.
• the amount obtained by removing dehydration from the total amount is taken as the total mass, and the mass of (OR 4 ) n in which the number of carbon atoms in R 4 is 2 is divided by the total mass and converted to a percentage, which is the above (OR 4 ) n It is expressed as mass % of the part. Furthermore, if there is an unreacted raw material, it is necessary to calculate the unreacted material from the reaction yield and remove the unreacted material from the mass ratio of (OR 4 ) n calculated as described above. It is also possible to analyze by 1 H-NMR using an internal standard.
• the total mass of the block copolymer (A1) and the polyether (B1) is preferably 5% by mass or more and 50% by mass or less with respect to the total mass of the block copolymer (A1) and the polyether (B1).
• R 5 is a hydrocarbon group having 1 to 22 carbon atoms.
• R 6 is a divalent hydrocarbon group having 2 to 4 carbon atoms.
• R 7 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
• q is an integer from 2 to 100.
• the number of carbon atoms in R 4 in the block copolymer (A1) is 2 (OR 4 ) n site and the number of carbon atoms in R 6 in polyether (B1) is 2 (OR 6 ) q site.
• the total mass is the mass and charge amount of R 4 contained in the block copolymer (A1) (OR 4 ) n , the carbon number of R 6 contained in the polyether (B1). is 2 (OR 6 )
• the total mass ratio (mass %) of the above (OR 4 ) n site and (OR 6 ) q site can be calculated. It is also possible to analyze by 1 H-NMR using an internal standard.
• R 7 of the polyether (B1) is H
• this is an example of a polyether that can be used as a raw material for synthesizing the block copolymer (A1).
• R 5 and R 6 are the same as R 3 and R 4 described above, respectively.
• q is the same as n mentioned above.
• R 7 is a hydrocarbon group having 1 to 4 carbon atoms
• R 7 is not particularly limited as long as it is a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. It may be a hydrogen group, and may be linear, branched, or cyclic.
• the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, and a cycloalkenyl group.
• the alkyl group and alkenyl group may be linear or branched.
• alkyl groups include methyl, ethyl, and propyl groups.
• Examples of cycloalkyl groups include cyclopropyl groups.
• the above-mentioned polyether (B1) is further included, at least a part of X in formula (1) is Y, and in the block copolymer (A1)
• the total mass of the n site in which R 4 has 2 carbon atoms (OR 4 ) and the q site in which R 6 in the polyether (B1) has 2 carbon atoms is the aqueous composition.
• the amount is preferably 5% by mass or more and 50% by mass or less based on the total mass of nonvolatile components therein.
• the number of carbon atoms in R 4 in the block copolymer (A1) is 2 (OR 4 ) n site and the number of carbon atoms in R 6 in polyether (B1) is 2 (OR 6 ) q site.
• the total mass is the mass and charge amount of R 4 contained in the block copolymer (A1) (OR 4 ) n , the carbon number of R 6 contained in the polyether (B1). is 2.
• a hydrophobic solid (crystalline substance) may be further added to the block copolymer (A1) represented by formula (1).
• Any hydrophobic solid may be used as long as it does not dissolve in water and is solid at room temperature. Examples include polyethylene waxes such as amide wax, hydrogenated castor oil, polyethylene, and oxidized polyethylene.
• a block copolymer (A1) in which all of the Xs in formula (1) are Y it is preferable that 80 mol% or more of all X in formula (1) be Y.
• the amount (mol%) of the compound in which X is Y has a value equal to the reaction yield when the reactive group ratio of polyether/polyamide is 1 or more when synthesizing the block copolymer (A1).
• the polyether/polyamide reactive group ratio is less than 1, it can be calculated by multiplying the reaction yield by this ratio. It is also possible to analyze by 1 H-NMR.
• the mixture further contains the above-mentioned polyether (B1) and the mixture of the block copolymer (A1) and the polyether (B1) has an acid value of 10 or less.
• the lower the acid value of this mixture the more effective the dispersion effect of pigments and the like by the aqueous composition of the present invention can be.
• the method for measuring the acid value is as described above.
• R 3 in formula (1) preferably has 1 to 4 carbon atoms, more preferably 1 carbon number.
• the block copolymer (A1) in which m 0 in formula (1) is It is preferable that the amount is 50% by mass or less.
• the above-mentioned polyether (B1) is further included, at least a part of X in formula (1) is Y, and the block copolymer (A1) is The total mass of the n site where R 4 has 2 carbon atoms (OR 4 ) and the q site where R 6 in the polyether (B1) has 2 carbon atoms is the block copolymer. It is preferably 50% by mass or more and 90% by mass or less based on the total mass of (A1) and polyether (B1).
• the above-mentioned polyether (B1) is further included, at least a part of X in formula (1) is Y, and the block copolymer (A1) is The total mass of the n site in which R 4 has 2 carbon atoms (OR 4 ) and the q site in which R 6 in the polyether (B1) has 2 carbon atoms is It is preferably 50% by mass or more and 90% by mass or less based on the total mass of nonvolatile components.
• the aqueous composition according to the present invention is for use in water-based paints, and is obtained by dispersing the block copolymer (A1) as an active ingredient in a medium mainly composed of water.
• water for example, deionized water (ion-exchanged water) can be used.
• viscosity can be imparted to water by adjusting the mass ratio of the block copolymer (A1) to water within a specific range.
• the mass ratio of the block copolymer (A1) to water is 5/95 to 50/50. If A1/water is less than 5/95, it is not economical because the viscosity-imparting effect and dispersion effect required by the present invention cannot be exhibited, or the amount of active ingredients is small. When A1/water exceeds 50/50, the amount of block copolymer (A1) relative to water is too large, and the block copolymer (A1) is not sufficiently dispersed in the aqueous composition, which is necessary for the present invention. The viscosity-imparting effect and dispersion effect that are supposed to be achieved cannot be achieved.
• the lower limit of A1/water is preferably 10/90 or more.
• the upper limit value of A1/water is preferably 40/60 or less, more preferably 35/65 or less, and even more preferably 30/70 or less.
• the aqueous composition of the present invention may contain auxiliary agents (other components) for the purpose of imparting other functions.
• auxiliary agents may be added for the purpose of improving the gloss retention of the coating film, the dispersibility of pigments, the antifoaming properties of water-based coating compositions, the flowability, and the like.
• Typical auxiliary agents in the aqueous composition of the present invention include, for example, neutralizing bases, solvents, surfactants, etc. described below.
• the aqueous composition according to the present invention can be used as a hydrophilic agent for dispersing the block copolymer (A1) in a medium mainly consisting of water (i.e., as a hydrophilic agent to help hydrophilize the block copolymer (A1). ), amines, and other neutralizing bases.
• the content of the neutralizing base is preferably at most 150 mol%, more preferably at most 110 mol%, based on the total amount of acids in the aqueous composition.
• organic bases and inorganic bases can be used as such neutralizing bases.
• organic bases include alkylamines such as ethylamine, diethylamine, and triethylamine, ethanolamine, diethanolamine (also referred to as 2,2'-iminodiethanol), and triethanolamine (also referred to as 2,2',2''-nitrilotriethanol).
• Alcohol amines such as N,N-dimethylethanolamine (also called 2-(dimethylamino)ethanol), 2-(diethylamino)ethanol, 2-amino-2-methyl-1-propanol, and Jeffamine (registered trademark) Polyether amines such as Trademark) M-1000 and Jeffamine M-2070 (manufactured by Huntsman) can be used.
• the inorganic base for example, sodium hydroxide, potassium hydroxide, ammonia, etc. can be used. These may be used alone or in combination of two or more.
• the aqueous composition according to the present invention may contain a solvent other than water in order to facilitate dispersion of the block copolymer (A1) into a medium mainly composed of water.
• the first solvent (C) is not particularly limited, but a solvent having at least one substituent selected from the group consisting of a hydroxyl group, an ether group, an ester group, an amide group, and a ketone group can be used. Examples of this solvent include alcohol solvents, glycol ether solvents, diglycol ether solvents, triglycol ether solvents, ester solvents, and amide solvents. However, among the first solvents (C), the diglycol solvent and triglycol solvent do not include those corresponding to polyether (B1).
• Alcohol solvents include monohydric alcohols, such as aliphatic alcohols such as methanol, ethanol, propanol, butanol, isobutanol, isopropanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, and benzyl.
• monohydric alcohols such as aliphatic alcohols such as methanol, ethanol, propanol, butanol, isobutanol, isopropanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, and benzyl.
• cyclic alcohols such as alcohol.
• glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether (also referred to as 2-butoxyethanol), ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, and 2-ethylhexyl glycol. , propylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, phenyl glycol, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, and the like.
• Examples of the diglycol ether solvent include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether.
• Examples of triglycol ether solvents include triethylene glycol dimethyl ether.
• ester solvents include dibasic acid esters such as methyl glutarate, methyl succinate, and methyl adipate, ethyl acetate, butyl acetate, hexyl acetate, heptyl acetate, propylene glycol monomethyl acetate, amyl propionate, Examples include ethyl ethoxypropionate, trimethylpentanediol monoisobutyrate (also referred to as Texanol), and the like.
• dibasic acid esters such as methyl glutarate, methyl succinate, and methyl adipate
• ethyl acetate butyl acetate, hexyl acetate, heptyl acetate
• propylene glycol monomethyl acetate amyl propionate
• Examples include ethyl ethoxypropionate, trimethylpentanediol monoisobutyrate (also referred to as Texano
• amide solvents examples include acyclic amides such as dimethylformamide, diethylformamide, dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide, and hexamethylphosphoamide, and cyclic amides such as N-methylpyrrolidone. Can be mentioned.
• polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, glycerin, sorbitol, and xylitol can also be used as the solvent.
• the above-mentioned solvents may be used alone or in combination of two or more.
• the aqueous composition according to the present invention may contain a surfactant as an optional component.
• This surfactant is used as a hydrophilic agent for making the block copolymer (A1) hydrophilic and facilitating dispersion of the block copolymer (A1) into a medium mainly composed of water.
• the above-mentioned polyether (B1) can be used.
• polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, and polyoxyethylene carboxylic acids such as polyoxyethylene stearate, polyoxyethylene laurate, and polyoxyethylene oleate are also available.
• esters polyoxyethylene glycerin fatty acid esters such as polyoxyethylene monoisostearate hydrogenated castor oil, polyoxyethylene triisostearate hydrogenated castor oil, polyoxyethylene glyceryl monoisostearate, and polyoxyethylene such as polyoxyethylene sorbitan monostearate.
• the aqueous composition of the present invention makes it possible to control the orientation of scale-like pigments when applied, and this effect can be used to improve the flip-flop properties of metallic paints. It is possible to improve the appearance of the paint film. For example, it is advantageous to have a low viscosity at a high shear rate such as during coating and a high viscosity at a low shear rate such as after coating in order to obtain a coating film exhibiting high flip-flop properties. Therefore, by using a material exhibiting such viscosity as the aqueous composition of the present invention, it becomes possible to provide a coating film exhibiting high flip-flop properties.
• Diluted compositions and water-based coating compositions using the aqueous composition of the present invention can be used in combination with other viscosity modifiers. By using it in combination with other viscosity modifiers, it is possible to have a different viscosity from that of the aqueous composition of the present invention. For example, when used in combination with a viscosity modifier that increases viscosity at high shear rates, it is possible to increase viscosity at both high and low shear rates.
• Viscosity modifiers that can thicken at such high shear rates include urethane-based viscosity modifiers, acrylic-based viscosity modifiers, cellulose-based modified viscosity modifiers, and polysaccharide-based viscosity modifiers. etc.
• Other viscosity modifiers that can be used in combination include amide viscosity modifiers, polyamide viscosity modifiers, urea viscosity modifiers, cellulose nanofibers (CNF), and inorganic viscosity modifiers.
• Urethane viscosity modifiers are not particularly limited, but include ADEKA NOL (registered trademark) UH-752, ADEKA NOL UH-540, ADEKA NOL UH-420 (manufactured by ADEKA Co., Ltd.), ACRYSOL RM-2020NPR, RM-8W, RM- 12W (manufactured by DOW CHEMICAL), SN Thickener 612, SN Thickener 621N (manufactured by San Nopco Co., Ltd.), RHEOLATE (registered trademark) 244, RHEOLATE 278 (manufactured by Elementis Japan), TAFIGEL (registered trademark) PUR- 45, TAFIGEL PUR-61 (manufactured by MUNZING), etc.
• ADEKA NOL registered trademark
• UH-752 ADEKA NOL UH-540
• ADEKA NOL UH-420 manufactured by ADEKA Co., Ltd.
• Acrylic viscosity modifiers are not particularly limited, but include Disparon (registered trademark) AQ-001, Disparon AQ-002, Disparon AQ-021 (manufactured by Kusumoto Kasei Co., Ltd.), and RHEOVIS (registered trademark) AS1130 (BSF Societas). ⁇ ACRYSOL ASE-60, ACRYSOL TT-615 (manufactured by DOW CHEMICAL), SN Thickener 617, SN Thickener 630, SN Thickener 640 (manufactured by Sannopco Co., Ltd.), Thikusol (registered trademark) K -1000 (manufactured by Kyoeisha Chemical Co., Ltd.).
• Cellulose-based modified viscosity modifiers are not particularly limited, but include carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, etc.
• Commercially available products include HEC Daicel (registered trademark) SP600N (manufactured by Daicel Corporation), Examples include Cellosize QP-4400-H and Cellosize QP-52000-H (manufactured by DOW CHEMICAL).
• Polysaccharide viscosity modifiers include, but are not particularly limited to, xanthan gum, carrageenan, guar gum, and the like.
• the amide viscosity modifier is not particularly limited, but those described in International Publication No.
• the polyamide viscosity modifier is not particularly limited, but includes Disparon AQ-600, Disparon AQ-630, Disparon AQ-633E, Disparon AQH-800, Disparon AQH-810 (manufactured by Kusumoto Kasei Co., Ltd.), and Thikusol W-310P. , Thikusol W-400LP (manufactured by Kyoeisha Chemical Co., Ltd.), ASA TW-121, ASA TW-124 (manufactured by Ito Oil & Chemicals Co., Ltd.), RHEOBYK (registered trademark) -440 (manufactured by Byk-Chemie).
• the urea-based viscosity modifier is not particularly limited, but examples include RHEOBYK-420 (manufactured by Byk-Chemie).
• CNF include, but are not particularly limited to, TEMPO-oxidized CNF, carboxymethylated CNF, phosphate-esterified CNF, sulfate-esterified CNF, mechanically defibrated CNF, and bacterial CNF.
• the inorganic viscosity modifier is not particularly limited, but may be either a natural mineral or a synthetic product.
• Examples include silicate clay minerals such as sepiolite, bentonite, and hectorite; Examples include PANGEL (registered trademark) AD (manufactured by Torsa Esse Inc.), LAPONITE (registered trademark) RD, LAPONITE RDS (manufactured by Byk-Chemie), BENTONE (registered trademark) EW (manufactured by Elementis Japan), etc. can be mentioned.
• PANGEL registered trademark
• AD manufactured by Torsa Esse Inc.
• LAPONITE registered trademark
• LAPONITE RDS manufactured by Byk-Chemie
• BENTONE registered trademark
• EW manufactured by Elementis Japan
• a block copolymer (A1) is prepared as raw materials for synthesizing the block copolymer (A1).
• a block copolymer (A1) can be obtained by subjecting the prepared polyamide and polyether to a dehydration reaction.
• the aqueous composition of the present invention can be obtained by dispersing this block copolymer (A1) in water.
• the above-mentioned neutralizing base and solvent may be added as necessary.
• the polyamide used in the synthesis of the block copolymer (A1) according to the present invention contains the above-mentioned diamine (which may contain a monoamine.
• amine component dicarboxylic acid and/or tricarboxylic acid
• dicarboxylic acid and/or tricarboxylic acid dicarboxylic acid and/or tricarboxylic acid
• monocarboxylic may contain an acid (hereinafter referred to as "carboxylic acid component”)) under known reaction conditions.
• raw materials such as an amine component and a carboxylic acid component are placed in a reaction container such as a four-necked flask, and the raw materials are stirred in an inert gas atmosphere (for example, under a nitrogen gas stream) to form a mixture.
• an inert gas atmosphere for example, under a nitrogen gas stream
• a polyamide is synthesized by heating the raw material mixture and carrying out a polycondensation reaction at 150° C. to 200° C. for 2 to 10 hours.
• the molar ratio of the amine component to the carboxylic acid component (mol% of the amine component/mol% of the carboxylic acid component) is less than 1. That is, it is preferable to carry out a polycondensation reaction with an excess amount of the carboxylic acid component relative to the amine component.
• at least one terminal of the polyamide (corresponding to X in formula (1)) becomes a carboxyl group.
• at least one end of the polyamide does not necessarily have to be a carboxyl group, and all the ends may be amino groups.
• the polyether used in the synthesis of the block copolymer (A1) according to the present invention can be synthesized by a method known to those skilled in the art. For example, it can be synthesized by the method described in JP-A-2002-212125.
• raw materials such as alkyl monool and potassium hydroxide are placed in a stainless steel autoclave equipped with stirring and temperature control functions, and after the atmosphere is replaced with nitrogen, the temperature is raised to 120° C. while stirring. Next, while maintaining the temperature at 120 ⁇ 5° C. and the pressure at about 3 atm, ethylene oxide was introduced under pressure and the reaction was carried out for 20 minutes.
• an alkyl polyether monool By aging at the same temperature for 2 hours and 30 minutes and then cooling to 40°C, an alkyl polyether monool can be obtained.
• a commercially available product may be used as the polyether used in the synthesis of the block copolymer (A1).
• Such commercial products include, for example, Brownon (registered trademark) SR-715, Brownon SR-720, Brownon BE-10, Brownon BE-20, Brownon BE-30, Brownon DSP-12.5, Brownon PH-5.
• a block copolymer (A1) is obtained by dehydrating the polyamide and polyether obtained as described above.
• the reaction vessel for example, the same reaction vessel as used in the synthesis of the polyamide described above can be used.
• the molar ratio of polyamide and polyether is preferably 0.10 to 1.50 mol per 1.00 mol of polyamide, and more preferably 0.20 to 1.00 mol per 1.00 mol of polyamide. suitable.
• the dehydration reaction may be carried out, for example, at 200 to 250°C for 3 to 5 hours.
• block copolymer (A1) is easily colored, for example, a small amount of hypophosphorous acid or the like may be added in an amount of 0.1 to 1.0 parts by mass based on a total of 100 parts by mass of polyamide and polyether. Coloring may be suppressed by
• the polyamide instead of synthesizing the polyamide in advance and then subjecting the polyamide and polyether to a dehydration reaction, it is possible to synthesize the polyamide by mixing the amine component and carboxylic acid component, which are raw materials for the polyamide, and the polyether, and subjecting them to a dehydration reaction.
• the block copolymer (A1) can also be obtained.
• the block copolymer (A1) can be dispersed in water by a known polymer dispersion method. For example, deionized water is poured into a container such as a four-necked flask and heated to 60 to 75°C. Meanwhile, a liquid mixture is prepared by mixing the block copolymer (A1) with a neutralizing base, a solvent, and the like. This liquid mixture is gradually added to the warmed deionized water in the container while stirring. After adding the liquid mixture, stirring is continued for about 5 to 120 minutes at a temperature of 50 to 80°C to obtain a dispersion. After stirring, the dispersion is transferred to another container and left to stand at room temperature for about 12 to 72 hours, thereby obtaining the aqueous composition of the present invention.
• a known polymer dispersion method For example, deionized water is poured into a container such as a four-necked flask and heated to 60 to 75°C. Meanwhile, a liquid mixture is prepared by mixing the block copoly
• aqueous composition according to the present invention is not particularly limited as long as it contains water; It can be suitably used in water-based metallic paints, or water-based anticorrosive paints that use pigments such as anticorrosive pigments that have large particle size and high specific gravity.
• the aqueous composition according to the present invention can be suitably used for water-based clear paints, water-based paints using general coloring pigments and extender pigments other than those mentioned above, and water-based coating materials such as water-based inks.
• the diluted composition according to the present invention is a composition obtained by diluting the aqueous composition described above.
• A1/water which is the mass ratio of block copolymer (A1) to water, is from 0.01/99.99 to 5/95, preferably from 0.05/99.95 to 5/95, more preferably 0.1/99.9 to 5/95, even more preferably 0.2/99.8 to 5/95. If A1/water is less than 0.01/99.99, the viscosity imparting effect and dispersing effect when diluting the aqueous composition are lost.
• Examples of the medium for diluting the aqueous composition include water, resin liquid (emulsion resin liquid, dispersion resin liquid, etc.), paint, ink, pigment slurry, etc. in which pigments and the like are dispersed in a predetermined medium.
• resin liquid emulsion resin liquid, dispersion resin liquid, etc.
• paint ink, pigment slurry, etc. in which pigments and the like are dispersed in a predetermined medium.
• the diluted composition is obtained by diluting the aqueous composition directly with the above-mentioned medium.
• a diluted composition may be obtained by preparing a masterbatch by diluting the aqueous composition with a predetermined medium (such as water), and diluting this masterbatch with the above-mentioned medium.
• a water-based coating composition according to a preferred embodiment of the present invention contains the above-described aqueous composition and a glitter pigment.
• the aqueous coating composition of the present invention also contains other additives such as an aqueous resin, a pigment other than the glitter pigment, an antifoaming agent, a film-forming aid, and a pH adjuster. It may further contain.
• the aqueous composition of the present invention differs depending on the type of aqueous resin that is the binder in the aqueous coating composition, the blending composition of pigments, etc., but usually the content of the block copolymer (A1) is higher than that of the aqueous coating composition. 0.01% by weight or more and 5% by weight or less, preferably 0.05% by weight or more and 2% by weight or less, more preferably 0.1% by weight or more and 1% by weight or less, even more preferably 0. It is contained in an amount of 2% by mass or more and 0.5% by mass or less.
• the aqueous resin contained as a binder in the aqueous coating composition according to the present invention is a resin component dispersed in a medium mainly composed of water, and examples of the resin component include acrylic resin, acrylic silicone resin, Examples include alkyd resins, polyester resins, urethane resins, epoxy resins, silicone resins, and fluororesins.
• the form of the aqueous resin is divided into water-soluble, (colloidal) dispersion, and emulsion depending on the dispersion form, and any form is applicable.
• These resins are, for example, heat-curable, ultraviolet-curable, electron beam-curable, oxidative-curable, photocation-curable, peroxide-curable, and cured through chemical reactions in the presence or absence of catalysts. It may also be a resin with a high glass transition point that forms a film simply by volatilization of the diluting medium without any chemical reaction.
• the curing agent include amino resins, melamine resins, isocyanate compounds, blocked isocyanate compounds, and epoxy compounds.
• the type of bright pigment used in the present invention is not limited as long as it gives the paint film a metallic-like shine or luster, but examples include aluminum, alumina, nickel, zinc, iron, Stainless steel, bismuth, and other metal pigments, pearl pigments such as mica, aluminum flakes, copper flakes, mica-like iron oxide, mica, and metallic pigments such as scaly powder of mica coated with metal oxides, glass flakes, graphite, etc. is used.
• pigments other than bright pigments include extender pigments and color pigments commonly used in water-based paints.
• extender pigments include calcium carbonate (ground calcium carbonate (GCC), precipitated calcium carbonate (PCC), etc.), barium sulfate, silicon dioxide, aluminum hydroxide, talc, organic fibers, glass powder, and the like.
• coloring pigments include titanium dioxide, carbon black, yellow lead, cadmium yellow, ocher, titanium yellow, zinc chromate, Bengara, aluminosilicate, quinacridone series, phthalocyanine series, anthroquinone series, and diketopyrrolopyrrole. These include benzimidazolone series, isoindolinone series, etc.
• the water-based coating composition of the present invention may contain other substances such as dehydrating agents (e.g., silane coupling agents), adhesion improvers, surfactants, curing agents, etc., to the extent that their properties and the purpose of the present invention are not impaired.
• dehydrating agents e.g., silane coupling agents
• adhesion improvers e.g., surfactants, curing agents, etc.
• Catalysts e.g., silane coupling agents
• adhesion improvers e.g., silane coupling agents
• surfactants e.g., curing agents, etc.
• curing agents e.g., etc.
• the water-based paint composition of the present invention can be manufactured according to known methods for manufacturing water-based paints. For example, after mixing the above-mentioned aqueous composition and components other than pigments in a water-based medium such as deionized water (ion-exchanged water) with stirring, the pH is adjusted as necessary to prepare a clear paint. do.
• a water-based paint composition can be produced by adding an aqueous composition and a pigment to this clear paint and dispersing them in the clear paint.
• the aqueous composition according to the present invention may be added to the water-based paint composition during the process of kneading the pigments as described above, or after the water-based paint is manufactured. Furthermore, it is also possible to make a masterbatch and add it. Further, as the equipment used for dispersing the aqueous composition and pigment, those commonly used in the production of water-based paints can be used. Further, the stirring speed and stirring time during dispersion of the aqueous composition and pigment are not particularly limited, and may be set as appropriate while checking the dispersion state of the aqueous composition and pigment.
• the water-based paint composition of the present invention can be suitably used as a water-based metallic paint or a water-based anti-corrosion paint that uses pearl pigments such as aluminum pigments and mica, or pigments with large particle size and high specific gravity such as anti-corrosion pigments. Further, the water-based paint composition of the present invention can be suitably used as a water-based paint using general coloring pigments and extender pigments other than those mentioned above, or as a water-based coating material such as a water-based ink.
• Aqueous compositions of Examples and Comparative Examples were prepared as follows.
• dimer acid trade name "Haridimer 250", manufactured by Harima Kasei Co., Ltd.
• Polyamides were synthesized in the same manner as in Polyamide Synthesis Example 1, except that the molar ratios of dicarboxylic acid and diamine were changed to those shown in Table 1, and polyamides P-2 to P-4 were obtained.
• polyamide-polyether block polymers of Synthesis Examples 5 to 16 were synthesized using polyamide P-1 or P-4 obtained as described above and the polyethers listed in Table 2 (see Table 2). reference).
• polyamide-polyether block polymers of Synthesis Examples 17 to 37 were synthesized using diamines and dicarboxylic acids, which are raw materials for polyamides, and polyethers without preparing polyamides in advance (see Table 3).
• Polyamide-polyether block polymer synthesis example 5> Using the same apparatus as in Polyamide Synthesis Example 1, 61.1 parts of polyamide P-1 of Synthesis Example 1 and 38.9 parts of stearoxy PEG (trade name "Brownon (registered trademark) SR-720", manufactured by Aoki Yushi Kogyo Co., Ltd.) (1.00 mol to 1.00 mol of polyamide, 50 mol % to acid equivalent) were mixed. A dehydration reaction was carried out at 240° C. for 5 hours to obtain polyamide-polyether block polymer P-5.
• stearoxy PEG trade name "Brownon (registered trademark) SR-720", manufactured by Aoki Yushi Kogyo Co., Ltd.
• a polyamide-polyether block polymer was produced in the same manner as in the synthesis method of Polyamide Synthesis Example 5, except that the molar ratio of polyamide P-1 or P-4 and polyether raw material was changed to the molar ratio shown in Table 2 (the polyether raw material was equivalent to the polyamide). were synthesized to obtain polyamide-polyether block polymers P-6 to P-16.
• the reaction temperature of the dehydration reaction is adjusted appropriately in the range of 200 to 250°C, and the reaction time is adjusted in the range of 3 to 5 hours. If coloring easily occurs, add about 0.1 to 1.0 parts of hypophosphorous acid. Coloring was suppressed by adding within a certain range.
• a polyamide-polyether block was produced in the same manner as in the synthesis method of Polyamide Synthesis Example 17, except that the dicarboxylic acid, diamine, and polyether raw materials were changed to the mol ratios shown in Table 3 (the mol ratios of the raw materials, not the functional group equivalents). Polymers were synthesized to obtain polyamide-polyether block polymers P-18 to P-37. In addition, the reaction temperature of the dehydration reaction is adjusted appropriately in the range of 200 to 250°C, and the reaction time is adjusted in the range of 3 to 5 hours. If coloring easily occurs, add about 0.1 to 1.0 parts of hypophosphorous acid. Coloring was suppressed by adding within a certain range.
• m Since m has a distribution, it cannot be specified, but the number average value can be determined from the acid/amine ratio.
• Example of preparation of aqueous composition Aqueous compositions of Examples and Comparative Examples were prepared as follows.
• Example 1 79.2 parts of deionized water was weighed into a 500 ml four-necked flask equipped with a stirrer, a condenser, and a thermometer, and heated to maintain a temperature of 60 to 75°C.
• 15.0 parts of polyamide-polyether block polymer P-5, 5.3 parts of 2-butoxyethanol as a solvent, and 0.5 parts of 2-(dimethylamino)ethanol as a neutralizing base were mixed at 120°C. , a liquid mixture was obtained.
• This liquid mixture was gradually added to the warm water in the flask while stirring. After the addition was completed, stirring was continued for 30 minutes while maintaining the temperature range of 50 to 80°C to obtain a dispersion. After stirring, this dispersion was transferred to another container and allowed to stand at room temperature for 24 hours to obtain aqueous composition E-1.
• Examples 2 to 18 and 33 to 35 Using the polyamide-polyether block polymer shown in Table 5 at the blending ratio shown in Table 4, the aqueous compositions E-2 to Examples 2 to 18 and Examples 33 to 35 were prepared in the same manner as in Example 1. E-18 and E-33 to E-35 were obtained.
• Example 19 Using the same apparatus as in Example 1, 89.7 parts of deionized water was weighed and heated to maintain the temperature at 60 to 75°C. On the other hand, 10.0 parts of polyamide-polyether block polymer P-6 and 0.3 parts of 2-(dimethylamino)ethanol as a neutralizing base were mixed at 120°C to obtain a liquid mixture. This liquid mixture was gradually added to the warm water in the flask while stirring. After the addition was completed, stirring was continued for 30 minutes while maintaining the temperature range of 50 to 80°C to obtain a dispersion. After the stirring was completed, this dispersion was transferred to another container and allowed to stand at room temperature for 24 hours to obtain aqueous composition E-19.
• Example 20 Using the same apparatus as in Example 1, 74.5 parts of deionized water was weighed and heated to maintain a temperature of 60 to 75°C. On the other hand, 15.0 parts of polyamide-polyether block polymer P-5, 10.0 parts of 4 mol adduct of 2-ethylhexanol with ethylene oxide as a surfactant, and 0.5 parts of 2-(dimethylamino)ethanol as a neutralizing base. The two parts were mixed at 120°C to obtain a liquid mixture. This liquid mixture was gradually added to the warm water in the flask while stirring. After the addition was completed, stirring was continued for 30 minutes while maintaining the temperature range of 50 to 80°C to obtain a dispersion. After the stirring was completed, this dispersion was transferred to another container and allowed to stand at room temperature for 24 hours to obtain aqueous composition E-20.
• Example 21 Using the same apparatus as in Example 1, 44.8 parts of deionized water was weighed and heated to maintain a temperature of 60 to 75°C. On the other hand, 18.0 parts of polyamide-polyether block polymer P-19, 36.0 parts of 2-butoxyethanol, and 1.2 parts of 2-(dimethylamino)ethanol as a neutralizing base were mixed at 120°C to form a liquid. A mixture was obtained. This liquid mixture was gradually added to the warm water in the flask while stirring. After the addition was completed, stirring was continued for 30 minutes while maintaining the temperature range of 50 to 80°C to obtain a dispersion. After stirring, this dispersion was transferred to another container and allowed to stand at room temperature for 24 hours to obtain aqueous composition E-21.
• Example 22 Using the same apparatus as in Example 1, 74.5 parts of deionized water was weighed and heated to maintain a temperature of 60 to 75°C. On the other hand, 15.0 parts of polyamide-polyether block polymer P-6, 10.0 parts of methoxy PEG (trade name "UNIOX M-400", manufactured by NOF Corporation) as a surfactant, 2 parts as a neutralizing base -(Dimethylamino)ethanol 0.5 part was mixed at 120°C to obtain a liquid mixture. This liquid mixture was gradually added to the warm water in the flask while stirring. After the addition was completed, stirring was continued for 30 minutes while maintaining the temperature range of 50 to 80°C to obtain a dispersion. After stirring, this dispersion was transferred to another container and allowed to stand at room temperature for 24 hours to obtain aqueous composition E-22.
• PEG trade name "UNIOX M-400"
• Example 23 Using the same apparatus as in Example 1, 30.0 parts of polyamide-polyether block polymer P-13 and 70.0 parts of deionized water were weighed. This mixture was heated to maintain a temperature of 60 to 75°C, and stirring was continued for 30 minutes to obtain a dispersion. After stirring, this dispersion was transferred to another container and allowed to stand at room temperature for 24 hours to obtain aqueous composition E-23.
• Examples 24 and 26-32 Aqueous compositions E-24 and E-26 to 32 were obtained using the same method as in Example 23, except that the polyamide-polyether block polymer was changed to P-14 and P-27 to P-33, respectively. .
• Example 25 Using the same apparatus as in Example 1, 10.0 parts of polyamide-polyether block polymer P-15 and 90.0 parts of deionized water were weighed. This mixture was heated to maintain a temperature of 60 to 75°C, and stirring was continued for 30 minutes to obtain a dispersion. After stirring, this dispersion was transferred to another container and allowed to stand at room temperature for 24 hours to obtain aqueous composition E-25.
• Example 36 Using the same apparatus as in Example 1, 79.9 parts of deionized water was weighed and heated to 50°C. On the other hand, 8.0 parts of polyamide-polyether block polymer P-36, 2.0 parts of B-4 listed in Table 2 of JP-A No. 2012-111832, 5.0 parts of propylene glycol monomethyl ether, and surfactant. 4.0 parts of a 4 mol ethylene oxide adduct of 2-ethylhexanol and 1.1 parts of 2-(dimethylamino)ethanol as a neutralizing base were mixed at 120°C to obtain a liquid mixture. This liquid mixture was gradually added to the warm water in the flask while stirring.
• Example 37 Using the same apparatus as in Example 1, 75.0 parts of deionized water was weighed and heated to 50°C. On the other hand, 8.0 parts of polyamide-polyether block polymer P-36, 4.0 parts of hydrogenated castor oil, 7.0 parts of propylene glycol monomethyl ether, and 5.0 parts of ethylene oxide 4 mol adduct of 2-ethylhexanol as a surfactant. and 1.1 parts of 2-(dimethylamino)ethanol as a neutralizing base were mixed at 120°C to obtain a liquid mixture. This liquid mixture was gradually added to the warm water in the flask while stirring.
• Example 38 Using the same apparatus as in Example 1, 78.5 parts of deionized water was weighed and heated to maintain a temperature of 60 to 75°C. On the other hand, 15.0 parts of polyamide-polyether block polymer P-5, 4.0 parts of propylene glycol monomethyl ether, 2.0 parts of diethylene glycol dibutyl ether, and 0.5 parts of 2-(dimethylamino)ethanol as a neutralizing base were added. The mixture was mixed at 120°C to obtain a liquid mixture. This liquid mixture was gradually added to the warm water in the flask while stirring. After the addition was completed, stirring was continued for 30 minutes while maintaining the temperature range of 50 to 80°C to obtain a dispersion. After the stirring was completed, this dispersion was transferred to another container and allowed to stand at room temperature for 24 hours to obtain aqueous composition E-38.
• Example 39 Using the same apparatus as in Example 1, 76.5 parts of deionized water was weighed and heated to maintain a temperature of 60 to 75°C. On the other hand, 15.0 parts of polyamide-polyether block polymer P-5, 3.0 parts of 2-butoxyethanol, 5.0 parts of tetraethylene glycol dimethyl ether, and 0.5 parts of 2-(dimethylamino)ethanol as a base for neutralization. were mixed at 120°C to obtain a liquid mixture. This liquid mixture was gradually added to the warm water in the flask while stirring. After the addition was completed, stirring was continued for 30 minutes while maintaining the temperature range of 50 to 80°C to obtain a dispersion. After the stirring was completed, this dispersion was transferred to another container and allowed to stand at room temperature for 24 hours to obtain aqueous composition E-39.
• Example 40> Using the same apparatus as in Example 1, 46.7 parts of deionized water was weighed and heated to maintain a temperature of 60 to 75°C. On the other hand, 22.0 parts of polyamide-polyether block polymer P-5, 3.5 parts of oleic acid, 7.0 parts of 2-butoxyethanol, and 20.8 parts of Jeffamine (registered trademark) M-1000 as a neutralizing base. were mixed at 120°C to obtain a liquid mixture. This liquid mixture was gradually added to the warm water in the flask while stirring. After the addition was completed, stirring was continued for 30 minutes while maintaining the temperature range of 50 to 80°C to obtain a dispersion. After the stirring was completed, this dispersion was transferred to another container and allowed to stand at room temperature for 24 hours to obtain aqueous composition E-40.
• Example 41 Using the same apparatus as in Example 1, 77.8 parts of deionized water was weighed and heated to maintain a temperature of 60 to 75°C. On the other hand, 12.0 parts of polyamide-polyether block polymer P-5, 4.0 parts of polyamide-polyether block polymer P-37, 5.6 parts of 2-butoxyethanol, and 2-(dimethylamino) as a neutralizing base. 0.6 part of ethanol was mixed at 120°C to obtain a liquid mixture. This liquid mixture was gradually added to the warm water in the flask while stirring. After the addition was completed, stirring was continued for 30 minutes while maintaining the temperature range of 50 to 80°C to obtain a dispersion. After stirring, this dispersion was transferred to another container and allowed to stand at room temperature for 24 hours to obtain aqueous composition E-41.
• Example 42 Using the same apparatus as in Example 1, 79.1 parts of deionized water was weighed and heated to maintain a temperature of 60 to 75°C. On the other hand, 10.0 parts of polyamide-polyether block polymer P-5, 5.0 parts of polyamide-polyether block polymer P-37, 5.3 parts of 2-butoxyethanol, and 2-(dimethylamino) as a neutralizing base. 0.6 part of ethanol was mixed at 120°C to obtain a liquid mixture. This liquid mixture was gradually added to the warm water in the flask while stirring. After the addition was completed, stirring was continued for 30 minutes while maintaining the temperature range of 50 to 80°C to obtain a dispersion. After stirring, this dispersion was transferred to another container and allowed to stand at room temperature for 24 hours to obtain aqueous composition E-42.
• Example 43 Using the same apparatus as in Example 1, 32.3 parts of deionized water was weighed and heated to maintain a temperature of 60 to 75°C. On the other hand, 18.0 parts of polyamide-polyether block polymer P-34, 35.0 parts of 2-butoxyethanol, 14.0 parts of propylene glycol monomethyl ether, and 0.8 parts of 2-(dimethylamino)ethanol as a neutralizing base. were mixed at 120°C to obtain a liquid mixture. This liquid mixture was gradually added to the warm water in the flask while stirring. After the addition was completed, stirring was continued for 30 minutes while maintaining the temperature range of 50 to 80°C to obtain a dispersion. After stirring, this dispersion was transferred to another container and allowed to stand at room temperature for 24 hours to obtain aqueous composition E-43.
• DMDG gel composition corresponding to E-1 DMDG gel composition corresponding to E-1> Weighed 15.0 parts of polyamide-polyether block polymer P-5 and 85.0 parts of diethylene glycol dimethyl ether (DMDG) into a 500 ml four-necked flask equipped with a stirrer, a cooling tube, and a thermometer. The mixture was stirred and dissolved for 30 minutes while maintaining the temperature range of .degree. After stirring, this solution was transferred to another container and allowed to stand at room temperature for 24 hours to obtain a DMDG gel composition corresponding to aqueous composition E-1.
• DMDG gel composition corresponding to E-1 DMDG gel composition corresponding to aqueous composition E-1.
• HG gel composition corresponding to E-1)> In a 500 ml four-necked flask equipped with a stirrer, condenser, and thermometer, 15.0 parts of polyamide-polyether block polymer P-5 and 2-methylpentane-2,4-diol (also known as hexylene glycol) were added. HG) was weighed out and stirred and dissolved for 30 minutes while maintaining a temperature range of 80 to 120°C. After stirring, this solution was transferred to another container and allowed to stand at room temperature for 24 hours to prepare an HG gel composition corresponding to aqueous composition E-1, but no gelation occurred. Since it did not gel, there was no hope that it would exhibit a viscosity adjusting function (viscosity imparting effect), so further tests were canceled.
• a 3% water masterbatch was prepared using the aqueous composition or gel composition of each Example and Comparative Example. Each composition was weighed out, and for those that were not neutralized, a neutralizing equivalent of 2-(dimethylamino)ethanol was added, and deionized water was added so that the solids content of the composition was 3%. The mixture was stirred using a lab body spar, and the rotation speed was gradually increased to avoid entraining air. A 3% water masterbatch was prepared by dispersing at a maximum of 2500 rpm for 10 minutes. However, for E-40 to E-43, dispersion was not completed in 10 minutes, so a 3% water masterbatch was prepared by dispersing for an additional 10 to 20 minutes. The formulation of the 3% water masterbatch is shown in Table 6.
• Test Example 1 Evaluation using aqueous dispersion
• This test example is an evaluation using an aqueous dispersion in which the aqueous compositions or gel compositions of Examples and Comparative Examples are diluted with water and dispersed.
• Test Example 2 Evaluation I using emulsion resin liquid
• This test example is an evaluation using an emulsion resin liquid in which the aqueous compositions or gel compositions of Examples and Comparative Examples are diluted and dispersed with emulsion resin.
• emulsion resin liquid Based on the formulation shown in Table 9, emulsion resin (trade name "Movinyl (registered trademark) 7110", manufactured by Japan Coating Resin Co., Ltd.), deionized water, and Texanol were stirred and mixed, and then obtained as described above. A 3% masterbatch was added and dispersed using a lab body spar (900-1500 rpm x 10 minutes).
• Test Example 3 Evaluation using dispersion resin liquid
• This test example is an evaluation using a dispersion resin liquid in which the aqueous compositions or gel compositions of Examples and Comparative Examples are diluted and dispersed with a dispersion resin.
• dispersion resin liquid Based on the formulation shown in Table 11, dispersion resin (trade name "Hydran (registered trademark) WLS-210", manufactured by DIC Corporation), deionized water, glycerin, and 2-propanol were stirred and mixed, and then as described above. The 3% masterbatch obtained in step 1 was added and dispersed using a lab body spar (900 to 1500 rpm x 10 minutes).
• Test Example 4 Evaluation II using emulsion resin liquid
• This test example is an evaluation using an emulsion resin liquid in which the aqueous compositions or gel compositions of Examples and Comparative Examples were diluted and dispersed with an emulsion resin different from Test Example 2.
• emulsion resin liquid Based on the formulation shown in Table 13, emulsion resin (trade name "Polydurex (registered trademark) G620S", manufactured by Asahi Kasei Corporation), deionized water, and Texanol were stirred and mixed, and then 3 was obtained as described above. % masterbatch was added and dispersed using a lab body spar (900 to 1500 rpm x 10 minutes).
• Polyamide and polyamide-polyether block polymers have the characteristic of increasing viscosity at low shear rates (0.1 s -1 in the above test example) while suppressing viscosity increases at high shear rates (1000 s -1 in the above test example). have.
• Such viscosity is a characteristic suitable for spray coating, and is advantageous in preventing sedimentation, preventing sagging, improving the orientation of bright pigments called flip-flop properties, and improving the appearance of the coating film.
• polyamide-polyether block polymers P-5 to P-12 and P-16 used in E-1 to E-8, E-19, E-20, E-22, and E-33 were , C-1 is obtained by reacting the polyamide P-1 with a polyether moiety.
• the 0.1s -1 viscosity of E-1 to E-8, E-19, E-20, E-22, and E-33 is higher than that of C-1, so they have better viscosity adjustment functions. It can be said that there are.
• the aqueous compositions using the polyamide-polyether block polymer generally showed a high viscosity imparting effect.
• E-22 in the aqueous dispersion although it was superior to C-1 having the same polyamide skeleton, it was inferior to C-2 and C-3.
• E-22 is a polyamide-polyether block polymer using the same P-6 as E-2, but it contains methoxy PEG in the formulation, R 4 is 2 (R 4 O), and the mass % of n is constant. It is considered that the viscosity-imparting effect is reduced because the amount exceeds the amount.
• E-19 was a blend containing only the amine salt of polyamide-polyether block polymer P-6 and water without containing a solvent, it was possible to prepare an aqueous composition.
• E-19 is an aqueous composition that has a viscosity adjustment function that can be used in such cases.
• polyamide-polyether block polymer P-6 it was not necessarily necessary to contain a solvent for dispersion in water, and it had a sufficient viscosity adjusting function.
• the aqueous compositions of Examples and Comparative Examples both maintained a 1000 s -1 viscosity similar to that of Blank (not containing polyamide and polyamide-polyether block polymer).
• Example 6 (E-6) and Comparative Example 1 (C-1).
• Dispersion resin (trade name "NeoPac (registered trademark) E-123", manufactured by Covestro (Netherlands) B.V.) is neutralized with 2-(dimethylamino)ethanol to a solid content of 3%.
• Each composition was added as follows. The mixture was stirred using a laboratory spar, and the rotation speed was gradually increased to avoid entraining air.
• a 3% resin masterbatch was prepared by dispersing at a maximum of 2500 rpm for 10 minutes. The formulation of the 3% resin masterbatch is shown in Table 15.
• Test Example 5 Evaluation of water-based paint composition containing glitter pigment
• the aqueous compositions of Examples and Comparative Examples were evaluated as a water-based paint composition containing an aluminum pigment as a glittering pigment.
• the obtained water-based coating composition was diluted with deionized water at 25° C. for 20 seconds using a #4 Ford cup the next day.
• the amount of dilution increases, the solid content of the paint changes significantly, so the amount of deionized water for dilution was made to not exceed 5% of the weight of the paint.
• acrylic system A was added in the same amount of solid content as the aqueous composition, the amount of deionized water required for dilution exceeded 5% of the weight of the paint, so the amount added was reduced and the same operation was performed again.
• ⁇ Painting test> The tin plate was coated using an automatic spray coating machine (trade name: "XY Coating Machine", manufactured by NCC Corporation) in an environment of 23° C. and 50% RH. The coating was applied by adjusting the discharge rate so that the dry film thickness was 11 to 14 ⁇ m, left to stand for 5 minutes, and then dried for 20 minutes in a constant temperature bath at 80° C. to harden. The lightness (L * ) of the cured coating film was measured at observation angles of 15°, 45°, and 110° using a portable multi-angle spectrophotometer (trade name "MA-T12", manufactured by X-Rite Inc.). It was measured.
• XY Coating Machine manufactured by NCC Corporation
• ⁇ Viscosity evaluation> The steady flow viscosity of the diluted aqueous coating composition was measured at 25° C. using a rheometer equipped with a 60 mm cone-shaped jig. After performing measurements at a shear rate of 0.01 s -1 to 1000 s -1 (Low-High measurement), measurements were performed at a shear rate of 1000 s -1 to 0.01 s -1 (High-Low measurement). The viscosity was read at shear rates of 0.1 s ⁇ 1 and 1000 s ⁇ 1 for High-Low measurements. Table 18 summarizes the results of the viscosity evaluation in this test example and the results of the coating test described above.
• Polyamide and polyamide-polyether block polymers increased the viscosity at low shear rates (0.1 s ⁇ 1 in the test example described above) while suppressing the increase in viscosity at high shear rates (1000 s ⁇ 1 in the test example described above). . It is thought that such viscous properties showed high flip-flop properties. Furthermore, the aqueous composition E-6 using polyamide-polyether block polymer P-10 had better flip-flop properties as a water-based coating composition than the aqueous composition C-1 using polyamide P-1. Ta. It is believed that by using an aqueous composition containing a polyamide-polyether block polymer as a viscosity modifier, it is possible to produce a coating film that exhibits better flip-flop properties.
• urethane type A urethane-based viscosity modifiers
• urethane type B product name "ADEKANOL UH-540”
• ⁇ Preparation of aqueous dispersion> Stir deionized water with a lab body spar, add a predetermined amount of the 3% water masterbatch obtained as described above, and further add a predetermined amount of other viscosity modifiers to be used together, and then disperse with a lab body spar ( 800-1500 rpm x 10 minutes).
• Table 19 shows the formulation of the aqueous dispersion.
• aqueous dispersions diluted with water such that each solid content was 1.0% were also prepared in the same manner.
• ⁇ Viscosity evaluation> The steady flow viscosity of the emulsion resin liquid was measured at 25° C. using a rheometer equipped with a 60 mm cone-shaped jig. After performing measurements at a shear rate of 0.01 s -1 to 1000 s -1 (Low-High measurement), measurements were performed at a shear rate of 1000 s -1 to 0.01 s -1 (High-Low measurement). The viscosity was read at shear rates of 0.1 s ⁇ 1 and 1000 s ⁇ 1 for High-Low measurements. Table 20 shows the results of viscosity evaluation in this test example.
• Test Example 7 Evaluation using emulsion resin liquid
• This test example is an evaluation using an emulsion resin liquid in which another viscosity modifier was mixed with an emulsion resin liquid in which the aqueous composition of the example was diluted and dispersed with an emulsion resin.
• a viscosity modifier an amide-based viscosity modifier (Production Example S1 described in International Publication No. 2022/097747 pamphlet (hereinafter abbreviated as "amide-based")) was used in combination with the emulsion resin liquid of the aqueous composition of the example. did.
• emulsion resin liquid Based on the formulation shown in Table 21, emulsion resin (trade name "Movinyl 7110", manufactured by Japan Coating Resin Co., Ltd.), deionized water, and Texanol were stirred and mixed, and then a 3% resin master obtained as described above was obtained. After adding the batch and further adding a predetermined amount of another viscosity modifier (sometimes referred to as "Rheocon agent” in this specification and tables), it was dispersed using a laboratory body spar (900 to 1500 rpm x 10 minutes). For comparison purposes, emulsion resin liquids with each solid content of 0.4% were also prepared in the same manner.
• a viscosity modifier sometimes referred to as "Rheocon agent” in this specification and tables
• Viscosity recovery of the emulsion resin liquid was measured at 25° C. using a rheometer equipped with a 60 mm cone-shaped jig. The viscosity was measured at 1 second intervals in the following order: 1 minute at a shear rate of 0.1 s -1 (Step 1), 10 seconds at a shear rate of 1000 s -1 (Step 2), and 2 minutes at a shear rate of 0.1 s -1 (Step 3). was measured. The viscosity was read 5 seconds after entering step 3. The results of the viscosity evaluation in this test example are shown in Table 22.
• Test Example 8 Evaluation using dispersion resin liquid
• This test example is an evaluation using a dispersion resin liquid in which the aqueous composition of the example was diluted and dispersed with a dispersion resin, and another viscosity modifier was mixed with the dispersion resin liquid.
• an acrylic viscosity modifier trade name "Disparon AQ-001” (hereinafter abbreviated as "acrylic C"), manufactured by Kusumoto Kasei Co., Ltd.) was added to the dispersion resin liquid of the aqueous composition of the example. Used in conjunction with
• dispersion resin liquid Based on the formulation shown in Table 23, dispersion resin (trade name "Hydran WLS-210", manufactured by DIC Corporation), deionized water, glycerin, and 2-propanol were stirred and mixed, and then obtained as described above. A 3% resin masterbatch was added thereto, and a predetermined amount of other viscosity modifiers used in combination were added, followed by dispersion using a lab body spar (900 to 1500 rpm x 10 minutes). For comparison purposes, dispersion resin liquids with each solid content of 0.4% were also prepared in the same manner.
• Viscosity recovery of the dispersion resin liquid was measured at 25° C. using a rheometer equipped with a 60 mm cone-shaped jig. The viscosity was measured at 1 second intervals in the following order: 1 minute at a shear rate of 0.1 s -1 (Step 1), 10 seconds at a shear rate of 1000 s -1 (Step 2), and 2 minutes at a shear rate of 0.1 s -1 (Step 3). was measured. The viscosity was read 10 seconds after entering step 3. Table 24 shows the results of viscosity evaluation in this test example.
• the viscosity of one or both of the viscosity modifiers is not in the amount necessary to develop viscosity, resulting in a viscosity that is even lower than the arithmetic average.
• the viscosity was even higher than the arithmetic average. It is believed that substances are likely to exhibit special interactions with other viscosity modifiers.
• Test Example 9 Dispersion function to CNT
• aqueous compositions E-23 to E-32
• deionized water deionized water
• CNT powder trade name "TUBALL (registered trademark) 01RW03", manufactured by OCSiAl
• Preliminary dispersion 10,000 to 11,000 rpm x 2 hours
• was carried out using a machine (trade name: "Clearmix (registered trademark) CLM-0.8S", manufactured by M Technique Co., Ltd.).
• the dispersion liquid after preliminary dispersion was subjected to main dispersion (the first pass was performed using the device settings
• the discharge amount was 30, the discharge pressure was 30 MPa for the second pass, and 70 MPa for the 3rd to 13th passes) to obtain a CNT dispersion.
• Test Example 10 Dispersion function in organic pigment
• the organic pigments are cyan: trade name "Heliogen (registered trademark) Blue D7088", or magenta: trade name “Cinquasia (registered trademark) Magenta D4500J” (manufactured by Sun Chemical Ltd.), Deionized water, aqueous compositions (E-26, E-27), and antifoaming agent (trade name "Disparon (registered trademark) AQ-7533N", manufactured by Kusumoto Kasei Co., Ltd.) were weighed out. Furthermore, 400 g of zirconia beads with a diameter of 0.3 mm were added. After being dispersed in a paint shaker for 3 hours, the mixture was separated from the zirconia beads to obtain an organic pigment dispersion.
• the organic pigment dispersion obtained as described above was evaluated in terms of viscosity and particle size distribution.
• the viscosity was determined by steady flow measurement of the organic pigment dispersion at a shear rate of 1 s -1 to 100 s -1 (low-high measurement) at 25° C. using a rheometer equipped with a 60 mm cone-shaped jig.
• the particle size distribution was measured using a dynamic light scattering particle size distribution measuring device.
• Dispersion performance was evaluated by viscosity at a shear rate of 10 s ⁇ 1 and D50. A viscosity of 100 mPa ⁇ s or less was judged to be "good dispersibility," and a D50 of 0.3 ⁇ m or less was judged to be "good dispersibility.”
• the evaluation results are shown in Table 28.
• Comparative Example 4 it was not possible to make an aqueous dispersion with a concentration of 30%, whereas in all Examples except E-25, the concentration could be adjusted to 30%, and the evaluated CNTs and organic pigments It showed good dispersibility.
• a polyamide with the highest acid value (highly hydrophilic) among P-1 to P-4 was used, but the hydrophilicity was insufficient.
• E-25 which has 18 carbon atoms at the terminal (R 3 ), it was not possible to make a 30% aqueous dispersion, but it was possible to test a 10% aqueous dispersion.
• the CNT dispersion performance of E-25 was slightly inferior to that of the others, and the preferable result was that the number of terminal carbons (R 3 ) was 1.

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