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WO2024165520A1 - Pud transparent et son application - Google Patents

Pud transparent et son application Download PDF

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Publication number
WO2024165520A1
WO2024165520A1 PCT/EP2024/052828 EP2024052828W WO2024165520A1 WO 2024165520 A1 WO2024165520 A1 WO 2024165520A1 EP 2024052828 W EP2024052828 W EP 2024052828W WO 2024165520 A1 WO2024165520 A1 WO 2024165520A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
polyurethane
component
dispersion
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2024/052828
Other languages
English (en)
Inventor
Ying Dan Zhu
Jan Weikard
Yi Hu
Deyong ZHU
Fei Xu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/CN2023/074895 external-priority patent/WO2024164160A1/fr
Priority claimed from EP23163907.1A external-priority patent/EP4435029A1/fr
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Priority to CN202480011087.4A priority Critical patent/CN120659819A/zh
Priority to EP24703373.1A priority patent/EP4662256A1/fr
Publication of WO2024165520A1 publication Critical patent/WO2024165520A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • 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

Definitions

  • the present invention relates an aqueous dispersion comprising at least one polyurethane, wherein the at least one polyurethane is prepared from at least the following components (A) at least one polyisocyanate, (B) at least one polymeric polyol having a number average molecular weight of 400 to 6000 g/mol, wherein at least one polycarbonate polyol is present in the polymeric polyol component (B) in an amount of 55 to 100% by weight, based on total weight of component (B), (C) optionally at least one monofunctional nonionic hydrophilizing agent, (D) at least one compound selected from the group consisting of polyols, aminopolyols, polyamines and mixtures thereof, in each case having a number average molecular weight of less than 400 g/mol, (E) at least one compound selected from the group consisting of monools, diols, polyols, monoamines, diamines, polyamines and mixtures thereof, in each case having at least one salt group
  • Good wet colour matching means that the colour difference between a paint film in wet condition and the colour of a paint film in dry condition is as close as possible.
  • a good wet colour matching is for example helpful in body shops to improve efficiency.
  • the key step is colour comparing or colour matching, i.e. a comparison between the paint that has been mixed in order to repair the exterior of a car and the corresponding colour of the car.
  • Solventbome paint formulations normally have better wet colour matching performance than waterborne ones. However, along with more and more strict restriction on VOC for paint makers, there is an increasingly obvious trend of transfer from solventbome to waterborne paint formulations. If a waterborne paint formulation has excellent wet colour matching performance, painters can save more than two hours on average by skipping time waiting for water evaporation.
  • the synthesis process of some polyurethane dispersions known from the prior comprises the use of solvents like N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP) to obtain a product wherein the polyurethane particles have a reduced particle size and the polyurethane dispersion itself has a lower viscosity.
  • solvents like N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP)
  • Objective of the present invention is therefore to provide a polyurethane dispersion which is essentially free of any organic solvents, in particular free of organic solvents being prohibited to be used in consumer products.
  • the polyurethane dispersion shall have both improved wet colour matching and lower odour, in particular compared to the polyurethane dispersions known from the prior art.
  • an aqueous dispersion comprising at least one polyurethane, wherein the at least one polyurethane is prepared from at least the following components:
  • (B) at least one polymeric polyol having a number average molecular weight of 400 to 6000 g/mol, wherein at least one polycarbonate polyol is present in the polymeric polyol component (B) in an amount of 55 to 100% by weight, based on total weight of component (B),
  • the polyurethane dispersion according to the present invention is described in detail in the following. In the sense of this invention the wording polyurethane means polyurethane and/or polyurethaneurea.
  • the wording “essentially free of any organic solvents” and “free of organic solvents” means the content of organic solvents no more than 1% by weight, based on the total amount of polyurethane dispersion.
  • the polyurethane dispersion according to the present invention comprises at least one polyurethane which is prepared from at least components (A), (B), (C), (D), (E) and (F) as mentioned above.
  • the at least one polyurethane which is used according to the present invention may comprise further components.
  • the at least one polyurethane used according to the present invention does not comprise further components beside components (A), (B), optionally (C), (D), (E) and (F), i.e. the at least one polyurethane which is used according to the present invention consists of (A), (B), optionally (C), (D), (E) and (F).
  • At least one polyisocyanate is used as component (A).
  • any polyisocyanate known to the skilled artisan can be used according to the present invention.
  • a mixture of at least two different polyisocyanates is used according to the present invention.
  • the at least one polyisocyanate is in general an organic compound having at least two isocyanate groups.
  • the at least one polyisocyanate which is used according to the present invention is therefore preferably selected from the group consisting of diisocyanates having the general formula Y(NCO)2.
  • Y is a C4-12 divalent aliphatic hydrocarbon group, i.e. an aliphatic diisocyanate compound, a C6-15 divalent alicyclic hydrocarbon group, i.e. an alicyclic diisocyanate compound, a C6-15 divalent aromatic hydrocarbon group, i.e. an aromatic diisocyanate compound, or a C7-15 divalent araliphatic hydrocarbon group, i.e. an araliphatic diisocyanate compound.
  • organic diisocyanate compounds include tetramethylene diisocyanate, methylpentamethylene diisocyanate, 1,5 -pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,2- bis(isocyanatomethyl)cyclohexane, 1 ,4-diisocyanatocyclohexane, 1 -isocyanato-3 ,3,5 -trimethyl -5 - isocyanatomethylcyclohexane (IPDI, isophorone diisocyanate), 4,4'- diisocyanatodicyclohexylmethane, 4,4'-diisocyanatodicyclohexylpropane-(2,2), 1 ,4- diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotolu
  • the at least one polyisocyanate which is used according to the present invention may also be a polyisocyanate having three or more isocyanate groups per molecule.
  • organic polyisocyanate compounds can be exemplified by polyisocyanate, which is, for example, prepared by modification of aliphatic, alicyclic, araliphatic and/or aromatic diisocyanate, composed of at least two types of diisocyanate, and has an uretdione, isocyanurate, urethane, allophanate, biuret, carbodiimide, iminooxadiazinedione and/or oxadiazinetrione structure.
  • An example of unmodified polyisocyanate having three or more isocyanate groups per molecule includes 4-isocyanatomethyl-l,8-octane diisocyanate (nonane triisocyanate).
  • the at least one polyisocyanate is selected from the group consisting of hexamethylene diisocyanate (HDI), l-isocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexane (IPDI, isophorone diisocyanate), 4,4'-diisocyanatodicyclohexylmethane (Desmodur® W), and mixtures thereof.
  • HDI hexamethylene diisocyanate
  • IPDI l-isocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexane
  • Desmodur® W 4,4'-diisocyanatodicyclohexylmethane
  • a mixture of 4,4'-diisocyanatodicyclohexylmethane (Desmodur® W) and 1- isocyanato-3,3,5-trimethyl-5- isocyanatomethylcyclohexane (IPDI, isophorone diisocyanate) is used.
  • Mole ratio of 4,4'-diisocyanatodicyclohexylmethane (Desmodur® W) and l-isocyanato-3,3,5- trimethyl-5- isocyanatomethylcyclohexane (IPDI, isophorone diisocyanate) is preferably from 1: 10 to 10: 1, more preferably from 1 : 6 to 6 : 1.
  • component (A) is present in the polyurethane according to the present invention in an amount of 5 to 60% by weight, preferably 10 to 50% by weight, particularly preferably 15 to 45% by weight, in each case in respect of the polyurethane.
  • the polymeric polyol used as component (B) having a molecular weight of 400 to 6000 g/mol has at least two isocyanate-reactive hydroxyl groups.
  • Examples of the at least one polymeric polyol compound used according to the present invention are selected from the group consisting of polyether polyols, polyester polyols, polycarbonate polyols, polycarbonate polyester polyols, polylactone polyols, polybutadiene polyols, silicone polyols and mixtures thereof.
  • a preferred component (B) preferably comprises two to four, particularly preferably two to three, most preferably two hydroxyl groups. Moreover, component (B) may also be a mixture of various compounds of such type.
  • polyether polyols examples include cyclic ether polyadducts and polyhydric alcohol condensates.
  • examples of the cyclic ether include styrene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide and epichlorohydrin, and these may be used alone or in combination.
  • Polyester polyols used according to the present invention are preferably polyester polyols having hydroxyl groups at least at both ends of the main chain.
  • examples of the polyester polyol include linear polyester diol and slightly branched polyester polyol. These can be prepared by a known method using aliphatic, alicyclic or aromatic dicarboxylic acids and diols and optionally using polycarboxylic acids and/or highly functional polyols.
  • polylactone polyols used as component (B) are homopolymers or copolymers of lactones, having hydroxyl groups at least at both ends of the main chain.
  • polycarbonate polyols used as component (B) according to the present invention are obtained by the reaction of diols and aryl carbonates, for example, diphenyl carbonate, and/or alkyl carbonates, for example, dimethyl carbonate, wherein said diols is one or more selected from a group consisting of consisting of 1,3 -propanediol, 1,4-butanediol, 1,5 -pentanediol, 1,6-hexanediol and 2,2- dimethyl-l,3-propanediol.
  • polycarbonate polyols obtained from dimethylcarbonate and 1,6- hexanediol are used.
  • the polycarbonate polyol according to the present invention has preferably hydroxyl groups at least at both ends of the main chain, which is produced by adjusting the production conditions of the polycarbonate.
  • At least one polycarbonate polyol is used as component (B) according to the present invention, which is selected from a group consisting of polycarbonate obtained by reaction of dimethyl carbonate with 1,6-hexanediol, polycarbonate obtained by reaction of dimethyl carbonate with 1,6- hexanediol and 1,4-butanediol, and/or a copolymer of polycaprolactone and polycarbonate obtained by reaction of dimethyl carbonate and 1,6-hexanediol.
  • the preferred number average molecular weight of polycarbonate polyester polyol is between 1000 to 4000 g/mol.
  • the at least one polycarbonate polyol is present in the polymeric polyol component (B) in an amount of 55 to 100% by weight.
  • the silicone polyol used as component (B) according to the present invention includes silicone oils having a hydroxyl group at the end having a siloxane bond in the molecule.
  • the at least one polymeric polyol (B) is selected from the group consisting of polycarbonate polyols, polyester polyols, polyether polyols, polycarbonate polycaprolactone polyols and mixtures thereof.
  • the polymeric polyol used as component (B) has a molecular weight of 400 to 6000 g/mol, preferably 800 to 5000 g/mol, more preferably 1000 to 4000 g/mol.
  • component (B) is contained in the polyurethane used according to the present invention by preferably 20 to 85 % by weight, more preferably 25 to 80% by weight, still more preferably 30 to 75% by weight, in each case in respect of the polyurethane.
  • At least one monofunctional nonionic hydrophilizing agent is used as optional component (C).
  • Examples of monofunctional nonionic hydrophilizing agent that can be used as component (C) according to the present invention are selected from the group consisting of polyethylene oxide mono alkyl ether and polyethylene oxide polypropylene oxide copolymer mono alkyl ether; preferred one or more selected from a group comprising of polyethylene oxide mono methyl ether and polyethylene oxide polypropylene oxide copolymer mono methyl ether and mixtures thereof.
  • At least one monofunctional nonionic hydrophilizing agent is present in the polyurethane according to the present invention, it is used in an amount of preferably less than 10% by weight, more preferably less than 5% by weight, based on the solid content of the aqueous polyurethane resin.
  • the lower limit of the amount is in general 0.1 % by weight, based on the solid content of the aqueous polyurethane resin.
  • Monoamines according to the present invention are compounds having one amino or imino group.
  • Examples of the monoamine compound include propylamine, butylamine, amylamine, hexylamine, 1- tetradecylamine and mixtures thereof.
  • Polyamines according to the present invention are compounds having two or more amino and/or imino groups.
  • the polyamine compound include triamine compounds such as diethylenetriamine, bis(2-aminopropyl)amine and bis(3-aminopropyl)amine, tetramine compounds such as triethylenetetramine, tripropylenetetramine, N-(benzyl)triethylenetetramine, N,N'- (dibenzyl)triethylenetetramine and N-(benzyl)-N"'-(2-ethylhexyl)triethylenetetramine, pentamine compounds such as tetraethylenepentamine and tetrapropylenepentamine, hexamine compounds such as pentaethylenehexamine and pentapropylenehexamine, and polyamine compounds such as polyethyleneimine and polypropyleneimine, and mixtures thereof.
  • polyamine is preferably polyamine having two amino groups and one or more imino groups, such as diethylenetriamine, triethylenetetramine, bis(2-aminopropyl)amine, bis(3- aminopropyl)amine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine or pentapropylenehexamine.
  • imino groups such as diethylenetriamine, triethylenetetramine, bis(2-aminopropyl)amine, bis(3- aminopropyl)amine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine or pentapropylenehexamine.
  • diamine compounds which can be used as component (D) include hydrazine, 1,2- ethanediamine, 1,4-tetramethylenediamine, 2 -methyl- 1,5 -pentanediamine, 1,6- hexamethylenediamine, 1,4-hexamethylenediamine, 3- aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3- bis(aminomethyl)cyclohexane, xylylenediamine, piperazine, 2,5 -dimethylpiperazine and mixtures thereof.
  • Monools according to the present invention are compounds having one hydroxyl groups.
  • Examples of monool compounds which can be used as component (D) include butyl glycol, diethylene glycol monobutylether, di(propylene glycol)butyl ether and mixtures thereof.
  • Polyols according to the present invention are compounds having two or more hydroxyl groups.
  • polyol compounds which can be used as component (D) include ethanediol, diethylene glycol, triethylene glycol and tetraethylene glycol, 1,2-propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,3 -propanediol, 1,4-butanediol, 1,3 -butanediol, 2,3-butanediol, 1,5- pentanediol, 1,6-hexanediol, 2,2- dimethyl- 1,3 -propanediol, 1,4-dihydroxycyclohexane, 1,4- dimethylcyclohexane, 1,8 -octanediol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glyco
  • Aminopolyols according to the present invention are organic compounds having one or more hydroxyl groups and one or more amino groups.
  • aminopolyols which can be used as component (D) include ethanolamine, propanolamine, butylethanolamine, l-amino-2 -methyl -2 -propanol, 2-amino-2-methylpropanol, diethanolamine, diisopropanolamine, dimethylaminopropylethanolamine, dipropanolamine, N-methylethanolamine, N-ethylethanolamine and mixtures thereof
  • one type may be used alone, or a plurality of types may be used in combination as component (D).
  • the amount of component (D) is preferably not more than the equivalent of the residual isocyanate group obtained after the reaction of polyisocyanate and polyol.
  • the amount of the reactive groups in component (D) is preferably 0.6 to 0.99 equivalent of the residual isocyanate group.
  • At least one compound selected from the group consisting of monools, diols, polyols, monoamines, diamines, polyamines and mixtures thereof, in each case having at least one salt group, preferably an anionic group, or a functional group that can be converted into a salt group, preferably into a anionic group is used as component (E).
  • the at least one salt group present in component (E) is preferably at least one acidic group.
  • the at least one acidic group can be selected from a carboxylic acid group or a sulfonic acid group.
  • Component (E) is preferably a compound having at least two or more hydroxy groups and/or two or more amino groups. Preferably at least one compound having at least two or more hydroxy groups is used a s component (E).
  • a combination of at least one carboxylic acid group-containing compound and at least one sulfonic acid group-containing compound may be used.
  • at least one carboxylic acid group- containing compound is used as component (E).
  • Component (E) is preferably present in the at least one polyurethane used according to the present invention in an amount that the total weight of the carboxylic acid group-containing compound and/or the sulfonic acid group-containing compound is preferably 0.5 to 10% by weight, more preferably 1 to 7% by weight, in each case in respect of the polyurethane.
  • the ratio of an acid value of the carboxylic acid group to the total acid value in the component (E) is preferably 0.20 to 1.00, more preferably 0.50 to 1.00, still more preferably 0.70 to 1.00.
  • the acid value herein refers to a calculated value (mgKOH/g) expressed in the number of mg of potassium hydroxide required to neutralize the carboxyl group or the sulfo group present in the polyurethane resin.
  • the total acid value refers to the sum total of the acid value of the carboxyl group and the acid value of the sulfo group.
  • component (E) is selected one or more from the group consisting of 2,2- dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N,N- bishydroxyethylglycine, N,N- bishydroxyethylalanine, 3,4- dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, 2-[(2-aminoethyl)amino]ethanesulphonic acid and their salts, and mixtures thereof.
  • the at least one neutralizer with boiling point higher than 100 °C at atmospheric pressure. is in general used to neutralize at least some of the acidic groups of the polyurethane prepolymer and disperse the polyurethane prepolymer in the aqueous medium.
  • tertiary amine compounds such as trialkylamines preferably include N,N-diisopropylethylamine, tributylamine and the like, N,N- dialkylalkanolamines including N,N-dimethylethanolamine, N,N-dimethylpropanolamine, N,N- dipropylethanolamine, l-dimethylamino-2 -methyl -2 -propanol and the like, N-alkyl-N,N- dialkanolamines, and trialkanolamines including triethanolamine, inorganic alkali salts of potassium hydroxide, sodium hydroxide and the like. These may be used alone or in combination of two or more.
  • the neutralizer is preferably organic amines, more preferably N,N-dimethylethanolamine or N,N-diisopropylethylamine.
  • the amount of the neutralizer is, for example, 0.4 to 1.2 equivalent, preferably 0.6 to 1.0 equivalent per equivalent of acidic groups possessed by the aqueous polyurethane resin composition.
  • Component (F) is preferably present in the at least one polyurethane used according to the present invention in an amount of 1 to 10% by weight, more preferably 1.5 to 8 % by weight, in each case in respect of the polyurethane.
  • the amounts of components (A), (B), optionally (C), (D), (E) and (F) add up to 100% by weight in each case.
  • the polyurethane dispersion according to the present invention comprises the at least one polyurethane in general in an amount of 20 to 60 % by weight, preferably 25 to 50% by weight, particularly preferably 30 to 40 % by weight, in each case in respect of the polyurethane dispersion.
  • This solid content is measured by Metteler Teredo Halogen Moisture Analyzer Excellence HS153 at 120 °C.
  • the polyurethane present in the polyurethane dispersion according to the present invention has an average particle size of in general 25 to 70 run, preferably 30 to 60 run, particularly preferably 30 to 55 nm.
  • the polyurethane dispersion according to the present invention has an average particle diameter D(i)90 in the range of 20 nm to 95 nm, preferably in the range of 50 nm to 90 nm.
  • This average particle diameter is tested by Malvern Zetasizer Nano ZS particle analyzer at 23 °C.
  • Average particle size refers to Z-A verage size used in dynamic light scattering defined in ISO 13321: 1996.
  • D(i)90 signifies the point in the size distribution, up to and including which, 90% of the total intensity of material in the sample is ‘contained’.
  • Average particle size and D(i)90 [nm] was measured as follows: 1 drop (about 0.05 g) PUD was added to 50 mb ultrapure water.
  • Diluted sample was tested by Malvern Zetasizer Nano ZS particle analyser at 23.0 ⁇ 0.1 °C.
  • Material polystyrene latex (RI: 1.590; Absorption: 0.010), dispersant: water (temperature: 23.0 °C; viscosity: 0.9308 cP; RI: 1.330), equilibration time: 60 seconds, cell type: Disposable cuvettes DTS0012, positioning method: automatic attenuation selection, seek for optimum position: yes, analysis model: general purpose (normal resolution), measurement angel: 173° Backscatter (NIBS default), number of runs: 3, run duration: 10 seconds, number of measurements: 10.
  • Average particle size refers to Z-Average size used in dynamic light scattering defined in ISO 13321: 1996.
  • D(i)90 signifies the point in the size distribution, up to and including which, 90% of the total intensity of material in the sample is ‘contained’.
  • the average particle diameter D(i)90 gives rise to the technical effect according to the present invention and to the solution of the objectives according to the present invention. If the average particle diameter D(i)90 is less than or equal to 100 nm, in particular in the range of 20 nm to 95 nm, the wet colour matching of a coating composition comprising this polyurethane dispersion is significantly improved.
  • the polyurethane dispersion according to the present invention has a viscosity of in general 50 to 1500 mPa s, preferably 70 to 1500 mPa s, particularly preferably 80 to 1200 mPa s. This viscosity is measured according to tested by Brookfield DV-II+ Pro viscometer at room temperature (23 ⁇ 2 °C), using spindle S62 at rotation speed 30 rpm according to ISO 3219: 1994.
  • the polyurethane dispersion according to the present invention has an average transmittance of in general more than 30%, preferably 40 to 99%, particularly preferably 55 to 99%. This average transmittance is tested by UV-2600 UV-VIS spectrophotometer (SHIMADZU, Japan) of light wavelength in the range between 420 nm and 700 nm at 23 °C.
  • UV-2600 UV-VIS spectrophotometer SHIMADZU, Japan
  • the average molecular weight of the polyurethane resin in the aqueous polyurethane resin composition of the present invention is not particularly limited and can be selected in a range that gives dispersibility and a good coating film as an aqueous coating material, which is preferably 5000 to 500000 g/mol, more preferably 10000 to 100000 g/mol.
  • the average molecular weight of the polyurethane resin is a number average molecular weight measured by gel permeation chromatography, and polystyrene is used as a standard substance.
  • the acid value of the carboxylic acid groups in the polyurethane in the aqueous polyurethane dispersion according to the present invention is preferably in the range from 4.5 to 30 mg KOH/g, more preferably in the range from 5 to 28 mg KOH/g, still more preferably in the range from 10 to 25 mg KOH/g.
  • the acid value of the resin means the number of mg of potassium hydroxide required to neutralize 1 g of the resin.
  • the acid value is a value measured in accordance with the indicator titration method of JIS K 1557:2007.
  • the hydroxyl value of the polyol in the aqueous polyurethane dispersion according to the present invention is not particularly limited, but is usually in the range from 1 to 100 mg KOH/g.
  • the hydroxyl value of the resin means the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl groups in 1 g of the polyol.
  • the hydroxyl value is a value measured in accordance with the indicator titration method of Method B of JIS K 1557:2007.
  • the polyurethane dispersion according to the present invention is an aqueous dispersion, which does not comprise any organic solvents.
  • the upper limit of the content of organic solvent in the polyurethane dispersion according to the present invention is 1% by weight.
  • the inventors of the present invention have surprisingly found that the polyurethane dispersion according to the present invention has a low viscosity even without the presence of an organic solvent.
  • the present invention further relates to the process for the preparation of the polyurethane dispersion according to the present invention, at least comprising the following steps: a. Charging a reaction vessel with at least one polymeric polyol (B) and optionally monofunctional nonionic hydrophilizing agent (C), optionally removing contained water below 0.2% by weight, preferably below 0.1% by weight, of the precharged mixture by increasing temperature and/or reducing pressure and/or purging with nitrogen under agitation, b. Charging a reaction vessel with part of or all amount of component (D) and/or part or all amount of component (E), c.
  • step d or e Before or after step d or e, adding at least one neutralizer, and g. Before, during or after step e, adding water to obtain the aqueous polyurethane-urea dispersion, h. Removing solvent, preferably by distillation.
  • the solvent that is miscible with water but inert to the isocyanate group is preferably selected from the group consisting of acetone, methyl ethyl ketone (MEK), propylene glycol dimethyl ether, any other ether/ester which have no OH functional group and mixtures thereof.
  • the step of neutralizing the acidic groups and the step of dispersing the polyurethane prepolymer in the aqueous medium may be performed separately or together.
  • the step of reacting the polyurethane prepolymer with the compound (D) may be after the step of dispersing the polyurethane prepolymer in the aqueous medium or may be performed together with the step of dispersing the polyurethane prepolymer in the aqueous medium.
  • Each step in the process for producing the aqueous polyurethane resin composition may be performed under an inert gas atmosphere or may be performed in the atmosphere.
  • the aqueous polyurethane dispersion can contain a neutralizer with boiling point higher than 100 °C at atmospheric pressure.
  • the neutralizer is used to neutralize at least some of the acidic groups of the polyurethane prepolymer and disperse the polyurethane prepolymer in the aqueous medium.
  • neutralizer examples include tertiary amine compounds such as trialkylamines including N,N- diisopropylethylamine, tributylamine and the like, N,N-dialkylalkanolamines including N,N- dimethylethanolamine, N,N-dimethylpropanolamine, N,N-dipropylethanolamine, 1-dimethylamino- 2-methyl-2-propanol and the like, N-alkyl-N,N-dialkanolamines, and trialkanolamines including triethanolamine, inorganic alkali salts of potassium hydroxide, sodium hydroxide and the like. These may be used alone or in combination of two or more.
  • trialkylamines including N,N- diisopropylethylamine, tributylamine and the like
  • N,N-dialkylalkanolamines including N,N- dimethylethanolamine, N,N-dimethylpropanolamine, N,N-diprop
  • the neutralizer is preferably organic amines, more preferably N,N-dimethylethanolamine or N,N- diisopropylethylamine.
  • the amount of the neutralizer is, for example, 0.4 to 1.2 equivalent, preferably 0.6 to 1.0 equivalent per equivalent of acidic groups possessed by the aqueous polyurethane resin composition.
  • the aqueous polyurethane dispersion according to the present invention can be further mixed with a solvent.
  • the solvent is one or more selected from a group consisting of: butyl glycol, butyl diglycol ethanol, l-methoxy-2 -propanol, dipropylene glycol monomethyl ether, propylene glycol butyl ether, di(propylene glycol) butyl ether and mixtures thereof.
  • the amount of this solvent s preferably 10 to 25% by weight, based on the amount of the PUD as 100% by weight.
  • the temperature of water introduced in step g is controlled and preferably set to a temperature between 0 and 40 °C, more preferably between 2 and 30 °C and especially preferred between 5 and 20 °C.
  • step g It is also beneficial to control the ionic content of the water added in step g which can be done by measuring conductivity or hardness of the water using established testing or measuring methods.
  • a low conductivity and low ion concentration is preferred as can be achieved for example by running the tab water through ion exchange resins.
  • the preferred conductivity of the water is below 0.2 pS/cm.
  • the present invention further relates to the coating formulation comprising at least one aqueous dispersion according to the present invention.
  • the present invention also relates to the use of the aqueous dispersion according to the present invention in a coating formulation.
  • the present invention also relates to the process for the coating of a substrate, wherein a coating formulation comprising the aqueous dispersion according to the present invention is used.
  • the present invention also relates to the use of a coating formulation according to the present invention for coating of a substrate.
  • the present invention also relates to a substrate coated with a coating formulation according to the present invention.
  • the coating composition can be a painting composition or an ink composition.
  • aqueous polyurethane dispersion In addition to the aqueous polyurethane dispersion, another resin may be added to the coating composition of the present invention.
  • Examples of another resin include a polyester resin, an acrylic resin, a polyether resin, a polycarbonate resin, a polyurethane resin, an epoxy resin, an alkyd resin, a polyolefin resin, a vinyl chloride resin and the like. These may be used alone or in combination of two or more. From the viewpoint of dispersibility in water, another resin preferably has one or more types of hydrophilic groups.
  • the hydrophilic groups include a hydroxyl group, a carboxy group, a sulfo group, a polyethylene glycol group and the like.
  • the polyester resin can be usually produced by esterification or transesterification between an acid component and an alcohol component.
  • an acid component a compound normally used as an acid component to produce a polyester resin can be used.
  • an aliphatic polybasic acid, an alicyclic polybasic acid, an aromatic polybasic acid or the like can be used as the acid component.
  • the acrylic resin is preferably a hydroxyl group- containing acrylic resin, for example.
  • the hydroxyl group- containing acrylic resin can be produced by a known method such as, for example, a solution polymerization method in an organic solvent or an emulsion polymerization method in water, in which a hydroxyl group-containing polymerizable unsaturated monomer is copolymerized with another polymerizable unsaturated monomer copolymerizable with the hydroxyl group-containing polymerizable unsaturated monomer.
  • the hydroxyl group-containing polymerizable unsaturated monomer is a compound having one or more hydroxyl group and one or more polymerizable unsaturated bond in one molecule.
  • examples thereof include: monoesterified products from a (meth)acrylic acid and a dihydric alcohol having 2 to 8 carbon atoms, such as 2- hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3- hydroxypropyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate; caprolactone modified products of these monoesterified products; N-hydroxymethyl (meth)acrylamide; allyl alcohol; (meth)acrylate having a polyoxyethylene chain with a hydroxyl group at the molecular end; and the like.
  • the hydroxyl group-containing acrylic resin preferably has an anionic functional group.
  • the hydroxyl group-containing acrylic resin having an anionic functional group can be produced by, for example, using a polymerizable unsaturated monomer having an anionic functional group such as a carboxylic acid group, a sulfonic acid group or a phosphoric acid group as one type of the polymerizable unsaturated monomer.
  • polyether resin examples include a polymer or copolymer having an ether bond, such as polyoxyethylene-based polyether, polyoxypropylene-based polyether, polyoxybutylene-based polyether, polyether derived from an aromatic polyhydroxy compound including bisphenol A, bisphenol F or the like, and the like.
  • polycarbonate resin examples include polymers produced from bisphenol A, 3-methyl-l,5- pentanediol and 1,6-hexanediol.
  • Examples of the epoxy resin include a resin obtained by reaction of a bisphenol compound with epichlorohydrin, and the like.
  • Examples of the bisphenol include bisphenol A and bisphenol F.
  • alkyd resin examples include alkyd resins obtained, for example, by reacting a polybasic acid such as phthalic acid, terephthalic acid or succinic acid and polyhydric alcohol further with a modifier such as fat and oil/fat and oil acid, e.g. soybean oil, flaxseed oil, palm oil, stearic acid or the like, or a natural resin, e.g. rosin, succinite or the like.
  • a polybasic acid such as phthalic acid, terephthalic acid or succinic acid and polyhydric alcohol further with a modifier such as fat and oil/fat and oil acid, e.g. soybean oil, flaxseed oil, palm oil, stearic acid or the like, or a natural resin, e.g. rosin, succinite or the like.
  • the polyolefin resin examples include a resin obtained by subjecting a polyolefin resin, which is obtained by polymerizing or copolymerizing an olefin-based monomer with another monomer in accordance with a normal polymerization method as appropriate, to water dispersion using an emulsifier or by emulsion polymerization of an olefin-based monomer together with another monomer as appropriate.
  • a so-called chlorinated polyolefin-modified resin which is obtained by chlorinating the polyolefin resin, may be used.
  • olefin-based monomer examples include olefins such as ethylene, propylene, 1-butene, 3- methyl-1- butene, 4-methyl-l -pentene, 3-methyl-l-pentene, 1-heptene, 1-hexene, 1-decene and 1- dodecne; and conjugated dienes and nonconjugated dienes such as butadiene, ethylidene norbomene, dicyclopentadiene, 1,5-hexadiene and styrenes. These monomers may be used alone or in combination of two or more.
  • Examples of another monomer copolymerizable with the olefin-based monomer include vinyl acetate, vinyl alcohol, maleic acid, citraconic acid, itaconic acid, maleic anhydride, citraconic anhydride and itaconic anhydride.
  • These monomers may be used alone or in combination of two or more.
  • the coating composition according to the present invention can further include a curing agent.
  • a curing agent By including a curing agent, it is possible to improve the durability of a painting fdm, a multilayer painting fdm, a coating fdm or a printed matter obtained by using the coating composition.
  • polyisocyanate blocked polyisocyanate, melamine resin, carbodiimide, oxazoline, aziridine, hydrazine or the like can be used as the curing agent.
  • curing agents may be used along or in combination of two or more.
  • the polyisocyanate is not particularly limited as long as the polyisocyanate has two or more isocyanate groups in the molecule, and examples thereof include those the same as those exemplified as the polyisocyanate compounds (a).
  • the blocked polyisocyanate is not particularly limited as long as the blocked polyisocyanate has two or more block isocyanate groups in the molecule, and examples thereof include the polyisocyanate compounds or compounds obtained by giving hydrophilicity to the polyisocyanate compounds blocked by a known blocking agent, like phenols, secondary or tertiary alcohols, oximes, aliphatic or aromatic secondary amines, phthalic imides, lactams, an active methylene compound, e.g. malonic acid dialkyl ester or the like, a pyrazole-based compound, e.g. pyrazole, 3,5-dimethylpyrazole or the like, acidic sodium sulfite, and the like.
  • a known blocking agent like phenols, secondary or tertiary alcohols, oximes, aliphatic or aromatic secondary amines, phthalic imides, lactams, an active methylene compound, e.g. malonic acid dialkyl ester or the like,
  • the melamine resin is not particularly limited, and one normally used as a curing agent can be used.
  • the melamine resin is preferably an alkyl etherified melamine resin obtained by alkyl etherification, more preferably a melamine resin substituted with a methoxy group and/or a butoxy group.
  • Such a melamine resin includes: those having a methoxy group alone, such as Cymel 325, Cymel 327, Cymel 370 and My Coat 723; those having both a methoxy group and a butoxy group, such as Cymel 202, Cymel 204, Cymel 211, Cymel 232, Cymel 235, Cymel 236, Cymel 238, Cymel 251, Cymel 254, Cymel 266, Cymel 267 and Cymel 285 (all of them are trade names, manufactured by Nippon Cytec Industries, Ltd.); and those having a butoxy group alone, such as My Coat 506 (a trade name, manufactured by Mitsui-Cytec Ltd.), U-VAN 20N60 and U-VAN 20SE (all of them are trade names, manufactured by Mitsui Chemicals, Inc.).
  • the carbodiimide is not particularly limited as long as the carbodiimide is a compound having two or more carbodiimide groups in the molecule.
  • aliphatic polycarbodiimide poly(hexamethylenecarbodiimide) and the like]
  • alicylic polycarbodiimide poly(4,4'- dicyclohexylmethanecarbodiimide) and the like
  • aromatic polycarbodiimide poly(p- phenylenecarbodiimide), poly(4,4'-diphenyhnethanecarbodiimide), poly(diisopropylphenyl- carbodiimide) and the like
  • aromatic polycarbodiimide poly(p- phenylenecarbodiimide), poly(4,4'-diphenyhnethanecarbodiimide), poly(diisopropylphenyl- carbodiimide) and the like
  • Carbodilite V-01 “Carbodilite V-02”, “Carbodilite V-03”, “Carbodilite V-04”, “Carbodilite V-05”, “Carbodilite V-07”, “Carbodilite V-09”, “Carbodilite E-02”, “Carbodilite E- 03A”, “Carbodilite E-04”, each manufactured by Nisshinbo Chemical Inc., and the like can be listed as commercially available products.
  • the oxazoline is not particularly limited as long as the oxazoline is a compound having two or more oxazoline groups (oxazoline backbone) in the molecule.
  • examples thereof include: a compound having two or more oxazoline groups, such as 2,2'-isopropylidenebis(4-phenyl-2- oxazoline); a (co)polymer of polymerizable oxazoline compounds such as 2-isopropenyl-2 -oxazoline, 2 -vinyl-2 - oxazoline and 2-vinyl-4-methyl-2-oxazoline; a copolymer of the polymerizable oxazoline compounds and a copolymerizable monomer that does not react with the oxazoline groups [(meth)acrylic esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, hydroxyethyl (meth)acrylate and polyethylene glycol (meth)
  • the aziridine is not particularly limited as long as the aziridine is a compound having two or more aziridinyl groups in the molecule. Examples thereof include tetramethylolmethane tris(aziridinylpropionate) and trimethylolpropane tris(aziridinylpropionate).
  • the hydrazine include hydrazine and compounds having two or more hydrazine groups (hydrazine backbone) in the molecule [e.g., dicarboxy lie acid dihydrazide having 2 to 10 carbon atoms (oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, itaconic acid dihydrazide and the like) and alkylene dihydrazine having 2 to 10 carbon atoms (ethylene dihydrazine, 1,3-propylene dihydrazine, 1,4-butylene dihydrazine, 1,6-hexylene dihydrazine or the like)]
  • a color pigment, an extender pigment and a bright pigment can be added to the coating composition of the present invention.
  • color pigment examples include titanium oxide, zinc white, carbon black, iron oxide yellow, iron oxide red, molybdenum red, Prussian blue, cobalt blue, azo pigment, phthalocyanine pigment, quinacridone pigment, isoindoline pigment, selenium-based pigment, perylene pigment and the like.
  • the extender pigment examples include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica and alumina white. It is preferable to use barium sulfate and/or talc as the extender pigment, and barium sulfate is more preferably used. These may be used alone or in combination of two or more.
  • aluminum, copper, zinc, brass, nickel, aluminum oxide, mica, aluminum oxide coated with titanium oxide or iron oxide, or mica coated with titanium oxide or iron oxide can be used as the bright pigment.
  • the coating composition of the present invention can contain ordinary additives, such as a thickener, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, a plasticizer, a surface conditioner and an antisettling agent, depending on the function or use thereof. These may be used alone or in combination of two or more, or a commercially available product may be used as it is.
  • a process for producing the coating composition of the present invention is not particularly limited and can adopt a known production method.
  • the coating compositions are suitably produced by mixing the aqueous polyurethane dispersion with various resins and additives mentioned above, further adding the aqueous medium, and adjusting the viscosity for the application method.
  • the present invention therefore also relates to a process for the production of the coating composition according to the present invention by mixing the aqueous polyurethane dispersion according to the present invention with suitable resins and additives, further adding the aqueous medium, and adjusting the viscosity.
  • Suitable substrates to which the coating composition according to the present invention can be applied include: metal materials usually used for automobile bodies or parts, road materials, building materials for home, and the like, e.g., an electrodeposition-coated steel sheet, a phosphated steel sheet, a galvanized steel sheet, a cold rolled steel sheet, an aluminum sheet, a stainless sheet, a zinc phosphate treated steel sheet, an iron phosphate treated steel sheet and the like, or plastic materials such as polyurethane, polycarbonate, polybutylene terephthalate, polyamide, polyphenylene oxide, an acrylonitrile/butadiene/styrene copolymer, i.e., ABS resin, polypropylene and unsaturated polyester, generally abbreviated as SMC.
  • SMC polypropylene and unsaturated polyester
  • the substrates may be used as they are or may be subjected to surface treatment such as degreasing or primer painting and/or intermediate painting. These treatments may be performed alone or in combination of two or more.
  • the coating film portion requiring a repair to solvent cleaning or sanding treatment and then paint.
  • the coating composition according to the present invention may be adjusted, before use, to have a specific viscosity which is suitable for a conventional coating method such as air spray, airless spray or electrostatic coating or for obtaining a desired film thickness.
  • aqueous painting composition is preferably adjusted, before use, to have a solid content of about 10 to 40% by weight and a viscosity of about 800 to 5.000 nr Pas (measured with a B-type viscometer) by adding deionized water and, if necessary, additives such as a thickener and an antifoaming agent.
  • the aforementioned suitable substrates may be coated with a monocoat of the coating composition according to the present invention, but an intermediate coating material can be applied, by a so-called wet-on-wet method or a wet-on-wet method after preheating, on the applied coating material of the coating composition according to the present invention.
  • top coating can be performed by a wet-on-wet method or a wet-on-wet method after preheating.
  • Preheating is a method for heating at 40 to 80 °C for 5 to 60 minutes, for example, at 80 °C for 5 minutes, and is performed by hot air heating, infrared irradiation or the like.
  • the dry film thickness of the coating composition used for coating may vary depending on the coating method or the necessity but may be usually about 10 to 50 pm.
  • the applied coating composition is then completely or incompletely dried by settings at room temperature, air drying or dried by the forced drying using hot air drying or an infrared heater or the like, or in some cases, is completely or incompletely cured by being baked at a temperature of not more than 120 °C to obtain an aqueous coating film.
  • aqueous polyurethane dispersion according to the present invention has good fluidity even when the composition has a high solid content, a coating material using the composition has good finished appearance.
  • the adhesion of the coating film using the composition to the substrate is good, and excellent impact resistance is given even in a single coating (monocoat) system and a multilayer coating system.
  • the aqueous polyurethane dispersion according to the present invention is suitable as a raw material for an aqueous coating material to coat an electrodeposition film.
  • a particular advantage of the polyurethane dispersion according to the present invention is that the wet colour matching is improved so that in case that, for example, automobile bodies or parts, have to be repaired, a significant amount of time can be saved, because there is no need to let the coating dry before evaluation, if the premixed colour is the colour of the automobile.
  • Polyester I a polyester diol comprising 1,6-hexanediol, neopentyl glycol and adipic acid, OH value 66, number-average molecular weight 1700 g/mol, commercially available from Covestro AG, Germany.
  • Polyether LB 25 a mono-hydroxyl functional polyether, number-average molecular weight 2250 g/mol, commercially available from Covestro AG, Germany.
  • Desmodur® H 1,6-hexamethylene diisocyanate, commercially available from Covestro AG, Germany.
  • Desmodur® W dicyclohexylmethane diisocyanate, commercially available from Covestro AG, Germany.
  • Desmodur® I isophorone diisocyanate, commercially available from Covestro AG, Germany.
  • Viscosity 474 mPa s
  • the resulting mixture was added to pre-weighted 765 g of water under stirring.
  • the water temperature was 9 °C.
  • a solution of 2.0 g of DETA, 4.2 g of ethylenediamine and 1.1 g of butylamine in 105.5 g of water was added to the mixture in 5 min .
  • acetone was removed by distillation.
  • the obtained PUD has features as below:
  • Average particle size 52.5 nm
  • Viscosity 9738 mPa s (using spindle S63, 30 rpm)
  • Viscosity 65 mPa s
  • the water temperature was 22.8 °C.
  • a solution of 18.9 g of ethylenediamine in 182.3 g of water was added to the reaction solution.
  • the resulting mixture was vigorously stirred for 20 minutes, and then acetone was removed by distillation.
  • the obtained PUD has features as below:
  • Viscosity 38 mPa s
  • a mixture of 308 g of Desmophen® C 1200, 25 g of dimethylolpropionic acid, 10 g of neopentyl glycol, 1 g of butylglycol and 161 g of acetone was heated to 55 °C and stirred. Then 41 g of Desmodur® W and 93 g of Desmodur® I were added and the mixture was heated to 65 °C. The mixture was stirred at this temperature until an NCO content of 1.8% had been attained. Thereafter, the mixture was cooled down to 60 °C and 12 g of dimethylethanolamine was added. 648 g of this solution were dispersed with vigorous stirring in 812 g of water that had been initially charged at a temperature of 35 °C.
  • the hydroxyl (OH) value of the resin means the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl groups in 1 g of the polyol.
  • the hydroxyl value is a value measured in accordance with the indicator titration method of Method B of JIS K 1557:2007.
  • Molecular weight For measuring the number-average molecular weight and the weight-average molecular weight of polyol or the polyurethane, a gel permeation chromatography is used. The polyol is weighted and dissolved in tetrahydrofuran at a concentration of 8 mg/mL.
  • the aqueous polyurethane dispersion is coated on a polytetrafluoroethylene plate, and the coated plate is naturally dried at room temperature to obtain a dry fdm.
  • An appropriate amount of dry fdm is weighed and dissolved in tetrahydrofuran at a concentration of 8 mg/mL.
  • Transmittance [%]: 3 mL PUD was filled in polystyrene cuvette. Transmittance of the sample was tested using a UV-2600 UV-VIS sepctrophotometer (SHIMADZU, Japan) at 24 ⁇ 1 °C, wavelength range: 420 to 700 nm, scan speed: fast, scan mode: single, slit width: 5.0, accumulation time: 0.1 sec, detector unit: direct.
  • UV-2600 UV-VIS sepctrophotometer SHIMADZU, Japan
  • Average particle size and D(i)90 [nm] 1 drop (about 0.05 g) PUD was added to 50 mL ultrapure water. Diluted sample was tested by Malvern Zetasizer Nano ZS particle analyser at 23.0 ⁇ 0.1 °C.
  • Material polystyrene latex (RI: 1.590; Absorption: 0.010), dispersant: water (temperature: 23.0 °C; viscosity: 0.9308 cP; RI: 1.330), equilibration time: 60 seconds, cell type: Disposable cuvettes DTS0012, positioning method: automatic attenuation selection, seek for optimum position: yes, analysis model: general purpose (normal resolution), measurement angel: 173° Backscatter (NIBS default), number of runs: 3, run duration: 10 seconds, number of measurements: 10.
  • Average particle size refers to Z-Average size used in dynamic light scattering defined in ISO 13321: 1996.
  • D(i)90 signifies the point in the size distribution, up to and including which, 90% of the total intensity of material in the sample is ‘contained’.
  • Solid content [% by weight]: about 1 g PUD was spread on glassfiber filter on top of an aluminum sample pan. Solid content was tested by Metteler Teredo Halogen Moisture Analyzer Excellence HS153. Drying program: standard, drying temperature: 120 °C, switch-off criterion: 5 (1 mg /140 seconds) (keep heating sample at 120 °C and keep weighing, if weight loss in 140 seconds is less than 1 mg, stop testing and record rest weight percentage as result.). Wet colour matching: 13 g Iron oxide yellow paste (commercially available from Axalta Coating System) is well mixed into 87 g of the respective PUD (done with PUD according to example 1, comparative example 4, comparative example 6 and comparative example 7).
  • the obtained formulation is then coated on glass plate by coiled rod, wet film thickness is 120 pm.
  • the wet film is dried at room temperature for 24 hours. Colour difference of the dried film and freshly coated wet film is evaluated visually, possible ratings are excellent, medium and poor. Smaller colour difference means better wet colour matching performance.
  • each test specimen has a dimension of 10 cm * 5 cm;
  • test specimens 4. store the test specimens in a sealed plastic bag for 24 hours;
  • test odour of the sample with Cosmos XP-329IIIR New Cosmos Electric (Shanghai) Co., Etd.) under “Batch Mode”: insert probe into the glass bottle immediately after open its cover, measure and record the value number;

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne une dispersion aqueuse comprenant au moins un polyuréthane, ledit au moins un polyuréthane étant préparé à partir d'au moins les composants suivants : (A) au moins un polyisocyanate, (B) au moins un polyol polymère présentant une masse moléculaire moyenne en nombre de 400 à 6000 g/mol, au moins un polycarbonate polyol étant présent dans le composant polyol polymère (B) à hauteur de 55 à 100 % en poids, sur la base du poids total du composant (B), (C) éventuellement au moins un agent hydrophilisant non ionique monofonctionnel, (D) au moins un composé choisi dans le groupe constitué des polyols, des aminopolyols, des polyamines et leurs mélanges, dans chaque cas ayant une masse moléculaire moyenne en nombre inférieure à 400 g/mol, (E) au moins un composé choisi dans le groupe constitué des monoalcools, des diols, des polyols, des monoamines, des diamines, des polyamines et leurs mélanges, dans chaque cas comprenant au moins un groupe sel, de préférence ou un groupe fonctionnel qui peut être converti en un groupe sel, de préférence en un groupe anionique, (F) au moins un neutralisant choisi dans le groupe constitué des composés amine tertiaire présentant un point d'ébullition supérieur à 100 °C à pression atmosphérique, un alcali inorganique, de préférence l'hydroxyde de potassium, l'hydroxyde de sodium, et leurs mélanges, la ou les dispersions de polyuréthane présentant un diamètre de particules moyen D(i)90 dans la plage de 20 nm à 95 nm et la viscosité de ladite dispersion étant de 50 à 1500 mPa·s, une formulation de revêtement comprenant une telle dispersion aqueuse, l'utilisation de cette dispersion aqueuse dans une formulation de revêtement, le processus de revêtement d'un substrat, une formulation de revêtement comprenant une telle dispersion aqueuse utilisée, l'utilisation de cette formulation de revêtement pour revêtir un substrat et un substrat revêtu de la formulation de revêtement.
PCT/EP2024/052828 2023-02-08 2024-02-06 Pud transparent et son application Ceased WO2024165520A1 (fr)

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CN202480011087.4A CN120659819A (zh) 2023-02-08 2024-02-06 透明pud及其应用
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PCT/CN2023/074895 WO2024164160A1 (fr) 2023-02-08 2023-02-08 Pud transparent et son application
CNPCT/CN2023/074895 2023-02-08
EP23163907.1A EP4435029A1 (fr) 2023-03-24 2023-03-24 Pud transparent et son application
EP23163907.1 2023-03-24

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060240264A1 (en) 2005-04-25 2006-10-26 Bayer Materialscience Ag N-methylpyrrolidone-free polyurethane dispersions based on dimethylolpropionic acid
WO2009076379A1 (fr) * 2007-12-10 2009-06-18 E. I. Du Pont De Nemours And Company Polyuréthanes à groupes de terminaison hydrophile non ionique et dispersions aqueuses de ceux-ci
EP2110396A1 (fr) * 2008-04-18 2009-10-21 Bayer MaterialScience AG Systèmes 1K-PUR en polyuréthanes aqueux ou solubles dans l'eau
WO2016111718A1 (fr) * 2015-01-05 2016-07-14 Rhodia Operations Agents de neutralisation d'amine-imino dialcool pour des compositions de revêtement organique aqueuses à faible teneur en composés volatils et leurs procédés d'utilisation
WO2016166096A1 (fr) 2015-04-13 2016-10-20 Covestro Deutschland Ag Dispersions aqueuses de polyuréthane - polyacrylate

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060240264A1 (en) 2005-04-25 2006-10-26 Bayer Materialscience Ag N-methylpyrrolidone-free polyurethane dispersions based on dimethylolpropionic acid
WO2009076379A1 (fr) * 2007-12-10 2009-06-18 E. I. Du Pont De Nemours And Company Polyuréthanes à groupes de terminaison hydrophile non ionique et dispersions aqueuses de ceux-ci
EP2110396A1 (fr) * 2008-04-18 2009-10-21 Bayer MaterialScience AG Systèmes 1K-PUR en polyuréthanes aqueux ou solubles dans l'eau
WO2016111718A1 (fr) * 2015-01-05 2016-07-14 Rhodia Operations Agents de neutralisation d'amine-imino dialcool pour des compositions de revêtement organique aqueuses à faible teneur en composés volatils et leurs procédés d'utilisation
WO2016166096A1 (fr) 2015-04-13 2016-10-20 Covestro Deutschland Ag Dispersions aqueuses de polyuréthane - polyacrylate
US20180118971A1 (en) 2015-04-13 2018-05-03 Covestro Deutschland Ag Aqueous polyurethane-polyacrylate dispersions

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