WO2019129692A1 - Fluorinate polyacrylate coating composition, the preparation method therefore and use thereof - Google Patents

Fluorinate polyacrylate coating composition, the preparation method therefore and use thereof Download PDF

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Publication number
WO2019129692A1
WO2019129692A1 PCT/EP2018/086524 EP2018086524W WO2019129692A1 WO 2019129692 A1 WO2019129692 A1 WO 2019129692A1 EP 2018086524 W EP2018086524 W EP 2018086524W WO 2019129692 A1 WO2019129692 A1 WO 2019129692A1
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WO
WIPO (PCT)
Prior art keywords
mixture
coating composition
polyol
diol
meth
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/EP2018/086524
Other languages
French (fr)
Inventor
Zheng Shi
Jianhui Wang
Junbiao Lu
Zhenglin Xu
Shili XING
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.)
Akzo Nobel Coatings International BV
Original Assignee
Akzo Nobel Coatings International BV
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
Application filed by Akzo Nobel Coatings International BV filed Critical Akzo Nobel Coatings International BV
Priority to PL18829856T priority Critical patent/PL3732221T3/en
Priority to US16/955,685 priority patent/US11613667B2/en
Priority to RU2020123397A priority patent/RU2795120C2/en
Priority to MX2020006583A priority patent/MX2020006583A/en
Priority to ES18829856T priority patent/ES2913266T3/en
Priority to BR112020012081-2A priority patent/BR112020012081B1/en
Priority to EP18829856.6A priority patent/EP3732221B1/en
Priority to CN201880082397.XA priority patent/CN111511790B/en
Priority to KR1020207018891A priority patent/KR102498083B1/en
Publication of WO2019129692A1 publication Critical patent/WO2019129692A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
    • C08G18/5015—Polyethers having heteroatoms other than oxygen having halogens having fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • 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
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic 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
    • 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
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
    • C08G18/3804—Polyhydroxy compounds
    • C08G18/3812—Polyhydroxy compounds having fluorine atoms
    • 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
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • 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
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy 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
    • 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
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester 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
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

Definitions

  • the invention relates to a coating composition for preparing a durable, stain-resistant, and scratch-resistant coating.
  • the coating composition comprises a fluorinated polyurethane acrylate resin (FPUA) and a polyurethane acrylate resin (PUA) that are curable with ultraviolet (UV) light radiation.
  • FPUA fluorinated polyurethane acrylate resin
  • PUA polyurethane acrylate resin
  • UV ultraviolet
  • the invention further relates to a method for preparing the coating composition, and the use thereof.
  • WO 2015/038454 disclosed a poly fluorine-containing silicone coating for use on glass substrates, wherein a PFPE was added into a coating formulation to improve the lubricating performance and colloidal silica was added into the formulation to improve the anti-scratch performance.
  • WO 2007/121110 disclosed a coating for use on a flooring substrate, comprising a PFPE component to provide the flooring substrate with repellence properties such as water, oil or stain repellence. It is mentioned that the reaction only took place at one end of the molecule chain of the PFPE.
  • US 2013/0084458 disclosed a hard coat agent composition
  • a hard coat agent composition comprising a urethane acrylate, a first fluorine-containing polyether compound having active energy ray reactive group via a urethane bond at each of both ends of molecular chain containing a PFPE group, a second fluorine-containing polyether compound having active energy ray reactive group via a urethane bond at one end of molecular chain containing a PFPE group.
  • the hard coat film is excellent in transparency, anti-stain, lubricating, solvent resistance, scratch resistance and abrasion resistance, as well as in punchability.
  • JP 2009256597 disclosed a urethane acrylate resin containing a PFPE group capable of imparting excellent transparency and anti-fouling properties to the cured film.
  • the present invention provides for a fluorinated resin composition, which, upon curing, is durable and has anti-stain and anti-scratch properties.
  • the composition generally comprises an oligomer prepared from an isocyanate, a diol or polyol, and a monomer that has at least one double bond and at least one hydroxyl group, and/or another oligomer prepared from an isocyanate, a diol or polyol, a fluorinated diol or polyol or a perfluoropolyether containing at least two hydroxyl groups, and a monomer that has at least one double bond and at least one hydroxyl group.
  • the preparation of the fluorinated resin composition is conducted with a one-pot multicomponent synthesis process, wherein multiple components are put together to carry out reactions simultaneously.
  • the process is especially suitable for industrial scale production, and open for adding additive components to further adjust the performance of the prepared composition.
  • the present invention also provides for the relevant oligomers prepared in the synthesis process, as well as the use of said composition or oligomer to form a coating onto a substrate.
  • a coating composition comprises at least two oligomers, wherein the first oligomer is prepared from an isocyanate, a diol or polyol, and a monomer that has at least one double bond and at least one hydroxyl group.
  • the second oligomer is prepared from an isocyanate, a diol or polyol, a fluorinated diol or polyol or a perfluoropolyether containing at least two hydroxyl groups, and a monomer that has at least one double bond and at least one hydroxyl group.
  • the coating composition of the present invention comprises:
  • A represents a diol or polyol structure
  • F represents a fluorinated diol or polyol structure or a perfluoropolyether structure that contains at least two hydroxyl groups, or a mixture thereof
  • B represents a monomer structure that has at least one double bond and at least one hydroxyl group
  • ni, n 2 , n 3 and n 4 are integers, the sum of ni and n 2 is ranging from 0 to 20, the sum of n 3 and n 4 is ranging from 1 to 20.
  • ni, n 2 , n 3 and n of structures (I) and (II) may independently represent any integer within the definition that the sum of ni and n 2 is ranging from 0 to 20, the sum of n 3 and n is ranging from 1 to 20.
  • the weight ratio between the oligomers (I) and (II) in the composition is from 100-0.01 to 0-100, preferably from 90-10 to 10-90, more preferably from 70-30 to 30-70.
  • a coating composition comprising oligomers of the following structures (III) and (IV) is provided.
  • the weight ratio between the oligomers (III) and (IV) in the composition is from 100-0.01 to 0-100, preferably from 90-10 to 10-90, more preferably from 70-30 to 30-70.
  • fluorinated polyacrylate oligomers having the above structures (II) and (IV) are provided.
  • the composition of the present invention is prepared through a one-pot multicomponent synthesis process, and the obtained mixture of oligomers can be used in coating formulations directly, it is possible in some cases that the oligomers are isolated and provided in the form of a pure component, which can be further added into coating formulations, acting as either a main resin component, or an additive component.
  • the double bond density of the monomer B structure may affect anti-stain and anti-scratch properties of the resulting coating.
  • the double bond functionality of the monomer B structure is at least 1 , preferably 3 or 5, and more preferably 5, so as to achieve satisfying anti-stain and anti-scratch properties of the resulting coating.
  • rigid and soft molecules may be introduced into the oligomers of the present invention during the synthesis process.
  • rigid molecules may be added to increase the hardness and durability of the resulting coating film
  • soft molecules may be added to increase the flexibility and elasticity of the coating film, and therefore increase the selfrecovery performance of the resulting coating film.
  • the term“rigid” is meant to be the characteristic of a molecule, with which, the molecule does not tend to bend or flex when receiving a force
  • the term“soft” is meant to be the characteristic of a molecule, with which, the molecule tends to bend or flex when receiving a force.
  • rigid molecules suitable for use in the present invention can be selected from polyols that have a relatively low glass transmission temperature (Tg) value or diols that have a relatively long carbon chain structure; soft molecules suitable for use in the present invention can be selected from polyols that have relatively high Tg or diols that have a ring structure.
  • Tg glass transmission temperature
  • soft molecules suitable for use in the present invention can be selected from polyols that have relatively high Tg or diols that have a ring structure.
  • a skilled person may select proper molecules by setting up standards of Tg values, chain length, etc., as per actual requirements.
  • the isocyanate U structure that is suitable for the present invention is selected from, but not limited to the group consisting of 1 ,6-hexane diisocyanate (HDI), isophoron diisocyanate (IPDI), 4,4’-diphenyl-methane-diisocyanate (MDI), 4,4’-dicyclohexylmethane diisocyanate (HMDI), xylylene diisocyanate (XDI), Tolylene-2, 4-diisocyanate (TDI), and a mixture thereof;
  • HDI 1 ,6-hexane diisocyanate
  • IPDI isophoron diisocyanate
  • MDI 4,4’-diphenyl-methane-diisocyanate
  • HMDI 4,4’-dicyclohexylmethane diisocyanate
  • XDI xylylene diisocyanate
  • TKI 4-diisocyanate
  • trimer Ui structure that is suitable for the present invention is selected from, but not limited to trimers of 1 ,6-hexane diisocyanate (HDI), isophoron diisocyanate (IPDI), and a mixture thereof.
  • HDI 1 ,6-hexane diisocyanate
  • IPDI isophoron diisocyanate
  • the diol or polyol A structure that is suitable for the present invention is selected from, but not limited to the group consisting of glycols, ethylene glycol, diethylene glycol, neopentyl glycol, 1 ,6-hexanediol, cyclohexanedimethanol, polyester diols, polycarbonate diols, polyether diols, PEG200, PEG400, PEG600, PPG1000, etc., and a mixture thereof.
  • the monomer B structure that is suitable for the present invention is selected from, but not limited to the group consisting of 2-hydroxyethyl(meth)acrylate, 2- hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 1-hydroxybutyl(meth)acrylate, neopentylglycolmono(meth)acrylate, 1 ,6-hexanediolmono(meth)acrylate, polycarprolactone polyol mono(meth)acrylate, pentaerythritolpenta(meth)acrylate, dipentaerythritolpenta(meth)acrylate and a mixture thereof.
  • the perfluoropolyether structure according to the present invention is a fluorine- containing polyether structure having at least two hydroxyl groups at each end of its molecule chain.
  • the fluorine-containing polyether structure may be in the form of either straight chain or branched chain, for example, having structures of --[CF 2 0]--, --[CF 2 CF 2 0]--, --[CF 2 CF 2 CF 2 0]--, --[CF(CF 3 )CF 2 0]--, or the likes.
  • the perfluoropolyether group may contain one or more types of perfluoropolyether units.
  • the fluoropolyether units may be arranged in random or block form when there are two or more perfluoropolyether units in the perfluoropolyether chain.
  • perfluoropolyether that is suitable for use in the present invention is selected from, but not limited to:
  • n, p, q are integers, m is from 1 to 50, n is from 1 to 50, p is from 1 ⁇ 5, q is from 1 ⁇ 5.
  • Fluorinated diol or polyol that is suitable for the present invention is selected from, but not limited to diols having the structure OHCH 2 (CF 2 ) r CH 2 OH, wherein r is from 2 to 10.
  • r is from 2 to 10.
  • they are selected from the group consisting of:
  • the resin composition according to the present invention is generally prepared from a fluorinated diol or polyol and/or a perfluoropolyether with at least two hydroxyl groups at the ends of its molecule chain (hereinafter referred to as “fluorinated compound (F)”), an isocyanate (U) that has at least two isocyanate functional groups (hereinafter referred to as “isocyanate (U)”), a diol or polyol (A) that has at least two hydroxyl functional groups (hereinafter referred to as“diol or polyol (A)”), and a monomer (B) that has at least one double bond and at least one hydroxyl group (hereinafter referred to as “monomer (B)”).
  • the preparation is conducted within a one-pot multicomponent synthesis system, wherein fluorinated polyurethane acrylate resin (FPUA) and polyurethane acrylate resin (PUA) are formed simultaneously from fluorinated compound (F), isocyanate (U), and diol or polyol (A), and then further reacted with monomer (B) for end-capping.
  • FPUA fluorinated polyurethane acrylate resin
  • POA polyurethane acrylate resin
  • F fluorinated compound
  • U isocyanate
  • A diol or polyol
  • B monomer
  • the obtained product normally presents as a mixture of oligomers, which can be used to formulate a coating composition directly.
  • this is an advantage of the present process in terms of industrial scale production and applications.
  • it is also possible to isolate one or more of the oligomers from the product of the present process, to provide it (them) as pure resin component(s) for addition into coating formulations.
  • Technology for isolation of the oligomers is well known in the art, thus it will not be discussed in detail in the present invention.
  • the isocyanate (U) reacts with the fluorinated compound (F) which is a fluorinated diol or a polyol to form a structure of -U-F-U-.
  • step b) dropping the solution of step a) into an isocyanate that has at least two isocyanate functional groups, with maintaining the temperature at 50 to 60 °C for 1 to 2 hours, preferably at 60 °C for 2 hours;
  • step b) adding a diol that has at least two hydroxyl functional groups into the mixture of step b), with maintaining the temperature at 50 to 60 °C for 1 to 2 hours, preferably at 60 °C for 2 hours, to result in a proper chain extension through the formation of urethane bonds between (U) and (A);
  • step c) adding a monomer that has at least one double bond and at least one hydroxyl group into the mixture of step c), with maintaining the temperature at 80 to 90 °C for 1 to 2 hours, preferably at 90 °C for 2 hours.
  • each of n ⁇ n 2 , n 3 and n 4 in structures (I) and (II) may independently represent any integer within the definition that the sum of n 1 and n 2 is ranging from 0 to 20, the sum of n 3 and n 4 is ranging from 1 to 20.
  • the ratio between the oligomers I and II in the composition is from 100-0.01 to 0-100.
  • fluorinated compound (F) is added with a predetermined weight percentage such as 2 wt.%o, the other components are then further mixed into the composition according to a predetermined proportion relative to the amount of fluorinated compound (F).
  • a predetermined weight percentage such as 2 wt.%o
  • the other components are then further mixed into the composition according to a predetermined proportion relative to the amount of fluorinated compound (F).
  • One of ordinary skill in the art may select proper relative proportions to achieve necessary characteristics of the composition such as the polymer length, the average number molecule weight, the number of repeat units in the molecule chain, etc.
  • the average number molecular weight and chain length of the oligomers can be varied from hundreds to thousands, or even more by changing the molar ratio between isocyanate and diols or polyols, or type of diols or polyols.
  • the inventors designed soft and rigid structures for PUA oligomers by introducing into the oligomers soft and rigid molecules respectively in the synthesis process, to form a structure as below:
  • the fluorinated diol or polyol or perfluoropolyether for use in the present invention contains at least two hydroxyl groups at its chain ends.
  • the hydroxyl groups may react with isocyanate, and thus make it possible for other chemical groups to be imbedded into the structure.
  • the resulting structure is shown below.
  • the oligomers of the coating composition of the present invention may also be prepared as branched structures based on trimers, as shown in the following structures (III) and (IV).
  • Ui refers to an isocyanate trimer such as HDI trimer, IPDI trimer, etc.;
  • the other components A, B, U, and F have the same meaning as discussed above.
  • the reaction mechanisms are also similar to those discussed above.
  • the method comprises steps of:
  • step b) adding into the mixture of step a) a diol that has at least two hydroxyl functional groups, with maintaining the temperature at 50 to 60 °C for 1 to 2 hours, preferably at 60 °C for 2 hours;
  • step c) dropping the solution of step c) into an isocyanate which is trimer of a diisocyanate, with maintaining the temperature at 50 to 60 °C for 1 to 2 hours;
  • step e) adding the mixture of step b) into the mixture of step d), with maintaining the temperature at 80 to 90 °C for 1 to 2 hours.
  • the fluorinated oligomer of the present invention may be added into coating compositions to improve the anti-stain, anti-scratch properties, and levelling effect of resulting coatings by virtue of its low surface energy, high cross-linking density, and the structural possibility for embedding rigid segments. Moreover, the fluorinated oligomer may also be helpful to improve the flexibility and self-recovery properties of the resulting coatings, where soft molecules like elastic diols or poly-diols exist in the structure of the oligomers.
  • Oligomers of the present invention may be used as a resin component singularly, or together with other resins and/or monomers in a coating formulation.
  • the oligomers of the present invention are compatible with most of other resins. Due to the unsaturated double bonds contained in their structures, they are curable with ultraviolet light. Therefore, the oligomers and compositions of the present invention may be widely used in the coatings industry.
  • Figures 1 , 2, and 3 show the GPC spectrum obtained according to examples 1 , 2, and 3, respectively;
  • Figures 4, 5, and 6 show the IR spectrum obtained according to examples 1 , 2, and 3, respectively;
  • Figures 7, 8, and 9 show the NMR spectra obtained according to examples 1 , 2, and 3, respectively;
  • Figure 10 shows the ccomparison of oil-based ink repellence on different UV resins.
  • Perfluoropolyether E-10H, Solvay
  • Dipentaerythritol hexaacrylate SR399, Sartomer
  • Pentaerythritol acrylate SR444D, Sartomer
  • Cyclohexanedimethanol CHDM, CAS No. 105-08-8, Sigma-Aldrich
  • PEG600 600PU, Clariant
  • Di-isocyanates HDI and IPDI, Wanhua
  • Trimer of HDI HT100, Wanhua
  • Number average molecular weight (Mn) and weight average molecular weight (Mw) of the resins were measured by gel permeation chromatography (GPC).
  • GPC was conducted with a commercially available polymer weight measuring apparatus (apparatus name: Agilent 1200). GPC samples were prepared by diluting fluorinated resins with tetrahydrofuran (THF) to 0.1 wt.% and pass through 0.5 pm filter.
  • THF tetrahydrofuran
  • NMR testing samples were dissolved in a mixture solvent of CDCI3 and DMSO, and measured by NMR (Nuclear Magnetic Resonance) spectroscopy.
  • the NMR data was obtained in a 400 MHz NMR system using a 5 mm probe at room temperature.
  • the sample was measured by means of 1 D (1 H, 13C) and 2D (COSY, HMQC) experiment.
  • HDI (30.86g) and dibutyl tin dilaurate (0.3g) and BHT (0.3g) were placed into a four-neck round bottom flask that was equipped with an agitator and a condenser.
  • Perfluoropolyether diol (0.6g) was dissolved in methyl isobutyl ketone (MiBK) and added to the mixture and heated to 60
  • the GPC results showed the distribution of the prepared resin, as seen in Figure 1.
  • the IR spectra showed the functional groups of the prepared resin, as seen in Figure 4;
  • the NMR spectra showed 1 H and 13 C of the prepared resin, as shown in Figure 7.
  • HDI 50.37g
  • dibutyl tin dilaurate 0.3g
  • BHT 0.3g
  • Perfluoropolyether diol 0.6g
  • PEG600 79.89g
  • PETA pentaerythritol acrylate
  • the GPC results showed the distribution of the prepared resin, as seen in Figure 2.
  • the IR spectra showed the functional groups of the prepared resin, as seen in Figure 5;
  • the NMR spectra showed 1 H and 13 C of the prepared resin, as shown in Figure 8.
  • IPDI (9.14g) and dibutyl tin dilaurate (0.1 g) and BHT (0.1 g) were placed into a four-neck round bottom flask that equipped with an agitator and a condenser.
  • Pentaerythritol acrylate (PETA) (20.97g) was dropped into the mixture within 1 hour at 60 °C and the mixture was cooked at 60 °C for 1 hour.
  • PETA Pentaerythritol acrylate
  • Perfluoropolyether diol (69.89g) was dissolved in methyl isobutyl ketone (MiBK) and added to the mixture and heated to 80 °C. The mixture was cooked at 80 °C for 1 hour to form the pre fluorinated oligomer.
  • MiBK methyl isobutyl ketone
  • HDI trimer in BAc (90%) (88.65g) and dibutyl tin dilaurate (0.3g) and BHT (0.3g) were placed into a four-neck round bottom flask that was equipped with an agitator and a condenser.
  • Pre fluorinated oligomer (0.86g) was added to the mixture and heated to 60 °C. The mixture was cooked at 60 °C for 1 hour. Then pentaerythritol acrylate (PETA) (211.32) was dropped into the mixture within 1 hour at 80 °C and the mixture was cooked at 90 °C for 1 hour or more until NCO group completely disappeared.
  • PETA pentaerythritol acrylate
  • Samples of the resin composition prepared according to example 1 were cured singly and mixed with other resin to form the coating films.
  • a sample of the resin prepared according to example 1 was mixed with another UV resin
  • composition of the present invention was capable of being cured by either exposure to ultraviolet light or heating at a temperature above 120 °C.
  • the dual curing mechanism allows the composition of the present invention to mix with different types of other resins, including thermosetting resins and UV curable resins.
  • Liquid contact angle tests were conducted for the fluorinated resins of the present invention.
  • the water and oil contact angles of coating film surface were measured with a commercially available apparatus named Dataphysics OCA20/6.
  • Two samples of coating-forming resins were prepared for comparison.
  • Both of the samples were applied onto PC/ABS substrates and cured by exposure to ultraviolet light.
  • n-Hexadecane contact angle was measured similarly with the same method.
  • the droplets were set as 2 mI/droplet, and the measurement temperature was about 20 ° C .
  • the test results are shown in the table 1 below as well.
  • Example 6 Oil-based ink repellence and anti-scratch performance test
  • Oil-based ink repellence tests were conducted for the fluorinated polymers of the present invention.
  • Two samples of coating-forming resins were prepared for comparison.
  • Both of the samples were applied onto PC/ABS substrates and cured by exposure to ultraviolet light.
  • Pens with different colors of oil-based inks were used to write and draw on top of the cured coatings, respectively. Pictures were taken to show the different appearance of the inks wrote onto the cured coatings, see (a) and (b) of Figure 10. It was seen that the inks wrote on the cured coating of the common UV resin were well spread and shown as regular lines, and that the inks wrote on the cured coating of the composition prepared according to example 1 were barely spread, while instead, shrank into small liquid beads, indicating that the latter coating surface has strong repellence to the oil-based inks. The oil-based inks wrote on the cured coating formed with the composition prepared according to example 1 were easily wiped off, with substantially no stain remains (not shown in the picture).

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Abstract

The present invention relates to a composition of a fluorinated polyurethane acrylate resin and a polyurethane acrylate resin, which, upon curing, is durable and has anti-stain and anti-scratch properties. The preparation of the composition is conducted with a one-pot multicomponent synthesis process, wherein multiple components are put together to carry out reactions simultaneously. The process is especially suitable for industrial scale production, and open for adding additive components to further adjust the performance of the prepared composition. The present invention also relates to oligomers prepared in the synthesis process, as well as the use of the composition or oligomer to form a coating onto a substrate.

Description

FLUORINATE POLYACRYLATE COATING COMPOSITION. THE PREPARATION METHOD
THEREFORE AND USE THEREOF
Technical Field
The invention relates to a coating composition for preparing a durable, stain-resistant, and scratch-resistant coating. The coating composition comprises a fluorinated polyurethane acrylate resin (FPUA) and a polyurethane acrylate resin (PUA) that are curable with ultraviolet (UV) light radiation. The invention further relates to a method for preparing the coating composition, and the use thereof.
Background
With the rapid development of coatings technology in the industry, there have been increasingly requirements for satisfying performances of coatings, such as durability, stain resistance, scratch resistance, etc., especially for those used on plastic, metal, wood, and glass substrates. Electronic apparatus like cell phones, personal and industrial computers, digital assistants, cameras, automotive upholstery, etc., have been widely used in the modern society. Besides enjoying the appliance functions of electronic apparatuses, people wish to keep the surface of electronic apparatuses clean and resistant to abrasion and scratching.
There have been a lot of literatures and patents discussing approaches to improve anti- stain, anti-fouling or anti-fingerprint properties of coatings. As mentioned by most of these references, hydrophobic and oleophobic characteristics of a coating surface play important roles in preventing stains, fingerprints and other fouling substance from being adhered on the surface, and make it easy to clean them off by wiping. As such, fluorinated resins and additives have been widely used in various coating formulations to decrease the surface energy, and thus to improve the anti-stain performance of the resulting coating. For instance, due to the low surface energy, perfluoropolyethers (PFPEs) have been used in many resin synthesis processes as an important component. It has also been reported in references that low surface energy of a resin component helps to improve the levelling effect of the resulting coating surface. However, there have been challenges for the application of fluorinated resins in coating formulations, especially for the application of PFPE components in coating formulations and relevant resin synthesis processes. Fluorine-based compounds are known to be incompatible with most common resins, which makes it hard to formulate a stable coating formulation with both fluorine-based compounds and other common resins. Moreover, when PFPEs are used in coating formulations, because of the low glass transition temperature of PFPEs, the resulting coating surface and coating matrix tend to be soft, and thus lead to decreased anti-scratch performance of the resulting coatings. Although existing patents and literatures have mentioned the use of fluorinated resins or PFPEs to improve anti-stain, anti-fingerprint, silky feeling and other properties of a coating or to form a hard coating with abrasion resistance, the applicable substrates are still limited, and there still exist limitations of the resulting anti-stain and antiscratch properties. In general, the properties achieved according to the state of the art are not satisfying enough in view of the rapidly developing industrial criteria.
WO 2015/038454 disclosed a poly fluorine-containing silicone coating for use on glass substrates, wherein a PFPE was added into a coating formulation to improve the lubricating performance and colloidal silica was added into the formulation to improve the anti-scratch performance.
WO 2007/121110 disclosed a coating for use on a flooring substrate, comprising a PFPE component to provide the flooring substrate with repellence properties such as water, oil or stain repellence. It is mentioned that the reaction only took place at one end of the molecule chain of the PFPE.
US 2013/0084458 disclosed a hard coat agent composition comprising a urethane acrylate, a first fluorine-containing polyether compound having active energy ray reactive group via a urethane bond at each of both ends of molecular chain containing a PFPE group, a second fluorine-containing polyether compound having active energy ray reactive group via a urethane bond at one end of molecular chain containing a PFPE group. The hard coat film is excellent in transparency, anti-stain, lubricating, solvent resistance, scratch resistance and abrasion resistance, as well as in punchability.
JP 2009256597 disclosed a urethane acrylate resin containing a PFPE group capable of imparting excellent transparency and anti-fouling properties to the cured film. The reaction product of a diol compound having a perfluoropolyether structure and an aromatic diisocyanate compound, obtained by reacting a compound having a hydroxyl group and 5 or more (meth) acryloyl group, perfluoropolyether compounds having groups, urethane groups and 10 or more (meth) acryloyl group.
With the development of coatings technology, however, there have been increasingly the demands for durability, scratch resistance and stain resistance properties of resulting coatings. It is still challenging in the prior art when a coating is required to have above mentioned properties.
Summary of the Invention
The present invention provides for a fluorinated resin composition, which, upon curing, is durable and has anti-stain and anti-scratch properties. The composition generally comprises an oligomer prepared from an isocyanate, a diol or polyol, and a monomer that has at least one double bond and at least one hydroxyl group, and/or another oligomer prepared from an isocyanate, a diol or polyol, a fluorinated diol or polyol or a perfluoropolyether containing at least two hydroxyl groups, and a monomer that has at least one double bond and at least one hydroxyl group.
The preparation of the fluorinated resin composition is conducted with a one-pot multicomponent synthesis process, wherein multiple components are put together to carry out reactions simultaneously. The process is especially suitable for industrial scale production, and open for adding additive components to further adjust the performance of the prepared composition.
The present invention also provides for the relevant oligomers prepared in the synthesis process, as well as the use of said composition or oligomer to form a coating onto a substrate.
Detailed description of the Invention
In one aspect of the present invention, a coating composition is provided. The coating composition comprises at least two oligomers, wherein the first oligomer is prepared from an isocyanate, a diol or polyol, and a monomer that has at least one double bond and at least one hydroxyl group. The second oligomer is prepared from an isocyanate, a diol or polyol, a fluorinated diol or polyol or a perfluoropolyether containing at least two hydroxyl groups, and a monomer that has at least one double bond and at least one hydroxyl group.
Specifically, the coating composition of the present invention comprises:
a first polyacrylate oligomer of the following structure (I)
Figure imgf000005_0001
a second fluorinated polyacrylate oligomer of the following structure (II)
Figure imgf000005_0002
wherein,
U represents an isocyanate structure that has at least two -N=C=0 functional groups; A represents a diol or polyol structure; F represents a fluorinated diol or polyol structure or a perfluoropolyether structure that contains at least two hydroxyl groups, or a mixture thereof; B represents a monomer structure that has at least one double bond and at least one hydroxyl group, ni, n2, n3 and n4 are integers, the sum of ni and n2 is ranging from 0 to 20, the sum of n3 and n4 is ranging from 1 to 20. It should be noticed that the structures of (I) and (II) don’t have to be symmetric necessarily ni, n2, n3 and n of structures (I) and (II) may independently represent any integer within the definition that the sum of ni and n2 is ranging from 0 to 20, the sum of n3 and n is ranging from 1 to 20. The weight ratio between the oligomers (I) and (II) in the composition is from 100-0.01 to 0-100, preferably from 90-10 to 10-90, more preferably from 70-30 to 30-70.
In a further aspect of the present invention, a coating composition comprising oligomers of the following structures (III) and (IV) is provided.
Figure imgf000006_0001
wherein,
U represents an isocyanate structure that has at least two -N=C=0 functional groups; Ui represents a trimer of a bifunctional isocyanate structure; A represents a diol or polyol structure; F represents fluorinated diol or polyol structure or a perfluoropolyether structure that contains at least two hydroxyl groups; B represents a monomer structure that has at least one double bonds and at least one hydroxyl group, n5, n6, n7, n8,n9 and n10 are integers, the sum of n5, n6, and n7 is ranging from 0 to 20, the sum of n8,n9 and n10 is ranging from 0 to 20. The weight ratio between the oligomers (III) and (IV) in the composition is from 100-0.01 to 0-100, preferably from 90-10 to 10-90, more preferably from 70-30 to 30-70. In a further aspect of the present invention, fluorinated polyacrylate oligomers having the above structures (II) and (IV) are provided. Although the composition of the present invention is prepared through a one-pot multicomponent synthesis process, and the obtained mixture of oligomers can be used in coating formulations directly, it is possible in some cases that the oligomers are isolated and provided in the form of a pure component, which can be further added into coating formulations, acting as either a main resin component, or an additive component.
It has been found that the double bond density of the monomer B structure may affect anti-stain and anti-scratch properties of the resulting coating. Specifically, for example, the double bond functionality of the monomer B structure is at least 1 , preferably 3 or 5, and more preferably 5, so as to achieve satisfying anti-stain and anti-scratch properties of the resulting coating.
It has also been found that rigid and soft molecules may be introduced into the oligomers of the present invention during the synthesis process. Generally, rigid molecules may be added to increase the hardness and durability of the resulting coating film, soft molecules may be added to increase the flexibility and elasticity of the coating film, and therefore increase the selfrecovery performance of the resulting coating film. When used herein in the present invention, the term“rigid” is meant to be the characteristic of a molecule, with which, the molecule does not tend to bend or flex when receiving a force, and on the contrary, the term“soft” is meant to be the characteristic of a molecule, with which, the molecule tends to bend or flex when receiving a force. A skilled person would understand that there is no clear boundary between “rigid” and“soft.” If introducing a molecule into the oligomers of the present invention leads to more“rigid” characteristic, the molecule is considered as a“rigid molecule,” and vice versa. Typically, for example, rigid molecules suitable for use in the present invention can be selected from polyols that have a relatively low glass transmission temperature (Tg) value or diols that have a relatively long carbon chain structure; soft molecules suitable for use in the present invention can be selected from polyols that have relatively high Tg or diols that have a ring structure. A skilled person may select proper molecules by setting up standards of Tg values, chain length, etc., as per actual requirements. Typically, the isocyanate U structure that is suitable for the present invention is selected from, but not limited to the group consisting of 1 ,6-hexane diisocyanate (HDI), isophoron diisocyanate (IPDI), 4,4’-diphenyl-methane-diisocyanate (MDI), 4,4’-dicyclohexylmethane diisocyanate (HMDI), xylylene diisocyanate (XDI), Tolylene-2, 4-diisocyanate (TDI), and a mixture thereof;
The trimer Ui structure that is suitable for the present invention is selected from, but not limited to trimers of 1 ,6-hexane diisocyanate (HDI), isophoron diisocyanate (IPDI), and a mixture thereof.
The diol or polyol A structure that is suitable for the present invention is selected from, but not limited to the group consisting of glycols, ethylene glycol, diethylene glycol, neopentyl glycol, 1 ,6-hexanediol, cyclohexanedimethanol, polyester diols, polycarbonate diols, polyether diols, PEG200, PEG400, PEG600, PPG1000, etc., and a mixture thereof.
The monomer B structure that is suitable for the present invention is selected from, but not limited to the group consisting of 2-hydroxyethyl(meth)acrylate, 2- hydroxypropyl(meth)acrylate, 2-hydroxybutyl(meth)acrylate, 1-hydroxybutyl(meth)acrylate, neopentylglycolmono(meth)acrylate, 1 ,6-hexanediolmono(meth)acrylate, polycarprolactone polyol mono(meth)acrylate, pentaerythritolpenta(meth)acrylate, dipentaerythritolpenta(meth)acrylate and a mixture thereof.
The perfluoropolyether structure according to the present invention is a fluorine- containing polyether structure having at least two hydroxyl groups at each end of its molecule chain. The fluorine-containing polyether structure may be in the form of either straight chain or branched chain, for example, having structures of --[CF20]--, --[CF2CF20]--, --[CF2CF2CF20]--, --[CF(CF3)CF20]--, or the likes. The perfluoropolyether group may contain one or more types of perfluoropolyether units. The fluoropolyether units may be arranged in random or block form when there are two or more perfluoropolyether units in the perfluoropolyether chain.
Specifically, perfluoropolyether that is suitable for use in the present invention is selected from, but not limited to:
H0(CH2CH20)nCH2CF20(CF2CF20)p(CF20)qCF2CH2(0CH2CH2)n0H
H0CH2CF20(CF2CF20)p(CF20)qCF2CH20H H0H2C(CF3)FC(CF(CF3)CF20)nCF(CF3)CH20H
H0H2C(CF3)CF(CF2CF20)nCF(CF3)CH20H
H0H2CCF2(CF2CF20)nCF2CH20H
H0H2CF2C(CF2CF20CF2CF2CF20)nCF2CH20H
H0H2CCH2CF20(CF2CF20)m(CF20)nCF2CH2CH20H
Wherein m, n, p, q are integers, m is from 1 to 50, n is from 1 to 50, p is from 1 ~5, q is from 1 ~5.
Fluorinated diol or polyol that is suitable for the present invention is selected from, but not limited to diols having the structure OHCH2(CF2)rCH2OH, wherein r is from 2 to 10. For example, they are selected from the group consisting of:
2,2,3,3-tetrafluoro-1 ,4-butanediol;
2,2,3,3,4,4,5,5-octafluoro-1 ,6-hexanediol;
2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1 ,8-octanediol;
2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluoro-1 ,9-nonanediol;
2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1 ,10-decanediol; and
1 H, 1 H,12H,12H-perfluoro-1 ,12-dodecanediol.
In another aspect of the present invention, methods for preparing coating compositions according to the present invention are provided.
The resin composition according to the present invention is generally prepared from a fluorinated diol or polyol and/or a perfluoropolyether with at least two hydroxyl groups at the ends of its molecule chain (hereinafter referred to as “fluorinated compound (F)”), an isocyanate (U) that has at least two isocyanate functional groups (hereinafter referred to as “isocyanate (U)”), a diol or polyol (A) that has at least two hydroxyl functional groups (hereinafter referred to as“diol or polyol (A)”), and a monomer (B) that has at least one double bond and at least one hydroxyl group (hereinafter referred to as “monomer (B)”). The preparation is conducted within a one-pot multicomponent synthesis system, wherein fluorinated polyurethane acrylate resin (FPUA) and polyurethane acrylate resin (PUA) are formed simultaneously from fluorinated compound (F), isocyanate (U), and diol or polyol (A), and then further reacted with monomer (B) for end-capping. As the multiple reactions are all carried out in a one-pot multicomponent system, the method is especially suitable for industrial scale practice, and also flexible for adding additive components to further adjust the performance of the prepared composition.
It should be noticed that, due to the one-pot multicomponent synthesis process, the obtained product normally presents as a mixture of oligomers, which can be used to formulate a coating composition directly. As discussed above, this is an advantage of the present process in terms of industrial scale production and applications. In some scenarios, however, it is also possible to isolate one or more of the oligomers from the product of the present process, to provide it (them) as pure resin component(s) for addition into coating formulations. Technology for isolation of the oligomers is well known in the art, thus it will not be discussed in detail in the present invention.
Specifically, the isocyanate (U) reacts with the fluorinated compound (F) which is a fluorinated diol or a polyol to form a structure of -U-F-U-.
U + F ® -U-F-U-
The obtained structure of -U-F-U-, together with unreacted isocyanate -U-, reacts with the diol or polyol (A) to form structures of -(U-A)n3-U-F-U-(A-U)n4- and -(U-A)nrU-(A-U)n2-;
-U-F-U- + A + -U- ® -(U-A)n3-U-F-U-(A-U)n4- -U- + A ®— (U-A)ni-U-(A-U)n2- The obtained structures of -(U-A)n3-U-F-U-(A-U)n4- and -(U-A)nrU-(A-U)n2- further react with the monomer (B) to form a composition of B-(U-A)n3-U-F-U-(A-U)n4-B and B-(U-A)nrU-(A- U)n2-B, respectively, to end-cap the structures.
-(U-A)n3-U-F-U-(A-U)n4- + B ® B-(U-A)n3-U-F-U-(A-U)n4-B
-(U-A)ni-U-(A-U)n2- + B ® B-(U-A)ni-U-(A-U)n2-B
The above reactions may be conducted as the steps below:
a) preparing a solution of a fluorinated diol or a perfluoropolyether that contains at least two hydroxyl groups in a solvent;
b) dropping the solution of step a) into an isocyanate that has at least two isocyanate functional groups, with maintaining the temperature at 50 to 60 °C for 1 to 2 hours, preferably at 60 °C for 2 hours;
c) adding a diol that has at least two hydroxyl functional groups into the mixture of step b), with maintaining the temperature at 50 to 60 °C for 1 to 2 hours, preferably at 60 °C for 2 hours, to result in a proper chain extension through the formation of urethane bonds between (U) and (A);
d) adding a monomer that has at least one double bond and at least one hydroxyl group into the mixture of step c), with maintaining the temperature at 80 to 90 °C for 1 to 2 hours, preferably at 90 °C for 2 hours.
By selecting isocyanates that have different reaction selectivity with hydroxyl functional groups, or controlling reaction conditions such as, for example, the speed of adding the reaction components, the reaction temperature, the catalyst and the amount thereof, the ways of adding catalyst, etc., the prepared structures (I) and (II) according to the present invention don’t have to be symmetric necessarily. As defined above, each of n^ n2, n3 and n4 in structures (I) and (II) may independently represent any integer within the definition that the sum of n1 and n2 is ranging from 0 to 20, the sum of n3 and n4 is ranging from 1 to 20. The ratio between the oligomers I and II in the composition is from 100-0.01 to 0-100.
It has been found that the ratio among the reaction components may affect the hardness and durability of the resulting coating film, therefore it is possible to increase anti-stain and antiscratch properties of the resulting coating film, by fine tuning the ratio among the reaction components. As a demonstration of means to adjust the ratio among compositions, but not for the purpose to limit the scope of the present invention, fluorinated compound (F) is added with a predetermined weight percentage such as 2 wt.%o, the other components are then further mixed into the composition according to a predetermined proportion relative to the amount of fluorinated compound (F). One of ordinary skill in the art may select proper relative proportions to achieve necessary characteristics of the composition such as the polymer length, the average number molecule weight, the number of repeat units in the molecule chain, etc. For instance, by selecting proper relative proportions of the components, the average number molecular weight and chain length of the oligomers can be varied from hundreds to thousands, or even more by changing the molar ratio between isocyanate and diols or polyols, or type of diols or polyols.
According to the present invention, the inventors designed soft and rigid structures for PUA oligomers by introducing into the oligomers soft and rigid molecules respectively in the synthesis process, to form a structure as below:
Figure imgf000012_0001
FPUA oligomers are modified in a similar way. The fluorinated diol or polyol or perfluoropolyether for use in the present invention contains at least two hydroxyl groups at its chain ends. The hydroxyl groups may react with isocyanate, and thus make it possible for other chemical groups to be imbedded into the structure. The resulting structure is shown below.
Figure imgf000012_0002
Besides the linear chain structures based on dimers as shown above, the oligomers of the coating composition of the present invention may also be prepared as branched structures based on trimers, as shown in the following structures (III) and (IV).
Figure imgf000012_0003
Figure imgf000013_0001
According to the present invention, Ui refers to an isocyanate trimer such as HDI trimer, IPDI trimer, etc.; The other components A, B, U, and F have the same meaning as discussed above. The reaction mechanisms are also similar to those discussed above.
To obtain the above trimer structures, method for preparing oligomers having branched structures based on trimers is provided. The method comprises steps of:
a) mixing a monomer that has at least one double bond and at least one hydroxyl group with an isocyanate that has at least two isocyanate functional groups, with maintaining the temperature at 50 to 60 °C for 1 to 2 hours, preferably at 60 °C for 2 hours;
b) adding into the mixture of step a) a diol that has at least two hydroxyl functional groups, with maintaining the temperature at 50 to 60 °C for 1 to 2 hours, preferably at 60 °C for 2 hours;
c) preparing a solution of a fluorinated diol or a perfluoropolyether that contains at least two hydroxyl groups in a solvent;
d) dropping the solution of step c) into an isocyanate which is trimer of a diisocyanate, with maintaining the temperature at 50 to 60 °C for 1 to 2 hours;
e) adding the mixture of step b) into the mixture of step d), with maintaining the temperature at 80 to 90 °C for 1 to 2 hours.
Application of the oligomer / composition of the present invention
The fluorinated oligomer of the present invention may be added into coating compositions to improve the anti-stain, anti-scratch properties, and levelling effect of resulting coatings by virtue of its low surface energy, high cross-linking density, and the structural possibility for embedding rigid segments. Moreover, the fluorinated oligomer may also be helpful to improve the flexibility and self-recovery properties of the resulting coatings, where soft molecules like elastic diols or poly-diols exist in the structure of the oligomers.
Oligomers of the present invention may be used as a resin component singularly, or together with other resins and/or monomers in a coating formulation. The oligomers of the present invention are compatible with most of other resins. Due to the unsaturated double bonds contained in their structures, they are curable with ultraviolet light. Therefore, the oligomers and compositions of the present invention may be widely used in the coatings industry.
Summary of the Figures
The above and other objectives, features and advantages of the present invention will become more apparent to those of ordinary skill in the art by describing in embodiments thereof with reference to the accompanying drawings.
Figures 1 , 2, and 3 show the GPC spectrum obtained according to examples 1 , 2, and 3, respectively;
Figures 4, 5, and 6 show the IR spectrum obtained according to examples 1 , 2, and 3, respectively;
Figures 7, 8, and 9 show the NMR spectra obtained according to examples 1 , 2, and 3, respectively;
Figure 10 shows the ccomparison of oil-based ink repellence on different UV resins.
Examples
The invention will be elucidated with reference to the following examples. These are intended to illustrate the invention but are not to be construed as limiting in any manner the scope thereof.
Raw material
Perfluoropolyether (E-10H, Solvay), Dipentaerythritol hexaacrylate (SR399, Sartomer), Pentaerythritol acrylate(SR444D, Sartomer), Cyclohexanedimethanol (CHDM, CAS No. 105-08-8, Sigma-Aldrich), PEG600 (600PU, Clariant), Di-isocyanates (HDI and IPDI, Wanhua)) and Trimer of HDI (HT100, Wanhua).
Measurement method and apparatus
Number average molecular weight (Mn) and weight average molecular weight (Mw) of the resins were measured by gel permeation chromatography (GPC). GPC was conducted with a commercially available polymer weight measuring apparatus (apparatus name: Agilent 1200). GPC samples were prepared by diluting fluorinated resins with tetrahydrofuran (THF) to 0.1 wt.% and pass through 0.5 pm filter.
All FtIR spectra were obtained at a resolution of 4 cm 1 by using PerkinElmer Spectrum 100 FTIR with ATR system . The wave-number range was selected from 4000 to 450 cm 1 and 32 scans were averaged to reduce the noise.
For NMR testing, samples were dissolved in a mixture solvent of CDCI3 and DMSO, and measured by NMR (Nuclear Magnetic Resonance) spectroscopy. The NMR data was obtained in a 400 MHz NMR system using a 5 mm probe at room temperature. The sample was measured by means of 1 D (1 H, 13C) and 2D (COSY, HMQC) experiment.
Example 1 - synthesis process
HDI (30.86g) and dibutyl tin dilaurate (0.3g) and BHT (0.3g) were placed into a four-neck round bottom flask that was equipped with an agitator and a condenser. Perfluoropolyether diol (0.6g) was dissolved in methyl isobutyl ketone (MiBK) and added to the mixture and heated to 60
°C. The mixture was cooked at 60 °C for 1 hour. Then cyclohexanedimethanol (CHDM) (13.23g) was dropped into the mixture within one hour at 60 °C and the mixture was cooked at 60 °C for one hour. Finally, dipentaerythritol hexaacrylate (DPHA) (246g) was added dropwise within 1 hour at 90 °C and the mixture was cooked at 90 °C for 1 hour or more until NCO group completely disappeared.
The GPC results showed the distribution of the prepared resin, as seen in Figure 1. The IR spectra showed the functional groups of the prepared resin, as seen in Figure 4; The NMR spectra showed 1H and 13C of the prepared resin, as shown in Figure 7. Example 2 - synthesis process
HDI (50.37g) and dibutyl tin dilaurate (0.3g) and BHT (0.3g) were placed into a four-neck round bottom flask that was equipped with an agitator and a condenser. Perfluoropolyether diol (0.6g) was dissolved in methyl isobutyl ketone (MiBK) and added to the mixture and heated to 60 °C. The mixture was cooked at 60 °C for 1 hour. Then PEG600 (79.89g) was dropped into the mixture within one hour at 60 °C and the mixture was cooked at 60 °C for one hour. Finally, pentaerythritol acrylate (PETA) (169.74g) was added dropwise within 1 hour at 90 °C and the mixture was cooked at 90 °C for 1 hour or more until NCO group completely disappeared.
The GPC results showed the distribution of the prepared resin, as seen in Figure 2. The IR spectra showed the functional groups of the prepared resin, as seen in Figure 5; The NMR spectra showed 1H and 13C of the prepared resin, as shown in Figure 8.
Example 3 - synthesis process
IPDI (9.14g) and dibutyl tin dilaurate (0.1 g) and BHT (0.1 g) were placed into a four-neck round bottom flask that equipped with an agitator and a condenser. Pentaerythritol acrylate (PETA) (20.97g) was dropped into the mixture within 1 hour at 60 °C and the mixture was cooked at 60 °C for 1 hour. Then Perfluoropolyether diol (69.89g) was dissolved in methyl isobutyl ketone (MiBK) and added to the mixture and heated to 80 °C. The mixture was cooked at 80 °C for 1 hour to form the pre fluorinated oligomer.
HDI trimer in BAc (90%) (88.65g) and dibutyl tin dilaurate (0.3g) and BHT (0.3g) were placed into a four-neck round bottom flask that was equipped with an agitator and a condenser. Pre fluorinated oligomer (0.86g) was added to the mixture and heated to 60 °C. The mixture was cooked at 60 °C for 1 hour. Then pentaerythritol acrylate (PETA) (211.32) was dropped into the mixture within 1 hour at 80 °C and the mixture was cooked at 90 °C for 1 hour or more until NCO group completely disappeared.
The GPC results showed the distribution of the prepared resin, as seen in Figure 3. The IR spectra showed the functional groups of the prepared resin, as seen in Figure 6; The NMR spectra showed 1H and 13C of the prepared resin, as shown in Figure 9. Example 4 - formation of coatings
Samples of the resin composition prepared according to example 1 were cured singly and mixed with other resin to form the coating films.
Two samples of the resin prepared according to example 1 were diluted with a mixed solvent of methyl isobutyl ketone (MiBK) and butyl acetate (BAc), sprayed onto a PC/ABS substrate, and then cured by exposure to UV light and being heated to 120 °C, respectively.
A sample of the resin prepared according to example 1 was mixed with another UV resin
(EM2692 available from Eternal) in a weight ratio of 7:3, sprayed onto a PC/ABS substrate, and then cured by exposure to UV light.
The results showed that the composition of the present invention was capable of being cured by either exposure to ultraviolet light or heating at a temperature above 120 °C. The dual curing mechanism allows the composition of the present invention to mix with different types of other resins, including thermosetting resins and UV curable resins. Example 5 - liquid contact angle test
Liquid contact angle tests were conducted for the fluorinated resins of the present invention. The water and oil contact angles of coating film surface were measured with a commercially available apparatus named Dataphysics OCA20/6.
Two samples of coating-forming resins were prepared for comparison. One was a common UV resin (UX-8800WIBAC20, KAYAKU CHEMICAL(WUXI) CO., LTD), and the other one was the composition prepared according to example 1 . Both of the samples were applied onto PC/ABS substrates and cured by exposure to ultraviolet light.
Water contact angle was measured on top of the cured coatings, respectively, with Sessile drop method. The droplets were set as 3 mI/droplet, and the measurement temperature was about 20 °C . The test results are shown in the table 1 below.
n-Hexadecane contact angle was measured similarly with the same method. The droplets were set as 2 mI/droplet, and the measurement temperature was about 20°C . The test results are shown in the table 1 below as well.
Table 1 the liquid contact angle of cured samples
Figure imgf000018_0001
Example 6 - Oil-based ink repellence and anti-scratch performance test
Oil-based ink repellence tests were conducted for the fluorinated polymers of the present invention.
Two samples of coating-forming resins were prepared for comparison. One was a common UV resin (UX-8800WIBAC20, KAYAKU CHEMICAL(WUXI) CO., LTD), and the other one was the composition prepared according to example 1 . Both of the samples were applied onto PC/ABS substrates and cured by exposure to ultraviolet light.
Pens with different colors of oil-based inks were used to write and draw on top of the cured coatings, respectively. Pictures were taken to show the different appearance of the inks wrote onto the cured coatings, see (a) and (b) of Figure 10. It was seen that the inks wrote on the cured coating of the common UV resin were well spread and shown as regular lines, and that the inks wrote on the cured coating of the composition prepared according to example 1 were barely spread, while instead, shrank into small liquid beads, indicating that the latter coating surface has strong repellence to the oil-based inks. The oil-based inks wrote on the cured coating formed with the composition prepared according to example 1 were easily wiped off, with substantially no stain remains (not shown in the picture).
Anti-scratch performance of the coatings was tested by scratching the coatings 500 cycles with steel wool under 1 Kg gram load. Upon test, the cured coating formed with the composition prepared according to example 1 still represented excellent oil-based ink repellence and without any visible scratch marks, as seen in (c) of Figure 10.

Claims

Claims
1 . A coating composition comprising:
(a) a polyacrylate oligomer of the following structure (I)
Figure imgf000019_0001
, and
(b) a fluorinated polyacrylate oligomer of the following structure (II)
Figure imgf000019_0002
wherein,
U represents an isocyanate structure that has at least two -N=C=0 functional groups; A represents a diol or polyol structure; F represents a fluorinated diol or polyol structure, a perfluoropolyether structure that contains at least two hydroxyl groups, or a mixture thereof; B represents a monomer structure that has at least one double bond and at least one hydroxyl group; ni, n2, n3 and n4 are integers, the sum of ni and n2 is ranging from 0 to 20, the sum of n3 and n4 is ranging from 1 to 20.
2. The coating composition according to claim 1 , wherein the weight ratio between the
oligomers (I) and (II) is from 100-0.01 to 0-100.
3. A coating composition comprising the following oligomers (III) and (IV)
Figure imgf000019_0003
Figure imgf000020_0001
wherein,
U represents an isocyanate structure that has at least two -N=C=0 functional groups; Ui represents a trimer of a bifunctional isocyanate structure; A represents a diol or polyol structure; F represents a fluorinated diol or polyol structure, a perfluoropolyether structure that contains at least two hydroxyl groups, or a mixture thereof; B represents a monomer structure that has at least one double bond and at least one hydroxyl group; n5, n6, n7, n8,n9 and n10 are integers, the sum of n5, n6, and n7 is ranging from 0 to 20, the sum of n8,n9 and n10 is ranging from 0 to 20.
4. The coating composition according to claim 3, wherein the weight ratio between the oligomers (III) and (IV) is from 100-0.01 to 0-100.
5. Afluorinated polyacrylate oligomer having structure (II) or (IV),
Figure imgf000020_0002
Figure imgf000021_0001
wherein,
U represents an isocyanate structure that has at least two -N=C=0 functional groups; Ui represents a trimer of a difunctional isocyanate structure; A represents a diol or polyol structure; F represents a fluorinated diol or polyol structure, a perfluoropolyether structure that contains at least two hydroxyl groups, or a mixture thereof; B represents a monomer structure that has at least one double bond and at least one hydroxyl group; n3, n4, n8, n9, and nio are integers, the sum of n3 and n4 is ranging from 1 to 20, the sum of n8,n9 and ni0 is ranging from 0 to 20.
6. The coating composition according to any one of claims 1 to 4 or the oligomer according to claim 5, wherein U is a diisocyanate structure selected from the group consisting of 1 ,6-hexane diisocyanate, isophoron diisocyanate, 4,4’-diphenyl-methane-diisocyanate, 4,4’-dicyclohexylmethane diisocyanate, xylylene diisocyanate, tolylene-2, 4-diisocyanate, and a mixture thereof.
7. The coating composition according to claim 3, 4 or the oligomer according to claim 5, wherein Ui is a trimer of a diisocyanate structure selected from trimers of 1 ,6-hexane diisocyanate, isophoron diisocyanate, and a mixture thereof.
8. The coating composition according to any one of claims 1 to 4 or the oligomer according to claim 5, wherein A is a diol structure or polyol structure selected from the group consisting of glycols, ethylene glycol, diethylene glycol, neopentyl glycol, 1 ,6-Hexanediol, cyclohexanedimethanol, polyester diols, polycarbonate diols, polyether diols, PEG200, PEG400, PEG600, PPG1000, and a mixture thereof.
9. The coating composition according to according to any one of claims 1 to 4 or the
oligomer according to claim 5, wherein B is a hydroxyl (meth)acrylate structure that contains at least one (meth)acryloyl group and one hydroxyl group, selected from the group consisting of 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2- hydroxybutyl(meth)acrylate, 1-hydroxybutyl(meth)acrylate,
neopentylglycolmono(meth)acrylate, 1 ,6-hexanediolmono(meth)acrylate,
polycarprolactone polyol mono(meth)acrylate, pentaerythritolpenta(meth)acrylate, dipentaerythritolpenta(meth)acrylate, and a mixture thereof.
10. The coating composition according to claim 9, wherein B has a double bond functionality of at least 1.
1 1 . The coating composition according to any one of claims 1 to 4 or the oligomer according to claim 5, wherein F is selected from the group consisting of:
2,2,3,3-tetrafluoro-1 ,4-butanediol;
2,2,3,3,4,4,5,5-octafluoro-1 ,6-hexanediol;
2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1 ,8-octanediol;
2,2,3,3,4,4,5,5,6,6,7,7,8,8-tetradecafluoro-1 ,9-nonanediol;
2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1 ,10-decanediol; and
1 H,1 H,12H,12H-Perfluoro-1 ,12-dodecanediol.
12. The coating composition according to any one of claims 1 to 4 or the oligomer according to claim 5, wherein F is selected from the group consisting of:
H0(CH2CH20)nCH2CF20(CF2CF20)p(CF20)qCF2CH2(0CH2CH2)n0H H0CH2CF20(CF2CF20)p(CF20)qCF2CH20H
H0H2C(CF3)FC(CF(CF3)CF20)nCF(CF3)CH20H
H0H2C(CF3)CF(CF2CF20)nCF(CF3)CH20H
H0H2CCF2(CF2CF20)nCF2CH20H
H0H2CF2C(CF2CF20CF2CF2CF20)nCF2CH20H
H0H2CCH2CF20(CF2CF20)m(CF20)nCF2CH2CH20H
wherein m is from 1 to 50, n is from 1 to 50, p is from 1 ~5, q is from 1 ~5.
13. A method for preparing the coating composition according to any one of claims 1 , 2 and 6 to 12, comprising steps of:
a) preparing a solution of a fluorinated diol or polyol, a perfluoropolyether that contains at least two hydroxyl groups, or a mixture thereof in a solvent;
b) dropping the solution of step a) into an isocyanate that has at least two isocyanate functional groups, with maintaining the temperature at 50 to 60 °C for 1 to 2 hours; c) adding a diol or polyol into the mixture of step b), with maintaining the temperature at 50 to 60 °C for 1 to 2 hours;
d) adding a monomer that has at least one double bond and at least one hydroxyl group into the mixture of step c), with maintaining the temperature at 80 to 90 °C for 1 to 2 hours.
14. A method for preparing the coating composition according to any one of claims 3, 4 and 6 to 12, comprising steps of:
a) mixing a monomer that has at least one double bond and at least one hydroxyl group with an isocyanate that has at least two isocyanate functional groups, with maintaining the temperature at 50 to 60 °C for 1 to 2 hours;
b) adding into the mixture of step a) a diol or polyol, with maintaining the temperature at 50 to 60 °C for 1 to 2 hours;
c) preparing a solution of a fluorinated diol or polyol, a perfluoropolyether that contains at least two hydroxyl groups, or a mixture thereof in a solvent;
d) dropping the solution of step c) into an isocyanate which is trimer of a diisocyanate, with maintaining the temperature at 50 to 60 °C for 1 to 2 hours;
e) adding the mixture of step b) into the mixture of step d), with maintaining the
temperature at 80 to 90 °C for 1 to 2 hours.
15. A method of using the coating composition or oligomer according to any one of claims 1 to
10 to form a coating film onto a substrate, comprising applying and then curing the coating composition or oligomer on the substrate.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021074113A1 (en) * 2019-10-15 2021-04-22 Akzo Nobel Coatings International B.V. Waterborne, uv curable coating composition for easy-clean coatings
KR20220137751A (en) * 2020-02-18 2022-10-12 아크조노벨코팅스인터내셔널비.브이. Water-Based UV Curable Coating Composition for Antifouling and Scratch Resistant Coatings
US11613667B2 (en) 2017-12-26 2023-03-28 Akzo Nobel Coatings International B.V. Fluorinate polyacrylate coating composition, the preparation method therefore and use thereof
CN120309824A (en) * 2025-05-12 2025-07-15 陕西科技大学 A kind of polyurethane-polyacrylate hybrid emulsion and preparation method thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113061390A (en) * 2021-04-30 2021-07-02 炫杰复合材料（上海）有限公司 Anti-doodling and anti-sticking coating and preparation method thereof
CN113201111A (en) * 2021-06-21 2021-08-03 东莞三桐材料科技有限公司 Fluorine-containing polyurethane acrylate resin, preparation method and application thereof
CN115304995A (en) * 2021-12-14 2022-11-08 中国电力科学研究院有限公司 Ultraviolet-curing flame-retardant waterproof coating for cable and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6376572B1 (en) * 1999-06-03 2002-04-23 Ausimont S.P.A. Compositions for films having a low refractive index
WO2007121110A2 (en) 2006-04-13 2007-10-25 3M Innovative Properties Company Flooring substrate having a coating of a curable composition
JP2009256597A (en) 2008-03-26 2009-11-05 Jsr Corp Compound having perfluoropolyether group, urethane group and (meth) acryloyl group
US20110118405A1 (en) * 2008-04-30 2011-05-19 Dic Corporation Active-energy-ray-curable coating composition, cured product thereof, and novel curable resin
US20130084458A1 (en) 2011-09-30 2013-04-04 Tdk Corporation Hard coat agent composition and hard coat film using the same
US8552083B1 (en) * 2009-12-03 2013-10-08 Ovation Polymer Technology And Engineered Materials, Inc. Ultra low refractive index curable coatings
WO2015038454A1 (en) 2013-09-16 2015-03-19 Honeywell International Inc. Poly fluorine-containing siloxane coatings
US20160304743A1 (en) * 2015-04-17 2016-10-20 Daikin Industries, Ltd. Surface treatment composition

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1156795A (en) 1979-04-11 1983-11-08 Richard G. Newell Curable fluorocarbon substituted polyetherurethaneacrylates
US4929692A (en) * 1989-01-11 1990-05-29 Ciba-Geigy Corporation Crosslinked copolymers and ophthalmic devices made from vinylic macromers containing perfluoropolyalkyl ether and polyalkyl ether segments and minor amounts of vinylic comonomers
EP1291373A3 (en) 1995-01-30 2004-01-07 DSM IP Assets B.V. Radiation curable composition comprising fluorinated urethaneoligomer
ITMI20011306A1 (en) 2001-06-21 2002-12-21 Ausimont Spa VULCANIZABLE POLYURETHANE
KR100487025B1 (en) 2002-02-28 2005-05-11 주식회사 루밴틱스 Photo-curable resin composition for optical waveguide and optical waveguide prepared therefrom
ITMI20040106A1 (en) 2004-01-27 2004-04-27 Solvay Solexis Spa POLIURETANI
US20080124555A1 (en) * 2006-11-29 2008-05-29 3M Innovative Properties Company Polymerizable composition comprising perfluoropolyether urethane having ethylene oxide repeat units
CN100500724C (en) * 2006-12-27 2009-06-17 武汉工程大学 High solid share fluorine-containing polyurethane preparation method
JP5218127B2 (en) 2008-03-26 2013-06-26 Ｊｓｒ株式会社 Curable composition, cured film and laminate
CN101367922A (en) 2008-09-12 2009-02-18 中国科学技术大学 A kind of fluorine-containing hyperbranched polyester acrylate and preparation method thereof
EP2412773B1 (en) 2009-03-23 2016-06-29 DIC Corporation Adhesive protective film, screen panel, and portable electronic terminal
EP2478033A1 (en) * 2009-09-16 2012-07-25 3M Innovative Properties Company Fluorinated coating and phototools made therewith
JP5803260B2 (en) 2011-05-17 2015-11-04 横浜ゴム株式会社 Curable resin composition
EP2583986A1 (en) 2011-10-17 2013-04-24 Cytec Surface Specialties, S.A. Fluorinated water-oil repellency agents
CN104736583B (en) 2012-10-04 2017-03-15 巴斯夫涂料有限公司 Fluorine-containing non-aqueous coating composition, coating method and use of coating composition
CN103980215B (en) 2014-05-23 2016-07-06 中国科学院长春应用化学研究所 A kind of aqueous polyurethane acrylate oligomer, its preparation method and UV-curable waterborne coatings
TWI688601B (en) * 2014-07-04 2020-03-21 瑞士商亞克羅瑪智財公司 Fluorine-containing water-repellent composition
CN111511790B (en) 2017-12-26 2022-07-15 阿克佐诺贝尔国际涂料股份有限公司 Fluorinated polyacrylate coating composition, process for its preparation and use thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6376572B1 (en) * 1999-06-03 2002-04-23 Ausimont S.P.A. Compositions for films having a low refractive index
WO2007121110A2 (en) 2006-04-13 2007-10-25 3M Innovative Properties Company Flooring substrate having a coating of a curable composition
JP2009256597A (en) 2008-03-26 2009-11-05 Jsr Corp Compound having perfluoropolyether group, urethane group and (meth) acryloyl group
US20110118405A1 (en) * 2008-04-30 2011-05-19 Dic Corporation Active-energy-ray-curable coating composition, cured product thereof, and novel curable resin
US8552083B1 (en) * 2009-12-03 2013-10-08 Ovation Polymer Technology And Engineered Materials, Inc. Ultra low refractive index curable coatings
US20130084458A1 (en) 2011-09-30 2013-04-04 Tdk Corporation Hard coat agent composition and hard coat film using the same
WO2015038454A1 (en) 2013-09-16 2015-03-19 Honeywell International Inc. Poly fluorine-containing siloxane coatings
US20160304743A1 (en) * 2015-04-17 2016-10-20 Daikin Industries, Ltd. Surface treatment composition

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11613667B2 (en) 2017-12-26 2023-03-28 Akzo Nobel Coatings International B.V. Fluorinate polyacrylate coating composition, the preparation method therefore and use thereof
WO2021074113A1 (en) * 2019-10-15 2021-04-22 Akzo Nobel Coatings International B.V. Waterborne, uv curable coating composition for easy-clean coatings
CN114599748A (en) * 2019-10-15 2022-06-07 阿克佐诺贝尔国际涂料股份有限公司 Water-based UV-curable coating compositions for easy-to-clean coatings
CN114599748B (en) * 2019-10-15 2023-09-15 阿克佐诺贝尔国际涂料股份有限公司 Water-based UV curable coating composition for easy-to-clean coatings
US12312490B2 (en) 2019-10-15 2025-05-27 Akzo Nobel Coatings International B.V. Waterborne, UV curable coating composition for easy-clean coatings
KR20220137751A (en) * 2020-02-18 2022-10-12 아크조노벨코팅스인터내셔널비.브이. Water-Based UV Curable Coating Composition for Antifouling and Scratch Resistant Coatings
KR102913970B1 (en) * 2020-02-18 2026-01-16 아크조노벨코팅스인터내셔널비.브이. Waterborne UV-curable coating composition for antifouling and scratch-resistant coating
CN120309824A (en) * 2025-05-12 2025-07-15 陕西科技大学 A kind of polyurethane-polyacrylate hybrid emulsion and preparation method thereof

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