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WO2013028135A1 - Composition de revêtement haute performance - Google Patents

Composition de revêtement haute performance Download PDF

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Publication number
WO2013028135A1
WO2013028135A1 PCT/SG2012/000298 SG2012000298W WO2013028135A1 WO 2013028135 A1 WO2013028135 A1 WO 2013028135A1 SG 2012000298 W SG2012000298 W SG 2012000298W WO 2013028135 A1 WO2013028135 A1 WO 2013028135A1
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WO
WIPO (PCT)
Prior art keywords
coating composition
silicon compound
group
coating
cross
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/SG2012/000298
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English (en)
Inventor
Shaofeng Wang
Thomas F. Choate
G. Sundararajan
Zeling Dou
Swee How SEOW
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.)
Nipsea Technologies Pte Ltd
Original Assignee
Nipsea Technologies Pte Ltd
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Filing date
Publication date
Application filed by Nipsea Technologies Pte Ltd filed Critical Nipsea Technologies Pte Ltd
Publication of WO2013028135A1 publication Critical patent/WO2013028135A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08G18/28—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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/715—Monoisocyanates or monoisothiocyanates containing sulfur in addition to isothiocyanate sulfur
    • 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
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/005—Dendritic macromolecules

Definitions

  • the present invention relates to a high performance coating composition, methods of preparing the same and uses of the composition.
  • Dendritic polymers are polymers with hyperbranched structures which can comprise a high number of reactive functional groups exposed at the peripheral edges of the Dendritic polymer. Dendritic polymers mimic the hydrodynamic volumes of spheres, and as such, they can be used to provide coatings of high molecular weights whilst maintaining relatively low viscosity.
  • coatings prepared from dendritic polymers have gained traction and popularity in the field of protective coatings. Due to the unique structure of dendritic polymers, the coatings display a variety of desirable traits, such as, high pencil hardness, chemical resistance, solvent resistance and water resistance. Accordingly, such coatings are capable of providing good protection for a surface from damage by elements such as water, snow, ice, heat, dirt, smog, organic waste matter, chemical attacks and acid precipitation.
  • dendritic polymer-based protective coatings not least to widen the scope of possible applications of such coatings but also to improve the utility of current applications. Accordingly, it is an object of the present invention to provide such a dendritic polymer-based coating, wherein the coating displays superior physical performance, such as improved pencil hardness and scratch resistance, and improved chemical performance, such as improved water resistance and solvent resistance compared to conventional dendrimer-based coatings. It is also an object of the present invention to provide a coating having improved adhesion properties in addition to the above technical improvements .
  • a coating composition comprising at least one dendritic polymer, at least one silicon compound, and at least one cross - linker, wherein the silicon compound is selected from the group consisting of siloxanes and SiX 4 ; wherein X in each instance is independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl , aryl, aralkyl, heteroaryl, halide, aminoalkyl, ethers, -OR 1 , and -OfCOlR 1 , wherein each instance of R 1 is independently selected from hydrogen, alkyl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, aralkyl, and heteroaryl; wherein at least one X is halide, -OR 1 , or -OCCOjR 1 ; and wherein the silicon compound is present in
  • a coating composition comprising at least one hyperbranched polyester, vinyltrimethoxysilane , and a cross-linker selected from the group consisting of hexamethylene diisocyanate, dimers of hexamethylene diisocyanate, biuret dimers of hexamethylene diisocyanate, isocyanurate trimers of hexamethylene diisocyanate, and mixtures thereof .
  • a coating composition comprising (a) one or more dendritic polymers; (b) a functionalizxng agent comprising at least one reactive group capable of bonding with an inorganic substrate and at least one organofunctional group capable of coupling with the dendritic polymer; and (c) one or more cross-linkers .
  • the disclosed coating compositions are capable of preparing coatings of unexpectedly high coating performance.
  • the disclosed coatings demonstrate superior pencil hardness and scratch resistance relative to coatings which do not comprise the above combination of dendritic polymers, functionalizing agent and cross-linkers.
  • the coating displays improved chemical resistance, such as resistance to organic solvents, bases and water, compared to a coating that does not comprise the above defined combination of elements.
  • the coating surprisingly retained good flexibility even with the improved hardness.
  • the coatings formed from the disclosed coating compositions possess a glossy and smooth surface appearance that is aesthetically pleasing. A pleasing aesthetical appearance is understandably important with respect to numerous commercial applications of the coatings .
  • the coating compositions described herein may advantageously increase the open time/pot life of the one or two component coating composition.
  • the disclosed polymer compositions in a coating composition experienced longer open time/pot life when compared with known one and two component coating compositions.
  • the increase in pot life may be due to the presence of the functionalizing agent, e.g., silicon compound, which in combination with the dendritic polymer, delays the additional cross-linking processes during curing and provides the coating film with a longer open time.
  • the open time/pot life can be extended by up to 50%-300% longer than traditional coating compositions.
  • Such increased open time/pot life can be realized with as little as 0.1 to 2% by weight of the functionalizing agent, e.g., silicon compound.
  • the improved coating performance of the coatings that comprise the silane compound may be due to the silane compounds having reactive hydrolysable groups, such as methoxy groups (-O e) .
  • the methpxy groups may react with H 2 0 to form silanol groups (-Si(OH) 3 ), which are able to crosslink with the hydroxyl dendritic polymer to form a -Si-O-Si- network, thereby forming a substantially hydrophobic layer on top surface of the coating.
  • This hydrophobic layer has a denser cross-linking density and may delay or prevent to a certain extent, the permeation of moisture as the coating composition is cured, thereby resulting in higher pencil hardness and longer open time of the moisture cured coating.
  • the disclosed coating composition also demonstrates improved coating adhesion properties, in particular, to non-organic substrates such as glass, metal, or ceramic.
  • the functionalizing agent which comprises one or more reactive groups capable of attaching themselves to an inorganic substrate.
  • this improves the overall adhesiveness of the coating composition.
  • a process for preparing a coating composition comprising the step of introducing: (a) one or more dendritic polymers; (b) a functionalizing agent comprising at least one reactive group capable of bonding with an inorganic substrate and at least one organofunctional group capable of coupling with said dendritic polymers; and (c) one or more cross- linkers ; to form said coating composition, wherein the introducing step comprises a mixing step.
  • the coating composition may be subjected to curing under increased temperature, ultra- violet radiation or a combination of both, in the presence of one or more catalysts, to form a highly cross-linked, high performance coating as defined above.
  • the technical advantages are as described above for the coating composition of the first aspect.
  • a process for preparing a coating comprising the step of curing the coating composition defined above.
  • a coating composition comprising (a) one or more dendritic polymers; (b) a functionalizing agent comprising at least one reactive group capable of bonding with an inorganic substrate and at least one organofunctional group capable of coupling with the dendritic polymer; (c) one or more blocked cross- linkers ; and one or more catalysts.
  • a coating composition comprising a first and a second component, the first component comprising: (i) one or more dendritic polymers; (ii) a functionalizing agent comprising at least one reactive group capable of bonding with an inorganic substrate and at least one organofunctional group capable of coupling with the dendritic polymer; and the second component comprising one or more cross - linkers; wherein said first and second component are mixed to form said coating composition.
  • the coating composition may be subjected to curing to form a coating after mixing the first and second components.
  • the curing may comprise an application of heat, ultra-violet (UV) radiation, electron-beam (EB) radiation or a combination thereof. Definitions
  • dendritic polymer refers to a three-dimensional macromolecular material comprising a polyvalent core that is covalently bonded to a plurality of dendrons (or tree-like structures) .
  • dendron means a tree-like structure having multiple branching layers (or “generations”) that emanates from a focal point, such as a polyvalent core.
  • branching layers or “generations” that emanates from a focal point, such as a polyvalent core.
  • Each succeeding branching layer or generation of a dendron extends from the prior generation, and each branching layer or generation in the dendron has one or more terminal reactive sites (or “terminal functional groups") from which the succeeding generation (if any) may extend, or in the case of the last generation, which may provide a terminal functional group on * the dendritic polymer.
  • Dendritic polymers generally have a large number of terminal functional groups, lack entanglements, and have a low hydrodynamic volume. Further, as used herein, the term “dendritic polymer” includes both “dendrimers” and “hyperbranched polymers”. In certain embodiments, the term “dendritic polymer” includes solely hyperbranched polymers. As used herein, the term “dendrimer” refers to a dendritic polymer having a symmetrical globular shape that results from a controlled process giving an essentially monodisperse molecular weight distribution.
  • hyperbranched polymer refers to a dendritic polymer having a certain degree of asymmetry and a polydisperse molecular weight distribution. In certain instances, the hyperbranched polymer has a globular shape . Hyperbranched polymers may be exemplified by those marketed by Perstorp under the Trademarks Boltorn H20TM, Boltorn H30TM, Boltorn H40TM, etc.
  • tack- free time refers broadly to the time taken for an applied coating to reach a physical state such that dry materials cannot be made to adhere to the coating surface. Tack- free time is typically measured through a standard measurement procedure known as the Zapon tack test, wherein a predetermined weight (usally 250 grams) is placed on a strip of aluminum, foil resting over the coating to be tested. The weight is removed from the aluminum after 5 seconds. The amount of time taken for the aluminum foil to dissociate from the coating is then measured. If the time taken for the aluminum foil to dissociate with the coating is 5 seconds or less, the coating is said to be tack- free.
  • the term "about”, in the context of concentrations of components of the formulations, typically means +/- 5% of the stated value, more typically +/- 4% of the stated value, more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value .
  • range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3 , from 1 to 4 , from 1 to 5, from 2 to 4 , from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
  • the dendritic polymers may be selected from any suitable hyperbranched polymer having reactive peripheral functional groups capable of reacting with the disclosed functionalizing agents and cross-linkers.
  • Exemplary dendritic polymers may include, but are not limited to, hydroxyl-terminated polyester, carboxyl-terminated polyester, acrylate-terminated polyester, blends of such polyesters and co-polymers thereof.
  • the dendritic polymer is a hydroxyl terminated polyester.
  • the hydroxyl terminated dendritic polymer may have from about 16 to about 128 theoretical peripheral hydroxyl groups per molecule of dendritic polymer. In another embodiment, the dendritic polymer may have from about 20 to about 80 peripheral hydroxyl grou s.
  • the dendritic polymer has 16, 32, 64, or 128 theoretical hydroxyl groups. In certain embodiments, the dendritic polymer has 32 or 64 theoretical hydroxyl groups. In certain embodiments, the dendritic polymer has 32 theoretical hydroxyl groups. In certain embodiments, the dendritic polymer has 64 theoretical hydroxyl groups.
  • the dendritic polymer is a second generation dendritic polymer having a theoretical number of 16 peripheral hydroxyl groups per polymer molecule.
  • the dendritic polymer is a third or fourth generation dendritic polymer having theoretical peripheral functionality of about 32 to 64. It is generally preferred to have a peripheral functionality of above 32, in order to provide sufficient peripheral functional groups for reaction with cross linkers and other cross-linkable components such as the functionalizing agents.
  • the dendritic polymer is selected from a polyester dendrimer, a polyamide dendrimer, a polyamine dendrimer, a polyether dendrimer, a polyurethane dendrimer, a polycarbonate dendrimer, and mixtures thereof .
  • the dendritic polymer is selected from hyprebranched polyesters, a hyperbranched polyamide, a hyperbranched polyamine, a hyperbranched polyether, a hyperbranched polyurethane, a hyperbranched polycarbonate, and mixtures thereof.
  • the dendritic polymer is a carboxyl- terminated polyester. In one embodiment, the dendritic polymer is an acrylate-terminated polyester.
  • the dendritic polymer is a hydroxyl- terminated polyester, a carboxyl- terminated polyester, an acrylate-terminated polyester, and mixtures thereof .
  • the dendritic polymer is a hyperbranched hydroxyl-terminated polyester, a hyperbranched carboxyl- terminated polyester, a hyperbranched acrylate-terminated polyester, and mixtures thereof .
  • the dendritic polymer is sold under the Boltorn trademark available from Perstorp Plyols, such as Boltorn H10, Boltorn H20, Boltorn H30 and Boltorn H40 . In one embodiment, the dendritic polymer is Boltorn H30. In one embodiment, the dendritic polymer is Boltorn H40
  • the functionalizing agent may comprise at least one reactive group capable of reacting with an inorganic compound and at least one organofunctional group capable of reacting with an organic compound, such as a peripheral functional group of a dendritic polymer.
  • the functional!zing agent is a silicon compound selected from the group consisting of siloxanes and SiX 4 ; wherein X in each instance is independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, aralkyl, heteroaryl, halide, aminoalkyl, ethers, -OR 1 , and -OlCOlR 1 , wherein each instance of R 1 is independently selected from hydrogen, alkyl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, aralkyl, and heteroaryl; wherein at least one X is halide, -OR 1 , or ' -O (CO) R 1 .
  • the silicon compound is SiX 4 .
  • the silicon compound is SiX 4 , wherein at least two X independently in each instance is selected from the group consisting of -OR 1 , and or - OtCOjR 1 .
  • the silicon compound is Si(OR 1 ) 3 X.
  • the silicon compound is Si(OR 1 ) 3 X, wherein X is alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl, aralkyl, heteroaryl, aminoalkyl, or ether. In certain embodiments, the silicon compound is Si(0R 1 ) 3 X, wherein X is alkyl.
  • the silicon compound and the cross-linker are not the same.
  • the reactive group and the organofunctional group maybe the same compound or functional group.
  • the reactive group may be an alkoxide having the general formula MA n , wherein n is an integer from 3 to 4 ;
  • M is an element selected from the group consisting of: Zirconium (Zr) , Aluminum (Al) , Titanium (Ti) , Tin (Sn) and Silicon (Si) ; and
  • A is a halide or an (OR) group, wherein R is acetyl, a phenyl group or an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group is selected from the group consisting of methoxy, and ethoxy.
  • the halide is selected from the group consisting of fluoride (F) , bromide (Br) , chloride (CI) and iodide (I) .
  • A is CI.
  • the reactive group of the functionalizing agent is a siloxane.
  • the siloxane functional group may have a general formula Si(OR) 3 .
  • the siloxane may be selected from the group consisting of: methoxy siloxane, ethoxy siloxane, acetoxy siloxane, chloro- siloxane and combinations thereof.
  • the siloxane functional group is methoxy siloxane, wherein (OR) is -OCH 3 .
  • the organofunctional group of the functionalizing agent may be selected from the group consisting of: amine, amino, amine, hydroxyl, carboxyl, epoxide, methacrylate, mercaptan (SH) , alkyl, alkylene, vinyl, isocyanate, carbamate and combinations thereof.
  • the organofunctional group is alkyl.
  • the organofunctional group is amine.
  • the functionalizing agent may be a siloxane having the general formula (I) : (Z 3 -Si- (CH 2 ) n ) m -X
  • n is an integer ranging from 0 to 10;
  • m is an integer ranging from 1 to 4 ;
  • Z is a reactive hydrolysable group selected from a halide or an (OR) group, wherein R is H, acetyl, a phenyl group or an alkyl group having 1 to 6 carbon atoms ;
  • X is an organofunctional group selected from the group consisting of amino, amine, hydroxyl, carboxyl, epoxide, methacrylate, mercaptan (SH) , alkyl, isocyanate, carbamate and combinations thereof.
  • the alkyl group is selected from the group consisting of methoxy, and ethoxy.
  • the halide is selected from the group consisting of fluoride (F) , bromide (Br) , chloride (CI) and iodide (I) .
  • A is CI.
  • the functionalizing agent may be a siloxane having the general formula (II) :
  • Y is an organic group selected from the group consisting of: alkyl, ether, ketone or aldehyde; and wherein Z, n, m and X are as defined above. In one embodiment, Y is not -CH 2 -.
  • the siloxane can be a bifunctional organosilane, that is, having a general formula (III) :
  • (Z 1 ) and (Z 2 ) being same or different, are hydrolysable groups selected from an (OR) group, wherein R is H, acetyl, a phenyl group or an alkyl group having 1 to 6 carbon atoms; and
  • a and b are integers, independently selected from 0 to 10.
  • the alkyl group is selected from the group consisting of methoxy, and ethoxy.
  • the functionalizing agent is a bifunctional trimethoxysilyl aminosilane, that is, wherein X is amino and where (Z 2 ) and (Z 1 ) are methoxy.
  • the functional!zing agent is a bifunctional organosilane possessing a reactive vinyl group and a hydrolysable inorganic tri-methoxysilyl group.
  • the functionalizing agent may be a bifunctional organosilane possessing a reactive secondary amine group and two hydrolysable inorganic tri- methoxysilyl group.
  • the organosilane compound is a monofunctional trimethoxysilyl epoxysilane, wherein X is epoxy and (Z 2 ) and (Z 1 ) are methoxy.
  • the functionalizing agent may be present in an amount of at least about 0.01% by weight based on the total weight of the coating composition. In another embodiment, the functionalizing agent may be in an amount from about 0.01% to about 20% by weight based on the total weight of the coating composition. In yet another embodiment, the functional!zing agent may be present in an amount of from about 0.2% to about 2.0% by weight.
  • the functionalizing agent may be in an amount of about 0.05%, about 0.1%, about 0.15%, about 0.25%, about 0.3%, about 0.35%, about 0.4%, about 0.45%, about 0.5%, about 0.55%, about 0.6%, about 0.65%, about 0.7%, about 0.75%, about 0.8wt%, about 0.85%, about 0.9%, about 0.95%, or about 1% by weight based on the total weight of the coating composition.
  • the functionalizing agent may be present in an amount of about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9% or about 10% of the coating composition.
  • the silicon compound is present in an amount between about 0.01% to about 7% by weight of the coating composition. In certain embodiments, the silicon compound is present in an amount between about 0.01% to about 5% by weight of the coating composition.
  • the silicon compound is present is present in an amount between about 0.01% to about 2% by weight of the coating composition.
  • the silicon compound is vinyltrimethoxysilane and vinyltrimethoxysilane is present in an amount between 0.1% and 20% by weight of the coating composition.
  • the vinyltrimethoxysilane is present in an amount between 0.1% to 10%, 0.1% to 5%, 0.1% to 4%, 0.1% to 3%, 0.1% to 2%, or 0.1% to 1% by weight of the coating composition.
  • the vinyltrimethoxysilane is present in an amount between 10% and 20%, 10% and 15%, or 15% and 20% by weight of the coating composition.
  • the silicon compound is vinyltrimethoxysilane and vinyltrimethoxysilane is present in an amount between 0.1% and 2% by weight of the coating composition.
  • the silicon compound is vinyltrimethoxysilane and vinyltrimethoxysilane is present in an amount between 10% and 20% by weight of the coating composition.
  • the silicon compound is present in an amount sufficient to extend the open time/pot life of the coating composition by at least about 20% to about 1,000%, about 50% to about 800%, about 50% to about 700%, about 50% to about 600%, about 50% to about 500%, about 50% to about 400%, about 50% to about 300%, about 50% to about 200%, about 50% to about 175%, about 50% to about 150%, about 50% to about 125%, or about 50% to about 100%.
  • the silicon compound is present in an amount sufficient to extend the pot life of the coating composition by at least about 50% when compared to the coating composition absent the silicon compound . In certain embodiments, the silicon compound is present in an amount sufficient to extend the pot life of the coating composition by at least about 100% when compared to the coating composition absent the silicon compound .
  • the silicon compound is selected from the group consisting of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, vinyltrimethoxysilane, vinyltriethoxysilane, bis (trimethoxysilylpropyl) amine, allyltrimethoxysilane, allyltriethoxysilane, 1,2- bis (trimethoxysilyl) ethane,
  • the silicon compound is selected from the group consisting of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, vinyltrimethoxysilane, vinyltriethoxysilane, bis (trimethoxysilylpropyl) amine, allyltrimethoxysilane, allyltriethoxysilane, 1,2- bis (trimethoxysilyl) ethane,
  • the silicon compound is vinyltrimethoxysilane or vinyltrimethoxysilane . In certain embodiments, the silicon compound is vinyltrimethoxysilane .
  • the silicon compound is selected from the group consisting of hexamethyldisiloxane, hexamethylcyclotrisiloxane, octamethyltrisiloxane, poly (dimethylsiloxane) , and octamethylcyclotetrasiloxane .
  • the functional!zing agent may help to improve the adhesion properties of a coating formed from the coating composition.
  • the functionalizing agent may improve the ability of the formed coating to adhere to inorganic substrates, such as glass, metal or minerals.
  • the functionalizing agent may also act as cross -linkers to promote cross -linking between the dendritic polymers, thereby increasing the cross-linking density of the coating.
  • the formed coatings may exhibit improved hardness, chemical and moisture resistance.
  • the functionalizing agent may also alter the "open time" of the coating film. In one embodiment, the functionalizing agent may prolong the coating film "open time” and broaden the application window during coating application process .
  • the disclosed coating composition may comprise one or more cross- linkers .
  • Any cross-linker compound comprising a functional moiety capable of reacting with the peripheral reactive groups of the dendritic polymers and/or the functionalizing agents may be employed as a cross -linker in the coating composition.
  • the cross-linker is selected from the group consisting of isocyanates, blocked isocyanates, anhydrides, melamine formaldehyde resins , urea- formaldehyde resins, and epoxides.
  • the cross- linker selected from the group consisting of isocyanante, blocked isocyanate, melamine formaldehyde, epoxy, carbodiimide, and azirdine; or mixtures thereof.
  • the cross-linker compound is a polyisocyanate .
  • the polyisocyanates may be selected from the group of diisocyanates , tri-isocyanates , and dimers, biuret dimers , and isocyanaurate trimers of the aforementioned polyisocyanates, and mixtures thereof.
  • Polyisocyanates can exist in different oligimeric forms, such as dimers, biuret dimers, and isocyanurates . These polyisocyanates can be represented by the structures shown below, wherein R 1 is as defined above.
  • the polyisocyanate may be of the general formula wherein R 1 is alkyl, alkenyl, alkynyl, cycloalky, heterocyclocalkyl, aryl, diaryl, dicycloalkyl, 5-6 membered heterocyclic compound optionally substituted with one or more of a halogen, oxygen, nitrogen, or C 2 -Ci 0 alkyl; and n is a whole number selected from 2-30; selected from 2-10, selected from 2-10; or selected from 3-7.
  • R 1 is selected from the group consisting of: Ci-C 10 alkyl, Ci-Ci 0 alkenyl, Ci-Ci 0 alkynyl, C3-C7 cycloalkyl, C 3 -C 7 heterocycloalkyl , C 6 -C 12 dicycloalkyl, C 6 -Ci 4 aryl, C 6 -C 14 heteroaryl, triazines, and isocyanurate, each optionally substituted by Ci-Ci 0 alkyl, halogen, or oxygen.
  • R 1 may be selected from the group consisting of: phenyl, diphenyl, methylene diphenyl, cyclohexyl, dicyclohexyl , methylene dicyclohexyl , xylene, toluene, and substituted triazinane.
  • the polyisocyanate is selected from the group consisting of: diphenylmethane 4 , 4' -diisocyanate, toluene diisocyanate (TDI) , methylene diphenyl diisocyanate (MDI) , methylene bis-4,4' - isocyanatocyclohexane, 1, -cyclohexane diisocyanate, triphenylmethane-4 , 4' ,4'' , -triioscyanate, 4' 4- dicyclohexamethylene diisocyanate (H 12 MDI) , xylene diisocyanate, p-phenyl diisocyanate (PPDI) , hexamethylene diisocyanate (HDI) , isophorone diisocyanate (IPDI) , trimethyl hexamethylene diisocyanate ⁇ (TMDI) , tetramethylxylene diiso
  • the polyisocyanate is a mixture comprising isocyanurate trimers of HDI and dimers of HDI.
  • the polyisocyanates prior to reaction with the dendritic polymer, may be modified to exhibit hydrophilicity.
  • the polyisocyanates may be ether-modified, polyether-modified or ionically modified to thereby exhibit hydrophilicity.
  • Exemplary hydrophilic polyisocyanates may include those marketed by Bayer Material Science AG, under the Trademark Bayhydur ® XP2547, Bayhydur ® XP2655, Bayhydur ® XP2759, Bayhydur ® XP2487, Desmodur ® N3300, Desmodur ® N3390, Desmodur ® N3400, Desmodur ® ⁇ 360 ⁇ , etc.
  • the cross-linker may also be a blocked compound wherein its cross-linkable moiety is chemically reacted with a blocking agent to substantially prevent it from reacting with the dendritic polymers and/or the functionalizing agent.
  • the cross- linker can be a blocked isocyanate selected from the list disclosed above.
  • the blocked isocyanate may be used in single component (IK) coating systems wherein the cross- linker is provided in admixture with the coating composition and does not require a separate mixing step prior to applying the composition as a coating onto a surface.
  • the blocked isocyanate may be freed for reaction via the application of heat. Blocked isocyanates are not used in two-part (2K) coating systems where the dendritic polymers, functionalizing agent and the cross-linkers are only mixed shortly before applying the composition as a coating onto a surface.
  • the cross-linker may also be selected from melamine formaldehyde resins.
  • the melamine formaldehyde resin is a hexamethoxymethyl-melamine formaldehyde resin.
  • the weight ratio of dendritic polymer to cross - linker may be from about 10:1 to about 1:10. In one embodiment, the weight ratio of dendritic polymer to cross -linker may be about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, i about 1:6, about 1:7, about 1:8 or about 1:9.
  • the coating compositions can further include one or more additives selected from the group consisiting of a catalyst; a silane-based curing compound; a polyol; a sterically hindered amine light stabilizer; a non-dendritic polymer, a UV absorber; and a photoinitiator .
  • the catalyst may be selected from organometallic compounds or tertiary amines.
  • exemplary catalysts may include a dibutyltin compound, such as dibutyltin dilaurate and dibutyltin diacetate, Triethylenediamine (TEDA) , Triethylamine (TEA),
  • the catalyst may be a strong acid or a weak acid, such as a sulfonic acid.
  • exemplary acid catalysts may include dodecylbenzyl sulfonic acid, p- toluenesulfonic acid, dinonylnapthalene disulphonic acid (DNNDSA) , dodecyl benzene sulphonic acid (DDBSA) , dinonylnapthalene monosulphonic acid (D SA) , phosphates such as alkyl acid phosphates, metal salts and carboxylic acids.
  • cross-linkers used belong to the class of melamine and expoxy resins
  • acid catalysts are used.
  • cross - linkers used belong to the class of isocyanates
  • organometallic compounds and tertiary amines are used as catalysts .
  • the coating composition may further comprise one or more non-dendritic polymers.
  • the non-dendritic polymer may be selected from the group consisting of aliphatic polyester, cyclic polyester, polyurethane, cyclic aliphatic polyester, polyacrylate, polyester polyol, polyurethane polyol, polyacrylate polyol, polycarbonate, polycarbonate polyol , copolymers and blends thereof .
  • the non-dendritic polymer is a polyurethane, such as an aliphatic polyurethane dispersion (PUD) .
  • the non- dendritic polymer is an aliphatic polyester diol.
  • the non-dendritic polymer may be a co-polymer comprising polyacrylate and a polyester polyol.
  • the non-dendritic polymer is PUD, which is selected for its good flexibility and good compatibility with a dendritic polymer.
  • the presence of a non-dendritic polymer further improves properties such as water and chemical resistance of the coating composition.
  • the coating composition may further comprise nanoparticles dispersed through the bulk of the coating composition. While not limited to these uses, nanoparticles may be added to the coating composition to impart physical strength, improve wear resistance and durability, increase solids content, improve the ease of cleaning the coating, improve physical appearance, and provide protection against ultra violent (UV) degradation.
  • the nanoparticles may be metal oxide nanoparticles.
  • the nanoparticles are selected from oxides of aluminum and zinc.
  • the average particle size of the nanoparticles ranges from about 1 nm to 500 nm.
  • these nanoparticles may be encapsulated within a polymer which has been suitably functionalized for compatibility with the dendritic polymers used .
  • the coating composition may further comprise one or more of the following: UV-absorbers , surfactants, organic solvents and stabilizers.
  • the coating composition may further comprise one or more types of acrylic functional monomers.
  • the acrylic functional monomers may be integrally linked with the dendritic polymers via reaction with cross-linkers, to thereby attach acrylic functional groups onto the dendritic polymer.
  • the presence of the terminal double bonds provided by the acrylic functional groups may aid formation of radicals upon exposure to UV radiation.
  • this allows for UV curing of a coating formed from the disclosed coating composition.
  • the acrylic functional monomers may be added to the coating composition in an amount sufficient to cause about 10% to about 50% substitution of the functional groups on the dendritic polymer with acrylic functional groups. In one embodiment , the acrylic functional monomer is added in an amount sufficient to cause about 20%, about 30%, or about 40% substitution of the functional groups on the dendritic polymers with acrylic functional groups .
  • Exemplary acrylic functional monomers may be selected from, but are not limited to, the group consisting of 2-hydroxyethylacrylate (HEA) , hydroxyl ethyl methacrylate (HE A) and glycidyl methacrylate (G A) and monomer blends thereof . Exemplary, non- limiting embodiments of the process for preparing a coating composition in accordance with the second aspect will now be disclosed.
  • the mixing step of the disclosed process may comprise a physical blending step.
  • Physical blending may be performed by mechanical blending through mixers and/or blenders.
  • the physical blending step may be undertaken at room temperature (i.e., cold blending) using a mechanical mixer.
  • the dendritic polymer may be functionalized with one or more hydrophilic functional groups prior to being physically blended with the functionalizing agent.
  • the hydrophilic functional groups may be selected from the group consisting of: primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium salt groups, an amide group, an aldehyde group, a carbonyl group, a carboxyl group, a carboxylate group, an ester group, a sulfonic acid group, phosphoric acid group and a hydroxyl group.
  • the hydrophilic functional group is a carboxyl group.
  • the mixing step may comprise a step (dl) of chemically reacting the dendritic polymers with the functionalizing agent to increase cross- linking density of the coating composition.
  • the reaction step (dl) may comprise at least one surface modification step (dl) (i) wherein the functionalizing agent attaches itself to the dendritic polymer by having its reactive group react with a peripheral functional group of the dendritic polymer (not shown explicitly in Fig.l).
  • the reactive group is amine and the dendritic polymer comprises hydroxyl functionality
  • amide bonds may be formed between the amine groups and the hydroxyl groups to thereby attach the functionalizing agent onto the dendritic polymer.
  • the surface modification step (dl) (i) may be followed by a de-alkylation step (dl) (ii) wherein the alkyl groups of the siloxane functional group are subsequently replaced by hydroxyl groups via addition of water and the removal of R(OH) groups.
  • a condensation step (dl) (iii) wherein two or more de-alkylated siloxane groups undergo a condensation step to form -Si-O-Si- bonds between two or more dendritic polymers.
  • the condensation reactions can be carried on for as long as required to allow sufficient cross-linking to occur to thereby form a densely cross- linked network of dendrimers .
  • a suitable catalyst such as, dibutyltin dilaureate.
  • the mixing step of the disclosed process may further comprise a step (d2) of chemically reacting the dendritic polymers with said cross-linkers to increase cross- linking density of the coating composition.
  • the reaction step (d2) may be carried out in the presence of one or more cross-linking catalysts.
  • the mixing step of the disclosed process may further comprise a step (d3) of chemically reacting the cross- linkers with the functionalizing agents to increase cross-linking density of said coating composition.
  • the reaction step (d3) may be carried out in the presence of one or more catalysts .
  • the disclosed mixing ste comprises one or more of the above defined steps (dl) , (d2) and (d3) , each step occurring independently and/or concurrently with each other.
  • the present disclosure further provides a process for preparing a coating, the coating being formed by curing a coating composition as defined above or by curing a coating composition obtained from the process described above.
  • the curing may be selected from heat curing, UV curing, EB curing and/or combinations thereof. Where heat curing is used, the curing may be undertaken at a temperature of greater than 25°C. In one embodiment, the heat curing may be performed at temperatures up to 250°C. In another embodiment, for 2 coating systems, the curing step may be undertaken at temperatures ranging from about 20°C to about 100°C. In yet another embodiment, for IK coating systems, the curing step may be undertaken at about 60°C to about 160°C.
  • the functionalizing agent is coupled to the dendritic polymer either by direct bonding or through bonding via a cross- linker.
  • the disclosed coating composition may be used in either a one component (IK) or two component (2K) coating composition for forming a high performance coating.
  • the coating can be water-dispersible or a solvent-based coating for application over a surface, depending on whether an organic solvent is used or water is used as the dissolution medium. It can be appreciated that where water is used as the dissolution medium, the dendritic polymers may be further functionalized with one or more hydrophilic ionic groups to impart the necessary polarity for dissolving or dispersing in water.
  • the coating composition consists of a two component coating composition, wherein the two component coating composition consists of a first component and a second component, wherein the first component comprises the dendritic polymer, the second component comprises the cross-linker, and wherein the first component or second component further comprises the silicon compound.
  • the first component further comprises the silicon compound.
  • the second component comprises the silicon compound.
  • the first component or the second component further comprises a catalyst.
  • the first component comprises the catalyst .
  • the second component comprises the catalyst .
  • the applied coating may also be cured via exposure to UV radiation.
  • temperature curing in combination with UV curing is also envisioned within the scope of the present invention.
  • Fig. 1 is a reaction scheme showing the reaction mechanisms between an exemplary functional!zing agent and a dendritic polymer.
  • Fig. 2 is a reaction scheme showing the mechanism how a dendritic polymer that has been reacted with a functionalizing agent can possess adhesive properties.
  • the dendrimer may have hydroxyl functional groups, carboxyl functional groups, acrylate functional groups or a combination of such functional groups disposed at the peripheral edge of the dendritic polymer molecule.
  • the shown dendrimer comprises hydroxyl functionality.
  • An exemplary functionalizing agent having a general formula (I) (Z 3 -Si- (CH 2 ) n ) m -X is reacted with the dendrimer in the presence of a catalyst.
  • the organofunctional X group reacts with the hydroxyl functional groups of the dendritic polymer to thereby attach the reactive, hydrolysable moieties -SiZ 3 onto the dendrimer.
  • X can be a amino group and forms an amide linkage (-NHCO-)with the dendrimer.
  • the surface modified dendrimer is then de-alkylated in the presence of water to substitute the reactive, hydrolysable moieties -SiZ 3 with -Si(OH) 3 groups. Thereafter, the de-alkylated dendrimers undergo condensation reactions in the presence of a catalyst to form -Si-O-Si- bonds, linking one dendrimer molecule to another dendrimer molecule. The condensation reactions may be proceeded to an extent until a densely cross- linked dendrimer is formed.
  • the pendant -OH groups of the siloxane moiety being substantially polar in nature, can strong electrostatic bonds with an adjacent surface, thereby imparting an adhesive property to the coating composition.
  • HDI hexamethylene diisocyanate
  • IPDI Isophorone diisocyanate
  • PID 163P Pure aliphatic polyurethane dispersion
  • a one-component (IK) coating composition was prepared comprising the components provided in Table 1 below.
  • UV Stabilizer (Tinuvin 384-2) 1
  • Table 2 below shows the amounts of silane dosage levels in each Example.
  • the IK moisture curable coating compositions from Examples 1(a) to 1(e) were dried at room temperature for 48 hours.
  • the dry film appearance of the IK moisture cured systems was clear and glossy.
  • the moisture cured coating of Example 1(e) i.e. 0 wt% of the silane compound, possessed a scratch hardness of H and a break hardness of 2H.
  • the break hardness doubled to 4H.
  • the break hardness increased to 5H.
  • the presence of the silane compound in the composition improved the adhesion of the coating to a substrate and delayed film drying time.
  • the composition is thus more flexible in a sense that it is possible to apply more than one layer of the coating to a relatively larger area because the open time of the applied coating has been substantially lengthened.
  • Table 3 summarizes the performance results of the moisture cured coatings.
  • the improved coating performance of the coatings that comprise the silane compound is due to silane compounds having reactive hydrolysable groups, such as methoxy groups (-OMe) .
  • the methoxy groups react with H 2 0 to form silanol groups (-Si(OH) 3 ), which are able to cross-link with the hydroxyl dendritic polymer to form a -Si-O-Si- network, thereby forming a hydrophobic layer on top of the clear coating.
  • This hydrophobic layer has a denser cross-linking density and it is further postulated that this hydrophobic layer delays, or prevents to a certain extent, the permeation of moisture as the coating composition is cured, thereby resulting in higher pencil hardness and longer open time of the IK moisture cured system.
  • a two-component (2K) coating composition was prepared comprising the components provided in Table 4 below. The two components are termed “Side A” and “Side B” .
  • Table 5 below shows the amounts of silane dosage levels in each Example.
  • the 2K coating compositions from Examples 3(a) to 3(c) were dried at 65°C for 45 minutes, followed by overnight post drying at room temperature. The dry film appearance of the 2K compositions was clear and glossy.
  • Example 3(c) i.e., having no silane compound
  • a scratch hardness of only 2H i.e., a scratch hardness of 3H
  • a break hardness of 3H 0.5 wt%
  • the presence of silane in the composition improved adhesio to the substrate and delayed film drying time from 25 minutes to 40 minutes, which confers on the coating greater flexibility.
  • the coating composition possess improved flow properties, enhancing its ability to be formed into a coating film.
  • the formed coating film also has an even smooth surface. Additionally, the dry coating film appears glossier and possesses a higher degree of a distinctiveness of image (DOI) .
  • DOI distinctiveness of image
  • the reactive vinyl groups of the silane increased the cross-linking density of the dry film when exposed to UV light.
  • a two-component (2K) aqueous dispersible PU coating composition comprising a Side A and Side B is prepared in this Example.
  • Side A comprises the water dispersible dendritic polymer blend (obtained from Example 5a) ; whereas Side B comprisesan isocyanate (HDI) .
  • Table 7 shows the composition of each of Side A and Side B.
  • silane (Silquest A-187) was loading into the 2K PU coating composition to study the synthetic effect of silane material in the 2K coating composition.
  • the 2K aqueous dispersible PU coating composition from Example 5(b) was dried at 85°C for 2 hours, followed by overnight post-drying at room temperature.
  • silane in the formulation also increases the chemical resistance, as the total MEK Rubs increased from 471 cycles to 566 cycles (Also see Table 8) .
  • This Example refers to an UV curable coating composition
  • an acrylate dendritic oligomer (CN 2304) about 95% t, UV photoinitiator (Irgacure 500) 5%wt.
  • silane Surquest A-1170 was loaded into the UV curable coating composition to study the synthetic effect of silane material in the dendritic polymer coating formulation.
  • UV curable coating composition from Example 6(a) was dried under UV light (Fusion Systems H bulb with 300 /cm) with Line speed 17 feet per min for irradiation.
  • a coating composition comprising, inter alia, a dendritic polymer, a functionalizing agent having at least one reactive group and at least one organofunctional group, and cross- linkers.
  • a coating prepared from the disclosed coating composition advantageously possesses improved coating properties, such as but not limited to, improved pencil hardness, increased adhesion to surface, improved flexibility for coating applications of wide surface area and enhanced solvent/water resistance. Therefore, the disclosed coatings can be applied to a wide variety of industrial applications requiring heavy-duty protective coatings.
  • the disclosed protective coatings foresee utility in industrial applications whereby equipment wear and tear is caused by prolonged exposure to abrasive forces.
  • the disclosed coatings can be potentially employed in chemically corrosive environments due to its improved chemical/water resistance.
  • the disclosed coating presents a smooth and glossy surface-, which is aesthetically pleasing and further expands its utility in commercial coating applications.

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Abstract

Cette invention concerne une composition de revêtement comprenant (a) un ou plusieurs polymères dendritiques ; (b) un agent de fonctionnalisation comprenant au moins un groupe réactif capable de se lier à un substrat inorganique et au moins un groupe organofonctionnel capable de se coupler aux polymères dendritiques ; et (c) un ou plusieurs agents de réticulation ; un procédé pour la préparer ; et les revêtements comprenant la composition ci-décrite.
PCT/SG2012/000298 2011-08-23 2012-08-22 Composition de revêtement haute performance Ceased WO2013028135A1 (fr)

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CN109181612A (zh) * 2018-09-14 2019-01-11 齐鲁工业大学 一种耐水性生物基胶黏剂及其制备方法
CN113717628A (zh) * 2021-09-18 2021-11-30 湖南松井新材料股份有限公司 水性pu涂料及其制备方法和应用
CN115029055A (zh) * 2022-05-06 2022-09-09 江苏利宏科技发展有限公司 一种耐候改性聚氨酯防水涂料及其制备方法
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US9308616B2 (en) 2013-01-21 2016-04-12 Innovative Finishes LLC Refurbished component, electronic device including the same, and method of refurbishing a component of an electronic device
WO2014152428A1 (fr) * 2013-03-15 2014-09-25 Curatolo Benedict S Composition durcissable double
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WO2016000537A1 (fr) * 2014-07-01 2016-01-07 廊坊立邦涂料有限公司 Composition de vernis aminé au four ayant une fonction d'auto-nettoyage, et son procédé de préparation
CN104194612A (zh) * 2014-07-28 2014-12-10 铜陵市远程艺术制品有限责任公司 一种铜雕用防水耐磨聚氨酯丙烯酸酯油漆
CN107337800B (zh) * 2017-07-11 2019-10-15 上海乘鹰新材料有限公司 抗污助剂及其在紫外光固化涂料中的应用
CN107337800A (zh) * 2017-07-11 2017-11-10 上海乘鹰新材料有限公司 抗污助剂及其在紫外光固化涂料中的应用
CN107674189A (zh) * 2017-09-30 2018-02-09 合众（佛山）化工有限公司 一种高固分超支化硅改性不饱和聚酯树脂及其制备方法
CN107674189B (zh) * 2017-09-30 2019-08-06 合众（佛山）化工有限公司 一种高固分超支化硅改性不饱和聚酯树脂及其制备方法
CN109181612A (zh) * 2018-09-14 2019-01-11 齐鲁工业大学 一种耐水性生物基胶黏剂及其制备方法
CN113717628A (zh) * 2021-09-18 2021-11-30 湖南松井新材料股份有限公司 水性pu涂料及其制备方法和应用
WO2023187731A1 (fr) * 2022-03-31 2023-10-05 Asian Paints Limited Composition de revêtement et procédé permettant sa préparation
CN115029055A (zh) * 2022-05-06 2022-09-09 江苏利宏科技发展有限公司 一种耐候改性聚氨酯防水涂料及其制备方法

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