EP1841809A2 - Materiau polymere formant des micro-domaines de surface - Google Patents

Materiau polymere formant des micro-domaines de surface

Info

Publication number
EP1841809A2
EP1841809A2 EP06733601A EP06733601A EP1841809A2 EP 1841809 A2 EP1841809 A2 EP 1841809A2 EP 06733601 A EP06733601 A EP 06733601A EP 06733601 A EP06733601 A EP 06733601A EP 1841809 A2 EP1841809 A2 EP 1841809A2
Authority
EP
European Patent Office
Prior art keywords
polymeric material
polyisocyanate
polyol
polyorganosiloxane
microdomains
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.)
Withdrawn
Application number
EP06733601A
Other languages
German (de)
English (en)
Other versions
EP1841809A4 (fr
Inventor
Dean C. Webster
Partha Majumdar
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.)
North Dakota State University Research Foundation
Original Assignee
North Dakota State University Research Foundation
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 North Dakota State University Research Foundation filed Critical North Dakota State University Research Foundation
Publication of EP1841809A2 publication Critical patent/EP1841809A2/fr
Publication of EP1841809A4 publication Critical patent/EP1841809A4/fr
Withdrawn legal-status Critical Current

Links

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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing polyurethane sequences
    • 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
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • 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
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/61—Polysiloxanes
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters

Definitions

  • Block copolymers containing poly(dimethyl siloxane) (PDMS) are well known. Typically, these are linear copolymers made up of long sequences of PDMS covalently coupled to another polymer. For example, diblock, triblock, and segmented/multiblock copolymers of PDMS with a variety of polymers have been prepared.
  • Block copolymers of PDMS with other polymers typically phase separate as a result of the immiscibility of the two different blocks. However, due to the covalent linkage between the blocks, the phase separation is restricted and only micro- or nano-scale phase separation occurs. In many PDMS block copolymer systems, PDMS has a significantly lower surface energy than the second block, and thus tends to predominate on the surface of the copolymer.
  • Block copolymers of PDMS with polyurethane are also known. In many cases, these may function as minimally adhesive surfaces. However, over time, the more hydrophilic polyurethane components may migrate to the surface resulting in a loss of the low surface energy. This is especially a problem when the copolymer is exposed to an aqueous environment (e.g., when used as a marine coating, etc.).
  • a cross linked polymeric material is described herein that includes polyorganosiloxane and polyurethane components and may form a topographical surface structure that can be stable in an aqueous environment.
  • the polymeric material may include raised microdomains, e.g., raised microdomains made predominantly of the polysiloxane component surrounded by a polyurethane matrix.
  • the microdomains may be regular microdomains.
  • the polymeric material may be prepared by reacting a composition which includes polyol, polyisocyanate, and polyorganosiloxane having functional groups capable of reacting with the polyisocyanate.
  • the polymeric material may have a surface that includes raised microdomains. The microdomains may also be stable when exposed to water for more than 14 days.
  • the polyorganosiloxane may include hydroxy functional polyorganosiloxane such as hydroxy functional polydimethylsiloxane (e.g., hydroxy alkyl functional polydimethylsiloxane).
  • the polyol may include polyester polyols, polyether polyols, polycarbonate polyols, and acrylic polyols. In one embodiment, the polyol may include polyol having at least three hydroxy groups.
  • the polyisocyanate may include polyisocyanate having at least three isocyanate groups.
  • the polymeric material may be prepared by reacting a composition which includes polyol, polyisocyanate, and polyorganosiloxane having functional groups capable of reacting with the polyisocyanate.
  • the polyol typically has at least three hydroxy groups and/or the polyisocyanate has at least three isocyanate groups.
  • the use of at least tri-funtional polyols and/or isocyanates can allow the polymeric material to cross link together to form a more stable surface structure.
  • a cross linked polymeric material may be prepared by reacting a composition comprising up to 15 wt % polyhydroxy functional polyorganosiloxane, base on the total solids content of the polymeric material, together with polyol and polyisocyanate.
  • a cross linked polymeric material may be prepared by reacting a composition comprising polyol, polyisocyanate, and polyorganosiloxane having functional groups capable of reacting with the polyisocyanate to form a polymeric material includes surface microdomains that are more hydrophobic than the surrounding polymer matrix.
  • the surface microdomains may include the siloxane polymer and the surrounding matrix may include polyurethane.
  • the surface domains may have a hydrophobicity which does not appreciably change when exposed to water for 14 days.
  • a coating composition may be prepared that may be used to coat a substrate such as metal, wood, glass, etc. so that upon curing, the coating composition forms the polymeric material described previously.
  • the coating composition may include up to 15 wt %, based on the total solids in the coating composition after the coating composition has cured, of polyol, polyisocyanate, polyorganosiloxane having functional groups which are capable of reacting with the polyisocyanate, and a solvent component.
  • the solvent component may include alkyl alkoxypropionate, dialkyl ketone, and/or alkyl acetate.
  • the coating composition may also include a pot life extender such as alkane-2,4- dione, N,N-dialkyl acetoacetamide, alkyl acetoacetate.
  • a pot life extender such as alkane-2,4- dione, N,N-dialkyl acetoacetamide, alkyl acetoacetate.
  • An isocyanate reaction catalyst such as an organotin compound or tertiary amine may be used to catalyze reaction of the components in the composition.
  • a method for preparing and using the coating composition comprises adding isocyanate reaction catalyst to a composition comprising polyol, polyisocyanate, and polyorganosiloxane having functional groups capable of reacting with the polyisocyanate to form a coating composition and applying the coating composition to a substrate.
  • the coating composition cures on the substrate to form a polymeric material that has raised microdomains.
  • Polymeric materials as described herein may be used in a number of different settings such as for creating minimally adhesive surfaces that may be useful as release paper for adhesive labels, anti-graffiti coating, and fouling release coatings for marine vessels.
  • FIGS. 1-2 are atomic force microscopy images of the surface of the polymeric material from Sample 1 in Table 2.
  • FIG. 3 is a scanning electron microscope image of the surface of the polymeric material from Sample 1 in Table 2.
  • FIG. 4 is a scanning electron microscope image of the surface of the polymeric material from Sample 3 in Table 2.
  • FIG. 5 is an atomic force microscopy image of the surface of the polymeric material from Sample 3 in Table 2.
  • FIG. 6 is (a) a scanning electron microscope image and (b) an X-ray mapping of silicon of the surface of the polymeric material from Sample 1 in Table 2.
  • FIG. 7 shows a comparison of atomic force microscopy images of the polymeric material from Sample 1 in Table 2 (a) before immersion in water and (b) after two weeks immersion in water.
  • FIG. 8 shows a comparison of atomic force microscopy images of the polymeric material from Sample 2 in Table 2 before water immersion (8(a) and (c)) and after immersion in water for two weeks (8(b) and (d)).
  • FIG. 9 shows atomic force microscopy images of the 35 polymeric materials prepared using the solvent compositions shown in Table 4.
  • FIG. 10 shows a plot of the mean diameter of microdomains formed in various polymeric materials versus the ratio of MAJL-EEP used in the solvent to prepare the polymeric materials.
  • FIG. 11 is a transmission electron microscopy image of the polymeric material from Si-PU 8 shown in Table 7.
  • FIG. 12 shows a number of atomic force microscopy images taken to show the effect of kinetics on formation of microdomains in one embodiment of the polymeric material.
  • FIG. 13 is a plot of domain size versus time for the polymeric materials formed in Series A and Series B from FIG. 12.
  • FIG. 14 shows scanning electron microscope images at (a) 0.5 hrs, (b) 3.5 hrs, and (c) 7.5 hrs and corresponding silicon mapping images for the polymeric materials from Series A in FIG. 12.
  • FIG. 15 is a plot of the loss modulus versus temperature as a function of mixing time for the polymeric material from Series A in FIG. 12.
  • the polymeric material may be capable of forming a topographical surface structure which is stable in an aqueous environment.
  • a surface structure may be stable in an aqueous environment, the polymeric material may be more useful and its properties more stable in applications such as marine coatings, coatings on medical instruments or devices, etc.
  • the polymeric material may be prepared by reacting a composition that includes polyol, polyisocyanate, and polyorganosiloxane that has functional groups capable of reacting with the polyisocyanate.
  • a composition that includes polyol, polyisocyanate, and polyorganosiloxane that has functional groups capable of reacting with the polyisocyanate.
  • at least one of the polyol, polyisocyanate, or the polyorganosiloxane includes at least three functional groups which can react with the other components in the composition.
  • the polyol may include three or more hydroxy groups or the polyisocyanate may include three or more isocyanate groups, hi some embodiments where more cross linking is desired, the composition may include polyol having at least three hydroxy groups and polyisocyanate having at least three isocyanate groups.
  • the polymeric material has a surface that includes regular, raised microdomains of the siloxane polymer surrounded by a polyurethane matrix. Because the siloxane polymer is more hydrophobic than the polyurethane, the polysiloxane rich microdomains are more hydrophobic than the surrounding polyurethane rich matrix, hi some embodiments, the surface morphology may be locked in place so that the microdomains do not appreciably change in size and shape when exposed to water for more than 14 days, hi other embodiments, the microdomains may remain upon exposure to water, but may undergo varying degrees of change or reorientation.
  • the microdomains may be any of a number of sizes.
  • the average diameter of the microdomains may range from about 0.1 microns to 10 microns, desirably, from about 0.5 microns to 5 microns, or, suitably, about 1 micron to 3 microns.
  • the average height of the microdomains may range from about 0.01 microns to 0.2 microns, desirably, from about 0.025 microns to 0.15 microns, or, suitably, from about 0.03 microns to 0.1 microns, hi one embodiment, the microdomains may be spaced apart at regular intervals and be of a substantially uniform size.
  • the microdomains may have an average spacing of about 0.5 microns to 10 microns or, desirably, about 1 micron to 5 microns.
  • the polymeric material may also have a microdomain surface density of about 0.1 to 1.5 microdomains/micron 2 or, typically, about 0.2 to 0.65 microdomains/micron 2 . It should be appreciated that the polymeric material may have any suitable microdomain surface density.
  • the polyol used to prepare the polymeric material may be any of a number of polyols. Suitable polyols may include polyester polyols, polyether polyols, polycarbonate polyols, and acrylic polyols. As mentioned previously, the polyol may have at least three hydroxy groups to facilitate cross linking of the polymeric material. In one embodiment, the polyol may include polycaprolactone polyol such as a polycaprolactone triol. In another embodiment, the polyol may have an average hydroxyl equivalent weight of about 100 to 300 or, desirably, 150 to 200. The polymeric material may include about 10 wt % to 40 wt % or, desirably, about 20 wt % to 30 wt % of the polyol, based on the total solids content of the polymeric material.
  • any of a number of suitable polyisocyanates may be used to prepare the polymeric material.
  • the polyisocyanate may have at least three isocyanate groups to facilitate cross linking of the polymeric material.
  • the polyisocyanate may include an isophorone based polyisocyanate.
  • the polyisocyanate may have an isocyanate equivalent weight of about 150 to 600 or, desirably about 250 to 450.
  • the polymeric material may include about 30 wt % to 85 wt % or, desirably, about 50 wt % to 75 wt % of polyisocyanate, based on the total solids content of the polymeric material.
  • any of a number of polyorganosiloxanes may be used as long as it is capable of reacting with the polyisocyanate.
  • the polyorganosiloxane may include hydroxy or amino functional polyorganosiloxane such as hydroxy or amino functional PDMS.
  • the polyorganosiloxane may include hydroxy or amino alkyl functional polyorganosiloxane such as hydroxy and/or amino propyl functional polyorganosiloxane.
  • the polyorganosiloxane may have an average hydroxyl equivalent weight of about 200 to 800 or, desirably, about 350 to 700.
  • One suitable polyorganosiloxane may be ⁇ , ⁇ -bis[3-(2'-hydroxyethoxy)propyl] polydimethylsiloxane.
  • the polymeric material may include about 1 wt % up to 15 wt %, based on the total solids content of the polymeric material, of polyorganosiloxane, while in other embodiments, the polymeric material may include less than about 15 wt % or no more than about 14 wt % of the polyorganosiloxane.
  • the polymeric material may include about 2 wt % to 14 wt %, about 3 wt % to 13 wt %, or, suitably, 5 wt % to 12 wt %.
  • the PDMS may also have any suitable molecular weight.
  • the molecular weight of the PDMS may be no more than about 10,000 g/mole, no more than about 7,500 g/mole, or, suitably, no more than about 5,000 g/mole.
  • the PDMS may have a molecular weight that is above 10,000 g/mole.
  • a coating composition may be prepared which can be applied to a substrate so that upon curing the polymeric material described herein is formed.
  • the coating composition may include polyol, polyisocyanate, polyorganosiloxane, and a solvent component.
  • the solvent component may include alkyl propionate (e.g., lower alkyl propionate, preferably having 5 to 10 carbon atoms), alkoxypropionate, alkyl alkoxypropionate (e.g., lower alkyl alkoxypropionate, preferably having 5 to 10 carbon atoms), alkoxyalkyl propionate (e.g., alkoxyalkyl propionate having 5 to 10 carbon atoms), dialkyl ketone (e.g., dialkyl ketone having 5 to 10 carbon atoms), alkyl acetate (e.g., lower alkyl acetate, preferably having 5 to 10 carbon atoms), alkyl alkoxyacetate (e.g., lower alkyl alk
  • the solvent component may include ethyl 3-ethoxypropionate (EEP), methyl n-amyl ketone (MAK), and/or butyl acetate.
  • the coating composition may also include a pot life extender such as alkane-2,4-dione (e.g., 2,4- pentadione), N,N-dialkyl acetoacetamide, or alkyl acetoacetate.
  • the amount of the components in the coating composition may be the amounts in the examples below or within 15 % above or below the amount of any particular component of any example in the examples section.
  • the solvent component may include BuAc, EEP, and MAK.
  • the ratio of MAK:EEP may vary from about 45:5 to 5:45. In general, the average diameter of the domains formed may incases as the ratio changes to include greater amounts of EEP.
  • the solvent component may have a formation vapor pressure that is no more than about 12 mm of Hg or, desirably, no more than about 11 mm of Hg.
  • the coating composition may also include an isocyanate reaction catalyst such as dialkyl tin dicarboxylate, trialkyltin hydroxide, dialkyltin oxide, dialkyltin dialkoxide, dialkyltin dihalide, or a mixture thereof, which is used to initiate the reaction.
  • an isocyanate reaction catalyst such as dialkyl tin dicarboxylate, trialkyltin hydroxide, dialkyltin oxide, dialkyltin dialkoxide, dialkyltin dihalide, or a mixture thereof, which is used to initiate the reaction.
  • Suitable examples of isocyanate reaction catalysts include diethyl tin diacetate, dibuyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, or a mixture thereof.
  • the isocyanate reaction catalyst includes a tin catalyst.
  • the coating composition may be prepared by mixing all of the components except for the polyisocyanate and the isocyanate reaction catalyst.
  • the polyisocyanate and the isocyanate reaction catalyst are added and then the composition is allowed to react for a time before it is applied to a substrate.
  • the amount of time before the coating is applied to the substrate is dependent on the inclusion level of the isocyanate reaction catalyst and/or inclusion levels of the polyorganosiloxane, polyol, and/or polyisocyanate.
  • PDMS A 1 (hydroxyl equiv. wt. of 500 g/eq.;
  • PDMS B 2 (amine equiv. wt. of 6215 g/eq.)
  • PDMS C 2 (amine equiv. wt. of 12307 g/eq.)
  • PCL Polycaprolactone
  • Polyisocyanate D (isocyanate equiv. wt. of Rhodia (Tolonate XIDT 7OB; 70% in 342 g/eq.) BuAc) Material Supplier
  • Polyisocyanate E 4 (isocyanate equiv. wt. of
  • Rhodia Tolonate HDT 90 212 g/eq.
  • MAK Methyl n-amyl ketone
  • PDMS B was synthesized as follows. In a 250-ml three necked round bottom flask 2.04 g l,3-bis(3-aminopropyl)-l,l,3,3-tetramethyldisiloxane and 10 g octamethylcyclotetrasiloxane were mixed. The solution was heated with stirring under nitrogen: By the time the temperature reached 80° C, 0.1% catalyst (tetramethylammonium 3-aminopropyl dimethyl silanolate) was placed into the solution. After one hour of heating the viscosity increased slightly, and the remaining octamethylcyclotetrasiloxane (90 g) was placed into an addition funnel and added drop wise into the solution.
  • 0.1% catalyst tetramethylammonium 3-aminopropyl dimethyl silanolate
  • PDMS C was synthesized by following the above procedure for PDMS B using 1.02 g l,3-bis(3-aminopropyl)-l,l,3,3-tetramethyldisiloxane, plus 5 g octamethylcyclotetrasiloxane in the initial charge with 95 g octamethylcyclotetrasiloxane added using the addition funnel.
  • Atomic force microscopy (AFM) studies were performed on a Dimension 3100 microscope with Nanoscope Ilia controller (Digital Instruments, Inc. California). Experiments were carried out by tapping mode in air under ambient conditions or by contact mode under water. Silicon probes with spring constant 0.1-0.4 N/m and resonant frequency 17-24 kHz were used. The setpoint ratio for collection of TMAFM data was 0.9.
  • Nanoindentation measurements were conducted using the Dimension 3100 microscope with a Berkovich type diamond indenter probe.
  • the spring constant for the probe was 177.3 N/m.
  • Force-deflection curves from a standard sapphire substrate were used for calibration of deflection voltage and found to average 220.8 nm/V.
  • a threshold force value of 20 ⁇ N was used to obtain an array of indentations over the surface of the coating.
  • Samples 1-9 were prepared by weighing and mixing the respective stock solutions of PDMS, PCL triol (90% solution in EEP for Sample 2 and 90% solution in MAK for the remainder of the Samples), and the 2,4- pentanedione thoroughly in a 20 ml vial via magnetic stirring. After thorough mixing, the DBTDA and the polyisocyanate were added and mixed for the specified amount of time shown in Table 2. Coatings were drawn down over aluminum panels and kept under ambient conditions for 24 hours followed by oven curing at 80° C for 45 minutes. Coating film thickness was 50 to 70 ⁇ m. Table 2
  • Wt. percent of catalyst is given with respect to total solid weight of polymeric material.
  • the coatings prepared in Samples 1-9 were cast as a solution of the reactive oligomers (e.g., PDMS, PCL triol, polyisocyanate, in the amounts shown in Table 2) in a solvent blend with a catalyst (DBTDA) and a pot-life extender (2,4-pentanedione) as already described. Since PDMS has a much lower surface energy than the polyurethane, the PDMS was expected to stratify to the coating surface during film formation and crosslinking, resulting in a polyurethane coating having a smooth, low surface energy PDMS outer layer with a tough polyurethane sub-layer.
  • the reactive oligomers e.g., PDMS, PCL triol, polyisocyanate, in the amounts shown in Table 2
  • DBTDA catalyst
  • a pot-life extender (2,4-pentanedione a pot-life extender
  • Sample 1 containing 10 % PDMS A yielded a microstructured surface with discrete domains as shown in FIG. 1.
  • the domains have an average diameter of about 1.4 ⁇ m and a height of about 50 run.
  • a planar view of the surface of the polymer formulation from Sample 1 is shown in FIG. 2.
  • An SEM image of Sample 1 is shown in FIG. 3.
  • Interspersed between the larger domains are numerous smaller domains as well.
  • the size distribution of the larger domains is fairly uniform. While it may be assumed that the domains are primarily composed of PDMS, the domain sizes are larger than expected if they were composed solely of the 1000 g/mol PDMS A block. Thus, these domains may include a mixture of PDMS A as well as some of the polyurethane components.
  • Nanoindentation measurements were conducted on the microstructured siloxane- urethane surface from Sample 1 and also on the control polyurethane surface under the application of the same threshold force value of 20 ⁇ N. Depth of indentation at peak load (h max ) over the microdomains was considerably higher (179.5 ⁇ 3.7 nm) than the surrounding area (83.6 ⁇ 1.8 nm). The h max value obtained on the pure polyurethane surface was 78.3 ⁇ 10.4 nm, close to the value obtained for the matrix of the microstructured surface. Thus, the higher indentation depth indicates that the microdomain modulus is significantly lower than that of the surrounding material and thus the microdomains are primarily composed of PDMS A, while the surrounding material consists of polyurethane containing little or no PDMS A.
  • FIG. 7(a) To study the stability of the microstructured surface of Sample 1 in water, tapping mode AFM images were made after two weeks of water immersion. For comparison purposes, the AFM image from FIG. 2 is reproduced as FIG. 7(a), and the AFM image of the coating from Sample 1 after two weeks of water immersion is shown in FIG 7(b).
  • the PDMS domains while they changed in size and size distribution, did not disappear.
  • the mean diameter of the domains was 1.4 ⁇ m before water immersion and after water immersion the mean diameter of the larger domains in FIG. 7(b) was 3.82 ⁇ m.
  • the fact that some domains were able to grow in size indicates that there is some degree of mobility of the polymer on the surface of this coating. Water can plasticize the polyurethane matrix and allow diffusion of PDMS-rich polymer from domain-to-domain.
  • FIGS. 8(a) and (c) show AFM images of the coating surface of Sample 2 obtained by tapping mode in air before water immersion and by contact mode under water before water immersion, respectively.
  • FIGS. 8(b) and (d) show AFM images of the coating after being immersed in water for two weeks obtained by tapping mode in air after water immersion and by contact mode under water after water immersion, respectively.
  • the microstructured surface domains of the coating of Sample 2 showed a change in mean diameter of 0.17 ⁇ m when the coating was immersed in water.
  • a number of Samples were prepared to determine the effect of the solvent on formation of microdomains in the polymeric material.
  • the formulation of the resin in all of the Samples was 10 wt % PDMS A, 26.67 wt % PCL triol, and 63.33 wt % polyisocyanate D.
  • the solvent study was done using a statistical experimental design approach, based on a D-optimal special cubic mixture design.
  • the solvents investigated in this study were MAK, Toluene, EEP, BuAc, and IPA. Since polyisocyanate D supplied in BuAc was used as a crosslinker, all solvent compositions had a minimum amount of BuAc. Hence during the design of the experiments, the amount of BuAc was varied from 45% to 100% and the balance of the solvents were varied from 0% to 55%.
  • Table 3 A summary of the design is shown in Table 3 below.
  • the Samples were prepared as follows. The thirty-five solvent compositions used are shown in Table 4 below. Stock solutions of 30 wt % of PDMS A, 90 wt % of PCL, 1 wt % of DBTDA were prepared separately in the five solvents studied (MAK, toluene, EEP, BuAc, and IPA). For each Sample, 0.075 wt % DBTDA and 10 wt % 2,4- ⁇ entanedione were added on a resin solid basis. Samples were prepared by weighing and mixing the respective stock solutions of PDMS A, PCL triol, 2,4-pentanedione, and DBTDA in a 20 ml vial with magnetic stirring.
  • AFM images 40 ⁇ m X 40 ⁇ m
  • AFM images 40 ⁇ m X 40 ⁇ m
  • Formation of microdomains and their density at the surface were guided by their solvent compositions. All thirty five AFM images are shown in FIG. 9.
  • a range of behavior is observed depending on the solvent compositions used. Domains are absent for some coatings and, when present, a range in domain size is apparent.
  • numerical responses were generated. Domain formation was considered as one of the responses. "No domain" at the surface was assigned "0" and "1" was assigned for the presence of domains, regardless of their size.
  • Equations 1 and 2 are the equations of the best fit models for domain formation and domain density, respectively:
  • Coatings were prepared using the automated formulation and application unit and each of the eight coatings was prepared three times to generate a single library of twenty four Samples. Drawdowns were made over primer coated aluminum panels and over bare aluminum panels. Another set of coatings were prepared in the laboratory over bare aluminum panels. AFM images by tapping mode revealed that these eight solvent compositions always generated microstructured surfaces, as predicted. Hence, the formation of microstructured surface was favored by the elimination of toluene and IPA from the solvent composition as indicated by the model response along with the use of minimum amount of BuAc.
  • the mean diameter of the domains was plotted against the MAK:EEP ratio, shown in FIG. 10.
  • the mean domain diameter varied from 0.41 ⁇ m to 1.35 ⁇ m when applied over a primer coated aluminum panel and was from 0.53 ⁇ m to 0.97 ⁇ m when applied over a bare aluminum panel.
  • the mean diameter increased from 1.2 ⁇ m to 1.9 ⁇ m as the MAK: EEP ratio was changed from 45:10 to 10:45. Since these are relatively thick films, it is not expected that the substrate will significantly affect the formation of surface domains, and this is reflected in the coatings prepared on two substrates using the automated equipment.
  • AFM images of the cured films were made in air using tapping mode of the series of coatings.
  • the images of Series A (0.075 % DBTDA) and Series B (0.15% DBTDA) are shown in FIG. 12.
  • Series A can be subdivided into three stages: 1) No domain formation was observed within first two hours of mixing (al to a4). 2) Domains were first observed after 2.5 hours of mixing (a5) and became uniform after three hours of mixing (a6). The domains were uniform in size up to 4.5 hours of mixing (a7 to a9). 3) The domains started to decrease in size after five hours of mixing (alO) and disappeared completely to generate a smooth uniform surface for coatings prepared after seven hours of mixing (al4). This indicates that the formation of microstructured surface domains is a function of mixing time and can be controlled kinetically.
  • DMA dynamic mechanical analysis
  • the effect of the wt. % of PDMS on the formation of surface domains was determined by introducing 5 wt. %, 8 wt. %, 12 wt. % and 15 wt. % PDMS in the formulations on a solid resin basis.
  • the polymeric material formulations shown as Samples 10-17 in Table 8 were prepared according to the procedure described in Example 1.
  • the effects of the solvent composition and mixing time were evaluated by using two different solvent compositions for each wt. % PDMS and by applying the coatings after 3, 4, and 5 hours of mixing.
  • Wt. percent of catalyst is given with respect to total solid weight of polymeric material.
  • the effect of the curing conditions on formation of domains was determined.
  • the formulation of the resin in all of the samples prepared in this example was 10 wt % PDMS A, 26.67 wt % PCL triol, and 63.33 wt % polyisocyanate D. Three different sets of curing conditions were tested.
  • the three sets of curing conditions are: (1) mix ingredients for 4 hours, apply mixture to Al panel and immediately place mixture in oven set at 80° C for 45 minutes, (2) mix ingredients for 4 hours, apply mixture to Al panel and let sit at room temperature for one hour, place panel in oven set at 80° C for 45 minutes, and (3) mix ingredients for 4 hours, apply mixture to Al panel and let sit at room temperature overnight, place panel in oven set at 80° C for 45 minutes.
  • the polymeric material cured under the first set of curing conditions formed microdomains having an average diameter of about 0.927 microns.
  • the polymeric material cured under the second and third set of curing conditions formed microdomains having an average diameter of about 1.35 to 1.5 microns.
  • a cross linked polymeric material prepared by reacting a composition comprising: polyol; polyisocyanate; and polyorganosiloxane having functional groups capable of reacting with the polyisocyanate; wherein the polymeric material has a surface which includes raised microdomains.
  • the microdomains may not appreciably change when exposed to water for more than 14 days.
  • the polyorganosiloxane may comprise hydroxy functional polyorganosiloxane.
  • the polyorganosiloxane may comprise hydroxy functional polydimethylsiloxane.
  • the polyol may have at least three hydroxy groups.
  • the polyol may comprise polycaprolactone polyol.
  • the polycaprolactone polyol may have at least three hydroxy groups.
  • the polyisocyanate may have at least three isocyanate groups.
  • the polyisocyanate may comprise isophorone based polyisocyanate.
  • a polymeric material prepared by reacting a composition comprising: polycaprolactone polyol; polyisocyanate; and polyorganosiloxane having functional groups capable of reacting with the polyisocyanate; wherein the polycaprolactone polyol includes polyol having at least three hydroxy groups and/or the polyisocyanate includes isocyanate having at least three isocyanate groups.
  • the polymeric material may have a surface which includes microdomains.
  • the microdomains may not appreciably change dimensionally when exposed to water for 14 days.
  • the microdomains may have an average diameter of about 0.5 micron to 5 microns.
  • the microdomains may have an average height of about 0.01 microns to 0.2 microns.
  • the microdomains may have an average spacing of about 0.5 microns to 10 microns.
  • the composition may comprises polycaprolactone polyol having at least three hydroxy groups; and polyisocyanate having at least three isocyanate groups.
  • the polyorganosiloxane may comprise hydroxy functional polyorganosiloxane.
  • the polyorganosiloxane may have an average hydroxyl equivalent weight of about 200 to 800, and desirably about 350 to 700.
  • the polyorganosiloxane may comprise ⁇ , ⁇ -bis[3-(2'-hydroxyethoxy)propyl] polydimethylsiloxane.
  • the polyorganosiloxane may comprise hydroxy functional polydimethylsiloxane.
  • the polyorganosiloxane may comprise hydroxy alkyl functional polydimethylsiloxane.
  • the polyorganosiloxane may comprise amino functional polyorganosiloxane.
  • the polyorganosiloxane may comprise amino alkyl functional polyorganosiloxane.
  • the polymeric material may comprise about 10 wt % to 40 wt % polycaprolactone polyol.
  • the polymeric material may comprise about 30 wt % to 85 wt % of polyisocyanate.
  • the polyisocyanate may have an average isocyanate equivalent weight of about 150 to 600, and desirably about 250 to 450.
  • the polymeric material may comprise: about 20 to 30 wt % polycaprolactone polyol which includes polyol having at least three hydroxy groups; about 50 to 75 wt % polyisocyanate, which includes isocyanate having at least three isocyanate groups; and about 3 to 13 wt % hydroxy functional polydimethylsiloxane.
  • the polycaprolactone polyol may comprise polycaprolactone triol having an average hydroxyl equivalent weight of about 150 to 200; the polyisocyanate may comprise isophorone diisocyanate based polyisocyanate having an average isocyanate equivalent weight of about 250 to 450; and the hydroxy functional polydimethylsiloxane may comprise ⁇ , ⁇ -bis[3-(2'- hydroxyethoxy)propyl] polydimethylsiloxane having an average hydroxyl equivalent weight of about 350 to 700.
  • the polymeric material may comprise: about 10 to 40 wt % of the polycaprolactone polyol; about 30 to 85 wt % of the polyisocyanate; and about 2 to 14 wt % of the polyorganosiloxane.
  • a cross linked polymeric material prepared by reacting precursors comprising: less than 15 wt %, based on the total solids content of the polymeric material, of polyhydroxy functional polyorganosiloxane; polyol; and polyisocyanate.
  • a cross linked polymeric material prepared by reacting a composition comprising: polyol; polyisocyanate; polyorganosiloxane having functional groups capable of reacting with the polyisocyanate; and wherein the polymeric material includes surface microdomains which are more hydrophobic than a surrounding matrix.
  • the microdomains may have a hydrophobicity which does not appreciably change when exposed to water for 14 days.
  • the microdomains may have a morphology which does not appreciably change when exposed to water for 14 days.
  • a coating composition comprises: less than 15 wt %, based on the total solids in the coating composition after the coating composition has cured, of a hydroxy functional polyorganosiloxane; polycaprolactone polyol; polyisocyanate; and a solvent component.
  • the solvent component may include alkyl alkoxypropionate, dialkyl ketone and/or alkyl acetate.
  • the solvent component may include lower alkyl alkoxypropionate; dialkyl ketone having 4 to 10 carbon atoms; and/or lower alkyl acetate.
  • the solvent component may include at least one of ethyl 3-ethoxypropionate, methyl n-amyl ketone, and butyl acetate.
  • the coating composition may comprise a pot life extender.
  • the pot life extender may include at least one of alkane-2,4-dione, N,N-dialkyl acetoacetamide, or alkyl acetoacetate.
  • the pot life extender may comprise 2,4- pentanedione.
  • the coating composition may comprise an isocyanate reaction catalyst.
  • the isocyanate reaction catalyst may comprise dialkyl tin dicarboxylate, trialkytin hydroxide, dialkytin oxide, dialkyltin dialkoxide, dialkyltin dihalide or a mixture thereof.
  • the isocyanate reaction catalyst may comprise diethyl tin diacetate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dilauryltin diacetate, dioctyltin diacetate, or a mixture thereof.
  • the isocyanate reaction catalyst may comprise a tin catalyst.
  • a substrate may comprise a surface coated with the polymeric materials from any of the embodiments described herein.
  • a method of preparing and using a coating composition comprises: adding isocyanate reaction catalyst to a composition comprising polyol, polyisocyanate, and polyorganosiloxane having functional groups capable of reacting with the polyisocyanate to form the coating composition; applying the coating composition to a substrate surface.
  • the coating composition may cure to form a polymeric coating on the substrate surface having raised microdomains.
  • the solvent component may have a vapor pressure no more than about 12 mm of Hg.
  • the solvent component may have a vapor pressure no more than about 11 mm of Hg.
  • the solvent component may have a vapor pressure of about 3 mm of Hg to 12 mm of Hg.
  • the solvent component may have a solubility parameter between about 8 (cal/cm 3 ) 0'5 and 8.62 (cal/cm 3 ) 0 5 .
  • the ratio of alkyl alkoxypropionate to dialkyl ketone may be between about 45:5 and 5:45.
  • a cross linked polymeric material may be prepared by reacting a composition comprising: polyol; polyisocyanate; polyorganosiloxane having functional groups capable of reacting with the polyisocyanate; and a solvent component that includes an alkyl alkoxypropionate, dialkyl ketone, and/or alkyl acetate; wherein the polymeric material has a surface which includes raised microdomains.
  • the word “or” when used without a preceding "either” shall be interpreted to be inclusive, that is “or” when it appears alone shall mean both “and” and “or.”
  • the term “and/or” shall also be interpreted to be inclusive in that the term shall mean both "and” and “or.” In situations where "and/or” or “or” are used as a conjunction for a group of three or more items, the group should be interpreted to include one item alone, all of the items together, or any combination or number of the items.
  • terms used in the specification and claims such as have, having, include, and including should be construed to be synonymous with the terms comprise and comprising.
  • a stated range of 1 to 10 should be considered to include any and all subranges between and inclusive of the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less (e.g., 5.5 to 10).

Landscapes

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

Abstract

L'invention porte sur un matériau polymère pouvant être préparé par réaction d'une composition qui contient du polyol, du polyisocyanate, et du polyorganosiloxane possédant des groupes fonctionnels capables de réagir avec le polyisocyanate, le matériau polymère présentant une surface qui contient des micro-domaines élevés.
EP06733601A 2005-01-14 2006-01-04 Materiau polymere formant des micro-domaines de surface Withdrawn EP1841809A4 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US64435505P 2005-01-14 2005-01-14
US69131705P 2005-06-16 2005-06-16
US74300505P 2005-12-02 2005-12-02
PCT/US2006/000166 WO2006086092A2 (fr) 2005-01-14 2006-01-04 Materiau polymere formant des micro-domaines de surface

Publications (2)

Publication Number Publication Date
EP1841809A2 true EP1841809A2 (fr) 2007-10-10
EP1841809A4 EP1841809A4 (fr) 2008-03-05

Family

ID=36793545

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06733601A Withdrawn EP1841809A4 (fr) 2005-01-14 2006-01-04 Materiau polymere formant des micro-domaines de surface

Country Status (3)

Country Link
EP (1) EP1841809A4 (fr)
JP (1) JP2008527145A (fr)
WO (1) WO2006086092A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8604152B2 (en) 2007-06-11 2013-12-10 Ndsu Research Foundation Anchored polysiloxane-modified polyurethane coatings and uses thereof

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8062729B2 (en) 2005-01-14 2011-11-22 Ndsu Research Foundation Polymeric material with surface microdomains
US7771833B2 (en) 2005-05-09 2010-08-10 Ndsu Research Foundation Anti-fouling materials containing cationic polysiloxanes
EP1913060A4 (fr) * 2005-07-29 2008-11-26 Ndsu Res Foundation Polymères de polysiloxane fonctionnalisés
US7989074B2 (en) 2006-06-09 2011-08-02 Ndsu Research Foundation Thermoset siloxane-urethane fouling release coatings
US8372384B2 (en) 2007-01-08 2013-02-12 Ndsu Research Foundation Quaternary ammonium functionalized cross-linked polyalkylsiloxanes with anti-fouling activity
CN101668786B (zh) * 2007-04-24 2012-12-05 日立化成工业株式会社 固化性树脂组合物、led封装件及其制造方法、以及光半导体
US8053535B2 (en) 2007-07-11 2011-11-08 Ndsu Research Foundation Polysiloxanes with anti-fouling activity
US8709394B2 (en) 2007-09-28 2014-04-29 Ndsu Research Foundation Antimicrobial polysiloxane materials containing metal species
US8071706B2 (en) 2008-02-13 2011-12-06 Ndsu Research Foundation Siloxane polymer containing tethered levofloxacin
DE102010039168A1 (de) 2010-08-10 2012-02-16 Schwering & Hasse Elektrodraht Gmbh Elektroisolierlacke aus modifizierten Polymeren und daraus hergestellte elektrische Leiter mit verbesserter Gleitfähigkeit
DE102010039169A1 (de) * 2010-08-10 2012-02-16 Universität Paderborn Selbststrukturierende Oberflächen durch PDMS-Phasentrennungen in harten Polymerbeschichtungen
EP2617778B1 (fr) 2012-01-19 2021-03-17 Jotun A/S Revêtement éliminant les salissures
JP6675847B2 (ja) * 2015-09-28 2020-04-08 理研ビタミン株式会社 熱可塑性樹脂用撥水剤
KR20210135275A (ko) * 2019-03-05 2021-11-12 다우 글로벌 테크놀로지스 엘엘씨 수성 폴리우레탄 분산액 및 이의 제조방법
WO2021031174A1 (fr) 2019-08-22 2021-02-25 Dow Global Technologies Llc Dispersion aqueuse de polyuréthane à base de polyéther à base de polyéther et son procédé de préparation
CN113214731A (zh) * 2021-04-26 2021-08-06 中科院广州化灌工程有限公司 一种耐久性植物油基抗涂鸦、易清洁涂料及其制备方法和应用
CN113527614B (zh) * 2021-07-05 2022-09-23 重庆交通大学 一种具有自补偿疏水表面功能的水性高分子乳液及其制备方法
CN118703109B (zh) * 2024-07-10 2025-10-17 南宁市雨宇建筑装饰工程有限公司 一种自喷式聚氨酯防水防腐涂料及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4902767A (en) * 1987-05-28 1990-02-20 Lord Corporation High slip urethane-siloxane coatings
US5750630A (en) * 1994-02-04 1998-05-12 Minnesota Mining And Manufacturing Company Water-based polyurethane polymer, release coating, adhesive tape and process of preparation
AUPO700297A0 (en) * 1997-05-26 1997-06-19 Cardiac Crc Nominees Pty Limited Silicon-based polycarbonates
DE10243667A1 (de) * 2002-09-20 2004-04-01 Bayer Ag Polyisocyanatharze
EP1567559A4 (fr) * 2002-11-12 2008-04-16 Polymer Technology Group Inc Regulation de l'architecture moleculaire de surface polymere au moyen de groupes terminaux amphipathiques

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8604152B2 (en) 2007-06-11 2013-12-10 Ndsu Research Foundation Anchored polysiloxane-modified polyurethane coatings and uses thereof

Also Published As

Publication number Publication date
EP1841809A4 (fr) 2008-03-05
WO2006086092A3 (fr) 2007-03-01
WO2006086092A2 (fr) 2006-08-17
JP2008527145A (ja) 2008-07-24

Similar Documents

Publication Publication Date Title
US8062729B2 (en) Polymeric material with surface microdomains
EP1841809A2 (fr) Materiau polymere formant des micro-domaines de surface
US7799434B2 (en) Functionalized polysiloxane polymers
EP2922718B1 (fr) Composition de revêtement pour formation d'un film lubrifiant
Ma et al. Degradable polyurethane for marine anti-biofouling
JP2007056268A (ja) 反応性二液型ポリウレタン組成物及びそれから形成される任意に自己回復可能な耐引掻性のコーティング
US7989074B2 (en) Thermoset siloxane-urethane fouling release coatings
WO2020180760A1 (fr) Compositions de polyuréthane omniphobes, articles associés et procédés associés
US20180127616A1 (en) Durable icephobic surfaces
Zhou et al. Study on the morphology and tribological properties of acrylic based polyurethane/fumed silica composite coatings
Pieper et al. Combinatorial approach to study the effect of acrylic polyol composition on the properties of crosslinked siloxane-polyurethane fouling-release coatings
WO2013052181A2 (fr) Silicones fonctionnalisés par des chaînes latérales de poly(oxyde d'alkylène)
WO2009029512A2 (fr) Revêtements de polyuréthane aqueux à deux composants pour une application anti-graffitis
Otts et al. Heterogeneous crosslinking of waterborne two-component polyurethanes (WB 2K-PUR); stratification processes and the role of water
EP2096128A1 (fr) Polymère contenant du fluor et composition de résine
Yi et al. Degradable polyurethane based on star-shaped polyester polyols (trimethylolpropane and ɛ-caprolactone) for marine antifouling
US6090886A (en) Finely dispersed polyurethane polyurea crosslinked particles and process for producing the same
Hasirci et al. Oxygen plasma modification of poly (3‐hydroxybutyrate‐co‐3‐hydroxyvalerate) film surfaces for tissue engineering purposes
EP0786489B1 (fr) Polymethylsilsesquioxane durcissable, son procede de durcissement et ses produits de durcissement
EP0802236B1 (fr) Composition de polymethylsilsesquioxane durcissable
Gevaux et al. Water erodible coatings based on a hydrolyzable PDMS/polyester network
EP3733799A1 (fr) Composition de peinture
Rechichi et al. Degradable block polyurethanes from nontoxic building blocks as scaffold materials to support cell growth and proliferation
Uilk et al. Surface Science of Elastomeric Coatings Prepared from α, ω-Dihydroxypoly (dimethylsiloxane) and the Ethoxysiloxane Mixture “ES40”
JPH08302210A (ja) 塗料およびワニス組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20070731

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR

A4 Supplementary search report drawn up and despatched

Effective date: 20080201

RIC1 Information provided on ipc code assigned before grant

Ipc: C08G 77/24 20060101AFI20070814BHEP

Ipc: C08G 18/40 20060101ALI20080128BHEP

Ipc: C08G 18/73 20060101ALI20080128BHEP

Ipc: C08G 18/42 20060101ALI20080128BHEP

Ipc: C09D 175/06 20060101ALI20080128BHEP

Ipc: C08G 18/61 20060101ALI20080128BHEP

Ipc: C08G 18/79 20060101ALI20080128BHEP

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20090401

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20091006