WO2013012699A2 - Compositions de revêtement à base de polyuréthane - Google Patents

Compositions de revêtement à base de polyuréthane Download PDF

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Publication number
WO2013012699A2
WO2013012699A2 PCT/US2012/046600 US2012046600W WO2013012699A2 WO 2013012699 A2 WO2013012699 A2 WO 2013012699A2 US 2012046600 W US2012046600 W US 2012046600W WO 2013012699 A2 WO2013012699 A2 WO 2013012699A2
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WO
WIPO (PCT)
Prior art keywords
coating composition
based coating
polyurethane based
present
amount
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/US2012/046600
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English (en)
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WO2013012699A3 (fr
Inventor
Vipulkumar H. PRAJAPATI
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3M Innovative Properties Co
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3M Innovative Properties Co
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Publication of WO2013012699A2 publication Critical patent/WO2013012699A2/fr
Publication of WO2013012699A3 publication Critical patent/WO2013012699A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38

Definitions

  • the present invention relates to novel polyurethane based coatings, particularly for selectively imparting excellent water vapour impermeability and in-can settling stability, in addition to low viscosity, for application in industrial coating.
  • the composition of the present invention is used particularly for protection of concrete and metal surfaces.
  • PU coatings are widely known for their versatility of application with many advantages over the conventional coating systems.
  • PU coatings can be divided into one pack and two pack systems, wherein the one pack system contains a dissolved fully reacted PU or blocked isocyanate, while the two pack system can contain various types of polyols, varying in functionality, chain length and backbone in one pack and isocyanate in the other pack. Both these systems can be further classified as solvent based, water based or solvent free systems. The solvent free
  • a frequently encountered problem with coating composition is that of the settling of paints over some period of storage thereby resulting in some of the pigments remaining at the bottom of the can/drum. Improper mixing affects the stoichiometry of the finished product and results in inconsistent & inferior performance on application. In case of sticky heavy settling, desired bits free consistency is not achieved even after considerable mixing during application, resulting in inferior performance.
  • a number of publications are known that deal with solvent free polyurethane compositions for application as a protective coating.
  • US 2007-185241 describes cured resin matrix with a plurality of bubbles which provide improved insulative properties and improved adhesion to overlying paint coatings which in turn offers protection against corrosion and acts as heat insulator.
  • US 2008-229976 discloses polyurea compositions and polyurethane compositions related to stain and fouling resistant coatings that provide durable, light weight coatings which exhibit oil- repellency, water-repellency, and stain resistance.
  • US 6977279 relates to solventless reactive system which cure at room temperature based on blocked polyisocyanates, primer amines, compounds with oxirane groups and 2,3 dimethyl-3,4,5,6- tetrahydropyridimine .
  • the objective of the present invention is to provide a cost effective coating which exhibits superior properties in terms of corrosion resistance, moisture impermeability, in-can settling stability and having low viscosity.
  • one embodiment of the present invention is to provide a polyurethane based coating composition having a base component and an activator as another component wherein the base component comprises polyols and ingredients such as catalyst, defoamer, molecular sieve and fillers; while the activator consists essentially of polyisocyanate.
  • the base component of the composition may comprise other ingredients such as pigments, additional polyols, amines and chain extenders.
  • the components of the coating composition interact synergistically to confer a unique combination of the physical and chemical properties to the resultant composition which make it superior to the state of the art compositions.
  • the instant coating composition comprises the individual components in the following concentration:
  • the base and an activator is in 3: 1 (v/v) proportion.
  • the polyol could be a diol, a triol, a higher polyol, or a mixture of one or more of the said polyols.
  • Some other additives such as pigments, chain extenders etc also may be used to control and modify the reaction process and performance characteristics of the polymer.
  • This invention also relates to a process for preparing the polyurethane based coating composition wherein the process comprises initially of preparing the base component and mixing the base with the activator in a suitable proportion to provide the coating composition for use in corrosion protection of metal and concrete structures.
  • This invention also relates to articles and surfaces coated with the instant coating composition.
  • Figure 1 shows a graph plotting the water vapour permeability of the standard coating composition of the invention.
  • Figure 2 shows a graph plotting the water vapour permeability of a coating composition without mica.
  • polyol may include two or more such polyols.
  • all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains.
  • the coating composition of the present invention is a solvent free urethane based
  • composition comprising a base and an activator, wherein the base comprises a number of additives like polyols, defoamer, molecular sieve, filler, catalyst and other optional additives; while the activator consists essentially of polyisocyanate.
  • the polyols form an essential ingredient of the base component of the present invention.
  • a polyol is an ploymeric alcohol containing multiple hydroxyl groups.
  • polyols are defined as compounds with multiple hydroxyl functional groups available for organic reactions.
  • a molecule with two hydroxyl groups is a diol, one with three is a triol, one with four is a tetrol and so on.
  • Monomeric polyols such as glycerin, pentaerythritol, ethylene glycol and sucrose often serve as the starting point for polymeric polyols. These materials are often referred to as the "initiators" and reacted with propylene oxide or ethylene oxide to produce polymeric polyols.
  • Polymeric polyols could be polyether polyols, polyester polyols or OH terminated polyacrylics or combination of them.
  • the characteristics of polyols depends on are their molecular backbone, initiator, molecular weight, percentage primary hydroxyl groups, functionality, viscosity and so on.
  • Many polyols are polydispersive materials, being blends of two or more polyols each of specific molecular weights, to give intermediate molecular weight materials.
  • Natural oil polyols or saturated aliphatic polyester polyols with low viscosities at room temperatures are used in the production of polyurethanes.
  • Natural oil polyols also known as NOPs or biopolyols, are polyols derived from vegetable oils by several different techniques. The primary use for these materials is in the production of polyurethanes.
  • the most promising natural oils for the industrial development of biobased polyols are soybean oil, castor oil, palm oil, and canola oil.
  • Castor oil which is obtained from castor seed, is a triglyceride of fatty acid wherein 90% of the fatty acid chains are ricinoleic acid, has presence of OH functional group on 12 th carbon atom, which makes it polar and reactable, which is not the case with other seed oils.
  • castor polyols derived from castor oil possess long C chains with a functional unbranched "OH" group which provides flexibility on reaction with isocyanate to form the polyurethane bond.
  • the castor oil of BSS Grade or commercial grade castor oil More particularly, the castor polyol is Jagropol 115.
  • tri-functional oil-derived polyol having hydroxyl number ranges from 320 to 350 mg KOH/g containing both primary and secondary hydroxyl groups, which are completely miscible with a wide variety of natural oil polyols, demonstrate ability to rapidly build polyurethane cross-linked networks.
  • the trifunctional polyol is polypropylene ether polyol (Desmophen 1380BT).
  • Di primary diols also can be used as an ingredient of the base composition of the present invention.
  • Diols - alcohols that contain two reactable hydroxyl groups can be classified as linear/branched or aliphatic/aromatic diols.
  • 2-methyl 1,3 dipropane diol due to its unique branched structure (i.e) asymmetrical nature, conferred upon it due the presence of the odd number of carbon atoms between the two hydroxyl groups thus inhibiting close packaging thereby exhibiting greater transparency, weatherability, longer shelf life, aiding in suspension of heavy fillers/solids, decreased viscosity, resist settling over the resin when stored for long periods of the end use applications.
  • the 2-methyl 1,3 dipropane diol is MPDiol.
  • 1,4 butane diol is also a preferred diol.
  • Fillers in this invention serve multiple functions based on the type of filler used. Fillers may thicken the composition, support its structure, prevent sagging, increase volume and also enhance the technical properties of the composition.
  • Mica acts as filler providing a smooth consistency, improving the workability of the compound, and providing resistance to cracking. Mica's value is based on its unique lamellar shape, which forms compact packing in the dried film and hence reduces film impermeability.
  • mica functions as a pigment extender that facilitates suspension, reduces chalking, prevents shrinking and shearing of the paint film, increases resistance of the paint film to water penetration and weathering, and brightens the tone of colored pigments.
  • mica coated with titanium dioxide (TiC ⁇ ) results in a pigment that produces a reflective color depending on the thickness of the coating.
  • Ti0 2 acts as a white pigment providing opacity to the dried film.
  • Ti0 2 Anatyze or Rutile In addition to Ti0 2, carbon black such as 318M Black serves as a black pigment which in combination with the white pigment provides a grey colour to the composition.
  • Various pigments can be added for different color of the final composition.
  • fillers such as barium sulphate not only might serve as a white pigment but also modify the consistency and help in providing impact resistance to the application. Of preference is Barytes 2080.
  • One other filler used in these polyurethane compositions is Silica. Silica not only leads to cost reductions by increasing the bulk of the composition but also prevents sagging of the resin.
  • Catalysts are used to catalyse the polymerization of the polyol with the polyisocyanate.
  • Amine compounds and organo metallic complexes are used as catalysts.
  • amines such as tertiary amines, difunctional primary amines etc are used.
  • aromatic diamine such as diethyl toluenediamine which is commercially available under the name Ethacure 100.
  • the catalyst could be used in an amount of 0 to 5% depending on the mode of application by spray or brush.
  • the composition is devoid of catalyst.
  • the said composition without catalyst is suitable for application by brush also by increasing the usable life.
  • Defoamers are used to modify the characteristics of polyurethane composition by eliminating process defects like entrapped bubbles and surface defects such as pin holes and orange peelmarks, acting as air release and anti-foaming agents.
  • silicone free defoamers such as BYK 054 or BYK 535 or BYK 1794 or Foamex N.
  • Molecular sieves or moisture scavengers which contain tiny pores of a precise and uniform size are used as an adsorbent for gases and liquids.
  • highly effective moisture scavenger for coating systems that adsorbs practically only water.
  • isocyanate which is highly reactive to water.
  • micronized, highly porous, crystalline aluminosilicate with pore openings of approximately 3 A such as SYLOSIV A3 or Purmol 3ST or A4 with 4 A pore openings.
  • Paste forms of the molecular sieves P3 and P4 can also be used.
  • Chain extenders are low molecular weight hydroxyl and amine terminated compounds that play an important role in the polymer morphology of polyurethane chains.
  • the chain extender is an amine. More preferably the amine is polyetheramines such as Jeffamine D 400.
  • Pigments which could be used in the invention comprises synthetic iron oxides.
  • Preferred examples of pigments are Bayferrox Black 318M along with Titanium dioxide to create Gray color of the composition.
  • the base of the polyurethane based coating composition comprises 35 to 75 % of polyol mix which includes 0.5 to 5 % of trifunctional polyol and 1-10% of 2-methyl 1,3 dipropane diol, 3 to 25% of mica, 0.5 to 1.5 % of defoamer, 2 to 10 % of molecular sieve, and 0 to 5% of catalyst.
  • composition may optionally contain 0 to 5% of chain extender, 5 to 40% of barium sulphate, 5 to 40% of silica, 2 tol0% of titanium dioxide and 0.15 to 5% of color pigments.
  • Another major embodiment of the present invention is related to a process for preparing the polyurethane based coating composition wherein the process comprises of initially preparing the base component.
  • the base component is nothing but mixture of OH functional polyol components with molecular sieve, fillers, pigments, catalysts and additives.
  • the base component is prepared by dispersing the solid materials viz., pigments, fillers & other additives in polyols in high speed disperser (HSD) or twin shaft disperser and stabilizing the same with rest of the resin and additives.
  • HSD high speed disperser
  • the solid matters can be ground to finer to medium grind depending on the application requirement.
  • the base component is mixed with the activator in a suitable proportion to provide the coating composition for use in corrosion protection of metal and concrete structures.
  • the solvent free urethane coating of the invention is applied by plural feed spray equipment.
  • Most of the known solvent-free urethane compositions are high in viscosity and hence the base component is always heated in the range of 40 to 55°C to reduce the viscosity (viscosity reduces with increase in material temperature) to facilitate the ease of application. Since the viscosity of the instant composition is low, it can be easily applied without heating the base part at temperature above 30°C.
  • the same product can be made applicable by brush also by increasing the usable life. This needs removal of the catalyst from the composition.
  • the standard urethane coating composition of the invention has the following composition.
  • the composition comprises A) Base component and B) Activator.
  • Base component has the composition as shown in Table 1
  • the base component was prepared by dispersing the solid materials viz., pigments, fillers and other additives in polyols in high speed disperser (HSD) or twin shaft disperser and stabilizing the same with rest of the resin and additives.
  • HSD high speed disperser
  • the polyols, especially polyester polyol and some portion of castor oil were taken in the vessel followed by addition of defoamer under stirring.
  • the mix was stirred at slow speed and subsequently the fillers like barium sulfate, silica, mica, molecular sieve, titanium dioxide and pigments were added in sequence under stirring.
  • the speed of the HSD blade was adjusted such a way to ensure proper vortex formation.
  • the solids were dispersed at a tip speed of about 3 to 8 meter per seconds till the finish was achieved.
  • the composition was stabilized with remaining resin, polyols, amines and additives. Defoamer is used to take care of process generated air-entrapments. During processing, the composition was maintained below 60°C by circulating cooling water through the jacket of vessel. The composition was then filtered through filter and packed.
  • the second part of the composition viz., the activator, was prepared by packing the solvent free polyisocyanate under nitrogen blanketing environment.
  • the polyurethane based coating composition was obtained by mixing 3 parts of the base with 1 part of the activator, by volume.
  • Example 1 The product as obtained by Example 1 was subjected to tests for various performance parameters such as specific gravity, flowability, tensile strength, elongation, flexibility, abrasion resistance etc., at the Corrosion Science and Engineering Laboratory of Indian Institute of
  • Tables 2 and 3 show the details and results of the tests for various performance parameters respectively.
  • the polyurethane based coating composition of the present invention exhibited excellent performance parameters that it can be very effectively applied to concrete and metal surfaces.
  • An ambient condition stability test for the urethane coating composition of the present invention was performed in order to ensure that the product is stable under recommended storage conditions.
  • Accelerated stability study was conducted to predict the long-term stability in short period. In this field, 8 week accelerated stability translates in to over 1 year stability in actual storage conditions.
  • the material was packed in 200 ml or 500 ml cans, sealed and was kept at elevated temperature of 60°C for weeks. Four packs were kept for taking observations at the interval of 1 week, 2 week, 4 week and 8 weeks. The observations were taken for degree of settling or phase separation. The material was also tested for performance parameters. The experiment the details are shown in Table 6 and the observations are shown in Table 7. Ratings are as explained in Table 5. Table 6
  • the instant composition was tested to determine the resistance of the coating towards various chemicals in case of chemical splash, spillage of complete immersion.
  • Standard panels were coated with the coating composition, edge sealed and were dipped in the chemicals at 23°C and 50% humidity conditions.
  • the coating film was observed at regular intervals for any defects like blistering, delamination, cracking or peeling.
  • the coating was also tested for adhesion and hardness.
  • the instant coating composition was observed to have excellent chemical resistance against chemicals such as ammonium hydroxide 25% (v/v), citric acid 5% (v/v), methanol, sodium
  • the instant composition was tested for permeability towards water vapors following standard ASTM E96.
  • the testing was done with Water method. Distilled water was filled in standard payne permeability cup and the cured film of the coating, which was of same dimension as the cup, was put on the cup opening. The edges were sealed with suitable sealant. The assembly was then kept under controlled temperature and humidity conditions. The temperature was maintained at 23 +/- 1°C and the relative humidity was maintained at 50 +/- 2 %.
  • Rate of Permeation 0.0003 gms/24Hr
  • Table 9 shows the details of the test with a composition without mica and Figure 2 shows its graphical representation.

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  • 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)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne une composition de revêtement à base de polyuréthane qui présente des propriétés supérieures en termes de stabilité, de résistance à la corrosion et de perméabilité à l'humidité, ladite composition de revêtement présentant une faible viscosité. La composition de revêtement à base de polyuréthane comprend une base et un activateur, le composant de base comprenant un polyol, une charge, un démoussant, un catalyseur et un tamis moléculaire et l'activateur comprenant un polyisocyanate. De préférence, le polyol comprend un polyol d'huile de ricin, du 2-méthyl-1,3-dipropanediol ou du 1,4-butanediol et la charge comprend du mica. Le mica, en plus d'être une charge, fonctionne également comme un diluant de pigment. Dans certains modes de réalisation, ladite composition est dépourvue de catalyseur. Ladite composition de revêtement est utile dans le revêtement de surfaces de béton et de métal.
PCT/US2012/046600 2011-07-15 2012-07-13 Compositions de revêtement à base de polyuréthane Ceased WO2013012699A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN2429/CHE/2011 2011-07-15
IN2429CH2011 2011-07-15

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WO2013012699A3 WO2013012699A3 (fr) 2013-04-11

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8850241B2 (en) 2012-03-02 2014-09-30 Microsoft Corporation Multi-stage power adapter configured to provide low power upon initial connection of the power adapter to the host device and high power thereafter upon notification from the host device to the power adapter
US8854799B2 (en) 2012-03-02 2014-10-07 Microsoft Corporation Flux fountain
US8873227B2 (en) 2012-03-02 2014-10-28 Microsoft Corporation Flexible hinge support layer
US8991473B2 (en) 2012-10-17 2015-03-31 Microsoft Technology Holding, LLC Metal alloy injection molding protrusions
US9075566B2 (en) 2012-03-02 2015-07-07 Microsoft Technoogy Licensing, LLC Flexible hinge spine
US9354748B2 (en) 2012-02-13 2016-05-31 Microsoft Technology Licensing, Llc Optical stylus interaction
US9426905B2 (en) 2012-03-02 2016-08-23 Microsoft Technology Licensing, Llc Connection device for computing devices
US9759854B2 (en) 2014-02-17 2017-09-12 Microsoft Technology Licensing, Llc Input device outer layer and backlighting
US9793073B2 (en) 2012-03-02 2017-10-17 Microsoft Technology Licensing, Llc Backlighting a fabric enclosure of a flexible cover
US9824808B2 (en) 2012-08-20 2017-11-21 Microsoft Technology Licensing, Llc Switchable magnetic lock
US9870066B2 (en) 2012-03-02 2018-01-16 Microsoft Technology Licensing, Llc Method of manufacturing an input device
US10120420B2 (en) 2014-03-21 2018-11-06 Microsoft Technology Licensing, Llc Lockable display and techniques enabling use of lockable displays
EP3218597B1 (fr) 2014-11-10 2019-03-27 Polytech A/S Matériau polyuréthane, son procédé de préparation et couche de protection pour pale d'éolienne
US10324733B2 (en) 2014-07-30 2019-06-18 Microsoft Technology Licensing, Llc Shutdown notifications
US10678743B2 (en) 2012-05-14 2020-06-09 Microsoft Technology Licensing, Llc System and method for accessory device architecture that passes via intermediate processor a descriptor when processing in a low power state
WO2020190899A1 (fr) 2019-03-21 2020-09-24 DDP Specialty Electronic Materials US, Inc. Composition de revêtement résistant à l'eau
US20210009874A1 (en) * 2017-12-27 2021-01-14 Dow Global Technologies Llc Two-component solventless adhesive compositions for adhesion to metal and/or metallized substrates
CN112574661A (zh) * 2020-12-31 2021-03-30 郑州双塔涂料有限公司 一种双组份丙烯酸聚氨酯中涂漆及其制备方法
CN113773743A (zh) * 2021-09-29 2021-12-10 惠州市惠阳区嘉泰涂料有限公司 耐高温、耐老化型低voc聚氨酯防腐涂料及其制备方法
USRE48963E1 (en) 2012-03-02 2022-03-08 Microsoft Technology Licensing, Llc Connection device for computing devices
WO2023194225A1 (fr) * 2022-04-06 2023-10-12 Basf Se Composition de polyuréthane pour barrière pare-vapeur dans le bâtiment à basse température intérieure
US12551461B2 (en) 2013-11-14 2026-02-17 Ultragenyx Pharmaceutical Inc. Compositions of triglycerides and uses thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108329821A (zh) * 2018-03-08 2018-07-27 江西铭川科技实业有限公司 一种耐黄变聚氨酯合成革用水性表面涂饰剂

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6992134B2 (en) * 2002-10-29 2006-01-31 Tim Croley Polyurethane system and application thereof
US7622541B2 (en) * 2003-01-17 2009-11-24 The United States Of America As Represented By The Secretary Of The Navy Polyurethane coating
DE10344379B4 (de) * 2003-09-23 2008-09-11 Mankiewicz Gebr. & Co (Gmbh & Co Kg) Verwendung einer Zweikomponenten-Zusammensetzung zur Herstellung von flexiblen Polyurethan-Gelcoats für Kunstharz-Verbundwerkstoffe, Verfahren zur Herstellung der Verbundwerkstoffe und Verbundwerkstoffe
US20070210476A1 (en) * 2004-03-23 2007-09-13 Sanyo Chemical Industries, Ltd. Machinable Resin Molded Product, Material For Forming The Same, And Model Made Of The Same
ATE440722T1 (de) * 2007-06-01 2009-09-15 Sika Technology Ag Wabenverbundplatten und verwendung eines zweikomponenten-polyurethan-klebemittels bei ihrer herstellung
CA2710918C (fr) * 2007-12-28 2017-02-14 Bostik, Inc. Procede continu pour la production de materiaux d'etancheite et d'adhesifs de polyurethane durcissant a l'humidite

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9354748B2 (en) 2012-02-13 2016-05-31 Microsoft Technology Licensing, Llc Optical stylus interaction
US9793073B2 (en) 2012-03-02 2017-10-17 Microsoft Technology Licensing, Llc Backlighting a fabric enclosure of a flexible cover
US9460029B2 (en) 2012-03-02 2016-10-04 Microsoft Technology Licensing, Llc Pressure sensitive keys
US8947864B2 (en) 2012-03-02 2015-02-03 Microsoft Corporation Flexible hinge and removable attachment
USRE48963E1 (en) 2012-03-02 2022-03-08 Microsoft Technology Licensing, Llc Connection device for computing devices
US9075566B2 (en) 2012-03-02 2015-07-07 Microsoft Technoogy Licensing, LLC Flexible hinge spine
US9134807B2 (en) 2012-03-02 2015-09-15 Microsoft Technology Licensing, Llc Pressure sensitive key normalization
US9134808B2 (en) 2012-03-02 2015-09-15 Microsoft Technology Licensing, Llc Device kickstand
US9158384B2 (en) 2012-03-02 2015-10-13 Microsoft Technology Licensing, Llc Flexible hinge protrusion attachment
US9176901B2 (en) 2012-03-02 2015-11-03 Microsoft Technology Licensing, Llc Flux fountain
US9176900B2 (en) 2012-03-02 2015-11-03 Microsoft Technology Licensing, Llc Flexible hinge and removable attachment
US9268373B2 (en) 2012-03-02 2016-02-23 Microsoft Technology Licensing, Llc Flexible hinge spine
US8854799B2 (en) 2012-03-02 2014-10-07 Microsoft Corporation Flux fountain
US9426905B2 (en) 2012-03-02 2016-08-23 Microsoft Technology Licensing, Llc Connection device for computing devices
US10013030B2 (en) 2012-03-02 2018-07-03 Microsoft Technology Licensing, Llc Multiple position input device cover
US9465412B2 (en) 2012-03-02 2016-10-11 Microsoft Technology Licensing, Llc Input device layers and nesting
US9618977B2 (en) 2012-03-02 2017-04-11 Microsoft Technology Licensing, Llc Input device securing techniques
US9619071B2 (en) 2012-03-02 2017-04-11 Microsoft Technology Licensing, Llc Computing device and an apparatus having sensors configured for measuring spatial information indicative of a position of the computing devices
US8850241B2 (en) 2012-03-02 2014-09-30 Microsoft Corporation Multi-stage power adapter configured to provide low power upon initial connection of the power adapter to the host device and high power thereafter upon notification from the host device to the power adapter
US9710093B2 (en) 2012-03-02 2017-07-18 Microsoft Technology Licensing, Llc Pressure sensitive key normalization
US10963087B2 (en) 2012-03-02 2021-03-30 Microsoft Technology Licensing, Llc Pressure sensitive keys
US8873227B2 (en) 2012-03-02 2014-10-28 Microsoft Corporation Flexible hinge support layer
US9766663B2 (en) 2012-03-02 2017-09-19 Microsoft Technology Licensing, Llc Hinge for component attachment
US9678542B2 (en) 2012-03-02 2017-06-13 Microsoft Technology Licensing, Llc Multiple position input device cover
US9852855B2 (en) 2012-03-02 2017-12-26 Microsoft Technology Licensing, Llc Pressure sensitive key normalization
US9870066B2 (en) 2012-03-02 2018-01-16 Microsoft Technology Licensing, Llc Method of manufacturing an input device
US9904327B2 (en) 2012-03-02 2018-02-27 Microsoft Technology Licensing, Llc Flexible hinge and removable attachment
US10678743B2 (en) 2012-05-14 2020-06-09 Microsoft Technology Licensing, Llc System and method for accessory device architecture that passes via intermediate processor a descriptor when processing in a low power state
US9824808B2 (en) 2012-08-20 2017-11-21 Microsoft Technology Licensing, Llc Switchable magnetic lock
US8991473B2 (en) 2012-10-17 2015-03-31 Microsoft Technology Holding, LLC Metal alloy injection molding protrusions
US12551461B2 (en) 2013-11-14 2026-02-17 Ultragenyx Pharmaceutical Inc. Compositions of triglycerides and uses thereof
US9759854B2 (en) 2014-02-17 2017-09-12 Microsoft Technology Licensing, Llc Input device outer layer and backlighting
US10120420B2 (en) 2014-03-21 2018-11-06 Microsoft Technology Licensing, Llc Lockable display and techniques enabling use of lockable displays
US10324733B2 (en) 2014-07-30 2019-06-18 Microsoft Technology Licensing, Llc Shutdown notifications
US11629689B2 (en) 2014-11-10 2023-04-18 Polytech A/S Polyurethane material, process for preparing such material and protective cover for wind turbine blade
EP3218597B1 (fr) 2014-11-10 2019-03-27 Polytech A/S Matériau polyuréthane, son procédé de préparation et couche de protection pour pale d'éolienne
EP3533816B1 (fr) 2014-11-10 2024-07-17 Polytech A/S Couvercle de protection préformé et pale d'éolienne
US20210009874A1 (en) * 2017-12-27 2021-01-14 Dow Global Technologies Llc Two-component solventless adhesive compositions for adhesion to metal and/or metallized substrates
US12398303B2 (en) * 2017-12-27 2025-08-26 Arkema France Two-component solventless adhesive compositions for adhesion to metal and/or metallized substrates
WO2020190899A1 (fr) 2019-03-21 2020-09-24 DDP Specialty Electronic Materials US, Inc. Composition de revêtement résistant à l'eau
US11198790B2 (en) 2019-03-21 2021-12-14 Ddp Specialty Electronic Materials Us, Llc Water-resistive coating composition
CN112574661A (zh) * 2020-12-31 2021-03-30 郑州双塔涂料有限公司 一种双组份丙烯酸聚氨酯中涂漆及其制备方法
CN113773743A (zh) * 2021-09-29 2021-12-10 惠州市惠阳区嘉泰涂料有限公司 耐高温、耐老化型低voc聚氨酯防腐涂料及其制备方法
WO2023194225A1 (fr) * 2022-04-06 2023-10-12 Basf Se Composition de polyuréthane pour barrière pare-vapeur dans le bâtiment à basse température intérieure

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