WO2002018501A2 - Improvements in colored polyurethane surface coatings - Google Patents
Improvements in colored polyurethane surface coatings Download PDFInfo
- Publication number
- WO2002018501A2 WO2002018501A2 PCT/US2001/023299 US0123299W WO0218501A2 WO 2002018501 A2 WO2002018501 A2 WO 2002018501A2 US 0123299 W US0123299 W US 0123299W WO 0218501 A2 WO0218501 A2 WO 0218501A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polyurethane
- surface coating
- article
- coating composition
- weight
- Prior art date
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
- B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
- B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
- B29C37/0032—In-mould coating, e.g. by introducing the coating material into the mould after forming the article the coating being applied upon the mould surface before introducing the moulding compound, e.g. applying a gelcoat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
- B29K2995/002—Coloured
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31554—Next to second layer of polyamidoester
Definitions
- This invention relates to improvements for in-mold polyurethane foam and/or resin products and the ability to provide surface coatings of such products exhibiting bright coloration and reduced colorant migration through utilization of easy-to-use polymeric colorants in simplified and environmentally friendly processing methods.
- inventive surface coating formulations include polyurethane-reactive polymeric colorants admixed with prepolymer and excess amounts of certain isocyanate compounds. Such a composition is applied (by spraying, for example) to an internal composition, such as, preferably, mixtures of isocyanates and polyols (for the production of the internal polyurethane article) which is then introduced within a mold in order to form a particularly shaped or configured polyurethane article with a colored surface coating.
- an internal composition such as, preferably, mixtures of isocyanates and polyols (for the production of the internal polyurethane article) which is then introduced within a mold in order to form a particularly shaped or configured polyurethane article with a colored surface coating.
- the coating composition Upon curing through exposure to heat, the coating composition reacts with the introduced polyurethane prepolymer to form a surface over the target internal polyurethane.
- the presence of excess isocyanate within the surface coating has been found to provide surprisingly good non-migration and non-bleed properties to the polymeric colorant thereby permitting the addition of such a highly desired, high color space, and effective polyurethane colorant within such surface coatings.
- the specific method as well as colored polyurethane articles are also contemplated within this invention.
- thermoplastic or resinous articles of various shapes, sizes, and configurations.
- Such articles include, without limitation, novelty items, such as foam balls, seat cushions, automobile interior parts, such as steering wheel cushions and dashboards, and the like.
- Such products have generally consisted of internal polyurethane foam or resin and external coatings of either the same or different polyurethane formulations.
- In-mold processes have been developed and practiced to provide strong surfaces over the internal foam or resin in order to improve the quality of the molded article itself.
- Such a coating layer reduces surface defects such as sink marks, pores, microcracks and surface waviness to provide a more resilient polyurethane product.
- Colored surface coatings are normally required to provide an acceptable appearance to the polyurethane article by masking the discoloration (yellowing) resulting from photochemical oxidation of bonded urethane during and after the in-mold curing process.
- both the internal and external compositions of such articles have been colored; however, different dyes and/or pigments have been required for both formulations due to the differences in processing and chemical constituents. Because of these differences, surface coatings have generally been prepared through the prior application of dyes, pigments, dyestuffs, or any combination thereof, to either the outer surface of the internal polyurethane or the mold surface itself.
- colored polyurethane coatings have been provided through the utilization of inorganic or organic pigments admixed with polyols to form a paste which is then coated over the mold surfaces within which the internal polyurethane prepolymer is then introduced. Upon curing, the coating attaches to the internal polyurethane to form the desired coated article.
- suitable dyes and pigments for this purpose is highly dependent on a number of qualities exhibited by such coloring agents, including dispensability, temperature stability, and migration stability in polyurethane.
- Polymeric colorants have been utilized in the past to possibly react with such surface polyurethanes to provide improvements in colorations.
- Such colorants including those taught within U.S. Patent Nos. 4,507,407 to Kluger et al., 4,751,254 to Kluger et al., 4,775,748 to Kluger et al., 4,846,846 to Rekers et al., 5,231,135 to Machell et al., and
- this invention encompasses a colored polyurethane surface coating composition present over an article, preferably, though not necessarily, comprising a polyurethane resin or foam, wherein said surface coating comprises polymeric colorants, wherein the degree of coloration of colored polyurethane surface coating is retained after continued frictional contact and/or exposure to moisture.
- This invention also encompasses a composition of polymeric colorants admixed with from 1 to 3 times the amount of such colorants with an isocyanate compound selected from the group consisting of phenyl-based isocyanates and alkyl-based isocyanates.
- a method of coloring a polyurethane surface coating of a polyurethane article comprising the steps of providing a polyurethane prepolymer composition; applying to the surface of such composition a formulation of polyurethane surface coating prepolymer further comprising a mixture of at least one polymeric colorant and (preferably, though not necessarily, from 1 to 3 times the amount of said polymeric colorant of) an isocyanate compound (preferably, though not necessarily, selected from the group consisting of phenyl-based isocyanates and alkyl-phenyl-based isocyanates); placing said coated polyurethane prepolymer within a mold; and curing said coated polyurethane polymer.
- the particularly preferred polymeric colorants of this invention are available from Millliken & Company. Such colorants include polyoxyalkylene chains attached to chromophore constituents fhrough linking groups. Such polyoxyalkylene moities, being hydroxyl terminated polyols, readily react with the isocyanates required to produce the target polyurethane and therefore become integrally part of the final polyurethane structure.
- the preferred colorants in this general class represented by the following formula (I):
- R is an organic chromophore
- A is a linking moiety in said chromophore selected from the group consisting of N, O, S, SO 2 N, and CO 2 ;
- B is an alkyleneoxy constituent contains from 2 to 4 carbon atoms; n is an integer of from 75 to about 500; m is 1 when A is O, S, or CO , and m is 2 when A is N or SO 2 N; and x is an integer of from 1 to about 5.
- the molecular weight of such colorants are at least 2000 and, due to the high oxyalkylenation present, are highly water soluble and liquid at room temperature.
- the organic chromophore is, more specifically, one or more of the following types of compounds: azo, diazo, disazo, trisazo, diphenylmethane, triphenylmethane, xanthene, nitro, nitroso, acridine, methine, styryl, indamine, thiazole, oxazine, stilbene, or anthraquinone.
- R is one or more of azo, diazo, triphenylmethane, methine, anthraquinone, or thiazole based compounds.
- Such a group may produce coloring effects that are evident to the eye; however, optical brightening chromophores are also contemplated in this respect.
- Group A is present on group R and is utilized to attach the polyoxyalkylene constituent to the organic chromophore. Nitrogen is the preferred linking moiety.
- the polyoxyalkylene group is generally a combination of ethylene oxide and propylene oxide monomers. Preferably propylene oxide is present in the major amount, and most preferably the entire polyoxyalkylene constituent is propylene oxide.
- the preferred number of moles (n) of polyoxyalkylene constituent per polyoxyalkylene chain is from 6 to 50, more preferably from 10 to 30. Also, preferably two such polymeric chains are present on each polymeric colorant compound (x, above, is preferably 2). In actuality, the number of moles (n) per polymeric chain is an average of the total number present since it is very difficult to control the addition of specific numbers of moles of alkyleneoxy groups.
- the Table below lists the particularly preferred colorants (with the range of alkoxylation present on the colorant listed due to the inexactness of production of specific chain lengths) for utilization within the inventive in-mold polyurethane surface coatings in relation to Structure (I), above:
- colorants provide excellent colorations for polyurethane formulations (be they resin, foam, or other structure). Furthermore, it is relatively easy to mix such differently shaded or colored colorants together to produce different shades and hues within the target surface coating (since such colorants are generally liquid in nature and mix thoroughly and homogeneously).
- problems do exist for such colorants in relation to their presence within relatively thin polyurethane surface coating compositions. Frictional contact (and thus slightly elevated temperatures), atmospheric exposure to light sources and/or sources of ultraviolet radiation, exposure to moisture, and the like, all contribute to the degradation of the bonds between the terminal polyol of the colorant and the isocyanate constituent within the surface coating composition. Upon degradation, the colorants exhibit increased degrees of migration from the polyurethane medium and thus color loss within the surface coating itself.
- isocyanate compounds within the prepolymer colorant-containing composition unexpectedly reduces the possibility of colorant/urethane degradation, and thus colorant migration and loss.
- isocyanates must be present in an amount of from 1 to 3 times the amount of the colorants themselves by weight.
- isocyanates selected from the group consisting of phenyl- based and alkyl-based isocyanates, as well as di- and tri-isocyanates.
- diphenylmethane diisocyanate MDI
- TDI toluene diisocyanate
- isocyanates are standard components within polyurethane systems (for reaction with polyol components to form the desired polyurehtanes), their addition as separate components within a prepolymer composition
- the resultant prepolymer mixture thus comprises the polyurethane prepolymer (which must be cured at elevated temperatures in a mold), at least one polymeric colorant, at least one isocyanate compound present in the amount noted above in relation to the polymeric colorant, and any other solvents, additives, and the like.
- Such a prepolymer composition may be prepared up to 8 hours prior to application within a mold without precipitation or separation difficulties and thus provides a relatively low-cost alternative to the dyes and pigments mentioned above.
- the amount of polymeric colorant present within the prepolymer composition is within the range of concentrations of 0.01 to 20 % by weight of the total prepolymer composition, preferably between about 1 to 10%.
- the isocyanate is added anywhere from between 0.01 to 300% by weight of the colorant present within the composition, preferably about 200%>.
- polyurethane foam is produced through the catalyzed polymerization of the reaction products of polyols and isocyanates. Such a reaction is well known throughout the polyurethane industry and has practiced for many years.
- polyols utilized within this invention are plentiful. Such a compound is defined as comprising at least two alcohol moieties, preferably at least three. The free hydroxyl groups react well with the isocyanates to form the urethane components which are then polymerized to form the desired polyurethanes. Blowing agents present within the polymerization step provide the necessary foam-making capability.
- Preferred polyols thus comprise between three and six alcohol moieties, comprising from between one and six carbon atoms per alcohol moiety. Most preferred are Yukol 3553 from SK Oxichemical (Korea) and F3022 polyol, available from Lyondell.
- Isocyanates and more specifically, diisocyanates, are well known components of such polyurethane foams and include any compounds which possess at least one free cyanate reactive group. Preferably such compounds comprise more than one such free cyanate reactive group, most preferably two, however, greater numbers may be utilized as well.
- Such preferred diisocyanates are also either aliphatic or aromatic in nature.
- the most prominently utilized isocyanates, and thus the most preferred types for this invention, are toluene diisocyanate and methylene diisocyanate.
- the polyol is reacted with a small excess of isocyanate (ratio of from 1:1.04 to 1:1.2) in order to produce flexible foam products; higher excesses of isocyanate produce more rigid foams.
- two separate streams of liquids one of polyol, the other of isocyanate
- two separate streams of liquids are mixed together in the presence of a gelation and, if a foam product is desired, blowing catalyst and a blowing agent
- the mixture comprises any well known polyols and isocyanate components, which form polyurethane upon curing at elevated temperatures (e.g., between about 50° and 100°C).
- MDI or TDI and polyols produced from ethylene oxide (EO) or propylene oxide (PO) are acceptable in this instance.
- the polyol is Yukol 3553
- the isocyanate is MDI 2412 (available from Imperial Chemical) in a ratio of about 70:30.
- the components present within the internal polyurethanes are of a different type from those within the surface coating composition.
- the preferred prepolymer fort he inventive surface coating is a commercially available prepolymer (isocyanate terminated) from Supro CT/E Industrial Corporation of Taiwan diluted about 10 times (by weight) with methylethyl ketone.
- Solvents may be present within the prepolymer composition as well, including, without limitation, methylethyl ketone (MEK), esters, and ether-esters. Aromatics, such as toluene and xylene, as merely examples, as well as aromatic-rich petroleum distillates may also be utilized. Some moisture is permitted to be present and, at times, aids in the polymerization procedure. Other additives may be present as well for different purposes, including, without limitation, antibacterial and antimicrobial agents, antistatic agents, perfumes, and the like. One preferred type of additive is fillers which aid in providing substantial opacity to the surface coating. It has been noted that certain polymeric colorants are rather transparent and thus the surface coating does not completely hinder viewing of the internal polyurethane.
- Such opacifying fillers thus prevent such a potential problem without modifying the color of the surface coating itself.
- opacifiers include, without limitation, calcium carbonate, and the like, and are added in amount of from about 5 to about 20% by weight of the total prepolymer composition, preferably about 10%.
- Polyurethane surface coatings may be broadly defined as coatings that contain urethane or urea groups.
- the coating itself may be divided into so-called one-component or two-component systems depending upon the reactive nature of the prepolymer.
- the isocyanate and polyol constituents are substantially all reacted to form the target urethane for polymerization.
- a reactive system is preferred for the surface coating composition in that there are an appreciable number of unreacted isocyanate sites within the prepolymer for reaction with atmospheric moisture or polyol-containing polymeric colorants to form the urethane or urea moieties.
- reaction between such isocyanates and the prepolymeric isocyanate constituents both the extra diisocyanates added and the isocyanate groups react with a colorant polyol
- reaction between such isocyanates and the prepolymeric isocyanate constituents both the extra diisocyanates added and the isocyanate groups react with a colorant polyol
- the polymeric colorants are permitted and produces an integrated, low migration, colored surface coating.
- the resultant surface coatings thus exhibit extremely bright colorations with simultaneously extremely low degrees of color migration and/or color loss.
- Such bright colors have heretofore not been possible in combination with the low migration and color loss characteristics due to the difficulties inherent with such polymeric colorants within the relatively thin layers of surface coating materials.
- the inventive introduction of excess isocyanate within the prepolymer composition has accorded the ability to produce such highly desirable polyurethane surface coatings for in-mold polyurethane articles.
- the inventive surface coating composition is particularly useful in coating compression molded thermoplastic resin substrates, and primarily thermoplastic resin substrates which have come to be known in the art as reaction injection molding (RIM), reinforced reaction injection molding (RRIM), resin transfer molding (RTM), structure rection injection molding (SRTM) and other types of thermoplastic composite substrates.
- the surface coating composition is thus sprayed onto the mold surface before the internal prepolymer is introduced and cured. After curing, the finished polyurethane article is then removed from the mold with the colored surface coating intact.
- composition Table lists the particular coating formulations tested within this invention, including comparative examples. The additives are listed with colorant
- T 5(2.5g) 150 g 25 g The resultant mixtures were stirred for 5 minutes after which they were ready for utilization within a coating application.
- a mold-releasing agent Jali of Taiwan, RA-314 diluted with methylene chloride at a 1:10 ratio
- the coating compositions from the Composition Table were individually sprayed on an even basis onto separate target mold surfaces;
- compositions listed in the Composition Table were integrally cured within the coating of a polyurethane article in accordance with this process internal polyurethane components of 70 parts of Yukol 3553 to 30 parts MDI 2412.
- the resultant articles were then tested for certain requisite characteristics, such as color bleed and color loss by extraction (with the particular composition designations from the Composition Table, above, used as the designations for the articles prepared from those specific compositions.
- the inventive coatings exhibited greatly improved extraction characteristics in comparison with the coatings not comprising the excess isocyanate component.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2001277995A AU2001277995A1 (en) | 2000-08-30 | 2001-07-24 | Improvements in colored polyurethane surface coatings |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/651,327 US6479561B1 (en) | 2000-08-30 | 2000-08-30 | Colored polyurethane surface coatings |
US09/651,327 | 2000-08-30 |
Publications (2)
Publication Number | Publication Date |
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WO2002018501A2 true WO2002018501A2 (en) | 2002-03-07 |
WO2002018501A3 WO2002018501A3 (en) | 2002-06-13 |
Family
ID=24612461
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2001/023299 WO2002018501A2 (en) | 2000-08-30 | 2001-07-24 | Improvements in colored polyurethane surface coatings |
Country Status (3)
Country | Link |
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US (2) | US6479561B1 (en) |
AU (1) | AU2001277995A1 (en) |
WO (1) | WO2002018501A2 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19957397C1 (en) * | 1999-11-29 | 2001-07-19 | Technogel Gmbh & Co Kg | Moldings made of polyurethane and process for its production |
US6479561B1 (en) * | 2000-08-30 | 2002-11-12 | Milliken & Company | Colored polyurethane surface coatings |
US20050229527A1 (en) * | 2004-04-19 | 2005-10-20 | Buchi Bryan M | Artifical wall |
US20050252102A1 (en) * | 2004-04-19 | 2005-11-17 | Buchi Bryan M | Window well liner |
US20050274821A1 (en) * | 2004-06-11 | 2005-12-15 | Lear Corporation | Heated spray applicator |
US20070145641A1 (en) * | 2005-12-22 | 2007-06-28 | Lear Corporation | Interior vehicle trim panel having colored dual density composite spray elastomer skin and system and method for making the same |
US8206463B2 (en) * | 2006-05-04 | 2012-06-26 | Bayer Materialscience Llc | Colored article of manufacture and a process for its preparation |
US20090127912A1 (en) * | 2007-11-19 | 2009-05-21 | Lear Corporation | Vehicle seat assembly having a cushion with a colored coating and method of making the same |
US8998309B2 (en) | 2013-01-10 | 2015-04-07 | Lear Corporation | Vehicle seat assembly having a permeable cushion with a colored coating and method of making the same |
US10689801B2 (en) | 2014-04-22 | 2020-06-23 | Millikan & Company | Colored coatings and artificial leathers containing colorant complexes |
US9903069B2 (en) | 2014-04-22 | 2018-02-27 | Milliken & Company | Colored coatings and artificial leathers |
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DE1114317B (en) * | 1959-01-22 | 1961-09-28 | Ciba Geigy | Process for the production of colored, optionally foamed polyurethane plastics |
US4284729A (en) * | 1980-03-31 | 1981-08-18 | Milliken Research Corporation | Process for coloring thermosetting resins |
EP0837082A1 (en) * | 1996-10-18 | 1998-04-22 | Milliken Research Corporation | Process for coloring polymer resins and products thereof |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5344522B2 (en) * | 1973-02-09 | 1978-11-29 | ||
US4507407A (en) | 1984-06-25 | 1985-03-26 | Milliken Research Corporation | Process for in situ coloration of thermosetting resins |
CA1243669A (en) | 1984-06-25 | 1988-10-25 | Edward W. Kluger | Reactive colorants |
US4751254A (en) | 1987-01-20 | 1988-06-14 | Milliken Research Corporation | Process for in situ coloration of thermosetting resins |
US4846846A (en) | 1988-06-20 | 1989-07-11 | Milliken Research Corporation | Process for preparing polyurethane resins colored with anthraquinone colorants and products produced thereby |
US5231135A (en) * | 1989-09-05 | 1993-07-27 | Milliken Research Corporation | Lightfast colored polymeric coatings and process for making same |
US6294590B1 (en) * | 2000-06-02 | 2001-09-25 | Milliken & Company | Reduction of color degradation of triphenylmethane polymeric colorants within polyurethane foams |
US6479561B1 (en) * | 2000-08-30 | 2002-11-12 | Milliken & Company | Colored polyurethane surface coatings |
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2000
- 2000-08-30 US US09/651,327 patent/US6479561B1/en not_active Expired - Fee Related
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2001
- 2001-07-24 AU AU2001277995A patent/AU2001277995A1/en not_active Abandoned
- 2001-07-24 WO PCT/US2001/023299 patent/WO2002018501A2/en active Application Filing
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2002
- 2002-04-24 US US10/131,735 patent/US6586051B2/en not_active Expired - Fee Related
Patent Citations (3)
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DE1114317B (en) * | 1959-01-22 | 1961-09-28 | Ciba Geigy | Process for the production of colored, optionally foamed polyurethane plastics |
US4284729A (en) * | 1980-03-31 | 1981-08-18 | Milliken Research Corporation | Process for coloring thermosetting resins |
EP0837082A1 (en) * | 1996-10-18 | 1998-04-22 | Milliken Research Corporation | Process for coloring polymer resins and products thereof |
Non-Patent Citations (1)
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DATABASE WPI Week 7538 Derwent Publications Ltd., London, GB; AN 1975-62787w XP002186630 "Colouring leather substitutes using polyurethane composition" & JP 49 102801 A (HODOGAYA CHEM IND), 28 September 1974 (1974-09-28) * |
Also Published As
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WO2002018501A3 (en) | 2002-06-13 |
AU2001277995A1 (en) | 2002-03-13 |
US6586051B2 (en) | 2003-07-01 |
US20020161064A1 (en) | 2002-10-31 |
US6479561B1 (en) | 2002-11-12 |
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