Source: http://www.google.com/patents/US5003026?dq=6233389
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Patent US5003026 - UV curable no-wax coating - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsGloss retention and stain resistance are improved in a no-wax UV cured flooring wear surface by reacting a phthalate polyester polyol and a long chain hydroxy acrylate with an aromatic or cycloalkyl diisocyanate to form an oligomer which is employed as a major ingredient of the UV curable coating composition...http://www.google.com/patents/US5003026?utm_source=gb-gplus-sharePatent US5003026 - UV curable no-wax coatingAdvanced Patent SearchPublication numberUS5003026 APublication typeGrantApplication numberUS 07/369,866Publication dateMar 26, 1991Filing dateJun 22, 1989Priority dateJun 22, 1989Fee statusPaidPublication number07369866, 369866, US 5003026 A, US 5003026A, US-A-5003026, US5003026 A, US5003026AInventorsWendell A. Ehrhart, David A. SmithOriginal AssigneeArmstrong World Industries, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (7), Referenced by (21), Classifications (10), Legal Events (6) External Links: USPTO, USPTO Assignment, EspacenetUV curable no-wax coating
US 5003026 AAbstract
Gloss retention and stain resistance are improved in a no-wax UV cured flooring wear surface by reacting a phthalate polyester polyol and a long chain hydroxy acrylate with an aromatic or cycloalkyl diisocyanate to form an oligomer which is employed as a major ingredient of the UV curable coating composition used to produce the wear surface.
1. A floor covering product comprising a wear layer including a polymerized urethane-acrylate oligomer, said oligomer comprising the reaction product of an aromatic or cycloalkyl diisocyanate, a monohydroxymonoacrylate having an hydroxyl equivalent weight of about 250 to about 600 and a phthalate polyester polyol having an hydroxyl equivalent weight of about 175 to about 500.
2. The floor covering product of claim 1 wherein the number of equivalents of isocyanate functionalities to equivalents of hydroxyl functionalities is about 0.7 to about 1.5, and the number of equivalents of hydroxyacrylate functionalities to equivalents of polyester polyol functionalities is greater than about 1.0.
The invention relates to UV curable coatings useful as wear surfaces for resilient floor coverings. More particularly, the invention relates to a UV cured wear surface which provides improved gloss and stain protection for floor coverings.
Urethane acrylates are known as radiation cured wear layers for flexible surface coverings, e.g. floor tile and sheet flooring. Products and processes using UV curing are described in U.S. Pat. Nos. 3,924,023; 3,935,364; 3,959,521; 4,016,306; 4,075,366; 4,421,782; and 4,138,299.
An improved UV curable coating for a floor covering comprises:
Ultraviolet (UV) cured no-wax coatings are commercially available based on the processes of U.S. Pat. Nos. 4,138,299 and 4,421,782. Oligomers based on 2-hydroxyethylacrylate, predominately aliphatic polyester polyol and 1,1'-methylenebis(4-isocyanatocyclohexane) are mixed with acrylate reactive diluents and photoinitiators and employed as no-wax wear surfaces for floor coverings. While these prior art compositions (particularly those containing substantial amounts of acrylic acid as reactive diluent) provided good no-wax performance, there were still some properties such as gloss retention, hydrolytic stability and stain resistance which could be improved. In addition, it was desirable to reduce or eliminate acrylic acid in the reactive diluent due to its volatility and corrosive properties. According to the practice of the present invention, it is possible to advance the state of the art to improve properties from good to excellent while lowering or eliminating acrylic acid.
It is preferred to employ a polycaprolactone based hydroxyacrylate (e.g. Union Carbide's Tone M-100) and a predominately 1,6-hexylene phthalate polyester polyol in preparing the oligomer. A predominately 1,6-hexylene phthalate polyester polyol is defined as a phthalate polyester polyol wherein at least 50 equivalent percent of the <150 eq. wt. polyol is 1,6-hexanediol and wherein at least 50 eq. percent of the polycarboxylic acid is phthalic acid or equivalent (e.g. phthalic anhydride).
The diisocyanate may be an aromatic or cycloalkyl diisocyanate such as 1,1'methylenebis(4-isocyanatocyclohexane), isophorone diisocyanate or tetramethyl xylene diisocyanate. The 1,1'-methylenebis(4-isocyanatocyclohexane) is commercially available as Desmodur� W from Mobay Corporation.
______________________________________A polyester polyol was prepared from the following ingredients______________________________________Phthalic Anhydride  20     equivalents1,6-Hexanediol      23.8   equivalentsGlycerine           6.0    equivalentsDibutyltin bislauryl               0.1    weight %mercaptide catalyst______________________________________
The ingredients were reacted at 220� C., under a nitrogen stream to a acid number less than one, producing a polyol with an hydroxyl eq. wt. of 315.
______________________________________1. Isodecyl acrylate, reactive diluent                     25.0   parts2. Hexanediol diacrylate, reactive diluent                     5.5    parts3. Tone M-100, hydroxyacrlyate mol. wt.                     30.0   parts344 from Union Carbide Corp.4. Polyester polyol (above)                     17.5   parts5. Dibutyltin dilaurate, catalyst                     0.2    parts6. Ionol �, polymerization inhibitor (Shell)                     0.02   parts7. Desmodur � W, diisocyanate (Mobay Corp.)                     19.0   parts______________________________________
The mixture was heated, with stirring and under a trickle of dry air, to 70� C. and held at 70� C. for four hours to react the NCO groups of ingredient 7 with the hydroxy groups of ingredients 3 and 4 to form the oligomer. Upon cooling to about 45� C., a solution of the following ingredients were charged with stirring:
The series of formulations in Table II was prepared and tested as in Example 1. All of the formulations except B and C were prepared using the same catalysts, inhibitor and procedure as in Example 1. B and C were made similarly except they were reacted for one hour at 70� C. prior to adding the water, then for six hours after the water was added.
TABLE II__________________________________________________________________________              Comparative 1                      A   B   C   D   E   F    G__________________________________________________________________________Polyester Polyol Reactants(In Equivalents)Phthalic anhydride         20.0                          20.0                              --  20.0                                      20.0                                          20.0 20.0Isophthalic Acid           --  --  20.0                                  --  --  --   --1,6-Hexanediol             27.5                          23.8                              --  29.7                                      29.7                                          29.2 33.0SR-100 Diol, Sartomer      --  --  15.5                                  --  --  --   --Cyclohexane dimethanol     --  --  9.70                                  --  --  --   --Glycerine                  2.30                          6.00                              12.5                                  2.30                                      2.30                                          0.30 --Polyol Hydroxyl Eq. Wt.    317 315 300 278 278 300  260Oligomer Reactants(Weight % in Oligomer)Polyester polyol   52.8    26.3                          30.6                              26.8                                  29.0                                      18.9                                          29.4 18.4Tone M-100                 45.1                          38.7                              42.3                                  41.6                                      52.8                                          43.1 50.6Desmodur W                 28.6                          30.6                              30.9                                  24.4                                      28.3                                          27.5 31.0Water1                --  1.04                              1.04                                  --  --  --   --Oligomer Equivalent RatiosNCO/OH                     1.01                          1.11                              1.11                                  1.00                                      0.976                                          0.994                                               1.09Hydroxyacrylate/Polyol              .67     1.50                          1.17                              1.16                                  1.16                                      2.33                                          1.42 2.08Reactive Diluents (Weight %of Total Reactive Diluent)Hexanediol diacrylate      20.9                          18.4                              16.4                                  --  --  --   --Isodecyl Acrylate          47.8                          69.7                              75.8                                  --  6.40                                          --   --Isobornyl Acrylate         31.3                          --  --  --  --  --   --Acrylic Acid       23.2    --  11.8                              7.80                                  --  --  --   --SR-3492               --  --  --  50.0                                      --  --   --Reactive Diluents (Weight %of Total Reactive Diluent)Alcocur PBDDA3        --  --  --  50.0                                      --  --   --Photomer 40284        --  --  --  --  70.2                                          --   --Chemlink 20005        --  --  --  --  23.4                                          26.5 --Photomer 40256        --  --  --  --  --  73.5 --Polyester Diacrylate7 --  --  --  --  --  --   100Oligomer in Complete Formula              69.8    66.5                          62.0                              61.5                                  50.0                                      53.0                                          51.0 49.0(Except for Photoinitiators)(Wt. %)Reactive Diluents in Complete Formula              30.2    33.5                          38.0                              38.5                                  50.0                                      47.0                                          49.0 51.0(Except for Photoinitiators)(Wt. %)Photoinitiators (PHR)Benzophenone               1.80                          2.00                              2.00                                  1.80                                      1.80                                          1.80 1.80Irgacure 184               0.90                          --  --  0.90                                      0.90                                          0.90 0.90Irgacure 651               --  0.90                              0.90                                  --  --  --   --Properties versusComparative FormulaRT VISC (CPS)      10000   3,600                          3,200                              3,200                                  9,000                                      4,600                                          5,400                                               15,000Stain Resistance   +       ++  ++  ++  +++ +++ +++  +++Gloss Retention    +       +++ ++  ++  +++ +++ ++++ +++Alkali Resistance  +       +++ ++  ++  +++ +++ +++  +++__________________________________________________________________________ 1 Parts added/100 parts of other oligomer ingrs. (not all of the water reacts) 2 Sartomer's ethoxylated Bisphenol A diacrylate (MW approximately 510) 3 Alcolac' s polybutanediol diacrylate (mol. wt. approximately 775) 4 Henkle's ethoxylated Bisphenol A diacrylate (MW approximately 540) 5 Sartomer's long straight chain aliphatic diacrylate (MW approximately 350) 6 Henkle's ethoxylated Bisphenol A diacrylate (MW approximately 690) 7 Acrylated 1,6hexylene phthalate (MW approximately 625)
Patent CitationsCited PatentFiling datePublication dateApplicantTitleUS3924023 *Apr 3, 1973Dec 2, 1975Gaf CorpFloor tile production and productsUS3935364 *Jan 11, 1974Jan 27, 1976Eternit-Werke Ludwig Hatschek & Ucb,S.A.Porous, heat-sensitive substrates coated with synthetic resinsUS3959521 *Dec 6, 1974May 25, 1976Mitsubishi Rayon Co., Ltd.Process for the formation of cured coatingsUS4016306 *Jul 3, 1975Apr 5, 1977Mitsubishi Rayon Co., Ltd.Process for forming a coated film in waterUS4075366 *Oct 21, 1976Feb 21, 1978Desoto, Inc.Low gloss radiation cureUS4138299 *Dec 23, 1977Feb 6, 1979Armstrong Cork CompanyProcess utilizing a photopolymerizable and moisture curable coating containing partially capped isocyanate prepolymers and acrylate monomersUS4421782 *Jun 17, 1982Dec 20, 1983Armstrong World Industries, Inc.Process for providing improved radiation-curable surface coverings and products produced thereby* Cited by examinerReferenced byCiting PatentFiling datePublication dateApplicantTitleUS5066713 *Apr 2, 1990Nov 19, 1991Huels AktiengesellschaftProcess for the preparation of aqueous, radiation-curable urethaneacrylate dispersionsUS5543232 *Apr 6, 1995Aug 6, 1996Armstrong World Industries, Inc.(Meth) acrylated aromatic polyester floor covering wear layerUS5616630 *Feb 17, 1995Apr 1, 1997Lord CorporationEster/urethane acrylate hybrid oligomersUS5663003 *May 10, 1996Sep 2, 1997Armstrong World Industries, Inc.(Meth)acrylated, aromatic polyester/highly ethoxylated (meth)acrylate blend floor covering wear layerUS5719227 *May 9, 1997Feb 17, 1998Armstrong World Industries, Inc.Coating compositionUS5800904 *Oct 29, 1993Sep 1, 1998Hallman; Robert A.Embossable surface covering with inorganic wear layerUS5830937 *May 25, 1993Nov 3, 1998Congoleum CorporationCoating and wearlayer compositions for surface coveringsUS5843576 *Nov 3, 1997Dec 1, 1998Armstrong World Industries, Inc.Floor covering with coating compositionUS5891582 *Jun 30, 1997Apr 6, 1999Armstrong World Industries, Inc.(Meth)acrylated, highly ethoxylated, aromatic polyestersUS6316535May 18, 1999Nov 13, 2001Armstrong World Industries, Inc.Coating system and method of applying the sameUS6440500Aug 15, 2000Aug 27, 2002Armstrong World Industries, Inc.Method for manufacturing a surface covering product having a controlled gloss surface coated wearlayerUS6569500Aug 15, 2000May 27, 2003Awi Licensing CompanyMethod for controlling gloss levelUS6572932Jan 31, 2002Jun 3, 2003Awi Licensing CompanyProcess for providing a gloss controlled, abrasion resistant coating on surface covering productsUS6890625Feb 5, 2001May 10, 2005Awi Licensing CompanySurface covering having gloss in-register and method of makingUS6908585Mar 24, 2003Jun 21, 2005Awi Licensing CompanyPigmented radiation cured wear layerUS6908663Nov 15, 2000Jun 21, 2005Awi Licensing CompanyPigmented radiation cured wear layerUS7098256Oct 9, 2002Aug 29, 2006Microban Products CompanyAntimicrobial radiation curable coatingUS7276265May 8, 2002Oct 2, 2007Awi Licensing CompanyMethod of making a surface covering having gloss-in-registerEP0783008A2Nov 18, 1996Jul 9, 1997Armstrong World Industries, Inc.Coating composition and floor covering including the compositionWO2003054045A2 *Oct 9, 2002Jul 3, 2003Microban ProductsAntimicrobial radiation curable coatingWO2010126618A1Apr 30, 2010Nov 4, 2010Armstrong World Industries, Inc.Uvv curable coating compositions and method for coating flooring and other substrates with same* Cited by examinerClassifications U.S. Classification528/49International ClassificationC08G18/42, D06N3/14, C08G18/67Cooperative ClassificationC08G18/672, C08G18/4219, D06N3/144European ClassificationC08G18/67B4, C08G18/42B2D9, D06N3/14D4Legal EventsDateCodeEventDescriptionJul 20, 1989ASAssignmentOwner name: ARMSTRONG WORLD INDUSTRIES, INC., PENNSYLVANIAFree format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:EHRHART, WENDELL A.;SMITH, DAVID A.;REEL/FRAME:005134/0569Effective date: 19890620Jun 14, 1994FPAYFee paymentYear of fee payment: 4Jul 2, 1998FPAYFee paymentYear of fee payment: 8Mar 19, 2001ASAssignmentJul 31, 2002FPAYFee paymentYear of fee payment: 12Nov 6, 2006ASAssignmentOwner name: BANK OF AMERICA, N.A., AS COLLATERAL AGENT, NORTHFree format text: NOTICE OF GRANT OF SECURITY INTEREST;ASSIGNOR:AWI LICENSING COMPANY;REEL/FRAME:018480/0430Effective date: 20061002RotateOriginal ImageGoogle Home - Sitemap - USPTO Bulk Downloads - Privacy Policy - Terms of Service - About Google Patents - Send FeedbackData provided by IFI CLAIMS Patent Services