AU2013231111B2 - UV/EB curable biobased coating for flooring application - Google Patents
UV/EB curable biobased coating for flooring application Download PDFInfo
- Publication number
- AU2013231111B2 AU2013231111B2 AU2013231111A AU2013231111A AU2013231111B2 AU 2013231111 B2 AU2013231111 B2 AU 2013231111B2 AU 2013231111 A AU2013231111 A AU 2013231111A AU 2013231111 A AU2013231111 A AU 2013231111A AU 2013231111 B2 AU2013231111 B2 AU 2013231111B2
- Authority
- AU
- Australia
- Prior art keywords
- biobased
- coating
- polyol
- materials
- radiation curable
- 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
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- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- PCSMJKASWLYICJ-UHFFFAOYSA-N Succinic aldehyde Chemical compound O=CCCC=O PCSMJKASWLYICJ-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
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- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 239000010828 animal waste Substances 0.000 description 1
- QXHOJXITPBLECI-UHFFFAOYSA-N benzene-1,4-diol 4-methoxyphenol phosphorous acid Chemical compound P(O)(O)O.COC1=CC=C(C=C1)O.C1(O)=CC=C(O)C=C1 QXHOJXITPBLECI-UHFFFAOYSA-N 0.000 description 1
- KGQLBLGDIQNGSB-UHFFFAOYSA-N benzene-1,4-diol;methoxymethane Chemical compound COC.OC1=CC=C(O)C=C1 KGQLBLGDIQNGSB-UHFFFAOYSA-N 0.000 description 1
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 description 1
- 239000012952 cationic photoinitiator Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000905 isomalt Substances 0.000 description 1
- 235000010439 isomalt Nutrition 0.000 description 1
- HPIGCVXMBGOWTF-UHFFFAOYSA-N isomaltol Natural products CC(=O)C=1OC=CC=1O HPIGCVXMBGOWTF-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000845 maltitol Substances 0.000 description 1
- VQHSOMBJVWLPSR-WUJBLJFYSA-N maltitol Chemical compound OC[C@H](O)[C@@H](O)[C@@H]([C@H](O)CO)O[C@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O VQHSOMBJVWLPSR-WUJBLJFYSA-N 0.000 description 1
- 235000010449 maltitol Nutrition 0.000 description 1
- 229940035436 maltitol Drugs 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- KRTSDMXIXPKRQR-AATRIKPKSA-N monocrotophos Chemical compound CNC(=O)\C=C(/C)OP(=O)(OC)OC KRTSDMXIXPKRQR-AATRIKPKSA-N 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229960002920 sorbitol Drugs 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
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- 238000005809 transesterification reaction Methods 0.000 description 1
- 235000021081 unsaturated fats Nutrition 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002916 wood waste Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
Abstract
A radiation curable biobased coating, such as a UV/EB curable biobased coating, for flooring applications includes a biobased component comprising renewable and/or biobased materials. The biobased component is selected from the group consisting of a biobased resin, a biobased polyol acrylate, or a biobased polyol. The biobased component is blended with a coating formula. The coating formula includes at least one initiator. The radiation curable biobased coating contains at least about 5% weight of renewable materials or biobased content. -20 of20-
Description
UV/EB CURABLE BIOBASED COATING FOR FLOORING APPLICATION [0001] This application claims priority from U.S. Patent Application Serial No. 61/125,918, filed April 30, 2008, which is hereby incorporated by reference in its entirety. [0002] The present invention relates to biobased coatings for flooring applications, and more particularly to an ultraviolet (UV)/ electron beam (EB) curable biobased coating for flooring applications. Radiation curable coatings, such as UV/EB curable coatings, are applied to various types of substrates to enhance their durability and finish. The radiation curable coatings are typically resin based mixtures of oligomers or monomers that are cured or cross linked after being applied to the substrate by radiation curing. The radiation curing polymerizes the resins to produce a high or low gloss coating having superior abrasion and chemical resistance properties. The radiation curable coatings of this type are often referred to as topcoats or wear layers and are used, for example, in a wide variety of flooring applications, such as on linoleum, hardwood, laminate, cork, bamboo, resilient sheet, and tile flooring. [0003) The above-described radiation curable coatings are made from fossil fuels, such as petroleum and coal. Because the use of fossil fuels negatively impacts the environment, new radiation curable coatings need to be developed which are derived from recycled materials or renewable resources, such as biobased materials. Recycled materials are materials that have been recovered or otherwise diverted from the solid waste stream, either during the manufacturing process (pre-consumer), or after consumer use (post-consumer). Recycled materials therefore include post-industrial, as well as, post-consumer materials. Biobased materials are organic materials containing an amount of non-fossil carbon sourced from biomass, -1 of 20 such as plants, agricultural crops, wood waste, animal waste, fats, and oils. The biobased materials formed from biomass processes therefore have a different radioactive C14 signature than those produced from fossil fuels. Because the biobased materials are organic materials containing an amount of non-fossil carbon sourced from biomass, the biobased materials may not necessarily be derived 100% from biomass. A test has therefore been established for determining the amount of biobased content in the biobased material. Generally, the amount of biobased content in the biobased material is the amount of biobased carbon in the material or product as a fraction weight (mass) or percentage weight (mass) of total organic carbon in the material or product. (0004] The calculation of the amount of biobased content in the material or product is important for ascertaining whether the material or product, when used in commercial construction, would qualify for Leadership in Energy and Environmental Design (LEED) certification. The US Green Building Council has established a LEED rating system which sets forth scientifically based criteria for obtaining LEED certification based on a point system. As shown in Table 1, under the LEED rating system, for new construction I point is granted for at least 5% wt of the total of post-consumer materials and K post-industrial materials. A second point is granted for at least 10% wt of the total of post-consumer materials and 1 % post-industrial materials. An additional point is granted for at least 5% wt of rapidly renewable building materials and products. For existing building 1 point is granted for at least 10% wt post consumer materials. A second point is granted for at least 20% wt of post-industrial materials. An additional point is granted for at least 50% wt of rapidly renewable materials. Thus, flooring products meeting the LEED criteria can be used to obtain points for LEED certification. Table I - LEED Rating System -2 of 20 - Rating System LEED Version 2.1 Rating System LEED -Version 20 New Construction Existing Building MR Credit 4.1 5% wt of post- MR Credit 21 10% vt of post 1 Point consumer materials + 1 Point consumer materials % post-industrial materials MR Credit 4.2 = 10% wt of post- MR Credit 2.1 20% wof f post I Point consumer materials + 1 oint. industrial materials I P0 v post-industrial materials MR Credit 6 =5 tof rapidly MR Credit 2.5 =50% wt of rapidly 1 Point renewable building 1 Point renewable materials materials and products [0051 ecasethere has been renewed mrarkerters in gvn rfrnet greene" fooring products based upon he I EED rating systemthee renewed to develop "ereener" looing product based upon exisng pod 5 srutues/roesesand availabe rele eaeil.Thle keyo this aprahis to integrat rapidly reewble mnatials, such as bioased materis iNo the radiaion urasuch as those used in application, to on lim."ited reouce uch as- fossJl fes [QOO l Any discussion of douents acts. material devi ces, a ic orIthe like which has been included in the present specificati is not to be taken as an admsion that any or al of Hese matters fo d art of the prior at. chase or were common general knowledge in the fd reaant to the pesen disclosure as it beireth priority d-ate ofeachcai f hsaplcain 3 of 20 10005131 Ihioughou this specincation the word "comprsdor variatons such as comprisess or comprisingg wil be understood to imply the inclusion of a stated cement, integer or step, or group of elements. tegem or steps, hut not the exclusion o' ayother lemnt integer or step. or group of elements, intgers or steps. b10005C1 In one aspect of the invention thee is provided a coating cmre an epoxy resin, or a biobased polyester acryate; when the biobased componem is blended with a coming formula, the coating formula including an initiator 10 wherein the coating includes at least about 5% by weight orenewableo biobased content 10005D} In another aspect of the invention there is provided a floor, comprising: a cellulosic substrate: and a coating applied to the ceilulosic substrate, the coating comprising a biobased 15 componem including a biobased polyol blended with a vinyl ether or an epoxy resin, or a bio based polyester acrylate; wherein the biobased component is blended with a coating formula, the coating formula including an initiator: wherein the coating includes at least about 5% by weight of renewable or 20 biobased content [0005E] Disclosed herein is a radiation curable biobased coating such as a UV/EB1 curable bobased coating. for flooring applications comprising a biobased component including renewable and/or biobased materials. The biobased component is selected from the group consisting of a biobased resin, a biobased polyol acrylate, or a 25 biobased polyol. The biobased component is blended with a coating formula, The coating formula includes at least one initiator. The radiation curable biobased coating contains at least about 5% weiAght of renewable materials or biobased content 3A of 20 [0 1Also disclosed herein is a flooring application comprising a substrate having at least one surface provided with a radiation curable biobased coating. The radiation curable biobased coating comprises a biobased component. The biobased component is selected from the group consisting of a biobased resin, abiobased polyol 5 acrylate, or a biobased polyol. The biobased component is blended with a coating formula. The coating formula includes at least one imitator. The radiation curable biobased coating contains at least about 5% weight of renewable materials or biobased content. [0006] Disclosed herein is a radiation curable biobased coating, such as a 1 V/EB curable biobased coating, for fooring applications wherein the radiation curable biobased coating contains a biobased component comprising renewable and/or biobased materials. The radiation curable biobased coating is generally formedby acrylating a biobased polyol and reacting the biobased polyol acrylate with di isocyanates or tri-isocyanates to make a biobased resin. The biobased resin is then I5 blended into a radiation curable biobased coating formulation comprising at least one initiator to form the radiation curable biobased coating. In another embodiment, the biobased polyol acrylate is directly blended into the radiation curable biobased coating formulation comprising the at least one initiator to form the radiation curable biobased coating. In a further embodiment, the biobased polyol is directly blended into a 20 radiation curable bia cotn iobased coti fmTion comprising at least one epoxy resin or vinyl ether and at least one initiator, which may be, for example, a cationic type photoinitiator, to form the radiation curable biobased coatin, [0007] The biobased polyol may be made from various diacids or diols, which are derived from renewable and/or biobased material. The biobased polyol is derived 5 from renewable andor biobased materials and contains a weight percentage of renewable materials or biobased content of at least about 5%, preferably at least about 75%, and more preferably at least about 95%, The biobased polyol may be derived, for example, from plant oils extracted frmn plant seeds, such as castor oil, linseed oil, soy oil tail oil (pine oil)l tung oil, vernonia oil, A of 20) lesquerella oil (bladderpod oil), cashew shell oil, or other plant oils rich in unsaturated fatty acids. The plant oils include triglycerides generally comprised of esters formed from glycerol and saturated and unsaturated fatty acids. A typical structure of a triglyceride unsaturated fat contains three fatty acids esterified to three hydroxyl groups of glycerol. The triglycerides are converted to individual saturated fatty acids, unsaturated fatty acids, and glycerol by acid or base catalyzed transesterification. Examples of some of the acid components in various plant oils are listed in Table 2. Table 2 - Plant Oil Acids Plant Oil Acid Castor Oil Ricinoleic Linseed Oil Linolenic, Linoleic, Oleic Soy Oil Palmitic, Linoleic, Oleic Tall Oil (Pine Oil) Palmitic, Linoleic, Oleic Tung Oil Eleaostearic Vernonia Oil Vernolic Lesquerella Oil (Bladderpod Oil) Lesquerolic, Oleic, Linoleic Cashew Shell Oil Cardanol [0008] The unsaturated fatty acids are of particular interest as precursor chemicals for polyol synthesis because they have the functionality for satisfactory derivitization. Specifically, the unsaturated fatty acids contain functional groups, such as olefinic, hydroxyl, and epoxy, on a long carbon chain. For example, castor oil and lesquerella oil (bladderod oil) have a pendent hydroxyl group, and vernonia oil has a natural epoxy group. Thus, the unsaturated fatty acids include several chemical functions that facilitate polymer synthesis, such as unsaturated carbon chains, hydroxyl groups, ester linkages, and epoxy functions. As a result, the unsaturated fatty acids of the plant oils enable direct radiation cross-linking or chemical modifications toward polyol synthesis. Because many biobased polyols made from plant oils are commercially - 5 of 20 availabic, and the method of forming biobased polyols from plant oils is well known in the art, further description of the biobased polyols made from plant oils has been omitted. [0009] Alternatively, the biobased polyol may be a biobased polyester polyol or biobased polyester-ether polyol. The biobased polyester polyols and the biobased polyester-ether polyols may be made, for example, from biobased diols and biobased diacids derived from renewable resources, such as corn, sugar cane, vegetable oil, and the like. The biobased diol may be selected from the group consisting, for example, of 1,3 propanediol, 1,4 butanediol, propylene glycol, glycerol, and combinations thereof. The biobased diacid may be selected from the group consisting, for example, of sebacic acid, fumaric acid, succinic acid, tumaric acid, malic acid, dicarboxylic acid, citric acid, azelaic acid, lactic acid, and any combination thereof. Additional additives include surfactant, defoamer, organic and/or inorganic flatting agents, abrasion fillers, texture particles, and the like. [0010] Table 3A shows some examples of some biobased polyester polyol formulations. Reaction of the diacid with the diol produces the biobased polyester polyol by condensation, with water as a by-product. For example, the biobased polyester polyol may be prepared according to the procedure set forth in Examples 1-4 of US Patent No. 5,543,232, which is hereby incorporated by reference in its entirety. Because the method of preparing polyester polyols is well known in the art, further description thereof has been omitted. Table 3A - Biobased Polyester Polyol Formulations EX-1 FX-2 EX-3 EX-4 EX-5 EX-6 EX-7 EX-8 Ingredient Amt (g) Amt (g) Amt (g) Amt (g) Amt (g) Amt (g) Amt (g) Amt (g) Sebacic 639.18 648.31 663.10 672.94 0 0 0 0 Acid Succinic 0 0 0 0 539.50 551.69 557.92 570.97 Acid 1,3 360.72 291.48 336.80 264.57 460.40 360.65 441.99 338.32 Propanediol , I I I I -6 of 20- Glycerine 0 60.10 0 62.39 0 87.56 0 90.81 Fascat4100 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 Wt % 99.99 99.99 99.99 99.99 99.99 99.99 99.99 99.99 Renewable Materials Wt % 99.99 99.99 99.99 99.99 99.99 99.99 99.99 99.99 Biobased Content [0011] The biobased polyester polyol may also be made by ring opening polymerization of lactone, lactide, and glycolide in the presence of a biobased diol or triol, such as 1,3 propanediol, 1,4 butanediol, glycerol, and combinations thereof, as initiator and a ring-opening polymerization catalyst. Table 3B shows some examples of some biobased polyester polyol formulations made by ring opening polymerization. These biobased polyester polyols may be prepared according to the procedure set forth in US Patent No. 6,916,547, which is hereby incorporated by reference in its entirety. For example, these biobased polyester polyols may be prepared by charging lactone/lactide monomer(s) and Bio-PDO into a I liter glass reactor equipped with anchor stirrer, temperature probe, nitrogen sparge tube and air condenser, and stirring at 175 rpm with 0.4 SCFH nitrogen sparge. The polymerization catalyst stannous 2-ethyl hexanoate is then charged. The nitrogen sparge is continued for 10 minutes. The nitrogen charge is then maintained, and the reactants are heated to 130 degrees Celsius over 30 minutes. The nitrogen sparge is then maintained at 130 degrees Celsius for 6 - 14 hours until the reaction is complete. The batch is then cooled to 30 degrees Celsius and discharged. Table 3B - Biobased Polyester Polyol Formulations EX-9 EX-10 EX-1I Ingredient Amt (g) Amt (g) Amt (g) Caprolactone 500.00 0 250.00 -7of20- Lactide 0 550.00 250.00 1,3-Propanediol 154.36 134.47 138.30 Stannous 2-ethyl hexanoate 0.0654 0.0684 0.0388 Wt % Renewable Materials 23.59 99.99 60.83 Wt % Biobased Content 19.21 99.99 54.91 [0012] The biobased polyol may also be a biobased polyether polyol. The biobased diol may be selected from the group consisting, for example, of 1,3 propanediol and 1,4 butanediol, propylene glycol, glycerol, and combinations thereof. Examples of biobased polyether polyols include poly(trimethylene ether glycol) and poly(tetramethylene ether glycol). One commercially available poly(trimethylene ether glycol) is CERENOL manufactured by E. 1. du Pont de Nemours and Company of Wilmington, Delaware. CERENOL is made 1,3 propanediol originating from corn sugar via aerobic fermentation. The biobased content of poly(trimethylene ether glycol) made from polycondensation of 1,3 propanediol originating from corn sugar via aerobic fermentation is about 100%. [0013] Additionally, the biobased polyol may be derived, for example, from vegetable oils, corn, oats, cellulose, starch, sugar, sugar alcohols, such as xylitol, sorbitol, maltitol, sucrose, glycol, glycerol, erythritol, arabitol, rebitol, mannitol, isomalt laetitol, fructose, or polysaccharides or monosaccharides originated from cellulose, starches, or sugars. It will be appreciated by those skilled in the art that other renewable and/or biobased materials containing -8 of 20 primary and secondary hydroxyl groups could also be used as the biobased polyol, because such renewable and/or biobased materials are capable of acylated, as described herein, to form the radiation curable biobased coating of the present invention. [0014] The biobased polyol is partially or fully acrylated to form a biobased polyol acrylate. Because the biobased polyol acrylate is derived from renewable and/or biobased materials, the biobased polyol acrylate contains a weight percentage of renewable materials of at least about 5%, preferably at least about 50%, and more preferably at least about 70%. The biobased polyol acrylate may be formed, for example, by reacting the biobased polyol with acrylic acid. Table 4 shows some examples of some biobased polyol acrylate formulations using the biobased polyols made from castor oil (Polycin D-290; Polycin M-280; Polycin D-265; Polycin D-140), and soy oil (Soyol R2-052-F; Soyol R3-17 10-F). Table 4 - Biobased Polyol Acrylate Formulations EX-12 EX-13 EX-14 EX-15 EX-16 EX-17 EX-18 Ingredient Amt Amt Amt Amt Amt Amt Amt (a) (g) (g) (g) (g) (g) (g) Polycin D-290 800.00 0 0 800.00 0 0 0 Polycin M-280 0 500.00 0 0 0 0 0 Polycin D-265 0 0 450.00 0 0 0 0 Polycin D-140 0 0 0 0 800.00 0 0 Soyol R2-052-F 0 0 0 0 0 800.00 0 Soyol R3-1710-F 0 0 0 0 0 0 800.00 Acrylic Acid 328.29 108.00 91.70 179.07 86.40 33.38 104.73 p-toluene 5.40 3.38 3.04 5.40 5.40 5.40 5.40 sulfonic acid Hydroquinone 0.12 0.08 0.07 0.12 0.12 0.12 0.12 Monomethyl ether 0.12 0.08 0.07 0.12 0.12 0.12 0.12 hydroquinone (p-methoxyphenol) Phosphorous Acid 0.62 0.39 0.35 0.62 0.62 0.62 0.62 n-heptane 200 ml 182.75 0 0 0 0 0 Toluene 0 0 130.06 200 ml 200 ml 200 ml 200 ml N-methyl- 0 0 0 0 0 0 0 diethanolamine Reaction 100- 100- 110 - 110 - 110 - 110- 110 - 9 of 20 - Temperature 105 *C 105 *C 112 *C 112 *C 112 "C 112 *C 112 "C Wt % Renewable 70.51 81.71 82.53 81.19 89.62 95.28 87.82 Materials [0015] A method for acrylating the biobased polyol using the formulation in Table 4, EX-14 will now be described. A 1.0 liter jacketed glass reaction flask is prepared for toluene reflux and water separation. The flask is sparged with about 0.5 standard cubic feet per hour of dry air and about 1.5 standard cubic feet per hour nitrogen blend. An anchor stirrer is activated at about 200 rpm. The polycin D-265, hydroquinone, monomethyl ether hydroquinone (p methoxyphenol), and phosphorous acid are charged. The reactants are then heated to about 60 degrees Celsius. The acrylic acid and p-toluene sulfonic acid are charged. The p-toluene sulfonic acid is allowed to dissolve. The toluene is charged. Thejacket of the glass reaction flask is heated to and maintained at a temperature of about 125 degrees Celsius. The reactants temperature is controlled at about 116 - 119 degrees Celsius by regulating the amount of the toluene. The toluene is refluxed back to the reactants and the reaction water is separated. The reaction water is then collected and measured. The conditions are maintained until the reaction water ceases. The jacket of the glass reaction flask is then reset to about 100 degrees Celsius, and a vacuum distillation is prepared to remove the toluene. When the reactants temperature reaches about 100 degrees Celsius, the blanket of dry air and nitrogen blend is slowly turned off and a vacuumed is slowly applied. The vacuum is continued at 26" Hg until the toluene distillation ceases. The batch is then cooled and discharged. [0016] The biobased polyol acrylate is then reacted with di-isocyanates or tri-isocyanates or reacted with di-isocyanates or tri-isocyanates and UV/EB moieties to form a biobased resin, such as a biobased urethane acrylate or a biobased polyester acrylate. Because the biobased resin is derived from renewable and/or biobased materials, the biobased resin contains a weight -10 of20percentage of renewable materials of at least about 5%, preferably at least about 50%, and more preferably at least about 65%. The biobased resin comprises a mixture of crosslinkable monomers and oligomers having reactive groups capable of providing the ability to polymerize upon exposure to radiation, such as UVIEB radiation. Table 5 shows some examples of some biobased resin formulations using the biobased polyol acrylates from Table 4. Table 5 - Biobased Resin Formulations EX-19 EX-20 EX-21 Ingredient Amt (g) Amt (g) A!nt (g) EX-14 600.00 0 459.85 EX-18 0 600.00 0 Desmodur W 132.48 23.60 101.53 Silwet L-7200 1.89 0 1.45 Iragacure 184 5.49 0 4.21 Benzophenone 21.97 0 16.84 Wt % Renewable 65.00 84.49 65.00 Materials [0017] A method for reacting the biobased polyol acrylate to produce the biobased resin using the formulation in Table 5, EX-21 will now be described. EX-14 from Table 4 is charged to a 1.0 liter jacketed glass reaction flask. An anchor stirrer is activated at about 200 rpm, and EX-14 is heated to about 35 degrees Celsius. The flask is blanketed with about 1.1 standard cubic feet per hour of dry air for about 30 minutes. EX-14 is heated to about 50 degrees Celsius. The blanket of dry air is adjusted to about 0.45 standard cubic feet per hour. Desmodur W is charged in one third increments (about 33.84 g) and exotherm is observed with each addition. The reactants are maintained at a temperature of about 85 degrees Celsius over about a 2 hour period. The reactants are then held at a temperature of about 85 degrees Celsius, and infrared is used to monitor the decline in the numerically controlled oscillator (NCO) peak. When the NCO peak is gone, the batch is cooled to about 60 degrees Celsius. The Silwet L-7200, Irgacure 184, -11 of20and benzophenone are then charged and mixed for about 30 minutes until all dissolved. The batch is then cooled and discharged. [0018] The biobased resin is then blended, for example, with an initiator, surfactant, and other additives, such as acrylate reactive diluents, defoamer, matting agent, abrasion agent, and texture particles, to form the radiation curable biobased coating. The acrylate reactive diluents may include, for example, (meth) acrylic acid, isobornyl (meth)acrylate, isodecyl (meth)acrylate, hexanediol di(meth)acrylate, N-vinyl formamide, tetraethylene glycol (meth)acrylate, tripropylene glycol(meth)acrylate, neopentyl glycol di (meth)acrylate, ethoxylated neopentyl glycol di (meth)acrylate, propoxylated neopentyl glycol di (meth)acrylate, trimethylol propan tri(meth)acrylate, ethoxylated trimethylol propan tri(meth)acrylate, propoxylated trimethylol propan tri(meth)acrylate, ethoxylated or propoxylated tripropylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tris (2-hydroxy ethyl) isocyanurate tri(meth)acrylate, and combinations thereof. The initiator may be any chemical capable of initiating, assisting, or catalyzing the polymerization and/or cross-linking of the biobased resin. The initiator may be, for example, a photoinitiator or photosensitizer that allows the biobased coating to cure when exposed to UV/EB radiation. The initiators may be chosen to increase curing rate and sensitivity to specific wavelengths of UV/EB radiation. The concentration of the initiator is the amount necessary to provide satisfactory curing for the biobased resin in the coating mixture. [0019] Table 6A shows some examples of some radiation curable biobased coating formulations using the biobased resins from Table 5 based on a free radical curing mechanism. Because the radiation curable biobased coating is derived from renewable and/or biobased materials, the radiation curable biobased coating contains a weight percentage of renewable - 12 of 20 materials of at least about 5%, preferably at least about 30%, and more preferably at least about 40%. Table 6A - Radiation Curable Biobased Coating Formulations EX-22 EX-23 EX-24 EX-25 Ingredient Amt (g) Amt (g) Amt (g) Amt (g) EX-21 50.00 50.00 50.00 50.00 SR-3010 28.13 20.00 12.50 6.00 Silwet L-7200 0.07 0.05 0.03 0.02 Irgacure 184 0.21 0.15 0.09 0.05 Benzophenone 0.84 0.60 0.38 0.18 Wt % Renewable 41.01 45.91 51.59 57.78 Materials [0020] In another embodiment, the biobased polyol acrylate is directly blended into a radiation curable biobased coating formulation similar to the radiation curable biobased coating formulations in Table 6A to form the radiation curable biobased coating. The biobased polyol acrylate may be, for example, any of the biobased polyol acrylates from Table 4, and the biobased polyol acrylate would be substituted for EX-21 in Table 6A. [0021] In a further embodiment, the biobased polyol is directly blended into a radiation curable biobased coating formulation comprising at least one epoxy resin or vinyl ether and at least one initiator, which may be, for example, a cationic type photoinitiator, to form the radiation curable biobased coating. The biobased polyol may be, for example, any of the biobased polyols from Tables 3A - 3B or combinations thereof. The epoxide resins may include, for example, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, bis-(3,4 epoxycyclohexyl) adipate, 3-ethyl-3-hydroxy-methyl-oxetane, 1,4-butanedial diglycidyl ether, 1,6 hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycol diglycidyl ether, propoxylated glycerin triglycidyl ether, monoglycidyl ester of neodecanoic acid, epoxidized soy, epoxidized linseed oil, epoxidized polybutadiene resins, or -13 of20 combinations thereof. The vinyl ether resins may include, for example, 1,4-butanediol divinyl ether, diethyleneglycol divinyl ether, triethyteneglycol divinyl ether, N-vinyl caprolactam, N vinylformamide, N-vinyl pyrrolidone, n-butyl vinyl ether, tert-butyl vinyl ether, cyclohexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, trimethylolpropane diallyl ether, allyl pentaerythritol, trimethylolpropane monoallyl ether, or combinations thereof. The initiator may be, for example, a cationic photoinitiator and a photosensitizer, such as triarylsulfonium hexafluoroantimonate salts, triarylsulfonium hexafluorophosphate salts, bis(4-methylphenyl) hexafluorophosphate-(1)-iodonium, isopropyl thioxanthone, 1-chloro-4-propoxy-thipxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, camphorquinone. [0022] Table 6B shows some examples of some radiation curable biobased coating formulations using the biobased polyols from Table 3A based on cationic curing mechanism. Table 6B - Radiation Curable Biobased Coating Formulations Ingredient EX-26 EX-27 Chemical Name Function Amt (g) Amt (g) EX-5 resin 12.5 12.5 3,4-epoxy cyclohexyl methyl-3,4 epoxy cyclohexane carboxylate resin 50 50 Silwet L-7200 surfactant 0.156 0.156 Isopropylthioxanthone photosensitizer 0.313 0 2,4-diethyl thioxanthone photosensitizer 0 0.313 Arylsulfoniumhexafluoro-phosphate photoinitiator 3.75 3.75 Gasil UV70C flatting agent 5.3375 5.3375 Wt % Renewable Materials 17.35 17.35 Wt % Biobased Content 13.32 13.31 -14 of20 - [0023] The radiation curable biobased coating is then applied to a surface of a substrate and is cured or cross-linked by radiation curing to form a topcoat or wear layer thereon. The substrate may be made, for example, from a variety of materials, such as wood, ceramic, plastic, or metal. Additionally, the substrate may be, for example, a substrate of a flooring application, such as linoleum, hardwood, laminate, cork, bamboo, resilient sheet, or tile. The radiation curable biobased coating may be radiation cured, for example, with UV/EB radiation. For example, standard high pressure mercury vapor type UV lamps with wavelengths of about 1800 - 4000 Angstrom units can be used to cure the radiation curable biobased coating, as well as UV lamps containing additives to enhance specific UV regimes. The radiation curable biobased coating is exposed to the UV lamps at about 0.5 - 2.5 joules per centimeter squared at about 0.3 1.2 watts megawatts per centimeter squared. It will be appreciated by those skilled in the art, however, that the length and intensity of the exposure to the radiation may vary depending on the thickness and composition of the radiation curable biobased coating and the desired finish, e.g., gloss level. Additionally, the radiation curable biobased coating may be cured in air or nitrogen depending upon the composition of the radiation curable biobased coating and the desired finish. [0024] The foregoing illustrates some of the possibilities for practicing the invention. Many other embodiments are possible within the scope and spirit of the invention. It is, therefore, intended that the foregoing description be regarded as illustrative rather than limiting, and that the scope of the invention is given by the appended claims together with their full range of equivalents. -15 of20 -
Claims (6)
- 3. The coating of clin or claim 2. hereinthe coating incde, at least about 15 40% by weight o enewable orbiobased content
- 4. The coating of any one of claims I to 3 wherein the initiator is a cationic type intiator 20 5. The coating of any one of claims 1 to 4, wherein the coating qualifies for at least one point tinder the LEED rating g system. 1-the coating of any one of claims 1 to 5, wherein the oatig is a radiation curable coating.
- 7. The coating of any one of claims 1 to 6, wherein the coating is positioned on a flooring
- 8. The coating of claim 7, wherein the flooring includes a cellulosic substrate and 30 the coating is positioned on the coating
- 9. A floor, comprising: a cellulosic substrate; and a coating applied to the cellulosic substrate, the coating comprising a biobased 35 component including a biobased polyol blended with a vinyl ether or an epoxy resin, or a biobased polyester acrylate; 17 wherein the biobased component is blended with a coating formula, the coating formula including an initiator; wherein the coating includes at least about 5% by weight of renewable or biobased content
- 10. The coating of any one of clairns I to 8. wherein the biobased polyol is a biobased polyester polyol. he coating of any one OFaims the bosed po comprises 10 a oobase d o o n eleceed rnm , 3-propanedaliol, I4-butanediol or glyer 1 2. Theoating of any one of caims to . whenahe biobased polyol cmprises a biobased diacid seled fom a dicarboxyie acid
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| US61/125,918 | 2008-04-30 | ||
| AU2009241803A AU2009241803B2 (en) | 2008-04-30 | 2009-04-30 | UV/EB curable biobased coating for flooring application |
| AU2013231111A AU2013231111B2 (en) | 2008-04-30 | 2013-09-19 | UV/EB curable biobased coating for flooring application |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3509234A (en) * | 1965-08-13 | 1970-04-28 | Ford Motor Co | Radiation curable paint binders containing vinyl monomers and a hydroxylated polymer reacted with a polyisocyanate and an hydroxyl alkyl acrylate |
| US4210693A (en) * | 1977-12-20 | 1980-07-01 | Dowdflor Corporation | Register emboss and method |
| US4861629A (en) * | 1987-12-23 | 1989-08-29 | Hercules Incorporated | Polyfunctional ethylenically unsaturated cellulosic polymer-based photocurable compositions |
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2013
- 2013-09-19 AU AU2013231111A patent/AU2013231111B2/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3509234A (en) * | 1965-08-13 | 1970-04-28 | Ford Motor Co | Radiation curable paint binders containing vinyl monomers and a hydroxylated polymer reacted with a polyisocyanate and an hydroxyl alkyl acrylate |
| US4210693A (en) * | 1977-12-20 | 1980-07-01 | Dowdflor Corporation | Register emboss and method |
| US4861629A (en) * | 1987-12-23 | 1989-08-29 | Hercules Incorporated | Polyfunctional ethylenically unsaturated cellulosic polymer-based photocurable compositions |
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