USRE27656E - Process of curing polymerizable resins having terminal vinyl ester groups using high energy electrons - Google Patents
Process of curing polymerizable resins having terminal vinyl ester groups using high energy electrons Download PDFInfo
- Publication number
- USRE27656E USRE27656E US27656DE USRE27656E US RE27656 E USRE27656 E US RE27656E US 27656D E US27656D E US 27656DE US RE27656 E USRE27656 E US RE27656E
- Authority
- US
- United States
- Prior art keywords
- acrylate
- coating
- vinyl ester
- terminal
- polyfunctional
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title abstract description 28
- 229920005989 resin Polymers 0.000 title abstract description 25
- 239000011347 resin Substances 0.000 title abstract description 25
- 229920001567 vinyl ester resin Polymers 0.000 title abstract description 22
- 230000008569 process Effects 0.000 title abstract description 10
- 125000004185 ester group Chemical group 0.000 title description 4
- 239000008199 coating composition Substances 0.000 abstract description 32
- 238000000576 coating method Methods 0.000 abstract description 29
- 239000000758 substrate Substances 0.000 abstract description 25
- 239000011248 coating agent Substances 0.000 abstract description 24
- 229920000647 polyepoxide Polymers 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 20
- 239000000178 monomer Substances 0.000 abstract description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 18
- 239000007788 liquid Substances 0.000 abstract description 12
- 239000002253 acid Substances 0.000 abstract description 11
- 150000002148 esters Chemical group 0.000 abstract description 11
- 239000012948 isocyanate Substances 0.000 abstract description 10
- 150000002513 isocyanates Chemical class 0.000 abstract description 10
- 230000005865 ionizing radiation Effects 0.000 abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 4
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 229920001228 polyisocyanate Polymers 0.000 abstract description 4
- 239000005056 polyisocyanate Substances 0.000 abstract description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 abstract description 3
- 229920000768 polyamine Polymers 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical group N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 abstract 1
- SGFJJNBUMXQSMU-PDBXOOCHSA-N oxiran-2-ylmethyl (9z,12z,15z)-octadeca-9,12,15-trienoate Chemical group CC\C=C/C\C=C/C\C=C/CCCCCCCC(=O)OCC1CO1 SGFJJNBUMXQSMU-PDBXOOCHSA-N 0.000 abstract 1
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical class C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 23
- 239000002023 wood Substances 0.000 description 18
- -1 aliphatic saturated dicarboxylic acid Chemical class 0.000 description 11
- 238000010894 electron beam technology Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000007859 condensation product Substances 0.000 description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 7
- 229940095095 2-hydroxyethyl acrylate Drugs 0.000 description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229920002799 BoPET Polymers 0.000 description 5
- 239000005041 Mylar™ Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 150000008064 anhydrides Chemical class 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- TWHMVKPVFOOAMY-UHFFFAOYSA-N octanedioic acid Chemical compound OC(=O)CCCCCCC(O)=O.OC(=O)CCCCCCC(O)=O TWHMVKPVFOOAMY-UHFFFAOYSA-N 0.000 description 2
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical class C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 239000012260 resinous material Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- OVYQSRKFHNKIBM-UHFFFAOYSA-N butanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCC(O)=O OVYQSRKFHNKIBM-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- WUNHMSSPKUNDEH-UHFFFAOYSA-N decanedioic acid;pentanedioic acid Chemical compound OC(=O)CCCC(O)=O.OC(=O)CCCCCCCCC(O)=O WUNHMSSPKUNDEH-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- YVSCCMNRWFOKDU-UHFFFAOYSA-N hexanedioic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)CCCCC(O)=O YVSCCMNRWFOKDU-UHFFFAOYSA-N 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical group CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- HJSRRUNWOFLQRG-UHFFFAOYSA-N propanedioic acid Chemical compound OC(=O)CC(O)=O.OC(=O)CC(O)=O HJSRRUNWOFLQRG-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/068—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using ionising radiations (gamma, X, electrons)
-
- 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
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
-
- 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
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
-
- 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]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
Definitions
- ABSTRACT OF THE DISCLOSURE A process of coating a porous or nonporous substrate with a liquid polymerizable film and subjecting the coated substrate to ionizing radiation sufiicient to impart to the coating composition a dose of from 1 to megarads in one second or less.
- the coating compositions capable of substantially complete polymerization in less than one second, contain undiluted vinyl ester resins having terminal vinyl ester groups, or the above dissolved in vinyl monomers.
- the vinyl ester resins are made by reacting:
- a polyfunctional material selected from the group consisting of (a) dicarboxylic acids or acid chlorides having from 4 to carbon atoms, and (b) [polyepoxides having terminal, reactive glycidyl groups, (0)] polyfunctional isocyanates having terminal, reactive isocyanate group or (d) dicarboxylic acid esters of polyepoxides, polyamines, po1yisocyanates,] with Z-hydroxyalkyl acrylates or methacrylates; or
- Particularly useful are coating compositions containing resins having terminal acrylate groups and an acrylate monomer, the polyfunctional acrylate having more than one 2-oxyalkylacrylate end group per molecule with the end groups being joined by a hydrophobic molecule such as a dicarboxylic acid, polyfunctional isocyanate or polyepoxide.
- This invention relates to a process of curing coating compositions having terminal unsaturation in a very short amount of time using high energy electrons.
- Electron irradiation has a number of distinct advantages over conventional methods of polymerization and cross-linking using catalytic agents, especially when used to cure coatings on wood and wood products, fabrics, rubber, glass, and other similar substrates.
- Use of electron irradiation to cure polymeric coatings avoids the sometimes lengthy induction period associated with catalyst-induced cure, enables the use of polymeric coating compositions having indefinite pot life, produces little temperature rise during polymerization, and produces, in many cases, a superior coating-to-substrate bond.
- One of the problems associated with electron irradiation is in finding a polymeric material which is suitable for the purpose desired and curable to a hard, tack-free condition in a short amount of time.
- a coating composition which is flexible, water resistant, and impact resistant.
- the polymeric composition cure or polymerize in a short amount of time at reasonable dose rates in order to make the process economically feasible.
- acrylates made by reacting polyhydric alcohols, such as ethylene glycol, with acrylic or methacrylic acids are curable by high energy radiation, as disclosed in US. Pat. No. 2,921,006.
- the diacrylates disclosed do not cure to a hard tack free state using economically feasible dose rates, are too brittle, and swell on exposure to moisture and weathering, making them unacceptable for coating wood and wood products.
- Other polyester coating materials curable by high energy radiation are disclosed in US. Pat. No. 3,247,012. These compositions also lack certain desired properties, making them unacceptable for coating of wood and wood products.
- This invention is directed to a process for coating a substrate with a composition containing a polymerizable material having terminal vinyl ester groups and thereafter subjecting the coating to high energy ionizing radiation in the form of electrons to cure the coating to a tack-free condition in times of one second or less. It pounds could be cured with high energy electrons at reasonable dose rates in such a short amount of time. Further, this invention is directed to a process of coating wood and wood products with vinyl ester resins which, on curing, have good flexibility, excellent water resistance, and excellent impact resistance.
- the vinyl ester resins of this invention can be used undiluted or dissolved in 0 to 50% by weight of a vinyl monomer. Pigments and other conventional additives can be added to the coating compositions. Vinyl ester resins made by reacting:
- a polyfunctional material selected from the group consisting of (a) dicarboxylic acids or acid chlorides having from 4 to 15 carbon atoms, and (b) [polyepoxides having terminal, reactive glycidyl groups, (0)] polyfunctional isocyanates having terminal, reactive isocyanate groups or (d) dicarboxylic acid esters of polyepoxides, polyamines, or polyisocyanates] with Z-hydroxyalkyl acrylates or merhacrylares; or
- Polymerizable vinyl ester resins described previously are liquids which may be used undiluted or dissolved in vinyl monomers which compolymerize with the vinyl ester resin upon subjection to irradiation. These resinous compositions are made by reacting Z-hydroxy'alkyl acrylates with polyfunctional, hydrophobic materials.
- the polyfunctional hydrophobic [group] material may be (1) an aliphatic saturated dicarboxylic acid having from 4 to [14] 15 carbon atoms, such as propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (sebacic acid), hexanedioic acid (adipic acid), octanedioic acid (suberic acid); (2) aromatic dicarboxylic acids such as phthalic acid; (3) a conventional epoxide compound having a 1,2-epoxy equivalency greater than 1 and having more than one epoxy group per molecule, for example, bis phenol A diglycidyl ether or other epoxy compounds obtained by reacting dihydric phenols with polyfunctional etherifying agents such as epichlorohydrin (described more fully in US.
- an aliphatic saturated dicarboxylic acid having from 4 to [14] 15 carbon atoms, such as propanedioic acid (
- T hese compositiorts are prepared by condensing 0.8 to 1.2 gram molecular propotrions of the polyfunctional material per 1.8 to 2.5 gram molecular proportions of the Z-hydroxyalkyl acrylate or methacrylate in the absence of a solvent.
- vinyl ester resins disclosed in UJS. Pat. No. 3,367,992, which is hereby incorporated by reference, are applicable in the process of this invention.
- Such resins are prepared according to said patent by reacting a half ester of a Z-hydroxyalkyl acrylate or methacrylate and a dibasic acid with a polyepoxide.
- these materials include adipoylbis (2-oxyethylacrylate); the half ester condensation product of 2-hydroxyethyl acrylate[,] and maleic anhydride and] reacted with a bis-phenol A diglycidyl ether; the condensation product of polypropylene glycol, toluene diisocyanate, and Z-hydroxyethyl acrylate; the half ester condensation product of Z-hydroxypropyl acrylate L] and maleic anhydride and] reacted with butanediol diglycidyl ether; the half ester condensation product of Z-hydroxyethyl acrylate and maleic anhydride [and] reacted with a brominated bisphenol A-based polyepoxide resin with an epoxide equivalent weight of 350-400; [the condensation product of Z-hydroxypropyl acrylate, maleic anhydride, a bisphenol A-based polyepoxide having an epoxide equivalent weight of l86-l
- the vinyl ester resin or resins may be spread on the substrate undiluted or dissolved in up to 50% by weight of a vinyl monomer.
- a vinyl monomer Preferably an acrylate monomer is used in combination with the vinyl ester compounds to achieve optimum results.
- Small amounts of styrene, vinyl toluene, t-butyl styrene, chlorostyrene, hydroxyalkyl methacrylates or alkyl methacrylates having 1 to 8 carbon atoms may be used in admixture with the acrylate monomer; however, the presence of too great a quantity of the above compounds lowers the cure rate significantly and affects the properties of the cured coating.
- Acrylate monomers which may be used include alkyl acrylates having from 1 to 8 carbon atoms, hydroxyalkyl acrylates, cycloalkyl acrylates, or glycidyl acrylates, such as acrylic acid, Z-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, cyclohexylacrylate, diacetonacrylamide, and others. It is preferred to use an acrylate monomer, such as n-butyl acrylate, which is readily available, economical, and has a low volatility.
- the monomer, if used, should be added in an amount which does not thin the coating composition to an extent that it penetrates the substrate too rapidly, if a porous substrate is used. Also, addition of too much monomer impairs the properties of high impact and water resistance present furnished by reason of the polyfunetional acrylate or methacrylate composition. Preferably, amounts up to 40% by weight or less are used.
- the coating compositions as defined can be used to coat any suitable porous or nonporous substrate such as wood or wood products, plastics, glass, rubber, metals, etc.
- suitable porous or nonporous substrate such as wood or wood products, plastics, glass, rubber, metals, etc.
- the properties of the resins are best utilized, however, in the coating of wood and wood products.
- No solvent is necessary for the coating compositions.
- Polymerization of the coating composition is initiated and completed by ionizing radiation in the form of high energy electrons.
- ionizing radiation dose rate of from 1 to 10 megarads in 1 second or less.
- the electron beam is maintained in the range of 250,000-550,000 volts with sufiicient milliamperes per inch width of scan to impart l to 10 megarads to the coating composition in 1 second or less.
- a number of commercially available high electron beam machines are available and can be used including those sold by General Electric Company, Radiation Dynamics (Dynacote), Texas Nuclear Company, and High Voltage Engineering (ICT 500).
- the current density is 20/18 or 1.1 milliamperes per inch of width.
- the substrate passes under the beam at a distance of, for example, 2 /2 inches below the window of the unit and at right angles to the scan, it is exposed to significant portions of the beam for a distance of about 4 inches. If the coated substrate is traveling at, for example, 60 feet per minute or 1 foot per second, it covers the 4 inches in /s second. The exposure times in the examples were computed in such a manner.
- Films of varying thickness can be cured depending on the voltage used. At about 300 kv. films ranging up to 12 mils in thickness can be easily cured. At about 500 kv. films up to 35 mils in thickness can be cured.
- cure in the presence of oxygen may leave a soft surface film on the coating. This may be prevented by conventional means such as using an inert atmosphere or irradiating the coated substrate under a covering film of release paper or plastic.
- the coating compositions of this invention may be added to the substrate by spraying dipping, brushing or any other suitable means. Clear coatings on hardwood surfaces having up to 35 mils in thickness have been made using curing times of 1 second and less with the resinous compositions of this invention. Such a fast cure rate is advantageous when the high energy radiation is used in a conventional coating line operating at speeds from 20 feet per minute to feet per minute.
- Pigments, dyes, and other suitable materials may be added to the resinous coating compositions if desired.
- EXAMPLE II A very viscous, resinous material, the condensation product of 2-hydroxyethyl acrylate, maleic anhydride and bis phenol a diglycidyl ether was coated on wood and passed under the 500 kilovolt electron beam as in Example I. The resinous oomposition was cured in 0.5 seconds to a hard and moderately tough film. The top surface of the film exposed to air was not tacky.
- EXAMPLE III The resinous composition of Example II was dissolved in n-butyl acrylate in a ratio of 20 parts butyl acrylate to 80 parts resin. A piece of wood was coated with the resinous composition to a thickness of 0.005 inch and cured with a 300 kilovolt beam in 0.67 seconds to a hard and tough film. An 8-ounce steel ball dropped from a height of three feet onto the surface did not crack or craze the film. The top surface of the film exposed to air was slightly softer than the main film. Polishing this surface with carborundum dust removed this soft surface and left a hard, smooth surface with a reduction in film thickness of less than 0.001 inch.
- EXAMPLE IV In a glass stoppered flask, 20 parts of polypropylene glycol was mixed with 14.2 parts of toluene diisocyanate. The flask became warm from a mild exothermic reaction. After standing for one hour, 12.4 parts of 2-hydroxyethyl acrylate were added. After standing overnight, a clear viscous liquid remained. A thin film of this resinous material was coated on aluminum, a 5 mil Mylar film placed over the coated substrate, and the sample passed under a 300 kilovolt electron beam. The coating cured in 0.33 second to a very flexible, tough film which adhered strongly to the aluminum.
- Vorite 63 a castor polyester diisocyanate prepolymer made by The Baker Castor Oil Company
- Z-hydroxyethyl acrylate 0.14 grams of tin octoate catalyst
- Free isocyanate in the final solution analyzed 0.02%.
- a 0.010 inch thick film of the product cured in about 0.67 seconds by irradiation under a 300 kv. electron beam to a dose of 7 megarads.
- a hard, impact resistant coating resulted.
- a solution of 11.3 parts product and 3.5 parts n-butyl acrylate gave a liquid which cured as above to a flexible, impact resistant film.
- EXAMPLE VI Five grams of DDI diisocyanate (an aliphatic long chain diisocyanate made by General Mills, Incorporated) was mixed with 1.93 grams of 2-hydroxyethyl acrylate and 0.04 grams of tin octoate at 90 C. for five minutes. Thin films of the product on aluminum and plywood were covered with Mylar film and irradiated to a dose of 7 megarads under a 300 kv. electron beam for about 0.67 seconds. The cured film was hard but very flexible.
- DDI diisocyanate an aliphatic long chain diisocyanate made by General Mills, Incorporated
- a method of coating a surface of a substrate with a flexible, impact resistant [vinyl ester] material comprising,
- a polyfunctional material selected from the group consisting of (a) dicarboxylic acids or acid chlorides having from 4 to 15 carbon atoms, and (b) [polyepoxides having terminal, reactive glycidyl groups, (c)] polyisocyanates having terminal, reactive isocyanate groups and (d) dicarboxylic acid esters of polyepoxides,] with Z-hydroxyalkyi acrylates or methacrylates; or
- the coating composition includes 0 to 50% by weight of a vinyl monomer.
- acrylate monomer is an alkylacrylate having from 1 to 10 carbon atoms.
- the [coating composition contains] polymerizable resin is a half ester condensation product of Z-hydroxyethyl acrylate L] and maleic anhydride and] reacted with a bisphenol A polyepoxide, and the coating composition contains up to 40% by weight of acrylate monomer.
- the [coating composition contains] polymerizable resin is the condensation product of a polyglycol, a polyfunctional isocyanate and 2-hydroxyethylacrylate, and the coating composition contains up to 40% by weight of acrylate monmer.
- polyfunctional material comprises a dicarboxylic acid or acid chloride having from 4 to 15 carbon atoms.
- polyfunctional material comprises a polyepoxide having terminal reactive glycidyl groups
- polyfunctional material comprises a polyisocyanate having terminal, reactive isocyanate groups.
- a method as in claim 1 wherein the polyfunctional material comprises a dicarboxylic acid ester of a polyepoxide] 18.
- a method of coating a surface of a substrate with a flexible, impact resistant [vinyl ester] material comprising,
- liquid vinyl ester coating composition comprising the condensation product of a half ester of Z-hydroxyalkyl acrylate 0r melhacrylate [J and a dibasic acid [anhydride, and] with a polyepoxide;
Abstract
A PROCESS OF COATING A POROUS OR NONPOROUS SUBSTRATE WITH A LIQUID POLYMERIZABLE FILM AND SUBJECTING THE COATED SUBSTRATE TO IONIZING RADIATION SUFFICIENT TO IMPART TO THE COATING COMPOSITION A DOSE OF FROM 1 TO 10 MEGARANDS IN ONE SECOND OR LESS. THE COATING COMPOSITIONS, CAPABLE OF SUBSTANTIALLY COMPLETE POLYMERIZATION IN LESS THAN ONE SECOND, CONTAIN UNDILUTED VINYL ESTER RESINS HAVING TERMINAL VINYL ESTER GROUPS, OR THE ABOVE DISSOLVED IN VINYL MONOMERS. THE VINYL ESTER RESINS ARE MADE BY REACTING: (1) A POLYFUNCTIONAL MATERIAL SELECTED FROM THE GROUP CONSISTING OF (A) DICARBOXYLIC ACIDS OR ACID CHLORIDES HAVING FROM 4 TO 15 CARBON ATOMS, AND (B) (POLYEPOXIDES HAVING TERMINAL, REACTIVE GLYCIDYL GROUPS, (C)) POLYFUNCTIONAL ISOCYANATES HAVING TERMINAL, REACTIVE ISOCYANATE GROUP (, OR (D) DICARBOXYLIC ACID ESTERS OF POLYEPOXIDES, POLYAMINES, POLYISOCYANATES,) WITH 2-HYDROXYALKYL ACRYLATES OR METHACRYLATES, OR (2) A HALF ESTER OF 2-HYDROXYALKYL ACRYLATE(S) OR METHACRYLATE(S) AND A DIBASIC ACID WITH A POLYEPOXIDE. PARTICULARLY USEFUL ARE COATING COMPOSITIONS CONTAINING RESINS HAVING TERMINAL ACRYLATE GROUPS AND AN ACRYLATE MONOMER, THE POLYFUNCTIONAL ACRYLATE HAVING MORE THAN ONE 2-OXYALKYLACRYLATE END GROUP PER MOLECULE WITH THE END GROUPS BEING JOINED BY A HYDROPHOBIC MOLECULE SUCH AS A DICARBOXYLIC ACID, POLYFUNCTIONAL ISOCYANATE OR POLYEPOXIDE.
Description
United States Patent PROCESS OF CURING POLYMERIZABLE RESINS HAVING TERMINAL VINYL ESTER GROUPS USING HIGH ENERGY ELECTRONS Lewis S. Miller, Bellevue, Wash., assignor to Weyerhaeuser Company, Tacoma, Wash.
No Drawing. Original No. 3,560,237, dated Feb. 2, 1971,
Ser. No. 721,152, Apr. 15, 1968. Applicah'on for reissue Oct. 28, 1971, Ser. No. 193,580
Int. Cl. B44d 1/50 US. Cl. 11793.31 16 Claims Matter enclosed in heavy brackets II] appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.
ABSTRACT OF THE DISCLOSURE A process of coating a porous or nonporous substrate with a liquid polymerizable film and subjecting the coated substrate to ionizing radiation sufiicient to impart to the coating composition a dose of from 1 to megarads in one second or less. The coating compositions, capable of substantially complete polymerization in less than one second, contain undiluted vinyl ester resins having terminal vinyl ester groups, or the above dissolved in vinyl monomers. The vinyl ester resins are made by reacting:
(l) A polyfunctional material selected from the group consisting of (a) dicarboxylic acids or acid chlorides having from 4 to carbon atoms, and (b) [polyepoxides having terminal, reactive glycidyl groups, (0)] polyfunctional isocyanates having terminal, reactive isocyanate group or (d) dicarboxylic acid esters of polyepoxides, polyamines, po1yisocyanates,] with Z-hydroxyalkyl acrylates or methacrylates; or
(2) a half ester of Z-hydroxyalkyl acrylateIIs] or methacrylateIIs] and a a'ibasz'c acid with a polyepoxide.
Particularly useful are coating compositions containing resins having terminal acrylate groups and an acrylate monomer, the polyfunctional acrylate having more than one 2-oxyalkylacrylate end group per molecule with the end groups being joined by a hydrophobic molecule such as a dicarboxylic acid, polyfunctional isocyanate or polyepoxide.
BACKGROUND OF THE INVENTION (1) Field of the invention This invention relates to a process of curing coating compositions having terminal unsaturation in a very short amount of time using high energy electrons.
(2) Description of the prior art It is known that many polymeric materials, when subjected to high energy radiation in the form of high energy electrons, can be rapidly cured. Electron irradiation has a number of distinct advantages over conventional methods of polymerization and cross-linking using catalytic agents, especially when used to cure coatings on wood and wood products, fabrics, rubber, glass, and other similar substrates. Use of electron irradiation to cure polymeric coatings avoids the sometimes lengthy induction period associated with catalyst-induced cure, enables the use of polymeric coating compositions having indefinite pot life, produces little temperature rise during polymerization, and produces, in many cases, a superior coating-to-substrate bond.
One of the problems associated with electron irradiation is in finding a polymeric material which is suitable for the purpose desired and curable to a hard, tack-free condition in a short amount of time. With particular reference to the coating of wood and wood products, it is desirable to have a coating composition which is flexible, water resistant, and impact resistant. In addition, it is necessary that the polymeric composition cure or polymerize in a short amount of time at reasonable dose rates in order to make the process economically feasible.
To obtain fast curing a cross-linking mechanism is needed. In the present coating composition this is furnished by acrylates. It is known that diacrylates made by reacting polyhydric alcohols, such as ethylene glycol, with acrylic or methacrylic acids are curable by high energy radiation, as disclosed in US. Pat. No. 2,921,006. The diacrylates disclosed, however, do not cure to a hard tack free state using economically feasible dose rates, are too brittle, and swell on exposure to moisture and weathering, making them unacceptable for coating wood and wood products. Other polyester coating materials curable by high energy radiation are disclosed in US. Pat. No. 3,247,012. These compositions also lack certain desired properties, making them unacceptable for coating of wood and wood products.
SUMMARY OF THE INVENTION This invention is directed to a process for coating a substrate with a composition containing a polymerizable material having terminal vinyl ester groups and thereafter subjecting the coating to high energy ionizing radiation in the form of electrons to cure the coating to a tack-free condition in times of one second or less. It pounds could be cured with high energy electrons at reasonable dose rates in such a short amount of time. Further, this invention is directed to a process of coating wood and wood products with vinyl ester resins which, on curing, have good flexibility, excellent water resistance, and excellent impact resistance. The vinyl ester resins of this invention can be used undiluted or dissolved in 0 to 50% by weight of a vinyl monomer. Pigments and other conventional additives can be added to the coating compositions. Vinyl ester resins made by reacting:
(1) A polyfunctional material selected from the group consisting of (a) dicarboxylic acids or acid chlorides having from 4 to 15 carbon atoms, and (b) [polyepoxides having terminal, reactive glycidyl groups, (0)] polyfunctional isocyanates having terminal, reactive isocyanate groups or (d) dicarboxylic acid esters of polyepoxides, polyamines, or polyisocyanates] with Z-hydroxyalkyl acrylates or merhacrylares; or
(2) a half ester of 2-hydroxyalkyl acrylatelIs] or methacrylateIIs] and a dibasic acid with a polyepoxide are suitable in the process of this invention.
Using compounds of this type cure rates of less than A second at a dose rate of 3 megarads have been obtained.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Polymerizable vinyl ester resins described previously are liquids which may be used undiluted or dissolved in vinyl monomers which compolymerize with the vinyl ester resin upon subjection to irradiation. These resinous compositions are made by reacting Z-hydroxy'alkyl acrylates with polyfunctional, hydrophobic materials. The polyfunctional hydrophobic [group] material may be (1) an aliphatic saturated dicarboxylic acid having from 4 to [14] 15 carbon atoms, such as propanedioic acid (malonic acid), butanedioic acid (succinic acid), pentanedioic acid (sebacic acid), hexanedioic acid (adipic acid), octanedioic acid (suberic acid); (2) aromatic dicarboxylic acids such as phthalic acid; (3) a conventional epoxide compound having a 1,2-epoxy equivalency greater than 1 and having more than one epoxy group per molecule, for example, bis phenol A diglycidyl ether or other epoxy compounds obtained by reacting dihydric phenols with polyfunctional etherifying agents such as epichlorohydrin (described more fully in US. Pats. 2,467,171; 2,538,072; 2,582,985; 2,615,007; and 2,698,314); (4) [an epoxy compound recated with a dibasic acid or anhydride, such as maleic acid or anhydride, salicylic acid or anhydride, fumaric acid, itaconic acid, phthalic acid or anhydride, an aliphatic, saturated] a dicarboxylic acid chloride having from 4 to 15 carbon atoms; (5) polyurethane prepolymers made by reacting an organic polyfunctional isocyanate, for example, toluene diisocyanate, with polyols such as propylene or polypropylene glycol or polyether polyols; and (-6) organic polyfunctional isocyanates including aromatic, aliphatic, aralkyl, alkaryl and cycloaliphatic polyfunctional isocyanates. T hese compositiorts are prepared by condensing 0.8 to 1.2 gram molecular propotrions of the polyfunctional material per 1.8 to 2.5 gram molecular proportions of the Z-hydroxyalkyl acrylate or methacrylate in the absence of a solvent. [More specifically] Further, vinyl ester resins disclosed in UJS. Pat. No. 3,367,992, which is hereby incorporated by reference, are applicable in the process of this invention. Such resins are prepared according to said patent by reacting a half ester of a Z-hydroxyalkyl acrylate or methacrylate and a dibasic acid with a polyepoxide.
Specific examples of these materials include adipoylbis (2-oxyethylacrylate); the half ester condensation product of 2-hydroxyethyl acrylate[,] and maleic anhydride and] reacted with a bis-phenol A diglycidyl ether; the condensation product of polypropylene glycol, toluene diisocyanate, and Z-hydroxyethyl acrylate; the half ester condensation product of Z-hydroxypropyl acrylate L] and maleic anhydride and] reacted with butanediol diglycidyl ether; the half ester condensation product of Z-hydroxyethyl acrylate and maleic anhydride [and] reacted with a brominated bisphenol A-based polyepoxide resin with an epoxide equivalent weight of 350-400; [the condensation product of Z-hydroxypropyl acrylate, maleic anhydride, a bisphenol A-based polyepoxide having an epoxide equivalent weight of l86-l92, and phthalie anhydride]; and the like. [These compounds are prepared by condensing 0.8 to 1.2 gram molecular proportions of the polyfunctional hydrophobic group per 1.8 to 2.5 gram molecular proportions of the Z-hydroxyalkyl acrylate or methacrylate in the absence of a solvent.]
The vinyl ester resin or resins may be spread on the substrate undiluted or dissolved in up to 50% by weight of a vinyl monomer. Preferably an acrylate monomer is used in combination with the vinyl ester compounds to achieve optimum results. Small amounts of styrene, vinyl toluene, t-butyl styrene, chlorostyrene, hydroxyalkyl methacrylates or alkyl methacrylates having 1 to 8 carbon atoms may be used in admixture with the acrylate monomer; however, the presence of too great a quantity of the above compounds lowers the cure rate significantly and affects the properties of the cured coating.
Acrylate monomers which may be used include alkyl acrylates having from 1 to 8 carbon atoms, hydroxyalkyl acrylates, cycloalkyl acrylates, or glycidyl acrylates, such as acrylic acid, Z-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, cyclohexylacrylate, diacetonacrylamide, and others. It is preferred to use an acrylate monomer, such as n-butyl acrylate, which is readily available, economical, and has a low volatility. The monomer, if used, should be added in an amount which does not thin the coating composition to an extent that it penetrates the substrate too rapidly, if a porous substrate is used. Also, addition of too much monomer impairs the properties of high impact and water resistance present furnished by reason of the polyfunetional acrylate or methacrylate composition. Preferably, amounts up to 40% by weight or less are used.
The coating compositions as defined can be used to coat any suitable porous or nonporous substrate such as wood or wood products, plastics, glass, rubber, metals, etc. The properties of the resins are best utilized, however, in the coating of wood and wood products.
No solvent is necessary for the coating compositions. Polymerization of the coating composition is initiated and completed by ionizing radiation in the form of high energy electrons. To cure the coating composition, it is necessary to impart to the coating an ionizing radiation dose rate of from 1 to 10 megarads in 1 second or less. Generally, the electron beam is maintained in the range of 250,000-550,000 volts with sufiicient milliamperes per inch width of scan to impart l to 10 megarads to the coating composition in 1 second or less. A number of commercially available high electron beam machines are available and can be used including those sold by General Electric Company, Radiation Dynamics (Dynacote), Texas Nuclear Company, and High Voltage Engineering (ICT 500). For example, using the High Voltage Engineering (ICT 500) machine operated at 300 kilovolts, 20 milliamperes and a beam scan of 18 inches width, the current density is 20/18 or 1.1 milliamperes per inch of width. As the substrate passes under the beam at a distance of, for example, 2 /2 inches below the window of the unit and at right angles to the scan, it is exposed to significant portions of the beam for a distance of about 4 inches. If the coated substrate is traveling at, for example, 60 feet per minute or 1 foot per second, it covers the 4 inches in /s second. The exposure times in the examples were computed in such a manner.
Films of varying thickness can be cured depending on the voltage used. At about 300 kv. films ranging up to 12 mils in thickness can be easily cured. At about 500 kv. films up to 35 mils in thickness can be cured.
It is preferable to maintain a distance between the coated substrate and the window of the machine through which the electron beam passes from about 6 inches to the minimum necessary for clearance of the coated substrate.
Using certain coatings, cure in the presence of oxygen may leave a soft surface film on the coating. This may be prevented by conventional means such as using an inert atmosphere or irradiating the coated substrate under a covering film of release paper or plastic.
The coating compositions of this invention may be added to the substrate by spraying dipping, brushing or any other suitable means. Clear coatings on hardwood surfaces having up to 35 mils in thickness have been made using curing times of 1 second and less with the resinous compositions of this invention. Such a fast cure rate is advantageous when the high energy radiation is used in a conventional coating line operating at speeds from 20 feet per minute to feet per minute.
Pigments, dyes, and other suitable materials may be added to the resinous coating compositions if desired.
The following examples are given by way of illustration and are not intending to be limiting in any manner.
EXAMPLE I A solution of 69.6 grams (0.6 mole) of 2-hydroxyethyl acrylate in 47.5 grams of pyridine and ml. of benzene was placed in a flask equipped with a stirrer, dropping funnel and condenser. A solution of 54.9 grams (0.3 mole) of adipoyl chloride in 75 ml. of benzene was added with stirring and cooling. After the addition was complete, the mixture was heated one-half hour on a steam bath. The clear solution was decanted from the precipitate and passed through a column of activated alumina. After removing the benzene on a steam bath, 82.8 grams of a clear residue, adipoyl-bis(2-oxyethylacrylate) remained. A sample of Wood and aluminum was given a 0.005 to 0.010 inch thick coating of the above resin composition and the coating covered with polyethylene terephthalate (Mylar) film 5 mils in thickness. The covered products where then passed under a two million volt electron beam from a Van deGralf accelerator in a way that the samples received 1.7 megarads in 0.3 seconds. After removing the Mylar cover, a clear hard coating remained on the substrates which did not appreciably soften in water and was not cracked or crazed by a sharp hammer blow.
A subsequent coating on aluminum of the same material was irradiated with a 500,000 volt electron beam giving a dose rate of two megarads in 0.5 second. Again a hard film resulted.
EXAMPLE II A very viscous, resinous material, the condensation product of 2-hydroxyethyl acrylate, maleic anhydride and bis phenol a diglycidyl ether was coated on wood and passed under the 500 kilovolt electron beam as in Example I. The resinous oomposition was cured in 0.5 seconds to a hard and moderately tough film. The top surface of the film exposed to air was not tacky.
EXAMPLE III The resinous composition of Example II was dissolved in n-butyl acrylate in a ratio of 20 parts butyl acrylate to 80 parts resin. A piece of wood was coated with the resinous composition to a thickness of 0.005 inch and cured with a 300 kilovolt beam in 0.67 seconds to a hard and tough film. An 8-ounce steel ball dropped from a height of three feet onto the surface did not crack or craze the film. The top surface of the film exposed to air was slightly softer than the main film. Polishing this surface with carborundum dust removed this soft surface and left a hard, smooth surface with a reduction in film thickness of less than 0.001 inch.
Identical coatings cured in the same way but with a 5 mil Mylar film or 3 mil coated paper placed over the coated substrate had hard, cured surfaces.
EXAMPLE IV In a glass stoppered flask, 20 parts of polypropylene glycol was mixed with 14.2 parts of toluene diisocyanate. The flask became warm from a mild exothermic reaction. After standing for one hour, 12.4 parts of 2-hydroxyethyl acrylate were added. After standing overnight, a clear viscous liquid remained. A thin film of this resinous material was coated on aluminum, a 5 mil Mylar film placed over the coated substrate, and the sample passed under a 300 kilovolt electron beam. The coating cured in 0.33 second to a very flexible, tough film which adhered strongly to the aluminum.
A solution of 90% of the above reaction product in n-butyl acrylate gave a harder, very flexible film on curing under the 300 kilovolt electron beam for 0.67 seconds.
EXAMPLE V One hundred grams of Vorite 63 (a castor polyester diisocyanate prepolymer made by The Baker Castor Oil Company), 43 grams of Z-hydroxyethyl acrylate and 0.14 grams of tin octoate catalyst were mixed in a 250 ml. rotating flask at 50 C. for 2 /2 hours. Free isocyanate in the final solution analyzed 0.02%. A 0.010 inch thick film of the product cured in about 0.67 seconds by irradiation under a 300 kv. electron beam to a dose of 7 megarads. A hard, impact resistant coating resulted. A solution of 11.3 parts product and 3.5 parts n-butyl acrylate gave a liquid which cured as above to a flexible, impact resistant film.
EXAMPLE VI Five grams of DDI diisocyanate (an aliphatic long chain diisocyanate made by General Mills, Incorporated) was mixed with 1.93 grams of 2-hydroxyethyl acrylate and 0.04 grams of tin octoate at 90 C. for five minutes. Thin films of the product on aluminum and plywood were covered with Mylar film and irradiated to a dose of 7 megarads under a 300 kv. electron beam for about 0.67 seconds. The cured film was hard but very flexible.
Other resins, for example those described in U.S. Pat. 3,367,992 can also be cured in a short length of time with high energy electrons in the same manner as set forth in the above examples.
What is claimed is:
l. A method of coating a surface of a substrate with a flexible, impact resistant [vinyl ester] material comprising,
(a) spreading over the surface of the substrate a liquid [vinyl ester] coating composition containing a polymerizable resin having terminal vinyl ester groups made by reacting:
(l) a polyfunctional material selected from the group consisting of (a) dicarboxylic acids or acid chlorides having from 4 to 15 carbon atoms, and (b) [polyepoxides having terminal, reactive glycidyl groups, (c)] polyisocyanates having terminal, reactive isocyanate groups and (d) dicarboxylic acid esters of polyepoxides,] with Z-hydroxyalkyi acrylates or methacrylates; or
(2) a half ester of 2-hydroxyalkyl acrylates [s] or methacrylateIs] and a a'ibasic acid with a polyepoxide,- and (b) exposing for one second or less the liquid coating composition to a beam of electrons having energy and current density suflicient to impart to the coating composition and ionizing radiation dose of 1 to 10 megarads.
2. The method according to claim 1 wherein the coating composition includes 0 to 50% by weight of a vinyl monomer.
3. The method according to claim 2 wherein the coating composition includes 0 to 50% by weight of an acrylate monomer.
4. The method according to claim 3 wherein the acrylate monomer is an alkylacrylate having from 1 to 10 carbon atoms.
5. The method according to claim 3 wherein the acrylate monomer is diacetoneacrylamide.
6. The method according to claim 3 wherein the acrylate monomer is a cycloalkyl acrylate.
7. The method according to claim 1 wherein the liquid composition includes a pigment.
8. The method according to claim 1 wherein the liquid composition includes a dye.
9. The method according to claim 1 wherein the electron beam has an energy of at least 250,000 volts.
10. The method according to claim 1 wherein the [liquid coating composition contains] polymerizable resin is adipoyl-bis (2-oxyethylacrylate) and the coating composoin'on contains up to 40% by weight of acrylate monomer.
11. The method according to claim. 1 wherein the [coating composition contains] polymerizable resin is a half ester condensation product of Z-hydroxyethyl acrylate L] and maleic anhydride and] reacted with a bisphenol A polyepoxide, and the coating composition contains up to 40% by weight of acrylate monomer.
12. The method according to claim 1 wherein the [coating composition contains] polymerizable resin is the condensation product of a polyglycol, a polyfunctional isocyanate and 2-hydroxyethylacrylate, and the coating composition contains up to 40% by weight of acrylate monmer.
13. The method according to claim 1 wherein the substrate is wood.
14. A method as in claim 1 wherein the polyfunctional material comprises a dicarboxylic acid or acid chloride having from 4 to 15 carbon atoms.
[15. A method as in claim 1 wherein the polyfunctional material comprises a polyepoxide having terminal reactive glycidyl groups] 16. A method as in claim 1 wherein the polyfunctional material comprises a polyisocyanate having terminal, reactive isocyanate groups.
[17. A method as in claim 1 wherein the polyfunctional material comprises a dicarboxylic acid ester of a polyepoxide] 18. A method of coating a surface of a substrate with a flexible, impact resistant [vinyl ester] material comprising,
(a) spreading over the surface of the substrate a liquid vinyl ester coating composition comprising the condensation product of a half ester of Z-hydroxyalkyl acrylate 0r melhacrylate [J and a dibasic acid [anhydride, and] with a polyepoxide; and
(b) exposing for one second or less the liquid coating composition to a beam of electrons having energy and current density suflicient to impart to the coating composition an ionizing radiation dose of 1 to 10 megarads.
References Cited UNITED STATES PATENTS 2/1968 Bearden 260837 4/1969 Burlant 11793.31
ALFRED L. LEAVITI, Primary Examiner J. H. NEWSOME, Assistant Examiner US. Cl. X.R.
117-148, 161 K, 161 KP, 161 ZB; 204159.19; 260- 837
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US72115268A | 1968-04-15 | 1968-04-15 | |
US19358071A | 1971-10-28 | 1971-10-28 |
Publications (1)
Publication Number | Publication Date |
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USRE27656E true USRE27656E (en) | 1973-06-05 |
Family
ID=26889142
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US27656D Expired USRE27656E (en) | 1968-04-15 | 1971-10-28 | Process of curing polymerizable resins having terminal vinyl ester groups using high energy electrons |
Country Status (1)
Country | Link |
---|---|
US (1) | USRE27656E (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5968605A (en) | 1997-02-27 | 1999-10-19 | Acushnet Company | Electron beam radiation curable inks for game balls, golf balls and the like |
-
1971
- 1971-10-28 US US27656D patent/USRE27656E/en not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5968605A (en) | 1997-02-27 | 1999-10-19 | Acushnet Company | Electron beam radiation curable inks for game balls, golf balls and the like |
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