CN114686092A - Photocureable coating capable of being used for metal protection and preparation method thereof - Google Patents
Photocureable coating capable of being used for metal protection and preparation method thereof Download PDFInfo
- Publication number
- CN114686092A CN114686092A CN202011585257.XA CN202011585257A CN114686092A CN 114686092 A CN114686092 A CN 114686092A CN 202011585257 A CN202011585257 A CN 202011585257A CN 114686092 A CN114686092 A CN 114686092A
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- China
- Prior art keywords
- unsaturated double
- carboxyl
- acrylate
- metal protection
- double bond
- 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.)
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 39
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 238000000576 coating method Methods 0.000 title claims abstract description 34
- 239000011248 coating agent Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 55
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 50
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 20
- -1 methacryloyl groups Chemical group 0.000 claims abstract description 14
- 230000009477 glass transition Effects 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000004814 polyurethane Substances 0.000 claims description 38
- 229920002635 polyurethane Polymers 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 19
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 14
- 238000004321 preservation Methods 0.000 claims description 14
- DLVZBSZXZDGKQY-UHFFFAOYSA-N 2,2-dihydroxybutanoic acid Chemical compound CCC(O)(O)C(O)=O DLVZBSZXZDGKQY-UHFFFAOYSA-N 0.000 claims description 10
- HPQUMJNDQVOTAZ-UHFFFAOYSA-N 2,2-dihydroxypropanoic acid Chemical compound CC(O)(O)C(O)=O HPQUMJNDQVOTAZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000002009 diols Chemical class 0.000 claims description 10
- 229920000728 polyester Polymers 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000008199 coating composition Substances 0.000 claims description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 4
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 4
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- VKQJCUYEEABXNK-UHFFFAOYSA-N 1-chloro-4-propoxythioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C(OCCC)=CC=C2Cl VKQJCUYEEABXNK-UHFFFAOYSA-N 0.000 claims description 3
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 3
- JTGHBEFBQXGABE-UHFFFAOYSA-N 2,2-dihydroxyheptanoic acid Chemical compound CCCCCC(O)(O)C(O)=O JTGHBEFBQXGABE-UHFFFAOYSA-N 0.000 claims description 3
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 claims description 3
- ZVAFZTLAMCXAII-UHFFFAOYSA-N 2-(1-ethoxyethyl)-2-(hydroxymethyl)propane-1,3-diol Chemical compound CCOC(C)C(CO)(CO)CO ZVAFZTLAMCXAII-UHFFFAOYSA-N 0.000 claims description 3
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 3
- CHBVGDXRMCSNPU-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCCOC(C)C(CO)(CO)CO Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCCOC(C)C(CO)(CO)CO CHBVGDXRMCSNPU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 244000028419 Styrax benzoin Species 0.000 claims description 3
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 229960002130 benzoin Drugs 0.000 claims description 3
- 235000019382 gum benzoic Nutrition 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- KJTLQQUUPVSXIM-ZCFIWIBFSA-N (R)-mevalonic acid Chemical compound OCC[C@](O)(C)CC(O)=O KJTLQQUUPVSXIM-ZCFIWIBFSA-N 0.000 claims description 2
- GKZPEYIPJQHPNC-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)CO GKZPEYIPJQHPNC-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims 3
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 claims 1
- 239000003973 paint Substances 0.000 description 15
- 238000001723 curing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N Michlers ketone Natural products C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 description 1
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- KJTLQQUUPVSXIM-UHFFFAOYSA-N mevalonic acid Chemical compound OCCC(O)(C)CC(O)=O KJTLQQUUPVSXIM-UHFFFAOYSA-N 0.000 description 1
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a photocureable coating for metal protection, which is mainly prepared from the following raw materials in percentage by mass: unsaturated double-bond urethane acrylate resin: 45-70% of unsaturated double bond-containing monomer: 15-40%, photoinitiator: 2-5%, auxiliary agent: 0.1-1%, wherein the auxiliary agent is the flatting agent and the defoaming agent; the unsaturated double bond-containing monomer is a compound containing at least 2 acryloyl groups or 2 methacryloyl groups; the carboxyl acrylic resin containing unsaturated double bonds has the number average molecular weight Mn of 2000-10000 and the glass transition temperature Tg of 0-45 ℃. The invention also provides a preparation method of the photocureable coating for metal protection.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a photocureable coating for metal protection and a preparation method thereof.
Background
The metal photocureable coating is suitable for light anticorrosion protection of steel, protection and decoration of metal labels, vacuum coating metal finish and the like. Most metal surfaces are susceptible to corrosion and rust, and some metal surfaces are not scratch resistant, which require a protective coating to solve the problem.
The photocureable coating has the characteristics of low energy consumption, low VOC volatilization and rapid drying, and has good social and economic benefits by being widely popularized and applied under the current requirements of energy conservation and environmental protection.
Disclosure of Invention
The invention aims to provide a photocureable coating for metal protection, which has excellent formula adhesion, chemical medium resistance of a coating film and good corrosion resistance. The invention also provides a preparation method of the photocureable coating for metal protection, and the coating is prepared from polyurethane acrylate resin containing unsaturated double bonds.
A photocureable coating for metal protection is mainly prepared from the following raw materials in percentage by mass: unsaturated double-bond urethane acrylate resin: 45-70% of a monomer containing an unsaturated double bond: 15-40%, photoinitiator: 2-5%, auxiliary agent: 0.1-1%, wherein the auxiliary agent is the flatting agent and the defoaming agent; the unsaturated double bond-containing monomer is a compound containing at least 2 acryloyl groups or 2 methacryloyl groups; the carboxyl acrylic resin containing unsaturated double bonds has the resin number average molecular weight Mn of 2000-10000 and the glass transition temperature Tg of 0-45 ℃.
In one embodiment, the number average molecular weight Mn of the resin containing the carboxyl acrylic resin containing unsaturated double bonds is 3000-7000, and the glass transition temperature Tg is 0-15 ℃.
In one embodiment, the resin of the carboxyl acrylic resin containing unsaturated double bonds has a number average molecular weight of 2800-5500, a Tg of 5-12 ℃ and a solid content of 88-92%.
In one embodiment, the number average molecular weight of the resin of the carboxyl acrylic resin containing unsaturated double bonds is 3000-7000, Tg is 8-25 ℃, and the solid content is 85-88%.
In one embodiment, the unsaturated double bond-containing urethane acrylate resin in the component adopts a dihydroxy monoacid monomer, and the formula is as follows: cm H2mO4Wherein m is more than or equal to 3.
In one embodiment, the carbon chain length of the dihydroxy monoacid monomer is 3-7.
In one embodiment, the dihydroxy monoacid monomer is selected from at least one of dihydroxy propionic acid, dihydroxy butyric acid, 3,5 dihydroxy-3-methyl pentanoic acid, dihydroxy heptanoic acid.
In one embodiment, the unsaturated double bond-containing monomer has a functionality of 2 to 4.
In one embodiment, the unsaturated double bond-containing monomer is at least one selected from the group consisting of tripropylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol diacrylate, 1, 4-butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxytrimethylolpropane tri (meth) acrylate, propoxytrimethylolpropane triacrylate, polyethylene glycol (400) di (meth) acrylate, pentaerythritol triacrylate, and pentaerythritol hexaacrylate.
In one embodiment, the photoinitiator is selected from at least any one of 1-hydroxycyclohexyl phenyl ketone, benzil dimethyl ether, benzoin dimethyl ether, 2-hydroxy-2-methyl-1-phenyl-1-acetone, isopropyl thioxanthone, 1-chloro-4-propoxy thioxanthone, 2, 4-diethyl thioxanthone, 4-ethyl dimethylaminobenzoate, tetramethyl Michler's ketone, and tetraethylMichler's ketone.
In one embodiment, the leveling agent and the defoaming agent are selected from at least any one of AFCONA-3777, EFKA-3600, BYK-333, BYK-3505, BYK-052 and AC-300.
In one embodiment, in the synthesis process of the unsaturated double bond and carboxyl group containing polyurethane acrylate resin, the molar ratio of the polyester diol to the dihydroxy monoacid is (0.8-1.1): (0.6-0.9).
The invention also provides two preparation methods of the unsaturated double bond carboxyl-containing polyurethane acrylate resin, which specifically comprise the following steps:
the scheme (1) comprises the following specific synthetic steps:
i, synthesizing polyurethane acrylic resin with NCO end groups containing carboxyl: adding 0.8-1.1mol of polyester diol with the molecular weight of 800 into a reaction flask, heating to 40-45 ℃, starting to dropwise add 2-2.3mol of IPDI isocyanate, controlling the temperature to be not more than 60 ℃, carrying out heat preservation reaction for 2-3 hours after the dropwise addition, adding a mixture of dihydroxypropionic acid and acetone, wherein the mixture contains 0.6-0.8mol of dihydroxypropionic acid, and carrying out heat preservation reaction for 2-3 hours at 50-60 ℃ for later use.
II, continuously dropwise adding 0.8-1.8mol of hydroxyethyl acrylate monomer to the intermediate product of the polyurethane acrylate resin containing carboxyl at the end NCO group for end capping, keeping the temperature at 70-80 ℃ for reaction for 4-5 hours, cooling to 60 ℃, filtering and discharging; the obtained polyurethane acrylate resin containing unsaturated double bonds and carboxyl groups has the number average molecular weight of 2800-5500, the Tg of 5-12 ℃ and the solid content of 88-92 percent.
The scheme (2) comprises the following specific synthetic steps:
i, synthesizing polyurethane acrylic resin with NCO end groups containing carboxyl: adding 0.8-1.1mol of polyester diol with the molecular weight of 1000 into a reaction flask, heating to 40-45 ℃, starting to dropwise add 2-2.4mol of IPDI isocyanate, controlling the temperature to be not more than 60 ℃, carrying out heat preservation reaction for 2-3 hours after the dropwise addition, adding a mixture of dihydroxybutyric acid and acetone, wherein the mixture contains 0.6-0.9mol of dihydroxybutyric acid, and carrying out heat preservation reaction for 2-3 hours at 50-60 ℃ for later use.
II, continuously dropwise adding 0.7-1.9mol of hydroxyethyl acrylate and 0.1-0.3mol of pentaerythritol triacrylate into the intermediate product of the polyurethane acrylate resin containing carboxyl at the end NCO group, keeping the temperature at 70-80 ℃ for reacting for 4-5 hours, cooling to 60 ℃, filtering and discharging; finally, the obtained unsaturated double bond carboxyl-containing polyurethane acrylate resin has the number average molecular weight of 3000-7000, the Tg of 8-25 ℃ and the solid content of 85-88%.
In one embodiment, the curing energy for the metal protection photocureable coating is 500-1500mJ/cm2。
The unsaturated double bond-containing carboxyl-containing polyurethane acrylic resin in the components of the metal protection photocureable coating has the number average molecular weight Mn of 2000-10000, so that the construction of the coating is facilitated, and the performance stability and strength of the coating are improved; the glass transition temperature Tg of the resin is 0-45 ℃, so that the adhesive force between a paint film formed by the metal protection photocureable coating and a substrate can be improved, and the paint film is prevented from falling off. Further, the carboxyl group in the dihydroxy monoacid functions to increase the metal surface adhesion. The photocureable coating for metal protection has excellent metal adhesion and good curing performance, and is suitable for preparing metal protection coatings.
Detailed Description
The present invention is further described below with reference to examples, but is not limited thereto. In the examples, "parts" refer to parts by weight unless otherwise indicated.
The invention provides a photocureable coating for metal protection, which is mainly prepared from the following raw materials in percentage by mass: unsaturated double-bond urethane acrylate resin: 45-70% of a monomer containing an unsaturated double bond: 15-40%, photoinitiator: 2-5%, auxiliary agent: 0.1-1%, and the auxiliary agent is the leveling agent and the defoaming agent.
The number average molecular weight Mn of the carboxyl acrylic resin containing unsaturated double bonds is 2000-10000, and the glass transition temperature Tg is 0-45 ℃, furthermore, the number average molecular weight Mn of the resin containing carboxyl acrylic resin containing unsaturated double bonds is 3000-7000, and the glass transition temperature Tg is 0-15 ℃.
The unsaturated double bond-containing polyurethane acrylate resin adopts a dihydroxy monoacid monomer, and the general formula of the dihydroxy monoacid monomer is as follows: cm H2mO4Wherein m is more than or equal to 3; further, the length of the carbon chain of the dihydroxy monoacid monomer is 3-7; the dihydroxy monoacid monomer is at least one selected from dihydroxy propionic acid, dihydroxy butyric acid, 3,5 dihydroxy-3-methyl valeric acid and dihydroxy heptanoic acid.
The unsaturated double bond-containing monomer is a compound containing at least 2 acryloyl groups or 2 methacryloyl groups; the unsaturated double bond-containing monomer is at least one selected from the group consisting of tripropylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol diacrylate, 1, 4-butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxytrimethylolpropane tri (meth) acrylate, propoxytrimethylolpropane triacrylate, polyethylene glycol (400) di (meth) acrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate.
The photoinitiator is selected from at least any one of 1-hydroxycyclohexyl phenyl ketone, benzil dimethyl ether, benzoin dimethyl ether, 2-hydroxy-2-methyl-1-phenyl-1-acetone, isopropyl thioxanthone, 1-chloro-4-propoxy thioxanthone, 2, 4-diethyl thioxanthone, 4-ethyl dimethylaminobenzoate, tetramethyl Michler's ketone, and tetraethylMichler's ketone.
The leveling agent and the defoaming agent are selected from at least one of AFCONA-3777, EFKA-3600, BYK-333, BYK-3505, BYK-052 and AC-300.
The technical core of the invention lies in the synthesis of the polyurethane acrylate resin containing unsaturated double bonds and carboxyl groups, and the preparation process comprises the following steps: firstly, synthesizing carboxyl-containing polyurethane acrylic resin with an NCO group at one end, wherein the synthetic reaction belongs to gradual addition polymerization and is characterized in that the reaction is carried out at low temperature, the temperature needs to be controlled to prevent side reaction, and secondly, a hydroxyl-containing monomer is added for sealing the end.
The number average molecular weight Mn of the polyurethane acrylic resin containing unsaturated double bonds and carboxyl groups in the component is 2000-10000, preferably 3000-7000, and the glass transition temperature Tg is 0-45 ℃, preferably 0-15 ℃. The larger the molecular weight is, the higher the resin viscosity is, which is not beneficial to construction, and the smaller the molecular weight is, the unstable performance of the coating film is and the strength is insufficient; the glass transition temperature Tg of the resin is between 0 and 45 ℃, preferably between 0 and 15 ℃. Tg lower than 0 ℃ may affect the medium resistance and the strength of the paint film, and Tg higher than 45 ℃ may affect the adhesion of the paint film to a substrate, possibly resulting in the falling off of the paint film.
The metal protection photocureable coating prepared according to the invention can be used for ultraviolet light curing by a high-pressure mercury lamp and an electrodeless lamp, wherein the high-pressure mercury lamp is preferred. The curing energy is 500-1500mJ/cm2Curing energy of less than 500mJ/cm2The incomplete photocuring is possibly caused, and the crosslinking density and the chemical medium resistance of a paint film are reduced; the curing energy is higher than 1500mJ/cm2It may cause local over-irradiation yellowing of the paint film and reduce the production efficiency.
The invention provides two preparation methods of polyurethane acrylate resin containing unsaturated double bonds and carboxyl groups, which specifically comprise the following steps:
the scheme (1) comprises the following specific synthetic steps:
i, synthesizing polyurethane acrylic resin with NCO end groups containing carboxyl: adding 0.8-1.1mol of polyester diol with the molecular weight of 800 into a reaction flask, heating to 40-45 ℃, starting to dropwise add 2-2.3mol of IPDI isocyanate, controlling the temperature to be not more than 60 ℃, carrying out heat preservation reaction for 2-3 hours after the dropwise addition, adding a mixture of dihydroxypropionic acid and acetone, wherein the mixture contains 0.6-0.8mol of dihydroxypropionic acid, and carrying out heat preservation reaction for 2-3 hours at 50-60 ℃ for later use.
II, continuously dropwise adding 0.8-1.8mol of hydroxyethyl acrylate monomer to the intermediate product of the polyurethane acrylate resin containing carboxyl at the end NCO group for end capping, keeping the temperature at 70-80 ℃ for reaction for 4-5 hours, cooling to 60 ℃, filtering and discharging.
The number average molecular weight of the obtained polyurethane acrylate resin containing unsaturated double bonds and carboxyl groups is 2800-5500, Tg is 5-12 ℃, and the solid content is 88-92%.
The scheme (2) comprises the following specific synthetic steps:
i, synthesizing polyurethane acrylic resin with NCO end groups containing carboxyl: adding 0.8-1.1mol of polyester diol with the molecular weight of 1000 into a reaction flask, heating to 40-45 ℃, starting to dropwise add 2-2.4mol of IPDI isocyanate, controlling the temperature to be not more than 60 ℃, carrying out heat preservation reaction for 2-3 hours after the dropwise addition, adding a mixture of dihydroxybutyric acid and acetone, wherein the mixture contains 0.6-0.9mol of dihydroxybutyric acid, and carrying out heat preservation reaction for 2-3 hours at 50-60 ℃ for later use.
II, continuously dropwise adding 0.7-1.9mol of hydroxyethyl acrylate and 0.1-0.3mol of pentaerythritol triacrylate into the intermediate product of the polyurethane acrylate resin containing carboxyl at the end NCO group, keeping the temperature at 70-80 ℃ for reacting for 4-5 hours, cooling to 60 ℃, filtering and discharging.
The number average molecular weight of the obtained unsaturated double bond carboxyl-containing polyurethane acrylate resin is 3000-7000, Tg is 8-25 ℃, and the solid content is 85-88%.
The molar ratio of the polyester diol to the dihydroxy monoacid is (0.8-1.1): (0.6-0.9), too little dihydroxy monoacid is used, which results in insufficient metal adhesion force of the unsaturated double bond carboxyl group-containing polyurethane acrylate resin; the larger the amount of the dihydroxy monoacid is, the lower the metal protection capability of a paint film formed by the paint of the unsaturated double bond carboxyl group-containing urethane acrylate resin is, and the metal is more easily corroded and rusted.
The unsaturated double bond carboxyl group-containing polyurethane acrylate resin has moderate molecular weight, high curing speed and better mechanical performance of a coating film. The light-cured coating formula using the resin as a main body has the advantages of simple components, excellent adhesive force, chemical medium resistance of a coating film and good corrosion resistance.
Examples 1 to 4 and comparative example 5
(I) Metal protective photocureable coating
Table 1 table of distribution ratio of each component in examples 1 to 4 and comparative example 5
Wherein, the unsaturated double bond and carboxyl group containing polyurethane acrylate resins (1) and (2) are self-made resins, TMPTA is trimethylolpropane triacrylate, HDDA is hexanediol diacrylate, TPGDA is tripropylene glycol diacrylate, DPHA is dipentaerythritol hexaacrylate, and the resins are both Changxing chemical products; 184 is 1-hydroxycyclohexyl phenyl ketone, 651 is benzil dimethyl ether, 1173 is 2-hydroxy-2-methyl-1-phenyl-1-acetone, and the compounds are Tianjin long-term chemical products; EFKA-3777 is a fluorine modified acrylic polymer leveling agent from BASF corporation, BYK-333 is an organosilicon leveling agent from BYK corporation, Germany, BYK-052 is an antifoaming agent from BYK corporation, Germany.
The specific synthetic steps of the polyurethane acrylate resin (1) containing unsaturated double bonds and carboxyl groups are as follows:
i, synthesizing polyurethane acrylic resin with NCO end groups containing carboxyl: adding 1mol of polyester diol with the molecular weight of 800 into a reaction flask, heating to 45 ℃, starting to dropwise add 2mol of IPDI isocyanate, controlling the temperature not to exceed 55 ℃, carrying out heat preservation reaction for 2 hours after completing dropwise addition, adding 0.6mol of mixture of dihydroxypropionic acid and acetone, carrying out heat preservation reaction for 3 hours at 50 ℃ for later use.
II, continuously dropwise adding 0.8mol of hydroxyethyl acrylate monomer to the intermediate product of the polyurethane acrylate resin with the NCO group at the end and containing carboxyl, keeping the temperature at 70 ℃ for reaction for 4 hours, cooling to 60 ℃, filtering and discharging. The number average molecular weight of the obtained unsaturated double bond carboxyl-containing polyurethane acrylate resin is 3470, the Tg is 9.2 ℃, and the solid content is 90%.
The concrete synthetic steps of the unsaturated double bond carboxyl group-containing polyurethane acrylate resin (2) are as follows:
i, synthesizing polyurethane acrylic resin with NCO end groups containing carboxyl: adding 1mol of polyester diol with the molecular weight of 1000 into a reaction flask, heating to 45 ℃, starting to dropwise add 2.2mol of IPDI isocyanate, controlling the temperature not to exceed 55 ℃, carrying out heat preservation reaction for 2 hours after completing dropwise addition, adding 0.7mol of a mixture of dihydroxybutyric acid and acetone, and carrying out heat preservation reaction for 3 hours at 50 ℃ for later use.
II, continuously dropwise adding 0.8mol of hydroxyethyl acrylate and 0.2mol of pentaerythritol triacrylate into the intermediate product of the polyurethane acrylate resin containing carboxyl at the end NCO group, keeping the temperature at 70 ℃ for reacting for 4 hours, cooling to 60 ℃, filtering and discharging.
The obtained unsaturated double bond carboxyl-containing polyurethane acrylate resin has the number average molecular weight of 4870, the Tg of 13.2 ℃ and the solid content of 85 percent.
And adding the resin, the monomer, the initiator and the auxiliary agent into a container, and fully and uniformly stirring to obtain the metal photocureable coating.
(II) construction curing
The prepared examples 1 to 4 and comparative example 5 were coated on a glass plate and a tin plate, respectively, and ultraviolet-cured under a high-pressure mercury lamp with a curing energy of about 1500mJ/cm2And testing the performance of the paint film.
(III) paint film Performance testing and results
The results of the paint film property test are shown in Table 2.
TABLE 2 cured paint film property test results of examples 1-4 and comparative example 5
As shown in Table 2, the photo-curable coating for metal protection prepared according to the methods of examples 1 to 4 of the present invention had good adhesion, and comparative example 5 had a relatively high film hardness, decreased film flexibility, deteriorated adhesion to metal, and easy separation from the substrate.
Since comparative example 5 employs a multifunctional monomer DPHA, which is a hexafunctional reactive monomer, the hardness of the paint film is improved, but the adhesion is decreased. Meanwhile, in the process of research and development, the inventor finds out through a large number of experiments that: most reactive resins and monomers with more than 5 functional groups are added to the formulation in a similar manner; mainly, the functionality of the selected monomer is increased, so that the crosslinking of a paint film is more compact, the hardness is improved, the shrinkage stress is increased, the flexibility is reduced, and the adhesive force is poor. Therefore, it is preferable that the unsaturated double bond-containing monomer has a functionality of less than 5.
Examples 1-4 had good adhesion, which is strongly related to the functionality of the resin being 2-4 and the relatively moderate molecular weight. The carboxyl in the dihydroxy monoacid plays a role in increasing the adhesive force of the metal surface, and the partially modified pentaerythritol triacrylate can improve the strength and the reaction activity of the resin and is suitable for quick curing.
Various other modifications and changes may be made by those skilled in the art based on the above-described technical solutions and concepts, and all such modifications and changes should fall within the scope of the claims of the present invention.
Claims (10)
1. The photocureable coating capable of being used for metal protection is characterized by being mainly prepared from the following raw materials in percentage by mass: unsaturated double-bond urethane acrylate resin: 45-70% of unsaturated double bond-containing monomer: 15-40%, photoinitiator: 2-5%, auxiliary agent: 0.1-1%, wherein the auxiliary agent is the flatting agent and the defoaming agent; the unsaturated double bond-containing monomer is a compound containing at least 2 acryloyl groups or 2 methacryloyl groups; the carboxyl acrylic resin containing unsaturated double bonds has the resin number average molecular weight Mn of 2000-10000 and the glass transition temperature Tg of 0-45 ℃.
2. The photo-curable coating material for metal protection as claimed in claim 1, wherein the resin number average molecular weight Mn of the carboxyl group-containing acrylic resin containing unsaturated double bonds is 3000-7000, and the glass transition temperature Tg is 0-15 ℃.
3. The photo-curable coating composition for protecting metal according to claim 1, wherein the urethane acrylate resin having unsaturated double bonds comprises dihydroxy monoacid monomers having the formula: cm H2mO4Wherein m is 3 to 7.
4. The photo-curable coating composition for metal protection according to claim 3, wherein the dihydroxy monobasic acid monomer is at least one selected from the group consisting of dihydroxy propionic acid, dihydroxy butyric acid, 3,5 dihydroxy-3-methyl valeric acid, dihydroxy heptanoic acid.
5. The photo-curable coating composition for metal protection according to claim 1, wherein the unsaturated double bond-containing monomer has a functionality of 2 to 4.
6. The photocurable coating for metal protection according to claim 1 or 5, wherein the unsaturated double bond-containing monomer is selected from at least any one of tripropylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyl glycol diacrylate, 1, 4-butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxytrimethylolpropane tri (meth) acrylate, propoxytrimethylolpropane triacrylate, polyethylene glycol (400) di (meth) acrylate, pentaerythritol triacrylate, and pentaerythritol hexaacrylate.
7. The metal-protecting photocurable coating according to claim 1, wherein said photoinitiator is selected from at least any one of 1-hydroxycyclohexyl phenyl ketone, benzil dimethyl ether, benzoin dimethyl ether, 2-hydroxy-2-methyl-1-phenyl-1-propanone, isopropyl thioxanthone, 1-chloro-4-propoxy thioxanthone, 2, 4-diethyl thioxanthone, ethyl 4-dimethylaminobenzoate, tetramethylmichler's ketone, and tetraethylmichler's ketone.
8. The photo-curable coating composition for metal protection according to claim 1, wherein the leveling agent and the defoaming agent are at least one selected from AFCONA-3777, EFKA-3600, BYK-333, BYK-3505, BYK-052 and AC-300.
9. The photo-curable coating material for metal protection according to claim 1, wherein the preparation method of the unsaturated double bond containing carboxyl group containing urethane acrylate resin comprises the following steps:
i, synthesizing polyurethane acrylic resin with NCO end groups containing carboxyl: adding 0.8-1.1mol of polyester diol with the molecular weight of 800 into a reaction flask, heating to 40-45 ℃, starting to dropwise add 2-2.3mol of IPDI isocyanate, controlling the temperature not to exceed 60 ℃, after dropwise adding, keeping the temperature and reacting for 2-3 hours, adding a mixture of dihydroxypropionic acid and acetone, wherein the mixture contains 0.6-0.8mol of dihydroxypropionic acid, keeping the temperature and reacting for 2-3 hours at 50-60 ℃ for later use;
II, continuously dropwise adding 0.8-1.8mol of hydroxyethyl acrylate monomer to the intermediate product of the carboxyl-containing polyurethane acrylate resin with the NCO group at the end, which is synthesized in the step I, sealing the end, keeping the temperature at 70-80 ℃ for reaction for 4-5 hours, cooling to 60 ℃, filtering and discharging; the obtained polyurethane acrylate resin containing unsaturated double bonds and carboxyl groups has the number average molecular weight of 2800-5500, the Tg of 5-12 ℃ and the solid content of 88-92 percent.
10. The photo-curable coating material for metal protection according to claim 1, wherein the preparation method of the unsaturated double bond containing carboxyl group containing urethane acrylate resin comprises the following steps:
i, synthesizing polyurethane acrylic resin with NCO end groups containing carboxyl: adding 0.8-1.1mol of polyester diol with the molecular weight of 1000 into a reaction flask, heating to 40-45 ℃, starting to dropwise add 2-2.4mol of IPDI isocyanate, controlling the temperature to be not more than 60 ℃, carrying out heat preservation reaction for 2-3 hours after the dropwise addition, adding a mixture of dihydroxybutyric acid and acetone, wherein the mixture contains 0.6-0.9mol of dihydroxybutyric acid, and carrying out heat preservation reaction for 2-3 hours at 50-60 ℃ for later use;
II, continuously dropwise adding 0.7-1.9mol of hydroxyethyl acrylate and 0.1-0.3mol of pentaerythritol triacrylate into the intermediate product of the carboxyl-containing polyurethane acrylate resin with the end NCO group synthesized in the step I, keeping the temperature at 70-80 ℃ for reacting for 4-5 hours, cooling to 60 ℃, and filtering to discharge; finally, the obtained unsaturated double bond carboxyl-containing polyurethane acrylate resin has the number average molecular weight of 3000-7000, the Tg of 8-25 ℃ and the solid content of 85-88%.
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| JPH02155957A (en) * | 1988-12-08 | 1990-06-15 | Mitsubishi Rayon Co Ltd | Actinic radiation-curable resin composition |
| CN1526771A (en) * | 2003-03-03 | 2004-09-08 | 珠海东诚化工有限公司 | Visible light cured metal paint |
| CN102212311A (en) * | 2011-05-09 | 2011-10-12 | 中国工程物理研究院化工材料研究所 | Colorful ultraviolet (UV) light solidifying paint |
| CN103833952A (en) * | 2014-02-20 | 2014-06-04 | 山西省应用化学研究所 | Preparation method of carboxyl modification polyurethane acrylic acid ester |
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2020
- 2020-12-28 CN CN202011585257.XA patent/CN114686092A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02155957A (en) * | 1988-12-08 | 1990-06-15 | Mitsubishi Rayon Co Ltd | Actinic radiation-curable resin composition |
| CN1526771A (en) * | 2003-03-03 | 2004-09-08 | 珠海东诚化工有限公司 | Visible light cured metal paint |
| CN102212311A (en) * | 2011-05-09 | 2011-10-12 | 中国工程物理研究院化工材料研究所 | Colorful ultraviolet (UV) light solidifying paint |
| CN103833952A (en) * | 2014-02-20 | 2014-06-04 | 山西省应用化学研究所 | Preparation method of carboxyl modification polyurethane acrylic acid ester |
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