CN115260948B - Flame-retardant UV (ultraviolet) curing adhesive and preparation method and application thereof - Google Patents
Flame-retardant UV (ultraviolet) curing adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN115260948B CN115260948B CN202211046958.5A CN202211046958A CN115260948B CN 115260948 B CN115260948 B CN 115260948B CN 202211046958 A CN202211046958 A CN 202211046958A CN 115260948 B CN115260948 B CN 115260948B
- Authority
- CN
- China
- Prior art keywords
- flame
- retardant
- parts
- adhesive
- tackifying resin
- 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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Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 116
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 108
- 239000000853 adhesive Substances 0.000 title claims abstract description 103
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 59
- 229920005989 resin Polymers 0.000 claims abstract description 59
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 32
- -1 flame-retardant polyol Chemical class 0.000 claims abstract description 29
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 25
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 23
- 229920005862 polyol Polymers 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 23
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 15
- 238000003848 UV Light-Curing Methods 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims description 44
- 230000001681 protective effect Effects 0.000 claims description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 39
- 229910052744 lithium Inorganic materials 0.000 claims description 39
- 239000000203 mixture Substances 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 22
- 239000012790 adhesive layer Substances 0.000 claims description 17
- 239000003085 diluting agent Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000012986 chain transfer agent Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 4
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 230000002195 synergetic effect Effects 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- MHVJRKBZMUDEEV-APQLOABGSA-N (+)-Pimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@](C=C)(C)C=C2CC1 MHVJRKBZMUDEEV-APQLOABGSA-N 0.000 claims description 2
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 claims description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 claims description 2
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 53
- 239000002243 precursor Substances 0.000 description 21
- 238000001816 cooling Methods 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002985 plastic film Substances 0.000 description 6
- 229920006255 plastic film Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 125000005456 glyceride group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000013022 formulation composition Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- 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
- 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 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/105—Pouches or flexible bags
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/33—Applications of adhesives in processes or use of adhesives in the form of films or foils for batteries or fuel cells
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a flame-retardant UV (ultraviolet) curing adhesive and a preparation method and application thereof. The flame-retardant UV curing adhesive comprises the following raw materials in parts by weight: 80-120 parts of acrylate prepolymer, 30-40 parts of modified tackifying resin, 0.1-1 part of cross-linking agent and 1-10 parts of photoinitiator; the modified tackifying resin comprises the following raw materials in parts by weight: 50-70 parts of rosin polybasic acid and 50-100 parts of flame-retardant polyol; the modified tackifying resin is polymerized from the raw materials. The flame-retardant UV-curable adhesive provided by the invention contains the acrylate prepolymer, the modified tackifying resin, the crosslinking agent and the photoinitiator, so that the adhesive has good flame-retardant performance, meanwhile, the compatibility among all components in the adhesive is not affected, the adhesive is ensured to have excellent adhesive performance, the adhesive is endowed with longer-lasting flame-retardant performance, and the curing can be realized under the irradiation of ultraviolet light with specific wavelength.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a flame-retardant UV (ultraviolet) curing adhesive and a preparation method and application thereof.
Background
With the rapid development of the lithium battery industry, the demand of lithium battery protective films also has a rapidly growing trend. The lithium battery protective film needs to have high mechanical strength and high pressure sensitivity, and since the use amount of the lithium battery protective film is huge and gradually increases every year, the production of the lithium battery protective film needs to reduce the production cost as much as possible on the basis of being friendly to the environment. At present, the lithium battery protective film adopted in the market can release a large amount of organic solvents in the curing process, so that the production cost of the lithium battery protective film is increased, and environmental pollution is easily caused.
In addition, the lithium battery protective film is liable to fire at high temperature during transportation and use, and in order to prevent this phenomenon, the lithium battery protective film needs to have good flame retardancy at the same time. Most of pressure-sensitive adhesives and protective films used at present are directly added with flame retardant in the process of preparing the pressure-sensitive adhesives to achieve flame retardant effect, but the addition of the flame retardant can lead to poor compatibility of all components of the pressure-sensitive adhesives, poor adhesive performance and non-lasting flame retardant performance.
Disclosure of Invention
The invention provides a flame-retardant UV-curable adhesive, a preparation method and application thereof, wherein the flame-retardant UV-curable adhesive contains acrylate prepolymer, modified tackifying resin, a crosslinking agent and a photoinitiator, so that the adhesive has good flame-retardant performance, meanwhile, the compatibility among all components in the adhesive is not influenced, the adhesive is ensured to have excellent adhesive performance, the adhesive is endowed with longer-lasting flame-retardant performance, and the curing can be realized under the irradiation of ultraviolet light with specific wavelength.
According to a first aspect of the present invention, there is provided a flame retardant UV curable adhesive comprising the following raw materials in parts by weight: 80-120 parts of acrylate prepolymer, 30-40 parts of modified tackifying resin, 0.1-1 part of cross-linking agent and 1-10 parts of photoinitiator; the modified tackifying resin comprises the following raw materials in parts by weight: 50-70 parts of rosin polybasic acid and 50-100 parts of flame-retardant polyol; the modified tackifying resin is polymerized from the raw materials.
The flame-retardant UV-curable adhesive provided by the invention contains the acrylate prepolymer and the modified tackifying resin, wherein the modified tackifying resin is prepared from the rosin polybasic acid and the flame-retardant polyol, the flame-retardant element contained in the flame-retardant polyol is copolymerized on the tackifying resin in a grafting manner, and the modified tackifying resin prepared in the specific grafting manner is used in combination with the acrylate prepolymer, the cross-linking agent and the photoinitiator, so that the adhesive has good flame-retardant performance, and meanwhile, the compatibility among all components in the adhesive is not influenced, thereby ensuring that the adhesive has excellent adhesive performance and further endowing the adhesive with longer-lasting flame-retardant performance. And compared with other polybasic acids, the modified tackifying resin prepared by using the rosin polybasic acid has better compatibility with acrylate prepolymer, so that the tackifying effect is better. In addition, when the adhesive provided by the invention is used for coating to prepare the adhesive layer, the adhesive layer can be cured under the irradiation of ultraviolet light with specific wavelength, the baking in an oven is not needed, the coating speed is greatly improved, the production cost is reduced, the energy is effectively saved, the use of solvents is avoided, and the adhesive is more environment-friendly.
Preferably, the crosslinking agent comprises at least one of hexamethylene diisocyanate, xylylene diisocyanate, and tripropylene glycol diacrylate.
Preferably, the photoinitiator comprises at least one of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl benzophenone, benzoin diethyl ether.
Preferably, the acid value of the modified tackifying resin is from 5 to 15mgKOH/g.
Preferably, the modified tackifying resin is prepared by the steps of:
(1) Uniformly mixing rosin polybasic acid, flame-retardant polyol and a catalyst to obtain a mixture, and reacting the mixture at 230-270 ℃ until the acid value of the mixture is 18-22 mgKOH/g;
(2) The mixture is reacted at 190-210 ℃ until the acid value of the mixture is 5-15 mgKOH/g, and the modified tackifying resin is obtained.
According to the scheme, a structural modification mode is adopted, rosin polybasic acid is used as a raw material, the rosin polybasic acid reacts with flame-retardant polyol under the action of a catalyst, the acid value of a reaction system is controlled within a certain range through the reaction at different temperatures, a flame-retardant element is copolymerized onto tackifying resin in a grafting mode to prepare the modified tackifying resin with a certain acid value range, the modified tackifying resin is added into an adhesive, the flame-retardant performance of the modified tackifying resin is improved, meanwhile, the compatibility among all components in the adhesive is improved, the excellent adhesive performance is endowed, meanwhile, the storage performance of the adhesive is more stable, and the subsequent adhesive is coated.
In addition, the acid value of the modified tackifying resin in the flame-retardant UV-curable adhesive is controlled within the range of 5-15 mgKOH/g, and the adhesive is applied to a lithium battery protective film, so that the stripping force of the lithium battery protective film can be kept within a reasonable range, and the practical application of the lithium battery protective film is facilitated. When the acid value of the modified tackifying resin is less than 5mgKOH/g, the peeling force of the lithium battery protective film is low, the lithium battery protective film is easy to fall off from the surface of an object to be pasted in the actual application process, and the object to be pasted cannot be well protected; when the acid value of the modified tackifying resin is more than 15mgKOH/g, the peeling force of the lithium battery protective film is too high, so that other adverse effects can be generated in the practical application process.
Preferably, the rosin polybasic acid comprises at least one of abietic acid type polybasic acid and pimaric acid type polybasic acid.
Preferably, the rosin polybasic acid is propenoic acid.
Preferably, the flame retardant polyol includes at least one of halogen flame retardant polyol, phosphorus flame retardant polyol, nitrogen flame retardant polyol, and phosphorus-nitrogen synergistic flame retardant polyol.
The flame retardant polyol contains a flame retardant element such as halogen, phosphorus, nitrogen, etc.; the phosphorus-nitrogen synergistic flame-retardant polyol refers to a polyol which contains two flame-retardant elements of phosphorus and nitrogen at the same time.
Preferably, the catalyst comprises at least one of zinc oxide, zinc chloride, calcium acetate.
Preferably, the acrylate prepolymer comprises the following raw materials in parts by weight: 50-70 parts of adhesive monomer, 10-20 parts of cohesive monomer, 10-20 parts of modified monomer, 0.1-1 part of thermal initiator and 1-5 parts of chain transfer agent.
Preferably, the acrylate prepolymer further comprises the following raw materials in parts by weight: 0.01 to 0.1 portion of polymerization inhibitor.
Preferably, the adhesive monomer includes at least one of butyl acrylate, ethyl acrylate, and isooctyl acrylate.
Preferably, the cohesive monomer comprises at least one of acrylonitrile, vinyl acetate, acrylamide, methyl methacrylate.
Preferably, the modifying monomer comprises at least one of methacrylic acid, acrylic acid, hydroxypropyl methacrylate.
Preferably, the thermal initiator is mixed by Azodiisobutyronitrile (AIBN) and dibenzoyl peroxide (BPO) according to a mass ratio of 1:2.
Preferably, the chain transfer agent is dodecyl mercaptan.
Preferably, the polymerization inhibitor comprises at least one of hydroquinone, methyl hydroquinone, and p-hydroxyanisole.
Preferably, the acrylate prepolymer is prepared by the steps of:
(1) Uniformly mixing an adhesive monomer, a cohesive monomer, a thermal initiator and a chain transfer agent to obtain a precursor solution;
(2) Reacting part of the precursor solution at 70-90 ℃ for 0.2-0.8 hours to obtain a prepolymer solution;
wherein the usage amount of the precursor solution in the step is 20-30wt% of the total amount of the precursor solution;
(3) Adding the rest precursor solution into the prepolymer solution, preserving heat for 0.2-0.8 hours at 70-90 ℃, then adding a modified monomer and a polymerization inhibitor into a reaction system, and reacting for 0.5-1.5 hours at 70-90 ℃ to prepare an acrylate prepolymer;
preferably, in step (3), a polymerization inhibitor is added to the reaction system together with the modifying monomer.
According to the scheme, the polymerization inhibitor is added in the process of preparing the acrylic ester prepolymer, so that the polymerization rate can be reduced, and the explosion polymerization caused by too fast reaction is prevented.
Preferably, in step (3), the precursor solution is added to the prepolymer solution by dropwise addition.
According to the scheme, the acrylate prepolymer is prepared from three monomers of the adhesive monomer, the cohesive monomer and the modified monomer, and is matched with the modified tackifying resin to be applied to the flame-retardant UV-curable adhesive, so that the adhesive has good compatibility with the modified tackifying resin, and has adhesive property and excellent flame-retardant property.
Preferably, the flame-retardant UV-curable adhesive further comprises the following raw materials in parts by weight: 30-50 parts of reactive diluent monomer.
Preferably, the reactive diluent monomer comprises at least one of isooctyl acrylate, isobornyl acrylate, tetraethylene glycol dimethacrylate, diethylene glycol diacrylate and glycidyl methacrylate.
Preferably, the flame-retardant UV-curable adhesive is prepared by the following steps: and weighing the acrylate prepolymer, the modified tackifying resin, the reactive diluent monomer, the photoinitiator and the crosslinking agent according to parts by weight, and uniformly stirring under the condition of nitrogen atmosphere and light shielding to prepare the flame-retardant UV curing adhesive.
According to a second aspect of the present invention, there is provided a protective film for a lithium battery, the protective film comprising an adhesive layer prepared from the above flame retardant UV curable adhesive.
Preferably, the thickness of the adhesive layer is 5 to 50 μm.
Preferably, the lithium battery protective film further comprises a base material layer.
Preferably, the substrate layer in the lithium battery protective film is combined with the adhesive layer.
Preferably, the thickness of the substrate layer is 25 to 100 μm.
Preferably, the material of the substrate layer comprises at least one of polyethylene terephthalate and polypropylene.
Preferably, the lithium battery protective film is prepared by the following steps: and coating the flame-retardant UV curing adhesive on the substrate layer, curing under ultraviolet light with the wavelength of 200-400 nm to obtain an adhesive layer, and simultaneously rolling to obtain the lithium battery protective film.
The flame-retardant UV-curable adhesive is used for preparing the adhesive layer of the lithium battery protective film, and the flame-retardant UV-curable adhesive contains acrylate prepolymer, modified tackifying resin, cross-linking agent and photoinitiator, so that the lithium battery protective film prepared by coating the adhesive on the substrate layer has good flame retardant property and adhesive property.
Drawings
Fig. 1 is a schematic structural diagram of a lithium battery protection film provided by the invention.
The reference numerals are: 1 a substrate layer and 2 an adhesive layer.
Detailed Description
The technical features of the technical solution provided in the present invention will be further clearly and completely described in connection with the detailed description below, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The flame-retardant UV curing adhesive comprises the following raw materials in parts by weight: 80 parts of acrylate prepolymer, 30 parts of modified tackifying resin, 0.1 part of cross-linking agent, 1 part of photoinitiator and 30 parts of reactive diluent monomer;
the acrylate prepolymer is prepared by the following steps:
(1) Uniformly mixing an adhesive monomer, a cohesive monomer, a thermal initiator and a chain transfer agent to obtain a precursor solution;
(2) Reacting part of the precursor solution in the step (1) for 0.8 hour at 70 ℃ to obtain a prepolymer solution;
wherein the precursor solution is used in an amount of 20wt% of the total amount of the precursor solution in this step;
(3) Dropwise adding the rest precursor solution into the prepolymer solution in the step (2), preserving heat for 0.8 hours at 70 ℃, then adding a modified monomer and a polymerization inhibitor into a reaction system, reacting for 1.5 hours at 70 ℃, and cooling and discharging to obtain an acrylic ester prepolymer;
the modified tackifying resin is prepared by the following steps:
(1) Uniformly mixing rosin polybasic acid, flame-retardant polyol and a catalyst to obtain a mixture, reacting the mixture at 230 ℃ until the acid value of the mixture is 18mgKOH/g, and vacuumizing;
(2) Cooling the mixture obtained in the step (1) to 190 ℃, reacting at 190 ℃ until the acid value of the mixture is 5mgKOH/g, and cooling and discharging to obtain modified tackifying resin;
the flame-retardant UV curing adhesive is prepared by the following steps: and weighing the acrylate prepolymer, the modified tackifying resin, the reactive diluent monomer, the photoinitiator and the crosslinking agent according to parts by weight, and uniformly stirring under the condition of nitrogen atmosphere and light shielding to prepare the flame-retardant UV curing adhesive.
TABLE 1 raw materials and formulation compositions of flame retardant UV curable adhesives
Example 2
The flame-retardant UV curing adhesive comprises the following raw materials in parts by weight: 120 parts of acrylate prepolymer, 40 parts of modified tackifying resin, 1 part of cross-linking agent, 10 parts of photoinitiator and 50 parts of reactive diluent monomer;
the acrylate prepolymer is prepared by the following steps:
(1) Uniformly mixing an adhesive monomer, a cohesive monomer, a thermal initiator and a chain transfer agent to obtain a precursor solution;
(2) Reacting part of the precursor solution in the step (1) for 0.2 hour at 90 ℃ to obtain a prepolymer solution;
wherein the precursor solution is used in an amount of 30wt% of the total amount of the precursor solution in this step;
(3) Dropwise adding the rest precursor solution into the prepolymer solution in the step (2), preserving heat for 0.2 hours at 90 ℃, then adding a modified monomer and a polymerization inhibitor into a reaction system, reacting for 0.5 hour at 90 ℃, and cooling and discharging to obtain an acrylic ester prepolymer;
the modified tackifying resin is prepared by the following steps:
(1) Uniformly mixing rosin polybasic acid, flame-retardant polyol and a catalyst to obtain a mixture, reacting the mixture at 270 ℃ until the acid value of the mixture is 22mgKOH/g, and vacuumizing;
(2) Cooling the mixture obtained in the step (1) to 210 ℃, reacting at 210 ℃ until the acid value of the mixture is 15mgKOH/g, and cooling and discharging to obtain modified tackifying resin;
the flame-retardant UV curing adhesive is prepared by the following steps: and weighing the acrylate prepolymer, the modified tackifying resin, the reactive diluent monomer, the photoinitiator and the crosslinking agent according to parts by weight, and uniformly stirring under the condition of nitrogen atmosphere and light shielding to prepare the flame-retardant UV curing adhesive.
TABLE 2 raw materials and formulation compositions of flame retardant UV curable adhesives
Example 3
The flame-retardant UV curing adhesive comprises the following raw materials in parts by weight: 100 parts of acrylate prepolymer, 35 parts of modified tackifying resin, 0.5 part of cross-linking agent, 5 parts of photoinitiator and 40 parts of reactive diluent monomer;
the acrylate prepolymer is prepared by the following steps:
(1) Uniformly mixing an adhesive monomer, a cohesive monomer, a thermal initiator and a chain transfer agent to obtain a precursor solution;
(2) Reacting part of the precursor solution in the step (1) for 0.5 hour at 80 ℃ to obtain a prepolymer solution;
wherein the precursor solution is used in the present step in an amount of 25wt% of the total amount of the precursor solution;
(3) Dropwise adding the rest precursor solution into the prepolymer solution in the step (2), preserving heat for 0.5 hour at 80 ℃, then adding a modified monomer and a polymerization inhibitor into a reaction system, reacting for 1 hour at 80 ℃, cooling, and cooling and discharging to obtain an acrylic ester prepolymer;
the modified tackifying resin is prepared by the following steps:
(1) Uniformly mixing rosin polybasic acid, flame-retardant polyol and a catalyst to obtain a mixture, reacting the mixture at 250 ℃ until the acid value of the mixture is 20mgKOH/g, and vacuumizing;
(2) Cooling the mixture obtained in the step (1) to 200 ℃, reacting at 200 ℃ until the acid value of the mixture is 10mgKOH/g, and cooling and discharging to obtain modified tackifying resin;
the flame-retardant UV curing adhesive is prepared by the following steps: and weighing the acrylate prepolymer, the modified tackifying resin, the reactive diluent monomer, the photoinitiator and the crosslinking agent according to parts by weight, and uniformly stirring under the condition of nitrogen atmosphere and light shielding to prepare the flame-retardant UV curing adhesive.
TABLE 3 raw materials and formulation compositions of flame retardant UV curable adhesives
Comparative example 1
This comparative example provides a flame retardant UV curable adhesive, which differs from example 1 in that: the modified tackifying resin was replaced with a conventional polymerized rosin glyceride (i.e., a rosin resin containing no flame retardant element), and the remainder was the same as in example 1.
Comparative example 2
This comparative example provides a flame retardant UV curable adhesive, which differs from example 2 in that: the modified tackifying resin was replaced with a conventional polymerized rosin glyceride (i.e., a rosin resin containing no flame retardant element), and the remainder was the same as in example 2.
Comparative example 3
This comparative example provides a flame retardant UV curable adhesive, which differs from example 3 in that: the modified tackifying resin was replaced with a conventional polymerized rosin glyceride (i.e., a rosin resin containing no flame retardant element), and the remainder was the same as in example 3.
Comparative example 4
This comparative example provides a flame retardant UV curable adhesive, which differs from example 3 in that: the acid value of the modified tackifying resin used was 3mgKOH/g.
Comparative example 5
This comparative example provides a flame retardant UV curable adhesive, which differs from example 3 in that: the acid value of the modified tackifying resin used was 20mgKOH/g.
Comparative example 6
This comparative example provides a flame retardant UV curable adhesive, which differs from example 3 in that: the modified tackifying resin was replaced with a conventional polymerized rosin glyceride (i.e., a rosin resin containing no flame retardant element), and 50 parts of a phosphorus-nitrogen synergistic flame retardant was simultaneously added during the preparation of the flame retardant UV curable adhesive, the remainder being the same as in example 3.
Comparative example 7
This comparative example provides a flame retardant UV curable adhesive, which differs from example 3 in that: the starting material of the acrylate prepolymer was the same as in example 3 except that the modified monomer was not contained.
Comparative example 8
This comparative example provides a flame retardant UV curable adhesive, which differs from example 3 in that: the starting material for the acrylate prepolymer was free of cohesive monomers, and the remainder was the same as in example 3.
Comparative example 9
This comparative example provides a flame retardant UV curable adhesive, which differs from example 3 in that: in the preparation of the acrylate prepolymer, the thermal initiator used was azobisisobutyronitrile, the remainder being the same as in example 3.
Comparative example 10
This comparative example provides a flame retardant UV curable adhesive, which differs from example 3 in that: in the preparation of the acrylate prepolymer, the thermal initiator used is dibenzoyl peroxide.
Examples 4 to 6 and comparative examples 11 to 20
The lithium battery protective film has a structure shown in figure 1, and comprises a substrate layer 1 and an adhesive layer 2, wherein the substrate layer 1 is made of polyethylene terephthalate, the adhesive layer 2 is prepared from flame-retardant UV-cured adhesives prepared in examples 1-3 and comparative examples 1-10, and raw materials of the adhesive layer 2 are shown in table 4;
the lithium battery protective film is prepared by the following steps: the flame-retardant UV-curable adhesives prepared in examples 1 to 3 and comparative examples 1 to 10 were fed to a coating head by a pump, the coating speed was set to 50 to 150m/min, the flame-retardant UV-curable adhesives prepared in examples 1 to 3 and comparative examples 1 to 10 were coated on a substrate layer 1, a UV lamp was turned on, and the UV radiation amount was set to 600mJ/cm under ultraviolet light having a wavelength of 200 to 400nnm 2 And (3) curing to obtain an adhesive layer 2, and simultaneously rolling to obtain the lithium battery protective film.
Table 4 raw materials for adhesive layer of lithium battery protective film
| Lithium battery protection film | Raw materials of adhesive layer |
| Example 4 | Flame retardant UV curable adhesive of example 1 |
| Example 5 | Flame retardant UV curable adhesive of example 2 |
| Example 6 | Example 3 flame retardant UV curable adhesive |
| Comparative example 11 | Flame retardant UV curable adhesive of comparative example 1 |
| Comparative example 12 | Flame retardant UV curable adhesive of comparative example 2 |
| Comparative example 13 | Flame retardant UV curable adhesive of comparative example 3 |
| Comparative example 14 | Flame retardant UV curable adhesive of comparative example 4 |
| Comparative example 15 | Flame retardant UV curable adhesive of comparative example 5 |
| Comparative example 16 | Flame retardant UV curable adhesive of comparative example 6 |
| Comparative example 17 | Flame retardant UV curable adhesive of comparative example 7 |
| Comparative example 18 | Flame retardant UV curable adhesive of comparative example 8 |
| Comparative example 19 | Flame retardant UV curable adhesive of comparative example 9 |
| Comparative example 20 | Flame retardant UV curable adhesive of comparative example 10 |
Test case
1. Experimental construction mode
The test subjects of this test example were lithium battery protective films of examples 4 to 6 and comparative examples 11 to 20, and various properties of the test subjects were tested.
(1) 180 DEG sheet peel force
Referring to national standard GB2792-2014, taking a 25mm wide lithium battery protective film, sticking a steel plate, rolling for 3 times by a 2kg roller, placing for 20min at 23+/-1 ℃ under 50+/-5% RH environment, and peeling the lithium battery protective film at a speed of 300mm/min by 180 degrees;
(2) High temperature and high pressure post aluminum plastic film peel force
2 strips of 100mm 25mm protective film sample strips are adhered to the smooth surface of a black aluminum plastic film in parallel, surface pressure is set to 1200kg, the temperature is 85 ℃, after the temperature is stable, the strips are placed in a hot platen press, hot pressed for 400min, then taken out, placed for 24h in an environment with the temperature of 23+/-1 ℃ and the RH of 50+/-5%, and a lithium battery protective film is peeled off at the speed of 300mm/min by using a pulling machine at 180 degrees;
(3) High-temperature high-pressure glue dipping experiment
2 strips of 100mm 25mm protective film sample strips are adhered to the smooth surface of the black aluminum plastic film in parallel, surface pressure is set to 1200kg, the temperature is 85 ℃, after the temperature is stable, the aluminum plastic film sample strips are placed in a hot platen press, hot pressed for 400min, then taken out, placed for 24h in an RH environment with the temperature of 23+/-1 ℃ and 50+/-5%, the protective film is rapidly torn off from the aluminum plastic film (less than 1 s), and the surface adhesive residue condition of the aluminum plastic film is observed;
(4) Flame retardant rating
Reference is made to UL94 flame retardant rating test.
2. Experimental results
Table 5 lithium battery protective film various performance test results
The results of the performance tests of the lithium battery protective films of examples 4 to 6 and comparative examples 11 to 20 are shown in table 5. As can be seen from examples 4 to 6 and comparative examples 11 to 13, the introduction of the flame retardant element into the acrylic pressure-sensitive adhesive by graft copolymerization does not destroy the adhesive property of the pressure-sensitive adhesive, and simultaneously greatly improves the flame retardant property of the pressure-sensitive adhesive; as is clear from comparative examples 14 and 15, an excessively high or excessively low acid value of the modified tackifying resin affects the number of active groups of the tackifying resin, thereby affecting the tackifying performance of the tackifying resin, and in the lithium battery protective film provided in comparative example 14, the acid value of the modified tackifying resin contained in the adhesive for preparing the adhesive layer is 3mgKOH/g, resulting in a lower peeling force of the lithium battery protective film, and in the lithium battery protective film provided in comparative example 15, the acid value of the modified tackifying resin contained in the adhesive for preparing the adhesive layer is 20mgKOH/g, resulting in an excessively high peeling force of the lithium battery protective film, and further resulting in other adverse effects in the practical application process; as can be seen from comparative example 16, the addition of the flame retardant directly to the acrylate system not only does not achieve the desired flame retardant properties, but also affects the adhesive properties of the pressure sensitive adhesive; from comparative examples 17 and 18, it is clear that cohesive monomers and modified monomers have a great influence on the adhesive properties of the acrylic esters; as is evident from comparative examples 19 and 20, the intended effect cannot be obtained by using a single initiator synthesis reaction, and the system is not suitable for the acrylate system designed according to the present invention.
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention, but these modifications or substitutions are all within the scope of the present invention.
Claims (7)
1. The flame-retardant UV curing adhesive is characterized by comprising the following raw materials in parts by weight: 80-120 parts of acrylate prepolymer, 30-40 parts of modified tackifying resin, 0.1-1 part of cross-linking agent and 1-10 parts of photoinitiator;
the modified tackifying resin is prepared by esterification reaction of rosin polybasic acid and flame-retardant polyhydric alcohol, and the acid value of the modified tackifying resin is 5-15 mgKOH/g;
the acrylate prepolymer comprises the following raw materials in parts by weight: 50-70 parts of adhesive monomer, 10-20 parts of cohesive monomer, 10-20 parts of modified monomer, 0.1-1 part of thermal initiator and 1-5 parts of chain transfer agent; the thermal initiator is formed by mixing azodiisobutyronitrile and dibenzoyl peroxide;
and, the raw materials used to prepare the acrylate prepolymer meet at least one of the following conditions: A. the viscous monomer comprises at least one of butyl acrylate, ethyl acrylate and isooctyl acrylate; B. the cohesive monomer comprises at least one of acrylonitrile, vinyl acetate, acrylamide and methyl methacrylate; C. the modified monomer comprises at least one of methacrylic acid, acrylic acid and hydroxypropyl methacrylate.
2. The flame retardant UV curable adhesive of claim 1, wherein the modified tackifying resin is prepared by:
(1) Uniformly mixing the rosin polybasic acid, the flame-retardant polyol and the catalyst to obtain a mixture, and reacting the mixture at 230-270 ℃ until the acid value of the mixture is 18-22 mgKOH/g;
(2) And (3) reacting the mixture at 190-210 ℃ until the acid value of the mixture is 5-15 mgKOH/g, thereby obtaining the modified tackifying resin.
3. The flame retardant UV curable adhesive of claim 1, wherein: the rosin polybasic acid comprises at least one of abietic acid type polybasic acid and pimaric acid type polybasic acid.
4. The flame retardant UV curable adhesive of claim 1, wherein: the flame-retardant polyol comprises at least one of halogen flame-retardant polyol, phosphorus flame-retardant polyol, nitrogen flame-retardant polyol and phosphorus-nitrogen synergistic flame-retardant polyol.
5. The flame retardant UV curable adhesive of claim 1, further comprising the following raw materials in parts by weight: 30-50 parts of reactive diluent monomer.
6. The flame retardant UV curable adhesive of claim 5, wherein: the reactive diluent monomer comprises at least one of isooctyl acrylate, isobornyl acrylate, tetraethylene glycol dimethacrylate, diethylene glycol diacrylate and glycidyl methacrylate.
7. A lithium battery protective film, characterized in that: comprising an adhesive layer prepared from the flame retardant UV curable adhesive according to any one of claims 1 to 6.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11236453A (en) * | 1998-02-20 | 1999-08-31 | Arakawa Chem Ind Co Ltd | Rosin derivative, flame-retardant plasticizer and flame-retardant plastic composition |
| CN1821333A (en) * | 2005-02-14 | 2006-08-23 | 日东电工株式会社 | Adhesive tape and adhesive composition |
| CN101891883A (en) * | 2010-06-25 | 2010-11-24 | 中国林业科学研究院林产化学工业研究所 | Rosin polyester polyol for flame-retardant rigid polyurethane foam plastic and preparation method and application thereof |
| CN110655872A (en) * | 2019-09-29 | 2020-01-07 | 湖南省和祥润新材料有限公司 | Halogen-free flame-retardant UV (ultraviolet) curing acrylate pressure-sensitive adhesive, pressure-sensitive adhesive tape and preparation method thereof |
| CN111484530A (en) * | 2020-04-22 | 2020-08-04 | 中航复材（北京）科技有限公司 | Rosin-based reactive flame-retardant curing agent and preparation method thereof |
| CN112341495A (en) * | 2020-10-27 | 2021-02-09 | 中国林业科学研究院林产化学工业研究所 | Rosinyl silicon-phosphorus synergistic flame retardant, preparation method thereof and polyurethane foam prepared from rosinyl silicon-phosphorus synergistic flame retardant |
| CN113528030A (en) * | 2020-04-17 | 2021-10-22 | 华南理工大学 | Flame-retardant UV (ultraviolet) photocuring acrylate pressure-sensitive adhesive as well as preparation method and application thereof |
-
2022
- 2022-08-30 CN CN202211046958.5A patent/CN115260948B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11236453A (en) * | 1998-02-20 | 1999-08-31 | Arakawa Chem Ind Co Ltd | Rosin derivative, flame-retardant plasticizer and flame-retardant plastic composition |
| CN1821333A (en) * | 2005-02-14 | 2006-08-23 | 日东电工株式会社 | Adhesive tape and adhesive composition |
| CN101891883A (en) * | 2010-06-25 | 2010-11-24 | 中国林业科学研究院林产化学工业研究所 | Rosin polyester polyol for flame-retardant rigid polyurethane foam plastic and preparation method and application thereof |
| CN110655872A (en) * | 2019-09-29 | 2020-01-07 | 湖南省和祥润新材料有限公司 | Halogen-free flame-retardant UV (ultraviolet) curing acrylate pressure-sensitive adhesive, pressure-sensitive adhesive tape and preparation method thereof |
| CN113528030A (en) * | 2020-04-17 | 2021-10-22 | 华南理工大学 | Flame-retardant UV (ultraviolet) photocuring acrylate pressure-sensitive adhesive as well as preparation method and application thereof |
| CN111484530A (en) * | 2020-04-22 | 2020-08-04 | 中航复材（北京）科技有限公司 | Rosin-based reactive flame-retardant curing agent and preparation method thereof |
| CN112341495A (en) * | 2020-10-27 | 2021-02-09 | 中国林业科学研究院林产化学工业研究所 | Rosinyl silicon-phosphorus synergistic flame retardant, preparation method thereof and polyurethane foam prepared from rosinyl silicon-phosphorus synergistic flame retardant |
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