CN117447913A - Easy reworking inorganic substrate surface treating agent and application thereof - Google Patents
Easy reworking inorganic substrate surface treating agent and application thereof Download PDFInfo
- Publication number
- CN117447913A CN117447913A CN202311766724.2A CN202311766724A CN117447913A CN 117447913 A CN117447913 A CN 117447913A CN 202311766724 A CN202311766724 A CN 202311766724A CN 117447913 A CN117447913 A CN 117447913A
- Authority
- CN
- China
- Prior art keywords
- inorganic substrate
- reworkable
- substrate surface
- surface treatment
- treatment agent
- 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.)
- Granted
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 63
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 35
- 229920002635 polyurethane Polymers 0.000 claims abstract description 53
- 239000004814 polyurethane Substances 0.000 claims abstract description 53
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 44
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 239000004944 Liquid Silicone Rubber Substances 0.000 claims abstract description 29
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 239000011521 glass Substances 0.000 claims abstract description 21
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims description 29
- 239000000126 substance Substances 0.000 claims description 26
- 239000012756 surface treatment agent Substances 0.000 claims description 26
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 19
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims description 17
- 229920001223 polyethylene glycol Polymers 0.000 claims description 17
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 16
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical compound OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 230000001070 adhesive effect Effects 0.000 claims description 12
- 239000012948 isocyanate Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- -1 isocyanate compound Chemical class 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- LZDXRPVSAKWYDH-UHFFFAOYSA-N 2-ethyl-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical group CCC(CO)(CO)COCC=C LZDXRPVSAKWYDH-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000570 polyether Polymers 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000741 silica gel Substances 0.000 abstract description 4
- 229910002027 silica gel Inorganic materials 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 238000011282 treatment Methods 0.000 description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 19
- 230000000694 effects Effects 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- 239000001257 hydrogen Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 13
- 238000006459 hydrosilylation reaction Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 238000009472 formulation Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000010703 silicon Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000004945 silicone rubber Substances 0.000 description 9
- 239000002987 primer (paints) Substances 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000306 component Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 125000003827 glycol group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 description 2
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 description 2
- 101000629400 Homo sapiens Mesoderm-specific transcript homolog protein Proteins 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 102100026821 Mesoderm-specific transcript homolog protein Human genes 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000008358 core component Substances 0.000 description 2
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate group Chemical group [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- INJAHHABQHQOMY-UHFFFAOYSA-N 2-(dihydroxymethyl)butanoic acid Chemical compound CCC(C(O)O)C(O)=O INJAHHABQHQOMY-UHFFFAOYSA-N 0.000 description 1
- UDVRROYKHLBOPZ-UHFFFAOYSA-N 3,3-dihydroxy-2-methylpropanoic acid Chemical compound OC(O)C(C)C(O)=O UDVRROYKHLBOPZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000002978 dental impression material Substances 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- XOSXWYQMOYSSKB-UHFFFAOYSA-M disodium;4-[4-[(4-amino-3-methyl-5-sulfophenyl)-[4-(4-sulfonatophenyl)azaniumylidenecyclohexa-2,5-dien-1-ylidene]methyl]anilino]benzenesulfonate Chemical compound [Na+].[Na+].OS(=O)(=O)C1=C(N)C(C)=CC(C(=C2C=CC(C=C2)=[NH+]C=2C=CC(=CC=2)S([O-])(=O)=O)C=2C=CC(NC=3C=CC(=CC=3)S([O-])(=O)=O)=CC=2)=C1 XOSXWYQMOYSSKB-UHFFFAOYSA-M 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 210000001503 joint Anatomy 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VUYXVWGKCKTUMF-UHFFFAOYSA-N tetratriacontaethylene glycol monomethyl ether Chemical compound COCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO VUYXVWGKCKTUMF-UHFFFAOYSA-N 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
- C08G18/675—Low-molecular-weight compounds
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
Abstract
The invention discloses an easy-reworking inorganic substrate surface treating agent and application thereof, which comprises the following components in parts by weight: 5 to 30 parts by weight of modified polyurethane polymer, 0.2 to 5 parts by weight of platinum catalyst and 20 to 95 parts by weight of organic solvent. The surface treating agent for reworking glass has high adhesion with addition type liquid silicone rubber and is easy to remove from a precise hard die, so that the recycling rate and the production efficiency of the precise hard die are improved. The invention also provides application and a using method of the reworkable glass surface treating agent in addition type liquid silica gel.
Description
Technical Field
The invention relates to the technical field of inorganic substrate surface bonding treatment agents, in particular to an easy-reworking inorganic substrate surface treatment agent and application thereof.
Background
The addition type liquid silicone rubber is a silicone rubber developed in recent years, which is based on polysiloxane containing vinyl, takes oligosiloxane containing silicon hydrogen bond as a vulcanization crosslinking agent, and forms an elastomer with a network structure through addition reaction under the action of platinum group metal and a complex thereof as a catalyst. In the preparation of such addition-type liquid silicone rubber, manufacturers pay special attention to the molar ratio of the silicon-hydrogen bond on the oligosiloxane and the vinyl content on the polysiloxane in the reactant, and only by matching them, the silicone rubber with the best performance can be obtained. In practical production, the vinyl is fully utilized and the loss of the silicon hydrogen is considered, and the silicon hydrogen groups are slightly excessive, so that in the industrial production, the finished product of the addition type liquid silicon rubber generally contains a small amount of residual (0.1% -0.2%) of oligosiloxane containing silicon hydrogen bonds besides the silicon rubber, and the silicon hydrogen bonds on the oligosiloxane always exist in the finished product.
In view of the low surface energy characteristic of addition type liquid silicone rubber, the addition type liquid silicone rubber is not sticky with most materials, and is particularly suitable for special applications such as impressions, such as dental impression materials, cultural relics, artware impression materials and the like. However, such silicone rubber is too soft, requires the use of a precision hard mold to provide support during stamping, and requires good adhesion between the mold surface and the silicone rubber. Currently, there are three main methods for improving the adhesion between silicone rubber and various mold substrates: (1) treating the surface of the substrate with a primer; (2) The cohesiveness is enhanced by changing the molecular structure of the base adhesive; (3) the adhesion is improved by adding a tackifier. The actual production process of the method (2) is complex, the cost is relatively high, and industrialization is difficult to realize; the method (3) has the problems of poor compatibility of the tackifier and the silicone rubber, easy poisoning of the catalyst and the like, so the method (1) is still mainly used at present. Specifically, the surface treatment agent is coated on the surface of the precise hard die, and then the addition type liquid silicone rubber is coated on the surface of the surface treatment agent, so that the silicone rubber can generate high bonding strength with the precise hard die.
However, some precise hard mold substrates are very costly and require repeated recycling. When the primer is used for treating the surface of the die base material to improve the cohesiveness between the silicon rubber and various die base materials, after the stamping is finished, the residual silicon rubber and primer on the surface of the die base material are required to be degraded and removed by a solvent of strong acid or strong alkali, so that the aim of repeatedly using the precise hard die is fulfilled. However, this solution for removing the solvent with strong acid or alkali has the following problems: on one hand, strong acid or alkali can generate corrosion damage to the die to a certain extent, and on the other hand, the die needs to be cleaned with clean solvent for multiple times, so that the production efficiency is low. Therefore, it is significant to develop a surface treatment agent for addition type liquid silicone rubber which has high adhesion and is easy to rework on the surface of an inorganic substrate.
Disclosure of Invention
In order to solve the technical problems, the invention provides the surface treating agent for the easily reworked inorganic substrate and the application thereof, wherein the surface treating agent has high cohesive force with the addition type liquid silicone rubber and is easy to remove from the surface of the inorganic substrate, and the recycling rate and the production efficiency of the precise hard die are improved.
The technical scheme of the invention is as follows:
in order to achieve the above object, the present invention provides an easy reworking inorganic substrate surface treatment agent comprising the following components in parts by weight: 5 to 30 parts by weight of modified polyurethane polymer, 0.2 to 5 parts by weight of platinum catalyst and 20 to 95 parts by weight of organic solvent.
One of the most core components in the surface treating agent is a modified polyurethane polymer, and the molecular main chain structure of the modified polyurethane polymer simultaneously comprises repeating unit structures of a chemical formula (I), a chemical formula (II) and a chemical formula (III), and the modified polyurethane polymer is shown as follows:
the chemical general formula (I) is；
The chemical general formula (II) is；
The chemical general formula (III) is；
Wherein the molar ratio of the chemical formula I to the chemical formula II to the chemical formula III is m to p, wherein m is an integer of 10-40, n is an integer of 1-10, and p is an integer of 1-10;
R 1 is thatWherein b is 35-50;
R 2 is thatWherein R is 4 Is->、/>；
R 3 Is that；
The modified polyurethane polymer is formed by reacting polyether glycol and a difunctional isocyanate compound to form a first polyurethane prepolymer with two end groups of isocyanate groups, then chain-extending the first polyurethane prepolymer by using a dihydroxycarboxylic acid monomer to form a second polyurethane prepolymer with two end groups of isocyanate groups, and finally further chain-extending and end-capping the second polyurethane prepolymer by using a dihydroxyallyl monomer. The weight average molecular weight of the modified polyurethane polymer is 5000-20000.
Wherein the difunctional isocyanate can be at least one of toluene diisocyanate, 1, 6-hexamethylene diisocyanate and diphenylmethane diisocyanate, preferably diphenylmethane diisocyanate (MDI).
Wherein the polyether glycol is polyethylene glycol, two ends of the polyethylene glycol are hydroxyl (-OH), the hydroxyl can react with isocyanate (-NCO) of the difunctional isocyanate compound to generate urethane groups, and the urethane groups can introduce polyethylene glycol chain segments into the main chain segments of the modified polyurethane polymer to provide a main resin structure; because the polyethylene glycol chain segment is easy to absorb water and expand, the modified polyurethane polymer has the characteristic of easy water absorption and expansion. The fact that the two end groups of the first polyurethane prepolymer are-NCO groups can be achieved by controlling the molar ratio of-OH in the polyether glycol to-NCO groups in the difunctional isocyanate, and the control scheme is a conventional technical scheme in the art, as described in CN101747487B, and is not repeated in the application. In addition, the reaction of hydroxyl and isocyanate groups can be catalyzed by adopting organic zinc, organic bismuth and amine catalysts, for example, dibutyl tin dilaurate, stannous octoate or/and triethylamine can be used as the catalysts, the dosage of the catalyst can be 0.01-0.2% of the total mass of polyether glycol and difunctional isocyanate, and the reaction conditions and parameters are all conventional technical schemes in the field and are not repeated in the application.
The dihydroxycarboxylic acid monomer may be at least one of 2, 2-dihydroxymethylpropanoic acid, 2-dihydroxymethylbutanoic acid, preferably 2, 2-dihydroxymethylpropanoic acid (DMPA). The hydroxyl groups in the dihydroxycarboxylic acid monomer can react with isocyanate groups (-NCO) at both ends of the first polyurethane prepolymer, and the carboxyl groups in the dihydroxycarboxylic acid monomer are more reactive than the carboxyl groups (-COOH) and the cyanate groups (-NCO) because of the large steric hindrance relative to the hydroxyl groups on the one hand, and the hydroxyl groups (-OH) are more reactive than the carboxyl groups (-COOH) and the cyanate groups (-NCO) on the other hand, so that the hydroxyl groups in the dihydroxycarboxylic acid monomer react with-NCO while the carboxyl groups of the dihydroxycarboxylic acid monomer remain when the dihydroxycarboxylic acid monomer reacts with the first polyurethane prepolymer. On the one hand, the process reaction utilizes the dihydroxycarboxylic acid monomer to chain-extend the first polyurethane prepolymer, so that the molecular weight of the first polyurethane prepolymer is obviously increased, and the cohesive energy of the treating agent is improved to increase the viscosity of the surface treating agent system; on the other hand, carboxyl groups are introduced into the molecular main chain of the modified polyurethane polymer. The carboxyl has strong polarity, and can form hydrogen bonding action with the surface of an inorganic substrate, especially glass, so that the modified polyurethane polymer has excellent adhesive force action with the surface of the inorganic substrate; in addition, the carboxyl has strong water absorbability, so that the modified polyurethane of the invention is easy to expand after absorbing water, and further, the surface treating agent of the invention can achieve good adhesive force in actual use and is easy to remove from the surface of a substrate, and the reworking effect of the surface treating agent of the invention is further improved. The two end groups of the second polyurethane prepolymer are-NCO groups, and the control scheme is a conventional technical scheme in the field and is not repeated in the application. In addition, the reaction conditions, the catalytic conditions and the like of the hydroxyl and the isocyanate groups are all conventional technical schemes in the field, and are not repeated in the application.
The dihydroxyallyl monomer may be trimethylolpropane monoallyl ether (TMPME). The dihydroxyl allyl monomer reacts with isocyanate groups at two ends of the second polyurethane prepolymer by utilizing hydroxyl groups on the dihydroxyl allyl monomer, and allyl groups are introduced into a modified polyurethane polymer main chain, so that the modified polyurethane main chain contains allyl groups. The allyl in the modified polyurethane polymer can react with the residual oligosiloxane containing silicon-hydrogen bond in the addition type liquid silicone rubber through the catalysis of the platinum catalyst to form an interface bridge, and the addition type liquid silicone rubber and the surface treating agent are tightly combined together through the action of the interface bridge. The terminal group of the final modified polyurethane polymer is hydroxyl by controlling the molar ratio of-OH in the dihydroxyallyl monomer to-NCO group in the second polyurethane prepolymer, and the control method is a conventional technical scheme in the field and is not repeated in the application. In addition, the reaction conditions, the catalytic conditions and the like of the hydroxyl and the isocyanate groups are all conventional technical schemes in the field, and are not repeated in the application.
The second core component in the reworkable inorganic substrate surface treating agent is a platinum catalyst, and the platinum catalyst has the main function of catalyzing the silicon-hydrogen addition reaction between carbon-carbon double bonds in allyl groups and residual silicon-hydrogen bonds in addition type liquid silica gel. The platinum-series catalyst used in the invention is an isopropanol solution of chloroplatinic acid, wherein the content of platinum is 0.5-1.5wt.%. The hydrosilylation reaction is a reaction in which an organic compound containing a silicon hydrogen bond and a compound containing an unsaturated bond are added under certain conditions to form an organic silicide. Unsaturated bond in hydrosilylation reaction, which can be carbon-carbonDouble bonds, carbon-carbon triple bonds, carbon-oxygen double bonds, hydrocarbon double bonds, and the like. The hydrosilylation reaction generally employs three methods: 1. the silicon-containing hydrogen bond compound is directly reacted with alkene or alkyne at 300 ℃ and 100-500 atm, the method involves high temperature and high pressure, and the obtained product is mostly oligomer. 2. The problem with this method is that the self-polymerization of alkene or alkyne may occur while the hydrosilylation reaction occurs by means of free radical hydrosilylation reaction initiated by ultraviolet rays, gamma rays, organic peroxides, or the like. 3. The reaction of the silicon and hydrogen is catalyzed by transition metals (Pt, pd, rh, etc.) and complexes thereof, and the method has mild reaction conditions and can be generally carried out at room temperature or medium temperature. The invention adopts a third method to carry out hydrosilylation reaction, specifically, chloroplatinic acid (H) 2 PtCl 6 ﹒6H 2 O) is taken as a catalyst for example, tetravalent platinum firstly reacts with olefin, is reduced to zero-valent platinum and generates a platinum-alkene complex, then a compound containing silicon-hydrogen bond is added to platinum of the platinum-alkene complex, pt-C bond and C-H bond are produced through pi-sigma rearrangement insertion reaction, then silane which is a product of the hydrosilylation reaction is generated through reduction elimination, and the reduced platinum-alkene complex can be recycled continuously. The control scheme is a conventional technical scheme in the art, and is not described in detail in this application.
In addition, the reworkable inorganic substrate surface treating agent also comprises an organic solvent, wherein the organic solvent is at least one of aliphatic hydrocarbon organic solvent, alcohol organic solvent and ester organic solvent. Wherein the aliphatic hydrocarbon organic solvent is at least one of pentane, hexane and octane; the alcohol organic solvent is at least one of methanol, ethanol, isopropanol, n-butanol and n-amyl alcohol; the ester organic solvent is at least one of methyl formate, ethyl formate, methyl acetate, ethyl acetate, n-propyl acetate, ethyl propionate and ethyl butyrate.
The invention also provides application of the reworkable inorganic substrate surface treating agent, which can be used as a primer for covering the surface of an inorganic substrate by adding liquid silicone rubber, wherein the inorganic substrate is one of glass, ceramic and metal. The more specific application method is as follows; firstly, cleaning and drying a die substrate, coating the surface treatment agent of the easily reworked inorganic substrate on the surface of the die substrate, drying, taking out, cooling to room temperature, coating the area coated with the surface treatment agent of the easily reworked inorganic substrate with addition type liquid silicone rubber, and standing for 8-15min at the temperature of 100-160 ℃.
The beneficial technical effects of the invention are as follows: firstly, the modified polyurethane polymer of the surface treating agent of the easy reworking inorganic substrate has polyethylene glycol chain segments which absorb water and are easy to expand, so that the surface treating agent and the silicon rubber bonded with the surface treating agent are easy to peel off from the substrate of the die, and the easy reworking effect of the die is achieved; secondly, the modified polyurethane molecular chain contains abundant and uniformly distributed allyl and carboxyl, the carboxyl has strong water absorption expansion capability, and can be easily removed from a precise hard die while achieving good adhesion with the die surface of an inorganic substrate (such as glass), so that the reworkability effect of the surface treating agent is further improved, and particularly, on the atomic level of the glass substrate, oxygen atoms among inorganic chemical components of the glass allow hydrogen atoms of the carboxyl in the modified polyurethane molecular chain to form hydrogen bonds, thereby promoting chemical adsorption. Finally, the allyl groups which are rich in the modified polyurethane molecular chains and uniformly distributed carry out hydrosilylation reaction with the hydrosilylation groups in the addition type liquid silicone rubber system under the catalysis of the platinum catalyst, so that the surface treating agent has high cohesive force on the addition type liquid silicone rubber.
The invention also provides application and a use method of the reworkable inorganic substrate surface treating agent on the addition type liquid silica gel.
Detailed Description
In order that the manner in which the above recited features of the present invention are attained and can be understood in detail, a more particular description of the invention, briefly summarized below, may be had by reference to specific embodiments thereof which are illustrated in the appended drawings. The instruments, materials and reagents used in the following examples are all available by conventional commercial means.
The modified polyurethane of the present invention is prepared from the following raw materials including polyethylene glycol MW1000 (Korean Letian PEG-1000), polyethylene glycol MW1500 (Korean Letian PEG-1500), diphenylmethane diisocyanate MDI (Letai Wanhua), toluene diisocyanate TDI (Letai Wanhua), 2-dihydroxymethylpropanoic acid DMPA (Aba Ding Shiji), 2, 3-dihydroxysuccinic acid DMBA (Aba Ding Shiji), trimethylolpropane allyl ether TMPME (Aba Ding Shiji), borchi Kat 315 (Borchers Co., ltd.), and ethyl acetate (Aba Ding Shiji).
Examples 1 to 10 are the amounts of the respective raw materials used for the preparation of the modified polyurethane of the present invention, and comparative examples 1 to 2 are the amounts of the respective raw materials used for the modified polyurethane for the comparative example of the present invention.
Wherein: the amounts of PEG1 (MW 1000), PEG2 (MW 1500), DMPA, DMBA, TMPME, MDI, TDI in table 1 were molar ratios of seven; the amounts of the organic bismuth and the ethyl acetate are respectively weight percentages of the total weight of the modified polyurethane raw material reaction system of the Borchi Kat 315.
In Table 1, 2mmol/g represents the molar concentration of hydroxyl groups in PEG1, MW1000, 1.33mmol/g represents the molar concentration of hydroxyl groups in PEG2, MW 1500.
The modified polyurethane polymers used in the examples were prepared according to the raw material formulations and amounts shown in Table 1, wherein the specific operations of examples 1 to 10 were as follows:
step 1: each raw material formulation was weighed and polyethylene glycol was vacuum dehydrated for 1-1.5h.
Step 2: and (2) dissolving the formula amount of difunctional isocyanate compound in part of organic solvent, placing the mixture in a reaction vessel, then dropwise adding the mixed solution of the formula amount of polyethylene glycol in a molten state and the formula amount of Borchi Kat 315 catalyst while stirring, reacting for 1-2h at 50+/-5 ℃, heating to 80 ℃, and continuing to react for 1-1.5h to obtain the first polyurethane prepolymer.
Step 3: after the dried dihydroxycarboxylic acid monomer powder is dissolved in a proper amount of organic solvent, the dried dihydroxycarboxylic acid monomer powder is added into the first polyurethane prepolymer in a continuously stirring state in batches, and the stirring reaction is continued for 1 to 1.5 hours at the temperature of 75+/-5 ℃ to obtain the second polyurethane prepolymer, and a proper amount of organic solvent is added in the reaction process to regulate the viscosity of the system.
Step 4: and (3) dropwise adding the dihydroxyl allyl monomer into the second polyurethane prepolymer in a continuously stirring state, continuously stirring and reacting for 1-1.5h at 75+/-5 ℃ to obtain the modified polyurethane polymer, and adding a proper amount of organic solvent in the reaction process to regulate the viscosity of the system. The modified polyurethane polymers A to J of the present invention were prepared in Table 1 in accordance with examples 1 to 10, respectively.
Comparative example 1: the modified polyurethane polymers used in comparative examples were prepared according to the raw material formulation and the amounts of comparative example 1 in table 1, in which no bishydroxycarboxylic acid type monomer was used, and only polyethylene glycol and bishydroxyallyl type monomer were used as functional monomers.
Step 1: each raw material formulation was weighed and polyethylene glycol was vacuum dehydrated for 1-1.5h.
Step 2: and (2) dissolving the formula amount of difunctional isocyanate compound in part of organic solvent, placing the mixture in a reaction vessel, then dropwise adding the mixed solution of the formula amount of polyethylene glycol in a molten state and the formula amount of Borchi Kat 315 catalyst while stirring, reacting for 1-2h at 50+/-5 ℃, heating to 80 ℃, and continuing to react for 1-1.5h to obtain the first polyurethane prepolymer.
Step 3: the dihydroxyl allyl monomer is dripped into the first polyurethane prepolymer in a continuously stirring state, the stirring reaction is continued for 1 to 1.5 hours at the temperature of 75+/-5 ℃ to obtain the modified polyurethane polymer, and a proper amount of organic solvent is added in the reaction process to regulate the viscosity of the system. Comparative example 1 in Table 1 corresponds to the modified polyurethane polymer A'.
Comparative example 2: the modified polyurethane polymers used in the comparative examples were prepared according to the raw material formulation and the amounts of comparative example 2 in table 1, in which no dihydroxyallyl monomers were used and only polyethylene glycol and dihydroxycarboxylic acid monomers were used as functional monomers.
Step 1: each raw material formulation was weighed and polyethylene glycol was vacuum dehydrated for 1-1.5h.
Step 2: and (2) dissolving the formula amount of difunctional isocyanate compound in part of organic solvent, placing the mixture in a reaction vessel, then dropwise adding the mixed solution of the formula amount of polyethylene glycol in a molten state and the formula amount of Borchi Kat 315 catalyst while stirring, reacting for 1-2h at 50+/-5 ℃, heating to 80 ℃, and continuing to react for 1-1.5h to obtain the first polyurethane prepolymer.
Step 3: after the dried dihydroxycarboxylic acid monomer powder is dissolved in a proper amount of organic solvent, the dried dihydroxycarboxylic acid monomer powder is added into the first polyurethane prepolymer in a continuously stirring state in batches, and the stirring reaction is continued for 1 to 1.5 hours at the temperature of 75+/-5 ℃ to obtain the modified polyurethane prepolymer, and a proper amount of organic solvent is added in the reaction process to regulate the viscosity of the system. Comparative example 2 in Table 1 corresponds to the modified polyurethane polymer B'.
Examples 11 to 19 in Table 2 below are the amounts of the respective raw materials used for the preparation of the reworkable inorganic substrate surface treatment agent of the present invention, and comparative examples 3 to 4 are the amounts of the respective raw materials used for the preparation of the surface treatment agent using the polyurethanes obtained by comparative examples 1 to 2 in Table 1.
Examples 11, 12, 13 in Table 2 are primer treatments of the present invention prepared using modified polyurethane A+catalyst+solvent, respectively. Wherein, the dosages of the modified polyurethane A, the catalyst and the solvent are used as variables to determine the optimal weight part ratio of each component of the primer coating agent.
Examples 14 to 19 in Table 2 are primer treatments of the present invention prepared by using the modified polymers B to G, the catalyst and the solvent, respectively, wherein the weight parts are compared based on the amount of example 12.
Comparative examples 3-4 in Table 2 are comparative primer treatments prepared using modified polyurethanes A 'and B', respectively, catalyst and solvent, respectively, wherein the parts by weight are compared based on the amount of example 12.
The surface treatment agents for the easily reworkable inorganic substrate of the present invention were prepared according to the raw material formulation and the amounts shown in Table 2, and the above materials were sequentially weighed and stirred at room temperature at 500r/min for 25 minutes, thus obtaining the surface treatment agents for each of examples 11 to 19 of the present invention and comparative examples 3 to 4.
Comparative examples 5-7 are prior art inorganic substrate surface treatment formulations.
According to the raw material formulation and the amount in Table 3, the inorganic substrate surface treating agent is prepared, the materials are weighed in sequence, and stirred for 25min at room temperature of 500r/min, thus obtaining the surface treating agent of each comparative example.
Wherein, the inorganic substrate is one of glass, ceramic and metal, and the invention takes the glass substrate as an experimental object.
Table 4 below shows the results of performance tests of the adhesive effect and reworkable effect of the inorganic substrate surface treatments of examples 11 to 19 and comparative examples 3 to 7 of the present invention. The test methods used therein are as follows.
Testing and preparing a sample: the test die base material is glass, firstly, 50mm 150mm 5mm glass sample plates are cleaned by absolute ethyl alcohol, a surface treating agent is coated on the surface of the glass sample plates by adopting a piezoelectric jet valve plate, and the coating amount of the surface treating agent is 0.5g each time; then placing the mixture into an oven for baking at 120 ℃ for 20min, taking out, cooling to room temperature, placing addition type liquid silicone rubber (STARSIL LSR 8600 of China blue Star (group) Co., ltd.) on the area of 50mm between the ends of two long strip samples, bonding the mixture together in a butt joint mode, standing for 3min at 150 ℃ after pressing, and cooling.
Sample adhesion test: under the conditions of 180 DEG peeling angle and peeling speed of 5mm/s, stretching two sides of two bonded templates obtained by the test sample by a universal tensile machine, recording cohesive failure conditions of the surfaces when the test sample is damaged, namely recording cohesive failure indexes by residue on 50mm of area, and recording to be 0% if no residue exists, namely the average residual adhesive area percentage on the templates, wherein the broken part is between a base material and silicon rubber, and the bonding effect is the worst; if all residues are recorded as 100%, the damage positions are all cohesive damage in the silicone rubber, and the bonding effect is optimal.
Sample easy reworking effect test: in each of the examples and comparative examples, two bonded panels were obtained by the test sample preparation described above, and after immersing in pure water at 60℃for 60 minutes, the two bonded panels were stretched by a universal tensile machine and the peel force was recorded.
Table 4 shows the results of performance analysis of the adhesion effect and reworkable effect of the reworkable inorganic substrate surface treatments of examples 11-19 and comparative examples 3-7 of the present invention.
The adhesive has good adhesive effect, namely the average residual adhesive area percentage is high, and the stripping force before water treatment is large. The reworking effect is easy, namely, the stripping force is small after water treatment, the glass cleaning degree is high, and no residue exists. As can be seen from a comparison of the experimental data of examples 11 to 19 and comparative examples 3 to 7 in Table 4, the reworkable inorganic substrate surface treating agents of examples 11 to 19 were excellent in both adhesion and reworkable effect when used, while the reworkable inorganic substrate surface treating agents of comparative examples 3 to 7 were not compatible with both high adhesion and reworkability.
As is clear from the test results in Table 4, the adhesive property and the reworkable property of example 12 are the best, and the test results of example 11 and examples 13 to 19 are different in relation to the composition system and the content in the composition system, i.e., example 12 is the optimum formulation of the present invention, and the following analyses are all described based on example 12. Specifically, the average residual gum area percentage of example 12 is 95.0%, and the peel force before water treatment is 20N, which shows that a strong adhesive force exists between the example 12 and the addition type liquid silicone rubber, and in this regard, since example 12 includes modified polyurethane a, a catalyst (chloroplatinic acid isopropyl alcohol solution, pt content is 1%) and a solvent, the modified polyurethane a contains abundant and uniformly distributed allyl groups in molecular chains, and the allyl groups undergo hydrosilylation reaction with the silicon hydrogen groups in the addition type liquid silicone rubber system under the catalysis of a platinum catalyst, so that example 12 has a high adhesive force to the addition type liquid silicone rubber.
After the water treatment, the peeling force of the example 12 is as low as 0.5N, the glass is clean, and no residue exists, namely the example 12 and the liquid silicone rubber bonded with the example are easy to peel off from the die base material, and the effect of easy reworking of the die is achieved. In contrast, the modified polyurethane a polymer in example 12 has a polyethylene glycol segment which absorbs water and is easy to expand, so that the modified polyurethane a polymer and the silicone rubber bonded with the surface treatment agent are easy to peel off from the mold base material, and the mold reworking effect is achieved; on the other hand, the modified polyurethane A molecular chain contains rich and uniformly distributed carboxyl groups, the carboxyl groups have strong water absorption expansion capacity, and can be easily removed from a precise hard die while achieving good adhesion with the die surface of an inorganic substrate (such as glass), so that the easy reworking effect of the surface treatment agent is further improved, and on the atomic level of the glass substrate, oxygen atoms among inorganic chemical components of the glass allow hydrogen atoms of the carboxyl groups in the modified polyurethane molecular chain to form hydrogen bonds, thereby promoting chemical adsorption. The hydrogen bonds are easily broken when water is applied, and thus are easily removed from the glass substrate after water treatment.
As is clear from the test results in Table 4, the average residual rubber area percentage of comparative example 3 was 91.2%, and the peel force before water treatment was 20N, that is, there was a strong adhesion between comparative example 3 and the addition type liquid silicone rubber, for which, since comparative example 3 includes modified polyurethane A ', catalyst (chloroplatinic acid isopropyl alcohol solution, pt content 1%) and solvent, since the modified polyurethane A' contains abundant and uniformly distributed allyl groups in the molecular chain, a strong adhesion was formed between comparative example 3 and the addition type liquid silicone rubber as in example 12. The average residual rubber area percentage in comparative example 4 was 12%, and the peel force before water treatment was 6N, indicating poor adhesion between comparative example 4 and the addition type liquid silicone rubber, whereas comparative example 4 includes modified polyurethane B ', a catalyst (chloroplatinic acid isopropyl alcohol solution, pt content 1%) and a solvent, in which no allyl group was contained in the main segment of modified polyurethane B', and therefore no hydrosilylation reaction could be performed between comparative example 4 and the addition type liquid silicone rubber, and good adhesion could not be formed therebetween.
Comparative example 3 and comparative example 4 were subjected to water treatment with a peel force of 15N after water treatment and residual glass surface, which means that comparative example 3 was relatively difficult to peel off from the mold base material with the addition type liquid silicone rubber bonded thereto after water treatment, and comparative example 4 was subjected to water treatment with a peel force of 0.5N and residual glass surface was not found, which means that comparative example 4 was easily peeled off from the mold base material with the addition type liquid silicone rubber bonded thereto after water treatment. In contrast, the main chain segment of the modified polyurethane B' in comparative example 4 has abundant and uniformly distributed carboxyl groups, and the carboxyl groups have strong water swelling capacity, so that the carboxyl groups are easily peeled from the mold after water treatment, as in the modified polyurethane A in example 12. In contrast, the modified polyurethane A' molecule segment in comparative example 3 does not contain carboxyl groups, and thus does not have an effect of easily peeling from the substrate after water treatment. In summary, comparative examples 3 and 4 do not combine both high adhesion and easy reworkability.
The coupling agent is a substance with an amphoteric structure, one part of groups in the molecules of the substance can react with chemical groups on the inorganic surface to form chemical bonding, and the other part of groups have the property of being organophilic and can chemically react with organic molecules or generate stronger intermolecular action, so that two materials with distinct properties are firmly combined, and the interface action between the two substances can be obviously improved. In comparative examples 5 to 7, allyltriethoxysilane, glycidoxypropyl trimethoxysilane was used as a silane-based coupling agent, and tetra-n-butyl titanate was used as a titanate-based coupling agent. As can be seen from the test data in Table 4, none of comparative examples 5 to 7 provides a combination of both high adhesion and easy reworkability. Specifically, the average residual gum area percentage of comparative example 6 was 10%, and the peel force before water treatment was 5N, and the average residual gum area percentage, the peel force before water treatment, were higher in comparative example 5 and comparative example 7 than in comparative example 6. In contrast, comparative example 6 was inferior in adhesion to the addition type liquid silica gel due to the lack of the allyl group-containing silane coupling agent. Although comparative examples 5 and 7 have better adhesion with addition type liquid silicone rubber, the peel force after water treatment is still much higher than that of examples 11 to 19, i.e., comparative examples 5 and 7 have poor reworkability.
In addition, the application method of the reworkable inorganic substrate surface treating agent for the addition type liquid silicone rubber comprises the following steps:
firstly, cleaning a die substrate by using absolute ethyl alcohol, and coating a layer of the surface treatment agent for the easily reworked inorganic substrate on the surface of the die substrate; then placing the mixture into an oven at 120 ℃, preserving heat for 20min, taking out, cooling to room temperature, coating the area of the area coated with the reworkable inorganic substrate surface treating agent with the reworkable area coated with the reworkable area, standing the mixture at 150 ℃ for 8min, and cooling.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, and it should be noted that it is possible for those skilled in the art to make several improvements and modifications without departing from the technical principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.
Claims (13)
1. An easy reworking inorganic substrate surface treating agent, which is characterized in that: the adhesive comprises the following components in parts by weight: 5 to 30 weight portions of modified polyurethane polymer, 0.2 to 5 weight portions of platinum catalyst and 20 to 95 weight portions of organic solvent;
wherein the main chain structure of the modified polyurethane polymer comprises the repeating unit structures of the chemical formula (I), the chemical formula (II) and the chemical formula (III) at the same time, and the repeating unit structures are shown as follows:
the chemical general formula (I) is:；
the chemical general formula (II) is:；
the chemical general formula (III) is:；
wherein the molar ratio of the chemical formula I to the chemical formula II to the chemical formula III is m to p, wherein m is an integer of 10-40, n is an integer of 1-10, and p is an integer of 1-10;
R 1 is thatWherein b is 35-50;
R 2 is thatWherein R is 4 Is->、/>；
R 3 Is that；
Wherein the organic solvent is at least one of aliphatic hydrocarbon organic solvent, alcohol organic solvent and ester organic solvent.
2. The reworkable inorganic substrate surface treatment agent according to claim 1, wherein: the weight average molecular weight of the modified polyurethane polymer is 5000-20000.
3. The reworkable inorganic substrate surface treatment agent according to claim 1, wherein: the platinum-series catalyst is an isopropanol solution of chloroplatinic acid, wherein the content of platinum is 0.5-1.5wt.%.
4. The reworkable inorganic substrate surface treatment agent according to claim 1, wherein: the modified polyurethane polymer is formed by reacting polyether glycol with a difunctional isocyanate compound to form a first polyurethane prepolymer, then chain-extending the first polyurethane prepolymer through a dihydroxyl carboxylic acid monomer to form a second polyurethane prepolymer, and finally further chain-extending and end-capping the second polyurethane prepolymer through a dihydroxyl allyl monomer.
5. The reworkable inorganic substrate surface treatment agent according to claim 4, wherein: the difunctional isocyanate compound is at least one of toluene diisocyanate, 1, 6-hexamethylene diisocyanate and diphenylmethane diisocyanate.
6. The reworkable inorganic substrate surface treatment agent according to claim 4, wherein: the dihydroxycarboxylic acid monomer is at least one of 2, 2-dihydroxymethylpropanoic acid and 2, 2-dihydroxymethylbutanoic acid.
7. The reworkable inorganic substrate surface treatment agent according to claim 4, wherein: the dihydroxyallyl monomer is trimethylolpropane monoallyl ether.
8. The reworkable inorganic substrate surface treatment agent according to claim 4, wherein: the polyether glycol is polyethylene glycol.
9. The reworkable inorganic substrate surface treatment agent according to claim 1, wherein: the aliphatic hydrocarbon organic solvent is at least one of pentane, hexane and octane.
10. The reworkable inorganic substrate surface treatment agent according to claim 1, wherein: the alcohol organic solvent is at least one of methanol, ethanol, isopropanol, n-butanol and n-amyl alcohol.
11. The reworkable inorganic substrate surface treatment agent according to claim 1, wherein: the ester organic solvent is at least one of methyl formate, ethyl formate, methyl acetate, ethyl acetate, n-propyl acetate, ethyl propionate and ethyl butyrate.
12. Use of a reworkable inorganic substrate surface treating agent according to any one of claims 1-11, wherein: the primer is used as a primer when the surface of an inorganic substrate is covered by the addition type liquid silicone rubber, wherein the inorganic substrate is one of glass, ceramic and metal.
13. The use of a reworkable inorganic substrate surface treating agent as claimed in claim 12, wherein: firstly cleaning and drying a mould base material, coating the surface treatment agent for the easily reworkable inorganic base material according to any one of claims 1-10 on the surface of the mould base material, drying, taking out, cooling to room temperature, coating addition type liquid silicone rubber on the area coated with the surface treatment agent for the easily reworkable inorganic base material, and standing for 8-15min at 100-160 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311766724.2A CN117447913B (en) | 2023-12-21 | 2023-12-21 | Easy reworking inorganic substrate surface treating agent and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311766724.2A CN117447913B (en) | 2023-12-21 | 2023-12-21 | Easy reworking inorganic substrate surface treating agent and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117447913A true CN117447913A (en) | 2024-01-26 |
| CN117447913B CN117447913B (en) | 2024-03-01 |
Family
ID=89583985
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311766724.2A Active CN117447913B (en) | 2023-12-21 | 2023-12-21 | Easy reworking inorganic substrate surface treating agent and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117447913B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030191231A1 (en) * | 2000-10-14 | 2003-10-09 | Emillio Martin | Aqueous polyester coating compositions |
| KR20040104132A (en) * | 2003-06-03 | 2004-12-10 | 에스케이케미칼주식회사 | Water soluble polyurethane resin for coating, the method for preparing the same and article thereof |
| CN115678415A (en) * | 2022-10-28 | 2023-02-03 | 上谷新材料(苏州)有限公司 | Water-resistant non-silicon surface treating agent and preparation method thereof |
| CN115895440A (en) * | 2022-10-28 | 2023-04-04 | 上谷新材料(苏州)有限公司 | Easy-reworking rubber surface treating agent and preparation method thereof |
-
2023
- 2023-12-21 CN CN202311766724.2A patent/CN117447913B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030191231A1 (en) * | 2000-10-14 | 2003-10-09 | Emillio Martin | Aqueous polyester coating compositions |
| KR20040104132A (en) * | 2003-06-03 | 2004-12-10 | 에스케이케미칼주식회사 | Water soluble polyurethane resin for coating, the method for preparing the same and article thereof |
| CN115678415A (en) * | 2022-10-28 | 2023-02-03 | 上谷新材料(苏州)有限公司 | Water-resistant non-silicon surface treating agent and preparation method thereof |
| CN115895440A (en) * | 2022-10-28 | 2023-04-04 | 上谷新材料(苏州)有限公司 | Easy-reworking rubber surface treating agent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117447913B (en) | 2024-03-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101359995B1 (en) | Silylated polymer derived from butadiene and solvent- resistant pressure sensitive adhesive composition containing same | |
| JP3622169B2 (en) | A hot melt adhesive comprising an isocyanate prepolymer with a low free monomer content and a low oligomer content | |
| EP1888663B1 (en) | Crosslinkable silane-terminated polymer and sealant composition made with same | |
| CN112143442B (en) | Water-resistant high-temperature-resistant mixed acrylate flexible ultraviolet curing adhesive and preparation method thereof | |
| CN86103179A (en) | The preparation method of the polyether polyols with reduced unsaturation of miosture curable and application thereof | |
| KR20100089078A (en) | Two-part moisture-curable resin composition and adhesive, sealant and coating compositions based thereon | |
| JPS5829818A (en) | Silicon-end polyurethane polymer | |
| CN110591521B (en) | Primer for bonding automobile composite material and preparation method thereof | |
| EP3052568A2 (en) | Fluid resistant, high performance reactive hot melt sealant and/or adhesive compositions | |
| CN117447913B (en) | Easy reworking inorganic substrate surface treating agent and application thereof | |
| CN113214773B (en) | High-temperature-resistant heat-insulating polyurethane sealant and preparation method thereof | |
| CN111675961B (en) | Photocuring polyurethane primer and preparation method thereof | |
| CN113337220A (en) | High-resilience ultraviolet light and moisture dual-curing hot melt adhesive and preparation method thereof | |
| CN1100838C (en) | Organosilicon modified polyurethane paint | |
| CN115678415A (en) | Water-resistant non-silicon surface treating agent and preparation method thereof | |
| CN115322670B (en) | Polyurethane glass primer and preparation method thereof | |
| CN116606415A (en) | Comb-type silane end-capped polyurethane polymer resin, and preparation method and application thereof | |
| CN115895440A (en) | Easy-reworking rubber surface treating agent and preparation method thereof | |
| WO2023160197A1 (en) | Single-component organic silicon-modified sealant capable of being rapidly deep-layer cured at low temperature, and preparation method therefor | |
| CN113801622A (en) | Foaming structure with flame-retardant automotive interior sealing function and preparation method thereof | |
| CN114524927A (en) | Preparation method of cardanol bio-based polyol and application of cardanol bio-based polyol in flexible packaging adhesive | |
| CN111349416A (en) | Reactive polyurethane hot melt adhesive for automotive interior and preparation method thereof | |
| JPS606747A (en) | Room temperature-curable composition | |
| CN116606592B (en) | UV (ultraviolet) light-cured waterborne polyurethane primer for vehicles and preparation method thereof | |
| CN116082935B (en) | Waterproof coating composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |