CN113637447A - High-humidity-heat-resistance polyurethane adhesive, high-humidity-heat-resistance polyurethane protective film and preparation method of high-humidity-heat-resistance polyurethane adhesive - Google Patents
High-humidity-heat-resistance polyurethane adhesive, high-humidity-heat-resistance polyurethane protective film and preparation method of high-humidity-heat-resistance polyurethane adhesive Download PDFInfo
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- CN113637447A CN113637447A CN202111007281.XA CN202111007281A CN113637447A CN 113637447 A CN113637447 A CN 113637447A CN 202111007281 A CN202111007281 A CN 202111007281A CN 113637447 A CN113637447 A CN 113637447A
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- heat
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- resistance
- polyurethane adhesive
- polyurethane
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 182
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 181
- 239000000853 adhesive Substances 0.000 title claims abstract description 104
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 104
- 230000001681 protective effect Effects 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000003292 glue Substances 0.000 claims abstract description 71
- 229920005862 polyol Polymers 0.000 claims abstract description 55
- 150000003077 polyols Chemical class 0.000 claims abstract description 55
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 52
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 32
- 239000002216 antistatic agent Substances 0.000 claims abstract description 29
- 239000004094 surface-active agent Substances 0.000 claims abstract description 28
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 27
- 239000004417 polycarbonate Substances 0.000 claims abstract description 27
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 26
- 229920000570 polyether Polymers 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000010410 layer Substances 0.000 claims description 68
- 239000000758 substrate Substances 0.000 claims description 36
- 239000012790 adhesive layer Substances 0.000 claims description 28
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 239000013638 trimer Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 15
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 238000013329 compounding Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 238000005096 rolling process Methods 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 13
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 12
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 12
- 150000003949 imides Chemical class 0.000 claims description 12
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- 229920001610 polycaprolactone Polymers 0.000 claims description 11
- 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 11
- 238000000034 method Methods 0.000 claims description 9
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 8
- 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
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 239000000539 dimer Substances 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- -1 imide salt Chemical class 0.000 claims 2
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 6
- 229920005749 polyurethane resin Polymers 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 239000002904 solvent Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 238000007865 diluting Methods 0.000 description 19
- 239000011521 glass Substances 0.000 description 11
- 150000001718 carbodiimides Chemical class 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 8
- 230000000379 polymerizing effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LOCPTSFJZDIICR-UHFFFAOYSA-N 1,3-bis(3-isocyanato-4-methylphenyl)-1,3-diazetidine-2,4-dione Chemical compound C1=C(N=C=O)C(C)=CC=C1N1C(=O)N(C=2C=C(C(C)=CC=2)N=C=O)C1=O LOCPTSFJZDIICR-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 231100000136 action limit Toxicity 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000080 wetting agent 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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
-
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
-
- 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
- C09J2475/00—Presence of polyurethane
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a high-humidity-heat-resistance polyurethane adhesive, a high-humidity-heat-resistance polyurethane protective film and a preparation method of the high-humidity-heat-resistance polyurethane adhesive. The high-humidity-heat-resistance polyurethane adhesive comprises the following components in parts by weight: 100 parts of polyurethane resin, 5-20 parts of curing agent, 0.1-2 parts of antistatic agent, 0.1-2 parts of antioxidant, 0.1-2 parts of catalyst and 0.1-3 parts of surfactant; the polyurethane glue is prepared from polycarbonate polyol, polyether polyol and other polyester polyol in a mass ratio of (60-90) - (10-40) - (1-20). The high-humidity-resistance and high-heat-resistance polyurethane adhesive has better heat resistance, hydrolysis resistance, oxidation resistance and wear resistance, and can be subjected to high-temperature and high-humidity environmental test for a long time without the phenomena of white fog, ring mark and the like.
Description
Technical Field
The invention relates to the technical field of polyurethane protective films, relates to a polyurethane adhesive, a protective film and a preparation method thereof, and particularly relates to a high-humidity-heat-resistance polyurethane adhesive, a high-humidity-heat-resistance polyurethane protective film and a preparation method thereof.
Background
In recent years, as the amount of the in-vehicle screen protective film used has been greatly increased, the weather resistance of the protective film has been more highly demanded. The protection film that commonly uses has silica gel system protection film, acrylic system protection film, Polyurethane (PU) system protection film, however, protection film silica gel system takes place silicon easily and shifts and influences the product appearance, the easy phenomenon that drops powder that appears when acrylic system protection film cross cutting, be unfavorable for the customer to use, PU protection film on the market at present can generally accomplish to AF cladding material screen 60 ℃ 90% RH 72h test pollution-free, but the on-vehicle screen is mostly plain glass, the surface does not have the cladding material, the water droplet angle is littleer, and it is longer to place the transport elapsed time, consequently, the requirement to the ring survey is higher, it has great meaning to develop a high moisture-proof hot PU protection film.
CN111732925A discloses a modified PU adhesive, a modified PU adhesive protective film with excellent weather resistance and a preparation method thereof, wherein the modified PU adhesive comprises the following components in parts by weight: 100 parts of main rubber, 6-15 parts of curing agent, 0-2 parts of antistatic agent, 0.25-10 parts of hard resin, 0.5-5 parts of resin containing F hydroxyl, 0-2 parts of surface wetting agent and 100 parts of solvent; the main adhesive is polyurethane resin, and the molecular weight of the main adhesive is 50000-85000. After the modified PU glue protective film is attached to (vehicle-mounted glass and plain glass) at normal temperature for 5 days, is annularly measured at 60 ℃ and 90% RH for 3 days (plain glass) and is annularly measured at 85 ℃ and 85% RH for 5-10 days (vehicle-mounted glass, AF touch screen glass and plain glass), the surface of the glass has no precipitation, fogging and ring mark, and the modified PU glue protective film is good in air exhausting property, small in stripping force and easy to strip when being attached to the surface of the glass, and can be used for process protection and shipment protection of the plain glass and the AF glass. According to the modified PU adhesive protective film, the hard resin and the main resin are added and blended to improve the tg of the PU adhesive and improve the temperature resistance of the material; adding resin containing F hydroxyl to crosslink with the main glue, and volatilizing the F-containing section to the surface of the glue layer along with the solvent to form a compact barrier layer. However, the addition of an excessive amount of the F hydroxyl group-containing resin affects the haze of the product, and when the amount is small, the barrier layer action limit is low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-humidity-heat-resistance polyurethane adhesive, a protective film and a preparation method thereof.
One of the purposes of the invention is to provide a high moisture-heat resistant polyurethane adhesive, and to achieve the purpose, the invention adopts the following technical scheme:
the high-humidity-heat-resistance polyurethane adhesive comprises the following components in parts by weight:
the polyurethane glue is prepared from polycarbonate polyol, polyether polyol and other polyester polyol in a mass ratio of (60-90) - (10-40) - (1-20).
According to the high-humidity-heat-resistance polyurethane adhesive, polycarbonate polyol is used as a main material, polyether polyol and polyester polyol are matched to synthesize polyurethane resin, and compared with a traditional material synthesized by polyether polyol, the high-humidity-heat-resistance polyurethane adhesive has better mechanical property, better scratch resistance and better acid and alkali resistance, and has better hydrolysis resistance compared with polyester polyol; meanwhile, the antioxidant is added, so that the crosslinking density of the adhesive layer is increased, the adhesive layer is more stable, and the environment measurement performance is better.
The high moisture and heat resistance of the polyurethane adhesive provided by the invention means that the polyurethane adhesive has better weather resistance, and particularly can be placed for a longer time under the condition of 85 ℃ and 85% humidity, so that the polyurethane adhesive has no pollution to mobile phones or vehicle-mounted screens and the like.
Specifically, the high-humidity-heat-resistance polyurethane adhesive comprises the following components in parts by weight:
the weight portion of the polyurethane resin is 100 portions;
the curing agent is present in an amount of 5 to 20 parts by weight, for example 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 parts by weight.
The antistatic agent is present in an amount of 0.1 to 2 parts by weight, for example 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2, etc.
The antioxidant is present in an amount of 0.1 to 2 parts by weight, for example 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2, etc.
The catalyst is used in an amount of 0.1 to 2 parts by weight, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9 or 2.
The surfactant is 0.1 to 3 parts by weight, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3.
The polyurethane glue is prepared from polycarbonate polyol, polyether polyol and polyester polyol in a mass ratio of (60-90) - (10-40) - (1-20).
In the present invention, the polycarbonate polyol is a bifunctional and/or trifunctional polycarbonate polyol.
Preferably, the polycarbonate polyol has a number average molecular weight of 1000 to 3000, such as 1000, 1500, 2000, 2500, 3000, or the like; a hydroxyl value of 34 to 88mgKOH/g, for example, 34mgKOH/g, 40mgKOH/g, 45mgKOH/g, 50mgKOH/g, 55mgKOH/g, 60mgKOH/g, 65mgKOH/g, 70mgKOH/g, 75mgKOH/g, 80mgKOH/g, 85mgKOH/g, 88mgKOH/g, etc.; the viscosity at 21-25 ℃ is 100-40000cps, such as 100cps, 1000cps, 2000cps, 3000cps, 4000cps, 5000cps, 6000cps, 7000cps, 8000cps, 9000cps, 10000cps, 20000cps, 21000cps, 22000cps, 23000cps, 24000cps, 25000cps, 26000cps, 27000cps, 28000cps, 29000cps, 30000cps, 31000cps, 32000cps, 33000cps, 34000cps, 35000cps, 36000cps, 37000cps, 38000cps, 39000cps, 40000cps, etc.
Preferably, the polyether polyol is a difunctional and/or trifunctional polyether polyol.
Preferably, the polyether polyol has a number average molecular weight of 400 to 4000, such as 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 3500 or 4000; a hydroxyl value of 34 to 88mgKOH/g, for example, 34mgKOH/g, 40mgKOH/g, 45mgKOH/g, 50mgKOH/g, 55mgKOH/g, 60mgKOH/g, 65mgKOH/g, 70mgKOH/g, 75mgKOH/g, 80mgKOH/g, 85mgKOH/g, 88mgKOH/g, etc.; a viscosity of 50 to 600cps, 50cps, 100cps, 150cps, 200cps, 250cps, 300cps, 350cps, 400cps, 450cps, 500cps, 550cps or 600cps at 21-25 deg.C.
The polyester polyol includes conventional polyester polyols, polycaprolactone polyols and polycarbonate diols, which contain an ester group or a carbonate group, but in practice, it is common to refer to a polyester polyol obtained by polycondensation of a dicarboxylic acid with a diol or the like.
Preferably, the polyester polyol is a difunctional and/or trifunctional conventional polyester polyol or polycaprolactone polyol.
Preferably, the polyester polyol has a number average molecular weight of 300 to 4000, such as 300, 400, 500, 600, 700, 800, 900, 1000, 1500, 2000, 2500, 3000, 3500 or 4000; a hydroxyl value of 34 to 88mgKOH/g, for example, 34mgKOH/g, 40mgKOH/g, 45mgKOH/g, 50mgKOH/g, 55mgKOH/g, 60mgKOH/g, 65mgKOH/g, 70mgKOH/g, 75mgKOH/g, 80mgKOH/g, 85mgKOH/g, 88mgKOH/g, etc.; the viscosity of the resin composition at 21-25 ℃ is 2000-30000 cps, such as 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, 24000, 25000, 26000, 27000, 28000, 29000, or 30000.
If the hydroxyl values of the polycarbonate polyol, polyether polyol and polyester polyol are outside the above blending ratio ranges, the film-forming properties will be poor.
In the invention, the curing agent is any one or a mixture of at least two of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate. Preferably, the curing agent is a dimer, trimer, pentamer, heptamer of each of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, such as toluene diisocyanate dimer, toluene diisocyanate trimer, toluene diisocyanate pentamer, toluene diisocyanate heptamer, diphenylmethane diisocyanate dimer, diphenylmethane diisocyanate trimer, diphenylmethane diisocyanate pentamer, diphenylmethane diisocyanate heptamer, hexamethylene diisocyanate dimer, hexamethylene diisocyanate trimer, hexamethylene diisocyanate pentamer, hexamethylene diisocyanate heptamer, isophorone diisocyanate dimer, isophorone diisocyanate trimer, isophorone diisocyanate pentamer, hexamethylene diisocyanate trimer, hexamethylene diisocyanate pentamer, hexamethylene diisocyanate dimer, hexamethylene diisocyanate pentamer, hexamethylene diisocyanate dimer, hexamethylene diisocyanate, or the like, An isophorone diisocyanate heptamer.
In the invention, the antistatic agent is any one or a mixture of at least two of 1-ethyl-3-methylimidazole bis (trifluoromethyl) sulfonyl imide salt, lithium bis (trifluoromethyl) sulfonyl imide and lithium bis (trifluoromethyl) sulfonyl imide.
In the invention, the antioxidant is carbodiimide.
In the invention, the catalyst is dibutyltin dilaurate.
In the invention, the surfactant is any one or a mixture of at least two of a fluorine-containing acrylate copolymer, a fluorine additive, a hydroxyl-containing organic silicon leveling agent, a polyester modified hydroxyl-containing functional poly-dimethyl siloxane solution and an organic silicon leveling agent.
The second purpose of the invention is to provide a preparation method of the high humidity and heat resistant polyurethane adhesive, which comprises the following steps: and uniformly mixing the polyurethane glue, the curing agent, the antistatic agent, the catalyst and the surfactant according to the proportion to obtain the high-humidity-heat-resistance polyurethane glue.
The invention also aims to provide a high-humidity-heat-resistance polyurethane protective film which comprises a base material layer, a high-humidity-heat-resistance polyurethane adhesive layer and a release film layer which are sequentially arranged from top to bottom, wherein the high-humidity-heat-resistance polyurethane adhesive layer comprises one of the purposes of the high-humidity-heat-resistance polyurethane adhesive.
Preferably, the substrate layer is a PET original film, single-sided antistatic PET or double-sided antistatic PET.
Preferably, the thickness of the substrate layer is 12-125 μm, such as 12 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 125 μm, and the like; the single-sided antistatic PET or the double-sided antistatic PET has an impedance value of 104～1011Omega, e.g. 104Ω、105Ω、106Ω、107Ω、108Ω、109Ω、1010Ω、1011Ω, and the like.
Preferably, the release film layer is a PET single silicon release film with a thickness of 12-125 μm, such as 12 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 125 μm, etc.; the release force is 10 to 30g/25mm, for example, 10g/25mm, 11g/25mm, 12g/25mm, 13g/25mm, 14g/25mm, 15g/25mm, 16g/25mm, 17g/25mm, 18g/25mm, 19g/25mm, 20g/25mm, 21g/25mm, 22g/25mm, 23g/25mm, 24g/25mm, 25g/25mm, 26g/25mm, 27g/25mm, 28g/25mm, 29g/25mm, or 30g/25 mm.
Preferably, the release film is a single-sided or double-sided antistatic release film, and the impedance value is 104～1011Omega, e.g. 104Ω、105Ω、106Ω、107Ω、108Ω、109Ω、1010Ω、1011Ω, and the like.
The fourth object of the present invention is to provide a method for preparing the highly moisture-resistant and heat-resistant polyurethane protective film, which comprises the following steps:
1) uniformly mixing polyurethane glue, a curing agent, an antistatic agent, a catalyst and a surfactant according to a ratio to prepare the high-humidity-heat-resistance polyurethane glue;
2) coating the high-humidity-heat-resistance polyurethane adhesive prepared in the step 1) on a substrate layer, drying, compounding with a release film, rolling, and curing to obtain the high-humidity-heat-resistance polyurethane protective film.
Preferably, the drying temperature is 80-120 ℃, such as 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃.
Preferably, the temperature of the curing is 40-50 ℃, such as 40 ℃, 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃, 49 ℃ or 50 ℃ and the like; the curing time is 60-84h, such as 60h, 61h, 62h, 63h, 64h, 65h, 66h, 67h, 68h, 69h, 70h, 71h, 72h, 73h, 74h, 75h, 76h, 77h, 78h, 79h, 80h, 81h, 82h, 83h or 84 h.
Compared with the prior art, the invention has the beneficial effects that:
according to the high-humidity-heat-resistance polyurethane adhesive, polycarbonate polyol is used as a main material, polyether polyol and polyester polyol are matched to synthesize polyurethane resin, and compared with a traditional material synthesized by polyether polyol, the high-humidity-heat-resistance polyurethane adhesive has better mechanical property, better scratch resistance and better acid and alkali resistance, and has better hydrolysis resistance compared with polyester polyol; meanwhile, the antioxidant is added, so that the crosslinking density of the adhesive layer is increased, the adhesive layer is more stable, and the environment measurement performance is better. The high-humidity-heat-resistance polyurethane adhesive disclosed by the invention has better heat resistance, hydrolysis resistance, oxidation resistance and wear resistance on the premise of ensuring good peeling force, light transmittance and haze, and can be subjected to high-temperature high-humidity environment measurement for a long time without the phenomena of white fog, ring mark and the like. Specifically, the stripping force of the protective film and SUS30420min is 0.987-1.645g/25mm, the light transmittance is 89.8-90.1%, the haze is 1.2-1.7%, no precipitation, no white fog and a small amount of ring marks are measured at 60 ℃ by 90% RH 72h, no precipitation, no white fog and a small amount of ring marks are measured at 85 ℃ by 85% RH 120h, and no precipitation, no white fog and a small amount of ring marks are measured at 85 ℃ by 85% RH 240 h.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.
Example 1
The high moisture-heat resistant polyurethane adhesive of the embodiment sequentially comprises a substrate layer, a high moisture-heat resistant polyurethane adhesive layer and a release film layer from top to bottom, wherein the substrate layer is specifically a 50 mu mPE original film; the high-humidity-heat-resistance polyurethane adhesive layer comprises the following components: 100 parts of polyurethane glue (the polyurethane glue is formed by polymerizing polycarbonate polyol (UH-300 number average molecular weight 3000 hydroxyl value 34-40, Utsui Kaishu, U.S. Pat. No. 2000), polyether polyol (number average molecular weight 2000 hydroxyl value 53-58, national chemical DP2000E) and polyester polyol (PCL 220AL number average molecular weight 2000 hydroxyl value 53-59, Kaishu chemical Co., Ltd.) in a mass ratio of 60:20: 20); 7.5 parts of a trimer curing agent of hexamethylene diisocyanate; 2 parts of an antistatic agent (lithium bistrifluoromethylsulfonimide); 1 part of carbodiimide; 1 part of a surfactant (silicone leveling agent, BYK3700, germany); 0.15 part of dibutyltin dilaurate; ethyl acetate is supplemented as a diluting solvent until the solid content is 40 percent; an antistatic polyurethane adhesive prepared by dispersion; the release film layer is a PET single-silicon release film with the thickness of 50 mu m and the release force of 20g/25 mm.
The preparation method of the high moisture-resistant heat-resistant polyurethane protective film of the embodiment comprises the following steps:
(1) mixing the polyurethane glue, a curing agent, an antistatic agent, a catalyst, a surfactant and a diluting solvent, and stirring at normal temperature for 30min to obtain a mixed solution, thereby obtaining the high-humidity-heat-resistance polyurethane glue;
(2) and coating the high-humidity-heat-resistance polyurethane adhesive on the substrate layer, drying the adhesive at 120 ℃ until the thickness of the adhesive is 15 mu m, then compounding the adhesive with a release film, rolling, and curing at 45 ℃ for 72 hours to obtain the protective film.
Example 2
The high moisture-heat resistant polyurethane adhesive of the embodiment sequentially comprises a substrate layer, a high moisture-heat resistant polyurethane adhesive layer and a release film layer from top to bottom, wherein the substrate layer is specifically a 50 mu mPE original film; the high-humidity-heat-resistance polyurethane adhesive layer comprises the following components: 100 parts of polyurethane glue (the polyurethane glue is prepared by polymerizing polycarbonate polyol (UH-300, Utsui Kaisha, Yu), polyether polyol (national chemical DP2000E) and polyester polyol (PCL 220AL, Dasailu chemical Co., Ltd.) in a mass ratio of 80:10: 10); 9 parts of a trimer curing agent of hexamethylene diisocyanate; 1 part of an antistatic agent (lithium bistrifluoromethylsulfonyl imide); 0.5 part of carbodiimide; 1 part of a surfactant (silicone leveling agent, BYK3700, germany); 0.12 part of dibutyltin dilaurate; ethyl acetate is supplemented as a diluting solvent until the solid content reaches 40 percent; an antistatic polyurethane adhesive prepared by dispersion; the release film layer is a PET single-silicon release film with the thickness of 50 mu m and the release force of 20g/25 mm.
The preparation method of the high moisture-resistant heat-resistant polyurethane protective film of the embodiment comprises the following steps:
(1) mixing the polyurethane glue, a curing agent, an antistatic agent, a catalyst, a surfactant and a diluting solvent, and stirring at normal temperature for 30min to obtain a mixed solution, thereby obtaining the high-humidity-heat-resistance polyurethane glue;
(2) and coating the high-humidity-heat-resistance polyurethane adhesive on the substrate layer, drying the adhesive at 120 ℃ until the thickness of the adhesive is 15 mu m, then compounding the adhesive with a release film, rolling, and curing at 45 ℃ for 72 hours to obtain the protective film.
Example 3
The high moisture-heat resistant polyurethane adhesive of the embodiment sequentially comprises a substrate layer, a high moisture-heat resistant polyurethane adhesive layer and a release film layer from top to bottom, wherein the substrate layer is specifically a 50 mu mPE original film; the high-humidity-heat-resistance polyurethane adhesive layer comprises the following components: 100 parts of polyurethane glue (the polyurethane glue is prepared by polymerizing polycarbonate polyol (UH-300, Utsui Kaisha, Yu), polyether polyol (national chemical DP2000E) and polyester polyol (PCL 220AL, Dasailu chemical Co., Ltd.) in a mass ratio of 70:10: 20); 9.2 parts of a trimer curing agent of hexamethylene diisocyanate; 1 part of an antistatic agent (lithium bistrifluoromethylsulfonyl imide); 1 part of carbodiimide; 1.2 parts of a surfactant (a silicone leveling agent, BYK3700, germany); 0.12 part of dibutyltin dilaurate; ethyl acetate is supplemented as a diluting solvent to 40% of solid content; an antistatic polyurethane adhesive prepared by dispersion; the release film layer is a PET single-silicon release film with the thickness of 50 mu m and the release force of 20g/25 mm.
The preparation method of the high moisture-resistant heat-resistant polyurethane protective film of the embodiment comprises the following steps:
(1) mixing the polyurethane glue, a curing agent, an antistatic agent, a catalyst, a surfactant and a diluting solvent, and stirring at normal temperature for 30min to obtain a mixed solution, thereby obtaining the high-humidity-heat-resistance polyurethane glue;
(2) and coating the high-humidity-heat-resistance polyurethane adhesive on the substrate layer, drying the adhesive at 120 ℃ until the thickness of the adhesive is 15 mu m, then compounding the adhesive with a release film, rolling, and curing at 45 ℃ for 72 hours to obtain the protective film.
Example 4
The high moisture-heat resistant polyurethane adhesive of the embodiment sequentially comprises a substrate layer, a high moisture-heat resistant polyurethane adhesive layer and a release film layer from top to bottom, wherein the substrate layer is specifically a 50 mu mPE original film; the high-humidity-heat-resistance polyurethane adhesive layer comprises the following components: 100 parts of polyurethane glue (the polyurethane glue is prepared by polymerizing polycarbonate polyol (UH-300, Utsui Kaisha, Yu), polyether polyol (national chemical DP2000E) and polyester polyol (PCL 220AL, Dasailu chemical Co., Ltd.) in a mass ratio of 70:15: 15); 9.2 parts of a trimer curing agent of hexamethylene diisocyanate; 1 part of an antistatic agent (lithium bistrifluoromethylsulfonyl imide); 1 part of carbodiimide; 0.8 part of a surfactant (a silicone leveling agent, BYK3700, germany); 0.12 part of dibutyltin dilaurate; ethyl acetate is supplemented as a diluting solvent to 40% of solid content; an antistatic polyurethane adhesive prepared by dispersion; the release film layer is a PET single-silicon release film with the thickness of 50 mu m and the release force of 20g/25 mm.
The preparation method of the high moisture-resistant heat-resistant polyurethane protective film of the embodiment comprises the following steps:
(1) mixing the polyurethane glue, a curing agent, an antistatic agent, a catalyst, a surfactant and a diluting solvent, and stirring at normal temperature for 30min to obtain a mixed solution, thereby obtaining the high-humidity-heat-resistance polyurethane glue;
(2) and coating the high-humidity-heat-resistance polyurethane adhesive on the substrate layer, drying the adhesive at 120 ℃ until the thickness of the adhesive is 15 mu m, then compounding the adhesive with a release film, rolling, and curing at 45 ℃ for 72 hours to obtain the protective film.
Example 5
The high moisture-heat resistant polyurethane adhesive of the embodiment sequentially comprises a substrate layer, a high moisture-heat resistant polyurethane adhesive layer and a release film layer from top to bottom, wherein the substrate layer is specifically a 50 mu mPE original film; the high-humidity-heat-resistance polyurethane adhesive layer comprises the following components: 100 parts of polyurethane glue (the polyurethane glue is prepared by polymerizing polycarbonate polyol (UH-300, Utsui Kaisha, Yu), polyether polyol (national chemical DP2000E) and polyester polyol (PCL 220AL, Dasailu chemical Co., Ltd.) in a mass ratio of 90:5: 5); 9 parts of a trimer curing agent of hexamethylene diisocyanate; 1 part of an antistatic agent (lithium bistrifluoromethylsulfonyl imide); 0.1 part of carbodiimide; 0.8 part of a surfactant (a silicone leveling agent, BYK3700, germany); 0.12 part of dibutyltin dilaurate; ethyl acetate is supplemented as a diluting solvent to 40% of solid content; an antistatic polyurethane adhesive prepared by dispersion; the release film layer is a PET single-silicon release film with the thickness of 50 mu m and the release force of 20g/25 mm.
The preparation method of the high moisture-resistant heat-resistant polyurethane protective film of the embodiment comprises the following steps:
(1) mixing the polyurethane glue, a curing agent, an antistatic agent, a catalyst, a surfactant and a diluting solvent, and stirring at normal temperature for 30min to obtain a mixed solution, thereby obtaining the high-humidity-heat-resistance polyurethane glue;
(2) and coating the high-humidity-heat-resistance polyurethane adhesive on the substrate layer, drying the adhesive at 120 ℃ until the thickness of the adhesive is 15 mu m, then compounding the adhesive with a release film, rolling, and curing at 45 ℃ for 72 hours to obtain the protective film.
Example 6
The high moisture-heat resistant polyurethane adhesive of the embodiment sequentially comprises a substrate layer, a high moisture-heat resistant polyurethane adhesive layer and a release film layer from top to bottom, wherein the substrate layer is specifically a 50 mu mPE original film; the high-humidity-heat-resistance polyurethane adhesive layer comprises the following components: 100 parts of polyurethane glue (the polyurethane glue is formed by polymerizing polycarbonate polyol (UH-200 number average molecular weight 2000 hydroxyl value 51-61, Utsui Kaishiki, Utsui), polyether polyol (national chemical DP4000E number average molecular weight 4000 hydroxyl value 26-30) and polyester polyol (PCL 220AL, Kaishuhua Co., Ltd.) in a mass ratio of 70:10: 20); 10.2 parts of a trimer curing agent of toluene diisocyanate; 1 part of an antistatic agent (lithium bistrifluoromethylsulfonyl imide); 1 part of carbodiimide; 1.2 parts of a surfactant (a silicone leveling agent, BYK3700, germany); 0.12 part of dibutyltin dilaurate; ethyl acetate is supplemented as a diluting solvent to 40% of solid content; an antistatic polyurethane adhesive prepared by dispersion; the release film layer is a PET single-silicon release film with the thickness of 50 mu m and the release force of 20g/25 mm.
The preparation method of the high moisture-resistant heat-resistant polyurethane protective film of the embodiment comprises the following steps:
(1) mixing the polyurethane glue, a curing agent, an antistatic agent, a catalyst, a surfactant and a diluting solvent, and stirring at normal temperature for 30min to obtain a mixed solution, thereby obtaining the high-humidity-heat-resistance polyurethane glue;
(2) and coating the high-humidity-heat-resistance polyurethane adhesive on the substrate layer, drying the adhesive at 120 ℃ until the thickness of the adhesive is 15 mu m, then compounding the adhesive with a release film, rolling, and curing at 45 ℃ for 72 hours to obtain the protective film.
Example 7
This example is different from example 1 in that the polycarbonate polyol (UH-50 from Uk) has a number average molecular weight of 500, a hydroxyl value of 224, 16 parts of a hexamethyldiisocyanate curing agent, and the rest is the same as example 1.
Example 8
This example is different from example 1 in that the polyester polyol (PCL 205, Daiiluo chemical Co., Ltd.) has a number average molecular weight of 530, a hydroxyl value of 207-.
Example 9
This example differs from example 1 in that the polyether polyol (national DE-1000) has a number average molecular weight of 1000, a hydroxyl number of 107-.
Example 10
This example is different from example 1 in that the curing agent was replaced with toluene diisocyanate, and the rest was the same as example 1.
Comparative example 1
The PU glue is prepared by mixing a PU glue purchased from Toyo ink with a model SH-109GS-ST, a hexamethylene diisocyanate curing agent and a lithium salt electrostatic agent on the market. Coating the PU glue on a 50-micron base material layer, drying the glue at 120 ℃ until the glue thickness is 15 microns, then compounding the glue with a 50-micron release film, rolling, and curing at 45 ℃ for 48 hours to obtain the protective film.
Comparative example 2
The PU glue is obtained from a third and coating PU glue model No. UA80-7, and is matched with a hexamethylene diisocyanate curing agent and an electrostatic agent lithium bistrifluoromethylsulfonyl imide. Coating the PU glue on a 50-micron base material layer, drying the glue at 120 ℃ until the glue thickness is 15 microns, then compounding the glue with a 50-micron release film, rolling, and curing at 45 ℃ for 48 hours to obtain the protective film.
Comparative example 3
The high-humidity-heat-resistance polyurethane adhesive of the comparative example sequentially comprises a substrate layer, a high-humidity-heat-resistance polyurethane adhesive layer and a release film layer from top to bottom, wherein the substrate layer is specifically 50 mu mPE single-side antistatic PET, and the antistatic side is positioned on the other side of the adhesive layer; the high-humidity-heat-resistance polyurethane adhesive layer comprises the following components: 100 parts of polyurethane glue (the polyurethane glue is polymerized by polycarbonate polyol and polyester polyol, and the mass ratio is 80: 20); 8 parts of a trimer curing agent of hexamethylene diisocyanate; 1 part of an antistatic agent (lithium bistrifluoromethylsulfonyl imide); 0.5 part of carbodiimide additive; 1 part of a surfactant (silicone leveling agent, BYK3700, germany); 0.1 part of dibutyltin dilaurate; ethyl acetate is supplemented as a diluting solvent to 40% of solid content; an antistatic polyurethane adhesive prepared by dispersion; the release film layer is a PET single-silicon release film with the thickness of 50 mu m and the release force of 20g/25 mm.
The preparation method of the high heat and humidity resistant polyurethane protective film of the comparative example comprises the following steps:
(1) mixing the polyurethane glue, a curing agent, an antistatic agent, a catalyst and a surfactant, and stirring at normal temperature for 30min to obtain a mixed solution, thereby obtaining the high-humidity-heat-resistance polyurethane glue;
(2) and coating the high-humidity-heat-resistance polyurethane adhesive on the substrate layer, drying the adhesive at 120 ℃ until the thickness of the adhesive is 15 mu m, then compounding the adhesive with a release film, rolling, and curing at 45 ℃ for 72 hours to obtain the protective film.
Comparative example 4
The high moisture-heat resistant polyurethane adhesive of the comparative example sequentially comprises a substrate layer, a high moisture-heat resistant polyurethane adhesive layer and a release film layer from top to bottom, wherein the substrate layer is specifically a 50 mu mPE original film; the high-humidity-heat-resistance polyurethane adhesive layer comprises the following components: 100 parts of polyurethane glue (the polyurethane glue is formed by polymerizing polycarbonate polyol (UH-200 number average molecular weight 2000 hydroxyl value 51-61, Utsui Kaishiki, Utsui), polyether polyol (national chemical DP4000E number average molecular weight 4000 hydroxyl value 26-30) and polyester polyol (PCL 220AL, Kaishuhua Co., Ltd.) in a mass ratio of 40:30: 30); 16 parts of a trimer curing agent of toluene diisocyanate; 1 part of an antistatic agent (lithium bistrifluoromethylsulfonyl imide); 2 parts of carbodiimide; 1 part of a surfactant (silicone leveling agent, BYK3700, germany); 0.12 part of dibutyltin dilaurate; ethyl acetate is supplemented as a diluting solvent to 40% of solid content; an antistatic polyurethane adhesive prepared by dispersion; the release film layer is a PET single-silicon release film with the thickness of 50 mu m and the release force of 20g/25 mm.
The preparation method of the high heat and humidity resistant polyurethane protective film of the comparative example comprises the following steps:
(1) mixing the polyurethane glue, a curing agent, an antistatic agent, a catalyst, a surfactant and a diluting solvent, and stirring at normal temperature for 30min to obtain a mixed solution, thereby obtaining the high-humidity-heat-resistance polyurethane glue;
(2) and coating the high-humidity-heat-resistance polyurethane adhesive on the substrate layer, drying the adhesive at 120 ℃ until the thickness of the adhesive is 15 mu m, then compounding the adhesive with a release film, rolling, and curing at 45 ℃ for 72 hours to obtain the protective film.
Comparative example 5
The high moisture-heat resistant polyurethane adhesive of the comparative example sequentially comprises a substrate layer, a high moisture-heat resistant polyurethane adhesive layer and a release film layer from top to bottom, wherein the substrate layer is specifically a 25 mu mPE original film; the high-humidity-heat-resistance polyurethane adhesive layer comprises the following components: 100 parts of polyurethane glue (the polyurethane glue is polymerized by polycarbonate polyol and polyester polyol, and the mass ratio is 90: 10); 8.5 parts of a trimer curing agent of hexamethylene diisocyanate; 1 part of an antistatic agent (lithium bistrifluoromethylsulfonyl imide); 2 parts of carbodiimide additive; 1 part of a surfactant (silicone leveling agent, BYK3700, germany); 0.15 part of dibutyltin dilaurate; ethyl acetate is supplemented as a diluting solvent to 40% of solid content; an antistatic polyurethane adhesive prepared by dispersion; the release film layer is a PET single-silicon release film with the thickness of 50 mu m and the release force of 20g/25 mm.
The preparation method of the high heat and humidity resistant polyurethane protective film of the comparative example comprises the following steps:
(1) mixing the polyurethane glue, a curing agent, an antistatic agent, a catalyst, a surfactant and a diluting solvent, and stirring at normal temperature for 30min to obtain a mixed solution, thereby obtaining the high-humidity-heat-resistance polyurethane glue;
(2) and coating the high-humidity-heat-resistance polyurethane adhesive on the substrate layer, drying the adhesive at 120 ℃ until the thickness of the adhesive is 15 mu m, then compounding the adhesive with a release film, rolling, and curing at 45 ℃ for 72 hours to obtain the protective film.
Comparative example 6
The high moisture-heat resistant polyurethane adhesive of the comparative example sequentially comprises a substrate layer, a high moisture-heat resistant polyurethane adhesive layer and a release film layer from top to bottom, wherein the substrate layer is specifically a 50 mu mPE original film; the high-humidity-heat-resistance polyurethane adhesive comprises the following components: 100 parts of polyurethane glue (the polyurethane glue is polymerized by polycarbonate polyol, polyether polyol and polyester polyol, and the mass ratio is 70:10: 20); 9 parts of a dimer curing agent for hexamethylene diisocyanate; 1 part of an antistatic agent (lithium bistrifluoromethylsulfonyl imide); 1 part of a surfactant (silicone leveling agent, BYK3700, germany); 0.15 part of dibutyltin dilaurate; ethyl acetate is supplemented as a diluting solvent to 40% of solid content; an antistatic polyurethane adhesive prepared by dispersion; the release film layer is a PET single-silicon release film with the thickness of 50 mu m and the release force of 20g/25 mm.
The preparation method of the high heat and humidity resistant polyurethane protective film of the comparative example comprises the following steps:
(1) mixing the polyurethane glue, a curing agent, an antistatic agent, a catalyst, a surfactant and a diluting solvent, and stirring at normal temperature for 30min to obtain a mixed solution, thereby obtaining the high-humidity-heat-resistance polyurethane glue;
(2) and coating the high-humidity-heat-resistance polyurethane adhesive on the substrate layer, drying the adhesive at 120 ℃ until the thickness of the adhesive is 15 mu m, then compounding the adhesive with a release film, rolling, and curing at 45 ℃ for 72 hours to obtain the protective film.
The protective films obtained in examples 1 to 7 and comparative examples 1 to 6 were subjected to performance tests, and the test results are shown in tables 1 and 2.
The test of the peeling force is carried out according to the GB/T2792-1998 standard, the light transmittance is measured by using an optical haze meter, and the haze is measured by using the optical haze meter.
TABLE 1
TABLE 2
As can be seen from tables 1 and 2, the high moisture and heat resistant polyurethane adhesive of the invention has better heat resistance, hydrolysis resistance, oxidation resistance and wear resistance on the premise of ensuring good peeling force, light transmittance and haze, and can be subjected to long-term high-temperature high-humidity environmental test without white fog, ring mark and other phenomena. Specifically, the stripping force of the protective film and SUS30420min is 0.987-1.645g/25mm, the light transmittance is 89.8-90.1%, the haze is 1.2-1.7%, no precipitation, no white fog and a small amount of ring marks are measured at 60 ℃ by 90% RH 72h, no precipitation, no white fog and a small amount of ring marks are measured at 85 ℃ by 85% RH 120h, and no precipitation, no white fog and a small amount of ring marks are measured at 85 ℃ by 85% RH 240 h.
Example 7 replacement of the curing agent with toluene diisocyanate slightly changed the tack of the protective film and had no effect on the ring test results.
Comparative examples 1 and 2 adopt glue only containing polyester polyol and polyether polyol, which can cause poor hydrolysis resistance and poor long-time environment measurement effect.
The polyurethane glue of comparative example 3 and comparative example 5 only contains two types of polycarbonate polyol and polyester polyol, so that the fitting property of the material is poor, water vapor enters between the protective film and the attached object in the process of environmental measurement, layering occurs, and the protective effect cannot be achieved.
Comparative example 4 the proportion of the polyether polyol, the polyester polyol and the polycarbonate polyol outside the standard range can increase the viscosity of the material, the ring mark is obvious, and simultaneously the hydrolysis resistance degree is deteriorated and the precipitation is increased.
Comparative example 6 has no carbodiimide antioxidant, resulting in a material having a deteriorated length of wet heat resistance, but still having an effect stronger than that of a conventional PU adhesive resin on the market.
The present invention is illustrated by the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, i.e. it is not meant to imply that the present invention must rely on the above-mentioned detailed process equipment and process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The high-humidity-heat-resistance polyurethane adhesive is characterized by comprising the following components in parts by weight:
the polyurethane glue is prepared from polycarbonate polyol, polyether polyol and other polyester polyol in a mass ratio of (60-90) - (10-40) - (1-20).
2. The polyurethane adhesive with high wet heat resistance as claimed in claim 1, wherein the polycarbonate polyol is a bifunctional and/or trifunctional polycarbonate polyol;
preferably, the number average molecular weight of the polycarbonate polyol is 1000-3000, the hydroxyl value is 34-88 mgKOH/g, and the viscosity at 21-25 ℃ is 100-40000 cps;
preferably, the polyether polyol is a difunctional and/or trifunctional polyether polyol;
preferably, the polyether polyol has the number average molecular weight of 400-4000, the hydroxyl value of 34-88 mgKOH/g and the viscosity of 50-600 cps at 21-25 ℃;
preferably, the polyester polyol is a difunctional and/or trifunctional conventional polyester polyol or polycaprolactone polyol;
preferably, the polyester polyol has a number average molecular weight of 300 to 4000, a hydroxyl value of 34 to 88mgKOH/g, and a viscosity of 2000 to 30000cps at 21 to 25 ℃.
3. The high wet heat resistant polyurethane adhesive according to claim 1 or 2, wherein the curing agent is any one or a mixture of at least two of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate;
preferably, the curing agent is a dimer, trimer, pentamer or heptamer of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, respectively.
4. The high wet heat resistant polyurethane adhesive according to any one of claims 1 to 3, wherein the antistatic agent is any one or a mixture of at least two of 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, lithium bistrifluoromethylsulfonyl imide and lithium bistrifluoromethylsulfonyl imide.
5. The high wet heat resistant polyurethane adhesive according to any one of claims 1 to 4, wherein the antioxidant is carbodiimide.
6. The high wet heat resistant polyurethane adhesive according to any one of claims 1 to 5, wherein the catalyst is dibutyltin dilaurate.
7. The high wet heat resistance polyurethane adhesive according to one of claims 1 to 6, wherein the surfactant is any one or a mixture of at least two of a fluorine-containing acrylate copolymer, a fluorine additive, a hydroxyl-containing silicone leveling agent, a polyester-modified hydroxyl-functional polydimethylsiloxane solution and a silicone leveling agent.
8. A method for preparing the polyurethane adhesive with high wet heat resistance according to any one of claims 1 to 7, which comprises the following steps: and uniformly mixing the polyurethane glue, the curing agent, the antistatic agent, the catalyst and the surfactant according to the proportion to obtain the high-humidity-heat-resistance polyurethane glue.
9. A high moisture-heat resistant polyurethane protective film is characterized by comprising a base material layer, a high moisture-heat resistant polyurethane adhesive layer and a release film layer which are sequentially arranged from top to bottom, wherein the high moisture-heat resistant polyurethane adhesive layer comprises the high moisture-heat resistant polyurethane adhesive according to any one of claims 1 to 7;
preferably, the substrate layer is a PET original film, single-sided antistatic PET or double-sided antistatic PET;
preferably, the substrate layer has a thickness of 12 to 125 μm, and the antistatic surface impedance value of the single-sided antistatic PET or the double-sided antistatic PET is independently 104～1011Ω；
Preferably, the thickness of the high wet heat resistant polyurethane glue layer is 5-80 μm, and the impedance is 106～1012Ω；
Preferably, the release film layer is a PET single-silicon release film with the thickness of 12-125 μm and the release force of 10-30g/25 mm;
preferably, the release film is a single-sided or double-sided antistatic release film, and the impedance value is 104～1011Ω。
10. The method for preparing the highly moisture-resistant polyurethane protective film according to claim 9, comprising the steps of:
1) uniformly mixing polyurethane glue, a curing agent, an antistatic agent, a catalyst and a surfactant according to a ratio to prepare the high-humidity-heat-resistance polyurethane glue;
2) coating the high-humidity-heat-resistance polyurethane adhesive prepared in the step 1) on a substrate layer, drying, compounding with a release film, rolling, and curing to obtain the high-humidity-heat-resistance polyurethane protective film;
preferably, the drying temperature is 80-120 ℃;
preferably, the curing temperature is 40-50 ℃, and the curing time is 60-84 h.
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