CN113861375B - Preparation method of yellowing-resistant TPU and TPU protective film - Google Patents
Preparation method of yellowing-resistant TPU and TPU protective film Download PDFInfo
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- CN113861375B CN113861375B CN202111235010.XA CN202111235010A CN113861375B CN 113861375 B CN113861375 B CN 113861375B CN 202111235010 A CN202111235010 A CN 202111235010A CN 113861375 B CN113861375 B CN 113861375B
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- tpu
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- resistant
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- 238000004383 yellowing Methods 0.000 title claims abstract description 78
- 230000001681 protective effect Effects 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims abstract description 74
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 33
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000005871 repellent Substances 0.000 claims abstract description 25
- 230000002940 repellent Effects 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000012948 isocyanate Substances 0.000 claims abstract description 17
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 8
- 229920000151 polyglycol Polymers 0.000 claims abstract description 7
- 239000010695 polyglycol Substances 0.000 claims abstract description 7
- 239000012257 stirred material Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 44
- 229920000223 polyglycerol Polymers 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 12
- 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 12
- 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 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- ZMWRRFHBXARRRT-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(N2N=C3C=CC=CC3=N2)=C1O ZMWRRFHBXARRRT-UHFFFAOYSA-N 0.000 claims description 6
- 238000007605 air drying Methods 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 239000013638 trimer Substances 0.000 claims description 6
- -1 TDI Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 6
- 239000000428 dust Substances 0.000 abstract description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 91
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 90
- 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 description 7
- 239000000463 material Substances 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical group O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
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- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
-
- 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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/61—Polysiloxanes
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- 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
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
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- 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
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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- 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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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- 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
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- 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
- C09J2475/006—Presence of polyurethane in the substrate
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A preparation method of a yellowing-resistant TPU and a TPU protective film comprises the following steps: step a1, placing isocyanate and a dihydroxyl water repellent agent into a reaction container, heating to 85-95 ℃ and stirring for more than 0.5h; step a2, putting polyglycol, 1,4 butanediol, graphene, a yellowing-resistant agent, an antioxidant and a catalyst into a reaction container, and stirring for more than 1h; step a3, placing the monohydroxy water-repellent agent into a reaction container, and stirring for more than 0.5h; and a4, baking the stirred material at the temperature of 75-85 ℃ for more than 10 hours to form the yellowing-resistant TPU. And spraying the pressure-sensitive adhesive on the yellowing-resistant TPU to form the TPU protective film. The graphene is added, so that the anti-static function is achieved, the adhesion of dust is reduced, the heat resistance is enhanced, and a better protection effect can be achieved.
Description
Technical Field
The invention relates to the field of TPU (thermoplastic polyurethane), in particular to a yellowing-resistant TPU and a preparation method of a TPU protective film.
Background
In order to protect the body paint of the automobile, some users can paste a protective film on the body of the automobile, and some protective films can also realize the purpose of decorating the body and can be easily removed at any time, thus being in clear contrast with the traditional chemical changes of the paint surfaces such as glaze sealing, coating, paint spraying and the like. The materials for manufacturing the automobile protective film mainly comprise PVC and TPU.
The environmental protection problem and the ageing problem of PVC can not be solved effectively, and the PVC has poorer yellowing resistance, so that the PVC needs to be replaced after being used for about 2 years. In addition, during the replacement process, the paint surface of the automobile is often scratched by the operation of removing the adhesive.
Although the TPU protective films on the market can basically realize the yellowing resistance effect, most of the TPU protective films do not meet the standard environmental protection requirement of no fluorine. In addition, most TPU protective films have no antistatic function, dust must be removed frequently after the use for a period of time, and after the protective films are torn off, residual glue often exists on the automobile baking finish.
Disclosure of Invention
The technical scheme of the invention aims at the above situation, and provides a preparation method of yellowing-resistant TPU, which comprises the following steps of:
step a1, placing isocyanate and a dihydroxyl water repellent agent into a reaction container, heating to 85-95 ℃ and stirring for more than 0.5h;
step a2, putting polyglycol, 1,4 butanediol, graphene, a yellowing-resistant agent, an antioxidant and a catalyst into a reaction container, and stirring for more than 1h;
step a3, placing the monohydroxy water-repellent agent into a reaction container, and stirring for more than 0.5h;
and a4, baking the stirred material at the temperature of 75-85 ℃ for more than 10 hours to form the yellowing-resistant TPU.
Further, the yellowing-resistant TPU comprises the following components in percentage by weight:
further, in step a1, the dihydroxyl water repellent agent is PSD; in step a3, the monohydroxy water repellent is PMS.
Further, in step a1, the isocyanate is one or more of IPDI, MDI, TDI, HDI and H12 MDI; in the step a2, the polyglycol is one or two of PC and PTMEG; the yellowing resisting agent is one or more of UV-328, UV-327, UV-P and UV-765; the antioxidant is one or more of 1010 antioxidant, 1076 antioxidant, 1098 antioxidant and 168 antioxidant; the catalyst is one or two of stannous octoate and amine catalysts.
The invention also provides a preparation method of the TPU protective film, which comprises the following steps:
step b1, extruding the yellowing-resistant TPU prepared by the preparation method of claim 1 to form a TPU film;
step b2, preparing a yellowing-resistant pressure-sensitive adhesive, spraying the yellowing-resistant pressure-sensitive adhesive to the bottom surface of the TPU film, and performing air drying treatment;
and b3, attaching a bottom release film on the yellowing-resistant pressure-sensitive adhesive to form a TPU protective film.
Further, in step b1, the method further comprises attaching a top release film to the top surface of the TPU film.
Further, in the step b2, the preparation process of the yellowing-resistant pressure-sensitive adhesive comprises the following steps: preparing a first pressure-sensitive adhesive raw material and a second pressure-sensitive adhesive raw material respectively, wherein the first pressure-sensitive adhesive raw material and the second pressure-sensitive adhesive raw material are prepared by the following steps of 1:1, mixing the materials in a proportion of 1,
the preparation process of the first pressure-sensitive adhesive raw material comprises the following steps:
step c1, placing polypropylene glycol, difunctional isocyanate and an antioxidant into a reaction container, heating to 65-75 ℃, and standing for more than 3 hours;
step c2, placing the isocyanate trimer into a reaction container, vacuumizing, and standing for more than 0.3h to form a first pressure-sensitive adhesive raw material;
the preparation process of the second pressure-sensitive adhesive raw material comprises the following steps:
step d1, placing polyglycerol, glycerol and a catalyst into a reaction container, heating to 65-75 ℃, and stirring for more than 0.3 h;
d2, vacuumizing, and standing for more than 0.3h to form a second pressure-sensitive adhesive raw material.
Further, the first pressure-sensitive adhesive comprises the following components in percentage by weight:
further, in step d1, the polyglycerol includes: polyglycerol 3000 and polyglycerol 700.
Further, the second pressure-sensitive adhesive comprises the following raw materials in percentage by weight:
the yellowing-resistant TPU formed by the preparation method has the following advantages:
1. the yellowing resistance is good, the aging problem is not easy to occur, and the service life is long.
2. No fluorine element is added, and meets the standard environmental protection requirement of no fluorine.
3. The graphene is added, so that the anti-static function is achieved, the adhesion of dust is reduced, the heat resistance is enhanced, and a better protection effect can be achieved.
4. Because the dihydroxyl water repellent agent and the monohydroxy water repellent agent are added, the main chain and the molecular chain tail end of the TPU have the water repellent function, and the situation that water marks appear at the local position of the film is avoided.
Detailed Description
The technical scheme of the invention is further described by the following examples:
the invention provides a preparation method of yellowing-resistant TPU, which comprises the following steps:
step a1, placing isocyanate and a dihydroxyl water repellent agent into a reaction container, heating to 85-95 ℃ and stirring for more than 0.5h;
step a2, putting polyglycol, 1,4 butanediol, graphene, a yellowing-resistant agent, an antioxidant and a catalyst into a reaction container, and stirring for more than 1h;
step a3, placing the monohydroxy water-repellent agent into a reaction container, and stirring for more than 0.5h;
and a4, baking the stirred material at the temperature of 75-85 ℃ for more than 10 hours to form the yellowing-resistant TPU.
Wherein, in step a1, the dihydroxyl water repellent agent participates in partial chain extension, and the purpose of the dihydroxyl water repellent agent is to ensure that the main chain of the TPU has enough water repellent function; the monohydroxy water-repellent agent is added on the one hand in order to terminate the reaction at the end of the preparation process and on the other hand in order to graft it at the terminal end of the TPU, forming a water-repellent function.
In the step a2, graphene is added to enable the TPU to have an antistatic function, so that adhesion of dust is reduced. In addition, the vehicle is very easy to damage and deform in the severe environment of dry and wet exchange such as insolation, rain and the like under the outdoor use environment, and the graphene is added to enhance the heat resistance of the TPU, so that a better protection effect is achieved.
From this, the above preparation method forms the yellowing resistant TPU with the following advantages:
1. the yellowing resistance is good, the aging problem is not easy to occur, and the service life is long.
2. No fluorine element is added, and meets the standard environmental protection requirement of no fluorine.
3. The graphene is added, so that the anti-static function is achieved, the adhesion of dust is reduced, the heat resistance is enhanced, and a better protection effect can be achieved.
4. Because the dihydroxyl water repellent agent and the monohydroxy water repellent agent are added, the main chain and the molecular chain tail end of the TPU have the water repellent function, and the situation that water marks appear at the local position of the film is avoided.
Specifically, the yellowing-resistant TPU comprises the following components in percentage by weight:
specifically, in step a1, the dihydroxyl water repellent agent is PSD (dihydroxyl polysiloxane) and has a molecular weight of 1000; in step a3, the monohydroxy water repellent is PMS (monohydroxy polysiloxane) having a molecular weight of 500.
Specifically, in step a1, the isocyanate is IPDI (isophorone diisocyanate), MDI (diphenylmethane diisocyanate), TDI (toluene diisocyanate), HDI (isophorone diisocyanate) and H 12 MDI (hydrogenated phenyl methane diisocyanate).
Specifically, in step a2, the polyglycol is one or a mixture of two of PC (polycarbonate) and PTMEG (polytetramethylene ether glycol); the yellowing resisting agent is one or more of UV-328, UV-327, UV-P and UV-765; the antioxidant is one or more of 1010 antioxidant, 1076 antioxidant, 1098 antioxidant and 168 antioxidant; the catalyst is one or two of stannous octoate and amine catalysts.
The invention also provides a preparation method of the TPU protective film, which comprises the following steps:
step b1, extruding the yellowing-resistant TPU to form a TPU film;
step b2, preparing a yellowing-resistant pressure-sensitive adhesive, spraying the yellowing-resistant pressure-sensitive adhesive to the bottom surface of the TPU film, and performing air drying treatment;
and b3, attaching a bottom release film on the yellowing-resistant pressure-sensitive adhesive to form a TPU protective film.
When the TPU protective film is used, the bottom release film is torn off, and the TPU protective film can be adhered to a vehicle body.
Specifically, in step b1, the method further comprises attaching a top release film to the top surface of the TPU film. Thus, the TPU protective film can be protected by the top and bottom release films prior to use.
More specifically, both the top and bottom release films are formed from PET material.
Specifically, in the step b2, the preparation process of the yellowing-resistant pressure-sensitive adhesive comprises the following steps: preparing a first pressure-sensitive adhesive raw material and a second pressure-sensitive adhesive raw material respectively, wherein the first pressure-sensitive adhesive raw material and the second pressure-sensitive adhesive raw material are prepared by the following steps of 1:1, mixing the materials in a proportion of 1,
the preparation process of the first pressure-sensitive adhesive raw material comprises the following steps:
step c1, placing polypropylene glycol, difunctional isocyanate and an antioxidant into a reaction container, heating to 65-75 ℃, and standing for more than 3 hours;
step c2, placing the isocyanate trimer into a reaction container, vacuumizing, and standing for more than 0.3h to form a first pressure-sensitive adhesive raw material;
the preparation process of the second pressure-sensitive adhesive raw material comprises the following steps:
step d1, placing polyglycerol, glycerol and a catalyst into a reaction container, heating to 65-75 ℃, and stirring for more than 0.3 h;
d2, vacuumizing, and standing for more than 0.3h to form a second pressure-sensitive adhesive raw material.
In step c1, the standing is performed for 3 hours or more in order to bring the NCO value of the material to 190. In step c2 and step d2, vacuum is drawn to defoam the material.
Specifically, in step c2 and step d2, the pressure after vacuum pumping is 600 to 700mmhg.
Specifically, the first pressure-sensitive adhesive comprises the following components in percentage by weight:
specifically, in step c1, the difunctional isocyanates are difunctional IPDI and difunctional H 12 One or two of MDI are mixed; isocyanate trimer is HDI trimer, IPDI trimer and H 12 One or more MDI trimers; the antioxidant is one or more of 1010 antioxidant, 1076 antioxidant, 1098 antioxidant and 168 antioxidant. The difunctional isocyanate belongs to aliphatic isocyanate, and has no yellowing problem.
Specifically, in step d1, the polyglycerol includes: polyglycerol 3000 and polyglycerol 700. Namely, a polyglycerol having a molecular weight of 3000 and a polyglycerol having a molecular weight of 700.
More specifically, the second pressure-sensitive adhesive comprises the following components in percentage by weight:
specifically, in the step d1, the catalyst is one or two of stannous octoate and amine catalysts.
[ example 1 ]
The embodiment provides a preparation method of a TPU protective film, which comprises the following steps:
in the first stage, preparing yellowing-resistant TPU:
the yellowing-resistant TPU comprises the following components in parts by weight:
step a1, placing IPDI and PDS 1000 into a reaction vessel, heating to 90 ℃ and stirring for 1h;
step a2, placing PC 2000, 1,4 butanediol, graphene, UV-328, 1010 antioxidant and stannous octoate into a reaction vessel, and stirring for 2h;
step a3, placing the PMS 500 into a reaction vessel, and stirring for 1h;
and a4, baking the stirred material at the temperature of 80 ℃ for 14 hours to form the yellowing-resistant TPU.
And in the second stage, preparing the yellowing-resistant pressure-sensitive adhesive:
preparing a first pressure-sensitive adhesive raw material, wherein the weight of each component is as follows:
step c1, placing polypropylene glycol 2000, difunctional IPDI and 1010 antioxidant into a reaction vessel, heating to 70 ℃, and standing for 4 hours;
step c2, placing the HDI trimer into a reaction container, vacuumizing to 650mmhg, and standing for 0.5h to form a first pressure-sensitive adhesive raw material;
preparing a second pressure-sensitive adhesive raw material, wherein the weight of each component is as follows:
step d1, putting polyglycerol 3000, polyglycerol 700, glycerol and stannous octoate into a reaction container, heating to 70 ℃, and stirring for 0.5h;
d2, vacuumizing to 650mmhg, and standing for 0.5h to form a second pressure-sensitive adhesive raw material.
The first pressure-sensitive adhesive raw material and the second pressure-sensitive adhesive raw material are mixed according to the following ratio of 1:1 to form the yellowing-resistant pressure-sensitive adhesive.
Third, preparing TPU protective film:
step b1, extruding the yellowing-resistant TPU to form a TPU film with the thickness of 0.15mm, and attaching a PET top-layer release film with the thickness of 0.1mm to the top surface of the TPU film;
step b2, spraying the yellowing-resistant pressure-sensitive adhesive to the bottom surface of the TPU film, and performing air drying treatment;
and b3, attaching a PET bottom layer release film with the thickness of 0.1mm to the yellowing-resistant pressure-sensitive adhesive to form the TPU protective film.
[ example 2 ]
The embodiment provides a preparation method of a TPU protective film, which comprises the following steps:
in the first stage, preparing yellowing-resistant TPU:
the yellowing-resistant TPU comprises the following components in parts by weight:
step a1, H 12 MDI and PDS 1000 are placed in a reaction vessel, heated to 90 ℃ and stirred for 1h;
step a2, placing PTMEG 2000, 1,4 butanediol, graphene, UV-328, 1010 antioxidant and stannous octoate into a reaction container, and stirring for 2 hours;
step a3, placing the PMS 500 into a reaction vessel, and stirring for 1h;
and a4, baking the stirred material at the temperature of 80 ℃ for 14 hours to form the yellowing-resistant TPU.
And in the second stage, preparing the yellowing-resistant pressure-sensitive adhesive:
preparing a first pressure-sensitive adhesive raw material, wherein the weight of each component is as follows:
step c1, placing polypropylene glycol 2000, difunctional IPDI and 1010 antioxidant into a reaction vessel, heating to 70 ℃, and standing for 4 hours;
step c2, placing the HDI trimer into a reaction container, vacuumizing to 650mmhg, and standing for 0.5h to form a first pressure-sensitive adhesive raw material;
preparing a second pressure-sensitive adhesive raw material, wherein the weight of each component is as follows:
step d1, putting polyglycerol 3000, polyglycerol 700, glycerol and stannous octoate into a reaction container, heating to 70 ℃, and stirring for 0.5h;
d2, vacuumizing to 650mmhg, and standing for 0.5h to form a second pressure-sensitive adhesive raw material.
The first pressure-sensitive adhesive raw material and the second pressure-sensitive adhesive raw material are mixed according to the following ratio of 1:1 to form the yellowing-resistant pressure-sensitive adhesive.
Third, preparing TPU protective film:
step b1, extruding the yellowing-resistant TPU to form a TPU film with the thickness of 0.15mm, and attaching a PET top-layer release film with the thickness of 0.1mm to the top surface of the TPU film;
step b2, spraying the yellowing-resistant pressure-sensitive adhesive to the bottom surface of the TPU film, and performing air drying treatment;
and b3, attaching a PET bottom layer release film with the thickness of 0.1mm to the yellowing-resistant pressure-sensitive adhesive to form the TPU protective film.
[ example 3 ]
The embodiment provides a preparation method of a TPU protective film, which comprises the following steps:
in the first stage, preparing yellowing-resistant TPU:
the yellowing-resistant TPU comprises the following components in parts by weight:
step a1, placing IPDI and PDS 1000 into a reaction vessel, heating to 90 ℃ and stirring for 1h;
step a2, placing PC 1000, 1,4 butanediol, graphene, UV-328, 1010 antioxidant and stannous octoate into a reaction container, and stirring for 2h;
step a3, placing the PMS 500 into a reaction vessel, and stirring for 1h;
and a4, baking the stirred material at the temperature of 80 ℃ for 14 hours to form the yellowing-resistant TPU.
And in the second stage, preparing the yellowing-resistant pressure-sensitive adhesive:
preparing a first pressure-sensitive adhesive raw material, wherein the weight of each component is as follows:
step c1, placing polypropylene glycol 2000, difunctional IPDI and 1010 antioxidant into a reaction vessel, heating to 70 ℃, and standing for 4 hours;
step c2, placing the HDI trimer into a reaction container, vacuumizing to 650mmhg, and standing for 0.5h to form a first pressure-sensitive adhesive raw material;
preparing a second pressure-sensitive adhesive raw material, wherein the weight of each component is as follows:
step d1, putting polyglycerol 3000, polyglycerol 700, glycerol and stannous octoate into a reaction container, heating to 70 ℃, and stirring for 0.5h;
d2, vacuumizing to 650mmhg, and standing for 0.5h to form a second pressure-sensitive adhesive raw material.
The first pressure-sensitive adhesive raw material and the second pressure-sensitive adhesive raw material are mixed according to the following ratio of 1:1 to form the yellowing-resistant pressure-sensitive adhesive.
Third, preparing TPU protective film:
step b1, extruding the yellowing-resistant TPU to form a TPU film with the thickness of 0.15mm, and attaching a PET top-layer release film with the thickness of 0.1mm to the top surface of the TPU film;
step b2, spraying the yellowing-resistant pressure-sensitive adhesive to the bottom surface of the TPU film, and performing air drying treatment;
and b3, attaching a PET bottom layer release film with the thickness of 0.1mm to the yellowing-resistant pressure-sensitive adhesive to form the TPU protective film.
[ basic physical Property test ]
The basic physical properties of the yellowing resistant TPUs of examples 1 to 3 and of a commercially available TPU, TPU3006 from Bayer, germany, were tested as follows:
| test item | Example 1 | Example 2 | Example 3 | Commercially available TPU |
| Shore A hardness | 91A | 92A | 90A | 90A |
| Elongation% | 862 | 845 | 892 | 888 |
| Tensile kg/cm 2 | 211 | 222 | 235 | 232 |
| 100% modulus | 66 | 67 | 66 | 63 |
| Tear resistance kg/cm 2 | 99 | 92 | 88 | 96 |
| Shrinkage percentage% | 0.02 | 0.02 | 0.01 | 0 |
TABLE 1
As can be seen from Table 1, the yellowing resistant TPU's of examples 1-3 have good hardness, elongation, tensile, 100% modulus and tear resistance, are not significantly different from the commercially available TPU's, and meet market demands. In addition, the yellowing-resistant TPU shrinkage of examples 1 to 3 is below 0.02, and the performance is still excellent.
[ anti-yellowing test ]
And (3) detecting the yellowing resistance grade of the TPU protective film by using a UVA340Lamp ultraviolet aging Lamp irradiation, wherein the total duration is 144 hours. The yellowing resistance level is classified into 1-5 levels, the higher the level is, the better the yellowing resistance effect is, wherein the 4 th level is yellowing resistance, and the 5 th level is no yellowing.
The TPU protective films of examples 1 to 3 were subjected to yellowing resistance test, and the test results are as follows:
TABLE 2
As can be seen from Table 2, the TPU protective films of examples 1-3 all had good yellowing resistance.
[ Heat resistance test ]
The deformation rate of the TPU protective film was tested in a high temperature (70 ℃) and low temperature (-20 ℃) reciprocating cycle environment, taking 12 hours as one period and the total duration as 144 hours.
The TPU protective films of examples 1 to 3 were subjected to a heat resistance test, and the length x width of the TPU protective films were: 100X 100mm, the test results are as follows:
| duration of time | Example 1 | Example 2 | Example 3 |
| 36h | 0 | 0 | 0 |
| 72h | 0 | 0 | 0 |
| 144h | 0.01％ | 0.01％ | 0 |
TABLE 3 Table 3
As can be seen from Table 3, the TPU protective films of examples 1-3 have very little deformation, on the order of one ten thousandth, within the standard range.
[ residual glue test ]
The TPU protective films of examples 1 to 3 are attached to a baking varnish steel plate, residual glue test is carried out, and after a period of time, the TPU protective film is torn off with the tearing strength of 0.5kg/cm 2 Observing the residual glue condition, wherein the length multiplied by the width of the TPU protective film is as follows: 100X 100mm, the test results are as follows:
TABLE 4 Table 4
From Table 4, it can be seen that the pressure-sensitive adhesives of the TPU protective films of examples 1 to 3 did not remain on the baked steel sheet during the stripping process.
[ antistatic test ]
Antistatic tests were carried out on the TPU protective films of examples 1 to 3, the length x width of the TPU protective films being: 100X 100mm, the test results are as follows:
| example 1 | Example 2 | Example 3 | |
| Impedance value omega | 8.0×10 -11 | 9.2×10 -11 | 5.5×10 -11 |
TABLE 4 Table 4
As is clear from table 4, the TPU protective films of examples 1 to 3 have low resistance values and good antistatic properties.
[ Water repellency test ]
The TPU protective films of examples 1 to 3 were subjected to a water repellency test, and the length X width of the TPU protective film was: 100X 100mm, the test results are as follows:
| example 1 | Example 2 | Example 3 | |
| Angle of water drop ° | 136 | 144 | 133 |
TABLE 5
As is clear from table 5, the TPU protective films of examples 1 to 3 have a large water drop angle (also called contact angle) and thus all meet the standards of hydrophobic materials and have good water repellency.
The above embodiments are only preferred examples of the present invention and are not intended to limit the scope of the present invention, so that all equivalent changes or modifications of the structure, characteristics and principles described in the claims are included in the scope of the present invention.
Claims (8)
1. A preparation method of a TPU protective film is characterized by comprising the following steps: the preparation method of the TPU protective film comprises the following steps:
step a1, placing isocyanate and a dihydroxyl water repellent agent into a reaction container, heating to 85-95 ℃ and stirring for more than 0.5h;
step a2, putting polyglycol, 1,4 butanediol, graphene, a yellowing-resistant agent, an antioxidant and a catalyst into a reaction container, and stirring for more than 1h;
step a3, placing the monohydroxy water-repellent agent into a reaction container, and stirring for more than 0.5h;
step a4, baking the stirred material at 75-85 ℃ for more than 10 hours to form yellowing-resistant TPU;
step b1, extruding yellowing-resistant TPU to form a TPU film;
step b2, preparing a yellowing-resistant pressure-sensitive adhesive, spraying the yellowing-resistant pressure-sensitive adhesive to the bottom surface of the TPU film, and performing air drying treatment;
step b3, attaching a bottom release film on the yellowing-resistant pressure-sensitive adhesive to form a TPU protective film;
in the step b2, the preparation process of the yellowing-resistant pressure-sensitive adhesive comprises the following steps: preparing a first pressure-sensitive adhesive raw material and a second pressure-sensitive adhesive raw material respectively, wherein the first pressure-sensitive adhesive raw material and the second pressure-sensitive adhesive raw material are prepared by the following steps of 1:1, and the preparation process of the first pressure-sensitive adhesive raw material comprises the following steps:
step c1, placing polypropylene glycol, difunctional isocyanate and an antioxidant into a reaction container, heating to 65-75 ℃, and standing for more than 3 hours;
step c2, placing the isocyanate trimer into a reaction container, vacuumizing, and standing for more than 0.3h to form a first pressure-sensitive adhesive raw material;
the preparation process of the second pressure-sensitive adhesive raw material comprises the following steps:
step d1, placing polyglycerol, glycerol and a catalyst into a reaction container, heating to 65-75 ℃, and stirring for more than 0.3 h;
d2, vacuumizing, and standing for more than 0.3h to form a second pressure-sensitive adhesive raw material.
2. The method for producing a TPU protective film according to claim 1, wherein: the yellowing-resistant TPU comprises the following components in percentage by weight:
3. the method for producing a TPU protective film according to claim 1, wherein: in the step a1, the dihydroxyl water repellent agent is PSD; in step a3, the monohydroxy water repellent is PMS.
4. The method for producing a TPU protective film according to claim 1, wherein: in step a1, the isocyanates are IPDI, MDI, TDI, HDI and H 12 One or more of MDI mixed; in the step a2, the polyglycol is one or two of PC and PTMEG; the yellowing resisting agent is one or more of UV-328, UV-327, UV-P and UV-765; the antioxidant is one or more of 1010 antioxidant, 1076 antioxidant, 1098 antioxidant and 168 antioxidant;
the catalyst is one or two of stannous octoate and amine catalysts.
5. The method for producing a TPU protective film according to claim 1, wherein: in step b1, the method further comprises attaching a top release film to the top surface of the TPU film.
6. The method for producing a TPU protective film according to claim 1, wherein: the first pressure-sensitive adhesive comprises the following components in percentage by weight:
7. the method for producing a TPU protective film according to claim 1, wherein: in step d1, the polyglycerol comprises: polyglycerol 3000 and polyglycerol 700.
8. The method for producing a TPU protective film according to claim 7, wherein: the second pressure-sensitive adhesive comprises the following raw materials in percentage by weight:
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