CN104531039B - A kind of preparation method of polyurethane pressure sensitive glue composition and protecting film - Google Patents
A kind of preparation method of polyurethane pressure sensitive glue composition and protecting film Download PDFInfo
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- CN104531039B CN104531039B CN201410848184.7A CN201410848184A CN104531039B CN 104531039 B CN104531039 B CN 104531039B CN 201410848184 A CN201410848184 A CN 201410848184A CN 104531039 B CN104531039 B CN 104531039B
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- polyurethane
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Abstract
The preparation method that the present invention relates to a kind of polyurethane pressure sensitive glue composition and protecting film, it is characterised in that include polyether polyol 1000 parts, modified isocyanate 100-400 part, catalyst 0.01-1 part, 0.05～10 part of antistatic additive, solvent 500～2000 parts；It is applied directly onto on base material after above-mentioned each component mix homogeneously, the polyurethane protective film that once reaction and availability are excellent on 60-130 DEG C。The preparation method of polyurethane formulations provided by the present invention and protecting film; eliminate the prepolymerization flow process of early stage; directly use the online catalytic reaction polymerization of starting monomer crosslinking curing molding; 100% film forming; saving great amount of cost and time, it is achieved that the accurate control of protecting film stabilizing quality, the adhesive mixed liquor configured at room temperature can long storage time; can certainly use immediately, greatly expand the operable time of coating stage。
Description
Technical field
The present invention relates to polyurethane protective film field, the preparation method referring specifically to a kind of antistatic polyurethane pressure sensitive adhesive composition and protecting film thereof。
Background technology
Owing to other component of adhesive is played the effect promoting crosslinking curing by catalyst; and adhesive be not once prepare be immediately applied to protection rete on; therefore; existing polyurethane contact adhesive protecting film generally adopts first prepolymerization to produce adhesive; in order to ensure the polymerization of adhesive and in the quality being coated on protecting film, adhesive needs to add substantial amounts of cross-linking agent in pre-polymerization process。And also need in prepolymerized adhesive addition curing catalysts before coating, curing rate during to ensure that the later stage is coated with and crosslinking degree。
Experience secondary solidifies and obtains polyurethane protective film, and later stage hydraulic performance decline is obvious, reduces the adherence between itself and rete；Furthermore, difference due to polyurethane adhesive self electric property, produce and the process of use protecting film is easy to produce electrostatic, but owing to antistatic additive is to add in prepolymerized adhesive together with cross-linking agent when the later stage is coated with, due in adhesive prepolymerization, major part active group is already engaged in cross-linking reaction, secondary cross-linking during coating solidifies the crosslinking of only fraction, the degree of cross linking is low, cannot completely stable for antistatic additive be coated in glue-line in the way of chemical bonds, adhesive is high with the difficulty of matching of antistatic additive, and antistatic composition easily precipitates out from glue-line in later stage use procedure, cause the low stain performance of protecting film。Meanwhile, the method for prior art separate operations not only synthesizes the complex procedures of film, and needs to control preparation time, preparing process, and the operator of factory are had certain technology requirement, causes that production cost rises substantially。
Summary of the invention
The technical problem to be solved is that the present situation offer for prior art is a kind of can effectively reduce the polyurethane pressure sensitive glue composition that cost, guarantee adhesive quality and antistatic effect are good。
Another technical problem to be solved by this invention is to provide a kind of preparation method that can effectively reduce the good polyurethane protective film of cost, guarantee adhesive quality and antistatic effect。
This invention address that the technical scheme that above-mentioned technical problem adopts is: this polyurethane pressure sensitive glue composition, it is characterised in that include following weight component:
Wherein, the mean molecule quantity of described polyether polyol is 1000～10000, and the hydroxyl quantity in each construction unit of polyether polyol is 3～5；
Described modified isocyanate is the addition compound product of isocyanates and hydroxy compounds, and described hydroxy compounds contains at least three hydroxyl；
Described antistatic additive is alkyl sulfonates or sulfimide and its esters permanent anti-static agent；
Described solvent at least one in ethyl acetate, toluene, butyl acetate, acetone, butanone, 2 pentanone, acetylacetone,2,4-pentanedione and ethanol；
Described catalyst is selected from triethylene diamine system, dimethylamine base system or tertiary amine system organic amine catalyst。
Described solvent is preferably the mixture of two kinds of materials, and one of which is ketones solvent, and the weight ratio of described ketones solvent and another kind of solvent is 0.005～1:1。In this programme, ketones solvent and antistatic additive synergism, play stable inhibitory action to catalyst, ketones solvent quickly volatilizees when heating, cancels the suppression to catalyst, and antistatic additive at high temperature disconnects the binding with catalyst simultaneously, catalyst activity excites, catalytic mixing thing fast reaction；Response speed is fast, and each component cross-link degree reaches 100%；Especially antistatic additive, is coated in cross-linked network completely, and antistatic effect is good, and the ratio of precipitation is substantially reduced, and farthest reduces surface contamination。
Preferably, described antistatic additive is selected from bis trifluoromethyl sulfimide salt antistatic additive。
In above-mentioned each scheme, described polyether polyol is glycerol, trimethylolpropane or propylene glycol and the addition polymerization product of oxirane, expoxy propane or epoxy butane。
Described isocyanates is selected from one of TDI, HDI, MDI or XDI。
Use the method that above-mentioned polyurethane pressure sensitive glue composition prepares polyurethane protective film, it is characterised in that comprise the steps:
1), under room temperature, the described each component of polyurethane pressure sensitive glue composition is mixed and stirs, namely obtains coating fluid；
2) by described coating fluid by 10～100g/m2It is coated on base material, dries 0.5-5 minute at 60-130 DEG C, namely obtain antistatic polyurethane protecting film；
3) by antistatic polyurethane protecting film ripening 5-9 days at 30-50 DEG C, antistatic polyurethane protecting film finished product is namely obtained。
Step 2) in preferred 80-120 DEG C of baking temperature, preferred 0.5-2 minute of drying time。
Step 3) in curing temperature preferably 40 DEG C, preferably 5～7 days curing time。
Described base material can select as required of the prior art any one, preferably, described base material can be selected from PET, PEN, PI, PMMA or PC, and the thickness of described base material is 25-125 μm。PI and Kapton, PMMA, PC, the thickness of described base material is 25-125 μm。
Compared with prior art, antistatic additive in antistatic polyurethane pressure sensitive adhesive composition provided by the present invention, when temperature is lower than 60 DEG C, can be combined with catalyst effective ingredient, effectively suppress the activity of catalyst so that it is can not the polymerization of quick catalysis polyhydric alcohol and isocyanates, that is, when temperature is less than 60 DEG C, polyurethane pressure sensitive glue composition is only a mixture, and the activity of catalyst is subject to the suppression of antistatic additive；And it is coated on rete when it, when 60-130 DEG C, the coalition of antistatic additive and organic amine decomposes, organic amine catalyst activity excitation, high temperature direct-on-line catalysis polyurethane contact adhesive each component reaction in baking oven during online coating, make its rapid polymerization film-forming, prepare and there is excellent surface adsorptivity；The degree of cross linking reaches 100%；Antistatic additive is to add in the little molecule stage, and it can participate in reaction, and the network structure that other component collectively forms crosslinking completely, reduces later stage ratio of the precipitation of antistatic additive when using, and anti-static effect is good, improves the low stain performance in protecting film product later stage；Production efficiency is high, the heat-resisting quantity of protecting film and Nai Gao is moist and stability is good。The preparation method of polyurethane protective film provided by the present invention; eliminate the prepolymerization flow process of early stage; directly use the online catalytic reaction polymerization of starting monomer crosslinking curing molding; 100% film forming; saving great amount of cost and time, it is achieved that the accurate control of protecting film stabilizing quality, the adhesive mixed liquor configured at room temperature can long storage time; can certainly use immediately, greatly expand the operable time of coating stage。
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail。
Embodiment 1～7
In embodiment 1 to embodiment 7 and comparative example 1, comparative example 2, comparative example 3 shown in the formula table 1 of polyurethane contact adhesive。
In table, TMP is the abbreviation of trimethylolpropane,
Wherein in embodiment 1 to 7, above-mentioned each formula material is mixed in proportion in pre-stirring container by polyurethane, after being sufficiently stirred for 30min standby, filter through the aperture filter less than or equal to 3 μm after bubble collapse, remove the impurity in solvent, use scraper type coating method by 15 ± 3g/m2Wet glue amount be coated in the PET base material of 50 μ m-thick, after oven drying 2min at 100 DEG C, be cooled to room temperature, 50 μm of mould release membrance rollings of fitting；Being then placed within 40 DEG C of thermostatic chambers ripening 7 days, point bar processed finished products prepares polyurethane protective film product。
Raw material in above-mentioned comparative example 1 is mixed in proportion in pre-stirring container; after being sufficiently stirred for 30min standby; treat that bubble collapse processes through particular filter equipment; it is coated on 50 μm of PET base material faces (coating method can be selected for scraper type, reticulate pattern formula, jet printing type) by the wet glue amount of 15 ± 3g/m2; it is cooled to room temperature after oven drying (about 2min); fitting 50 μm of mould release membrance rollings, after placing in 40 DEG C of thermostatic chambers ripening 7 days, point bar processing prepares light exfoliated protecting film product。
Raw material in above-mentioned comparative example 1 is mixed in proportion in pre-stirring container, after being sufficiently stirred for 30min standby, treat that bubble collapse processes through particular filter equipment, (coating method can be selected for scraper type to be coated on 50 μm of PET base material faces by the wet glue amount of 15 ± 3g/m2, reticulate pattern formula, jet printing type), it is cooled to room temperature after oven drying (about 2min), fit 50 μm of mould release membrance rollings, after placing in 40 DEG C of thermostatic chambers ripening 7 days, prepare a protecting film product, but there is substantially deterioration in adsorptivity, adhesion strength also has the trend of rising, estimate that use is caused certain impact by the excessive meeting of sclerosing agent。
Raw material in above-mentioned comparative example 2 is mixed in proportion in pre-stirring container, after being sufficiently stirred for 30min standby, treat that bubble collapse processes through particular filter equipment, (coating method can be selected for scraper type to be coated on 50 μm of PET base material faces by the wet glue amount of 15 ± 3g/m2, reticulate pattern formula, jet printing type), it is cooled to room temperature after oven drying (about 2min), fit 50 μm of mould release membrance rollings, after placing in 40 DEG C of thermostatic chambers ripening 7 days, prepare a protecting film product without electrostatic-proof function, but operability occurs in that obvious decline, room temperature can substantially shorten the resting period, impact coating uses。
Raw material in above-mentioned comparative example 3 is mixed in proportion in pre-stirring container, standby after being sufficiently stirred for 30min, treat that bubble collapse processes through particular filter equipment, by 15 ± 3g/m2Wet glue amount be coated on 50 μm of PET base material faces (coating method can be selected for scraper type, reticulate pattern formula, jet printing type); it is cooled to room temperature after oven drying (about 2min); fit 50 μm of mould release membrance rollings; after placing in 40 DEG C of thermostatic chambers ripening 7 days; preparing a protecting film product, there is the possibility of certain pollution on the surface of glass by it。
Method of testing:
Optical property: protecting film product peels off mould release membrance, mist degree instrument measures full light transmission rate and the mist degree of sample under each condition, with specific reference to JISK73611 standard, JISK71361 standard；
Adhesion strength: glass plate placement 20min 180 DEG C of peeling forces of mensuration that the laminating of 25mm wide cut sample is clean, 300mm/min speed, parallel testing is averaged for 2 times, with specific reference to STS-TT-01 standard；
Adsorptivity: cut out 5 × 7cm2Sample, tests it to glass pane surface automatic absorbing area 5 × 5cm2Time, manual time-keeping, fitting area 5 × 5cm2, retest is averaged for 2 times；
Glue surface resistance: use sheet resistance tester to measure the sheet resistance of sample glue surface；
Contaminative: sample laminating glass plate is placed under respective environment, is taken out to room temperature, the pollution condition of glass pane surface after protecting film is peeled off observed by darkroom major light。
Note: in table 1, each constituent content is weight portion；
Zero: represent pollution-free, without cull, △: represent light contamination, there are the white mist of point-like or brilliant point etc. to pollute in glass pane surface；
1831 is the abbreviation of octadecyl trimethyl ammonium chloride。
Claims (9)
1. a polyurethane pressure sensitive glue composition, it is characterised in that include following weight component:
Wherein, the mean molecule quantity of described polyether polyol is 1000～10000, and the hydroxyl quantity in each construction unit of polyether polyol is 3～5；
Described modified isocyanate is the addition compound product of isocyanates and hydroxy compounds, and described hydroxy compounds contains at least three hydroxyl；
Described antistatic additive is alkyl sulfonates or sulfimide and its esters permanent anti-static agent；
Described solvent at least one in ethyl acetate, toluene, butyl acetate, acetone, butanone, 2 pentanone, acetylacetone,2,4-pentanedione and ethanol；
Described catalyst is selected from triethylene diamine system, dimethylamine base system or tertiary amine system organic amine catalyst。
2. polyurethane pressure sensitive glue composition according to claim 1, it is characterised in that described solvent is the mixture of two kinds of materials, and one of which is ketones solvent, the weight ratio of described ketones solvent and another kind of solvent is 0.005～1:1。
3. polyurethane pressure sensitive glue composition according to claim 1 and 2, it is characterised in that described antistatic additive is selected from bis trifluoromethyl sulfimide salt antistatic additive。
4. polyurethane pressure sensitive glue composition according to claim 3, it is characterised in that described polyether polyol is glycerol, trimethylolpropane or propylene glycol and the addition polymerization product of oxirane, expoxy propane or epoxy butane。
5. polyurethane pressure sensitive glue composition according to claim 4, it is characterised in that described isocyanates is selected from one of TDI, HDI, MDI or XDI。
6. use the method that polyurethane pressure sensitive glue composition as claimed in claim 1 prepares polyurethane protective film, it is characterised in that comprise the steps:
1), under room temperature, the described each component of polyurethane pressure sensitive glue composition is mixed and stirs, namely obtains coating fluid；
2) by described coating fluid by 10～100g/m2It is coated on base material, dries 0.5-5 minute at 60-130 DEG C, namely obtain antistatic polyurethane protecting film；
3) by antistatic polyurethane protecting film ripening 5-9 days at 30-50 DEG C, antistatic polyurethane protecting film finished product is namely obtained。
7. the preparation method of polyurethane protective film according to claim 6, it is characterised in that step 2) in baking temperature be 80-120 DEG C, drying time is 0.5-2 minute。
8. the preparation method of polyurethane protective film according to claim 7, it is characterised in that step 3) in curing temperature be 40 DEG C, the curing time is 5～7 days。
9. the preparation method of polyurethane protective film according to claim 8, it is characterised in that described base material is selected from PET, PEN, PI, PMMA or PC, and the thickness of described base material is 25-125 μm。
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| CN104531039B true CN104531039B (en) | 2016-06-22 |
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| CN106147683A (en) * | 2015-04-01 | 2016-11-23 | 上海精涂新材料技术有限公司 | A kind of protecting film polyurethane glue |
| CN106147688A (en) * | 2015-04-01 | 2016-11-23 | 上海精涂新材料技术有限公司 | A kind of antistatic protection film glue and a kind of antistatic protection film |
| CN104890331A (en) * | 2015-05-12 | 2015-09-09 | 浙江明士达新材料有限公司 | Lamp-box fabric material with good transmittance |
| CN104877587A (en) * | 2015-06-08 | 2015-09-02 | 佛山伟利信电子材料有限公司 | Protective film with polyurethane adhesive |
| CN105176432B (en) * | 2015-09-14 | 2017-10-20 | 宁波长阳科技股份有限公司 | A kind of preparation method of antistatic polyester diaphragm |
| CN105754536A (en) * | 2016-03-10 | 2016-07-13 | 张家港锐码新材料有限公司 | Transparent antistatic pressure-sensitive adhesive |
| CN106318254A (en) * | 2016-08-23 | 2017-01-11 | 中山市鼎立森电子材料有限公司 | Bicomponent polyurethane protective film pressure-sensitive adhesive and synthetic process thereof |
| CN106753169A (en) * | 2016-08-23 | 2017-05-31 | 中山市鼎立森电子材料有限公司 | A kind of mono-component polyurethane diaphragm pressure sensitive adhesive and its synthesis technique |
| CN106432666A (en) * | 2016-10-26 | 2017-02-22 | 江苏怡丽科姆新材料股份有限公司 | Self-repairing film |
| CN107365562A (en) * | 2017-08-15 | 2017-11-21 | 张家港康得新光电材料有限公司 | A kind of diaphragm |
| CN110511667A (en) * | 2019-10-12 | 2019-11-29 | 无锡阿尔梅新材料有限公司 | A kind of LED UV solidification permanent anti-static stiffened coating for TAC film |
| CN111484598B (en) * | 2020-04-14 | 2022-03-08 | 中国铁道科学研究院集团有限公司铁道建筑研究所 | High-strength single-component tunnel lining structure protective coating |
| CN112795330B (en) * | 2020-12-16 | 2023-05-02 | 苏州恒悦新材料股份有限公司 | Ultralow-stripping static voltage PU protective film and preparation method thereof |
| CN112778931A (en) * | 2020-12-31 | 2021-05-11 | 江苏伊诺尔新材料科技有限公司 | PMMA (polymethyl methacrylate) composite material optical protective film adhesive tape and preparation method thereof |
| CN114395341A (en) * | 2021-12-30 | 2022-04-26 | 崴思新材料泰州有限公司 | Low-tear-film electrostatic-voltage PU protective film and preparation method thereof |
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| JP2005154492A (en) * | 2003-11-21 | 2005-06-16 | Toyo Ink Mfg Co Ltd | Antistatic self-adhesive film and its manufacturing method |
| CN101497776A (en) * | 2008-01-28 | 2009-08-05 | 国家淀粉及化学投资控股公司 | Adhesive and use thereof |
| JP5526646B2 (en) * | 2009-08-07 | 2014-06-18 | 東洋インキＳｃホールディングス株式会社 | Antistatic pressure-sensitive adhesive composition, and antistatic pressure-sensitive adhesive sheet and laminate using the same |
| CN102020969A (en) * | 2009-09-18 | 2011-04-20 | 上海合达聚合物科技有限公司 | Bi-component fast-curing polyurethane adhesive and application thereof |
| CN102532469A (en) * | 2011-12-28 | 2012-07-04 | 南京双威生物医学科技有限公司 | Graphite composite modified fire-retardant anti-static polyurethane and adhesive plaster |
| JP5961474B2 (en) * | 2012-07-31 | 2016-08-02 | 日東電工株式会社 | Surface protection film |
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