CN103923334A - Fluorosilicone release film and preparation method thereof - Google Patents
Fluorosilicone release film and preparation method thereof Download PDFInfo
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- CN103923334A CN103923334A CN201410141581.0A CN201410141581A CN103923334A CN 103923334 A CN103923334 A CN 103923334A CN 201410141581 A CN201410141581 A CN 201410141581A CN 103923334 A CN103923334 A CN 103923334A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 101
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000002904 solvent Substances 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 17
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 7
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims description 45
- -1 acrylic ester Chemical class 0.000 claims description 44
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 20
- 239000012530 fluid Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000010792 warming Methods 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 229960004756 ethanol Drugs 0.000 claims description 4
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 238000009998 heat setting Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- HCOKJWUULRTBRS-UHFFFAOYSA-N propan-2-yloxysilane Chemical compound CC(C)O[SiH3] HCOKJWUULRTBRS-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 abstract description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011737 fluorine Substances 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 238000001723 curing Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 150000007530 organic bases Chemical class 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 abstract 1
- 238000001029 thermal curing Methods 0.000 abstract 1
- 229920001296 polysiloxane Polymers 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
The invention aims to provide a fluorosilicone release film and a preparation method thereof. The preparation method comprises the following steps: preparing silicon dioxide sol, and adding acrylate monomers, fluorine-containing monomers and silicon-containing monomers in a nitrogen atmosphere to perform free radical co-polymerization to obtain a fluorosilicone release agent; mixing the release agent, a composite solvent and an isocyanate curing agent to prepare a coating liquid; applying the coating liquid to an organic base material; and performing thermal curing to prepare the fluorosilicone release film. The fluorosilicone release film has the advantages of high hydrophobicity, low release force, low water absorption rate, high residual adhesion rate and the like, and has excellent release performance.
Description
Technical field
The invention belongs to industrial foundation Application Areas; be particularly related to a kind of fluorine silicon release film and preparation method thereof; this release film has lighter and stable off-type force, can be applicable to the industry fields such as liquid crystal screen protection film, packing, sealing material use film, light reflecting material, water-proof material, adhesive article, the processing of cross cutting stamp.
Background technology
Further opening along with Chinese market, large quantities ofly take the foreign capital affiliate that the conventional industries such as electronics, plastic cement, gift, toy are main body and in succession enter Chinese market, the production of release film is developed thereupon faster, wherein silicone release material is widely used in all trades and professions, develop unprecedented rapidly.Along with scientific and technical development, organosilicon polymer exposes the shortcomings such as resistant to chemical media is poor gradually, also silicone release product has been proposed to new requirement.At present, although China's development has in this respect had raising by a relatively large margin, compare with American-European, Japan and other countries, also have very large gap, also need further to develop and can reach advanced world standards.
Current domestic main production solvent-borne type parting agent, its concrete use by release film manufacturer is determined according to equipment situation and product requirement separately, wherein silicone release agent is with its good peeling force, thermotolerance and stability, become one of focus of parting agent investigation of materials, silicone release agent can be made emulsion shape, solvent shape and no-solvent type, silicone release agent has become parting agent material of greatest concern, at Pressuresensitive Tape, water-proof material, PCB manufactures, in the industries such as the manufacture of car moulded material and telecommunications, be widely used, and along with being penetrated in more industry, scientific and technical development plays an important role.Patent CN1931926A discloses a kind of release film by preparing containing vinyl polysiloxane, hydrogen containing siloxane, the silicone composition that forms containing epoxycyclohexyl silane, platinum catalyst and polyethers or lauryl ether, compare with external product, domestic silicone release agent also has a certain distance on fast setting; In the adjusting of peeling force, lack effective and cheap conditioning agent, also poor aspect package stability.
When process at the back side that parting agent is used to Pressuresensitive Tape, the uncoiling of Pressuresensitive Tape is easily the main purpose that adhesive tape carries out release treatment, silicone release agent is antiseized, isolation effect is better, therefore be widely used, but silicone release agent is found in using: long-time placement there will be sticky volume phenomenon, can not play the anti-adhesion effects of expection, therefore, silicone based parting agent be carried out to the interest that study on the modification has caused people.The synthetic macromolecular compound that fluoropolymer general reference macromolecular main chain or side chain contain fluorine atom, fluoropolymer is owing to having unique excellent properties, no matter from kind, quality, Application Areas, be still all developed rapidly in quantity, patent CN1821286A discloses a kind of by 2, release film and working method thereof that 4-hexafluoroethylene methyl siloxane is made, the performance of film improves.That the present invention adopts is fluorine-containing, silicon-containing monomer carries out modification to acrylate and made fluorine silicon parting agent, has higher hydrophobicity, lower low and good advantages such as release performance of peeling force, water-intake rate.
Summary of the invention
Technical problem: the object of the invention is in order to solve the main dependence on import of current domestic parting agent, and exist wayward, synthetic cost high and be difficult to reach the problem of release performance in the building-up process of parting agent, and a kind of preparation method of novel fluorine silicon release film is provided.
Technical scheme: the preparation method of fluorine silicon release film of the present invention is:
This release film is first to prepare silicon dioxide gel, under nitrogen atmosphere, add again acrylic ester monomer, fluorochemical monomer and silicon-containing monomer, carry out the free-radical polymerized fluorine silicon parting agent that obtains, again this parting agent is mixed into coating fluid with double solvents, isocyanates solidifying agent, this coating fluid is coated on organic substrate, through thermofixation, make fluorine silicon release film, this preparation method's matrix is:
Step a) at room temperature, by tetraethoxy and dehydrated alcohol in mass ratio 1:1～1:10 join in reactor, stirring 5～20min mixes, the deionized water that slowly dropping and tetraethoxy mass ratio are 0.1:1～0.5:1 is again to reactor, drip off rear continuation and stir ageing 24～30h, obtain silicon dioxide gel;
Step b) under nitrogen atmosphere, the silicon dioxide gel that step is made in a) adds reactor, adds solvent, acrylic ester monomer, is warming up to 40～80 ℃, drip initiator solution, time for adding is 0.5～5h, adds fluorochemical monomer, silicon-containing monomer after dripping off, after reaction 2～5h, be warming up to 60～90 ℃, continue reaction 1～5h, be cooled to room temperature, obtain fluorine silicon parting agent;
Step c) under nitrogen atmosphere, room temperature, by step b) in make fluorine silicon parting agent and add reactor, the double solvents that adds 2～3 times of fluorine silicon parting agent quality, the isocyanates solidifying agent that adds again 0.01～0.1 times of fluorine silicon parting agent quality, mix, be made into coating fluid, use spreader that this coating fluid is coated on clean organic substrate, at 120～150 ℃, solidify 1～5min, make transparent fluorine silicon release film.
Described fluorochemical monomer is one or more mixtures in trifluoroethyl methacrylate, tetrafluoropropyl propyl ester, Hexafluorobutyl mathacrylate or methacrylic acid octafluoro pentyl ester; Described silicon-containing monomer is one or more mixtures in vinyltrimethoxy silane, vinyltriethoxysilane, methacryloxypropyl three isopropoxy silane, methyl allyl acyloxypropyl trimethoxysilane; Described acrylic ester monomer is one or more mixtures of Isooctyl methacrylate, butyl acrylate, glycidyl methacrylate, Hydroxyethyl acrylate; Described initiator is one or more the mixture in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, peroxidized t-butyl perbenzoate, dicumyl peroxide.
Described fluorochemical monomer, silicon-containing monomer, acrylic ester monomer are to add in polyreaction the massfraction of monomer to be:
A) content of silicon-containing monomer accounts for 10%～30% of total monomer quality;
B) content of fluorochemical monomer accounts for 5%～30% of total monomer quality;
C) content of acrylic ester monomer accounts for 40%～65% of total monomer quality.
Described solvent is one or more mixtures in toluene, hexanaphthene, hexone, ethanol, and usage quantity is 50%～200% of monomer total mass.
The mass concentration of described initiator solution is 5%～30%, initiator preparation solvent for use is one or more the mixture in toluene, hexanaphthene, hexone, ethanol, ethyl acetate, and initiator dripping quantity accounts for 0.05%～1.5% of total monomer quality.
Described double solvents is ethylene glycol monomethyl ether and the ethyl acetate mixed solution that 1:3～1:5 is mixed with in mass ratio; Described isocyanates solidifying agent is a kind of in hexamethylene diisocyanate, 2,4 toluene diisocyanate, dimethyl diphenyl vulcabond; Described organic substrate is a kind of in polyethylene terephthalate film, polyethylene film or polypropylene screen.
Beneficial effect: the invention provides a kind of fluorine silicon release film and preparation method thereof, this fluorine silicon release film has higher hydrophobicity, lower low and good advantages such as release performance of peeling force, water-intake rate.
Feature of the present invention is:
(1) fluorine-containing, the silicon-containing group of fluorine silicon release film surface enrichment, therefore this release film has the lower energy that shows, the introducing of fluoroalkyl, siloxy group, make fluorine silicon release film there is good chemical stability, thereby the not sticky volume of this fluorine silicon release film, release effective, also there is good solvent resistance simultaneously.
(2) the release film water-intake rate that prepared by the present invention is low, stability is better, can be used for, in the industries such as Pressuresensitive Tape, water-proof material, having higher economic worth.
Embodiment
Embodiment 1:
Step a) at room temperature, joins 5g tetraethoxy and 5g dehydrated alcohol in reactor, stirs 10min and mixes, more slowly drip 1g deionized water to reactor, and time for adding is 1h, drips off rear continuation and stirs ageing 24h, obtains silicon dioxide gel;
Step b) under nitrogen atmosphere, the silicon dioxide gel that step is made in a) adds reactor, adds 30mL solvent hexone, acrylic ester monomer, is warming up to 60 ℃, drip the hexone solution of the Diisopropyl azodicarboxylate that 1.6g mass concentration is 25%, time for adding is 1h, adds fluorochemical monomer, silicon-containing monomer after dripping off, after reaction 5h, be warming up to 75 ℃, continue reaction 2h, be cooled to room temperature, obtain fluorine silicon parting agent;
Step c) under nitrogen atmosphere, room temperature, by 5g step b) in make fluorine silicon parting agent and add reactor, add 2.5g ethylene glycol monomethyl ether and 10.0g ethyl acetate, add again 0.25g hexamethylene diisocyanate solidifying agent, mix, be made into coating fluid, use spreader that this coating fluid is coated on clean polyethylene terephthalate film, at 150 ℃, solidify 1min, make transparent fluorine silicon release film.
Monomer total mass is 50g, and wherein fluorochemical monomer used, silicon-containing monomer, acrylic ester monomer comprise:
D) accounting for total monomer quality 30% is 15g vinyltriethoxysilane;
E) accounting for total monomer quality 5% is 2.5g Hexafluorobutyl mathacrylate;
F) accounting for total monomer quality 20% is 10g vinylformic acid;
G) accounting for total monomer quality 45% is 22.5g butyl acrylate.
The parting agent of present embodiment gained is prepared into after release film, and the water-intake rate of film is 2.1%, surface free energy 31.4mN/m, and peeling away the peeling force required with standard Pressuresensitive Tape TESA7475 is 1.913～1.922N/25mm, residue adhesion rate is 82.5%.
Embodiment 2:
Step a) at room temperature, joins 5g tetraethoxy and 15g dehydrated alcohol in reactor, stirs 10min and mixes, more slowly drip 1g deionized water to reactor, and time for adding is 1h, drips off rear continuation and stirs ageing 24h, obtains silicon dioxide gel.
Step b) under nitrogen atmosphere, the silicon dioxide gel that step is made in a) adds reactor, adds 40mL solvent hexone, acrylic ester monomer, is warming up to 60 ℃, drip the hexone solution of the Diisopropyl azodicarboxylate that 2.0g mass concentration is 25%, time for adding is 1h, adds fluorochemical monomer, silicon-containing monomer after dripping off, after reaction 5h, be warming up to 75 ℃, continue reaction 2h, be cooled to room temperature, obtain fluorine silicon parting agent;
Step c) under nitrogen atmosphere, room temperature, by 5g step b) in make fluorine silicon parting agent and add reactor, add 2.5g ethylene glycol monomethyl ether and 10.0g ethyl acetate, add again 0.25g hexamethylene diisocyanate solidifying agent, mix, be made into coating fluid, use spreader that this coating fluid is coated on clean polyethylene terephthalate film, at 150 ℃, solidify 1min, make transparent fluorine silicon release film.
Monomer total mass is 50g, and wherein fluorochemical monomer used, silicon-containing monomer, acrylic ester monomer comprise:
D) accounting for total monomer quality 25% is 12.5g vinyltriethoxysilane;
E) accounting for total monomer quality 10% is 5g Hexafluorobutyl mathacrylate;
F) accounting for total monomer quality 20% is 10g vinylformic acid;
G) accounting for total monomer quality 45% is 22.5g butyl acrylate.
The parting agent of present embodiment gained is prepared into after release film, and the water-intake rate of film is 1.7%, surface free energy 25.3mN/m, and peeling away the peeling force required with standard Pressuresensitive Tape TESA7475 is 1.566～1.664N/25mm, residue adhesion rate is 88.0%.
Embodiment 3:
Step a) at room temperature, joins 5g tetraethoxy and 25g dehydrated alcohol in reactor, stirs 10min and mixes, more slowly drip 1g deionized water to reactor, and time for adding is 1h, drips off rear continuation and stirs ageing 24h, obtains silicon dioxide gel.
Step b) under nitrogen atmosphere, the silicon dioxide gel that step is made in a) adds reactor, adds 50mL solvent hexone, acrylic ester monomer, is warming up to 60 ℃, drip the hexone solution of the Diisopropyl azodicarboxylate that 2.2g mass concentration is 25%, time for adding is 1h, adds fluorochemical monomer, silicon-containing monomer after dripping off, after reaction 5h, be warming up to 75 ℃, continue reaction 2h, be cooled to room temperature, obtain fluorine silicon parting agent;
Step c) under nitrogen atmosphere, room temperature, by 5g step b) in make fluorine silicon parting agent and add reactor, add 3.0g ethylene glycol monomethyl ether and 9.5g ethyl acetate, add again 0.25g hexamethylene diisocyanate solidifying agent, mix, be made into coating fluid, use spreader that this coating fluid is coated on clean polyethylene terephthalate film, at 150 ℃, solidify 1min, make transparent fluorine silicon release film.
Monomer total mass is 50g, and wherein fluorochemical monomer used, silicon-containing monomer, acrylic ester monomer comprise:
D) accounting for total monomer quality 20% is 10g vinyltriethoxysilane;
E) accounting for total monomer quality 15% is 7.5g Hexafluorobutyl mathacrylate;
F) accounting for total monomer quality 20% is 10g vinylformic acid;
G) accounting for total monomer quality 45% is 22.5g butyl acrylate.
The parting agent of present embodiment gained is prepared into after release film, and the water-intake rate of film is 0.66%, surface free energy 16.2mN/m, and peeling away the peeling force required with standard Pressuresensitive Tape TESA7475 is 1.122～1.221N/25mm, residue adhesion rate is 90.8%.
Embodiment 4:
Step a) at room temperature, joins 5g tetraethoxy and 15g dehydrated alcohol in reactor, stirs 10min and mixes, more slowly drip 1g deionized water to reactor, and time for adding is 1h, drips off rear continuation and stirs ageing 24h, obtains silicon dioxide gel.
Step b) under nitrogen atmosphere, the silicon dioxide gel that step is made in a) adds reactor, adds 30mL solvent hexone, acrylic ester monomer, is warming up to 60 ℃, drip the hexone solution of the Diisopropyl azodicarboxylate that 2.2g mass concentration is 25%, time for adding is 1h, adds fluorochemical monomer, silicon-containing monomer after dripping off, after reaction 5h, be warming up to 75 ℃, continue reaction 2h, be cooled to room temperature, obtain fluorine silicon parting agent;
Step c) under nitrogen atmosphere, room temperature, by 5g step b) in make fluorine silicon parting agent and add reactor, add 2.5g ethylene glycol monomethyl ether and 10.0g ethyl acetate, add again 0.25g hexamethylene diisocyanate solidifying agent, mix, be made into coating fluid, use spreader that this coating fluid is coated on clean polyethylene terephthalate film, at 150 ℃, solidify 1min, make transparent fluorine silicon release film.
Monomer total mass is 50g, and wherein fluorochemical monomer used, silicon-containing monomer, acrylic ester monomer comprise:
D) accounting for total monomer quality 20% is 10g vinyltriethoxysilane;
E) accounting for total monomer quality 20% is 10g Hexafluorobutyl mathacrylate;
F) accounting for total monomer quality 20% is 10g vinylformic acid;
G) accounting for total monomer quality 40% is 20g butyl acrylate.
The parting agent of present embodiment gained is prepared into after release film, and the water-intake rate of film is 0.51%, surface free energy 14.6mN/m, and peeling away the peeling force required with standard Pressuresensitive Tape TESA7475 is 0.879～0.882N/25mm, residue adhesion rate is 91.9%.
Embodiment 5:
Step a) at room temperature, joins 5g tetraethoxy and 15g dehydrated alcohol in reactor, stirs 10min and mixes, more slowly drip 1g deionized water to reactor, and time for adding is 1h, drips off rear continuation and stirs ageing 24h, obtains silicon dioxide gel.
Step b) under nitrogen atmosphere, the silicon dioxide gel that step is made in a) adds reactor, adds 30mL solvent hexone, acrylic ester monomer, is warming up to 60 ℃, drip the hexone solution of the Diisopropyl azodicarboxylate that 2.2g mass concentration is 25%, time for adding is 1h, adds fluorochemical monomer, silicon-containing monomer after dripping off, after reaction 5h, be warming up to 75 ℃, continue reaction 2h, be cooled to room temperature, obtain fluorine silicon parting agent;
Step c) under nitrogen atmosphere, room temperature, by 5g step b) in make fluorine silicon parting agent and add reactor, add 2.5g ethylene glycol monomethyl ether and 10.0g ethyl acetate, add again 0.25g hexamethylene diisocyanate solidifying agent, mix, be made into coating fluid, use spreader that this coating fluid is coated on clean polyethylene terephthalate film, at 150 ℃, solidify 1min, make transparent fluorine silicon release film.
Monomer total mass is 50g, and wherein fluorochemical monomer used, silicon-containing monomer, acrylic ester monomer comprise:
D) accounting for total monomer quality 20% is 10g vinyltriethoxysilane;
E) accounting for total monomer quality 25% is 12.5g Hexafluorobutyl mathacrylate;
F) accounting for total monomer quality 15% is 7.5g vinylformic acid;
G) accounting for total monomer quality 40% is 20g butyl acrylate.
The parting agent of present embodiment gained is prepared into after release film, and the water-intake rate of film is 0.32%, surface free energy 12.5mN/m, and peeling away the peeling force required with standard Pressuresensitive Tape TESA7475 is 0.565～0.576N/25mm, residue adhesion rate is 92.7%.
Claims (6)
1. the preparation method of a fluorine silicon release film, it is characterized in that this release film is first to prepare silicon dioxide gel, under nitrogen atmosphere, add again acrylic ester monomer, fluorochemical monomer and silicon-containing monomer, carry out the free-radical polymerized fluorine silicon parting agent that obtains, again this parting agent is mixed into coating fluid with double solvents, isocyanates solidifying agent, this coating fluid is coated on organic substrate, through thermofixation, makes fluorine silicon release film, this preparation method's matrix is:
Step a) at room temperature, by tetraethoxy and dehydrated alcohol in mass ratio 1:1～1:10 join in reactor, stirring 5～20min mixes, the deionized water that slowly dropping and tetraethoxy mass ratio are 0.1:1～0.5:1 is again to reactor, drip off rear continuation and stir ageing 24～30h, obtain silicon dioxide gel;
Step b) under nitrogen atmosphere, the silicon dioxide gel that step is made in a) adds reactor, adds solvent, acrylic ester monomer, is warming up to 40～80 ℃, drip initiator solution, time for adding is 0.5～5h, adds fluorochemical monomer, silicon-containing monomer after dripping off, after reaction 2～5h, be warming up to 60～90 ℃, continue reaction 1～5h, be cooled to room temperature, obtain fluorine silicon parting agent;
Step c) under nitrogen atmosphere, room temperature, by step b) in make fluorine silicon parting agent and add reactor, the double solvents that adds 2～3 times of fluorine silicon parting agent quality, the isocyanates solidifying agent that adds again 0.01～0.1 times of fluorine silicon parting agent quality, mix, be made into coating fluid, use spreader that this coating fluid is coated on clean organic substrate, at 120～150 ℃, solidify 1～5min, make transparent fluorine silicon release film.
2. the preparation method of fluorine silicon release film according to claim 1, is characterized in that this preparation method's step b) described in fluorochemical monomer be one or more mixtures in trifluoroethyl methacrylate, tetrafluoropropyl propyl ester, Hexafluorobutyl mathacrylate or methacrylic acid octafluoro pentyl ester; Described silicon-containing monomer is one or more mixtures in vinyltrimethoxy silane, vinyltriethoxysilane, methacryloxypropyl three isopropoxy silane, methyl allyl acyloxypropyl trimethoxysilane; Described acrylic ester monomer is one or more mixtures of Isooctyl methacrylate, butyl acrylate, glycidyl methacrylate, Hydroxyethyl acrylate; Described initiator is one or more the mixture in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), benzoyl peroxide, peroxidized t-butyl perbenzoate, dicumyl peroxide.
3. the preparation method of fluorine silicon release film according to claim 1, is characterized in that described fluorochemical monomer, silicon-containing monomer, acrylic ester monomer are to add in polyreaction the massfraction of monomer to be:
A) content of silicon-containing monomer accounts for 10%～30% of total monomer quality;
B) content of fluorochemical monomer accounts for 5%～30% of total monomer quality;
C) content of acrylic ester monomer accounts for 40%～65% of total monomer quality.
4. the preparation method of fluorine silicon release film according to claim 1, is characterized in that described solvent is one or more mixtures in toluene, hexanaphthene, hexone, ethanol, and usage quantity is 50%～200% of monomer total mass.
5. the preparation method of fluorine silicon release film according to claim 1, it is characterized in that this preparation method's step b) described in the mass concentration of initiator solution be 5%～30%, initiator preparation solvent for use is one or more the mixture in toluene, hexanaphthene, hexone, ethanol, ethyl acetate, and initiator dripping quantity accounts for 0.05%～1.5% of total monomer quality.
6. the preparation method of fluorine silicon release film according to claim 1, is characterized in that this preparation method's step c) described in double solvents be ethylene glycol monomethyl ether and the ethyl acetate mixed solution that 1:3～1:5 is mixed with in mass ratio; Described isocyanates solidifying agent is a kind of in hexamethylene diisocyanate, 2,4 toluene diisocyanate, dimethyl diphenyl vulcabond; Described organic substrate is a kind of in polyethylene terephthalate film, polyethylene film or polypropylene screen.
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