CN103923334B - A kind of fluorine silicon release film and preparation method thereof - Google Patents
A kind of fluorine silicon release film and preparation method thereof Download PDFInfo
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- CN103923334B CN103923334B CN201410141581.0A CN201410141581A CN103923334B CN 103923334 B CN103923334 B CN 103923334B CN 201410141581 A CN201410141581 A CN 201410141581A CN 103923334 B CN103923334 B CN 103923334B
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- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 101
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 65
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000010703 silicon Substances 0.000 claims abstract description 31
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 238000000576 coating method Methods 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 acrylic ester Chemical class 0.000 claims abstract description 17
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- 239000012948 isocyanate Substances 0.000 claims abstract description 7
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 24
- 239000011737 fluorine Substances 0.000 claims description 24
- 229910052731 fluorine Inorganic materials 0.000 claims description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000001723 curing Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 14
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 239000000463 material Substances 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- LCPUCXXYIYXLJY-UHFFFAOYSA-N 1,1,2,4,4,4-hexafluorobutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(F)CC(F)(F)F LCPUCXXYIYXLJY-UHFFFAOYSA-N 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 238000001816 cooling Methods 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
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- GWYSWOQRJGLJPA-UHFFFAOYSA-N 1,1,2,2-tetrafluoropropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)C(C)(F)F GWYSWOQRJGLJPA-UHFFFAOYSA-N 0.000 claims description 2
- 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
- ZNJXRXXJPIFFAO-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluoropentyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)F ZNJXRXXJPIFFAO-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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- CHPNMYQJQQGAJS-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCOC(=O)C(C)=C CHPNMYQJQQGAJS-UHFFFAOYSA-N 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-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
- WUKNPIYSKBLCQI-UHFFFAOYSA-N CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O Chemical compound CC(C=C1)=CC=C1C1=CC=C(C)C=C1.N=C=O.N=C=O WUKNPIYSKBLCQI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 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
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-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
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 150000003254 radicals Chemical class 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
- 238000001029 thermal curing Methods 0.000 claims 1
- 239000012530 fluid Substances 0.000 abstract 1
- 238000009998 heat setting Methods 0.000 abstract 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 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
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- UMQOSQJMIIITHA-UHFFFAOYSA-N cyclohexylsilane Chemical compound [SiH3]C1CCCCC1 UMQOSQJMIIITHA-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 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
- 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
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 230000000149 penetrating effect Effects 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
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
The object of this invention is to provide a kind of fluorine silicon release film and preparation method thereof, the preparation method of this fluorine silicon release film is: first prepare silicon dioxide gel, add acrylic ester monomer more under nitrogen atmosphere, fluorochemical monomer, silicon-containing monomer, carry out free-radical polymerized and obtain fluorine silicon parting agent, again by this parting agent and double solvents, isocyanates solidifying agent mixture becomes coating fluid, by this coating solution on organic substrate, fluorine silicon release film is obtained through thermofixation, this fluorine silicon release film has higher hydrophobicity, lower peeling force, water-intake rate is low, the advantages such as higher residue adhesion rate, it has good release performance.
Description
Technical Field
The invention belongs to the field of industrial basic application, and particularly relates to a fluorosilicone release film and a preparation method thereof.
Background
With the further opening of the Chinese market, a large number of foreign enterprises mainly comprising traditional industries such as electronics, plastics, gifts, toys and the like enter the Chinese market successively, and the production of release films is developed rapidly, wherein the organic silicon release material is widely applied in various industries and is developed rapidly in the unprecedented way. With the development of science and technology, the organic silicon polymer gradually exposes the defects of poor chemical medium resistance and the like, and also provides new requirements for organic silicon release products. At present, although the development of China in this aspect is greatly improved, compared with countries such as Europe, America, Japan and the like, a great gap exists, and further development is needed to reach the international advanced level.
At present, the solvent type release agent is mainly produced in China, and the specific use of the solvent type release agent is determined by release film manufacturers according to respective equipment conditions and product requirements, wherein the organic silicon release agent becomes one of hot spots of release agent material research due to good stripping force, heat resistance and stability of the organic silicon release agent, the organic silicon release agent can be prepared into emulsion, solvent and solvent-free type, the organic silicon release agent becomes the most concerned release agent material, the organic silicon release agent is widely applied to the industries such as pressure sensitive adhesive tapes, waterproof materials, PCB manufacturing, automobile mould pressing material manufacturing and electronic communication, and plays an important role in penetrating into more industries along with the development of scientific technology. Patent CN1931926A discloses a release film prepared from a siloxane composition consisting of vinyl-containing polysiloxane, hydrogen-containing polysiloxane, epoxy-containing cyclohexylsilane, platinum catalyst and polyether or lauryl ether, and compared with foreign products, the domestic organosilicon release agent has a certain difference in rapid curing; in the regulation of the peeling force, an effective and inexpensive regulator is lacking, and the storage stability is inferior.
When the release agent is used for the back treatment of the pressure-sensitive adhesive tape, the unwinding of the pressure-sensitive adhesive tape is easy to be the main purpose of the anti-sticking treatment of the tape, and the silicone release agent has good anti-sticking and isolating effects, so the silicone release agent is widely applied, but the silicone release agent is found in the use process: the adhesive tape can be stuck after being placed for a long time and cannot achieve the expected anti-sticking effect, so that the research on modifying the organic silicon type release agent arouses people's interest. The fluorine-containing polymer generally refers to a synthetic high molecular compound with a main chain or a side chain containing fluorine atoms, the fluorine-containing polymer is rapidly developed from the aspects of variety, quality, application field and quantity due to the unique excellent performance, and the patent CN1821286A discloses a release film prepared from 2, 4-hexafluoro vinyl methyl siloxane and a processing method thereof, and the performance of the film is improved to a certain extent. The fluorine-containing silicon-containing monomer is adopted to modify the acrylic ester to prepare the fluorine-silicon release agent, and the fluorine-silicon release agent has the advantages of higher hydrophobicity, lower peeling force, low water absorption, good release performance and the like.
Disclosure of Invention
The technical problem is as follows: the invention aims to solve the problems that the release agent in China is mainly imported at present, and the synthetic process of the release agent is not easy to control, the synthetic cost is high, and the release performance is difficult to achieve.
The technical scheme is as follows: the preparation method of the fluorosilicone release film comprises the following steps:
the release film is prepared by preparing silicon dioxide sol, adding acrylate monomer, fluorine-containing monomer and silicon-containing monomer under nitrogen atmosphere, carrying out free radical copolymerization to obtain fluorosilicone release agent, mixing the release agent with a composite solvent and an isocyanate curing agent to obtain a coating liquid, coating the coating liquid on an organic base material, and carrying out thermosetting to obtain the fluorosilicone release film, wherein the preparation method comprises the following steps:
step a), at room temperature, adding tetraethoxysilane and absolute ethyl alcohol into a reaction kettle according to the mass ratio of 1: 1-1: 10, stirring for 5-20 min, uniformly mixing, slowly adding deionized water with the mass ratio of tetraethoxysilane being 0.1: 1-0.5: 1 dropwise into the reaction kettle, and continuing stirring and aging for 24-30 h after dropwise adding is finished to obtain silicon dioxide sol;
step b) adding the silica sol prepared in the step a) into a reaction kettle under a nitrogen atmosphere, adding a solvent and an acrylate monomer, heating to 40-80 ℃, dropwise adding an initiator solution for 0.5-5 h, adding a fluorine-containing monomer and a silicon-containing monomer after dropwise adding, reacting for 2-5 h, heating to 60-90 ℃, continuing to react for 1-5 h, and cooling to room temperature to obtain a fluorine-silicon release agent;
and c) adding the fluorosilicone release agent prepared in the step b) into a reaction kettle in nitrogen atmosphere at room temperature, adding a composite solvent in an amount which is 2-3 times the mass of the fluorosilicone release agent, adding an isocyanate curing agent in an amount which is 0.01-0.1 time the mass of the fluorosilicone release agent, uniformly mixing to prepare a coating liquid, coating the coating liquid on a clean organic substrate by using an applicator, and curing for 1-5 min at 120-150 ℃ to prepare the transparent fluorosilicone release film.
The fluorine-containing monomer is one or a mixture of more of trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluorobutyl methacrylate or octafluoropentyl methacrylate; the silicon-containing monomer is one or a mixture of more of vinyl trimethoxy silane, vinyl triethoxy silane, methacryloxypropyl triisopropoxy silane and methacryloxypropyl trimethoxy silane; the acrylate monomer is one or a mixture of isooctyl methacrylate, butyl acrylate, glycidyl methacrylate and hydroxyethyl acrylate; the initiator is one or a mixture of more than one of azodiisobutyronitrile, azodiisoheptonitrile, benzoyl peroxide, tert-butyl peroxybenzoate and dicumyl peroxide.
The fluorine-containing monomer, the silicon-containing monomer and the acrylate monomer are added in the polymerization reaction, and the mass fraction of the monomers is as follows:
a) the content of the silicon-containing monomer accounts for 10 to 30 percent of the total mass of the monomers;
b) the content of the fluorine-containing monomer accounts for 5 to 30 percent of the total mass of the monomers;
c) the content of the acrylate monomer accounts for 40-65% of the total monomer mass.
The solvent is one or a mixture of toluene, cyclohexane, methyl isobutyl ketone and ethanol, and the using amount of the solvent is 50-200% of the total mass of the monomers.
The mass concentration of the initiator solution is 5-30%, the solvent used for preparing the initiator is one or a mixture of more than one of toluene, cyclohexane, methyl isobutyl ketone, ethanol and ethyl acetate, and the dropping amount of the initiator accounts for 0.05-1.5% of the total monomer mass.
The composite solvent is a mixed solution prepared from ethylene glycol monomethyl ether and ethyl acetate according to the mass ratio of 1: 3-1: 5; the isocyanate curing agent is one of hexamethylene diisocyanate, 2, 4-toluene diisocyanate and dimethyl biphenyl diisocyanate; the organic base material is one of polyethylene terephthalate film, polyethylene film or polypropylene film.
Has the advantages that: the invention provides a fluorosilicone release film and a preparation method thereof.
The invention has the characteristics that:
(1) fluorine-containing and silicon-containing groups are enriched on the surface of the fluorine-silicon release film, so that the release film has lower surface energy, and the fluorine-silicon release film has better chemical stability due to the introduction of the fluoroalkyl and siloxane groups, so that the fluorine-silicon release film is not sticky to rolls, has good release effect and also has better solvent resistance.
(2) The release film prepared by the invention has low water absorption rate and good stability, can be used in the industries of pressure-sensitive adhesive tapes, waterproof materials and the like, and has high economic value.
Detailed Description
Example 1:
step a) at room temperature, adding 5g of tetraethoxysilane and 5g of absolute ethyl alcohol into a reaction kettle, stirring for 10min, uniformly mixing, slowly dropwise adding 1g of deionized water into the reaction kettle for 1h, and continuously stirring and aging for 24h after dropwise adding is finished to obtain silicon dioxide sol;
step b) adding the silica sol prepared in the step a) into a reaction kettle under nitrogen atmosphere, adding 30mL of solvent methyl isobutyl ketone and acrylate monomer, heating to 60 ℃, dropwise adding 1.6g of methyl isobutyl ketone solution of azodiisobutyronitrile with the mass concentration of 25%, dropwise adding fluorine-containing monomer and silicon-containing monomer for 1h, reacting for 5h, heating to 75 ℃, continuing to react for 2h, and cooling to room temperature to obtain the fluorosilicone release agent;
and c) adding 5g of the fluorosilicone release agent prepared in the step b) into a reaction kettle at room temperature in a nitrogen atmosphere, adding 2.5g of ethylene glycol monomethyl ether and 10.0g of ethyl acetate, then adding 0.25g of hexamethylene diisocyanate curing agent, uniformly mixing to prepare a coating liquid, coating the coating liquid on a clean polyethylene terephthalate film by using an applicator, and curing for 1min at 150 ℃ to prepare the transparent fluorosilicone release film.
The total mass of the monomers is 50g, wherein the fluorine-containing monomers, the silicon-containing monomers and the acrylate monomers comprise:
d) 15g of vinyltriethoxysilane accounting for 30 percent of the total monomer mass;
e) 2.5g of hexafluorobutyl methacrylate accounting for 5 percent of the total monomer mass;
f) 10g of acrylic acid, which accounts for 20% of the total monomer mass;
g) accounting for 45 percent of the total monomer mass, namely 22.5g of butyl acrylate.
After the release agent obtained in the embodiment is prepared into a release film, the water absorption rate of the film is 2.1%, the surface free energy is 31.4mN/m, the stripping force required for stripping the release agent from a standard pressure-sensitive adhesive tape TESA7475 is 1.913-1.922N/25 mm, and the residual adhesion rate is 82.5%.
Example 2:
step a) adding 5g of ethyl orthosilicate and 15g of absolute ethyl alcohol into a reaction kettle at room temperature, stirring for 10min, uniformly mixing, slowly dropwise adding 1g of deionized water into the reaction kettle for 1h, and continuing stirring and aging for 24h after dropwise adding is finished to obtain the silicon dioxide sol.
Step b) adding the silica sol prepared in the step a) into a reaction kettle under nitrogen atmosphere, adding 40mL of solvent methyl isobutyl ketone and acrylate monomer, heating to 60 ℃, dropwise adding 2.0g of methyl isobutyl ketone solution of azodiisobutyronitrile with the mass concentration of 25%, dropwise adding fluorine-containing monomer and silicon-containing monomer for 1h, reacting for 5h, heating to 75 ℃, continuing to react for 2h, and cooling to room temperature to obtain the fluorosilicone release agent;
and c) adding 5g of the fluorosilicone release agent prepared in the step b) into a reaction kettle at room temperature in a nitrogen atmosphere, adding 2.5g of ethylene glycol monomethyl ether and 10.0g of ethyl acetate, then adding 0.25g of hexamethylene diisocyanate curing agent, uniformly mixing to prepare a coating liquid, coating the coating liquid on a clean polyethylene terephthalate film by using an applicator, and curing for 1min at 150 ℃ to prepare the transparent fluorosilicone release film.
The total mass of the monomers is 50g, wherein the fluorine-containing monomers, the silicon-containing monomers and the acrylate monomers comprise:
d) 12.5g of vinyltriethoxysilane accounting for 25% of the total monomer mass;
e) 5g of hexafluorobutyl methacrylate accounting for 10 percent of the total monomer mass;
f) 10g of acrylic acid, which accounts for 20% of the total monomer mass;
g) accounting for 45 percent of the total monomer mass, namely 22.5g of butyl acrylate.
After the release agent obtained in the embodiment is prepared into a release film, the water absorption rate of the film is 1.7%, the surface free energy is 25.3mN/m, the stripping force required for stripping the release agent from a standard pressure-sensitive adhesive tape TESA7475 is 1.566-1.664N/25 mm, and the residual adhesion rate is 88.0%.
Example 3:
step a) adding 5g of ethyl orthosilicate and 25g of absolute ethyl alcohol into a reaction kettle at room temperature, stirring for 10min, uniformly mixing, slowly dropwise adding 1g of deionized water into the reaction kettle for 1h, and continuing stirring and aging for 24h after dropwise adding is finished to obtain the silicon dioxide sol.
Step b) adding the silica sol prepared in the step a) into a reaction kettle under nitrogen atmosphere, adding 50mL of solvent methyl isobutyl ketone and acrylate monomer, heating to 60 ℃, dropwise adding 2.2g of methyl isobutyl ketone solution of azodiisobutyronitrile with the mass concentration of 25%, dropwise adding fluorine-containing monomer and silicon-containing monomer for 1h, reacting for 5h, heating to 75 ℃, continuing to react for 2h, and cooling to room temperature to obtain the fluorosilicone release agent;
and c) adding 5g of the fluorosilicone release agent prepared in the step b) into a reaction kettle at room temperature in a nitrogen atmosphere, adding 3.0g of ethylene glycol monomethyl ether and 9.5g of ethyl acetate, adding 0.25g of hexamethylene diisocyanate curing agent, uniformly mixing to prepare a coating liquid, coating the coating liquid on a clean polyethylene terephthalate film by using an applicator, and curing for 1min at 150 ℃ to prepare the transparent fluorosilicone release film.
The total mass of the monomers is 50g, wherein the fluorine-containing monomers, the silicon-containing monomers and the acrylate monomers comprise:
d) 10g of vinyltriethoxysilane accounting for 20% of the total monomer mass;
e) 7.5g of hexafluorobutyl methacrylate accounting for 15 percent of the total monomer mass;
f) 10g of acrylic acid, which accounts for 20% of the total monomer mass;
g) accounting for 45 percent of the total monomer mass, namely 22.5g of butyl acrylate.
After the release agent obtained in the embodiment is prepared into a release film, the water absorption rate of the film is 0.66%, the surface free energy is 16.2mN/m, the stripping force required for stripping the release agent from a standard pressure-sensitive adhesive tape TESA7475 is 1.122-1.221N/25 mm, and the residual adhesion rate is 90.8%.
Example 4:
step a) adding 5g of ethyl orthosilicate and 15g of absolute ethyl alcohol into a reaction kettle at room temperature, stirring for 10min, uniformly mixing, slowly dropwise adding 1g of deionized water into the reaction kettle for 1h, and continuing stirring and aging for 24h after dropwise adding is finished to obtain the silicon dioxide sol.
Step b) adding the silica sol prepared in the step a) into a reaction kettle under nitrogen atmosphere, adding 30mL of solvent methyl isobutyl ketone and acrylate monomer, heating to 60 ℃, dropwise adding 2.2g of methyl isobutyl ketone solution of azodiisobutyronitrile with the mass concentration of 25%, dropwise adding fluorine-containing monomer and silicon-containing monomer for 1h, reacting for 5h, heating to 75 ℃, continuing to react for 2h, and cooling to room temperature to obtain the fluorosilicone release agent;
and c) adding 5g of the fluorosilicone release agent prepared in the step b) into a reaction kettle at room temperature in a nitrogen atmosphere, adding 2.5g of ethylene glycol monomethyl ether and 10.0g of ethyl acetate, then adding 0.25g of hexamethylene diisocyanate curing agent, uniformly mixing to prepare a coating liquid, coating the coating liquid on a clean polyethylene terephthalate film by using an applicator, and curing for 1min at 150 ℃ to prepare the transparent fluorosilicone release film.
The total mass of the monomers is 50g, wherein the fluorine-containing monomers, the silicon-containing monomers and the acrylate monomers comprise:
d) 10g of vinyltriethoxysilane accounting for 20% of the total monomer mass;
e) 10g of hexafluorobutyl methacrylate accounting for 20 percent of the total monomer mass;
f) 10g of acrylic acid, which accounts for 20% of the total monomer mass;
g) accounting for 40 percent of the total monomer mass, namely 20 grams of butyl acrylate.
After the release agent obtained in the embodiment is prepared into a release film, the water absorption rate of the film is 0.51%, the surface free energy is 14.6mN/m, the peeling force required for peeling the release agent from a standard pressure-sensitive adhesive tape TESA7475 is 0.879-0.882N/25 mm, and the residual adhesion rate is 91.9%.
Example 5:
step a) adding 5g of ethyl orthosilicate and 15g of absolute ethyl alcohol into a reaction kettle at room temperature, stirring for 10min, uniformly mixing, slowly dropwise adding 1g of deionized water into the reaction kettle for 1h, and continuing stirring and aging for 24h after dropwise adding is finished to obtain the silicon dioxide sol.
Step b) adding the silica sol prepared in the step a) into a reaction kettle under nitrogen atmosphere, adding 30mL of solvent methyl isobutyl ketone and acrylate monomer, heating to 60 ℃, dropwise adding 2.2g of methyl isobutyl ketone solution of azodiisobutyronitrile with the mass concentration of 25%, dropwise adding fluorine-containing monomer and silicon-containing monomer for 1h, reacting for 5h, heating to 75 ℃, continuing to react for 2h, and cooling to room temperature to obtain the fluorosilicone release agent;
and c) adding 5g of the fluorosilicone release agent prepared in the step b) into a reaction kettle at room temperature in a nitrogen atmosphere, adding 2.5g of ethylene glycol monomethyl ether and 10.0g of ethyl acetate, then adding 0.25g of hexamethylene diisocyanate curing agent, uniformly mixing to prepare a coating liquid, coating the coating liquid on a clean polyethylene terephthalate film by using an applicator, and curing for 1min at 150 ℃ to prepare the transparent fluorosilicone release film.
The total mass of the monomers is 50g, wherein the fluorine-containing monomers, the silicon-containing monomers and the acrylate monomers comprise:
d) 10g of vinyltriethoxysilane accounting for 20% of the total monomer mass;
e) 12.5g of hexafluorobutyl methacrylate accounting for 25 percent of the total monomer mass;
f) 7.5g of acrylic acid, which accounts for 15% of the total monomer mass;
g) accounting for 40 percent of the total monomer mass, namely 20 grams of butyl acrylate.
After the release agent obtained in the embodiment is prepared into a release film, the water absorption rate of the film is 0.32%, the surface free energy is 12.5mN/m, the stripping force required for stripping the release agent from a standard pressure-sensitive adhesive tape TESA7475 is 0.565-0.576N/25 mm, and the residual adhesion rate is 92.7%.
Claims (5)
1. A method for preparing fluorine-silicon release film is characterized in that the release film is prepared by firstly preparing silicon dioxide sol, adding acrylate monomer, fluorine-containing monomer and silicon-containing monomer under nitrogen atmosphere, carrying out free radical copolymerization to obtain fluorine-silicon release agent, then mixing the release agent, composite solvent and isocyanate curing agent to obtain coating liquid, coating the coating liquid on organic base material, and carrying out thermal curing to obtain the fluorine-silicon release film, wherein the preparation method comprises the following steps:
step a), at room temperature, adding tetraethoxysilane and absolute ethyl alcohol into a reaction kettle according to the mass ratio of 1: 1-1: 10, stirring for 5-20 min, uniformly mixing, slowly adding deionized water with the mass ratio of tetraethoxysilane being 0.1: 1-0.5: 1 dropwise into the reaction kettle, and continuing stirring and aging for 24-30 h after dropwise adding is finished to obtain silicon dioxide sol;
step b) adding the silica sol prepared in the step a) into a reaction kettle under a nitrogen atmosphere, adding a solvent and an acrylate monomer, heating to 40-80 ℃, dropwise adding an initiator solution for 0.5-5 h, adding a fluorine-containing monomer and a silicon-containing monomer after dropwise adding, reacting for 2-5 h, heating to 60-90 ℃, continuing to react for 1-5 h, and cooling to room temperature to obtain a fluorine-silicon release agent;
step c) adding the fluorosilicone release agent prepared in the step b) into a reaction kettle in nitrogen atmosphere at room temperature, adding a composite solvent 2-3 times the mass of the fluorosilicone release agent, adding an isocyanate curing agent 0.01-0.1 times the mass of the fluorosilicone release agent, uniformly mixing to prepare a coating liquid, coating the coating liquid on a clean organic substrate by using an applicator, and curing for 1-5 min at 120-150 ℃ to prepare a transparent fluorosilicone release film;
wherein,
the fluorine-containing monomer, the silicon-containing monomer and the acrylate monomer are added in the polymerization reaction, and the mass fraction of the monomers is as follows:
a) the content of the silicon-containing monomer accounts for 10 to 30 percent of the total mass of the monomers;
b) the content of the fluorine-containing monomer accounts for 5 to 30 percent of the total mass of the monomers;
c) the content of the acrylate monomer accounts for 40-65% of the total monomer mass.
2. The method for preparing a fluorosilicone release film according to claim 1, wherein the fluorine-containing monomer in step b) is one or more selected from trifluoroethyl methacrylate, tetrafluoropropyl methacrylate, hexafluorobutyl methacrylate and octafluoropentyl methacrylate; the silicon-containing monomer is one or a mixture of more of vinyl trimethoxy silane, vinyl triethoxy silane, methacryloxypropyl triisopropoxy silane and methacryloxypropyl trimethoxy silane; the acrylate monomer is one or a mixture of isooctyl methacrylate, butyl acrylate, glycidyl methacrylate and hydroxyethyl acrylate; the initiator is one or a mixture of more than one of azodiisobutyronitrile, azodiisoheptonitrile, benzoyl peroxide, tert-butyl peroxybenzoate and dicumyl peroxide.
3. The method for preparing a fluorosilicone release film according to claim 1, wherein the solvent is one or more of toluene, cyclohexane, methyl isobutyl ketone and ethanol, and the amount of the solvent is 50-200% of the total mass of the monomers.
4. The method for preparing a fluorosilicone release film according to claim 1, wherein the mass concentration of the initiator solution in step b) of the preparation method is 5-30%, the solvent used for preparing the initiator is one or a mixture of more than one of toluene, cyclohexane, methyl isobutyl ketone, ethanol and ethyl acetate, and the dropping amount of the initiator accounts for 0.05-1.5% of the total monomer mass.
5. The preparation method of the fluorosilicone release film according to claim 1, wherein the composite solvent in step c) of the preparation method is a mixed solution prepared from ethylene glycol monomethyl ether and ethyl acetate in a mass ratio of 1:3 to 1: 5; the isocyanate curing agent is one of hexamethylene diisocyanate, 2, 4-toluene diisocyanate and dimethyl biphenyl diisocyanate; the organic base material is one of polyethylene terephthalate film, polyethylene film or polypropylene film.
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| CN113185636A (en) * | 2021-04-20 | 2021-07-30 | 浙江工业大学 | Short-fluorocarbon-chain acrylate polymer, preparation method thereof and application of short-fluorocarbon-chain acrylate polymer in mold release agent |
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| CN116478612B (en) * | 2023-05-17 | 2024-03-08 | 千浪化研新材料(上海)有限公司 | Nylon glass fiber high-hardness super-weather-resistant environment-friendly paint and preparation method thereof |
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