CN113896924A - Metal glass modified release film - Google Patents
Metal glass modified release film Download PDFInfo
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- CN113896924A CN113896924A CN202111179946.5A CN202111179946A CN113896924A CN 113896924 A CN113896924 A CN 113896924A CN 202111179946 A CN202111179946 A CN 202111179946A CN 113896924 A CN113896924 A CN 113896924A
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- modified
- glass fiber
- metal glass
- release
- release film
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 92
- 239000002184 metal Substances 0.000 title claims abstract description 92
- 239000011521 glass Substances 0.000 title claims abstract description 24
- 239000003365 glass fiber Substances 0.000 claims abstract description 68
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 19
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 16
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 dodecyl alcohol ester Chemical class 0.000 claims abstract description 15
- LQZZUXJYWNFBMV-UHFFFAOYSA-N ethyl butylhexanol Natural products CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims abstract description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 14
- 239000004332 silver Substances 0.000 claims abstract description 14
- 238000007747 plating Methods 0.000 claims abstract description 7
- 150000002505 iron Chemical class 0.000 claims description 32
- 239000005300 metallic glass Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000006082 mold release agent Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 11
- PPCDEFQVKBXBPS-UHFFFAOYSA-N 11-hydroxyundecylphosphonic acid Chemical compound OCCCCCCCCCCCP(O)(O)=O PPCDEFQVKBXBPS-UHFFFAOYSA-N 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000001994 activation Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 6
- 206010070834 Sensitisation Diseases 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 230000008313 sensitization Effects 0.000 claims description 2
- 229920002050 silicone resin Polymers 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 5
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 5
- 101710134784 Agnoprotein Proteins 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000006870 function Effects 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 1
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
- C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Laminated Bodies (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The invention provides a metal glass modified release film, which comprises a base film layer and a release layer, wherein the base film layer is PET, the release layer is formed by coating a release agent, and the release agent comprises 10-40 parts of vinyl organic silicon resin, 8-15 parts of modified metal glass fiber, 2-4 parts of curing agent dodecyl alcohol ester, 0.2-2 parts of defoaming agent ethylene glycol distearate and 50-60 parts of ethanol; the modified metal glass fiber is formed by plating a silver electric layer and a cobalt magnetic layer on the surface of an iron-based metal glass fiber, and the modified metal glass fiber and vinyl organic silicon resin are connected through hydrogen bond self-assembly. The magnetic-electric-magnetic alternating multilayer structure of the modified metal glass fiber forces electromagnetic waves to be reflected and absorbed back and forth between the layers until the electromagnetic waves are completely consumed, so that the electromagnetic absorption effect of the metal glass fiber is improved, and the electromagnetic shielding effect of the release film is greatly enhanced.
Description
Technical Field
The invention relates to the technical field of release films, in particular to a release film modified by metal glass.
Background
With the widespread use of radio technology, electromagnetic pollution is more and more prevalent, and electromagnetic leakage not only harms human physical and mental health, but also influences the normal work of precision instruments. The anti-electromagnetic interference film is plated on the shell of the product, so that the product can be protected from being influenced by external electromagnetic interference, and the interference of the product to the outside can be reduced.
The release film is a film whose surface can be distinguished, and the release film has no viscosity or slight viscosity after being contacted with a specific material under a limited condition, and in general, in order to increase the release force of the plastic film, plasma treatment and fluorine coating treatment are carried out on the plastic film such as PET, PE, OPP and the like to enable the plastic film to have the release force, or a silicon release agent is coated on the surface layer of the film material, so that the silicon release agent can show extremely light and stable release force. However, the existing release film cannot have a good release effect under the electromagnetic shielding function, and the application range of the release film is influenced.
Chinese patent CN201910342591.3 discloses a release film with wave-absorbing function, which comprises a base film layer and a release layer, wherein the base film layer is any one of PE, PET, BOPP or PS; the release layer is prepared from the following raw materials in parts by weight: 30-40 parts of vinyl organic silicon resin, 15-25 parts of butyl acrylate, 40-50 parts of acrylic acid, 8-16 parts of wave-absorbing powder, 5-7 parts of titanium dioxide, 8-12 parts of butanone, 12-15 parts of cyclohexanone, 0.2-1 part of antioxidant, 0.2-1 part of coupling agent, 0.2-1 part of defoaming agent and 50-60 parts of solvent. However, the release film with the wave absorbing function prepared in the patent has an unsatisfactory effect and has the problem that titanium dioxide is easy to agglomerate.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a release film modified by metal glass, and aims to solve the problem of poor electromagnetic shielding capability of the release film.
(II) technical scheme
In order to solve the above problems, the present invention provides the following technical solutions:
the invention provides a metal glass modified release film, which comprises a base film layer and a release layer, wherein the base film layer is PET, the release layer is formed by coating a release agent, and the release agent comprises 10-40 parts of vinyl organic silicon resin, 8-15 parts of modified metal glass fiber, 2-4 parts of curing agent dodecyl alcohol ester, 0.2-2 parts of defoaming agent ethylene glycol distearate and 50-60 parts of ethanol; the modified metal glass fiber is formed by plating a silver electric layer and a cobalt magnetic layer on the surface of an iron-based metal glass fiber, and the modified metal glass fiber and vinyl organic silicon resin are connected through hydrogen bond self-assembly.
A release film modified by metal glass is prepared by the following steps:
(1) preparation of modified iron-based metal glass fiber
Placing the iron-based metal glass fiber in SnCl2And HCl in solution; followed by washing with deionized water and then adding PbCl2And HCl, and is washed again with deionized water and then soaked in AgNO3Stirring in the solution to obtain the iron-based metal glass fiber of the silver-plated electric layer; the obtained product is sensitized and activated again and then immersed in CoSO4Stirring the solution for reaction; finally, washing with ethanol and drying in the air to obtain the modified iron-based metal glass fiber modified by the silver electric layer and the cobalt magnetic layer;
(2) introducing hydroxyl on the surface of the cobalt magnetic layer
Adding the modified iron-based metal glass fiber obtained in the step (1) into an 11-hydroxyundecyl phosphonic acid solution, and performing heat preservation reaction after ultrasonic treatment to obtain a hydroxylated modified iron-based metal glass fiber;
(3) preparation of mold release agent with electromagnetic shielding capability
Adding vinyl organic silicon resin, hydroxylated modified metal glass fiber, curing agent dodecyl alcohol ester and defoaming agent ethylene glycol distearate into an ethanol solvent, and stirring for reaction to prepare a mold release agent with electromagnetic shielding capability;
(4) coating of
And coating the release agent with electromagnetic shielding capability on a clean PET substrate by using an applicator, and curing to obtain the release film modified by the metallic glass.
Preferably, in the step (1), the iron-based metal glass fiber and the SnCl2The mass ratio of HCl to HCl is 10: 10-30: 40-60.
Preferably, in the step (1), the sensitization condition is kept at 25-40 ℃ for 5-20 min.
Preferably, in the step (1), PbCl is added2The mass ratio of HCl to HCl is 1: 10-20.
Preferably, in the step (1), the activation reaction condition is 30-50 ℃ for 10-60 min.
Preferably, in the step (1), AgNO is immersed3The solution is continuously stirred for 8-30min under the reaction condition of 80-100 ℃.
Preferably, in the step (1), CoSO is immersed4The solution is continuously stirred for 5-20min under the reaction condition of 80-100 ℃.
Preferably, in the step (2), the pH of the 11-hydroxyundecylphosphonic acid is 7 to 10.
Preferably, in the step (2), the mass ratio of the modified iron-based metal glass fiber to the 11-hydroxyundecyl phosphonic acid is 1: 5-20.
Preferably, in the step (2), the reaction condition is that the reaction is carried out for 5 to 20 hours after the ultrasonic treatment is carried out for 5 to 30 minutes.
Preferably, in the step (3), the mass ratio of the vinyl silicone resin, the modified metal glass fiber, the curing agent dodecyl alcohol ester, the defoaming agent ethylene glycol distearate to the solvent ethanol is 10-40: 8-15: 2-4: 0.2-2: 50-60.
Preferably, in the step (3), the stirring reaction condition is that the temperature is raised to 30-50 ℃ and then the stirring is carried out for 0.5-3 h.
Preferably, in the step (4), the curing condition is 120-150 ℃ for 10-60 min.
(III) advantageous technical effects
Compared with the prior art, the invention has the following chemical mechanism and beneficial technical effects:
(1) the chemical mechanism of the invention is as follows: firstly, plating a conductive silver layer on the iron-based metal glass fiber by using a chemical plating preparation method, and then plating a magnetic cobalt layer to obtain a modified iron-based metal glass fiber modified by a silver electric layer and a cobalt magnetic layer; then, hydroxyl is introduced to the surface of the modified iron-based metal glass fiber, hydrogen bond self-assembly is carried out on the hydroxyl on the surface of the modified iron-based metal glass fiber and the abundant hydroxyl on the vinyl organic silicon resin, then the modified iron-based metal glass fiber and curing agent dodecyl alcohol ester and defoaming agent ethylene glycol distearate are prepared into a release agent, and finally the prepared release agent is coated on a PET base film and cured to obtain the release film modified by the metal glass.
(2) According to the release film modified by the metal glass, the modified metal glass fibers are uniformly distributed in the vinyl organic silicon resin of the release layer through hydrogen bond self-assembly, so that an excellent electromagnetic shielding effect is achieved; the cobalt magnetic particles on the surface of the metal glass fiber provide a large number of receiving sites for electromagnetic waves, so that the electromagnetic waves enter the silver conductive layer, the silver conductive layer has a reflection effect on the electromagnetic waves, the metal glass of the inner layer is magnetic, and the magnetic-electric-magnetic alternating multilayer structure forces the electromagnetic waves to be reflected and absorbed back and forth between the layers until the electromagnetic waves are completely consumed, so that the electromagnetic absorption effect of the metal glass fiber is improved, and the electromagnetic shielding effect of the release film is greatly enhanced.
Detailed Description
To achieve the above object, the present invention provides the following examples and comparative examples:
example 1
A release film modified by metal glass is prepared by the following steps:
(1) preparation of modified iron-based metal glass fiber
Iron-based metallic glass fibers (10g) were placed in SnCl2(10g) And HCl (40g) at 25 ℃ for 5 min; followed by washing with deionized water and then adding PbCl2(1g) And HCl (10g) for 10min at 30 deg.C to complete the activation process, and washed again with deionized water and then soaked in AgNO at 20g/L3Continuously stirring the solution for 8min at 80 ℃ to obtain the iron-based metal glass fiber of the silver-plated electric layer; after the obtained product is sensitized and activated again, the product is immersed in CoSO with the concentration of 35g/L4Stirring the solution at 80 deg.C for 5 min; finally, washing with ethanol and drying in the air to obtain the modified iron-based metal glass fiber modified by the silver electric layer and the cobalt magnetic layer;
(2) introducing hydroxyl on the surface of the cobalt magnetic layer
Adding the modified iron-based metal glass fiber (1g) obtained in the step (1) into a 11-hydroxyundecylphosphonic acid solution (5g) with the pH value of 7, carrying out ultrasonic treatment for 5 minutes, and then carrying out heat preservation reaction for 5 hours to obtain a hydroxylated modified iron-based metal glass fiber;
(3) preparation of mold release agent with electromagnetic shielding capability
Adding 10g of vinyl organic silicon resin, 8g of hydroxylated modified metal glass fiber, 2g of dodecyl alcohol ester serving as a curing agent and 0.2g of ethylene glycol distearate serving as a defoaming agent into 50g of an ethanol solvent, heating to 30 ℃, and stirring for 0.5h to prepare a mold release agent with electromagnetic shielding capability;
(4) coating of
And (3) coating the release agent with electromagnetic shielding capability on a clean PET substrate by using an applicator, and curing for 10min at 120 ℃ to obtain the release film modified by the metallic glass.
Example 2
A release film modified by metal glass is prepared by the following steps:
(1) preparation of modified iron-based metal glass fiber
Iron-based metallic glass fibers (10g) were placed in a solution of SnCl2(20g) and HCl (40g) and held at 30 ℃ for 10 min; followed by washing with deionized water and then adding PbCl2(1g) And HCl (20g) at 30 deg.C for 20min to complete the activation process, again washed with deionized water, and then immersed inAgNO concentration of 20g/L3Continuously stirring the solution for 10min at 80 ℃ to obtain the iron-based metal glass fiber of the silver-plated electric layer; after the obtained product is sensitized and activated again, the product is immersed in CoSO with the concentration of 35g/L4Stirring the solution at 90 deg.C for 10 min; finally, washing with ethanol and drying in the air to obtain the modified iron-based metal glass fiber modified by the silver electric layer and the cobalt magnetic layer;
(2) introducing hydroxyl on the surface of the cobalt magnetic layer
Adding the modified iron-based metal glass fiber (1g) obtained in the step (1) into a 11-hydroxyundecylphosphonic acid solution (10g) with the pH value of 8, carrying out ultrasonic treatment for 10 minutes, and then carrying out heat preservation reaction for 6 hours to obtain a hydroxylated modified iron-based metal glass fiber;
(3) preparation of mold release agent with electromagnetic shielding capability
Adding vinyl organic silicon resin (20g), hydroxylated modified metal glass fiber (10g), curing agent dodecyl alcohol ester (3g) and defoaming agent ethylene glycol distearate (1g) into an ethanol solvent (50g), heating to 30 ℃, and stirring for 1h to prepare a release agent with electromagnetic shielding capability;
(4) coating of
And (3) coating the release agent with electromagnetic shielding capability on a clean PET substrate by using an applicator, and curing for 30min at 130 ℃ to obtain the release film modified by the metallic glass.
Example 3
A release film modified by metal glass is prepared by the following steps:
(1) preparation of modified iron-based metal glass fiber
Iron-based metallic glass fibers (10g) were placed in SnCl2(20g) And HCl (50g) at 35 ℃ for 15 min; followed by washing with deionized water and then adding PbCl2(1g) And HCl (20g) at 50 deg.C for 40min to complete the activation process, and washed again with deionized water and then soaked in AgNO at 20g/L3Continuously stirring the solution for 25min at 90 ℃ to obtain the iron-based metal glass fiber of the silver-plated electric layer; after the obtained product is sensitized and activated again, the product is immersed in CoSO with the concentration of 35g/L4In solution at 90 deg.CContinuously stirring for 15 min; finally, washing with ethanol and drying in the air to obtain the modified iron-based metal glass fiber modified by the silver electric layer and the cobalt magnetic layer;
(2) introducing hydroxyl on the surface of the cobalt magnetic layer
Adding the modified iron-based metal glass fiber (1g) obtained in the step (1) into an 11-hydroxyundecylphosphonic acid solution (15g) with ph of 9, performing ultrasonic treatment for 30 minutes, and then performing heat preservation reaction for 16 hours to obtain a hydroxylated modified iron-based metal glass fiber;
(3) preparation of mold release agent with electromagnetic shielding capability
Adding vinyl organic silicon resin (30g), hydroxylated modified metal glass fiber (13g), curing agent dodecyl alcohol ester (3g) and defoaming agent ethylene glycol distearate (2g) into an ethanol solvent (60g), heating to 50 ℃, and stirring for 2 hours to prepare a release agent with electromagnetic shielding capability;
(4) coating of
And (3) coating the release agent with electromagnetic shielding capability on a clean PET substrate by using an applicator, and curing for 45min at 150 ℃ to obtain the release film modified by the metal glass.
Example 4
A release film modified by metal glass is prepared by the following steps:
(1) preparation of modified iron-based metal glass fiber
Iron-based metallic glass fibers (10g) were placed in SnCl2(30g) And HCl (60g) at 40 ℃ for 20 min; followed by washing with deionized water and then adding PbCl2(1g) And HCl (20g) at 50 deg.C for 60min to complete the activation process, and washed again with deionized water and then soaked in 20g/L AgNO3Continuously stirring the solution for 30min at 100 ℃ to obtain the iron-based metal glass fiber of the silver-plated electric layer; after the obtained product is sensitized and activated again, the product is immersed in CoSO with the concentration of 35g/L4Stirring the solution at 100 deg.C for 20 min; finally, washing with ethanol and drying in the air to obtain the modified iron-based metal glass fiber modified by the silver electric layer and the cobalt magnetic layer;
(2) introducing hydroxyl on the surface of the cobalt magnetic layer
Adding the modified iron-based metal glass fiber (1g) obtained in the step (1) into a 11-hydroxyundecyl phosphonic acid solution (20g) with ph of 10, carrying out ultrasonic treatment for 30 minutes, and then carrying out heat preservation reaction for 20 hours to obtain a hydroxylated modified iron-based metal glass fiber;
(3) preparation of mold release agent with electromagnetic shielding capability
Adding vinyl organic silicon resin (40g), hydroxylated modified metal glass fiber (15g), curing agent dodecyl alcohol ester (4g) and defoaming agent ethylene glycol distearate (2g) into an ethanol solvent (60g), heating to 50 ℃, and stirring for 3h to prepare a release agent with electromagnetic shielding capability;
(4) coating of
And (3) coating the release agent with electromagnetic shielding capability on a clean PET substrate by using an applicator, and curing for 50min at 150 ℃ to obtain the release film modified by the metal glass.
Comparative example 1
A release film modified by metal glass is prepared by the following steps:
(1) preparation of mold Release agent
Adding vinyl organic silicon resin (40g), iron-based metal glass fiber (8g), curing agent dodecyl alcohol ester (2g) and defoaming agent ethylene glycol distearate (0.2g) into an ethanol solvent (50g), heating to 30 ℃, and stirring for 0.5h to prepare a mold release agent;
(2) coating of
Coating the prepared release agent on a clean PET substrate by using an applicator, and curing for 10min at 120 ℃ to prepare the release film modified by the metal glass.
Comparative example 2
A release film modified by metal glass is prepared by the following steps:
(1) preparation of modified iron-based metal glass fiber
Iron-based metallic glass fibers (10g) were placed in SnCl2(10g) And HCl (40g) at 25 ℃ for 5 min; followed by washing with deionized water and then adding PbCl2(1g) And HCl (10g) for 10min at 30 ℃ to complete the activation process, and again rinsed with deionized waterAfter washing, the substrate was immersed in AgNO at a concentration of 20g/L3Continuously stirring the solution for 8min at 80 ℃ to obtain the iron-based metal glass fiber of the silver-plated electric layer; after the obtained product is sensitized and activated again, the product is immersed in CoSO with the concentration of 35g/L4Stirring the solution at 80 deg.C for 5 min; finally, washing with ethanol and drying in the air to obtain the modified iron-based metal glass fiber modified by the silver electric layer and the cobalt magnetic layer;
(2) preparation of mold Release agent
Adding vinyl organic silicon resin (40g), modified metal glass fiber (8g), curing agent dodecyl alcohol ester (2g) and defoaming agent ethylene glycol distearate (0.2g) into an ethanol solvent (50g), heating to 30 ℃, and stirring for 0.5h to prepare a release agent with electromagnetic shielding capability; (3) coating of
And (3) coating the release agent with electromagnetic shielding capability on a clean PET substrate by using an applicator, and curing for 10min at 120 ℃ to obtain the release film modified by the metallic glass.
Comparative example 3
A preparation method of the release film comprises the following steps:
adding vinyl organic silicon resin (40g), curing agent dodecyl alcohol ester (2g) and defoaming agent ethylene glycol distearate (0.2g) into an ethanol solvent (50g), heating to 30 ℃, and stirring for 0.5h to prepare a release agent; and (3) coating the release agent with electromagnetic shielding capability on a clean PET substrate by using an applicator, and curing for 10min at 120 ℃ to obtain the release film modified by the metallic glass.
The metallic glass modified release films obtained in examples 1 to 4 and comparative examples 1 to 3 were subjected to a performance test:
the electromagnetic shielding test method of the release film comprises the following steps: the release film to be tested is made into a size of 22mm multiplied by 10mm multiplied by 0.1mm, the electromagnetic shielding performance is tested by using a waveguide testing device under the wave band frequency of 10GHz, and the test results are as shown in the following table 1:
TABLE 1
As can be seen from the examples 1-4 in the table 1, the release film modified by the metallic glass prepared by the invention has better electromagnetic shielding effect. Comparative example 1 is that there is no metal glass plating layer and magnetic layer, other conditions are the same as example 1, it can be seen that the electromagnetic shielding effect is greatly weakened, it is demonstrated that the magnetic-electric-magnetic alternating metal glass fiber multilayer structure constructed by the invention can generate excellent loss and absorption effect on electromagnetic wave; comparative example 2 is that the metallic glass fiber is not hydroxylated, and other conditions are consistent with those of example 1, it can be seen that the electromagnetic shielding effect of the metallic glass without hydroxylation is reduced, which may be the reduction of the electromagnetic shielding effect caused by the poor compatibility of the metallic glass fiber and the release layer; comparative example 3 is a release film without metallic glass, and compared with example 1, the electromagnetic shielding capability is very small; in conclusion, the release film modified by the metallic glass prepared by the invention has excellent electromagnetic shielding effect.
The method for testing the release force of the release film comprises the following steps: according to GB/T2792-2014, the release film to be tested is made into a standard sample of 25mm multiplied by 200 mm. The four-dimensional adhesive tape MY-2G is attached to a release film to be tested according to a standard method, the release film is rolled back and forth for 4 times by a standard compression roller, then the release film is placed for 24 hours at room temperature, a release force tester (AR-1500) is used for testing 180-degree peel strength, the testing tensile speed is 300mm/min, and the tested force is the release force.
The method for testing the adhesive force of the release film comprises the following steps: and testing according to the GB/T9286-1998 standard, marking out squares on the release film sample by using a grid scriber, wherein each square is scribed through the coating to the substrate, and checking whether the release coating falls off or not on the surface appearance of the crossed cutting area by using a visual magnifier.
The test results are given in table 2 below:
TABLE 2
Compared with the comparative example 3, the release films modified by the metal glass in the examples 1 to 4 still have excellent release force and adhesion. The introduction of the modified metal glass not only improves the electromagnetic shielding, but also does not reduce the mechanical property of the release film, and in conclusion, the release film modified by the metal glass prepared by the method has good use performance and electromagnetic shielding effect.
Although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (9)
1. The release film modified by the metal glass is characterized by comprising a base film layer and a release layer, wherein the base film layer is PET, the release layer is formed by coating a release agent, and the release agent comprises 10-40 parts of vinyl organic silicon resin, 8-15 parts of modified metal glass fiber, 2-4 parts of curing agent dodecyl alcohol ester, 0.2-2 parts of defoaming agent ethylene glycol distearate and 50-60 parts of ethanol; the modified metal glass fiber is obtained by plating a silver electric layer and a cobalt magnetic layer on the surface of an iron-based metal glass fiber.
2. The preparation method of the metallic glass modified release film according to claim 1, characterized by comprising the following steps:
(1) preparation of modified iron-based metal glass fiber
Placing the iron-based metal glass fiber in SnCl2And HCl in solution; followed by washing with deionized water and then adding PbCl2And HCl, and is washed again with deionized water and then soaked in AgNO3Stirring in the solution to obtain the iron-based metal glass fiber of the silver-plated electric layer; the obtained product is sensitized and activated again and then immersed in CoSO4Stirring the solution for reaction; finally, washing with ethanol and drying in the air to obtain the modified iron-based metal glass fiber modified by the silver electric layer and the cobalt magnetic layer;
(2) introducing hydroxyl on the surface of the cobalt magnetic layer
Adding the modified iron-based metal glass fiber obtained in the step (1) into an 11-hydroxyundecyl phosphonic acid solution, and performing heat preservation reaction after ultrasonic treatment to obtain a hydroxylated modified iron-based metal glass fiber;
(3) preparation of mold release agent with electromagnetic shielding capability
Adding vinyl organic silicon resin, hydroxylated modified metal glass fiber, curing agent dodecyl alcohol ester and defoaming agent ethylene glycol distearate into an ethanol solvent, and stirring for reaction to prepare a mold release agent with electromagnetic shielding capability;
(4) coating of
And coating the release agent with electromagnetic shielding capability on a clean PET substrate by using an applicator, and curing to obtain the release film modified by the metallic glass.
3. The method for preparing the metallic glass modified release film according to claim 2, wherein the step (1) comprises the steps of preparing the ferrous metallic glass fiber, SnCl and the like2The mass ratio of the HCl to the HCl is 10: 10-30: 40-60; PbCl2The mass ratio of HCl to HCl is 1: 10-20.
4. The method for preparing the release film modified by the metallic glass according to claim 2, wherein the sensitization condition in the step (1) is kept at 25-40 ℃ for 5-20 min; the activation reaction condition is that the temperature is 30-50 ℃ and the time lasts for 10-60 min; immersion in AgN03The solution is continuously stirred for 8-30min under the reaction condition of 80-100 ℃; immersion in CoSO4The solution is continuously stirred for 5-20min under the reaction condition of 80-100 ℃.
5. The method for preparing the release film modified by the metallic glass according to claim 2, wherein the mass ratio of the modified iron-based metallic glass fiber and the 11-hydroxyundecyl phosphonic acid in the step (2) is 1: 5-20.
6. The method for preparing the metallic glass modified release film according to claim 2, wherein in the step (2), the ph of the 11-hydroxyundecyl phosphonic acid is 7-11; the reaction condition is that the reaction is carried out for 5 to 20 hours after the ultrasonic treatment is carried out for 5 to 30 minutes.
7. The method for preparing the release film modified by the metallic glass according to claim 2, wherein the mass ratio of the vinyl silicone resin, the modified metallic glass fiber, the curing agent dodecyl alcohol ester, the defoaming agent ethylene glycol distearate and the solvent ethanol in the step (3) is 10-40: 8-15: 2-4: 0.2-2: 50-60.
8. The method for preparing the release film modified by the metallic glass according to claim 2, wherein the stirring reaction condition in the step (3) is that the temperature is raised to 30-50 ℃ and then the stirring is carried out for 0.5-3 h.
9. The method for preparing the release film modified by metallic glass according to claim 2, wherein the curing condition in the step (4) is 120-150 ℃ for 10-60 min.
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Denomination of invention: A release film modified with metallic glass Effective date of registration: 20231227 Granted publication date: 20230428 Pledgee: Shunde Guangdong rural commercial bank Limited by Share Ltd. Daliang branch Pledgor: FOSHAN JIASHIDA FILM TECHNOLOGY Co.,Ltd. Registration number: Y2023980074818 |