CN115820144B - Optical temperature-resistant ultraviolet viscosity-reducing composite film and preparation method thereof - Google Patents
Optical temperature-resistant ultraviolet viscosity-reducing composite film and preparation method thereof Download PDFInfo
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- CN115820144B CN115820144B CN202211657881.5A CN202211657881A CN115820144B CN 115820144 B CN115820144 B CN 115820144B CN 202211657881 A CN202211657881 A CN 202211657881A CN 115820144 B CN115820144 B CN 115820144B
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- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 230000003287 optical effect Effects 0.000 title claims abstract description 22
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229920002635 polyurethane Polymers 0.000 claims abstract description 60
- 239000004814 polyurethane Substances 0.000 claims abstract description 60
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 52
- 229920002545 silicone oil Polymers 0.000 claims abstract description 52
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims abstract description 34
- 239000000178 monomer Substances 0.000 claims abstract description 27
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 21
- 239000005058 Isophorone diisocyanate Substances 0.000 claims abstract description 15
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 13
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 10
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- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 10
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 10
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000853 adhesive Substances 0.000 claims description 38
- 230000001070 adhesive effect Effects 0.000 claims description 38
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 11
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
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- AICIYIDUYNFPRY-UHFFFAOYSA-N 1,3-dihydro-2H-imidazol-2-one Chemical compound O=C1NC=CN1 AICIYIDUYNFPRY-UHFFFAOYSA-N 0.000 claims description 8
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 6
- 229920002799 BoPET Polymers 0.000 claims description 6
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
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- 238000001035 drying Methods 0.000 claims description 5
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000005292 vacuum distillation Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 4
- ZKVZWOFJEDEZFP-UHFFFAOYSA-N 6-[4-[[4-(6-prop-2-enoyloxyhexoxy)phenyl]diazenyl]phenoxy]hexyl prop-2-enoate Chemical compound C1=CC(OCCCCCCOC(=O)C=C)=CC=C1N=NC1=CC=C(OCCCCCCOC(=O)C=C)C=C1 ZKVZWOFJEDEZFP-UHFFFAOYSA-N 0.000 claims description 3
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 claims description 2
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 230000008014 freezing Effects 0.000 claims 1
- 238000007710 freezing Methods 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 239000003292 glue Substances 0.000 abstract description 10
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 4
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 abstract description 4
- 229920000570 polyether Polymers 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- 230000009467 reduction Effects 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
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- 239000003999 initiator Substances 0.000 description 4
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- 230000036211 photosensitivity Effects 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
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- 230000003746 surface roughness Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 239000000463 material Substances 0.000 description 1
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Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of visbreaking composite films, in particular to an optical temperature-resistant ultraviolet visbreaking composite film and a preparation method thereof; the 180-degree peeling strength of the ultraviolet visbreaking composite film prepared by the invention reaches 22-25N/25mm before ultraviolet irradiation, and the peeling strength is 0-0.5N/25mm after ultraviolet irradiation; introducing isocyanate group terminated silicone oil, preparing multi-polyether silicone oil by using hydrogen-containing silicone oil and allyl polyoxyethylene ether, and carrying out end capping by using isophorone diisocyanate; the hydroxyl-terminated polybutadiene is used as a soft segment to synthesize modified polyurethane; introducing a liquid crystal oligomer, and reacting a liquid crystal monomer containing azobenzene and phenyl benzoate with n-butylamine to obtain a main chain type liquid crystal oligomer with controllable molecular weight; the quality ratio of the polyurethane prepolymer, the liquid crystal oligomer and the zeolite-like imidazole ester skeleton of the hydroxyl-terminated polybutadiene in the modified polyurethane is controlled, so that the obtained ultraviolet viscosity-reducing composite film has moderate hardness, and the effect of easy removal and no residual glue under ultraviolet irradiation is achieved.
Description
Technical Field
The invention relates to the technical field of viscosity-reducing composite films, in particular to an optical temperature-resistant ultraviolet viscosity-reducing composite film and a preparation method thereof.
Background
With the development of the electronic industry, the semiconductor assembly and the electronic components are developed to be light, thin and exquisite, the electronic components are easy to damage in the processing and transportation processes, the electronic components are required to be temporarily fixed and protected by a film, and the adhesion-reducing composite film is used as a pressure-sensitive adhesive with adjustable peeling strength, so that the adhesion-reducing composite film can be easily removed on the premise of not damaging the electronic components after the processing is finished.
The ultraviolet anti-adhesion composite film is widely applied to the assembly processing of the electronic industry, for example, the ultraviolet anti-adhesion composite film is utilized to temporarily fix and protect the mobile phone in the mobile phone screen manufacturing process, so that the problems of scratch, abrasion, pollution, corrosion and the like of the mobile phone are prevented. When the fixing or protecting function is not needed, ultraviolet irradiation is carried out on the adhesive, so that the adhesive can be easily separated from the surface of an adherend on the premise of not damaging a product.
The ultraviolet visbreaking composite film which is applied to electronic products in the market at present is mainly composed of acrylic pressure-sensitive adhesives, wherein ultraviolet curing crosslinking points are fewer, so that ultraviolet curing is low in crosslinking density and volume shrinkage degree, the visbreaking effect after ultraviolet curing is poor, meanwhile, the problem of poor temperature resistance exists, and the product is easy to displace when being fixed due to the high elastic property of the ultraviolet visbreaking composite film, so that accurate assembly is not facilitated.
Disclosure of Invention
The invention aims to provide an optical temperature-resistant ultraviolet viscosity-reducing composite film and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
an optical temperature-resistant ultraviolet visbreaking composite film comprises a base film and an visbreaking layer, wherein the visbreaking layer is a coating of an visbreaking adhesive; preparing modified polyurethane, polyfunctional acrylic monomer, isocyanate group end-capped silicone oil and photoinitiator to obtain a viscosity reducing adhesive; the modified polyurethane is prepared by compounding a polyurethane prepolymer based on hydroxyl-terminated polybutadiene, a liquid crystal oligomer and a zeolite-like imidazole ester skeleton.
Aiming at the problems of poor viscosity reduction effect, poor temperature resistance and the like of an ultraviolet viscosity reduction composite film after ultraviolet curing in the existing market, the invention provides an optical temperature-resistant ultraviolet viscosity reduction composite film, wherein the viscosity reduction layer prepared by the invention contains a large number of unsaturated double bonds, and the crosslinking effect is generated after ultraviolet irradiation, so that a semi-interpenetrating network structure is formed with a linear polymer molecular chain of a matrix, the viscosity of the viscosity reduction composite film is reduced, and the interface between the viscosity reduction composite film and an object to be bonded is wrinkled and microporous due to larger volume shrinkage generated by crosslinking, the bonding interface is damaged, the effective bonding area is reduced, and the peeling strength of the viscosity reduction composite film after ultraviolet curing is reduced; the ultraviolet visbreaking composite film prepared by the invention has 180 DEG peel strength reaching 22-25N/25mm before ultraviolet irradiation, 0-0.5N/25mm after ultraviolet irradiation, wide peel strength range and high maximum peel strength, can meet the market demand of visbreaking composite films, and effectively prolongs the service life of the visbreaking composite film through component adjustment.
Further, the polyfunctional acrylate monomer is one of trimethylolpropane triacrylate and tripropylene glycol diacrylate.
Further, the photoinitiator is an initiator which can reach the maximum absorption peak under the irradiation of ultraviolet rays of 200nm-400 nm. The photoinitiator is one or more of 1-hydroxycyclohexyl phenyl ketone, alpha-hydroxyisobutyryl benzene, benzoin dimethyl ether and 2-isopropyl thioxanthone; the organic solvent is one or more of toluene, ethyl acetate and 120# solvent oil.
Further, the viscosity reducing adhesive comprises the following components in parts by weight: 45-55 parts of modified polyurethane, 8-12 parts of polyfunctional acrylate monomer, 2-8 parts of isocyanate group end-capped silicone oil, 1.5-2 parts of photoinitiator and 44-56 parts of organic solvent.
Introducing isocyanate-terminated silicone oil into the viscosity reducing adhesive, preparing multi-component polyether silicone oil by using hydrogen-containing silicone oil and allyl polyoxyethylene ether, and blocking by using isophorone diisocyanate to obtain the isocyanate-terminated silicone oil, and improving the thermal stability of the viscosity reducing composite film by using the low modulus and high temperature resistance of the silicone oil in the isocyanate-terminated silicone oil.
Further, the preparation of the isocyanate-terminated silicone oil comprises the following steps:
1) Mixing hydrogen-containing silicone oil, allyl polyoxyethylene ether and toluene, heating to 50 ℃, adding chloroplatinic acid, preserving heat for 20-30min, heating to 85-90 ℃ and preserving heat for 2-3h, and carrying out vacuum distillation to obtain modified polysiloxane;
2) Mixing the modified polysiloxane and acetone, heating to 50 ℃, adding the mixture into the mixed solution of isophorone diisocyanate and acetone, stirring for 1-2h, adding dibutyltin dilaurate, heating to 60 ℃, preserving heat for 20-30min, adding methyl ethyl ketoxime, and continuously stirring for 20-30min to obtain the isocyanate-terminated silicone oil.
Further, the preparation of the modified polyurethane comprises the following steps:
(1) Under the nitrogen atmosphere, mixing ethyl acetate, hydroxyl-terminated polybutadiene, dibutyl tin dilaurate and hydroquinone, heating to 55-60 ℃, adding isophorone diisocyanate, and preserving heat for 2 hours to obtain a polyurethane prepolymer based on the hydroxyl-terminated polybutadiene;
(2) Mixing polyurethane prepolymer based on hydroxyl-terminated polybutadiene, liquid crystal oligomer, zeolite-like imidazole ester skeleton and 1, 4-butylene glycol, reacting at 55-60 ℃ for 2h until the mass fraction of isocyanate groups in the product is 1%, and ending the reaction to obtain modified polyurethane.
According to the invention, the hydroxyl-terminated polybutadiene is used as a soft segment to synthesize the modified polyurethane, unsaturated carbon-carbon double bonds of a main chain and a side group of the hydroxyl-terminated polybutadiene can endow the anti-adhesion composite film with good ultraviolet corresponding characteristics, so that the C=C in the modified polyurethane and the polyfunctional monomer is polymerized under the action of an ultraviolet initiator to generate a three-dimensional crosslinking structure, the volume of the adhesive is shrunk, the adhesive is wrinkled, the surface roughness is increased, and the bonding points with an adherend are reduced, thereby greatly reducing the peeling strength of the adhesive.
Introducing a liquid crystal oligomer into modified polyurethane, effectively synergistically improving the thermal stability of the viscosity-reducing composite film, carrying out Michael addition reaction on a liquid crystal monomer containing azobenzene and phenyl benzoate and n-butylamine to obtain a main chain type liquid crystal oligomer with controllable molecular weight, and effectively reducing the crosslinking density of a high molecular network by chain extension reaction between the liquid crystal monomer and primary amine, thereby reducing the glass transition temperature of the viscosity-reducing composite film; the liquid crystal oligomer has photosensitivity, and can effectively reduce the peeling strength of the visbreaking composite film after ultraviolet irradiation under the condition of not damaging a protective object, thereby achieving the effects of easy removal and no residual glue.
Further, the preparation of the liquid crystal oligomer comprises the following steps: under the argon environment, 4' -di [6- (acryloyloxy) hexyloxy ] azobenzene and 1, 4-di (4- (6-acryloyloxy) n-nonyloxy) benzoyloxy-2-methylbenzene are mixed, methylene dichloride is added, the system is frozen by utilizing liquid nitrogen, vacuumizing and deoxidizing are carried out, a mixed solution of n-butylamine and methylene dichloride is added under the protection of argon, the mixed solution is kept for 22-24 hours in an oil bath at 45 ℃, sedimentation is carried out in n-hexane, and a liquid crystal oligomer is obtained after drying.
Further, the preparation of the zeolite-like imidazole ester skeleton comprises the following steps: adding zinc nitrate hexahydrate into the mixed solution of 2-hydroxyimidazole and deionized water, stirring for 2-3h, centrifuging and precipitating to obtain zeolite-like imidazole ester skeleton.
The zeolite-like imidazole ester skeleton is an organic-inorganic hybrid material formed by coordination of transition metal ions and imidazole or imidazole derivatives, and zinc ions and hydroxyl imidazole ligands are utilized to form a coordination polymer with unique structure and good porosity;
according to the invention, the toughening effect of the modified polyurethane is improved by controlling the introduction of the liquid crystal oligomer, the semi-interpenetrating network structure formed by the liquid crystal oligomer and the modified polyurethane also plays a role in improving the lifting performance of the composite film, the zeolite-like imidazole ester skeleton is introduced into the modified polyurethane to increase the second phase, the synergistic toughening effect is achieved, and the zeolite-like imidazole ester skeleton has good ultraviolet absorptivity and high thermal stability, and can effectively improve the ultraviolet light utilization rate and the thermal stability of the viscosity-reducing composite film.
Further, the modified polyurethane is polyurethane prepolymer based on hydroxyl-terminated polybutadiene, liquid crystal oligomer and zeolite-like imidazole ester skeleton in a mass ratio of 10:2: and 0.5.
The quality ratio of the polyurethane prepolymer, the liquid crystal oligomer and the zeolite-like imidazole ester skeleton of the hydroxyl-terminated polybutadiene in the modified polyurethane is controlled, so that the obtained modified polyurethane has moderate hardness, the prepared viscosity-reducing composite film keeps higher peel strength when the ultraviolet light irradiation is not available, the effective protection and fixation are achieved, and the effects of easy removal, no precipitation of small molecules and no residual glue are achieved under the ultraviolet light irradiation.
Further, the preparation method of the optical temperature-resistant ultraviolet visbreaking composite film comprises the following steps:
s1: selecting one of a PET film, a polyethylene film and a grid release film as a base film, and carrying out corona treatment;
s2: mixing modified polyurethane, a polyfunctional acrylate monomer, a photoinitiator and isocyanate-terminated silicone oil, adding an organic solvent, stirring and dissolving, standing and defoaming to obtain a viscosity reducing adhesive;
s3: coating the viscosity reducing adhesive on the surface of the base film after corona treatment, preserving heat for 1-2h at 30-40 ℃, and standing for 20-22h at 18-25 ℃ to obtain the optical temperature-resistant ultraviolet viscosity reducing composite film.
Further, the working conditions of the corona treatment are as follows: treating with corona instrument with power of 50V for 2-5min; the stripping force of the composite film is 20-22N/25mm before ultraviolet irradiation, and the stripping force of the composite film is 0-0.5N/25mm after ultraviolet irradiation; the exposure time under the ultraviolet light source is 5-10s; the wavelength of the ultraviolet light source is 300-400nm, and the illuminance of the ultraviolet light source is 80-95mW/cm 2 。
The binding force between the base film and the viscosity-reducing adhesive can be effectively improved by corona treatment of the base film.
The invention has the beneficial effects that:
the invention provides an optical temperature-resistant ultraviolet viscosity-reducing composite film and a preparation method thereof, wherein the 180-degree peeling strength of the ultraviolet viscosity-reducing composite film prepared by the invention reaches 22-25N/25mm before ultraviolet irradiation, and is 0-0.5N/25mm after ultraviolet irradiation, the peeling strength range is wide, the maximum peeling strength is high, the ultraviolet viscosity-reducing composite film has higher thermal stability, and the requirements of the electronic industry are met.
The method is characterized in that hydrogen-containing silicone oil and allyl polyoxyethylene ether are used for preparing multi-polyether silicone oil, isophorone diisocyanate is used for blocking, isocyanate-terminated silicone oil is obtained, the low modulus and high temperature resistance of the silicone oil in the isocyanate-terminated silicone oil are utilized, the thermal stability of the viscosity-reducing composite film is improved, the isocyanate is used for blocking, the interfacial property of the silicone oil and a modified polyurethane matrix can be effectively improved, and the small molecular precipitation is reduced on the basis of easy stripping after ultraviolet irradiation, so that the situation of no residual glue is achieved.
According to the invention, the hydroxyl-terminated polybutadiene is used as a soft segment to synthesize the modified polyurethane, unsaturated carbon-carbon double bonds of a main chain and a side group of the hydroxyl-terminated polybutadiene can endow the anti-adhesion composite film with good ultraviolet corresponding characteristics, so that the C=C in the modified polyurethane and the polyfunctional monomer is polymerized under the action of an ultraviolet initiator to generate a three-dimensional crosslinking structure, the volume of the adhesive is shrunk, the adhesive is wrinkled, the surface roughness is increased, and the bonding points with an adherend are reduced, thereby greatly reducing the peeling strength of the adhesive.
Introducing a liquid crystal oligomer into modified polyurethane, effectively synergistically improving the thermal stability of the viscosity-reducing composite film, carrying out Michael addition reaction on a liquid crystal monomer containing azobenzene and phenyl benzoate and n-butylamine to obtain a main chain type liquid crystal oligomer with controllable molecular weight, and effectively reducing the crosslinking density of a high molecular network by chain extension reaction between the liquid crystal monomer and primary amine, thereby reducing the glass transition temperature of the viscosity-reducing composite film; the liquid crystal oligomer has photosensitivity, and can effectively reduce the peeling strength of the visbreaking composite film after ultraviolet irradiation under the condition of not damaging a protective object, thereby achieving the effects of easy removal and no residual glue.
The toughening effect of the modified polyurethane is improved by controlling the introduction of the liquid crystal oligomer, the semi-interpenetrating network structure formed by the liquid crystal oligomer and the modified polyurethane also plays an effect of improving the pulling performance of the composite film, the zeolite-like imidazole ester skeleton is introduced into the modified polyurethane to increase the second phase, the synergistic toughening effect is achieved, and the zeolite-like imidazole ester skeleton has good ultraviolet absorptivity and high thermal stability, and can effectively improve the ultraviolet light utilization rate and the thermal stability of the viscosity-reducing composite film.
The quality ratio of the polyurethane prepolymer, the liquid crystal oligomer and the zeolite-like imidazole ester skeleton of the hydroxyl-terminated polybutadiene in the modified polyurethane is controlled, so that the obtained modified polyurethane is moderate in softness and hardness, and the prepared viscosity-reducing composite film is improved in heat resistance and tensile strength on the basis that the viscosity-reducing composite film is kept soft and easy to attach when the ultraviolet light is not irradiated, the reworking performance is improved, and the effects of easy removal, no precipitation of small molecules and no residual glue are achieved under the ultraviolet light irradiation.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that, if directional indications such as up, down, left, right, front, and rear … … are involved in the embodiment of the present invention, the directional indications are merely used to explain a relative positional relationship, a movement condition, and the like between a certain posture such as the respective components, and if the certain posture is changed, the directional indications are changed accordingly. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The following description of the embodiments of the present invention will be presented in further detail with reference to the examples, which should be understood as being merely illustrative of the present invention and not limiting.
Example 1
The preparation method of the optical temperature-resistant ultraviolet visbreaking composite film comprises the following steps:
s1: selecting a PET film as a base film, and carrying out corona treatment;
s2: mixing modified polyurethane, a polyfunctional acrylate monomer, a photoinitiator and isocyanate-terminated silicone oil, adding an organic solvent, stirring and dissolving, standing and defoaming to obtain a viscosity reducing adhesive;
the adhesive comprises the following components in parts by weight: 45 parts of modified polyurethane, 8 parts of polyfunctional acrylate monomer, 2 parts of isocyanate group end-capped silicone oil, 1.5 parts of photoinitiator and 44 parts of organic solvent;
the polyfunctional acrylic monomer is trimethylolpropane triacrylate; the photoinitiator is 1-hydroxycyclohexyl phenyl ketone; the organic solvent is toluene;
the preparation of the modified polyurethane comprises the following steps:
(1) 30mL of ethyl acetate, 0.585mol of hydroxyl-terminated polybutadiene, 3.45mmol of dibutyltin dilaurate and 20.4mmol of hydroquinone are mixed under the nitrogen atmosphere, 9.44mmol of isophorone diisocyanate is added after the temperature is raised to 55 ℃, and the temperature is kept for 2 hours, so as to obtain a polyurethane prepolymer based on the hydroxyl-terminated polybutadiene;
(2) 10g of polyurethane prepolymer based on hydroxyl-terminated polybutadiene, 2g of liquid crystal oligomer, 0.5g of zeolite-like imidazole ester skeleton and 1.04g of 1, 4-butylene glycol are mixed, and the mixture is reacted for 2 hours at 55 ℃ until the mass fraction of isocyanate groups in the product is 1%, and the reaction is finished to obtain modified polyurethane;
the preparation of the liquid crystal oligomer comprises the following steps: 52.8mg of 4,4' -di [6- (acryloyloxy) hexyloxy ] azobenzene and 71.9mg of 1, 4-di (4- (6-acryloyloxy) n-nonyloxy) benzoyloxy-2-methylbenzene are mixed under the argon atmosphere, 0.3mL of methylene dichloride is added, the system is frozen by utilizing liquid nitrogen, vacuumizing and deoxidizing are carried out, 49 mu L of mixed solution of n-butylamine and 0.5mL of methylene dichloride are added under the argon protection, the mixed solution is kept in an oil bath at 45 ℃ for 22 hours, sedimentation is carried out in n-hexane, and liquid crystal oligomer is obtained by drying;
the preparation of the zeolite-like imidazole ester skeleton comprises the following steps: adding 2.7g of zinc nitrate hexahydrate into a mixed solution of 8.2g of 2-hydroxyimidazole and 500mL of deionized water, stirring for 2 hours, centrifuging, and precipitating to obtain zeolite-like imidazole ester skeleton;
the preparation of the isocyanate-terminated silicone oil comprises the following steps:
1) Mixing 1mmol of hydrogen-containing silicone oil, 1.2mmol of allyl polyoxyethylene ether and 30mL of toluene, heating to 50 ℃, adding 1mg of chloroplatinic acid, preserving heat for 20min, heating to 85 ℃, preserving heat for 3h, and carrying out vacuum distillation to obtain modified polysiloxane;
2) Mixing 1g of modified polysiloxane with 15mL of acetone, heating to 50 ℃, adding the mixture into a mixed solution of 0.2g of isophorone diisocyanate and 15mL of acetone, stirring for 1h, adding 1mg of dibutyltin dilaurate, heating to 60 ℃, preserving heat for 20min, adding 0.1g of methyl ethyl ketoxime, and continuing stirring for 20min to obtain isocyanate-terminated silicone oil;
s3: coating a viscosity reducing adhesive on the surface of the base film after corona treatment, preserving heat for 2 hours at 30 ℃, and standing for 22 hours at 18 ℃ to obtain an optical temperature-resistant ultraviolet viscosity reducing composite film;
the working conditions of the corona treatment are as follows: treating with corona instrument with power of 50V for 2min; the exposure time under the ultraviolet light source is 5s; the wavelength of the ultraviolet light source is 300nm, and the illuminance of the light radiation of the ultraviolet light source is 95mW/cm 2 。
Example 2
The preparation method of the optical temperature-resistant ultraviolet visbreaking composite film comprises the following steps:
s1: selecting a PET film as a base film, and carrying out corona treatment;
s2: mixing modified polyurethane, a polyfunctional acrylate monomer, a photoinitiator and isocyanate-terminated silicone oil, adding an organic solvent, stirring and dissolving, standing and defoaming to obtain a viscosity reducing adhesive;
the adhesive comprises the following components in parts by weight: 50 parts of modified polyurethane, 10 parts of polyfunctional acrylate monomer, 5 parts of isocyanate group end-capped silicone oil, 1.8 parts of photoinitiator and 50 parts of organic solvent;
the polyfunctional acrylic monomer is trimethylolpropane triacrylate; the photoinitiator is 1-hydroxycyclohexyl phenyl ketone; the organic solvent is ethyl acetate;
the preparation of the modified polyurethane comprises the following steps:
(1) 30mL of ethyl acetate, 0.585mol of hydroxyl-terminated polybutadiene, 3.45mmol of dibutyltin dilaurate and 20.4mmol of hydroquinone are mixed under the nitrogen atmosphere, 9.44mmol of isophorone diisocyanate is added after the temperature is raised to 58 ℃, and the temperature is kept for 2 hours, so as to obtain a polyurethane prepolymer based on the hydroxyl-terminated polybutadiene;
(2) 10g of polyurethane prepolymer based on hydroxyl-terminated polybutadiene, 2g of liquid crystal oligomer, 0.5g of zeolite-like imidazole ester skeleton and 1.04g of 1, 4-butylene glycol are mixed, and reacted for 2 hours at 58 ℃ until the mass fraction of isocyanate groups in the product is 1%, and the reaction is finished to obtain modified polyurethane;
the preparation of the liquid crystal oligomer comprises the following steps: 52.8mg of 4,4' -di [6- (acryloyloxy) hexyloxy ] azobenzene and 71.9mg of 1, 4-di (4- (6-acryloyloxy) n-nonyloxy) benzoyloxy-2-methylbenzene are mixed under the argon atmosphere, 0.3mL of methylene dichloride is added, the system is frozen by utilizing liquid nitrogen, vacuumizing and deoxidizing are carried out, 49 mu L of mixed solution of n-butylamine and 0.5mL of methylene dichloride are added under the argon protection, the mixed solution is kept in an oil bath at 45 ℃ for 23 hours, sedimentation is carried out in n-hexane, and liquid crystal oligomer is obtained by drying;
the preparation of the zeolite-like imidazole ester skeleton comprises the following steps: adding 2.7g of zinc nitrate hexahydrate into a mixed solution of 8.2g of 2-hydroxyimidazole and 500mL of deionized water, stirring for 2.5h, centrifuging, and precipitating to obtain zeolite-like imidazole ester skeleton;
the preparation of the isocyanate-terminated silicone oil comprises the following steps:
1) Mixing 1mmol hydrogen-containing silicone oil, 1.2mmol allyl polyoxyethylene ether and 30mL toluene, heating to 50 ℃, adding 1mg chloroplatinic acid, preserving heat for 20-30min, heating to 88 ℃ and preserving heat for 2.5h, and carrying out vacuum distillation to obtain modified polysiloxane;
2) Mixing 1g of modified polysiloxane with 15mL of acetone, heating to 50 ℃, adding the mixture into a mixed solution of 0.2g of isophorone diisocyanate and 15mL of acetone, stirring for 1.5h, adding 1mg of dibutyltin dilaurate, heating to 60 ℃, preserving heat for 25min, adding 0.1g of methyl ethyl ketoxime, and continuing stirring for 25min to obtain isocyanate-terminated silicone oil;
s3: coating a viscosity reducing adhesive on the surface of the base film after corona treatment, preserving heat for 1.5h at 35 ℃, and standing for 21h at 20 ℃ to obtain an optical temperature-resistant ultraviolet viscosity reducing composite film;
the working conditions of the corona treatment are as follows: treating with corona instrument with power of 50V for 3min; the exposure time under the ultraviolet light source is 8s; the wavelength of the ultraviolet light source is 365nm, and the illuminance of the ultraviolet light source is 85mW/cm 2 。
Example 3
The preparation method of the optical temperature-resistant ultraviolet visbreaking composite film comprises the following steps:
s1: selecting a PET film as a base film, and carrying out corona treatment;
s2: mixing modified polyurethane, a polyfunctional acrylate monomer, a photoinitiator and isocyanate-terminated silicone oil, adding an organic solvent, stirring and dissolving, standing and defoaming to obtain a viscosity reducing adhesive;
the adhesive comprises the following components in parts by weight: 55 parts of modified polyurethane, 12 parts of polyfunctional acrylate monomer, 8 parts of isocyanate group end-capped silicone oil, 2 parts of photoinitiator and 56 parts of organic solvent;
the polyfunctional acrylic monomer is trimethylolpropane triacrylate; the photoinitiator is 1-hydroxycyclohexyl phenyl ketone; the organic solvent is ethyl acetate;
the preparation of the modified polyurethane comprises the following steps:
(1) 30mL of ethyl acetate, 0.585mol of hydroxyl-terminated polybutadiene, 3.45mmol of dibutyltin dilaurate and 20.4mmol of hydroquinone are mixed under the nitrogen atmosphere, 9.44mmol of isophorone diisocyanate is added after the temperature is raised to 60 ℃, and the temperature is kept for 2 hours, so as to obtain a polyurethane prepolymer based on the hydroxyl-terminated polybutadiene;
(2) 10g of polyurethane prepolymer based on hydroxyl-terminated polybutadiene, 2g of liquid crystal oligomer, 0.5g of zeolite-like imidazole ester skeleton and 1.04g of 1, 4-butylene glycol are mixed, and reacted for 2 hours at 60 ℃ until the mass fraction of isocyanate groups in the product is 1%, and the reaction is finished to obtain modified polyurethane;
the preparation of the liquid crystal oligomer comprises the following steps: 52.8mg of 4,4' -di [6- (acryloyloxy) hexyloxy ] azobenzene and 71.9mg of 1, 4-di (4- (6-acryloyloxy) n-nonyloxy) benzoyloxy-2-methylbenzene are mixed under the argon atmosphere, 0.3mL of methylene dichloride is added, the system is frozen by utilizing liquid nitrogen, vacuumizing and deoxidizing are carried out, 49 mu L of mixed solution of n-butylamine and 0.5mL of methylene dichloride are added under the argon protection, the mixed solution is kept in an oil bath at 45 ℃ for 24 hours, sedimentation is carried out in n-hexane, and liquid crystal oligomer is obtained by drying;
the preparation of the zeolite-like imidazole ester skeleton comprises the following steps: adding 2.7g of zinc nitrate hexahydrate into a mixed solution of 8.2g of 2-hydroxyimidazole and 500mL of deionized water, stirring for 3h, centrifuging and precipitating to obtain zeolite-like imidazole ester skeleton;
the preparation of the isocyanate-terminated silicone oil comprises the following steps:
1) Mixing 1mmol of hydrogen-containing silicone oil, 1.2mmol of allyl polyoxyethylene ether and 30mL of toluene, heating to 50 ℃, adding 1mg of chloroplatinic acid, preserving heat for 30min, heating to 90 ℃, preserving heat for 2h, and carrying out vacuum distillation to obtain modified polysiloxane;
2) Mixing 1g of modified polysiloxane with 15mL of acetone, heating to 50 ℃, adding the mixture into a mixed solution of 0.2g of isophorone diisocyanate and 15mL of acetone, stirring for 1h, adding 1mg of dibutyltin dilaurate, heating to 60 ℃, preserving heat for 30min, adding 0.1g of methyl ethyl ketoxime, and continuing stirring for 30min to obtain isocyanate-terminated silicone oil;
s3: coating a viscosity reducing adhesive on the surface of the base film after corona treatment, preserving heat for 1h at 40 ℃, and standing for 20h at 25 ℃ to obtain an optical temperature-resistant ultraviolet viscosity reducing composite film;
the working conditions of the corona treatment are as follows: treating with corona instrument with power of 50V for 5min; the exposure time under the ultraviolet light source is 10s, and the wavelength of the ultraviolet light source is 400nm; the illuminance of the light radiation of the ultraviolet light source is 80mW/cm 2 。
The thickness of the adhesion-reducing adhesives of examples 1-3 applied to the surface of the base film was 100 μm.
Comparative example 1
Using example 3 as a control, the isocyanate-terminated silicone oil was replaced with a hydrogen-containing silicone oil, and the other procedures were normal.
Comparative example 2
In the case of example 3 as a control, no liquid crystal oligomer was added during the preparation of the modified polyurethane, and the other steps were normal.
Comparative example 3
In the case of example 3 as a control group, the zeolite-like imidazole ester skeleton was not added in the preparation of the modified polyurethane, and the other procedures were normal.
Comparative example 4
Using example 3 as a control, the polyurethane prepolymer of the hydroxyl-terminated polybutadiene was replaced with polyurethane (polymeric MDI polyurethane: jin Jinle chemical Co., ltd.) in the preparation of the modified polyurethane, and the other procedures were normal.
Comparative example 5
Taking example 3 as a control group, the mass ratio of the polyurethane prepolymer, the liquid crystal oligomer and the zeolite-like imidazole ester skeleton based on the hydroxyl-terminated polybutadiene is not 10:1:0.5, adding polyurethane prepolymer based on hydroxyl-terminated polybutadiene, 1g of liquid crystal oligomer and 0.5g of zeolite-like imidazole ester skeleton in the preparation of modified polyurethane, and other working procedures are normal.
The sources of the raw materials are as follows:
PET film NITTO5602 (0.02 mm): shenzhen City one science and technology Co., ltd; trimethylolpropane triacrylate T477244, dibutyltin dilaurate D100274, hydroquinone H108945, isophorone diisocyanate I109582, 1, 4-butylene glycol B107560, n-butylamine D111219, zinc nitrate hexahydrate Z111703, allyl polyoxyethylene ether A303301, chloroplatinic acid C139933: ala Ding Shiji; 1-hydroxycyclohexyl phenyl ketone 405612: sigma aldrich (Shanghai) trade limited; toluene, ethyl acetate, dichloromethane, n-hexane, acetone, analytically pure: a national drug group reagent; hydroxyl-terminated polybutadiene 69102-90-5: the WUHANXIN Jiali Biotechnology Co.Ltd; 4,4' -bis [6- (acryloyloxy) hexyloxy ] azobenzene 1011714-83-2, hydrogen-containing silicone oil 63148-57-2: zhengzhou alpha chemical Co., ltd; 1, 4-bis (4- (6-acryloyloxy) n-nonyloxy) benzoyloxy-2-methylbenzrm 82: beijing eight hundred million space time liquid crystal technology Co.Ltd; 2-hydroxyimidazole 5918-93-4: hubei Heng Jing Rui chemical Co., ltd; methyl ethyl ketoxime 96-29-7: wuhan Ji Xinyi, bang Biotechnology Co.
Performance test: the 180-degree peel strength and the residual adhesive remaining rate after ultraviolet irradiation of the composite films prepared in examples 1 to 3 and comparative examples 1 to5 were tested, and the test results are shown in Table 1;
180 ° peel strength: according to the testing method of 180-degree peel strength of GB/T2792-1998 adhesive, a stainless steel cold-rolled steel plate is used for testing, the width of a sample is 20mm, the length of the sample is 200mm, and the stretching rate is 300mm/min;
and (3) temperature resistance test: the temperature is kept at 120 ℃ for 12 hours, and 180-degree peeling strength before ultraviolet irradiation is measured;
residual gum remaining rate after ultraviolet irradiation: and recording that the residual glue is unqualified after ultraviolet irradiation in the 180-degree peel strength test, 20 residual glue is unqualified in each group, and calculating the unqualified rate.
TABLE 1
The invention provides an optical temperature-resistant ultraviolet viscosity-reducing composite film and a preparation method thereof, wherein the 180-degree peeling strength of the ultraviolet viscosity-reducing composite film prepared by the invention reaches 22-25N/25mm before ultraviolet irradiation, and is 0-0.5N/25mm after ultraviolet irradiation, the peeling strength range is wide, the maximum peeling strength is high, the ultraviolet viscosity-reducing composite film has higher thermal stability, and the requirements of the electronic industry are met.
Comparing example 3 with comparative example 1, introducing isocyanate group-terminated silicone oil into the viscosity reducing adhesive, preparing multielement polyether silicone oil by hydrogen-containing silicone oil and allyl polyoxyethylene ether, and carrying out end-capping by isophorone diisocyanate to obtain isocyanate group-terminated silicone oil, and improving the thermal stability of the viscosity reducing composite film by utilizing the low modulus and high temperature resistance of the silicone oil in the isocyanate group-terminated silicone oil, wherein the interface between the silicone oil and the modified polyurethane matrix can be effectively improved by end-capping by isocyanate, and the precipitation of small molecules is reduced on the basis of easy stripping after ultraviolet irradiation, so that the condition of no residual adhesive is achieved.
Comparing example 3 with comparative example 2, introducing a liquid crystal oligomer into the modified polyurethane, effectively synergistically improving the thermal stability of the viscosity-reducing composite film, carrying out Michael addition reaction on a liquid crystal monomer containing azobenzene and phenyl benzoate and n-butylamine to obtain a main chain type liquid crystal oligomer with controllable molecular weight, and effectively reducing the crosslinking density of a high molecular network by chain extension reaction between the liquid crystal monomer and primary amine, thereby reducing the glass transition temperature of the viscosity-reducing composite film; the liquid crystal oligomer has photosensitivity, and can effectively reduce the peeling strength of the visbreaking composite film after ultraviolet irradiation under the condition of not damaging a protective object, thereby achieving the effects of easy removal and no residual glue.
By comparing the embodiment 3 with the comparative example 3, the toughening effect of the modified polyurethane is improved by controlling the introduction of the liquid crystal oligomer, the semi-interpenetrating network structure formed by the liquid crystal oligomer and the modified polyurethane also plays a role in improving the pulling performance of the composite film, the zeolite-like imidazole ester skeleton is introduced into the modified polyurethane to increase the second phase, the synergistic toughening effect is achieved, and the zeolite-like imidazole ester skeleton has good ultraviolet absorptivity and high thermal stability, and can effectively improve the ultraviolet light utilization rate and the thermal stability of the viscosity-reduced composite film.
By comparing the embodiment 3 with the comparative example 4, the invention synthesizes the modified polyurethane by taking the hydroxyl-terminated polybutadiene as a soft segment, and unsaturated carbon-carbon double bonds of the main chain and the side groups of the hydroxyl-terminated polybutadiene can endow the viscosity-reducing composite film with good ultraviolet corresponding characteristics, so that the C=C in the modified polyurethane and the polyfunctional monomer is polymerized under the action of an ultraviolet initiator to generate a three-dimensional crosslinking structure, the volume of the adhesive is shrunk, the adhesive is wrinkled, the surface roughness is increased, and the bonding points between the adhesive and an adherend are reduced, thereby greatly reducing the peel strength of the adhesive.
Comparing example 3 with comparative example 5, the modified polyurethane obtained by controlling the mass ratio of the hydroxyl-terminated polybutadiene polyurethane prepolymer, the liquid crystal oligomer and the zeolite-like imidazole ester skeleton in the modified polyurethane has moderate softness and hardness, and the prepared viscosity-reducing composite film has the advantages of improving the heat resistance and the tensile strength of the viscosity-reducing composite film, improving the reworking performance, achieving the effects of easy removal under ultraviolet irradiation, no precipitation of small molecules and no residual glue on the basis that the viscosity-reducing composite film is kept soft and easy to be adhered when the ultraviolet irradiation is not carried out.
The foregoing description is only exemplary embodiments of the present invention and is not intended to limit the scope of the invention, but rather, the equivalent structural changes made by the present invention in the light of the inventive concept, or the direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (4)
1. The optical temperature-resistant ultraviolet visbreaking composite film is characterized by comprising a base film and an visbreaking layer, wherein the visbreaking layer is a coating of an visbreaking adhesive; preparing modified polyurethane, polyfunctional acrylic monomer, isocyanate group end-capped silicone oil and photoinitiator to obtain a viscosity reducing adhesive; the modified polyurethane is obtained by compounding a polyurethane prepolymer based on hydroxyl-terminated polybutadiene, a liquid crystal oligomer and a zeolite-like imidazole ester skeleton;
the adhesive comprises the following components in parts by weight: 45-55 parts of modified polyurethane, 8-12 parts of polyfunctional acrylate monomer, 2-8 parts of isocyanate group end-capped silicone oil, 1.5-2 parts of photoinitiator and 44-56 parts of organic solvent;
the mass ratio of the polyurethane prepolymer based on hydroxyl-terminated polybutadiene to the liquid crystal oligomer to the zeolite-like imidazole ester skeleton in the modified polyurethane is 10:2:0.5;
the preparation of the liquid crystal oligomer comprises the following steps: mixing 4,4' -di [6- (acryloyloxy) hexyloxy ] azobenzene and 1, 4-di (4- (6-acryloyloxy) n-nonyloxy) benzoyloxy-2-methylbenzene under the argon environment, adding methylene dichloride, freezing the system by utilizing liquid nitrogen, vacuumizing to remove oxygen, adding a mixed solution of n-butylamine and methylene dichloride under the protection of argon, keeping the mixed solution in an oil bath at 45 ℃ for 22-24 hours, settling in n-hexane, and drying to obtain a liquid crystal oligomer;
in the preparation of the liquid crystal oligomer, the mass-volume ratio of the 4,4' -bis [6- (acryloyloxy) hexyloxy ] azobenzene to the 1, 4-bis (4- (6-acryloyloxy) n-nonyloxy) benzoyloxy-2-methylbenzene to the n-butylamine is 52.8mg:71.9mg: 49. Mu.L;
the preparation of the zeolite-like imidazole ester skeleton comprises the following steps: adding zinc nitrate hexahydrate into the mixed solution of 2-hydroxyimidazole and deionized water, stirring for 2-3 hours, centrifuging and precipitating to obtain zeolite-like imidazole ester skeleton;
the preparation of the modified polyurethane comprises the following steps:
(1) Under the nitrogen atmosphere, mixing ethyl acetate, hydroxyl-terminated polybutadiene, dibutyl tin dilaurate and hydroquinone, heating to 55-60 ℃, adding isophorone diisocyanate, and preserving heat for 2 hours to obtain a polyurethane prepolymer based on the hydroxyl-terminated polybutadiene;
(2) Mixing polyurethane prepolymer based on hydroxyl-terminated polybutadiene, liquid crystal oligomer, zeolite-like imidazole ester skeleton and 1, 4-butylene glycol, reacting at 55-60 ℃ for 2h until the mass fraction of isocyanate groups in the product is 1%, and ending the reaction to obtain modified polyurethane;
the preparation of the isocyanate-terminated silicone oil comprises the following steps:
1) Mixing hydrogen-containing silicone oil, allyl polyoxyethylene ether and toluene, heating to 50 ℃, adding chloroplatinic acid, preserving heat for 20-30min, heating to 85-90 ℃ and preserving heat for 2-3h, and carrying out vacuum distillation to obtain modified polysiloxane;
2) Mixing the modified polysiloxane and acetone, heating to 50 ℃, adding the mixture into the mixed solution of isophorone diisocyanate and acetone, stirring for 1-2h, adding dibutyltin dilaurate, heating to 60 ℃, preserving heat for 20-30min, adding methyl ethyl ketoxime, and continuously stirring for 20-30min to obtain the isocyanate-terminated silicone oil.
2. The optical temperature-resistant ultraviolet visbreaking composite film according to claim 1, wherein the polyfunctional acrylate monomer is one of trimethylolpropane triacrylate and tripropylene glycol diacrylate; the photoinitiator is one or more of 1-hydroxycyclohexyl phenyl ketone, alpha-hydroxyisobutyryl benzene, benzoin dimethyl ether and 2-isopropyl thioxanthone; the organic solvent is one or more of toluene, ethyl acetate and 120# solvent oil.
3. The method for preparing an optical temperature-resistant ultraviolet visbreaking composite film according to any one of claims 1 to 2, comprising the steps of:
s1: selecting one of a PET film, a polyethylene film and a grid release film as a base film, and carrying out corona treatment;
s2: mixing modified polyurethane, a polyfunctional acrylate monomer, a photoinitiator and isocyanate-terminated silicone oil, adding an organic solvent, stirring and dissolving, standing and defoaming to obtain a viscosity reducing adhesive;
s3: coating the viscosity reducing adhesive on the surface of the base film after corona treatment, preserving heat for 1-2h at 30-40 ℃, and standing for 20-22h at 18-25 ℃ to obtain the optical temperature-resistant ultraviolet viscosity reducing composite film.
4. The method for preparing the optical temperature-resistant ultraviolet visbreaking composite film according to claim 3, wherein the working conditions of the corona treatment are as follows: treating with corona instrument with power of 50V for 2-5min; the 180-degree peeling strength of the composite film is 22-25N/25mm before ultraviolet irradiation, and the 180-degree peeling strength of the composite film is 0-0.5N/25mm after ultraviolet irradiation; the exposure time under the ultraviolet light source is 5-10s; the wavelength of the ultraviolet light source is 300-400nm, and the illuminance of the ultraviolet light source is 80-95mW/cm 2 。
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Denomination of invention: An optical temperature resistant UV anti adhesive composite film and its preparation method Granted publication date: 20230620 Pledgee: CITIC Bank Limited by Share Ltd. Shanghai branch Pledgor: SHANGHAI LANQING INNOVATIVE MATERIAL & TECHNOLOGY STOCK CO.,LTD. Registration number: Y2024310000056 |