CN115820144A - 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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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
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- JBFYUZGYRGXSFL-UHFFFAOYSA-N imidazolide Chemical compound C1=C[N-]C=N1 JBFYUZGYRGXSFL-UHFFFAOYSA-N 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
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 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 4
- 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
- OZCRKDNRAAKDAN-UHFFFAOYSA-N but-1-ene-1,4-diol Chemical compound O[CH][CH]CCO OZCRKDNRAAKDAN-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 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
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- 230000001603 reducing effect Effects 0.000 abstract description 19
- 239000003292 glue Substances 0.000 abstract description 8
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 abstract description 7
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 6
- 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
- 229920005862 polyol Polymers 0.000 abstract description 4
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- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- 230000000181 anti-adherent effect Effects 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 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 description 3
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- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 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 a viscosity reducing composite film, in particular to an optical temperature-resistant ultraviolet viscosity reducing composite film and a preparation method thereof; the ultraviolet visbreaking composite film prepared by the invention has the peel strength of 180 degrees before ultraviolet irradiation of 22-25N/25mm and the peel strength after ultraviolet irradiation of 0-0.5N/25mm; introducing isocyanate group terminated silicone oil, preparing the polyether polyol silicone oil by using hydrogen-containing silicone oil and allyl polyoxyethylene ether, and blocking with isophorone diisocyanate; 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 obtained ultraviolet visbreaking composite film is moderate in hardness by controlling the mass ratio of the polyurethane prepolymer of the hydroxyl-terminated polybutadiene in the modified polyurethane, the liquid crystal oligomer and the zeolite-like imidazole ester framework, and can be easily removed under the irradiation of ultraviolet light without residual glue.
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, semiconductor components and electronic components are developed to be light, thin and exquisite, and are easily damaged in the processing and transportation processes, the electronic components need to be temporarily fixed and protected by a film, and the anti-adhesion composite film can be easily removed as a pressure-sensitive adhesive with adjustable peel strength on the premise of not damaging the electronic components after the processing.
The ultraviolet anti-sticking composite film is widely applied to assembly and processing in the electronic industry, for example, the ultraviolet anti-sticking composite film is used for temporarily fixing and protecting a mobile phone in a mobile phone screen manufacturing process, and the problems of scratching, abrasion, pollution, corrosion and the like of the mobile phone are prevented. When the fixing or protection is not needed, the ultraviolet light is irradiated on the surface of the adherend, so that the adherend can be easily separated from the surface of the adherend without damaging the product.
The ultraviolet visbreaking composite film which is currently applied to electronic products in market circulation mainly comprises acrylate pressure-sensitive adhesives, wherein the number of crosslinking points of ultraviolet curing is small, so that the crosslinking density is small after the ultraviolet curing, the volume shrinkage degree is small, the visbreaking effect is poor after the ultraviolet curing, meanwhile, the problem of poor temperature resistance exists, and due to the high elastic characteristic of the ultraviolet visbreaking composite film, the product is easy to displace when being fixed, and the ultraviolet visbreaking composite film is not favorable for accurate assembly.
Disclosure of Invention
The invention aims to provide an optical temperature-resistant ultraviolet viscosity-reducing composite film and a preparation method thereof, and aims to solve 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 a visbreaking layer, wherein the visbreaking layer is a coating of a visbreaking adhesive; preparing modified polyurethane, a multifunctional acrylate monomer, isocyanate-terminated silicone oil and a photoinitiator to obtain the 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 framework.
Aiming at the problems of poor viscosity reducing effect, poor temperature resistance and the like of an ultraviolet viscosity reducing composite film in the existing market after ultraviolet curing, the invention provides an optical temperature-resistant ultraviolet viscosity reducing composite film, wherein a prepared viscosity reducing layer contains a large amount of unsaturated double bonds, and the unsaturated double bonds are subjected to crosslinking action after ultraviolet illumination and form a semi-interpenetrating network structure with a linear polymer molecular chain of a matrix, so that the viscosity of the viscosity reducing composite film is reduced, and the interface between the viscosity reducing composite film and an adherend is wrinkled and microporous due to large volume shrinkage generated by crosslinking, the bonding interface is damaged, the effective bonding area is reduced, and the peeling strength of the viscosity reducing composite film after ultraviolet curing is reduced; the ultraviolet visbreaking composite film prepared by the invention has the advantages that the peeling strength of 180 degrees before ultraviolet irradiation reaches 22-25N/25mm, the peeling strength after ultraviolet irradiation is 0-0.5N/25mm, the peeling strength range is wide, the maximum peeling strength is high, the market requirements on the visbreaking composite film can be met, and the service life of the visbreaking composite film is effectively prolonged through component adjustment.
Furthermore, the multifunctional acrylate monomer is one of trimethylolpropane triacrylate and tripropylene glycol diacrylate.
Furthermore, the photoinitiator can reach a 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-hydroxyisobutyrophenone, 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 mass: 45-55 parts of modified polyurethane, 8-12 parts of polyfunctional acrylate monomer, 2-8 parts of isocyanate-terminated 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 polyether-polyol silicone oil by using hydrogen-containing silicone oil and allyl polyoxyethylene ether, and terminating by using isophorone diisocyanate to obtain isocyanate-terminated silicone oil, wherein the thermal stability of the viscosity-reducing composite film is improved by using the low modulus and high temperature resistance of the silicone oil in the isocyanate-terminated silicone oil, and the isocyanate is used for terminating, so that the interfacial property of the silicone oil and a modified polyurethane matrix can be effectively improved, and the precipitation of small molecules is reduced on the basis of maintaining easy stripping after ultraviolet irradiation, and the condition of no residual gum is achieved.
Further, the preparation of the isocyanate group-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 ℃, preserving heat for 2-3h, and carrying out vacuum distillation to obtain modified polysiloxane;
2) Mixing modified polysiloxane and acetone, heating to 50 ℃, adding the mixture into a mixed solution of isophorone diisocyanate and acetone, stirring for 1-2h, adding dibutyltin dilaurate, heating to 60 ℃, keeping the temperature for 20-30min, adding methyl ethyl ketoxime, and continuously stirring for 20-30min to obtain the isocyanate-group-terminated silicone oil.
Further, the preparation of the modified polyurethane comprises the following steps:
(1) Mixing ethyl acetate, hydroxyl-terminated polybutadiene, dibutyltin dilaurate and hydroquinone in a nitrogen atmosphere, 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 a hydroxyl-terminated polybutadiene-based polyurethane prepolymer, a liquid crystal oligomer, a zeolite-like imidazole ester framework and 1,4-butenediol, reacting at 55-60 ℃ for 2 hours, and finishing the reaction when the content of an isocyanate matrix in the product is 1%, thereby obtaining the modified polyurethane.
According to the invention, the hydroxyl-terminated polybutadiene is used as a soft segment to synthesize the modified polyurethane, and the unsaturated carbon-carbon double bonds of the main chain and the side group of the hydroxyl-terminated polybutadiene can endow the anti-adhesive composite film with good ultraviolet corresponding characteristics, so that the modified polyurethane and C = C in the multifunctional monomer are polymerized under the action of an ultraviolet initiator to generate a three-dimensional cross-linking structure, thereby causing the volume of the adhesive to shrink, enabling the adhesive to wrinkle, increasing the surface roughness and reducing the bonding point with an adherend, and further greatly reducing the peeling strength.
Introducing a liquid crystal oligomer into the modified polyurethane, effectively improving the thermal stability of the viscosity-reducing composite film in a synergistic manner, 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 through chain extension reaction between the liquid crystal monomer and primary amine so as to reduce the glass transition temperature of the viscosity-reducing composite film; and the liquid crystal oligomer has photosensitivity, and can effectively reduce the peeling strength of the anti-sticking composite film after ultraviolet irradiation under the condition of not damaging a protective object, so that the effects of easy removal and no residual glue are achieved.
Further, the preparation of the liquid crystal oligomer comprises the following steps: mixing 4,4' -bis [6- (acryloyloxy) hexyloxy ] azobenzene and 1,4-bis (4- (6-acryloyloxy) n-nonyloxy) benzoyloxy-2-methylbenzene under an argon atmosphere, adding dichloromethane, freezing the system by using liquid nitrogen, vacuumizing to remove oxygen, adding a mixed solution of n-butylamine and dichloromethane 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 the liquid crystal oligomer.
Further, the preparation of the zeolite-like imidazolate framework comprises the following steps: adding zinc nitrate hexahydrate into a mixed solution of 2-hydroxyimidazole and deionized water, stirring for 2-3h, centrifuging, and precipitating to obtain the zeolite-like imidazole ester framework.
The zeolite-like imidazole ester framework is an organic-inorganic hybrid material formed by coordination of transition metal ions and imidazole or imidazole derivatives, and a coordination polymer with a unique structure and good porosity is formed by utilizing zinc ions and hydroxyl imidazole ligands;
the toughening effect of the modified polyurethane is improved by controlling the introduction of the liquid crystal oligomer, the influence of improving the pulling-up performance of the composite film is also realized by utilizing a semi-interpenetrating network structure formed by the liquid crystal oligomer and the modified polyurethane, a zeolite-like imidazole ester framework is introduced into the modified polyurethane to increase a second phase, so that the synergistic toughening effect is achieved, and the zeolite-like imidazole ester framework has good ultraviolet absorptivity and high thermal stability, and can effectively improve the ultraviolet light utilization rate and the thermal stability of the visbreaking composite film.
Further, the modified polyurethane is a polyurethane prepolymer based on hydroxyl-terminated polybutadiene, a liquid crystal oligomer and a zeolite-like imidazole ester framework in a mass ratio of 10:2:0.5 is compounded to obtain.
The obtained modified polyurethane has moderate hardness by controlling the mass ratio of the polyurethane prepolymer of the hydroxyl-terminated polybutadiene in the modified polyurethane, the liquid crystal oligomer and the zeolite-like imidazole ester framework, the prepared viscosity-reducing composite film keeps higher peel strength when no ultraviolet light is irradiated, effective protection and fixation are achieved, the film can be easily removed under the irradiation of the ultraviolet light, no micromolecule is separated out, and no adhesive residue is generated.
Further, a preparation method of the optical temperature-resistant ultraviolet viscosity-reducing 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 multifunctional acrylate monomer, a photoinitiator and isocyanate-terminated silicone oil, adding an organic solvent, stirring for dissolving, standing for defoaming, and obtaining a viscosity-reducing adhesive;
s3: and (3) coating the visbreaking adhesive on the surface of the base film subjected to 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 visbreaking composite film.
Further, the working conditions of the corona treatment are as follows: treating with corona instrument at power of 50V for 2-5min; the stripping force of the composite film before ultraviolet irradiation is 20-22N/25mm, and the stripping force after ultraviolet irradiation is 0-0.5N/25mm; the exposure time under the ultraviolet light source is 5-10s; the wavelength of the ultraviolet light source is 300-400nm, and the light radiation illuminance of the ultraviolet light source is 80-95mW/cm 2 。
The base film is treated by corona, so that the binding force between the base film and the viscosity reducing adhesive can be effectively improved.
The invention has the beneficial effects that:
the ultraviolet visbreaking composite film prepared by the invention has the peel strength of 22-25N/25mm at 180 degrees before ultraviolet illumination and 0-0.5N/25mm after ultraviolet illumination, has wide peel strength range and high maximum peel strength, has higher thermal stability and meets the requirements of the electronic industry.
The preparation method comprises the steps of preparing polyether polyol silicone oil by using hydrogen-containing silicone oil and allyl polyoxyethylene ether, and blocking by using isophorone diisocyanate to obtain isocyanate group blocked silicone oil, wherein the low modulus and high temperature resistance of the silicone oil in the isocyanate group blocked silicone oil are utilized to improve the thermal stability of the viscosity-reducing composite film, the isocyanate is used for blocking, the interfacial property of the silicone oil and a modified polyurethane matrix can be effectively improved, and on the basis of maintaining easy stripping after ultraviolet irradiation, the precipitation of small molecules is reduced, so that the condition of no residual gum is achieved.
According to the invention, the hydroxyl-terminated polybutadiene is used as a soft segment to synthesize the modified polyurethane, and the unsaturated carbon-carbon double bonds of the main chain and the side group of the hydroxyl-terminated polybutadiene can endow the anti-adhesive composite film with good ultraviolet corresponding characteristics, so that the modified polyurethane and C = C in the multifunctional monomer are polymerized under the action of an ultraviolet initiator to generate a three-dimensional cross-linking structure, thereby causing the volume of the adhesive to shrink, enabling the adhesive to wrinkle, increasing the surface roughness and reducing the bonding point with an adherend, and further greatly reducing the peeling strength.
Introducing a liquid crystal oligomer into the modified polyurethane, effectively improving the thermal stability of the viscosity-reducing composite film in a synergistic manner, 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 through chain extension reaction between the liquid crystal monomer and primary amine so as to reduce the glass transition temperature of the viscosity-reducing composite film; and 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 influence of improving the pull-up performance of the composite film is also realized by utilizing a semi-interpenetrating network structure formed by the liquid crystal oligomer and the modified polyurethane, a zeolite-like imidazole ester framework is introduced into the modified polyurethane to increase a second phase, so that the synergistic toughening effect is achieved, and the zeolite-like imidazole ester framework has good ultraviolet absorptivity and high thermal stability, and can effectively improve the ultraviolet light utilization rate and the thermal stability of the visbreaking composite film.
The obtained modified polyurethane is moderate in hardness by controlling the mass ratio of the polyurethane prepolymer of the hydroxyl-terminated polybutadiene in the modified polyurethane, the liquid crystal oligomer and the zeolite-like imidazole ester framework, the prepared viscosity-reducing composite film is kept soft and easy to adhere to the surface without ultraviolet irradiation, the heat resistance and the tensile strength of the viscosity-reducing composite film are improved, the reworkability is improved, and the effects of easy removal, no micromolecule precipitation and no residual glue are achieved under the ultraviolet irradiation.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that, if directional indications such as up, down, left, right, front, and back … … are involved in the embodiment of the present invention, the directional indications are only used for explaining a specific posture, such as a relative positional relationship between components, a motion situation, and the like, and if the specific posture changes, the directional indications also change accordingly. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The technical solutions of the present invention are further described in detail with reference to specific examples, which should be understood that the following examples are only illustrative of the present invention and are not intended to limit the present invention.
Example 1
A preparation method of an optical temperature-resistant ultraviolet viscosity-reducing 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 multifunctional acrylate monomer, a photoinitiator and isocyanate-terminated silicone oil, adding an organic solvent, stirring for dissolving, standing for defoaming, and obtaining a viscosity-reducing adhesive;
the anti-sticking adhesive comprises the following components in parts by mass: 45 parts of modified polyurethane, 8 parts of polyfunctional acrylate monomer, 2 parts of isocyanate-terminated silicone oil, 1.5 parts of photoinitiator and 44 parts of organic solvent;
the polyfunctional acrylate 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) Mixing 30mL of ethyl acetate, 0.585mol of hydroxyl-terminated polybutadiene, 3.45mmol of dibutyltin dilaurate and 20.4mmol of hydroquinone in a nitrogen atmosphere, heating to 55 ℃, adding 9.44mmol of isophorone diisocyanate, and keeping the temperature for 2 hours to obtain a polyurethane prepolymer based on the hydroxyl-terminated polybutadiene;
(2) Mixing 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, reacting for 2 hours at 55 ℃, and finishing the reaction when the content of isocyanate matrix in the product is 1%, thereby obtaining modified polyurethane;
the preparation of the liquid crystal oligomer comprises the following steps: under argon atmosphere, mixing 52.8mg4,4' -bis [6- (acryloyloxy) hexyloxy ] azobenzene and 71.9mg1, 4-bis (4- (6-acryloyloxy) n-nonyloxy) benzoyloxy-2-methylbenzene, adding 0.3mL of dichloromethane, freezing the system by using liquid nitrogen, vacuumizing to remove oxygen, adding a mixed solution of 49 mu L of n-butylamine and 0.5mL of dichloromethane under the protection of argon, keeping the mixed solution in an oil bath at 45 ℃ for 22 hours, settling in n-hexane, and drying to obtain a liquid crystal oligomer;
the preparation of the zeolite-like imidazolate framework 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 a zeolite-like imidazole ester framework;
the preparation of the isocyanate group-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, keeping the temperature for 20min, heating to 85 ℃, keeping the temperature 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 ℃, keeping the temperature for 20min, adding 0.1g of methyl ethyl ketoxime, and continuing stirring for 20min to obtain isocyanate-group-terminated silicone oil;
s3: coating the surface of the base film subjected to corona treatment with a viscosity reducing adhesive, preserving heat at 30 ℃ for 2h, and standing at 18 ℃ for 22h 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 at 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 light radiation illuminance of the ultraviolet light source is 95mW/cm 2 。
Example 2
A preparation method of an optical temperature-resistant ultraviolet viscosity-reducing 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 multifunctional acrylate monomer, a photoinitiator and isocyanate-terminated silicone oil, adding an organic solvent, stirring for dissolving, standing for defoaming, and obtaining a viscosity-reducing adhesive;
the visbreaking adhesive comprises the following components in parts by mass: 50 parts of modified polyurethane, 10 parts of polyfunctional acrylate monomer, 5 parts of isocyanate-terminated silicone oil, 1.8 parts of photoinitiator and 50 parts of organic solvent;
the polyfunctional acrylate 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) Under the nitrogen atmosphere, mixing 30mL of ethyl acetate, 0.585mol of hydroxyl-terminated polybutadiene, 3.45mmol of dibutyltin dilaurate and 20.4mmol of hydroquinone, heating to 58 ℃, adding 9.44mmol of isophorone diisocyanate, and keeping the temperature for 2 hours to obtain a polyurethane prepolymer based on the hydroxyl-terminated polybutadiene;
(2) Mixing 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, reacting for 2 hours at 58 ℃, and finishing the reaction when the content of isocyanate matrix in the product is 1%, thereby obtaining modified polyurethane;
the preparation of the liquid crystal oligomer comprises the following steps: under argon atmosphere, mixing 52.8mg4,4' -bis [6- (acryloyloxy) hexyloxy ] azobenzene and 71.9mg1, 4-bis (4- (6-acryloyloxy) n-nonyloxy) benzoyloxy-2-methylbenzene, adding 0.3mL of dichloromethane, freezing the system by using liquid nitrogen, vacuumizing to remove oxygen, adding a mixed solution of 49 mu L of n-butylamine and 0.5mL of dichloromethane under the protection of argon, keeping the mixed solution in an oil bath at 45 ℃ for 23 hours, settling in n-hexane, and drying to obtain a liquid crystal oligomer;
the preparation of the zeolite-like imidazolate framework 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 2.5 hours, centrifuging, and precipitating to obtain a zeolite-like imidazole ester framework;
the preparation of the isocyanate group-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 20-30min, heating to 88 ℃, 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 ℃, keeping the temperature for 25min, adding 0.1g of methyl ethyl ketoxime, and continuing stirring for 25min to obtain isocyanate-terminated silicone oil;
s3: coating the anti-sticking adhesive on the surface of the base membrane subjected to corona treatment, preserving heat at 35 ℃ for 1.5h, and standing at 20 ℃ for 21h to obtain an optical temperature-resistant ultraviolet anti-sticking composite membrane;
corona dischargeThe working conditions of the treatment are as follows: treating with corona instrument at 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 light radiation illumination of the ultraviolet light source is 85mW/cm 2 。
Example 3
A preparation method of an optical temperature-resistant ultraviolet viscosity-reducing 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 multifunctional acrylate monomer, a photoinitiator and isocyanate-terminated silicone oil, adding an organic solvent, stirring for dissolving, standing for defoaming, and obtaining a viscosity-reducing adhesive;
the visbreaking adhesive comprises the following components in parts by mass: 55 parts of modified polyurethane, 12 parts of polyfunctional acrylate monomer, 8 parts of isocyanate-terminated silicone oil, 2 parts of photoinitiator and 56 parts of organic solvent;
the polyfunctional acrylate 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) In the nitrogen atmosphere, mixing 30mL of ethyl acetate, 0.585mol of hydroxyl-terminated polybutadiene, 3.45mmol of dibutyltin dilaurate and 20.4mmol of hydroquinone, heating to 60 ℃, adding 9.44mmol of isophorone diisocyanate, and keeping the temperature for 2 hours to obtain a polyurethane prepolymer based on the hydroxyl-terminated polybutadiene;
(2) Mixing 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, reacting for 2 hours at 60 ℃, and finishing the reaction when the content of isocyanate matrix in the product is 1%, thereby obtaining modified polyurethane;
the preparation of the liquid crystal oligomer comprises the following steps: under argon atmosphere, mixing 52.8mg4,4' -bis [6- (acryloyloxy) hexyloxy ] azobenzene and 71.9mg1, 4-bis (4- (6-acryloyloxy) n-nonyloxy) benzoyloxy-2-methylbenzene, adding 0.3mL of dichloromethane, freezing the system by using liquid nitrogen, vacuumizing to remove oxygen, adding a mixed solution of 49 mu L of n-butylamine and 0.5mL of dichloromethane under the protection of argon, keeping the mixed solution in an oil bath at 45 ℃ for 24 hours, settling in n-hexane, and drying to obtain a liquid crystal oligomer;
the preparation of the zeolite-like imidazolate framework 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 3 hours, centrifuging and precipitating to obtain a zeolite-like imidazole ester framework;
the preparation of the isocyanate group-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, keeping the temperature for 30min, heating to 90 ℃, keeping the temperature 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 ℃, keeping the temperature for 30min, adding 0.1g of methyl ethyl ketoxime, and continuing stirring for 30min to obtain isocyanate-group-terminated silicone oil;
s3: coating the anti-sticking adhesive on the surface of the base membrane subjected to corona treatment, preserving heat for 1h at 40 ℃, and standing for 20h at 25 ℃ to obtain an optical temperature-resistant ultraviolet anti-sticking composite membrane;
the working conditions of the corona treatment are as follows: treating with corona instrument at 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 light radiation illuminance of the ultraviolet light source is 80mW/cm 2 。
The anti-tack adhesives of examples 1 to 3 were coated to a thickness of 100 μm on the surface of the base film.
Comparative example 1
Using example 3 as a control, the isocyanate group-terminated silicone oil was replaced with a hydrogen-containing silicone oil, and the other steps were normal.
Comparative example 2
With example 3 as a control, no liquid crystal oligomer was added to the preparation of the modified polyurethane, and the other steps were normal.
Comparative example 3
With example 3 as a control, no zeolite-like imidazolate framework was added to the preparation of the modified polyurethane, and the other steps were normal.
Comparative example 4
Using example 3 as a control, the hydroxyl-terminated polybutadiene polyurethane prepolymer was replaced with polyurethane (polymeric MDI polyurethane: jin Jinle chemical Co., ltd.) in the preparation of the modified polyurethane, and the other steps were carried out normally.
Comparative example 5
Taking example 3 as a control group, the mass ratio of the hydroxyl-terminated polybutadiene-based polyurethane prepolymer, the liquid crystal oligomer and the zeolite-like imidazole ester skeleton is not 10:1:0.5, adding a polyurethane prepolymer based on hydroxyl-terminated polybutadiene, 1g of liquid crystal oligomer and 0.5g of zeolite-like imidazole ester framework in the preparation of the modified polyurethane, wherein other working procedures are normal.
The used raw material sources are as follows:
PET film NITTO5602 (0.02 mm): shenzhen, science and technology Limited; trimethylolpropane triacrylate T477244, dibutyltin dilaurate D100274, hydroquinone H108945, isophorone diisocyanate I109582, 1,4-butenediol B107560, n-butylamine D111219, zinc nitrate hexahydrate Z111703, allyl polyoxyethylene ether A303301, chloroplatinic acid C139933: an avastin reagent; 1-hydroxycyclohexylphenylketone 405612: sigma aldrich (shanghai) trade ltd; toluene, ethyl acetate, dichloromethane, n-hexane, acetone, analytically pure: a pharmaceutical group reagent; hydroxyl-terminated polybutadiene 69102-90-5: wuhanxin Jiali Biotech GmbH; 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-methylbenzene RM82: beijing, eight billion space-time liquid crystal technology, inc.; 2-hydroxyimidazole 5918-93-4: hubeiheng Jing Rui chemical Limited; 96-29-7 parts of methyl ethyl ketoxime: wuhan Ji Xinyi, bo Biotechnology Ltd.
And (4) performance testing: the composite films prepared in examples 1 to 3 and comparative examples 1 to5 were tested for 180 ° peel strength and residual gum after ultraviolet irradiation, and the test results are shown in table 1;
180 ° peel strength: according to a test 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 test sample is 20mm, the length of the test sample is 200mm, and the tensile rate of the test sample is 300mm/min;
and (3) temperature resistance test: keeping the temperature at 120 ℃ for 12h, and measuring the 180-degree peel strength before ultraviolet irradiation;
residual gum retention after ultraviolet illumination: and in the 180-degree peel strength test, after ultraviolet irradiation, the residual glue is recorded as unqualified, 20 residual glues in each group are recorded as qualified, and the unqualified rate is calculated.
TABLE 1
The ultraviolet visbreaking composite film prepared by the invention has the peel strength of 22-25N/25mm at 180 degrees before ultraviolet illumination and 0-0.5N/25mm after ultraviolet illumination, has wide peel strength range and high maximum peel strength, has higher thermal stability and meets the requirements of the electronic industry.
Comparing the embodiment 3 with the comparative example 1, introducing isocyanate group terminated silicone oil into the viscosity-reducing adhesive, preparing polyether polyol silicone oil by using hydrogen-containing silicone oil and allyl polyoxyethylene ether, and terminating by using isophorone diisocyanate to obtain isocyanate group terminated silicone oil, 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 group terminated silicone oil, terminating by using isocyanate, effectively improving the interfacial property of the silicone oil and the modified polyurethane matrix, reducing the precipitation of small molecules on the basis of maintaining easy stripping after ultraviolet irradiation, and achieving the condition of no residual gum.
Comparing the example 3 with the comparative example 2, introducing a liquid crystal oligomer into the modified polyurethane to effectively improve the thermal stability of the viscosity-reducing composite film in a synergistic manner, 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, wherein the chain extension reaction between the liquid crystal monomer and primary amine effectively reduces the crosslinking density of a polymer network, and further reduces the glass transition temperature of the viscosity-reducing composite film; and the liquid crystal oligomer has photosensitivity, and can effectively reduce the peeling strength of the anti-sticking composite film after ultraviolet irradiation under the condition of not damaging a protective object, so that the effects of easy removal and no residual glue are achieved.
Comparing the example 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 influence of improving the pulling-up performance of the composite film is also realized by utilizing a semi-interpenetrating network structure formed by the liquid crystal oligomer and the modified polyurethane, the second phase is increased by introducing the zeolite-like imidazole ester framework into the modified polyurethane, the synergistic toughening effect is achieved, and the zeolite-like imidazole ester framework has good ultraviolet absorptivity and high thermal stability, and can effectively improve the ultraviolet light utilization rate and the thermal stability of the visbreaking composite film.
Compared with the comparative example 4, the modified polyurethane is synthesized by taking hydroxyl-terminated polybutadiene as a soft segment, and the unsaturated carbon-carbon double bond of the main chain and the side group of the hydroxyl-terminated polybutadiene can endow the anti-adhesive composite film with good ultraviolet corresponding characteristics, so that the modified polyurethane and C = C in a polyfunctional monomer are polymerized under the action of an ultraviolet initiator to generate a three-dimensional cross-linking structure, the volume of the adhesive is shrunk, the adhesive is wrinkled, the surface roughness is increased, the bonding point with an adherend is reduced, and the peeling strength of the adhesive is greatly reduced.
Comparing the example 3 with the comparative example 5, the obtained modified polyurethane has moderate hardness by controlling the mass ratio of the polyurethane prepolymer of the hydroxyl-terminated polybutadiene in the modified polyurethane, the liquid crystal oligomer and the zeolite-like imidazole ester framework, and the prepared viscosity-reducing composite film improves the heat resistance and the tensile strength of the viscosity-reducing composite film and improves the reworkability on the basis that the prepared viscosity-reducing composite film keeps soft and easy to adhere when not irradiated by ultraviolet light, and the effects of easy removal, no micromolecule precipitation and no residual glue are achieved under the irradiation of the ultraviolet light.
The above description is only an example of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The optical temperature-resistant ultraviolet visbreaking composite film is characterized by comprising a base film and a visbreaking layer, wherein the visbreaking layer is a coating of a visbreaking adhesive; preparing modified polyurethane, a multifunctional acrylate monomer, isocyanate-terminated silicone oil and a photoinitiator to obtain the 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 framework.
2. The optical temperature-resistant ultraviolet visbreaking composite film of claim 1, wherein the visbreaking adhesive comprises the following components in parts by mass: 45-50-55 parts of modified polyurethane, 8-12 parts of polyfunctional acrylate monomer, 2-8 parts of isocyanate group-terminated silicone oil, 1.5-2 parts of photoinitiator and 44-56 parts of organic solvent.
3. The optical temperature-resistant ultraviolet-viscosity reduction composite film according to claim 1, wherein the multifunctional acrylate monomer is one of trimethylolpropane triacrylate and tripropylene glycol diacrylate; the photoinitiator is one or more of 1-hydroxycyclohexyl phenyl ketone, alpha-hydroxyisobutyrophenone, benzoin dimethyl ether and 2-isopropyl thioxanthone; the organic solvent is one or more of toluene, ethyl acetate and 120# solvent oil.
4. The optical temperature-resistant ultraviolet viscosity-reducing composite film according to claim 1, wherein the modified polyurethane contains a hydroxyl-terminated polybutadiene-based polyurethane prepolymer, a liquid crystal oligomer and a zeolite-like imidazole ester skeleton in a mass ratio of 10:2:0.5.
5. the optical temperature-resistant ultraviolet visbreaking composite film of claim 1, wherein the preparation of the liquid crystal oligomer comprises the following steps: mixing 4,4' -bis [6- (acryloyloxy) hexyloxy ] azobenzene and 1,4-bis (4- (6-acryloyloxy) n-nonyloxy) benzoyloxy-2-methylbenzene under an argon atmosphere, adding dichloromethane, freezing the system by using liquid nitrogen, vacuumizing to remove oxygen, adding a mixed solution of n-butylamine and dichloromethane 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 the liquid crystal oligomer.
6. The optical temperature-resistant ultraviolet visbreaking composite film of claim 1, wherein the preparation of the zeolite-like imidazolate framework 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 the zeolite-like imidazole ester skeleton.
7. The optical temperature-resistant ultraviolet viscosity-reducing composite film according to claim 1, wherein the preparation of the modified polyurethane comprises the following steps:
(1) Mixing ethyl acetate, hydroxyl-terminated polybutadiene, dibutyltin dilaurate and hydroquinone in a nitrogen atmosphere, 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 a hydroxyl-terminated polybutadiene-based polyurethane prepolymer, a liquid crystal oligomer, a zeolite-like imidazole ester framework and 1,4-butenediol, reacting at 55-60 ℃ for 2 hours, and finishing the reaction when the content of an isocyanate matrix in the product is 1%, thereby obtaining the modified polyurethane.
8. The optical temperature-resistant ultraviolet viscosity-reducing composite film according to claim 1, wherein the preparation of the isocyanate group-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 ℃, preserving heat for 2-3h, and carrying out vacuum distillation to obtain modified polysiloxane;
2) Mixing modified polysiloxane and acetone, heating to 50 ℃, adding the mixture into a mixed solution of isophorone diisocyanate and acetone, stirring for 1-2h, adding dibutyltin dilaurate, heating to 60 ℃, keeping the temperature for 20-30min, adding methyl ethyl ketoxime, and continuously stirring for 20-30min to obtain the isocyanate-group-terminated silicone oil.
9. The preparation method of the optical temperature-resistant ultraviolet viscosity-reducing composite film according to any one of claims 1 to 8, characterized by comprising 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 multifunctional acrylate monomer, a photoinitiator and isocyanate-terminated silicone oil, adding an organic solvent, stirring for dissolving, standing for defoaming, and obtaining a viscosity-reducing adhesive;
s3: and (3) coating the anti-adhesion adhesive on the surface of the base film subjected to corona treatment, keeping the temperature at 30-40 ℃ for 1-2h, and standing at 18-25 ℃ for 20-22h to obtain the optical temperature-resistant ultraviolet anti-adhesion composite film.
10. The method for preparing the optical temperature-resistant ultraviolet viscosity-reducing composite film according to claim 9, wherein the working conditions of the corona treatment are as follows: treating with corona instrument at power of 50V for 2-5min; the peel strength of the composite film at 180 degrees before ultraviolet irradiation is 22-25N/25mm, and the peel strength at 180 degrees after ultraviolet irradiation is 0-0.5N/25mm; the exposure time under the ultraviolet light source is 5-10s; the wavelength of the ultraviolet light source is 300-400nm, and the light radiation illuminance of the ultraviolet light source is 80-95mW/cm 2 。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101012180A (en) * | 2007-02-05 | 2007-08-08 | 武汉大学 | Single-component hydrogen-capture-type light initiator and its preparing method and use |
| CN101029095A (en) * | 2007-02-13 | 2007-09-05 | 武汉大学 | Mono-stripped hydrogen light initiating agent, its production and use |
| US20100151240A1 (en) * | 2005-10-24 | 2010-06-17 | Roy Melvin Griswold | Laminate Containing Solvent Resistant Polyurethane Adhesive Compositions |
| JP2019157127A (en) * | 2018-03-09 | 2019-09-19 | 三菱ケミカル株式会社 | Active energy ray-curable peelable adhesive composition and peelable adhesive sheet |
| CN113683996A (en) * | 2021-09-06 | 2021-11-23 | 合肥工业大学 | Hydroxyl-terminated polybutadiene-based polyurethane type UV (ultraviolet) light viscosity-reducing adhesive and preparation method thereof |
-
2022
- 2022-12-22 CN CN202211657881.5A patent/CN115820144B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100151240A1 (en) * | 2005-10-24 | 2010-06-17 | Roy Melvin Griswold | Laminate Containing Solvent Resistant Polyurethane Adhesive Compositions |
| CN101012180A (en) * | 2007-02-05 | 2007-08-08 | 武汉大学 | Single-component hydrogen-capture-type light initiator and its preparing method and use |
| CN101029095A (en) * | 2007-02-13 | 2007-09-05 | 武汉大学 | Mono-stripped hydrogen light initiating agent, its production and use |
| JP2019157127A (en) * | 2018-03-09 | 2019-09-19 | 三菱ケミカル株式会社 | Active energy ray-curable peelable adhesive composition and peelable adhesive sheet |
| CN113683996A (en) * | 2021-09-06 | 2021-11-23 | 合肥工业大学 | Hydroxyl-terminated polybutadiene-based polyurethane type UV (ultraviolet) light viscosity-reducing adhesive and preparation method thereof |
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| CN115820144B (en) | 2023-06-20 |
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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 |