CN113637436B - Acrylate pressure-sensitive adhesive, preparation method thereof and polarizer protective film - Google Patents
Acrylate pressure-sensitive adhesive, preparation method thereof and polarizer protective film Download PDFInfo
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- CN113637436B CN113637436B CN202111038344.8A CN202111038344A CN113637436B CN 113637436 B CN113637436 B CN 113637436B CN 202111038344 A CN202111038344 A CN 202111038344A CN 113637436 B CN113637436 B CN 113637436B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C09J151/085—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds on to polysiloxanes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention provides an acrylate pressure-sensitive adhesive, a preparation method thereof and a polarizer protective film, wherein the acrylate pressure-sensitive adhesive comprises 40-60 parts of acrylate resin, 0.01-0.1 part of antistatic agent, 0.0001-0.001 part of catalyst and 0.5-2.5 parts of cross-linking agent; the acrylate resin comprises a main monomer and a comonomer; the main monomer comprises a hard monomer, a soft monomer and a crosslinking monomer; the comonomer comprises an acylamino-containing acrylic monomer, an ether bond-containing acrylic monomer and straight-chain vinyl silicone oil. The acrylic monomer containing the amido improves the wettability and the temperature resistance of the acrylic resin to the base material. The acrylic monomer containing ether bond improves the compatibility of the lithium salt antistatic agent and the pressure-sensitive adhesive and improves the antistatic property of the pressure-sensitive adhesive. The straight-chain vinyl silicone oil improves the temperature resistance of the acrylate resin, improves the wettability of the acrylate and effectively reduces the stripping force of the pressure-sensitive adhesive. The surface resistivity of the polarizer protective film is less than 10 11 Omega/□, and no residue is generated on the surface of the polarizer.
Description
Technical Field
The invention belongs to the technical field of films, and particularly relates to an acrylate pressure-sensitive adhesive, a preparation method thereof and a polarizer protective film.
Background
The polarizer is an important component of a Liquid Crystal Display (LCD), an upper polarizer and a lower polarizer are required in a liquid crystal panel, the lower polarizer converts a backlight beam into polarized light, the upper polarizer analyzes the polarized light, and a picture cannot be displayed if any one polarizer is lacked. In order to prevent the polarizer from being contaminated or damaged on the surface during the assembling step or the transportation process, a protective film is attached to the surface of the polarizer, and after the polarizer is assembled into a liquid crystal display, the protective film is peeled off from the surface of the polarizer. In the process of peeling the protective film, electrostatic voltage is easily generated, which may damage liquid crystal molecules and control circuits in the liquid crystal display. Therefore, the pressure-sensitive adhesive used for the polarizer protective film needs to have certain antistatic performance. In addition, after the protective film is stripped, no residue is left on the surface of the polaroid, and an antistatic agent cannot be separated out, so that optical misjudgment caused by pollution of the polaroid is avoided.
Although the prior art provides related technical solutions, for example, chinese patent CN110734711A discloses a pressure sensitive adhesive for polarizer protective films and a preparation method thereof, wherein methacroyloxyethyl trimethyl ammonium chloride participates in copolymerization, and quaternary ammonium salt can adsorb water molecules in air to form a conductive path to improve the antistatic property of the polarizer protective film and the high temperature precipitation of an antistatic agent. However, the quaternary ammonium salt monomer is difficult to dissolve in an organic solvent, so that the coating is inevitably turbid, and in addition, the antistatic performance of the quaternary ammonium salt monomer is greatly influenced by humidity, so that the quaternary ammonium salt monomer has great limitation in use.
Disclosure of Invention
In view of the above-mentioned defects of the prior art, the present invention aims to provide an acrylate pressure-sensitive adhesive, a preparation method thereof and a polarizer protective film, wherein the acrylate pressure-sensitive adhesive is obtained by free radical polymerization, and then a release film is coated, dried and attached to obtain the polarizer protective film, wherein the surface resistivity of the polarizer protective film is less than 10 11 Omega/□, and no residue on the surface of the polarizer after the protective film is peeled off.
In order to achieve the above and other objects, in one aspect, the present invention provides an acrylate pressure-sensitive adhesive, which includes, by mass, 40 to 60 parts of an acrylate resin, 0.01 to 0.1 part of an antistatic agent, 0.0001 to 0.001 part of a catalyst, and 0.5 to 2.5 parts of a crosslinking agent.
Preferably, the acrylate resin comprises a main monomer and a comonomer; the main monomer comprises a hard monomer, a soft monomer and a crosslinking monomer; the comonomer comprises an acylamino-containing acrylic monomer, an ether bond-containing acrylic monomer and straight-chain vinyl silicone oil; the weight percentage of each component is as follows:
preferably, the hard monomer comprises one or both of methyl methacrylate and methyl acrylate; the soft monomer comprises one or two of isooctyl acrylate and butyl acrylate; the crosslinking monomer comprises one or two of hydroxyethyl acrylate and hydroxypropyl acrylate.
Preferably, the amide group-containing acrylic monomer comprises a combination of one or more of diacetone acrylamide, methacrylamide, and methylol acrylamide.
Preferably, the ether bond-containing acrylic monomer comprises one or more of ethoxyethoxyethyl acrylate, ethyl 3-ethoxyacrylate and 2-phenoxyethyl acrylate.
Preferably, the acrylate resin further comprises an initiator and a solvent, wherein the initiator is one of benzoyl peroxide or azobisisobutyronitrile, and the weight percentage of the initiator is 0.5-1%; the solvent is one or a combination of ethyl acetate, butyl acetate and toluene.
Preferably, the antistatic agent is a lithium salt antistatic agent; the cross-linking agent is polyisocyanate cross-linking agent.
More preferably, the lithium salt-based antistatic agent includes Li (C) 2 F 5 SO 2 ) 2 N、Li(CF 3 SO 2 ) 2 N、Li(CF 3 SO 2 ) 3 C, one or more combinations thereof.
Preferably, the catalyst is one or more of dibutyltin dilaurate, stannous octoate and triethylamine.
On the other hand, the invention also provides a preparation method of the acrylate pressure-sensitive adhesive, which comprises the following steps:
uniformly mixing a hard monomer, a soft monomer, a comonomer and an initiator to obtain a mixed solution;
under the protection of inert gas, adding a solvent and part of the mixed solution into a container, and stirring and reacting at 70-90 ℃ for 30-50 min to obtain an acrylate prepolymer;
uniformly mixing the residual mixed solution with a crosslinking monomer and a solvent, adding the mixture into an acrylate prepolymer, carrying out heat preservation reaction at 70-90 ℃ for 3-5 h, then adding the solvent, uniformly stirring, cooling, and discharging to obtain an acrylate resin;
weighing acrylate resin, an antistatic agent, a cross-linking agent and a catalyst, and uniformly mixing to obtain acrylate pressure-sensitive adhesive;
the solvent is one or a combination of ethyl acetate, butyl acetate and toluene.
In addition, the invention also provides a polarizer protective film which comprises the acrylate pressure-sensitive adhesive.
Preferably, the method for preparing the polarizer protective film comprises the following steps:
coating the acrylate pressure-sensitive adhesive coating liquid on the surface of a polyester film;
drying, attaching a release film and curing.
Preferably, the curing temperature is 35-45 ℃, and the curing time is 24-72 h.
As described above, the acrylate pressure-sensitive adhesive of the present invention has the following advantageous effects:
firstly, the acrylic monomer containing the acylamino is introduced into the acrylic resin, so that the acrylic resin has higher polarity, the cohesive force of the acrylic resin is improved, the wettability of the acrylic resin to a base material is improved, and the temperature resistance of the acrylic resin is improved.
Secondly, an acrylic monomer containing an ether bond is introduced into the acrylate resin, which is introduced into the main chain by copolymerization. On one hand, ether bond can generate chelating action with lithium ions in the lithium salt antistatic agent, so that the compatibility of the lithium salt antistatic agent and the pressure-sensitive adhesive is improved; on the other hand, the ether bond can be combined with water in the air, so that the antistatic property of the pressure sensitive adhesive is improved.
Thirdly, linear vinyl silicone oil is introduced into the acrylate resin, so that on one hand, the temperature resistance of the acrylate resin is improved; on the other hand, the surface energy of the acrylate resin is reduced, and the wettability of the acrylate is improved; on the other hand, the long-chain branched rubber can form a long-chain branched chain in a polymer system to play a role in internal plasticization, and also has a function similar to an internal crosslinking agent, and vinyl groups at two ends are copolymerized to different macromolecular chains to play a role in improving cohesion, so that the stripping force of the pressure-sensitive adhesive can be effectively reduced.
The polarizer protective film has a surface resistivity of less than 10 11 Omega/□, and no residue on the surface of the polarizer after the protective film is peeled off.
Of course, it is not necessary for any product to practice the invention to achieve all of the above-described advantages at the same time.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs and the description of the present invention, and any methods, apparatuses, and materials similar or equivalent to those described in the examples of the present invention may be used to practice the present invention.
Note that "%" and "part(s)" shown in the description herein mean "% by mass" and "part(s) by mass", respectively, unless otherwise specified.
The invention provides an acrylate pressure-sensitive adhesive which comprises, by mass, 40-60 parts of acrylate resin, 0.01-0.1 part of antistatic agent, 0.0001-0.001 part of catalyst and 0.5-2.5 parts of crosslinking agent.
In a specific embodiment of the present invention, the acrylate resin includes a main monomer and a comonomer; the main monomer comprises a hard monomer, a soft monomer and a crosslinking monomer; the comonomer comprises an acylamino-containing acrylic monomer, an ether bond-containing acrylic monomer and straight-chain vinyl silicone oil; the weight percentage of each component is as follows:
the acrylic monomer containing the amide group has larger polarity, and the amide group can form a hydrogen bond, thereby effectively improving the cohesive force of the polymer and simultaneously improving the adhesive force of the acrylate resin. In one embodiment, the mass percent of the acylamino-containing acrylic monomer can be 2-6%, and when the mass percent of the acylamino-containing acrylic monomer is less than 2%, the pressure-sensitive adhesive prepared from the obtained acrylate resin has low cohesive force, poor adhesive force and unobvious improvement of the overall performance; when the mass percentage of the acylamino-containing acrylic monomer is higher than 6%, excessive hydrogen bonds are formed, so that the initial adhesion of the prepared pressure-sensitive adhesive is reduced, and the wettability of the pressure-sensitive adhesive to an adhered object is reduced.
The acrylic monomer containing ether bond has ether branched chain, and the ether bond can generate chelating action with lithium ions in the lithium salt antistatic agent, so that the compatibility of the antistatic agent and the pressure-sensitive adhesive is improved. In one embodiment, the mass percent of the acrylic monomer containing ether bonds can be 3-7%, when the mass percent of the acrylic monomer containing ether bonds is less than 3%, the ether bonds contained in the system are less, and the system cannot generate a chelating effect with all lithium ions, so that the antistatic agent is easily separated out; when the mass percentage of the ether bond-containing acrylic monomer is more than 7%, the compatibility of the antistatic agent with the pressure-sensitive adhesive cannot be further improved.
The straight-chain vinyl silicone oil contains a silicone segment, and can improve the heat resistance of the acrylate resin; meanwhile, the long-chain branch and the internal crosslinking function formed by the pressure-sensitive adhesive can obviously reduce the stripping force of the pressure-sensitive adhesive. In one embodiment, the weight percentage of the straight-chain vinyl silicone oil can be 1-5%, and when the weight percentage of the straight-chain vinyl silicone oil is less than 1%, the heat resistance of the acrylate resin is not improved and the 180-degree peeling force of the acrylate resin is not reduced obviously; when the content exceeds 5% by mass, the viscosity during polymerization becomes too high, a large amount of gel is generated, and the viscosity of the resulting acrylate resin is remarkably lowered.
In one embodiment of the present invention, the linear vinyl silicone oil is selected from one or more of SM-401-10 (viscosity 10mPa. s) from Nicotimin New materials, DY-V401-40 (viscosity 40mPa. s) from Shandong Dayi Limited, KX-220-70 (viscosity 70mPa. s) from Guangzhou Kangxi Silicone materials, Limited, DY-V401-90 (viscosity 90mPa. s) from Shandong Dayi Limited.
In a more preferred embodiment of the present invention, the weight percentage of the hard monomer is 5 to 15%, the weight percentage of the soft monomer is 70 to 90%, and the weight percentage of the crosslinking monomer is 5 to 10%. When the weight percentage of the hard monomer is less than 5% or the weight percentage of the soft monomer is more than 90%, the cohesive force of the pressure-sensitive adhesive prepared from the obtained acrylate resin is too low, and the prepared polarizer protective film is easy to generate adhesive residue during stripping. When the weight percentage of the hard monomer is more than 15% or the weight percentage of the soft monomer is less than 70%, the wettability of the pressure-sensitive adhesive prepared from the resultant acrylate resin may be significantly reduced. When the weight percentage of the crosslinking monomer is less than 5%, the adhesive base force of the acrylate resin is poor, the crosslinking points are not enough, the cohesion of the prepared pressure-sensitive adhesive resin is low, and adhesive residue is easily caused; when the weight percentage of the crosslinking monomer is higher than 10%, excessive crosslinking is caused, the toughness of the adhesive layer is poor, the initial viscosity is obviously reduced, and even the characteristics of the pressure-sensitive adhesive are lost.
In a specific embodiment, the preparation method of the acrylate pressure-sensitive adhesive comprises the following steps:
s1, uniformly mixing the hard monomer, the soft monomer, the comonomer and the initiator to obtain a mixed solution;
under the protection of inert gas, adding a solvent and part of the mixed solution into a container, and stirring and reacting at 70-90 ℃ for 30-50 min to obtain an acrylate prepolymer;
s2, uniformly mixing the residual mixed solution with a crosslinking monomer and a part of solvent, adding the mixture into an acrylate prepolymer, carrying out heat preservation reaction for 3-5 hours at 70-90 ℃, then adding the solvent, uniformly stirring, cooling and discharging to obtain acrylate resin;
s3, weighing acrylate resin, an antistatic agent, a cross-linking agent and a catalyst, and uniformly mixing to obtain acrylate pressure-sensitive adhesive;
in a specific embodiment, in step S1 and step S2, the solvent may be one or more of ethyl acetate, butyl acetate, and toluene, such as ethyl acetate, and a mixture of ethyl acetate and butyl acetate.
In a specific embodiment, in step S1, the hard monomer may be one or both of methyl methacrylate and methyl acrylate, such as methyl methacrylate, methyl acrylate, or a mixture of methyl methacrylate and methyl acrylate.
In a specific embodiment, in step S1, the soft monomer may be one or both of isooctyl acrylate and butyl acrylate, for example, isooctyl acrylate, butyl acrylate, or a mixture of isooctyl acrylate and butyl acrylate.
In one embodiment, in step S1, the comonomers include amide group-containing acrylic monomer, ether bond-containing acrylic monomer, and linear vinyl silicone oil. The amido-containing acrylic monomer comprises one or more of diacetone acrylamide, methacrylamide and hydroxymethyl acrylamide, such as diacetone acrylamide, methacrylamide, a mixture of diacetone acrylamide, acrylamide and methacrylamide, and the like. The acrylic monomer containing the ether bond comprises one or more of ethoxyethoxyethyl acrylate, 3-ethoxyethyl acrylate and 2-phenoxyethyl acrylate, such as ethoxyethoxyethyl acrylate, a mixture of ethoxyethoxyethyl acrylate and 3-ethoxyethyl acrylate, a mixture of ethoxyethoxyethoxyethyl acrylate, 3-ethoxyethyl acrylate and 2-phenoxyethyl acrylate, and the like. The linear vinyl silicone oil is, for example, a linear vinyl silicone oil having a viscosity of, for example, 10 to 90 mpa.s.
In a specific embodiment, in step S1, the initiator may be one of benzoyl peroxide or azobisisobutyronitrile, such as benzoyl peroxide, and further such as azobisisobutyronitrile. The mass percentage of the initiator is, for example, 0.5-1% of the acrylate pressure-sensitive adhesive.
In a specific embodiment, in step S2, the crosslinking monomer may be one or both of hydroxyethyl acrylate and hydroxypropyl acrylate, such as hydroxyethyl acrylate, hydroxypropyl acrylate, and a mixture of hydroxyethyl acrylate and hydroxypropyl acrylate.
In one embodiment, in step S2, the remaining mixed solution, the crosslinking monomer and a part of the solvent are uniformly mixed and then added to the acrylate prepolymer, and the mixture may be added dropwise, for example, the mixture may be added dropwise to the acrylate prepolymer through a dropping funnel, and the dropwise adding time may be controlled to be 2-4 hours, for example.
In one embodiment, in step S3, the antistatic agent is a lithium salt antistatic agent, preferably Li (C) 2 F 5 SO 2 ) 2 N、Li(CF 3 SO 2 ) 2 N、Li(CF 3 SO 2 ) 3 Combinations of one or more of C, e.g. Li (C) 2 F 5 SO 2 ) 2 N, in turn, for example, being Li (C) 2 F 5 SO 2 ) 2 N and Li (CF) 3 SO 2 ) 2 Mixtures of N, further e.g. Li (C) 2 F 5 SO 2 ) 2 N、Li(CF 3 SO 2 ) 2 N and Li (CF) 3 SO 2 ) 3 Mixtures of C, and the like.
In one embodiment, in step S3, the crosslinking agent is a polyisocyanate-based crosslinking agent, preferably one or a combination of N3390 of bayer, and TSE-100 of asahi chemical, such as N3390 of bayer.
In a specific embodiment, the invention further provides a polarizer protective film, which is obtained by coating the acrylate pressure-sensitive adhesive coating liquid prepared by the method on the surface of a polyester film, drying, attaching a release film and curing.
In one embodiment, the curing temperature may be 35-45 ℃, for example, 35 ℃/40 ℃/45 ℃. The curing time can be 24-72 h, for example, 24h/36h/48h/60h/72 h.
The invention will now be described by way of the following examples.
Example 1
(1) Preparation of acrylate prepolymer
Under the protection of inert gas, 20g of ethyl acetate is added into a reaction container with a dropping funnel, the temperature is raised to 80 ℃ for reflux, then 6g of methyl acrylate, 10g of methyl methacrylate, 50g of isooctyl acrylate, 15g of butyl acrylate, 2g of diacetone acrylamide, 2g of acrylamide, 3g of ethoxy ethyl acrylate, 2g of KX-220-70 and 0.4g of benzoyl peroxide are uniformly mixed to obtain a mixed solution, and 1/6 mixed solution is added into a reaction instrument for reaction for 50min to obtain an acrylate prepolymer.
(2) Preparation of acrylate resins
Weighing 5g of hydroxyethyl acrylate, 5g of hydroxypropyl acrylate and 20g of ethyl acetate, mixing with the rest mixed solution, dropwise adding into a reaction container, continuously reacting for 5h after dropwise adding is finished for 3h, finally adding 20g of ethyl acetate, naturally cooling to 40 ℃, and discharging to obtain the acrylate resin.
(3) Preparation of acrylate pressure-sensitive adhesive
Weighing 40g of the acrylate resin prepared in the step (2) and 0.01g of Li (C) 2 F 5 SO 2 ) 2 N, 1.0g N3390, 0.5g of TSE-100 and 0.1g of dibutyltin dilaurate diluent are uniformly mixed to obtain the pressure-sensitive adhesive coating liquid.
(4) Preparation of polarizer protective film
And (4) coating the pressure-sensitive adhesive coating liquid prepared in the step (3) on the surface of a polyester film, drying, attaching a release film, and curing at 40 ℃ for 48 hours to obtain the polarizer protective film.
Example 2
(1) Preparation of acrylate prepolymer
Under the protection of inert gas, 30g of ethyl acetate is firstly added into a reaction container with a dropping funnel, the temperature is raised to 75 ℃ for reflux, then 4g of methyl methacrylate, 45g of isooctyl acrylate, 40g of butyl acrylate, 1g of methacrylamide, 1g of hydroxymethyl acrylamide, 1g of ethoxy ethyl acrylate, 3g of 2-phenoxyethyl acrylate, 1g of DY-V401-90 and 0.6g of azobisisobutyronitrile are uniformly mixed to obtain a mixed solution, and 1/2 mixed solution is added into a reaction instrument for reaction for 30min to obtain an acrylate prepolymer.
(2) Preparation of acrylate resins
Weighing 4g of hydroxyethyl acrylate, 20g of ethyl acetate and the rest of mixed solution components, mixing, dropwise adding into a reaction container, reacting for 4 hours after dropwise adding is finished, finally adding 20g of ethyl acetate, naturally cooling to 40 ℃, discharging, and obtaining the acrylate resin.
(3) Preparation of acrylate pressure-sensitive adhesive
60g of the acrylate resin prepared in step (2) and 0.02g of Li (C) were weighed 2 F 5 SO 2 ) 2 N、0.04g Li(CF 3 SO 2 ) 2 N、0.04g Li(CF 3 SO 2 ) 3 C. 2.5g of TSE-100 and 0.5g of stannous octoate diluent, and uniformly mixing to obtain the pressure-sensitive adhesive coating liquid.
(4) Preparation of polarizer protective film
And (4) coating the pressure-sensitive adhesive coating liquid prepared in the step (3) on the surface of a polyester film, drying, attaching a release film, and curing at 40 ℃ for 48 hours to obtain the polarizer protective film.
Example 3
(1) Preparation of acrylate prepolymer
Under the protection of inert gas, 10g of ethyl acetate is firstly added into a reaction container with a dropping funnel, the temperature is raised to 85 ℃ for reflux, then 10g of methyl acrylate, 75g of isooctyl acrylate, 5g of diacetone acrylamide, 2g of ethoxy ethyl acrylate, 2g of 3-ethoxy ethyl acrylate, 2g of 2-phenoxy ethyl acrylate, 2g of DY-V401-40 and 0.8g of benzoyl peroxide are uniformly mixed to obtain a mixed solution, and 1/3 mixed solution is added into a reaction instrument for reaction for 40min to obtain an acrylate prepolymer.
(2) Preparation of acrylate resins
Weighing 2g of hydroxypropyl acrylate, 15g of ethyl acetate and the rest of mixed solution, uniformly mixing, dropwise adding into a reaction container, reacting for 4 hours after 2.5 hours of dropwise adding, finally adding 15g of ethyl acetate, naturally cooling to 40 ℃, and discharging to obtain the acrylate resin.
(3) Preparation of acrylate pressure-sensitive adhesive
50g of the acrylate resin prepared in step (2) and 0.03g of Li (CF) were weighed 3 SO 2 ) 2 N、0.02g Li(CF 3 SO 2 ) 3 C. 2.0g N3390 and 1g of triethylamine diluent, and uniformly mixing to obtain the pressure-sensitive adhesive coating liquid.
(4) Preparation of polarizer protective film
And (4) coating the pressure-sensitive adhesive coating liquid prepared in the step (3) on the surface of a polyester film, drying, attaching a release film, and curing at 40 ℃ for 48 hours to obtain the polarizer protective film.
Example 4
(1) Preparation of acrylate prepolymer
Under the protection of inert gas, adding 10g of butyl acetate and 10g of ethyl acetate into a reaction container with a dropping funnel, heating to 90 ℃ for reflux, then uniformly mixing 12g of methyl methacrylate, 67g of isooctyl acrylate, 2g of diacetone acrylamide, 1g of acrylamide, 2g of methacrylamide, 1g of hydroxymethyl acrylamide, 3g of ethoxyethoxyethyl acrylate, 2g of 3-ethoxyethyl acrylate, 1g of KX-220-70, 2g of SM-401-10 and 1.2g of benzoyl peroxide to obtain a mixed solution, adding the 1/3 mixed solution into a reaction instrument, and reacting for 45min to obtain an acrylate prepolymer.
(2) Preparation of acrylate resins
Weighing 7g of hydroxypropyl acrylate, 20g of ethyl acetate and the rest of mixed solution, uniformly mixing, dropwise adding into a reaction container, continuously reacting for 3 hours after dropwise adding is completed for 2.5 hours, then adding 20g of ethyl acetate, naturally cooling to 40 ℃, and discharging to obtain the acrylate resin.
(3) Preparation of acrylate pressure-sensitive adhesive
45g of the acrylate resin prepared in step (2) and 0.08g of Li (C) were weighed 2 F 5 SO 2 ) 2 N, 0.5g N3390 and 0.3g of stannous octoate diluent are uniformly mixed to obtain the pressure-sensitive adhesive coating liquid.
(4) Preparation of polarizer protective film
And (4) coating the pressure-sensitive adhesive coating liquid prepared in the step (3) on the surface of a polyester film, drying, attaching a release film, and curing at 40 ℃ for 48 hours to obtain the polarizer protective film.
Example 5
(1) Preparation of acrylate prepolymer
Under the protection of inert gas, 20g of ethyl acetate and 10g of toluene are firstly added into a reaction container with a dropping funnel, the temperature is raised to 70 ℃ for reflux, then 6g of methyl methacrylate, 78g of isooctyl acrylate, 2g of diacetone acrylamide, 7g of ethoxy ethyl acrylate, 5g of DY-V401-40, 0.2g of benzoyl peroxide and 0.6g of azobisisobutyronitrile are uniformly mixed to obtain a mixed solution, and the 1/3 mixed solution is added into a reaction instrument for reaction for 35min to obtain the acrylate prepolymer.
(2) Preparation of acrylate resins
Weighing 2g of hydroxyethyl acrylate, 20g of ethyl acetate and the rest of mixed solution components, mixing, dropwise adding into a reaction container, reacting for 5 hours after dropwise adding is finished for 3 hours, finally adding 20g of ethyl acetate, naturally cooling to 40 ℃, discharging, and obtaining the acrylate resin.
(3) Preparation of acrylate pressure-sensitive adhesive
55g of the acrylate resin prepared in step (2) and 0.03g of Li (C) were weighed 2 F 5 SO 2 ) 2 N, 1.0g of TSE-100 and 0.8g of stannous octoate diluent are uniformly mixed to obtain the pressure-sensitive adhesive coating liquid.
(4) Preparation of polarizer protective film
And (4) coating the pressure-sensitive adhesive coating liquid prepared in the step (3) on the surface of a polyester film, drying, attaching a release film, and curing at 40 ℃ for 48 hours to obtain the polarizer protective film.
Comparative example 1
(1) Preparation of acrylate prepolymer
Under the protection of inert gas, 20g of ethyl acetate is added into a reaction container with a dropping funnel, the temperature is raised to 80 ℃ for reflux, then 20g of methyl methacrylate, 65g of isooctyl acrylate, 8g of diacetone acrylamide and 0.6g of benzoyl peroxide are uniformly mixed to obtain a mixed solution, and the 1/3 mixed solution is added into a reaction instrument for reaction for 35min to obtain the acrylate prepolymer.
(2) Preparation of acrylate resins
Weighing 7g of hydroxyethyl acrylate, 20g of ethyl acetate, mixing with the rest of mixed solution components, dropwise adding into a reaction container, continuously reacting for 5 hours after dropwise adding is finished for 3 hours, finally adding 20g of ethyl acetate, naturally cooling to 40 ℃, discharging, and obtaining the acrylate resin.
(3) Preparation of acrylate pressure-sensitive adhesive
55g of the acrylate resin prepared in the step (2) was weighed and0.1g Li(C 2 F 5 SO 2 ) 2 n, 1.5g of TSE-100 and 0.8g of stannous octoate diluent are uniformly mixed to obtain the pressure-sensitive adhesive coating liquid.
(4) Preparation of polarizer protective film
And (4) coating the pressure-sensitive adhesive coating liquid prepared in the step (3) on the surface of a polyester film, drying, attaching a release film, and curing at 40 ℃ for 48 hours to obtain the polarizer protective film.
Comparative example 2
(1) Preparation of acrylate prepolymer
Under the protection of inert gas, 20g of ethyl acetate is added into a reaction container with a dropping funnel, the temperature is raised to 80 ℃ for reflux, then 25 g of methyl methacrylate, 60g of isooctyl acrylate, 4g of diacetone acrylamide, 7g of ethoxy ethyl acrylate and 0.6g of benzoyl peroxide are uniformly mixed to obtain a mixed solution, and 1/3 mixed solution is added into a reaction instrument for reaction for 35min to obtain the acrylate prepolymer.
(2) Preparation of acrylate resins
Weighing 4g of hydroxyethyl acrylate, 20g of ethyl acetate, mixing with the rest mixed solution, dropwise adding into a reaction container, continuing to react for 5 hours after the dropwise adding is finished for 3 hours, then adding 20g of ethyl acetate, naturally cooling to 40 ℃, discharging, and obtaining the acrylate resin.
(3) Preparation of acrylate pressure-sensitive adhesive
55g of the acrylate resin prepared in step (2) and 0.1g of Li (C) were weighed 2 F 5 SO 2 ) 2 N, 1.5g of TSE-100 and 0.8g of stannous octoate diluent are uniformly mixed to obtain the pressure-sensitive adhesive coating liquid.
(4) Preparation of polarizer protective film
And (4) coating the pressure-sensitive adhesive coating liquid prepared in the step (3) on the surface of a polyester film, drying, attaching a release film, and curing at 40 ℃ for 48 hours to obtain the polarizer protective film.
Comparative example 3
(1) Preparation of acrylate prepolymer
Under the protection of inert gas, 20g of ethyl acetate is added into a reaction container with a dropping funnel, the temperature is raised to 80 ℃ for reflux, then 30g of methyl methacrylate, 60g of isooctyl acrylate, 3g of diacetone acrylamide, 2g of SM-401-10 and 0.6g of benzoyl peroxide are uniformly mixed to obtain a mixed solution, and the 1/3 mixed solution is added into a reaction instrument for reaction for 35min to obtain the acrylate prepolymer.
(2) Preparation of acrylate resins
Weighing 5g of hydroxyethyl acrylate, 20g of ethyl acetate and the rest of mixed solution, uniformly mixing, dropwise adding into a reaction container, continuously reacting for 5 hours after dropwise adding is completed for 3 hours, then adding 20g of ethyl acetate, naturally cooling to 40 ℃, discharging, and obtaining the acrylate resin.
(3) Preparation of acrylate pressure-sensitive adhesive
55g of the acrylate resin prepared in step (2) and 0.1g of Li (C) were weighed 2 F 5 SO 2 ) 2 N, 2.0g of TSE-100 and 0.8g of stannous octoate diluent are uniformly mixed to obtain the pressure-sensitive adhesive coating liquid.
(4) Preparation of polarizer protective film
And (4) coating the pressure-sensitive adhesive coating liquid prepared in the step (3) on the surface of a polyester film, drying, attaching a release film, and curing at 40 ℃ for 48 hours to obtain the polarizer protective film.
Performance testing
The polarizer protective films obtained in examples 1 to 5 and comparative examples 1 to 3 were tested for antistatic coating resistance, 180 ° peel force, high temperature residue, and high temperature and high humidity residue properties according to the following test methods.
(1) Resistance test of antistatic coatings
The polarizer protective film is cut into 12 x 12mm, the release film is torn off, and the pressure sensitive adhesive layer resistance of the polarizer protective film is tested on a high resistance meter (model: SME-8310).
(2)180 degree peel force test
Cutting the polarizer protective film into size of 300mm × 25mm, peeling off the release film, attaching to the surface of the polarizer, and performing peel force test at 180 deg.C at a tensile speed of 300mm/min by using an electronic universal tester (AGS-X).
(3) High temperature residual Performance test
And (3) tearing off the release film from the polarizer protective film, adhering the release film to the surface of the polarizer to ensure that no bubbles are adhered, cutting the adhered polarizer into a sample with the size of 6cm multiplied by 10cm, putting the sample into an electric heating constant temperature blast drying oven (model: DHG-9140A) at 80 ℃ for 7d, tearing off the polarizer protective film, and observing the existence of residues on the surface of the polarizer under a three-wavelength lamp.
(4) High temperature high humidity residual Performance test
And (3) tearing off the release film from the polarizer protective film, attaching the polarizer protective film to the surface of the polarizer to ensure that the attachment is free of bubbles, cutting the attached polarizer into a sample with the size of 6cm multiplied by 10cm, putting the sample into a programmable constant temperature and humidity test chamber (model: WHTH-150L-40-880) with the temperature of 60 ℃ and the humidity of 90% RH for 7d, finally tearing off the polarizer protective film, and observing the surface of the polarizer for existence of residues under a three-wavelength lamp.
The test results are shown in table 1.
TABLE 1 Performance test tables for examples 1 to 5 and comparative examples 1 to 3
Note: o indicates no residue; Δ indicates slight residue; and x represents a significant residue.
Compared with examples 1-5, comparative example 1 does not contain an acrylic monomer containing ether bond and straight-chain type vinyl silicone oil; comparative example 2 does not contain straight-chain vinyl silicone oil; comparative example 3 does not contain an ether bond-containing acrylic monomer.
As can be seen from the above table, the polarizer protective films of examples 1 to 5 of the present invention had surface resistivities of less than 10 11 Omega/□, significantly smaller than the surface resistance of comparative examples 1-3. And the residue on the surface of the polaroid can not be generated under the conditions of high temperature and high humidity.
The above examples are intended to illustrate the disclosed embodiments of the present invention and are not to be construed as limiting the invention. In addition, various modifications of the methods and compositions set forth herein, as well as variations of the methods and compositions of the present invention, will be apparent to those skilled in the art without departing from the scope and spirit of the invention. While the invention has been specifically described in connection with various specific preferred embodiments thereof, it should be understood that the invention should not be unduly limited to such specific embodiments. Indeed, various modifications of the above-described embodiments which are obvious to those skilled in the art to which the invention pertains are intended to be covered by the scope of the present invention.
Claims (9)
1. The acrylate pressure-sensitive adhesive is characterized by comprising, by mass, 40-60 parts of acrylate resin, 0.01-0.1 part of antistatic agent, 0.0001-0.001 part of catalyst and 0.5-2.5 parts of crosslinking agent;
wherein the acrylate resin comprises a main monomer and a comonomer; the main monomer comprises a hard monomer, a soft monomer and a crosslinking monomer; the comonomer comprises an acylamino-containing acrylic monomer, an ether bond-containing acrylic monomer and straight-chain vinyl silicone oil; the mass percentage of each component is as follows:
2. the acrylate pressure-sensitive adhesive of claim 1, wherein the hard monomer comprises one or both of methyl methacrylate and methyl acrylate; the soft monomer comprises one or two of isooctyl acrylate and butyl acrylate; the crosslinking monomer comprises one or two of hydroxyethyl acrylate and hydroxypropyl acrylate.
3. The acrylate pressure-sensitive adhesive according to claim 1, wherein the acrylate resin further comprises an initiator and a solvent, the initiator is one of benzoyl peroxide or azobisisobutyronitrile, and the weight percentage of the initiator is 0.5-1%; the solvent is one or a combination of ethyl acetate, butyl acetate and toluene.
4. The acrylate pressure-sensitive adhesive according to claim 1, wherein the antistatic agent is a lithium salt antistatic agent; the cross-linking agent is polyisocyanate cross-linking agent.
5. The acrylate pressure sensitive adhesive of claim 1, wherein the catalyst is a combination of one or more of dibutyl tin dilaurate, stannous octoate, and triethylamine.
6. The preparation method of the acrylate pressure-sensitive adhesive is characterized by comprising the following steps:
uniformly mixing a hard monomer, a soft monomer, a comonomer and an initiator to obtain a mixed solution;
under the protection of inert gas, adding a solvent and part of the mixed solution into a container, and stirring and reacting at 70-90 ℃ for 30-50 min to obtain an acrylate prepolymer;
uniformly mixing the residual mixed solution with a crosslinking monomer and a solvent, adding the mixture into an acrylate prepolymer, carrying out heat preservation reaction at 70-90 ℃ for 3-5 h, then adding the solvent, uniformly stirring, cooling, and discharging to obtain acrylate resin;
weighing acrylate resin, an antistatic agent, a cross-linking agent and a catalyst, and uniformly mixing to obtain acrylate pressure-sensitive adhesive;
the solvent is one or a combination of ethyl acetate, butyl acetate and toluene;
wherein the acrylate resin comprises a main monomer and a comonomer; the main monomer comprises a hard monomer, a soft monomer and a crosslinking monomer; the comonomer comprises an acylamino-containing acrylic monomer, an ether bond-containing acrylic monomer and straight-chain vinyl silicone oil; the mass percentage of each component is as follows:
7. a polarizer protective film comprising the acrylate pressure-sensitive adhesive according to any one of claims 1 to 5.
8. The method for producing a polarizer protective film according to claim 7, comprising the steps of:
coating the acrylate pressure-sensitive adhesive coating liquid on the surface of a polyester film;
drying, attaching a release film and curing.
9. The method of preparing a polarizer protective film according to claim 8, wherein the curing temperature is 35 to 45 ℃ and the curing time is 24 to 72 hours.
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| US4077932A (en) * | 1974-03-21 | 1978-03-07 | Borden, Inc. | Acrylate adhesive aqueous dispersions |
| CN104293249A (en) * | 2014-10-23 | 2015-01-21 | 深圳市三利谱光电科技股份有限公司 | Preparation method of pressure-sensitive adhesive, pressure-sensitive adhesive and application of pressure-sensitive adhesive |
| CN106520032A (en) * | 2016-10-18 | 2017-03-22 | 无锡海特新材料研究院有限公司 | High-temperature-resistant and low-peel-strength acrylate pressure-sensitive adhesive and preparation method thereof |
| CN106597596A (en) * | 2016-12-14 | 2017-04-26 | 合肥乐凯科技产业有限公司 | Pressure-sensitive adhesive for polaroid protection film and polaroid protection film |
| CN111073547A (en) * | 2019-12-27 | 2020-04-28 | 合肥乐凯科技产业有限公司 | Polyester film protective film and preparation method thereof |
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| US4077932A (en) * | 1974-03-21 | 1978-03-07 | Borden, Inc. | Acrylate adhesive aqueous dispersions |
| CN104293249A (en) * | 2014-10-23 | 2015-01-21 | 深圳市三利谱光电科技股份有限公司 | Preparation method of pressure-sensitive adhesive, pressure-sensitive adhesive and application of pressure-sensitive adhesive |
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