CN111234727A - Waterborne environmental protection acrylic emulsion pressure sensitive adhesive protection film - Google Patents
Waterborne environmental protection acrylic emulsion pressure sensitive adhesive protection film Download PDFInfo
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- CN111234727A CN111234727A CN202010235579.5A CN202010235579A CN111234727A CN 111234727 A CN111234727 A CN 111234727A CN 202010235579 A CN202010235579 A CN 202010235579A CN 111234727 A CN111234727 A CN 111234727A
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- Prior art keywords
- sensitive adhesive
- pressure
- protective film
- acrylic emulsion
- emulsion
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- 239000000839 emulsion Substances 0.000 title claims abstract description 50
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 49
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 230000007613 environmental effect Effects 0.000 title description 2
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 230000001681 protective effect Effects 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 125000004069 aziridinyl group Chemical group 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 150000002191 fatty alcohols Chemical class 0.000 claims description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000003851 corona treatment Methods 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical compound COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 11
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 6
- 238000004945 emulsification Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000005336 cracking Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- -1 sodium fatty alcohol Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004908 Emulsion polymer Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/064—Copolymers with monomers not covered by C09J133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- 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
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/24—Homopolymers or copolymers of amides or imides
-
- 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
- C09J2423/00—Presence of polyolefin
- C09J2423/04—Presence of homo or copolymers of ethene
- C09J2423/046—Presence of homo or copolymers of ethene in the substrate
-
- 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
- C09J2433/00—Presence of (meth)acrylic polymer
Abstract
The invention relates to a water-based environment-friendly acrylic emulsion pressure-sensitive adhesive protective film and a preparation method thereof, wherein the protective film comprises a pressure-sensitive adhesive and an external cross-linking agent, the weight of the external cross-linking agent is 0.1-0.5% of the weight of the pressure-sensitive adhesive, the external cross-linking agent is aziridine, a special functional monomer and an imported high-quality emulsifier are selected, an advanced pre-emulsification semi-continuous emulsion polymerization technology is adopted, the prepared emulsion is high in content, few in crystal points after coating, drying and film forming, high in film surface transparency and free of cracking.
Description
Technical Field
The invention belongs to the technical field of protective films, and particularly relates to a water-based environment-friendly acrylic emulsion pressure-sensitive adhesive protective film.
Background
The surface protection film is a kind of packaging film developed for protecting the surface of material, and comprises a base material and a pressure-sensitive adhesive. The acrylic emulsion pressure-sensitive adhesive is an adhesive with better pressure-sensitive property, aging resistance, weather resistance and high bonding property, which is prepared by polymerizing various acrylate monomers. The high-solid-content acrylic emulsion pressure-sensitive adhesive produced by the industry has the advantages of high production efficiency, low transportation and storage cost, no environmental pollution and the like, and is widely used for preparing and applying surface protection films. The surface protection film is mainly applied to the surface of a material, protects the material from being scratched and polluted by dust in the processes of processing, manufacturing, carrying and storing, is not corroded by harmful gas and microorganisms, and simultaneously protects the original high-brightness cleanliness of the surface of the material.
At present, in the high-solid acrylic acid protective film emulsion in the high-end application field, such as the application on household electrical boards and plastic panels, the film surface of the protective film has fine particles like pockmarks, on one hand, the transparency of the film surface is poor and the beauty is influenced; on the other hand, when the film is pasted, the fine particles can damage the protected board surface, become defective products and even cause product rejection.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to solve the problems of film surface transparency and high rejection rate of the conventional protective film produced by pressure-sensitive adhesive.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the water-based environment-friendly acrylic emulsion pressure-sensitive adhesive protective film comprises a pressure-sensitive adhesive and an external cross-linking agent, wherein the weight of the external cross-linking agent is 0.1-0.5% of that of the pressure-sensitive adhesive, and the external cross-linking agent is aziridine.
Preferably, the pressure-sensitive adhesive comprises the following components: hard monomer, soft monomer, functional monomer, emulsifier, initiator, pH regulator and deionized water.
Preferably, the pressure-sensitive adhesive comprises the following components in percentage by weight: 1-10 parts of hard monomer, 40-65 parts of soft monomer, 1-7 parts of functional monomer, 0.2-1 part of emulsifier, 0.2-0.7 part of initiator and 1-5 parts of pH regulator
And 40-50 parts of deionized water.
Preferably, the hard monomer is at least one of styrene, methyl methacrylate and vinyl acetate.
Preferably, the soft monomer is at least one of butyl acrylate, isooctyl acrylate, ethyl acrylate and butyl methacrylate.
Preferably, the functional monomer is at least one of acrylic acid, maleic acid, hydroxyethyl acrylate, N-methoxymethyl acrylamide and allyl glycidyl ether.
Preferably, the emulsifier is at least one of fatty alcohol polyoxyethylene ether sodium sulfate, sulfosuccinate, branched dodecylbenzene sulfonic acid sodium salt, EO/PO polyether block copolymer series and fatty alcohol ethoxylate.
Preferably, the initiator is at least one of ammonium persulfate, potassium persulfate and sodium persulfate.
A preparation method of a water-based environment-friendly acrylic emulsion pressure-sensitive adhesive protective film comprises the following steps:
s100, preparing a pre-emulsion, namely adding 30-45% of deionized water and 60-76% of an emulsifier into an emulsifying cylinder, stirring and dispersing for 15-20 minutes, adding all monomers including hard monomers, soft monomers and functional monomers, and quickly stirring and dispersing for 30-60 minutes to prepare the pre-emulsion;
s200, preparing an initiator solution, and adding 10-15% of deionized water into the initiator to dissolve the initiator to prepare the initiator solution;
s300, emulsifying, namely adding the residual deionized water into a reaction kettle, heating to 80-85 ℃, adding 3-10% of pre-emulsion, adding 60-70% of initiator solution, reacting for 8-15 minutes, beginning to dropwise add the residual pre-emulsion and the initiator solution for 4-6 hours, controlling the reaction temperature to be 80-90 ℃, and keeping the temperature for 1 hour after dropwise adding;
s400, adjusting the pH, cooling the emulsion subjected to heat preservation in the step S300 to below 50 ℃, adding ammonia water, uniformly stirring, adjusting the pH to 7-9, and filtering and discharging through 200-mesh filter cloth to obtain the pressure-sensitive adhesive;
s500, preparing a film, namely mixing and stirring the pressure-sensitive adhesive and an aziridine serving as an external crosslinking agent uniformly, coating and drying, wherein the thickness of the dried coating is 20-30 microns, so that the protective film is prepared.
Preferably, the coating in step S500 is specifically coated on a 70 μm PE film subjected to corona treatment, and the drying is specifically drying at a temperature of 90 ℃ for 3 minutes.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following beneficial effects:
the invention relates to an aqueous environment-friendly acrylic emulsion pressure-sensitive adhesive protective film, which comprises a pressure-sensitive adhesive and an external cross-linking agent, wherein the weight of the external cross-linking agent is 0.1-0.5% of the weight of the pressure-sensitive adhesive, the external cross-linking agent is aziridine, a special functional monomer and an imported high-quality emulsifier are selected, an advanced pre-emulsification semi-continuous emulsion polymerization technology is adopted, the content of the prepared emulsion is high, crystal points are few after coating, drying and film forming, the transparency of a film surface is high, and the film surface is not cracked.
Detailed Description
The present invention will now be described more fully hereinafter by way of examples for purposes of facilitating an understanding of the invention, but the invention may be embodied in many different forms and is not limited to the examples described herein, which examples are provided for purposes of providing a more thorough disclosure of the invention.
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; the terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention; as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Example 1
The preparation process of the protective film in this example is:
(1) weighing 17.4g of deionized water, 0.3g of sodium fatty alcohol polyoxyethylene ether sulfate and 0.1g of fatty alcohol ethoxylate, adding into an emulsifying cylinder, stirring for 15 minutes, adding 2.75g of styrene, 47.575g of butyl acrylate, 2.75g of isooctyl acrylate, 0.825g of acrylic acid and 1.1g N-methoxymethyl acrylamide, and quickly stirring for 60 minutes to obtain a pre-emulsion.
(2) 0.3g of sodium persulfate was weighed and dissolved in 5.75g of deionized water to prepare an initiator solution.
(3) Weighing 20g of deionized water, 0.1g of sodium fatty alcohol polyoxyethylene ether sulfate and 0.05g of fatty alcohol ethoxylate, adding into a reaction kettle, stirring and heating to 80-85 ℃, adding 5% of pre-emulsion and 60% of initiator solution, reacting for 8 minutes, beginning to dropwise add the rest of pre-emulsion and initiator solution, wherein the dropwise adding time is 5 hours, the reaction temperature is 80-90 ℃, and keeping the temperature for 1 hour after the addition.
(4) Cooling to below 50 ℃, adding 1g of ammonia water, uniformly stirring, adjusting the pH to 7-9, and filtering and discharging by using 200-mesh filter cloth to obtain the pressure-sensitive adhesive;
(5) and mixing and stirring the pressure-sensitive adhesive and the aziridine serving as an external crosslinking agent uniformly, coating, drying, and drying to obtain the protective film, wherein the thickness of the coating is 30 microns.
And (3) testing the performance of the protective film: mixing emulsion acrylic pressure-sensitive adhesive and aziridine serving as an external crosslinking agent, uniformly stirring, coating on a PE film with the thickness of 70 microns and subjected to corona treatment, drying at 90 ℃ for 3 minutes until the thickness of the coating is about 30 microns, sticking a protective film on a high-end household appliance board or a plastic panel, and observing the state of the film surface and the existence of crystal points.
And (3) testing results: the film surface is clean, has no particles and crystal points, and has high transparency.
Example 2
The preparation process of the protective film in this example is:
(1) 89.73g of deionized water, 1.75g of branched-chain dodecylbenzene sulfonic acid sodium salt and 0.55g of fatty alcohol ethoxylate are weighed and added into an emulsifying cylinder, stirred for 15 minutes, and then added with 12.38g of styrene, 233.75g of butyl acrylate, 18.01g of isooctyl acrylate, 5.5g of acrylic acid and 4.95g of allyl glycidyl ether, and quickly stirred for 60 minutes to prepare the pre-emulsion.
(2) 1.65g of ammonium persulfate was weighed and dissolved in 30g of deionized water to prepare an initiator solution.
(3) Weighing 95g of deionized water, 0.45g of branched-chain dodecyl benzene sulfonic acid sodium salt and 0.28g of fatty alcohol ethoxylate, adding the deionized water, the branched-chain dodecyl benzene sulfonic acid sodium salt and the fatty alcohol ethoxylate into a reaction kettle, stirring and heating to 80-85 ℃, adding 5% of pre-emulsion and 65% of initiator solution, reacting for 8 minutes, beginning to dropwise add the rest pre-emulsion and the initiator solution, wherein the dropwise adding time is 5 hours, the reaction temperature is 80-90 ℃, and after the addition, keeping the temperature and reacting for 1 hour.
(4) Cooling to below 50 ℃, adding 6g of ammonia water, uniformly stirring, adjusting the pH to 7-9, and filtering and discharging by using 200-mesh filter cloth to obtain the pressure-sensitive adhesive;
(5) and mixing and stirring the pressure-sensitive adhesive and the aziridine serving as an external crosslinking agent uniformly, coating, drying, and drying to obtain the protective film, wherein the thickness of the coating is 30 microns.
And (3) testing the performance of the protective film: mixing emulsion acrylic pressure-sensitive adhesive and aziridine serving as an external crosslinking agent, uniformly stirring, coating on a PE film with the thickness of 70 microns and subjected to corona treatment, drying at 90 ℃ for 3 minutes until the thickness of the coating is about 30 microns, sticking a protective film on a high-end household appliance board or a plastic panel, and observing the state of the film surface and the existence of crystal points.
And (3) testing results: the film surface is clean, has no particles and crystal points, and has high transparency.
Example 3
The preparation process of the protective film in this example is:
(1) 180.0g of deionized water, 3.0g of sulfosuccinate and 1.3g of fatty alcohol ethoxylate are weighed into an emulsifying cylinder, stirred for 15 minutes, added with 33g of styrene, 484g of ethyl acrylate, 11.0g of isooctyl acrylate, 9.0g of acrylic acid and 13.0g of hydroxyethyl acrylate, and quickly stirred for 60 minutes to prepare a pre-emulsion.
(2) 3.5g of ammonium persulfate was weighed and dissolved in 50g of deionized water to prepare an initiator solution.
(3) Weighing 200g of deionized water, 1.32g of sulfosuccinate and 0.88g of fatty alcohol ethoxylate, adding into a reaction kettle, stirring and heating to 80-85 ℃, adding 5% of pre-emulsion and 65% of initiator solution, reacting for 10 minutes, beginning to dropwise add the rest pre-emulsion and the initiator solution, wherein the dropwise adding time is 5 hours, the reaction temperature is 80-90 ℃, and keeping the temperature for 1 hour after the addition.
(4) Cooling to below 50 ℃, adding 10g of ammonia water, uniformly stirring, adjusting the pH to 7-9, and filtering and discharging by using 200-mesh filter cloth to obtain the pressure-sensitive adhesive;
(5) and mixing and stirring the pressure-sensitive adhesive and the aziridine serving as an external crosslinking agent uniformly, coating, drying, and drying to obtain the protective film, wherein the thickness of the coating is 30 microns.
And (3) testing the performance of the protective film: mixing emulsion acrylic pressure-sensitive adhesive and aziridine serving as an external crosslinking agent, uniformly stirring, coating on a PE film with the thickness of 70 microns and subjected to corona treatment, drying at 90 ℃ for 3 minutes until the thickness of the coating is about 30 microns, sticking a protective film on a high-end household appliance board or a plastic panel, and observing the state of the film surface and the existence of crystal points.
And (3) testing results: the film surface is clean, has no particles and crystal points, and has high transparency.
In summary, the following steps: the protective film prepared by the invention selects special functional monomers and imported high-quality emulsifiers, adopts advanced pre-emulsification semi-continuous emulsion polymerization technology, has high content of prepared emulsion, has few crystal points after coating, drying and film forming, and has high film surface transparency and no cracking. The specific analysis is as follows:
the soft monomer has very low glass transition temperature and can endow the pressure-sensitive adhesive with bonding performance and flexibility;
the hard monomer has higher glass transition temperature, provides cohesive force and peel strength, and after being copolymerized with the soft monomer, the rigidity of a polymer molecular chain is improved, and the cohesive strength of the adhesive is higher. Therefore, according to different application requirements, the ratio of the soft monomer to the hard monomer is moderate, and the pressure-sensitive adhesive with good performance can be prepared so as to meet different use requirements.
The functional monomer is mainly used for carrying out crosslinking modification on a polymer to improve the water resistance, heat resistance, aging resistance, bonding strength, cohesive force and adhesive force of the polymer, the crosslinking method is to introduce a comonomer with a special crosslinking group in the emulsion polymerization process to ensure that the main chain of the emulsion polymer is provided with the crosslinking group, and in the later emulsion film forming process, a crosslinking bond is generated through the chemical reaction between the crosslinking groups on the molecular chain of the copolymer or the chemical reaction between the crosslinking groups on the main chain of the polymer and an external crosslinking agent under certain conditions to form the crosslinked polymer, for example: the epoxy type crosslinking monomer contains double bonds and epoxy groups, can participate in emulsion polymerization reaction, introduces the epoxy groups onto the main chain of the copolymer, and in the emulsion film-forming process, the epoxy groups can react with carboxyl, amino, hydroxyl and other groups on the main chain of the polymer or the added crosslinking agent molecules to produce crosslinking bonds, so that the linear emulsion polymer is changed into a molecular network structure, and the water resistance, the bonding strength and the heat resistance of the polymer emulsion are improved.
The crystal points in the existing protective film are mainly caused by unstable polymerization of high-solid emulsion and small aggregates which cannot be filtered out from the emulsion. And a pre-emulsification semi-continuous emulsion polymerization process is adopted, the polymerization reaction is stably carried out, few gel particles are generated in the polymerization reaction process, and the film surface crystal points can be greatly reduced in later application.
The above-mentioned embodiments only express a certain implementation mode of the present invention, and the description thereof is specific and detailed, but not construed as limiting the scope of the present invention; it should be noted that, for those skilled in the art, without departing from the concept of the present invention, several variations and modifications can be made, which are within the protection scope of the present invention; therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The water-based environment-friendly acrylic emulsion pressure-sensitive adhesive protective film is characterized in that: the pressure-sensitive adhesive comprises a pressure-sensitive adhesive and an external cross-linking agent, wherein the weight of the external cross-linking agent is 0.1-0.5% of that of the pressure-sensitive adhesive, and the external cross-linking agent is aziridine.
2. The protective film of the waterborne environmental-friendly acrylic emulsion pressure-sensitive adhesive according to claim 1, wherein: the pressure-sensitive adhesive comprises the following components: hard monomer, soft monomer, functional monomer, emulsifier, initiator, pH regulator and deionized water.
3. The water-based environment-friendly acrylic emulsion pressure-sensitive adhesive protective film according to claim 2, wherein the weight content of each component of the pressure-sensitive adhesive is as follows: 1-10 parts of hard monomer, 40-65 parts of soft monomer, 1-7 parts of functional monomer, 0.2-1 part of emulsifier, 0.2-0.7 part of initiator, 1-5 parts of pH regulator and 40-50 parts of deionized water.
4. The protective film of the waterborne environmental-friendly acrylic emulsion pressure-sensitive adhesive according to claim 3, wherein: the hard monomer is at least one of styrene, methyl methacrylate and vinyl acetate.
5. The protective film of the waterborne environmental-friendly acrylic emulsion pressure-sensitive adhesive according to claim 3, wherein: the soft monomer is at least one of butyl acrylate, isooctyl acrylate, ethyl acrylate and butyl methacrylate.
6. The protective film of the waterborne environmental-friendly acrylic emulsion pressure-sensitive adhesive according to claim 3, wherein: the functional monomer is at least one of acrylic acid, maleic acid, hydroxyethyl acrylate, N-methoxymethyl acrylamide and allyl glycidyl ether.
7. The protective film of the waterborne environmental-friendly acrylic emulsion pressure-sensitive adhesive according to claim 3, wherein: the emulsifier is at least one of fatty alcohol polyoxyethylene ether sodium sulfate, sulfosuccinate, branched-chain dodecylbenzene sulfonic acid sodium salt, EO/PO polyether block copolymer series and fatty alcohol ethoxylate.
8. The protective film of the waterborne environmental-friendly acrylic emulsion pressure-sensitive adhesive according to claim 3, wherein: the initiator is at least one of ammonium persulfate, potassium persulfate and sodium persulfate.
9. The preparation method of the water-based environment-friendly acrylic emulsion pressure-sensitive adhesive protective film according to any one of claims 3 to 8, characterized by comprising the following steps:
s100, preparing a pre-emulsion, namely adding 30-45% of deionized water and 60-76% of an emulsifier into an emulsifying cylinder, stirring and dispersing for 15-20 minutes, adding all monomers including hard monomers, soft monomers and functional monomers, and quickly stirring and dispersing for 30-60 minutes to prepare the pre-emulsion;
s200, preparing an initiator solution, and adding 10-15% of deionized water into the initiator to dissolve the initiator to prepare the initiator solution;
s300, emulsifying, namely adding the residual deionized water into a reaction kettle, heating to 80-85 ℃, adding 3-10% of pre-emulsion, adding 60-70% of initiator solution, reacting for 8-15 minutes, beginning to dropwise add the residual pre-emulsion and the initiator solution for 4-6 hours, controlling the reaction temperature to be 80-90 ℃, and keeping the temperature for 1 hour after dropwise adding;
s400, adjusting the pH, cooling the emulsion subjected to heat preservation in the step S300 to below 50 ℃, adding ammonia water, uniformly stirring, adjusting the pH to 7-9, and filtering and discharging through 200-mesh filter cloth to obtain the pressure-sensitive adhesive;
s500, preparing a film, namely mixing and stirring the pressure-sensitive adhesive and an aziridine serving as an external crosslinking agent uniformly, coating and drying, wherein the thickness of the dried coating is 20-30 microns, so that the protective film is prepared.
10. The preparation method of the water-based environment-friendly acrylic emulsion pressure-sensitive adhesive protective film according to claim 9, wherein the preparation method comprises the following steps: the coating in the step S500 is specifically coated on a 70 μm PE film subjected to corona treatment, and the drying is specifically drying at 90 ℃ for 3 minutes.
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