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CN110791209A - Easily-removed high-peeling-force adhesive sticker and preparation method thereof - Google Patents

Easily-removed high-peeling-force adhesive sticker and preparation method thereof Download PDF

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Publication number
CN110791209A
CN110791209A CN201910916100.1A CN201910916100A CN110791209A CN 110791209 A CN110791209 A CN 110791209A CN 201910916100 A CN201910916100 A CN 201910916100A CN 110791209 A CN110791209 A CN 110791209A
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parts
adhesive
acrylate
stirring
emulsion
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CN201910916100.1A
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CN110791209B (en
Inventor
陈凯
吴林群
周晓南
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Jiangsu Jinghua New Materials Technology Co Ltd
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Jiangsu Jinghua New Materials Technology Co Ltd
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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
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/245—Vinyl resins, e.g. polyvinyl chloride [PVC]
    • 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
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • 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
    • C09J2427/00—Presence of halogenated polymer
    • C09J2427/006—Presence of halogenated polymer 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides an easily-removed high-stripping-force adhesive sticker which comprises a PVC (polyvinyl chloride) base material layer and an adhesive layer, wherein the adhesive layer is prepared from the following raw materials in percentage by weight: 80-90% of vinyl copolymer emulsion, 7-17% of rubber latex, 1-1.6% of wetting agent, 0.2-0.4% of ammonia water and 0.5-1% of fumed silica. The adhesive PVC film provided by the invention does not need corona treatment, and has very high adhesive force, better initial adhesion, good plasticizer migration resistance and water resistance; the acrylic copolymer with polar nitrogen-containing monomer or special functional monomer is not needed to be used, and the manufacturing cost is low.

Description

Easily-removed high-peeling-force adhesive sticker and preparation method thereof
Technical Field
The invention relates to adhesive paste, in particular to high-peeling-force adhesive paste.
Background
The SPVC film has low price, and the polyvinyl chloride adhesive tape obtained after coating the pressure-sensitive adhesive can be widely used for the decoration of doors and windows, wall surfaces, furniture, outdoor advertisements and the like. The soft polyvinyl chloride film is prepared by adding plasticizer into polyvinyl chloride resin to make it slide between polyvinyl chloride chain-like molecules, to expand the distance between molecular chains and reduce the attraction between molecular chains, thereby achieving the purpose of plasticizing and softening. Plasticizers generally refer to organic substances that increase the plasticity and flowability of plastics and rubbers during processing and impart flexibility to the finished product. Plasticizers (especially monomeric plasticizers) have a tendency to migrate during film use due to purely physical processes of mixing the plasticizer with the polyvinyl chloride resin. For example, diisooctyl phthalate (DOP) is widely used in the manufacture of soft advertising cloth as a plasticizer in China. If the decorative film is adhered to the advertising cloth by a pressure-sensitive adhesive, the performance of the pressure-sensitive adhesive is potentially compromised by migration of the plasticizer to the surface of the flexible advertising cloth. In order to prevent the plasticizer from migrating to the surface to cause the pressure-sensitive adhesive to be deteriorated in tack (tack/peel force), the prior art has improved the composition of the pressure-sensitive adhesive or the structure of the finished product.
The first method comprises the following steps: conventional solvent-based PSAs impart removability to adhesive products in flat poster applications. The main mechanism is as follows: the force between these PSAs and the SPVC backing film (the adhesive force) is stronger than the force between it and the surface to which it is adhered (the peel force), and when the SPVC film is peeled off, the PSA is completely removed from the surface to which it is adhered. The reason for the super-strong adhesive force is the etching effect of the solvent. The SPVC does not require additional processing prior to coating of the solvent-based PSA. However, under the environmental protection requirement, a large amount of waterborne products are developed, and the waterborne PSA has a lower acting force with the SPVC film due to lack of etching action of the solvent, and is easily degummed in the practical application process, so the SPVC film needs to be subjected to corona treatment to increase the surface energy thereof, thereby improving the adhesive force. Meanwhile, the plasticizer in the SPVC migrates to the interface of the adhesive layer and the substrate, so that the adhesive force is poorer, and the corona treatment is more necessary.
The second method comprises the following steps: US4284681 and US4045600 propose the incorporation of a barrier layer between a pressure sensitive adhesive and a flexible substrate of polyvinyl chloride. Although this method solves the problem of viscosity reduction of the pressure-sensitive adhesive due to migration of the plasticizer to the surface of the substrate, this method causes accumulation of the concentration of plasticizer molecules between the adhesive and the substrate, which impairs the bonding between the interfaces.
The third method comprises the following steps: US5800919 discloses that not only is the resistance of the adhesive to plasticizer migration improved by the addition of a plasticizer, but also the superiority of the adhesive itself to low temperature construction is conferred. However, the limitations of this approach are: the plasticizer added to the adhesive must be the same as the plasticizer used for the PVC substrate in order to be effective. Otherwise, there is still a concentration gradient of the plasticizer, resulting in migration of the plasticizer to the low-concentration adhesive side, and ultimately impairing the adhesive strength of the pressure-sensitive adhesive.
The fourth method comprises the following steps: polar structural units containing nitrogen or carbonyl groups, such as acrylic acid, acrylonitrile, acrylamide, N-vinylpyridine, N-vinylpyrrolidone, etc., are introduced by copolymerization in the preparation of pressure-sensitive adhesives (see U.S. Pat. Nos. 4364972, 4605592, 4946742, 501977, 5861211, EP615983A 2). The method has the defects of complex manufacturing process and low peeling force and initial viscosity of the prepared adhesive.
The fifth method comprises the following steps: japanese laid-open patent publication No. 53-57239 proposes an aqueous latex adhesive prepared by using a nitrile latex having a nitrile group content of 15 to 40% (by mole) as a tackifier resin and a polyacrylate blend latex. Although the plasticizer resistance of the double-sided pressure-sensitive adhesive film is improved, the water resistance of the pressure-sensitive adhesive is poor due to the emulsifier in the adhesive film, and the double-sided pressure-sensitive adhesive film is not suitable for long-term outdoor use.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the low-cost adhesive plaster with high adhesive base force, better initial adhesive force, good plasticizer migration resistance and water resistance.
The technical scheme adopted by the invention is as follows:
the adhesive sticker with high peel force and easy removal comprises a PVC base material layer and an adhesive layer, wherein the adhesive layer is prepared from the following raw materials in percentage by weight:
Figure BDA0002215963430000031
further, the preparation raw materials of the vinyl copolymer emulsion comprise the following components in percentage by weight:
further, the monomer A comprises one or more of n-butyl acrylate, isobutyl acrylate, hexyl acrylate, n-butyl methacrylate, isobutyl methacrylate, isooctyl acrylate and hexyl methacrylate.
Further, the monomer B comprises one or more of methyl acrylate, styrene, methyl methacrylate and methyl styrene.
Further, the monomer C comprises one or more of acrylic acid, hydroxyethyl acrylate, methacrylic acid and hydroxyethyl methacrylate.
Further, the emulsifier is preferably ammonium 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether sulfate.
Further, the defoamer is preferably a basf WBA defoamer.
Further, the fumed silica preferably has a particle size in the range of 0 to 100 nm.
Further, the rubber latex comprises one or more of styrene-butadiene rubber latex, natural rubber latex, nitrile-butadiene rubber latex and chloroprene rubber latex; the rubber or modified rubber with smaller molecular polarity not only has good flexibility, but also can be more separated from the surface of the PVC substrate with larger molecular polarity during coating and drying processes, and is distributed on the surface of the adhesive layer (because the affinity between the rubber molecules with smaller polarity and the PVC molecules with larger polarity is smaller), so that the surface of the adhesive layer has more nonpolar characteristics, and the initial adhesive property and the adhesive property are improved.
Further, the wetting agent is a surfactant.
Further, the surfactant of the wetting agent is dioctyl sodium sulfosuccinate.
Further, the average particle diameter of the vinyl copolymer emulsion is 60 to 500 nm.
A preparation method of an easily-removed high-peel-force adhesive sticker comprises the following steps:
step 1: weighing raw materials required for preparing the vinyl copolymer emulsion;
step 2: adding part of emulsifier and part of sodium bicarbonate into a pre-emulsification kettle, adding part of deionized water, stirring and mixing uniformly, then mixing all the monomer A, the monomer B and the monomer C, adding into the pre-emulsification kettle, and stirring and mixing uniformly to obtain a pre-emulsion;
and step 3: adding the rest of emulsifier, sodium bicarbonate and deionized water into the main reaction kettle, heating while continuously stirring, and adding 2% of pre-emulsion and part of ammonium persulfate after the temperature is raised to 83-85 ℃;
and 4, step 4: keeping the temperature for 10-15min, adding the rest of the pre-emulsion and the rest of ammonium persulfate into the main reaction kettle at a constant speed, keeping the temperature at 83-85 ℃ after the addition is finished, continuously stirring for reaction for 1-2h, cooling to below 40 ℃, adding a defoaming agent, and stirring for 10-30min to obtain an alkene copolymer emulsion;
and 5: adding a wetting agent, ammonia water and gas-phase silica into the vinyl copolymer emulsion in sequence, stirring uniformly, adding rubber latex, stirring uniformly, filtering by using a 200-mesh and 300-mesh filter screen, and discharging to obtain an adhesive;
step 6: coating the prepared adhesive on release paper with the coating weight of 17-20g/m2And drying to form an adhesive layer, and then adhering a PVC base material layer to the adhesive layer to obtain the easily-removed high-peeling-force adhesive sticker.
Further, the glass transition temperature of the vinyl copolymer emulsion prepared in the step 4 is from-60 ℃ to-20 ℃, preferably from-55 ℃ to-35 ℃; the vinyl copolymer with lower glass transition temperature and larger molecular polarity not only has larger cohesive strength, but also can be more attached to the surface of the PVC substrate with larger molecular polarity in the drying process (because the polar molecules of the vinyl copolymer and the polar molecules of the PVC substrate have larger affinity), thereby improving the adhesive force with the substrate.
The invention has the beneficial effects that:
the adhesive PVC film provided by the invention does not need corona treatment, and has very high adhesive force, better initial adhesion, good plasticizer migration resistance and water resistance; the acrylic copolymer with polar nitrogen-containing monomer or special functional monomer is not needed to be used, the manufacturing cost is low, the intermiscibility of the aromatic vinyl monomer and the plasticizer in the PVC base material is improved, and the influence of the migration of the plasticizer on the pressure-sensitive performance of the adhesive is avoided; the adhesive sticker is suitable for sticking indoor and outdoor plane advertisements and marks, and is particularly suitable for posters, decorations and the like which need to be removed after being stuck.
Detailed Description
In order to more fully understand the technical contents of the present invention, the technical solutions of the present invention will be further described and illustrated by the following specific examples.
Example 1
Weighing 190 parts of isobutyl methacrylate, 190 parts of isooctyl acrylate, 35 parts of methyl methacrylate, 40 parts of styrene, 10 parts of hydroxyethyl acrylate, 10 parts of acrylic acid, 9 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, 10 parts of ammonium persulfate, 4.5 parts of a basf WBA defoaming agent, 1.5 parts of sodium bicarbonate and 500 parts of deionized water.
Adding 8 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate and 1.3 parts of sodium bicarbonate into a pre-emulsification kettle, adding 250 parts of deionized water, stirring and mixing uniformly, then adding 190 parts of weighed n-butyl acrylate, 190 parts of isooctyl acrylate, 35 parts of methyl methacrylate, 40 parts of styrene, 10 parts of hydroxyethyl acrylate and 10 parts of acrylic acid into the pre-emulsification kettle after uniformly mixing, and stirring and mixing uniformly by using a stirrer to obtain a pre-emulsion.
Adding the rest 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, sodium bicarbonate and deionized water into a main reaction kettle, heating while continuously stirring, and adding 2% of prepared pre-emulsion and 5 parts of ammonium persulfate after the temperature is raised to 83 ℃; keeping the temperature for 15min, adding the rest pre-emulsion and the rest ammonium persulfate at constant speed, keeping the temperature at 83 ℃ after the addition is finished, continuing stirring for reaction for 2h, cooling to below 40 ℃, stirring for 30min by 4.5 parts of a Pasteur WBA defoaming agent, and obtaining the alkene copolymer emulsion.
Sequentially adding 17 parts of dioctyl sodium sulfosuccinate, 4.5 parts of ammonia water and 10 parts of fumed silica into the vinyl copolymer emulsion, uniformly stirring, adding 78 parts of nitrile rubber latex, uniformly stirring, filtering by using a 300-mesh filter screen, and discharging to obtain an adhesive; the prepared adhesive is uniformly coated on release paper, and the coating weight is 19g/m2And drying to form an adhesive layer, and then adhering a PVC base material layer to the adhesive layer to obtain the easily-removed high-peeling-force adhesive sticker.
Example 2
350 parts of isobutyl acrylate, 80 parts of methyl acrylate, 40 parts of methacrylic acid, 10 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, 3 parts of ammonium persulfate, 5 parts of a basf WBA defoaming agent, 2 parts of sodium bicarbonate and 510 parts of deionized water are weighed.
Adding 9 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate and 1.8 parts of sodium bicarbonate into a pre-emulsification kettle, adding 250 parts of deionized water, stirring and mixing uniformly, then adding 350 parts of weighed isobutyl acrylate, 80 parts of methyl acrylate and 40 parts of methacrylic acid into the pre-emulsification kettle after uniformly mixing, and stirring and mixing uniformly by using a stirrer to obtain a pre-emulsion.
Adding the rest 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, sodium bicarbonate and deionized water into a main reaction kettle, heating while continuously stirring, and adding 2% of prepared pre-emulsion and 5 parts of ammonium persulfate after the temperature is increased to 85 ℃; keeping the temperature for 10min, adding the rest pre-emulsion and the rest ammonium persulfate at constant speed, keeping the temperature at 85 ℃ after the addition is finished, continuing stirring for reaction for 1h, cooling to below 40 ℃, adding 5 parts of a basf WBA defoaming agent, and stirring for 10min to obtain the alkene copolymer emulsion.
Sequentially adding 20 parts of surfactant, 5 parts of ammonia water and 12.5 parts of fumed silica into the vinyl copolymer emulsion, uniformly stirring, adding 212.5 parts of styrene-butadiene rubber latex, uniformly stirring, filtering by using a 200-mesh filter screen, and discharging to obtain an adhesive; the prepared adhesive is uniformly coated on release paper, and the coating weight is 17g/m2And drying to form an adhesive layer, and then adhering a PVC base material layer to the adhesive layer to obtain the easily-removed high-peeling-force adhesive sticker.
Example 3
Weighing 225 parts of hexyl acrylate, 225 parts of n-butyl methacrylate, 20 parts of methyl acrylate, 20 parts of methyl styrene, 5 parts of hydroxyethyl methacrylate, 5 parts of methacrylic acid, 6 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, 3.5 parts of ammonium persulfate, 0.5 part of a BASF WBA defoaming agent and 490 parts of deionized water.
Adding 5.5 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ammonium ether sulfate into a pre-emulsification kettle, adding 240 parts of deionized water, uniformly stirring and mixing, then uniformly mixing 225 parts of weighed caproleic acid ester, 225 parts of n-butyl methacrylate, 20 parts of methyl acrylate, 20 parts of methyl styrene, 5 parts of hydroxyethyl methacrylate and 5 parts of methacrylic acid, adding into the pre-emulsification kettle, and uniformly stirring and mixing by using a stirrer to obtain a pre-emulsion.
Adding the rest 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate and deionized water into a main reaction kettle, heating while continuously stirring, and adding 2% of prepared pre-emulsion and 2 parts of ammonium persulfate after the temperature is increased to 84 ℃; keeping the temperature for 12min, adding the rest pre-emulsion and the rest ammonium persulfate at constant speed, keeping the temperature at 84 ℃ after the addition is finished, continuously stirring for reaction for 1h, cooling to below 40 ℃, stirring for 30min to obtain the alkene copolymer emulsion, wherein the Pasteur WBA defoaming agent accounts for 0.5 part.
Then, sequentially adding 11.4 parts of dioctyl sodium sulfosuccinate, 2.3 parts of ammonia water and 5.7 parts of fumed silica into the vinyl copolymer emulsion, uniformly stirring, then adding 55 parts of natural rubber latex and 62 parts of chloroprene rubber latex, uniformly stirring, filtering by using a 300-mesh filter screen, and discharging to obtain an adhesive; the prepared adhesive is uniformly coated on release paper, and the coating weight is 18g/m2And drying to form an adhesive layer, and then adhering a PVC base material layer to the adhesive layer to obtain the easily-removed high-peeling-force adhesive sticker.
Example 4
Weighing 200 parts of hexyl methacrylate, 200 parts of acrylic acid-2-ethylhexyl ester, 30 parts of methyl methacrylate, 30 parts of styrene, 20 parts of hydroxyethyl acrylate, 10 parts of acrylic acid, 7 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, 1 part of ammonium persulfate, 1 part of a Pasteur WBA defoaming agent, 1 part of sodium bicarbonate and 500 parts of deionized water.
6 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate and 0.9 part of sodium bicarbonate are added into a pre-emulsification kettle, 250 parts of deionized water is added into the pre-emulsification kettle, the mixture is stirred and mixed uniformly, then 200 parts of weighed hexyl methacrylate, 200 parts of 2-ethylhexyl acrylate, 30 parts of methyl methacrylate, 30 parts of styrene, 20 parts of hydroxyethyl acrylate and 10 parts of acrylic acid are mixed uniformly, added into the pre-emulsification kettle, and stirred and mixed uniformly by a stirrer to obtain a pre-emulsion.
Adding the rest 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, sodium bicarbonate and deionized water into a main reaction kettle, heating while continuously stirring, and adding 2% of prepared pre-emulsion and 0.5 part of ammonium persulfate after the temperature is raised to 83 ℃; keeping the temperature for 15min, adding the rest pre-emulsion and the rest ammonium persulfate at constant speed, keeping the temperature at 83 ℃ after the addition is finished, continuing stirring for reaction for 2h, cooling to below 40 ℃, adding 1 part of a BASF WBA defoaming agent, and stirring for 30min to obtain the alkene copolymer emulsion.
Sequentially adding 15 parts of dioctyl sodium sulfosuccinate, 3.5 parts of ammonia water and 8 parts of fumed silica into the vinyl copolymer emulsion, uniformly stirring, adding 114 parts of nitrile rubber latex, uniformly stirring, filtering by using a 300-mesh filter screen, and discharging to obtain an adhesive; the prepared adhesive is uniformly coated on release paper, and the coating weight is 20g/m2And drying to form an adhesive layer, and then adhering a PVC base material layer to the adhesive layer to obtain the easily-removed high-peeling-force adhesive sticker.
Example 5
Weighing 205 parts of n-butyl acrylate, 205 parts of isooctyl acrylate, 27.5 parts of methyl methacrylate, 30 parts of styrene, 22.5 parts of hydroxyethyl acrylate, 10 parts of acrylic acid, 6 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, 2 parts of ammonium persulfate, 1 part of a BASF WBA defoaming agent, 1 part of sodium bicarbonate and 490 parts of deionized water.
5.5 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ammonium ether sulfate and 0.9 part of sodium bicarbonate are added into a pre-emulsification kettle, 240 parts of deionized water is added into the pre-emulsification kettle, the mixture is stirred and mixed uniformly, and then 205 parts of n-butyl acrylate, 205 parts of isooctyl acrylate, 27.5 parts of methyl methacrylate, 30 parts of styrene, 22.5 parts of hydroxyethyl acrylate and 10 parts of acrylic acid are weighed and mixed uniformly, added into the pre-emulsification kettle, and stirred and mixed uniformly by a stirrer to obtain the pre-emulsion.
Adding the rest 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, sodium bicarbonate and deionized water into a main reaction kettle, heating while continuously stirring, and adding 2% of prepared pre-emulsion and 1 part of ammonium persulfate after the temperature is raised to 83 ℃; keeping the temperature for 15min, adding the rest pre-emulsion and the rest ammonium persulfate at constant speed, keeping the temperature at 83 ℃ after the addition is finished, continuing stirring for reaction for 2h, cooling to below 40 ℃, adding 1 part of a BASF WBA defoaming agent, and stirring for 30min to obtain the alkene copolymer emulsion.
Sequentially adding 15 parts of dioctyl sodium sulfosuccinate, 4 parts of ammonia water and 8 parts of fumed silica into the vinyl copolymer emulsion, uniformly stirring, adding 100 parts of nitrile rubber latex, uniformly stirring, filtering by using a 300-mesh filter screen, and discharging to obtain an adhesive; the prepared adhesive is uniformly coated on release paper, and the coating weight is 20g/m2And drying to form an adhesive layer, and then adhering a PVC base material layer to the adhesive layer to obtain the easily-removed high-peeling-force adhesive sticker.
Example 6
Weighing monomer A (150 parts of isobutyl acrylate, 130 parts of hexyl acrylate and 120 parts of n-butyl methacrylate), monomer B (20 parts of methyl acrylate, 20 parts of styrene and 20 parts of methyl methacrylate), monomer C (10 parts of hydroxyethyl acrylate, 10 parts of methacrylic acid and 10 parts of hydroxyethyl methacrylate), 6 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, 2 parts of ammonium persulfate, 1 part of a BASF WBA defoaming agent, 1 part of sodium bicarbonate and 500 parts of deionized water.
Adding 5.5 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate and 0.9 part of sodium bicarbonate into a pre-emulsification kettle, adding 240 parts of deionized water, stirring and mixing uniformly, then adding the weighed monomer A, monomer B and monomer C into the pre-emulsification kettle after uniformly mixing, and stirring and mixing uniformly by using a stirrer to obtain a pre-emulsion.
Adding the rest 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, sodium bicarbonate and deionized water into a main reaction kettle, heating while continuously stirring, and adding 2% of prepared pre-emulsion and 1 part of ammonium persulfate after the temperature is raised to 83 ℃; keeping the temperature for 15min, adding the rest pre-emulsion and the rest ammonium persulfate at constant speed, keeping the temperature at 83 ℃ after the addition is finished, continuing stirring for reaction for 2h, cooling to below 40 ℃, adding 1 part of a BASF WBA defoaming agent, and stirring for 30min to obtain the alkene copolymer emulsion.
Sequentially adding 15 parts of dioctyl sodium sulfosuccinate, 4 parts of ammonia water and 8 parts of fumed silica into the vinyl copolymer emulsion, uniformly stirring, adding 100 parts of nitrile rubber latex, uniformly stirring, filtering by using a 300-mesh filter screen, and discharging to obtain an adhesive; the prepared adhesive is uniformly coated on release paper, and the coating weight is 20g/m2And drying to form an adhesive layer, and then adhering a PVC base material layer to the adhesive layer to obtain the easily-removed high-peeling-force adhesive sticker.
Example 7
The composition of the monomer a was changed compared to example 6 to: 100 parts of n-butyl acrylate, 100 parts of isobutyl methacrylate, 100 parts of hexyl methacrylate and 100 parts of 2-ethylhexyl acrylate; changing the composition of the monomer B into: 15 parts of methyl acrylate, 15 parts of styrene, 15 parts of methyl methacrylate and 15 parts of methyl styrene; changing the composition of the monomer C to be: 8 parts of acrylic acid, 8 parts of hydroxyethyl acrylate, 8 parts of methacrylic acid and 6 parts of hydroxyethyl methacrylate; other components and preparation methods are consistent.
Example 8
The composition of the monomer a was changed compared to example 6 to: 80 parts of n-butyl acrylate, 80 parts of isobutyl acrylate, 80 parts of hexyl acrylate, 80 parts of n-butyl methacrylate and 80 parts of isobutyl methacrylate; changing the composition of the monomer B into: 20 parts of styrene, 20 parts of methyl methacrylate and 20 parts of methyl styrene; changing the composition of the monomer C to be: 10 parts of acrylic acid, 10 parts of hydroxyethyl acrylate and 10 parts of methacrylic acid; other components and preparation methods are consistent.
Example 9
The composition of the monomer a was changed compared to example 6 to: 60 parts of isobutyl acrylate, 60 parts of hexyl acrylate, 80 parts of n-butyl methacrylate, 60 parts of isobutyl methacrylate, 80 parts of isooctyl acrylate and 60 parts of hexyl methacrylate; changing the composition of the monomer B into: 20 parts of methyl acrylate, 20 parts of methyl methacrylate and 20 parts of methyl styrene; changing the composition of the monomer C to be: 10 parts of acrylic acid, 10 parts of hydroxyethyl acrylate and 10 parts of hydroxyethyl methacrylate; other components and preparation methods are consistent.
Example 10
The composition of the monomer a was changed compared to example 6 to: 50 parts of n-butyl acrylate, 50 parts of isobutyl acrylate, 50 parts of hexyl acrylate, 50 parts of n-butyl methacrylate, 50 parts of isobutyl methacrylate, 100 parts of isooctyl acrylate and 50 parts of hexyl methacrylate; other components and preparation methods are consistent.
Comparative example 1 (comparison with example 5, without addition of rubber latex and fumed silica)
Weighing 205 parts of n-butyl acrylate, 205 parts of isooctyl acrylate, 27.5 parts of methyl methacrylate, 30 parts of styrene, 22.5 parts of hydroxyethyl acrylate, 10 parts of acrylic acid, 6 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, 2 parts of ammonium persulfate, 1 part of a BASF WBA defoaming agent, 1 part of sodium bicarbonate and 490 parts of deionized water.
5.5 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ammonium ether sulfate and 0.9 part of sodium bicarbonate are added into a pre-emulsification kettle, 240 parts of deionized water is added into the pre-emulsification kettle, the mixture is stirred and mixed uniformly, and then 205 parts of n-butyl acrylate, 205 parts of isooctyl acrylate, 27.5 parts of methyl methacrylate, 30 parts of styrene, 22.5 parts of hydroxyethyl acrylate and 10 parts of acrylic acid are weighed and mixed uniformly, added into the pre-emulsification kettle, and stirred and mixed uniformly by a stirrer to obtain the pre-emulsion.
Adding the rest 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, sodium bicarbonate and deionized water into a main reaction kettle, heating while continuously stirring, and adding 2% of prepared pre-emulsion and 1 part of ammonium persulfate after the temperature is raised to 83 ℃; keeping the temperature for 15min, adding the rest pre-emulsion and the rest ammonium persulfate at constant speed, keeping the temperature at 83 ℃ after the addition is finished, continuing stirring for reaction for 2h, cooling to below 40 ℃, adding 1 part of a BASF WBA defoaming agent, and stirring for 30min to obtain the alkene copolymer emulsion.
Sequentially adding 15 parts of dioctyl sodium sulfosuccinate and 4 parts of ammonia water into the vinyl copolymer emulsion, uniformly stirring, and filtering and discharging by using a 300-mesh filter screen to obtain an adhesive; the prepared adhesive is uniformly coated on release paper, and the coating weight is 20g/m2And drying to form an adhesive layer, and then adhering a PVC base material layer to the adhesive layer to obtain the easily-removed high-peeling-force adhesive sticker.
Comparative example 2 (comparison with example 5, without addition of rubber latex)
Weighing 205 parts of n-butyl acrylate, 205 parts of isooctyl acrylate, 27.5 parts of methyl methacrylate, 30 parts of styrene, 22.5 parts of hydroxyethyl acrylate, 10 parts of acrylic acid, 6 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, 2 parts of ammonium persulfate, 1 part of a BASF WBA defoaming agent, 1 part of sodium bicarbonate and 490 parts of deionized water.
5.5 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ammonium ether sulfate and 0.9 part of sodium bicarbonate are added into a pre-emulsification kettle, 240 parts of deionized water is added into the pre-emulsification kettle, the mixture is stirred and mixed uniformly, and then 205 parts of n-butyl acrylate, 205 parts of isooctyl acrylate, 27.5 parts of methyl methacrylate, 30 parts of styrene, 22.5 parts of hydroxyethyl acrylate and 10 parts of acrylic acid are weighed and mixed uniformly, added into the pre-emulsification kettle, and stirred and mixed uniformly by a stirrer to obtain the pre-emulsion.
Adding the rest 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, sodium bicarbonate and deionized water into a main reaction kettle, heating while continuously stirring, and adding 2% of prepared pre-emulsion and 1 part of ammonium persulfate after the temperature is raised to 83 ℃; keeping the temperature for 15min, adding the rest pre-emulsion and the rest ammonium persulfate at constant speed, keeping the temperature at 83 ℃ after the addition is finished, continuing stirring for reaction for 2h, cooling to below 40 ℃, adding 1 part of a BASF WBA defoaming agent, and stirring for 30min to obtain the alkene copolymer emulsion.
Sequentially adding 15 parts of dioctyl sodium sulfosuccinate, 4 parts of ammonia water and 8 parts of fumed silica into the vinyl copolymer emulsion, uniformly stirring, and filtering and discharging by using a 300-mesh filter screen to obtain an adhesive; the prepared adhesive is uniformly coated on release paper, and the coating weight is 20g/m2And drying to form an adhesive layer, and then adhering a PVC base material layer to the adhesive layer to obtain the easily-removed high-peeling-force adhesive sticker.
COMPARATIVE EXAMPLE 3 (COMPARATIVE EXAMPLE 5, without fumed silica)
Weighing 205 parts of n-butyl acrylate, 205 parts of isooctyl acrylate, 27.5 parts of methyl methacrylate, 30 parts of styrene, 22.5 parts of hydroxyethyl acrylate, 10 parts of acrylic acid, 6 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, 2 parts of ammonium persulfate, 1 part of a BASF WBA defoaming agent, 1 part of sodium bicarbonate and 490 parts of deionized water.
5.5 parts of 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ammonium ether sulfate and 0.9 part of sodium bicarbonate are added into a pre-emulsification kettle, 240 parts of deionized water is added into the pre-emulsification kettle, the mixture is stirred and mixed uniformly, and then 205 parts of n-butyl acrylate, 205 parts of isooctyl acrylate, 27.5 parts of methyl methacrylate, 30 parts of styrene, 22.5 parts of hydroxyethyl acrylate and 10 parts of acrylic acid are weighed and mixed uniformly, added into the pre-emulsification kettle, and stirred and mixed uniformly by a stirrer to obtain the pre-emulsion.
Adding the rest 1-allyloxy-3- (4-nonylphenol) -2-propanol polyoxyethylene (10) ether ammonium sulfate, sodium bicarbonate and deionized water into a main reaction kettle, heating while continuously stirring, and adding 2% of prepared pre-emulsion and 1 part of ammonium persulfate after the temperature is raised to 83 ℃; keeping the temperature for 15min, adding the rest pre-emulsion and the rest ammonium persulfate at constant speed, keeping the temperature at 83 ℃ after the addition is finished, continuing stirring for reaction for 2h, cooling to below 40 ℃, adding 1 part of a BASF WBA defoaming agent, and stirring for 30min to obtain the alkene copolymer emulsion.
Sequentially adding 15 parts of dioctyl sodium sulfosuccinate and 4 parts of ammonia water into the vinyl copolymer emulsion, uniformly stirring, adding 100 parts of nitrile rubber latex, uniformly stirring, filtering by using a 300-mesh filter screen, and discharging to obtain an adhesive; the prepared adhesive is uniformly coated on release paper, and the coating weight is 20g/m2And drying to form an adhesive layer, and then adhering a PVC base material layer to the adhesive layer to obtain the easily-removed high-peeling-force adhesive sticker.
And (3) performance testing:
the adhesives obtained in examples 1 to 10 and comparative examples 1 to 3 were placed in a constant temperature and humidity environment (22 ℃ to 24 ℃ C., relative humidity 45% to 55%) for at least 24 hours, and then physical properties were measured.
Testing the 180-degree peel strength of the adhesive tape according to the Chinese national standard GB/T2792-1998;
testing the initial adhesive property of the adhesive tape according to the Chinese national standard GB/T4852-1984;
the permanent adhesive performance of the adhesive tape is tested according to the Chinese national standard GB/T8451-1998.
Plasticizer migration resistance test: the adhesive paste was pre-aged in an oven at 70 ℃ for 7 days, and the plasticizer resistance was characterized by peel strength at 180 ℃.
Removability test: and (3) aging the adhesive bonding surface at 65 ℃ for 1 day, 2 days and 3 days respectively, attaching the sample strip to a stainless steel plate, testing the removability in a 180-degree stripping manner, and if the adhesive residue or the adhesive failure occurs, determining that the sample strip is unqualified.
The test results are given in the following table:
Figure BDA0002215963430000131
Figure BDA0002215963430000141
it is true that the above-described embodiments are only preferred embodiments of the present invention, and any other embodiments that do not exceed the scope of the present invention are also included in the present invention.
Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims (10)

1. The adhesive sticker with high peel force and easy removal comprises a PVC base material layer and an adhesive layer, wherein the adhesive layer is prepared from the following raw materials in percentage by weight:
Figure FDA0002215963420000011
2. the easy-to-remove high peel force adhesive sticker according to claim 1, wherein the vinyl copolymer emulsion is prepared from the following raw materials in percentage by weight:
Figure FDA0002215963420000012
3. the easy to remove high peel force adhesive of claim 2 wherein monomer a comprises one or more of n-butyl acrylate, isobutyl acrylate, hexyl acrylate, n-butyl methacrylate, isobutyl methacrylate, isooctyl acrylate, hexyl methacrylate, and 2-ethylhexyl acrylate.
4. The easily removable high peel force adhesive sticker of claim 2, wherein the monomer B comprises one or more of methyl acrylate, styrene, methyl methacrylate, and methyl styrene.
5. The easily removable high peel force adhesive sticker of claim 2, wherein the monomer C comprises one or more of acrylic acid, hydroxyethyl acrylate, methacrylic acid, and hydroxyethyl methacrylate.
6. The easily removable high peel force adhesive sticker of claim 1, wherein the rubber latex comprises one or more of styrene-butadiene rubber latex, natural rubber latex, nitrile-butadiene rubber latex, and neoprene rubber latex.
7. The easy to remove high peel force adhesive sticker of claim 1, where the wetting agent is a surfactant.
8. The easy to remove high peel force adhesive sticker of claim 7, wherein the surfactant of the wetting agent is dioctyl sodium sulfosuccinate.
9. The easy-to-remove high peel force adhesive tape according to any one of claims 1-2, wherein the average particle size of the vinyl copolymer emulsion is 60-500 nm.
10. The preparation method of the easily-removed high-peel-force adhesive sticker is characterized by comprising the following steps of:
step 1: weighing raw materials required for preparing the vinyl copolymer emulsion;
step 2: adding part of emulsifier and part of sodium bicarbonate into a pre-emulsification kettle, adding part of deionized water, stirring and mixing uniformly, then mixing all the monomer A, the monomer B and the monomer C, adding into the pre-emulsification kettle, and stirring and mixing uniformly to obtain a pre-emulsion;
and step 3: adding the rest of emulsifier, sodium bicarbonate and deionized water into the main reaction kettle, heating while continuously stirring, and adding 2% of pre-emulsion and part of ammonium persulfate after the temperature is raised to 83-85 ℃;
and 4, step 4: keeping the temperature for 10-15min, adding the rest of the pre-emulsion and the rest of ammonium persulfate into the main reaction kettle at a constant speed, keeping the temperature at 83-85 ℃ after the addition is finished, continuously stirring for reaction for 1-2h, cooling to below 40 ℃, adding a defoaming agent, and stirring for 10-30min to obtain an alkene copolymer emulsion;
and 5: adding a wetting agent, ammonia water and gas-phase silica into the vinyl copolymer emulsion in sequence, stirring uniformly, adding rubber latex, stirring uniformly, filtering by using a 200-mesh and 300-mesh filter screen, and discharging to obtain an adhesive;
step 6: coating the prepared adhesive on release paper with the coating weight of 17-20g/m2And drying to form an adhesive layer, and then adhering a PVC base material layer to the adhesive layer to obtain the easily-removed high-peeling-force adhesive sticker.
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