CN109575835B - Anti-counterfeiting water-based pressure-sensitive adhesive protective film and preparation method thereof - Google Patents
Anti-counterfeiting water-based pressure-sensitive adhesive protective film and preparation method thereof Download PDFInfo
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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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- 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
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- 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
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- 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
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- 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
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- 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
- C09J7/241—Polyolefin, e.g.rubber
- C09J7/243—Ethylene or propylene polymers
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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
- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- 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
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/338—Applications of adhesives in processes or use of adhesives in the form of films or foils as tamper-evident tape or label
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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
- 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
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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
- 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
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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
- 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
Abstract
The invention discloses an anti-counterfeiting water-based pressure-sensitive adhesive protective film and a preparation method thereof, wherein the anti-counterfeiting water-based pressure-sensitive adhesive protective film comprises the following components in parts by mass: 70-95 parts of soft monomer, 5-20 parts of hard monomer, 2-15 parts of functional monomer, 0.2-2.0 parts of emulsifier, 0.2-1.5 parts of initiator, 0.02-1.2 parts of pH buffer, 0.1-5 parts of luminous assistant and 35-140 parts of deionized water, wherein the preparation method comprises the following steps of S1 and preparation of luminous assistant; s2, preparing emulsion; and S3, preparing the anti-counterfeiting protective film. The formula provided by the invention takes water as a solvent, so that the cost is reduced while the environment is protected; the uniformity and the luminous efficiency of the protective film are good, the anti-counterfeiting protective film can show bright visible light colors only under the irradiation of ultraviolet light, the anti-counterfeiting inspection operation is simple, the cost is low, the repetition is reliable, the concealed anti-counterfeiting purpose is achieved, and the ultraviolet aging resistance of the protective film can be greatly improved.
Description
Technical Field
The invention relates to the technical field of pressure-sensitive adhesive protective films, in particular to an anti-counterfeiting water-based pressure-sensitive adhesive protective film and a preparation method thereof.
Background
With the development of society and the exquisite pursuit of people to product appearance, the application field of protection film is more and more extensive to trend such as diversified varieties, high-quality, product functionalization, customization individuation appears, and its effect is not only play antifouling, prevent functions such as scraping to the outward appearance of protected product, has certain pleasing to the eye, effect such as function assistance more, plays the effect of propaganda and quality promotion for protected product. Therefore, the market demands for various indexes of the protective film are continuously improved, and under the condition of a fierce market competition mechanism, the anti-counterfeiting technology of the protective film is developed to avoid unnecessary loss while the product quality is deeply improved.
The pressure-sensitive adhesive protective film is mainly formed by combining a high-molecular base film (PE, PET, PVC, PP and the like) and a pressure-sensitive adhesive bonding layer, and the pressure-sensitive adhesive bonding layer mostly uses a water-based environment-friendly body due to the requirements on environment protection and performance, and the current pressure-sensitive adhesive protective film is mostly anti-counterfeit by adopting a film surface code-spraying identification mode: and (3) code spraying is carried out on the surface of the base film of the protective film, and the code spraying is input on specific software, so that the authenticity of the section of the protective film can be identified. The anti-counterfeiting mode needs a whole set of digital management system in production, a query party needs a specific identification system, identification codes are discontinuous, and protective films are continuous, namely, each protective film has an anti-counterfeiting identification function, code spraying identification is not applicable to transparent protective films, so that an anti-counterfeiting water-based pressure-sensitive adhesive protective film and a preparation method thereof are designed to solve the problems.
Disclosure of Invention
The invention aims to solve the defects in the prior art and provides an anti-counterfeiting water-based pressure-sensitive adhesive protective film and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the formula of the anti-counterfeiting water-based pressure-sensitive adhesive protective film comprises the following components in parts by mass: 70-95 parts of soft monomer, 5-20 parts of hard monomer, 2-15 parts of functional monomer, 0.2-2.0 parts of emulsifier, 0.2-1.5 parts of initiator, 0.02-1.2 parts of pH buffer, 0.1-5 parts of luminous auxiliary agent and 35-140 parts of deionized water.
Preferably, the soft monomer is selected from one or more of ethyl acrylate, butyl acrylate, isooctyl acrylate and dodecyl acrylate.
Preferably, the hard monomer is selected from one or more of methyl acrylate, methyl methacrylate, butyl methacrylate and vinyl acetate.
Preferably, the functional monomer is selected from one or more of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, glycidyl methacrylate and N-methylol acrylamide.
Preferably, the emulsifier is one or more of an anionic-nonionic emulsifier A501, an anionic emulsifier 2A1, a nonionic emulsifier TX-10, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and allyl polyether sulfate.
Preferably, the initiator is one of potassium persulfate and ammonium persulfate.
Preferably, the PH buffer is one or more of sodium bicarbonate and sodium carbonate.
A preparation method of an anti-counterfeiting water-based pressure-sensitive adhesive protective film comprises the following steps:
s1, preparing a luminescent assistant: adding a compound 3, 5-dimethoxyacyl phenoxyacetic acid methyl ester serving as a ligand and a metal salt according to a certain proportion, simultaneously adding an emulsifier and deionized water, sealing, heating to 120-160 ℃, reacting for 40-60 hours under heat preservation, and then cooling to room temperature within 50-100 hours to prepare a luminous auxiliary agent;
s2, preparation of emulsion: 1) mixing and emulsifying an emulsifier, a soft monomer and a hard monomer for 20-40 min at an emulsifying speed of 600-900 r/min to prepare a pre-emulsion;
2) dissolving a pH buffer by using deionized water, adding 10-30% by mass of the pre-emulsion obtained in the step 1), heating to 70-80 ℃ while stirring, and adding 10-35% by mass of an initiator to prepare a base phase emulsion;
3) adding the luminescent auxiliary agent and the rest of the initiator into the rest of the pre-emulsion, and uniformly stirring at the speed of 50-200 r/min to obtain dropwise added phase emulsion;
4) heating the bottom phase emulsion to 80-85 ℃, starting adding the dropwise addition phase emulsion for 2-4 hours, heating to 85-90 ℃ after finishing dropping, carrying out heat preservation reaction for 1-2 hours, then cooling to 40-50 ℃, adjusting the pH to 7-8 with ammonia water, filtering with 200-300-mesh filter cloth, and discharging to obtain the pressure-sensitive adhesive emulsion;
s3, preparing an anti-counterfeiting protective film: uniformly coating the obtained pressure-sensitive adhesive emulsion on a PE film after corona, then putting the film into an oven, and drying for 3-5 min at the temperature of 90-100 ℃ to obtain the anti-counterfeiting water-based pressure-sensitive adhesive protective film.
Preferably, the metal salt used in S1 is EuCl 3 or TbCl 3.
Compared with the prior art, the invention has the beneficial effects that:
1. the formula provided by the invention takes water as a solvent, so that the cost is reduced while the environment is protected;
2. the invention adopts the method of combining the soft template agent in-situ polymerization with the pre-emulsion semi-continuous polymerization to introduce the luminous auxiliary agent, so that the rare earth luminous auxiliary agent and the macromolecules in the pressure-sensitive adhesive have chemical bonding effect, and the uniformity and the luminous efficiency of the protective film are improved;
3. the anti-counterfeiting protective film prepared by the invention can show bright visible light colors only under the irradiation of ultraviolet light, has simple anti-counterfeiting inspection operation, low cost and repeated reliability, achieves the aim of concealed anti-counterfeiting, and can greatly improve the ultraviolet aging resistance of the protective film.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments.
Example one
The formula of the anti-counterfeiting water-based pressure-sensitive adhesive protective film comprises the following components in parts by mass: 85 parts of soft monomer, 5.2 parts of hard monomer, 6.5 parts of functional monomer, 1.3 parts of emulsifier, 0.35 part of initiator, 0.5 part of PH buffering agent, 2 parts of luminous auxiliary agent and 40 parts of deionized water.
It is worth to say that the soft monomer is a mixture of butyl acrylate and isooctyl acrylate, and the mass ratio of the butyl acrylate to the isooctyl acrylate is 3: 1; the hard monomer is butyl methacrylate: the functional monomer is a mixture of acrylic acid and hydroxypropyl acrylate, and the mass ratio of the acrylic acid to the hydroxypropyl acrylate is 2: 1; the emulsifier is a mixture of CO-436 and a nonionic emulsifier TX-10, and the mass ratio of CO-436 to TX-10 is 6: 1; the initiator is potassium persulfate; the pH buffer is sodium bicarbonate.
A preparation method of an anti-counterfeiting water-based pressure-sensitive adhesive protective film comprises the following steps:
s1, preparing a luminescent assistant: adding 1 part by mass of emulsifier into 100 parts by mass of compound 3, 5-dimethoxyacyl phenoxyacetic acid methyl ester serving as a ligand and 1.5 parts by mass of metal salt EuCl 3 respectively, sealing, heating to 130 ℃, carrying out heat preservation reaction for 60 hours, and then cooling to room temperature within 100 hours to prepare the luminous auxiliary agent;
s2, preparation of emulsion: 1) mixing and emulsifying an emulsifier, a soft monomer and a hard monomer for 20min at an emulsifying speed of 900r/min to prepare a pre-emulsion;
2) dissolving a pH buffer by using deionized water, adding 30% by mass of the pre-emulsion obtained in the step 1), heating to 75 ℃ while stirring, and adding 30% by mass of an initiator to prepare a bottom phase emulsion;
3) adding the luminescent auxiliary agent and the rest of the initiator into the rest of the pre-emulsion, and uniformly stirring at the speed of 90r/min to obtain dropwise added phase emulsion;
4) heating the bottom phase emulsion to 80 ℃, starting to add the dropwise addition phase emulsion for 2 hours, heating to 87 ℃ after the dropwise addition, carrying out heat preservation reaction for 2 hours, then cooling to 40 ℃, adjusting the pH to 8 by using ammonia water, and filtering by using 200-mesh filter cloth to obtain the pressure-sensitive adhesive emulsion;
s3, preparing an anti-counterfeiting protective film: and uniformly coating the obtained pressure-sensitive adhesive emulsion on a transparent PE film with the thickness of 50 mu m after corona by using a No. 50 wire rod, then putting the film into an oven, and drying for 3min at the temperature of 100 ℃ to obtain the anti-counterfeiting water-based pressure-sensitive adhesive protective film.
Example two
The formula of the anti-counterfeiting water-based pressure-sensitive adhesive protective film comprises the following components in parts by mass: 90 parts of soft monomer, 5 parts of hard monomer, 3 parts of functional monomer, 0.35 part of emulsifier, 0.65 part of initiator, 0.5 part of PH buffer, 3 parts of luminous auxiliary agent and 82 parts of deionized water.
It is worth to be noted that the soft monomer is a mixture of ethyl acrylate, butyl acrylate and isooctyl acrylate, and the mass ratio of the ethyl acrylate, the butyl acrylate and the isooctyl acrylate is 1:2: 3; the hard monomer is a mixture of methyl methacrylate and methacrylic acid, and the mass ratio of the methyl methacrylate to the butyl methacrylate is 2.5: 1; the functional monomer is a mixture of methacrylic acid and N-hydroxymethyl acrylamide, and the mass ratio of the methacrylic acid to the N-hydroxymethyl acrylamide is 1: 2; the emulsifier is a mixture of A501 and 2A1, and the mass ratio of A501 to 2A1 is 1: 2; the initiator is ammonium persulfate; the pH buffer is sodium bicarbonate.
S1, preparing a luminescent assistant: adding 1.5 parts by mass of each of 3, 5-dimethoxyacyl phenoxyacetic acid methyl ester and metal salt TbCl 3 and 1.5 parts by mass of emulsifier into 100 parts by mass of deionized water, sealing, heating to 150 ℃, carrying out heat preservation reaction for 60 hours, and then cooling to room temperature within 100 hours to prepare the luminescent additive;
s2, preparation of emulsion: 1) mixing and emulsifying an emulsifier, a soft monomer and a hard monomer for 20min at an emulsifying speed of 900r/min to prepare a pre-emulsion;
2) dissolving a pH buffer by using deionized water, adding 20% by mass of the pre-emulsion obtained in the step 1), heating to 80 ℃ while stirring, and adding 20% by mass of an initiator to prepare a bottom phase emulsion;
3) adding the luminescent auxiliary agent and the rest of the initiator into the rest of the pre-emulsion, and uniformly stirring at the speed of 90r/min to obtain dropwise added phase emulsion;
4) heating the bottom phase emulsion to 85 ℃, starting to add the dropwise addition phase emulsion for 3 hours, heating to 90 ℃ after the dropwise addition, carrying out heat preservation reaction for 3 hours, then cooling to 40 ℃, adjusting the pH to 8 by using ammonia water, and filtering by using 200-mesh filter cloth to obtain the pressure-sensitive adhesive emulsion;
s3, preparing an anti-counterfeiting protective film: and uniformly coating the obtained pressure-sensitive adhesive emulsion on a transparent PE film with the thickness of 50 mu m after corona by using a No. 50 wire rod, then putting the film into an oven, and drying for 3min at the temperature of 100 ℃ to obtain the anti-counterfeiting water-based pressure-sensitive adhesive protective film.
EXAMPLE III
The formula of the anti-counterfeiting water-based pressure-sensitive adhesive protective film comprises the following components in parts by mass: 80 parts of soft monomer, 15 parts of hard monomer, 5 parts of functional monomer, 0.5 part of emulsifier, 0.6 part of initiator, 0.5 part of PH buffer, 4 parts of luminous auxiliary agent and 120 parts of deionized water.
Notably, the soft monomer is isooctyl acrylate; the hard monomer is a mixture of methacrylic acid, methyl methacrylate and butyl methacrylate, and the mass ratio of the methacrylic acid to the methyl methacrylate to the butyl methacrylate is 1:1: 1; the functional monomer is a mixture of hydroxypropyl acrylate, glycidyl methacrylate and acrylic acid, and the mass ratio of the hydroxypropyl acrylate to the glycidyl methacrylate to the acrylic acid is 6:1: 3; the emulsifier is a mixture of sodium dodecyl sulfate and TX-10, and the mass ratio of the sodium dodecyl sulfate to the TX-10 is 9: 1; the initiator is potassium persulfate; the pH buffer is sodium bicarbonate.
S1, preparing a luminescent assistant: adding 1.5 parts by mass of each of methyl 3, 5-dimethoxyacylphenoxyacetate and metal salt EuCl 3 and 1.5 parts by mass of emulsifier into 100 parts by mass of deionized water, sealing, heating to 130 ℃, reacting for 60 hours in a heat preservation manner, and then cooling to room temperature within 100 hours to prepare the luminescent assistant;
s2, preparation of emulsion: 1) mixing and emulsifying an emulsifier, a soft monomer and a hard monomer for 20min at an emulsifying speed of 900r/min to prepare a pre-emulsion;
2) dissolving a pH buffer by using deionized water, adding 30% by mass of the pre-emulsion obtained in the step 1), heating to 80 ℃ while stirring, and adding 30% by mass of an initiator to prepare a bottom phase emulsion;
3) adding the luminescent auxiliary agent and the rest of the initiator into the rest of the pre-emulsion, and uniformly stirring at the speed of 90r/min to obtain dropwise added phase emulsion;
4) heating the bottom phase emulsion to 85 ℃, starting to add the dropwise addition phase emulsion for 2 hours, heating to 90 ℃ after the dropwise addition, carrying out heat preservation reaction for 2 hours, then cooling to 40 ℃, adjusting the pH to 8 by using ammonia water, and filtering by using 200-mesh filter cloth to obtain the pressure-sensitive adhesive emulsion;
s3, preparing an anti-counterfeiting protective film: uniformly coating the corona-treated transparent PE film with the thickness of 50 mu m on a No. 50 wire rod, then putting the film into an oven, and drying for 3min at the temperature of 100 ℃ to obtain the anti-counterfeiting water-based pressure-sensitive adhesive protective film.
Comparative example 1
The preparation and the use of the luminescent assistant are omitted on the basis of the third example, and other steps and the use amount of raw materials are unchanged.
The relevant performance tests were performed on examples one, two, three and comparative example 1.
The solid content is measured according to GB/T11175-2002, the viscosity is measured by a digital display rotational viscometer, the peel strength is measured according to GB/T2792-1998, and the detection results of the above detection items are shown in a performance test result table 1.
Appearance and stability of the emulsion: observing the state and color of the emulsion, filling the emulsion into a transparent bottle, standing for one hour, and observing whether the emulsion is layered, wherein the layering indicates instability.
Anti-counterfeiting time: and (3) placing the prepared protective film in a room at normal temperature for a period of time, and irradiating by using an ultraviolet lamp to see whether the luminous effect still exists, wherein if the luminous effect is weak or even not, the anti-counterfeiting failure is indicated.
Anti-counterfeiting performance: and (3) placing the protective film in an ultraviolet lamp box, observing whether the pressure-sensitive adhesive layer of the protective film has a special luminous phenomenon under the irradiation of an ultraviolet lamp, and if so, indicating that the protective film has an anti-counterfeiting function and recording the luminous color.
Ultraviolet aging resistance: and (3) attaching the protective film on a stainless steel plate, placing the stainless steel plate in an ultraviolet aging box for aging test, wherein the aging condition is that the temperature is 50 ℃ and the humidity is 100 percent until the residual glue phenomenon appears after stripping, and recording the aging time before the residual glue phenomenon appears after the steel plate is stripped.
The detection results of the appearance and stability, the anti-counterfeiting time, the anti-counterfeiting performance and the ultraviolet aging resistance of the emulsion are shown in a performance test result table 2.
Results of the performance testing table 1:
results of the performance tests table 2:
as can be seen from the performance test results shown in Table 1, the addition of the luminescent auxiliary agent has little influence on the basic performances of the pressure-sensitive adhesive emulsion and the pressure-sensitive adhesive.
As can be seen from the performance test results shown in Table 2, the addition of the luminescent auxiliary agent does not affect the appearance and stability of the pressure-sensitive adhesive emulsion, and the ultraviolet aging resistance of the protective film can be greatly improved. The protective film added with the luminous auxiliary agent can emit special bright light under an ultraviolet lamp, has obvious anti-counterfeiting performance, and the performance duration time can exceed the use validity period of the protective film.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A preparation method of an anti-counterfeiting water-based pressure-sensitive adhesive protective film is characterized by comprising the following steps,
s1, preparing the following raw materials in parts by mass: 70-95 parts of soft monomer, 5-20 parts of hard monomer, 2-15 parts of functional monomer, 0.2-2.0 parts of emulsifier, 0.2-1.5 parts of initiator, 0.02-1.2 parts of pH buffer, 0.1-5 parts of luminous auxiliary agent and 35-140 parts of deionized water;
preparation of luminescent aids in S2 and S1: adding a compound 3, 5-dimethoxyacyl phenoxyacetic acid methyl ester serving as a ligand and a metal salt according to a certain proportion, simultaneously adding an emulsifier and deionized water, sealing, heating to 120-160 ℃, reacting for 40-60 hours under heat preservation, and then cooling to room temperature within 50-100 hours to prepare a luminous auxiliary agent;
s3, preparation of emulsion:
1) mixing and emulsifying an emulsifier, a soft monomer and a hard monomer for 20-40 min at an emulsifying speed of 600-900 r/min to prepare a pre-emulsion;
2) dissolving a pH buffer by using deionized water, adding 10-30% by mass of the pre-emulsion obtained in the step 1), heating to 70-80 ℃ while stirring, and adding 10-35% by mass of an initiator to prepare a base phase emulsion;
3) adding the luminescent auxiliary agent and the rest of the initiator into the rest of the pre-emulsion, and uniformly stirring at the speed of 50-200 r/min to obtain dropwise added phase emulsion;
4) heating the bottom phase emulsion to 80-85 ℃, starting adding the dropwise addition phase emulsion for 2-4 hours, heating to 85-90 ℃ after finishing dropping, carrying out heat preservation reaction for 1-2 hours, then cooling to 40-50 ℃, adjusting the pH to 7-8 with ammonia water, filtering with 200-300-mesh filter cloth, and discharging to obtain the pressure-sensitive adhesive emulsion;
s4, preparing an anti-counterfeiting protective film: uniformly coating the obtained pressure-sensitive adhesive emulsion on a PE film after corona, then putting the film into an oven, and drying for 3-5 min at the temperature of 90-100 ℃ to obtain the anti-counterfeiting water-based pressure-sensitive adhesive protective film.
2. The method for preparing the anti-counterfeiting water-based pressure-sensitive adhesive protective film according to claim 1, wherein the metal salt used in S2 is EuCl 3 or TbCl 3.
3. The method for preparing a protective film of an anti-counterfeiting water-based pressure-sensitive adhesive according to claim 1, wherein the soft monomer used in S1 is one or more selected from ethyl acrylate, butyl acrylate, isooctyl acrylate and dodecyl acrylate.
4. The method for preparing a protective film of an anti-counterfeiting water-based pressure-sensitive adhesive according to claim 1, wherein the hard monomer used in S1 is one or more selected from methyl acrylate, methyl methacrylate, butyl methacrylate and vinyl acetate.
5. The method for preparing a protective film of an anti-counterfeiting water-based pressure-sensitive adhesive according to claim 1, wherein the functional monomer used in S1 is one or more selected from acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, glycidyl methacrylate and N-methylol acrylamide.
6. The method for preparing a protective film of an anti-counterfeiting water-based pressure-sensitive adhesive according to claim 1, wherein the emulsifier used in S1 is one or more of anionic-nonionic emulsifier A501, CO-436, anionic emulsifier 2A1, nonionic emulsifier TX-10, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and allyl polyether sulfate.
7. The method for preparing a protective film of an anti-counterfeiting water-based pressure-sensitive adhesive according to claim 1, wherein the initiator used in S1 is one of potassium persulfate and ammonium persulfate.
8. The method for preparing a protective film of an anti-counterfeiting water-based pressure-sensitive adhesive according to claim 1, wherein the pH buffer used in S1 is one or more of sodium bicarbonate and sodium carbonate.
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| CN110642975B (en) * | 2019-09-29 | 2020-10-09 | 江南大学 | Water-based fluorescent polymer resin with shape memory function and preparation method thereof |
| CN111655020A (en) * | 2020-06-15 | 2020-09-11 | 扬州深研新材料科技有限公司 | Light-transmitting electromagnetic shielding film and manufacturing method thereof |
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