CN111117502A - Improved protective film capable of being granulated together with glue and PET (polyethylene terephthalate) base material and manufacturing method thereof - Google Patents
Improved protective film capable of being granulated together with glue and PET (polyethylene terephthalate) base material and manufacturing method thereof Download PDFInfo
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- CN111117502A CN111117502A CN201911364414.1A CN201911364414A CN111117502A CN 111117502 A CN111117502 A CN 111117502A CN 201911364414 A CN201911364414 A CN 201911364414A CN 111117502 A CN111117502 A CN 111117502A
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- saturated polyester
- protective film
- sensitive adhesive
- solubilization
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- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 4
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Images
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
-
- 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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
-
- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a co-granulation type protective film of an improved adhesive and a PET (polyethylene terephthalate) base material and a manufacturing method thereof, the protective film comprises the PET base material, the surface of the corona-treated PET base material is coated with a properly-crosslinked improved saturated polyester pressure-sensitive adhesive coating which is treated by solubilization and graft modification, a release film can be attached to the properly-crosslinked improved saturated polyester pressure-sensitive adhesive coating which is treated by solubilization and graft modification, and the properly-crosslinked improved saturated polyester pressure-sensitive adhesive which is treated by solubilization and graft modification in the properly-crosslinked improved saturated polyester pressure-sensitive adhesive coating which is treated by solubilization and graft modification comprises graft-modified saturated polyester macromolecules, polycaprolactone and polyacrylate components; the pressure-sensitive adhesive prepared by the invention has excellent adhesive property, has good compatibility with the traditional protective film preparation process, can directly extrude and granulate the waste protective film after use to obtain novel plastic particles which can be recycled, and is more convenient for subsequent recycling.
Description
Technical Field
The invention relates to the field of pressure-sensitive adhesive products, in particular to an improved protective film capable of being granulated together with a PET (polyethylene terephthalate) base material and a manufacturing method thereof.
Background
The pressure-sensitive adhesive product can show viscosity without heating or using solvent, and is widely applied to the aspects of die cutting, electronics, medicine, optics, electroplating protection, material processing and the like.
At present, the protective film/adhesive tape is prepared by coating a pressure-sensitive adhesive on a base material with a certain surface free energy, drying, crosslinking and curing, and then performing adhesive layer anti-sticking treatment. The pressure-sensitive adhesive layer used for the protective film/adhesive tape generally consists of PSAs such as poly (meth) acrylates, rubbers, polyurethanes, or silicones, and these pressure-sensitive adhesive layers are usually insoluble and infusible polymers, are chemically stable, and are difficult to remove from the substrate by means of dissolution or the like. After the protective film/adhesive tape is used, the protective film/adhesive tape is usually discarded, and the base material on the protective film/adhesive tape cannot be recycled, so that resources are seriously wasted, and the environment on which human beings rely to live is polluted.
However, with the growing awareness of environmental protection, people pay more and more attention to environment-friendly materials and the recyclability of the materials, and the requirements for resources, markets and environmental protection are higher and higher. The protective film products belong to polymer materials which are difficult to degrade, and some types can exist in natural environment even hundreds of years!
However, due to the limitations of capital, technology and the like, the protective film products in the market at present are not generally used as solid hazardous wastes but are often used as common wastes to be buried, burned or even not effectively treated and mixed in the common social wastes after being used, so that the living space of people is seriously polluted, and the resource waste is also caused.
The common protective film/adhesive tape products comprise base materials such as films and the like in about 80-90% by mass and pressure-sensitive adhesive coatings in about 10-20% by mass, and the stability of the high molecular substances in nature is an important reason for the protective film to become pollutants, particularly the insoluble characteristic of the pressure-sensitive adhesive coatings, so that the treatment is particularly difficult.
The existing methods for treating the protective film generally include the following methods:
1. direct landfill or incineration: the used protective film is directly buried in a refuse disposal landfill or is subjected to incineration disposal, and the disposal method can actually pollute underground water or atmospheric environment;
2. as solid hazardous waste, please have professional institutions for processing qualification: the treatment cost is high, the price per ton of treatment cost is 4000 yuan to 5000 yuan, the storage and transportation conditions are harsh, and common enterprises are difficult to bear;
3. removing the glue layer by using a solvent: soaking the preliminarily cleaned protective film in an organic solvent with a certain toxic action, removing the pressure-sensitive adhesive coating of the protective film by a mechanical method after the pressure-sensitive adhesive coating is dissolved or swelled in the organic solvent such as ethyl acetate, toluene and the like to obtain a relatively pure base material, and recycling the base material. The disadvantages of this treatment are: because of using organic solvent, there are fire-fighting safety and occupational health potential safety hazards; the high price of the organic solvent causes unreasonable economy, and the used organic solvent also has the problem of treatment. In addition, the functional coating of the protective film is a crosslinked pressure-sensitive adhesive which is difficult to effectively dissolve in an organic solvent, so that the treated base material still has adhesive seriously and is not beneficial to the subsequent recycling;
4. chemical sol: the protective film which is preliminarily cleaned is reacted with strong alkaline solution such as NaOH under the conditions of high temperature, pressure and long time so as to achieve the purpose of dissolving the pressure-sensitive adhesive coating. The treatment method has the defects that the selectivity is poor, only the protective film of the poly (methyl) acrylate coating can be treated, and the poly (methyl) acrylate coating uses a large amount of acrylate monomers with long-chain side groups, so that the problems of high hydrolysis temperature, harsh alkali dissolution conditions, long reaction time, high energy consumption, more generated sewage, damaged film base materials and the like exist, and the treatment effect of the protective films of other types of coatings is poor.
5. The method for adding the foaming agent in the adhesive comprises the following steps: the method comprises the steps of adding a foaming agent with a certain foaming temperature into the pressure-sensitive adhesive, treating the used protective film at a certain temperature after the protective film is used, foaming the foaming agent in the pressure-sensitive adhesive, and enabling the pressure-sensitive adhesive coating to be disintegrated and fall off from a base material, so that the aim of recycling the base material can be fulfilled. The method has specific use conditions, mainly because the glass transition temperature point of the pressure-sensitive adhesive is very low (about-20 ℃ to-70 ℃), the pressure-sensitive adhesive coating is in a viscous state under the foaming temperature condition of the foaming agent, gaseous substances formed by the foaming agent at the beginning of foaming rapidly penetrate through the pressure-sensitive adhesive coating and overflow, the foaming condition of the foaming agent cannot be met at all, the foamed pressure-sensitive adhesive coating cannot be obtained, and the purpose of disintegrating and falling off the pressure-sensitive adhesive coating from a base material through the foaming effect cannot be achieved. Therefore, only microcapsule type foaming agent can be added by adding foaming agent into the rubber layer. The defect that the protective film base material is recycled by adopting the microcapsule foaming agent is obvious, namely the microcapsule foaming agent is expensive and has poor economy; secondly, the average particle size of the microcapsule foaming agent generally exceeds 20 μm, so that the microcapsule foaming agent is difficult to be used on a protective film with the glue thickness of less than 20 μm; moreover, after the microcapsule foaming agent is foamed, the pressure-sensitive adhesive coating cannot be guaranteed to fall off from the base material completely, and the effective recovery of the base material of the protective film cannot be met;
6. direct mixing granulation recovery method: cutting the protective film which is cleaned preliminarily, and directly granulating the protective film containing the pressure-sensitive adhesive coating by a coextrusion method in a molten state to prepare plastic particles with certain physical properties for recycling. The method is characterized in that the selectivity of the adhesive is too narrow. Because of the chemical components and chemical structures of the base material and the pressure-sensitive adhesive coating, the coextrusion granulation can be carried out only on the base material adopting polyolefin and the protective film coated with the polyolefin adhesives such as SBR, EVA and the like, and the mechanical property of the produced particles is poor.
The PET polyester film has the advantages of good mechanical property, good temperature resistance, outstanding optical property and electrical property and the like, and is cheap, thereby being the base material of the protective film/adhesive tape which is most widely used at present. However, in view of the great difference between the chemical composition, molecular structure, molecular weight, modulus, melt index, surface free energy and solubility parameters of PET and various pressure-sensitive adhesives, various protective films/adhesive tapes using PET as a base material are difficult to recycle by a co-extrusion granulation method, so how to solve the compatibility problem of the PET and the pressure-sensitive adhesive coating coated thereon during extrusion granulation is a key to the production and research and development of the co-granulation type protective film of the PET base material.
The polyester pressure-sensitive polymer material can effectively solve the problem of polymer compatibility of an adhesive coating and a PET (polyethylene terephthalate) base material in the co-extrusion granulation process, but the polyester pressure-sensitive polymer material has few types and high glass transition temperature (Tg), and is difficult to meet the use requirement of a conventional protective film/adhesive tape, such as ETERKYD5016-TS-52 type thermoplastic saturated copolymerization high molecular weight polyester resin produced by Changxing chemistry (ETERNAL MATERIALS Co., LTD), wherein the Tg of the polyester resin is 17 ℃, the initial adhesion of a protective film made of the polyester polymer is very small, the adhesion requirement of the protective film/adhesive tape is basically difficult to meet, and the polyester pressure-sensitive polymer material is generally used for coating of a bonding adhesive or a metal baking paint.
Although the disadvantage of high glass transition temperature point of polyester pressure-sensitive polymer materials can be partially solved by grafting monomers with low glass transition temperature point, the stability problem caused by self-phase separation of the adhesive is very easy to occur under the condition that the grafting efficiency of the polymer materials is generally very low and the using amount of the low Tg monomer is more, so that the use of the graft modified polyester pressure-sensitive adhesive is limited.
At present, the annual production volume of the protective film/adhesive tape in mainland areas of China is in the order of billions of square meters, so that an improved protective film which can be co-granulated by adhesive and PET base material and a manufacturing method thereof are needed to be found urgently in the aspects of environmental protection and resource recycling.
Disclosure of Invention
The invention aims to provide an improved protective film capable of co-granulating a glue and a PET (polyethylene terephthalate) base material and a manufacturing method thereof, the prepared pressure-sensitive adhesive has excellent bonding performance and good compatibility with the traditional protective film preparation process, and after the protective film is used, the waste protective film can be directly extruded and granulated to obtain novel plastic particles capable of being recycled, so that the subsequent recycling is more convenient.
The purpose of the invention can be realized by the following technical scheme:
the utility model provides a but improved generation glue and PET substrate pelletization type protection film altogether, includes the PET substrate, PET substrate surface corona treatment, corona treatment PET substrate surface coating has the properly crosslinked improved generation saturated polyester pressure sensitive adhesive coating through solubilization and graft modification treatment, can laminate on the properly crosslinked improved generation saturated polyester pressure sensitive adhesive coating through solubilization and graft modification treatment and have from the type membrane.
As a further scheme of the invention: the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and graft modification treatment in the moderately crosslinked improved saturated polyester pressure-sensitive adhesive coating subjected to solubilization and graft modification treatment comprises graft-modified saturated polyester macromolecules, polycaprolactone and polyacrylate components, and the moderately crosslinked improved saturated polyester pressure-sensitive adhesive coating subjected to solubilization and graft modification treatment comprises the following components in percentage by weight: 40-60% of saturated polyester polymer resin, 40-60% of polycaprolactone and 20-5% of polyacrylate.
As a further scheme of the invention: the saturated polyester polymer subjected to graft modification in the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and graft modification treatment is a linear saturated polyester polymer with a terminal hydroxyl group and/or a terminal carboxyl group, the glass transition temperature Tg of the linear saturated polyester polymer is 0 +/-20 ℃, and the molecular weight Mn of the linear saturated polyester polymer is between 15000 and 45000.
As a further scheme of the invention: the polycaprolactone in the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and graft modification is polycaprolactone which is polymerized in a xylene solvent and is terminated by hydroxyl and/or carboxyl.
As a further scheme of the invention: the polycaprolactone uses at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate as an end-capping reagent, and the amount of the end-capping reagent is 0.5-5% of the mass of the caprolactone.
As a further scheme of the invention, the mass percentages of the monomers of the polyacrylate are 1-10% of acrylic acid, 0-90% of butyl acrylate, 0-90% of isooctyl acrylate and 1-10% of acrylic acid- β -hydroxyethyl ester.
A method for manufacturing an improved adhesive and PET substrate co-pelletizable protective film is characterized in that: the method comprises the following steps:
the method comprises the following steps: preparing a monomer mixed solution;
step two: preparing an initiator solution, an initiator dropping liquid and an initiator supplementing liquid;
step three: preparing a terminated polycaprolactone polymer solution in xylene;
step four: the preparation method comprises the following steps of (1) carrying out free radical polymerization-grafting on terminated polycaprolactone macromolecules, saturated polyester resin macromolecules, an initiator solution, a monomer mixed solution and an initiator supplementing liquid in an organic solvent to obtain the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment;
step five: preparing a coating liquid from the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment, a solvent, a plasticizer and a crosslinking agent;
step six: coating the coating liquid on the surface of the PET substrate subjected to corona treatment, drying and curing to obtain a moderately cross-linked improved saturated polyester pressure-sensitive adhesive coating subjected to solubilization and graft modification;
step seven: and attaching a release film to the moderately-crosslinked improved saturated polyester pressure-sensitive adhesive coating subjected to solubilization and graft modification, and performing post-curing treatment to obtain the co-pelletizable protective film of the improved adhesive and the PET substrate.
As a further scheme of the invention: the first step also comprises the steps of uniformly mixing accurately metered caprolactone, at least one of acrylic acid and hydroxyethyl acrylate and xylene, heating the solution to over 135 ℃, adding a catalyst for polymerization to obtain an end-capped polycaprolactone xylene solution, wherein the reaction temperature is between 135 ℃ and 160 ℃, and the polymerization time is not less than 240 minutes.
And as a further scheme of the invention, the second step also comprises uniformly mixing at least one of accurately metered acrylic acid and methacrylic acid, at least one of acrylic acid- β -hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate, and at least one of monomers of butyl acrylate, isooctyl acrylate and isooctyl methacrylate, and further optimized to be acrylic acid, acrylic acid- β -hydroxyethyl acrylate and isooctyl acrylate, adding 55-65% of a specified amount of solvent into the monomer mixed solution, and uniformly stirring to obtain the monomer mixed solution.
As a further scheme of the invention: and step three, accurately weighing the initiator according to the calculated amount, stirring and dissolving the initiator completely by using toluene with the mass more than 10 times that of the initiator, standing for more than 60 minutes, separating impurities in the solution after the impurities in the initiator solution are completely precipitated, and taking supernate to prepare the initiator solution, initiator dropping liquid and initiator supplementing liquid.
As a further scheme of the invention: adding the refined initiator solution into the monomer mixed solution, and continuously stirring to obtain a monomer dropping liquid; adding a specified amount of 30% of solvent, all saturated polyester resin and all terminated polycaprolactone xylene solution into a reaction kettle, and heating to reflux and stabilize for 10 minutes or more under the nitrogen-introducing protective atmosphere; dropwise adding monomer dropwise adding liquid into the reaction kettle, and controlling the dropwise adding time to be 180 minutes; washing the dripping tank and the pipeline by using a 10 percent specified amount of solvent; controlling the reaction temperature in the reaction kettle between 75 and 95 ℃, controlling the stability of reflux to prevent material flushing or implosion, continuously carrying out reflux heat preservation for 60 minutes under the condition of nitrogen introduction protection, supplementing initiator supplementing liquid, and continuously reacting for 60 minutes or more; after the heat preservation is finished, adding a catalyst for carrying out hydroxyl and carboxyl interactive condensation to further improve the grafting effect; the condensation reaction time is not less than 60 minutes, and the condensation reaction temperature is between 75 and 95 ℃.
As a further scheme of the invention: cooling the reaction materials, continuously stirring and cooling to below 40 ℃, closing nitrogen protection, filtering and discharging the materials into a charging basket, and hermetically storing to obtain the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment; weighing a specified amount of the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment, a solvent, a plasticizer and a crosslinking agent, and preparing a coating liquid.
As a further scheme of the invention: the drying and curing time is more than 48h, and the drying and curing temperature is 45-60 ℃.
The invention has the beneficial effects that: the preparation method is simple and easy to implement, and the prepared pressure-sensitive adhesive has excellent adhesive property; compared with the traditional protective film preparation process, the preparation method has good bearing performance, can directly extrude and granulate the waste protective film after use to obtain the novel plastic particles which can be recycled, is more convenient for subsequent recycling, and because the saturated polyester pressure-sensitive adhesive which is solubilized and grafted and modified in an organic phase is used, the glass transition temperature point of the pressure-sensitive adhesive is lower, and more functional groups can be used for crosslinking, so that the pressure-sensitive adhesive coating has good initial adhesion, excellent cohesion, good cohesive property, high retention force, good temperature resistance, better mechanical property and better resistance to the influence of environmental moisture, can be used as protective film and adhesive tape for manufacturing process and shipment protection, the PET substrate co-granulation type protective film can be directly extruded and granulated by an extruder after being used, thereby achieving the effect of changing waste into valuable and realizing the win-win purpose of economic benefit and social environmental benefit.
Drawings
In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.
FIG. 1 is a schematic view of a single-sided protective film structure according to the present invention;
FIG. 2 is a schematic view of a double-sided protective film according to the present invention;
in the figure: 1. a PET substrate; 2. a moderately cross-linked improved saturated polyester pressure-sensitive adhesive coating which is treated by solubilization and graft modification; 3. and (4) a release film.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in FIGS. 1-2, the title of the present invention is an improved protective film capable of co-granulating with PET substrate and its manufacturing method:
an improved adhesive and PET substrate co-granulable protective film comprises a PET substrate 1, wherein the surface of the PET substrate 1 is subjected to corona treatment, the surface of the corona-treated PET substrate 1 is coated with a moderately-crosslinked improved saturated polyester pressure-sensitive adhesive coating 2 subjected to solubilization and graft modification treatment, and a release film 3 can be attached to the moderately-crosslinked improved saturated polyester pressure-sensitive adhesive coating 2 subjected to solubilization and graft modification treatment;
the modified saturated polyester pressure-sensitive adhesive coating 2 and the release film 3 which are moderately crosslinked and subjected to solubilization and graft modification treatment are sequentially stacked on one side of the PET substrate 1 to form a single-sided protective film, or the modified saturated polyester pressure-sensitive adhesive coating 2 and the release film 3 which are moderately crosslinked and subjected to solubilization and graft modification treatment are sequentially stacked on two sides of the PET substrate 1 to form a double-sided protective film;
the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and graft modification treatment in the moderately crosslinked improved saturated polyester pressure-sensitive adhesive coating 2 subjected to solubilization and graft modification treatment comprises graft-modified saturated polyester macromolecules, polycaprolactone and polyacrylate components, and the moderately crosslinked improved saturated polyester pressure-sensitive adhesive coating 2 subjected to solubilization and graft modification treatment comprises the following components in percentage by weight: 40-60% of saturated polyester polymer resin, 40-60% of polycaprolactone and 20-5% of polyacrylate;
the saturated polyester polymer subjected to graft modification in the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and graft modification treatment is a linear saturated polyester polymer with a terminal hydroxyl group and/or a terminal carboxyl group, the glass transition temperature point Tg of the linear saturated polyester polymer is 0 +/-20 ℃, and the molecular weight Mn of the linear saturated polyester polymer is between 15000-45000;
polycaprolactone in the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and graft modification is polycaprolactone which is polymerized in a xylene solvent and is terminated by hydroxyl and/or carboxyl;
the polycaprolactone uses at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate as a blocking agent, and the amount of the blocking agent is 0.5-5% of the mass of the caprolactone;
the mass percentage of the monomers of the polyacrylate is 1-10 percent of acrylic acid, 0-90 percent of butyl acrylate, 0-90 percent of isooctyl acrylate and 1-10 percent of acrylic acid- β -hydroxyethyl ester.
A method for manufacturing an improved protective film capable of being co-granulated with a PET (polyethylene terephthalate) base material comprises the following steps:
the method comprises the following steps: preparing a monomer mixed solution;
uniformly mixing accurately metered caprolactone, at least one of acrylic acid and hydroxyethyl acrylate and xylene, heating the solution to over 135 ℃, adding a catalyst for polymerization to obtain an end-capped polycaprolactone xylene solution, wherein the reaction temperature is between 135 ℃ and 160 ℃, and the polymerization time is not less than 240 minutes;
step two: preparing an initiator solution, an initiator dropping liquid and an initiator supplementing liquid;
at least one of acrylic acid and methacrylic acid, at least one of acrylic acid- β -hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate, and at least one of butyl acrylate, isooctyl acrylate and isooctyl methacrylate, which are accurately metered, are further optimized to be acrylic acid, acrylic acid- β -hydroxyethyl acrylate and isooctyl acrylate, are mixed uniformly together, 55-65% of a specified amount of solvent is added into the monomer mixed solution, and the monomer mixed solution is obtained after uniform stirring;
step three: preparing a terminated polycaprolactone polymer solution in xylene;
accurately weighing the initiator according to the calculated amount, stirring and dissolving the initiator completely by using toluene with the mass more than 10 times that of the initiator, standing for more than 60 minutes, separating impurities in the solution after the impurities in the initiator solution are completely precipitated, and taking supernate to prepare an initiator solution, initiator dropping liquid and initiator supplementing liquid;
adding the refined initiator solution into the monomer mixed solution, and continuously stirring to obtain a monomer dropping liquid; adding a specified amount of 30% of solvent, all saturated polyester resin and all terminated polycaprolactone xylene solution into a reaction kettle, and heating to reflux and stabilize for 10 minutes or more under the nitrogen-introducing protective atmosphere; dropwise adding monomer dropwise adding liquid into the reaction kettle, and controlling the dropwise adding time to be 180 minutes; washing the dripping tank and the pipeline by using a 10 percent specified amount of solvent; controlling the reaction temperature in the reaction kettle between 75 and 95 ℃, controlling the stability of reflux to prevent material flushing or implosion, continuously carrying out reflux heat preservation for 60 minutes under the condition of nitrogen introduction protection, supplementing initiator supplementing liquid, and continuously reacting for 60 minutes or more; after the heat preservation is finished, adding a catalyst for carrying out hydroxyl and carboxyl interactive condensation to further improve the grafting effect; the condensation reaction time is not less than 60 minutes, and the condensation reaction temperature is between 75 and 95 ℃;
step four: the preparation method comprises the following steps of (1) carrying out free radical polymerization-grafting on terminated polycaprolactone macromolecules, saturated polyester resin macromolecules, an initiator solution, a monomer mixed solution and an initiator supplementing liquid in an organic solvent to obtain the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment;
cooling the reaction materials, continuously stirring and cooling to below 40 ℃, closing nitrogen protection, filtering and discharging the materials into a charging basket, and hermetically storing the materials to obtain the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment; weighing a specified amount of the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment, a solvent, a plasticizer and a crosslinking agent, and preparing a coating liquid;
step five: preparing a coating liquid from the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment, a solvent, a plasticizer and a crosslinking agent;
step six: coating the coating liquid on the surface of the PET substrate 1 subjected to corona treatment, drying and curing to form a moderately cross-linked improved saturated polyester pressure-sensitive adhesive coating subjected to solubilization and graft modification;
the drying and curing time is more than 48h, and the drying and curing temperature is 45-60 ℃;
step seven: attaching a release film 3 on a moderately cross-linked improved saturated polyester pressure-sensitive adhesive coating subjected to solubilization and graft modification, and performing post-curing treatment to obtain a co-pelletizable protective film of the improved adhesive and a PET (polyethylene terephthalate) substrate;
specifically, the method comprises the following steps:
A. chemical synthesis of the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment:
a. uniformly mixing a specified amount of caprolactone monomer, acrylic acid, hydroxyethyl acrylate and xylene in a reaction kettle, heating to a specified temperature, adding a polymerization catalyst for polymerization, wherein the polymerization temperature is 135-;
b. putting a specified amount of saturated polyester polymer and 30% of solvent into a reaction kettle, heating to raise the temperature until the reflux is stable for more than 15 minutes;
c. uniformly mixing at least one of acrylic acid and methacrylic acid, at least one of butyl acrylate, isooctyl acrylate and isooctyl methacrylate, at least one of 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate with specified mass, adding 60 percent of specified solvent into the mixed solution, and uniformly stirring to obtain a monomer mixed solution for later use;
d. accurately weighing the initiator according to the calculated amount, stirring and dissolving the initiator completely by using toluene with the mass more than 10 times that of the initiator, standing for more than 30 minutes, separating the water in the solution after the water in the toluene solution of the initiator is completely precipitated, and taking supernatant to obtain an initiator solution, initiator dropping liquid and initiator supplementing liquid;
e. adding the refined initiator solution into the monomer mixed solution, and continuously stirring to obtain a monomer dropping liquid;
f. dripping an initiator solution into the reaction kettle, after the initial initiation, dripping monomer dripping liquid into the reaction kettle, and controlling the dripping time to be 170 and 190 minutes to finish the dripping;
g. washing the dripping tank and the pipeline by using a 10 percent specified amount of solvent;
h. controlling the reaction temperature in the reaction kettle between 85 ℃ and 95 ℃, controlling the stability of reflux to prevent material flushing or implosion, continuously carrying out reflux heat preservation for 60 minutes under the condition of nitrogen introduction protection, then dropwise adding an initiator supplementing liquid, and continuously carrying out heat preservation for 60 minutes or more;
i. adding a specified amount of hydroxyl and carboxyl condensation catalyst under the stirring state, and carrying out grafting reaction between carboxyl and hydroxyl under the reaction condition of 85-95 ℃, wherein the grafting reaction time is not less than 60 minutes;
j. cooling to 40 ℃, closing nitrogen protection, discharging into a charging bucket, and hermetically storing to obtain the grafting improved saturated polyester pressure-sensitive adhesive;
B. preparation and coating of the improved saturated polyester pressure-sensitive adhesive coating liquid subjected to solubilization and grafting treatment:
a. weighing a specified amount of the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment, a solvent, a crosslinking agent and a plasticizer for later use;
b. adding the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment into a solvent in a stirring state, uniformly stirring, then respectively adding diluted plasticizer diluent and curing agent diluent into the adhesive solution in a stirring state, and continuously and uniformly stirring to obtain an improved saturated polyester pressure-sensitive adhesive coating liquid subjected to solubilization and grafting treatment;
c. coating the improved saturated polyester pressure-sensitive adhesive coating liquid subjected to solubilization and grafting treatment on the corona surface of the PET substrate 1 by using a multifunctional coating machine, controlling the highest drying temperature to be 130-140 ℃, attaching an anti-sticking release film 3 to a winding station, and performing post-curing treatment to obtain the co-granulation type protective film of the improved adhesive and the PET substrate;
C. the improved glue and PET base material can be used for recycling and granulating the granulating protective film:
a. cutting the used improved glue and the PET substrate co-pelletizable protective film into 25-30mm, and extruding the used PET substrate co-pelletizable protective film into strip-shaped solution through screw extrusion pelletizing equipment;
b. the strip-shaped solution is cooled by water, dried by air and cut to obtain brand new plastic particles;
c. the prepared brand-new plastic particles can be sold or used continuously.
Example 1
A method for manufacturing an improved protective film capable of being co-granulated by glue and a PET (polyethylene terephthalate) base material comprises the following steps:
A. chemical synthesis of the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment:
firstly, polymerization of a compatilizer:
1) uniformly mixing 90Kg of caprolactone monomer, 3.0Kg of acrylic acid, 3.0Kg of hydroxyethyl acrylate and 60Kg of xylene which are accurately measured in a reaction kettle, heating to 140-150 ℃, and stabilizing the reflux for more than 10 minutes;
2) dissolving 0.50Kg of stannous octoate by using 10Kg of dimethylbenzene and dripping the solution into a reaction kettle within 10 minutes; respectively washing a preparation container and a dropping tank of stannous octoate twice with 10Kg of dimethylbenzene, and converging washing liquid into a reaction kettle;
3) continuously keeping the temperature at 140-150 ℃ to stabilize the reflux for more than 15 minutes;
4) the polymerization time is not less than 240 minutes; preparing a solubilizer solution;
secondly, synthesizing the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment:
1) respectively weighing 185Kg of toluene together with 70Kg, 15Kg, 10Kg, 50Kg, 10Kg and 10Kg of toluene for later use;
2) accurately measured 300Kg of ETERKYD5016-TS-52 type thermoplastic saturated copolymerization high molecular weight polyester resin solution containing 52 +/-2 percent of solid and 70Kg of toluene are added into a reaction kettle to be uniformly stirred and dissolved with the solubilizer solution, then the temperature is increased to between 88 and 95 ℃, and the reflux is kept stable for 15 minutes or more;
3) stirring and dissolving 1000g of BPO containing 20% of water in 15Kg of toluene, standing for more than 60 minutes, removing water precipitated at the bottom of liquid after the solution becomes clear and transparent to obtain an initiator dropping liquid, stirring and dissolving 1000g of BPO containing 20% of water in 10Kg of toluene, standing for more than 60 minutes, removing water precipitated at the bottom of liquid after the solution becomes clear and transparent to obtain a monomer initiator solution, stirring and dissolving 800g of BPO containing 20% of water in 10Kg of toluene, standing for more than 60 minutes, removing water precipitated at the bottom of liquid after the solution becomes clear and transparent to obtain an initiator supplementing solution;
4) uniformly mixing 21.6Kg of isooctyl acrylate, 2.7Kg of acrylic acid and 2.7Kg of hydroxyethyl acrylate which are accurately measured in a stainless steel container, and adding a monomer initiator solution to obtain a monomer dropping liquid;
5) dripping initiator within 10 minutes into the reaction kettle, controlling the reaction temperature at 88-95 ℃ and reacting for 20-30 minutes;
6) uniformly dropwise adding monomer dropping liquid into the reaction kettle, wherein the dropping time is 180 minutes;
7) after the dropwise addition is finished, the initiator supplementing liquid is dropwise added within 10 minutes after the reaction is carried out for 60 minutes, and the reaction is continuously carried out for more than 60 minutes at the temperature of 88-95 ℃;
8) dissolving 0.68Kg of grafting catalyst stannous octoate in 10Kg of toluene to obtain a catalyst solution; adding the catalyst solution into a reaction kettle, washing the dropping tank and the related pipelines for 2 times by respectively using 10Kg of toluene, and uniformly placing the washing liquid into the reaction kettle within 5-10 minutes;
9) keeping the temperature between 88 and 95 ℃, and continuing the reaction for 60 minutes or more to complete the grafting reaction;
10) cooling the reaction kettle to 35-45 ℃, closing nitrogen protection, and stopping stirring;
11) filtering and discharging the materials into a barrel, and hermetically storing the materials to obtain a solubilized grafting improved saturated polyester pressure-sensitive adhesive with solid content of 40%;
B. preparation of the improved saturated polyester pressure-sensitive adhesive coating liquid subjected to solubilization and grafting treatment:
1) stirring and dissolving 5KgCymel303 type methyl etherified melamine resin with 10Kg of ethyl acetate uniformly to obtain a cross-linking agent diluent;
2) slowly adding 50Kg of improved saturated polyester pressure-sensitive adhesive subjected to grafting treatment by a solubilizer into 25Kg of ethyl acetate under the stirring state, and continuously stirring for more than 30 minutes to obtain a glue diluent;
3) respectively adding crosslinking agent diluent and 875g of tributyl citrate into the glue diluent under the stirring state, and continuously stirring for more than 30 minutes to obtain the improved saturated polyester pressure-sensitive adhesive coating liquid subjected to solubilization and grafting treatment;
C. coating of the improved saturated polyester pressure-sensitive adhesive coating:
coating the prepared improved saturated polyester pressure-sensitive adhesive coating liquid subjected to solubilization and grafting treatment on the corona surface of the PET substrate 1 by using a multifunctional coating machine, wherein the corona value is not lower than 52mN/m, the thickness of the coated dry adhesive is controlled to be 10 micrometers, the time of the protective film passing through a 135 ℃ oven drying section is controlled to be not lower than 1 minute, and an anti-sticking release film 3 is attached to a winding station, so that the improved co-pelletizable protective film which takes PET as the substrate and is subjected to solubilization and grafting treatment is prepared. The coated protective film can achieve stable viscosity and meet the use requirements of customers after post-curing treatment at 55 ℃ for not less than 48 hours.
D. Re-granulation test of the improved adhesive and PET base material co-granulation type protective film:
1) simply sorting the improved glue to be re-granulated and recycled after use and the PET substrate pelletizable protective film together to remove other types of materials;
2) cutting the protective film to be recovered and granulated into a specification with a proper size according to the feeding size of the screw extrusion granulator;
3) setting parameters such as screw rotating speed, temperature of an extruder and the like, and granulating and recovering;
4) cutting the extruded molten material strip into plastic particles with the specification after water cooling and air cooling, wherein the particles are light yellow;
the recovered novel plastic particles can be used for further processing or sale.
The basic properties of the improved adhesive and PET substrate co-pelletizable protective film prepared in example 1 are shown in Table 1
The basic performance of the improved adhesive and the PET substrate co-pelletizable protective film in the embodiment 1 can meet the use requirement of the protective film, the manufactured particles are light yellow, the surface is smooth, the mechanical strength is high, the polyester and adhesive are good in compatibility, the processing technologies such as injection molding, extrusion molding and blow molding can be met, the improved adhesive can be used as new PET for blending, fibers and the like, and the recycling requirement is met.
Example 2
A method for manufacturing an improved protective film capable of being co-granulated by glue and a PET (polyethylene terephthalate) base material comprises the following steps:
A. preparation of the improved saturated polyester pressure-sensitive adhesive coating liquid subjected to solubilization and grafting treatment:
1) stirring and dissolving 6KgCymel303 type methyl etherified melamine resin with 10Kg of ethyl acetate uniformly to obtain a cross-linking agent diluent;
2) slowly adding 40Kg of the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and graft modification into 24Kg of ethyl acetate under the stirring state, and continuously stirring for more than 30 minutes to obtain an adhesive diluent;
3) respectively adding the cross-linking agent diluent and 700g of tributyl citrate into the glue diluent under the stirring state, and continuously stirring for more than 30 minutes to obtain the improved saturated polyester pressure-sensitive adhesive coating liquid subjected to solubilization and grafting treatment;
B. coating of the improved saturated polyester pressure-sensitive adhesive coating:
coating the prepared solubilizing and grafting improved saturated polyester pressure-sensitive adhesive coating liquid on the corona surface of a PET (polyethylene terephthalate) substrate 1 by using a multifunctional coating machine, wherein the corona value is not lower than 52mN/m, the thickness of a coated dry adhesive is controlled to be 10 micrometers, the time of the protective film passing through a 135 ℃ oven drying section is controlled to be not less than 1 minute, and an anti-sticking release film 3 is attached to a winding station to prepare a co-pelletizable protective film taking PET as the substrate, wherein the coated protective film can reach stable viscosity and meet the use requirements of customers only after post-curing treatment at 55 ℃ for not less than 48 hours;
C. re-granulation test of the improved adhesive and PET base material co-granulation type protective film:
1) simply sorting the PET base material to be re-granulated and recycled after use to obtain a granulation type protective film, and removing other types of materials;
2) cutting the protective film to be recovered and granulated into a specification with a proper size according to the feeding size of the screw extrusion granulator;
3) setting parameters such as screw rotating speed, temperature of an extruder and the like, and granulating and recovering;
4) cutting the extruded molten material strip into plastic particles with the specification after water cooling and air cooling, wherein the particles are light yellow; the recovered novel plastic particles can be used for further processing or sale;
the basic properties of the improved adhesive prepared in example 2 and the co-pelletizable protective film of PET substrate are shown in Table 2
TABLE 2 basic Properties of Copelletizable protective films of improved adhesive and PET substrate
It can be seen that the basic performance of the improved adhesive and the PET substrate co-pelletizable protective film in example 2 can meet the use requirements of the protective film, the manufactured particles are light yellow, the surface is smooth, the mechanical strength is high, the compatibility of the polyester and the adhesive is good, the processing technologies such as injection molding, extrusion molding and blow molding can be met, the improved adhesive can be used as new PET for blending, fiber and the like, and the recycling requirements are met.
Example 3
A method for manufacturing an improved adhesive and PET substrate co-pelletizable double-sided protective film comprises the following steps:
A. preparation of the improved saturated polyester pressure-sensitive adhesive coating liquid subjected to solubilization and grafting treatment:
1) stirring and dissolving 10Kg of cymel303 type methyl etherified melamine resin with 10Kg of ethyl acetate uniformly to obtain a cross-linking agent diluent;
2) slowly adding 50Kg of improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment into 40Kg of ethyl acetate under the stirring state, and continuously stirring for more than 30 minutes to obtain a glue diluent;
3) respectively adding crosslinking agent diluent and 875g of tributyl citrate into the glue diluent under the stirring state, and continuously stirring for more than 30 minutes to obtain the improved saturated polyester pressure-sensitive adhesive coating liquid subjected to solubilization and grafting treatment;
B. coating of the improved saturated polyester pressure-sensitive adhesive coating:
coating the prepared improved saturated polyester pressure-sensitive adhesive coating liquid subjected to solubilization and grafting treatment on the corona surface of a PET (polyethylene terephthalate) substrate 1 by using a multifunctional coating machine, wherein the corona value is not lower than 52mN/m, the thickness of a coated dry adhesive is controlled to be 10 micrometers, the time of the protective film passing through a 135 ℃ oven drying section is controlled to be not lower than 1 minute, an anti-sticking release film 3 is attached to a winding station, the other surface of the PET substrate 1 is repeatedly coated, so that the improved co-pelletizable double-sided protective film taking PET as the substrate is prepared, and the viscosity of the coated protective film can be stable and the use requirement of a client can be met only after post-curing treatment at 55 ℃ for not lower than 48 hours;
C. re-granulation test of the improved adhesive and PET substrate co-granulable double-sided protective film:
1) the PET base material to be re-granulated and recycled after being used can be simply sorted together with the granulation type double-sided protective film, and other types of materials are removed;
2) cutting the double-sided protective film to be recycled and granulated into a specification with a proper size according to the feeding size of the screw extrusion granulator;
3) setting parameters such as screw rotating speed, temperature of an extruder and the like, and granulating and recovering;
4) cutting the extruded molten material strip into plastic particles with the specification after water cooling and air cooling, wherein the particles are yellowish; the recovered novel plastic particles can be used for further processing or sale.
The basic properties of the improved adhesive prepared in example 3 and the co-pelletizable double-sided protective film made of PET substrate are shown in Table 3
Therefore, the basic performance of the improved adhesive and the PET substrate co-pelletizable double-sided protective film in the embodiment 3 can meet the use requirement of the protective film, the manufactured particles are light yellow, the surface is smooth, the mechanical strength is high, the polyester and adhesive are good in compatibility, the processing technologies such as injection molding, extrusion molding and blow molding can be met, the improved adhesive can be used as new PET for blending, fibers and the like, and the recycling requirement is met.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (13)
1. The utility model provides a but improved generation glue and PET substrate pelletization type protection film altogether, its characterized in that, including PET substrate (1), PET substrate (1) surface corona treatment, corona treatment PET substrate (1) surface coating has the solubilization of moderate degree crosslinking and grafting modification treatment's improved generation saturated polyester pressure sensitive adhesive coating (2), can laminate on the solubilization of moderate degree crosslinking and grafting modification treatment's improved generation saturated polyester pressure sensitive adhesive coating (2) and have from type membrane (3).
2. The improved adhesive and PET substrate co-granulable protective film according to claim 1, wherein the solubilized and graft-modified improved saturated polyester pressure sensitive adhesive in the moderately cross-linked solubilized and graft-modified improved saturated polyester pressure sensitive adhesive coating (2) comprises graft-modified saturated polyester macromolecules, polycaprolactone and polyacrylate components, and the moderately cross-linked solubilized and graft-modified improved saturated polyester pressure sensitive adhesive coating (2) comprises the following components in percentage by weight: 40-60% of saturated polyester polymer resin, 40-60% of polycaprolactone and 20-5% of polyacrylate.
3. The improved adhesive and PET substrate co-pelletizable protective film as claimed in claim 2, wherein the saturated polyester polymer graft-modified in the solubilized and graft-modified improved saturated polyester pressure-sensitive adhesive is a hydroxyl-terminated and/or carboxyl-terminated linear saturated polyester polymer, and has a Tg of 0 ± 20 ℃ and a molecular weight Mn of 15000-45000.
4. The improved adhesive and PET substrate co-granulatable protective film according to claim 2, wherein the polycaprolactone in the improved saturated polyester pressure sensitive adhesive subjected to solubilization and graft modification treatment is hydroxyl-and/or carboxyl-terminated polycaprolactone polymerized in a xylene solvent.
5. The improved protective film capable of being co-granulated with PET substrate according to claim 4, wherein the polycaprolactone is terminated with at least one of acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate, and the amount of the termination is 0.5-5% of the mass of caprolactone.
6. The improved adhesive and PET substrate co-pelletizable protective film according to claim 2, wherein the polyacrylate comprises, by mass, 1-10% of acrylic acid, 0-90% of butyl acrylate, 0-90% of isooctyl acrylate, and 1-10% of acrylic acid- β -hydroxyethyl ester.
7. A method for manufacturing an improved adhesive and PET substrate co-pelletizable protective film is characterized in that: the method comprises the following steps:
the method comprises the following steps: preparing a monomer mixed solution;
step two: preparing an initiator solution, an initiator dropping liquid and an initiator supplementing liquid;
step three: preparing a terminated polycaprolactone polymer solution in xylene;
step four: the preparation method comprises the following steps of (1) carrying out free radical polymerization-grafting on terminated polycaprolactone macromolecules, saturated polyester resin macromolecules, an initiator solution, a monomer mixed solution and an initiator supplementing liquid in an organic solvent to obtain the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment;
step five: preparing a coating liquid from the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment, a solvent, a plasticizer and a crosslinking agent;
step six: coating the coating liquid on the surface of the PET substrate (1) subjected to corona treatment, drying and curing to form a moderately-crosslinked modified saturated polyester pressure-sensitive adhesive coating subjected to solubilization and graft modification;
step seven: and (3) attaching a release film (3) to the moderately-crosslinked improved saturated polyester pressure-sensitive adhesive coating subjected to solubilization and graft modification, and performing post-curing treatment to obtain the co-pelletizable protective film of the improved adhesive and the PET substrate.
8. The method as claimed in claim 7, wherein the first step further comprises mixing caprolactone, at least one of acrylic acid and hydroxyethyl acrylate, and xylene in a predetermined amount, heating the solution to 135 deg.C or higher, adding a catalyst to polymerize the mixture to obtain the terminated polycaprolactone xylene solution, reacting at 135-160 deg.C for a period of not less than 240 minutes.
9. The method as claimed in claim 7, wherein the second step further comprises mixing at least one of acrylic acid and methacrylic acid, at least one of acrylic acid- β -hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate, at least one of butyl acrylate, isooctyl acrylate and isooctyl methacrylate, preferably acrylic acid, β -hydroxyethyl acrylate and isooctyl acrylate, with a predetermined amount of solvent, 55-65% of the solvent is added to the monomer mixture, and the mixture is stirred to obtain the monomer mixture.
10. The method for preparing the improved co-pelletizable protective film for the glue and PET substrate according to claim 7, wherein the third step further comprises accurately weighing the initiator in the calculated amount, stirring and dissolving the initiator completely with toluene in an amount which is more than 10 times the mass of the initiator, standing for more than 60 minutes, separating the impurities in the solution after the impurities in the initiator solution are completely precipitated, and taking the supernatant to prepare the initiator solution, the initiator dropping liquid and the initiator supplementing liquid.
11. The method for manufacturing the improved adhesive and PET substrate co-pelletizable protective film according to claim 7, wherein the third step further comprises adding the refined initiator solution into the monomer mixture, and continuing to stir to obtain a monomer dropping solution; adding a specified amount of 30% of solvent, all saturated polyester resin and all terminated polycaprolactone xylene solution into a reaction kettle, and heating to reflux and stabilize for 10 minutes or more under the nitrogen-introducing protective atmosphere; dropwise adding monomer dropwise adding liquid into the reaction kettle, and controlling the dropwise adding time to be 180 minutes; washing the dripping tank and the pipeline by using a 10 percent specified amount of solvent; controlling the reaction temperature in the reaction kettle between 75 and 95 ℃, controlling the stability of reflux to prevent material flushing or implosion, continuously carrying out reflux heat preservation for 60 minutes under the condition of nitrogen introduction protection, supplementing initiator supplementing liquid, and continuously reacting for 60 minutes or more; after the heat preservation is finished, adding a catalyst for carrying out hydroxyl and carboxyl interactive condensation to further improve the grafting effect; the condensation reaction time is not less than 60 minutes, and the condensation reaction temperature is between 75 and 95 ℃.
12. The method for manufacturing the improved adhesive and PET substrate co-pelletizable protective film according to claim 7, wherein the fourth step further comprises cooling the reaction materials, continuously stirring and cooling to a temperature below 40 ℃, closing nitrogen protection, filtering and discharging the materials into a charging basket, and hermetically storing the materials to obtain the solubilized and grafted improved saturated polyester pressure-sensitive adhesive; weighing a specified amount of the improved saturated polyester pressure-sensitive adhesive subjected to solubilization and grafting treatment, a solvent, a plasticizer and a crosslinking agent, and preparing a coating liquid.
13. The method for manufacturing the improved adhesive and PET substrate co-pelletizable protective film according to claim 7, wherein the drying and curing time is 48 hours or more, and the drying and curing temperature is 45-60 ℃.
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| CN112724877A (en) * | 2020-12-31 | 2021-04-30 | 安徽明讯新材料科技股份有限公司 | Preparation method of improved adhesive and polyolefin substrate co-granulable protective film and protective film |
| CN115537136A (en) * | 2022-11-04 | 2022-12-30 | 江阴通利光电科技有限公司 | Composite protective film capable of being recycled and granulated and recycling method |
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| CN106832103A (en) * | 2017-01-05 | 2017-06-13 | 无锡海特新材料研究院有限公司 | A kind of acrylate pressure-sensitive adhesive of strong adherence PC base materials and preparation method thereof |
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| CN102775943A (en) * | 2012-08-06 | 2012-11-14 | 滁州云林数码影像耗材有限公司 | Acrylate pressure-sensitive adhesive containing crystalline polyester and preparation method thereof |
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