CN112724873A - Preparation method of improved adhesive and polyolefin substrate co-granulable protective film and protective film - Google Patents

Preparation method of improved adhesive and polyolefin substrate co-granulable protective film and protective film Download PDF

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CN112724873A
CN112724873A CN202011642932.8A CN202011642932A CN112724873A CN 112724873 A CN112724873 A CN 112724873A CN 202011642932 A CN202011642932 A CN 202011642932A CN 112724873 A CN112724873 A CN 112724873A
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solution
initiator
poly
protective film
methyl
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潘成诚
汪洋
谢璐生
雷芬
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Anhui Mingxun New Material Technology Co ltd
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Anhui Mingxun New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/026—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethylene-vinylester copolymers
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09J151/003—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 by reactions only involving unsaturated carbon-to-carbon 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
    • C09J7/24—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/046—Presence of homo or copolymers of ethene in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/10—Presence of homo or copolymers of propene
    • C09J2423/106—Presence of homo or copolymers of propene in the substrate

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

Abstract

The invention relates to a preparation method of an improved protective film capable of being co-granulated by glue and a polyolefin base material and the protective film, wherein the preparation process comprises the following steps: preparing a modified polycaprolactone xylene solution, preparing poly (methyl) acrylic acid hydroxy polycaprolactone on the basis, synthesizing a poly (methyl) acrylic acid ester pressure-sensitive adhesive by taking poly (methyl) acrylic acid hydroxy polycaprolactone and a (methyl) acrylic acid ester monomer as raw materials, preparing a coating liquid by using the adhesive, and coating to obtain the protective film. The pressure-sensitive adhesive and the protective film prepared by the invention have excellent adhesive property; after the protective film is used, novel plastic particles which can be recycled can be obtained by directly extruding and granulating, so that the subsequent recycling is facilitated; the preparation method is simple and easy to implement, and has good bearing performance compared with the traditional protective film preparation process.

Description

Preparation method of improved adhesive and polyolefin substrate co-granulable protective film and protective film
Technical Field
The invention relates to the field of pressure-sensitive adhesive products, in particular to a preparation method of an improved protective film capable of granulating together with an adhesive and a polyolefin substrate and the protective film.
Background
The protective film used in the fields of medicine, electronics, electroplating, material processing and the like is obtained by coating a pressure-sensitive adhesive on a base material with a certain surface free energy and then carrying out drying curing and anti-sticking treatment, wherein the adopted pressure-sensitive adhesive generally comprises polymethacrylates, rubbers, polyurethanes and the like, and the raw materials are insoluble and infusible polymers and are difficult to remove from the base material by means of dissolution and the like. After the protective film using these materials as the adhesive layer is used, the protective film is usually discarded, and the base material thereof cannot be recycled, which not only wastes resources, but also causes environmental pollution. However, the existing methods for processing the protective film inevitably have the defects of high cost, large limitation, potential safety hazard and incomplete processing. One of the processing methods is a mixed granulation recycling method, which is based on the principle that a protective film is cut up, and the protective film containing a pressure-sensitive adhesive coating is granulated by a coextrusion method in a molten state to prepare plastic particles with certain physical properties for recycling. Due to the chemical components of the protective film substrate and the pressure-sensitive adhesive, only the protective film which adopts the polyolefin substrate and is coated with the polyolefin adhesive can be subjected to coextrusion granulation, and the selection range of the adhesive is narrow.
The polyolefin base material protective film is a large class of pressure-sensitive plastic products which comprise PE, BOPP, CPP and the like and take polyolefin polymer films as base materials, is an important component in the current protective film products, and the polymethacrylate pressure-sensitive adhesive has excellent performances in various aspects as a common adhesive in the field, but the compatibility of the polymethacrylate pressure-sensitive adhesive and the polymethacrylate pressure-sensitive adhesive is difficult to meet the requirement of common granulation and recovery due to the reasons of molecular structure, chemical composition and the like.
The PCL is a linear thermoplastic high polymer material, has the characteristics of low glass transition temperature, good compatibility with various high polymer materials, biodegradability and the like, so the PCL is a very suitable physical solubilizing material which can be effectively compatible with the polymethacrylate pressure-sensitive high polymer and the polyolefin high polymer, and the use of the modified PCL undoubtedly provides a solution for the co-extrusion granulation of the polyolefin and the polymethacrylate pressure-sensitive high polymer material. However, PCL and polymethacrylate pressure-sensitive polymers are also prone to cause instability in the viscosity of the applied protective film due to differences in chemical structure, molecular surface energy, and the like.
Therefore, it is necessary to solve the problem of the compatibility stability of PCL with the polymethacrylate pressure-sensitive polymer, and thus the problem of co-extrusion and granulation of the polymethacrylate pressure-sensitive polymer and the polyolefin substrate.
Disclosure of Invention
The invention aims to provide a preparation method of an improved protective film capable of granulating together with glue and a polyolefin substrate and the protective film.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of an improved adhesive and polyolefin substrate co-granulable protective film, which comprises the following specific steps:
A. preparation of modified polycaprolactone xylene solution:
A1. adding a catalyst into xylene, stirring, standing for 60-80 min, filtering, and adjusting the concentration to obtain a 5% catalyst and xylene mixed solution;
A2. mixing xylene, caprolactone and a first initiator, heating to 135-145 ℃, and refluxing for 30-50 min;
A3. dropwise adding all the mixed solution of the catalyst and the xylene prepared in the step A1 into the mixed solution in the step A2 for 20-30 min, and refluxing for 5-6 h at 135-145 ℃ to prepare a modified polycaprolactone xylene solution;
B. preparation of poly (meth) acrylic acid hydroxy polycaprolactone:
B1. adding a second initiator into dimethylbenzene, stirring, standing for 60-80 min, removing water and impurities separated from a solution after the solution is layered, clarified and transparent, and averagely dividing the remaining solution into 3 parts, namely a first initiator solution, a second initiator solution and a third initiator solution;
B2. heating all the modified polycaprolactone xylene solution prepared by A3 to 82-85 ℃, and keeping the temperature for 30-50 min; dropwise adding all the first initiator solution prepared in the step B1 for 10-15 min, heating to 82-100 ℃, and keeping the temperature for 60-80 min; dropwise adding all the second initiator solution prepared in the step B1 for 10-15 min, and keeping the temperature for 60-80 min; dropwise adding all the third initiator solution prepared in the step B1 for 10-15 min, and keeping the temperature for 90-120 min; cooling to 35-45 ℃ to obtain poly (methyl) acrylic acid hydroxy polycaprolactone;
C. synthesizing a poly (methyl) acrylate pressure-sensitive adhesive:
C1. adding a second initiator into dimethylbenzene, stirring, standing for 60-80 min, and removing water and impurities separated from a solution after the solution is layered, clarified and transparent to obtain a fourth initiator solution; adding a second initiator into dimethylbenzene, stirring, standing for 60-80 min, and removing water and impurities separated by layering after the solution is layered, clarified and transparent to obtain a fifth initiator solution; adding a second initiator into dimethylbenzene, stirring, standing for 60-80 min, and removing water and impurities separated by layering after the solution is layered, clarified and transparent to obtain a sixth initiator solution;
C2. mixing (methyl) acrylate monomers to obtain a monomer mixed solution;
C3. adding the organic solution and all the fifth initiator solution prepared in the step C1 into 75-80% of the total weight of the monomer mixed solution prepared in the step C2, and stirring for 5-10 min to prepare monomer dropping liquid;
C4. mixing the residual monomer mixed solution used in the step C3 with an organic solvent, heating to 78-82 ℃, and refluxing for 10-20 min; dropwise adding all the fourth initiator solution prepared in the step C1 for 10-15 min; refluxing for 30-50 min; dropwise adding all the monomer dropwise added liquid prepared in the step C3 for 180-200 min; preserving the heat for 60-80 min; dropwise adding all the sixth initiator solution prepared in the step C1 for 10-15 min; refluxing for 120-160 min at 80-88 ℃; adding an organic solvent, and dropwise adding for 5-10 min; cooling to 35-40 ℃ to obtain a pre-adhesive;
C5. filtering all the pre-adhesives obtained in the step C4, and hermetically storing to obtain a poly (methyl) acrylate pressure-sensitive adhesive with the solid content of 35%;
D. preparing an improved poly (methyl) acrylate pressure-sensitive adhesive coating liquid:
D1. mixing the poly (meth) acrylate polycaprolactone prepared in the step B2 and the poly (meth) acrylate pressure-sensitive adhesive prepared in the step C5 to obtain an improved poly (meth) acrylate pressure-sensitive adhesive;
D2. mixing and stirring a curing agent and an organic solvent to obtain a cross-linking agent diluent;
D3. adding the improved poly (methyl) acrylate pressure-sensitive adhesive obtained in the step D1 into an organic solvent, and stirring for 30-50 min to obtain an adhesive diluent;
D4. adding all the cross-linking agent diluent obtained in the step D2 into the glue diluent obtained in the step D3, and stirring for 30-50 min to obtain an improved poly (methyl) acrylate pressure-sensitive adhesive coating liquid;
E. coating an improved poly (methyl) acrylate pressure-sensitive adhesive:
and D4, coating the improved poly (methyl) acrylate pressure-sensitive adhesive coating liquid prepared in the step D to the surface of the polyolefin substrate, drying to obtain an improved poly (methyl) acrylate pressure-sensitive adhesive coating, attaching a release film to the surface of the coating, and performing post-curing treatment to obtain the co-pelletizable protective film of the improved adhesive and the polyolefin substrate.
Further, the steps A2, A3, B2 and C4 are all carried out under the condition of introducing nitrogen; in the step C4, the part of monomer mixed solution is stirred while the weight of the organic solution and the fifth initiator solution is 75-80% of the total weight of the monomer mixed solution; step D3, adding the improved poly (methyl) acrylate pressure-sensitive adhesive into the organic solvent and stirring the organic solvent at the same time; d4, adding the cross-linking agent diluent into the glue diluent and stirring the glue diluent at the same time; the operation of step C2 was performed in a stainless steel vessel; c4, before dripping, washing the dripping device by the organic solvent added in the last operation step; the caprolactone, the first initiator and all the xylene used in the preparation process in the step A2 are rectified and purified before use.
Further, in the step E, the surface of the base layer is subjected to corona treatment, and the corona value is not lower than 40 mN/m; the temperature of post-curing treatment is not lower than 50 ℃ and the time is not lower than 48 hours.
Further, the mass ratio of xylene mixed with the second initiator and the second initiator in step B1 is at least 10: 1; the amount of the catalyst used in the step A1 is 1/500-1/50 of the mole number of the caprolactone in the step A2.
Further, the catalyst in the step a1 is an alkoxy metal compound or lewis acid; the first initiator in step a2 is hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate; the caprolactone in the step A2 is epsilon-CL; the second initiators in step B1 were all BPO; the organic solvent used in the preparation method of the modified glue and polyolefin substrate co-granulable protective film is ethyl acetate.
Further, the improved poly (meth) acrylate pressure-sensitive adhesive comprises 60% -95% of poly (meth) acrylate polymers and 5% -40% of modified polycaprolactone polymers. The total mass of the poly (methyl) acrylate polymer is one hundred percent, and the composition of the poly (methyl) acrylate polymer is as follows: 0-3% of acrylic acid, 20-50% of butyl acrylate, 10-40% of isooctyl acrylate, 1-3% of beta-hydroxyethyl acrylate, and 0-20% of MMA or EVA or a mixture of MMA and EVA.
Specifically, in the preparation process, caprolactone and a first initiator undergo ring opening polymerization in a xylene solution under the action of a catalyst to obtain a (meth) acrylic acid hydroxy polycaprolactone xylene solution; and (meth) acrylate monomers and (meth) acrylic acid hydroxy polycaprolactone are subjected to free radical polymerization respectively to obtain poly (meth) acrylate pressure-sensitive adhesive and poly (meth) acrylic acid hydroxy polycaprolactone macromolecules, then the poly (meth) acrylate pressure-sensitive adhesive and the poly (meth) acrylic acid hydroxy polycaprolactone macromolecules are mixed in proportion, the modified poly (meth) acrylate pressure-sensitive adhesive coating liquid is obtained, under the action of a curing agent, a blocking group on the poly (meth) acrylic acid hydroxy polycaprolactone macromolecules and a group on the poly (meth) acrylate macromolecules are crosslinked with the curing agent together, and a stable modified pressure-sensitive adhesive coating is formed.
On the basis, the invention also provides a protective film, and the protective film is prepared by the preparation method.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the pressure-sensitive adhesive and the protective film prepared by the invention have excellent adhesive property; 2. after the protective film is used, the plastic particles can be directly extruded and granulated by an extruder to obtain reusable novel plastic particles, so that the subsequent reutilization is facilitated; 3. the preparation method is simple and easy to implement, and has good bearing performance compared with the traditional protective film preparation process.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without making any creative effort, shall fall within the protection scope of the present invention. In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
A. Preparation of modified polycaprolactone xylene solution:
A1. adding 1.4kg of triisopropoxyaluminum (catalyst) into 24kg of dimethylbenzene, stirring, standing for 60-80 min, filtering, and adjusting the concentration to obtain 25kg of a 5% triisopropoxyaluminum dimethylbenzene solution;
A2. mixing 47.1kg of xylene, 70kg of epsilon-CL (caprolactone) and 4.25kg of hydroxyethyl methacrylate (first initiator) under the condition of introducing nitrogen, heating to 135-145 ℃, and refluxing for 30-50 min;
A3. dropwise adding all the triisopropoxyaluminum xylene solution prepared in the step A1 into the mixed solution prepared in the step A2 under the condition of introducing nitrogen, wherein the dropwise adding time is 20-30 min, and refluxing for 5-6 h at 135-145 ℃ to prepare a (methyl) acrylic acid hydroxy polycaprolactone xylene solution;
B. preparation of poly (meth) acrylic acid hydroxy polycaprolactone:
B1. adding 0.36kg of BPO (second initiator) with water content of 80% into 6kg of dimethylbenzene, stirring, standing for 60-80 min, removing water and impurities separated out after the solution is layered, clarified and transparent, and averagely dividing the rest solution into 3 parts, namely a first initiator solution, a second initiator solution and a third initiator solution;
B2. heating all the methacrylic acid hydroxy polycaprolactone xylene solution prepared by A3 to 82-85 ℃ under the condition of introducing nitrogen, and keeping the temperature for 30-50 min under the condition; dropwise adding all the first initiator solution prepared in the step B1 for 10-15 min, heating to 82-100 ℃, and keeping the temperature for 60-80 min; dropwise adding all the second initiator solution prepared in the step B1 for 10-15 min, and keeping the temperature for 60-80 min; dropwise adding all the third initiator solution prepared in the step B1 for 10-15 min, and keeping the temperature for 90-120 min; cooling to 35-45 ℃ to obtain poly (methyl) acrylic acid hydroxy polycaprolactone;
C. synthesizing a poly (methyl) acrylate pressure-sensitive adhesive:
C1. adding 0.3kg of BPO (second initiator) with 20% of water into 7kg of dimethylbenzene, stirring, standing for 60-80 min, and removing water and impurities separated out after the solution is layered, clarified and transparent to obtain a fourth initiator solution; adding 1.2kg of BPO (second initiator) with 20% of water into 20kg of dimethylbenzene, stirring, standing for 60-80 min, and removing water and impurities separated out after the solution is layered, clarified and transparent to obtain a fifth initiator solution; adding 0.5kg of BPO (second initiator) with 20% of water content into 10kg of dimethylbenzene, stirring, standing for 60-80 min, and removing water and impurities separated out after the solution is layered, clarified and transparent to obtain a sixth initiator solution;
C2. mixing 75kg of isooctyl acrylate, 165kg of butyl acrylate, 6kg of hydroxyethyl acrylate, 6kg of acrylic acid and 48kg of MMA ((meth) acrylate monomer) to obtain 300kg of monomer mixed solution;
C3. adding 400kg of ethyl acetate (organic solution) and all the fifth initiator solution prepared in the step C1 into 240kg of monomer mixed solution, and stirring for 5-10 min to prepare monomer dropping liquid;
C4. mixing the residual 60kg of monomer mixed solution with 100kg of ethyl acetate (organic solution) under the condition of introducing nitrogen, heating to 78-82 ℃, and refluxing for 10-20 min; dropwise adding all the fourth initiator solution prepared in the step C1 for 10-15 min; refluxing for 30-50 min; dropwise adding all the monomer dropwise added liquid prepared in the step C3 for 180-200 min; preserving the heat for 60-80 min; dropwise adding all the sixth initiator solution prepared in the step C1 for 10-15 min; refluxing for 120-160 min at 80-88 ℃; adding 20kg of ethyl acetate (organic solvent), and dripping for 5-10 min; cooling to 35-40 ℃ to obtain a pre-adhesive;
C5. filtering all the pre-adhesives obtained in the step C4, and hermetically storing to obtain a poly (methyl) acrylate pressure-sensitive adhesive with the solid content of 35%;
D. preparing an improved poly (methyl) acrylate pressure-sensitive adhesive coating liquid:
D1. mixing 10kg of poly (methyl) acrylic acid hydroxy polycaprolactone and 85kg of poly (methyl) acrylate pressure-sensitive adhesive to obtain improved poly (methyl) acrylate pressure-sensitive adhesive;
D2. 1kg of HDI dimer (curing agent) and 10kg of ethyl acetate (organic solvent) were mixed and stirred to obtain a crosslinking agent diluent;
D3. adding 100kg of improved poly (methyl) acrylate pressure-sensitive adhesive into 34kg of ethyl acetate (organic solvent), and stirring for 30-50 min to obtain a glue diluent;
D4. adding all the cross-linking agent diluent obtained in the step D2 into the glue diluent obtained in the step D3, and stirring for 30-50 min to obtain an improved poly (methyl) acrylate pressure-sensitive adhesive coating liquid;
E. coating an improved poly (methyl) acrylate pressure-sensitive adhesive:
and D4, coating the improved poly (methyl) acrylate pressure-sensitive adhesive coating liquid prepared in the step D4 on the surface of the PE base material, wherein the corona value of the PE base material is not lower than 40mN/m, the coating thickness is about 5 microns, drying for 1 minute by an oven at 80 ℃ to obtain an improved poly (methyl) acrylate pressure-sensitive adhesive coating, attaching a release film on the surface of the coating, and performing post-curing treatment at 50 ℃ for not lower than 48 hours to obtain the co-pelletizable protective film of the improved adhesive and the PE base material.
And E, taking the improved adhesive prepared in the step E and the PE base material co-granulation type protective film to perform performance test according to the standard of the table 1.
Item Unit of Reference value Test standard
Appearance of the product --- Smooth surface, no spot, impurity, dirt, scratch, and no adhesive migration Visualization
Total thickness of μm 80±3 GB/T 7125-2014
Thickness of the substrate μm 50±1 GB/T 7125-2014
Thickness of release film μm 25±1 GB/T 7125-2014
180 degree peel force gf/25mm 350±75 GB/T 2792-2014
Viscosity-holding property Hour(s) ≥96 GB/T 4851-2014
Temperature resistance 65℃/30min No crack, no residual glue, no falling off and no cracking Enterprise standard
TABLE 1
And taking the improved adhesive prepared in the used step E and the PE base material co-granulable protective film to perform a re-granulation test, wherein the steps are as follows: cutting the improved glue and the PE base material co-pelletizable protective film into a specification with a proper size according to the feeding size of a screw extrusion pelletizer; setting parameters such as screw rotating speed, temperature and the like of an extruder, and granulating and recovering; and cutting the extruded molten material strip into plastic particles with specifications after water cooling and air cooling.
The basic performance of the improved adhesive prepared in the embodiment 1 and the PE base material co-pelletizable protective film meets the use requirement of the protective film; the particles produced by re-granulation are light yellow, have smooth surfaces, higher mechanical strength and good compatibility of PE and adhesive, meet the processing technology requirements of injection molding, extrusion molding, blow molding and the like, and can be used for further processing or sale.
Example 2
A. Preparation of modified polycaprolactone xylene solution:
A1. adding 1.4kg of triisopropoxyaluminum (catalyst) into 24kg of dimethylbenzene, stirring, standing for 60-80 min, filtering, and adjusting the concentration to obtain 25kg of a 5% triisopropoxyaluminum dimethylbenzene solution;
A2. mixing 47.1kg of xylene, 70kg of epsilon-CL (caprolactone) and 4.76kg of hydroxyethyl methacrylate (first initiator) under the condition of introducing nitrogen, heating to 135-145 ℃, and refluxing for 30-50 min;
A3. dropwise adding all the triisopropoxyaluminum xylene solution prepared in the step A1 into the mixed solution prepared in the step A2 under the condition of introducing nitrogen, wherein the dropwise adding time is 20-30 min, and refluxing for 5-6 h at 135-145 ℃ to prepare a methacrylic acid hydroxy polycaprolactone xylene solution;
B. preparation of poly (meth) acrylic acid hydroxy polycaprolactone:
B1. adding 0.36kg of BPO (second initiator) with water content of 80% into 6kg of dimethylbenzene, stirring, standing for 60-80 min, removing water and impurities separated out after the solution is layered, clarified and transparent, and averagely dividing the rest solution into 3 parts, namely a first initiator solution, a second initiator solution and a third initiator solution;
B2. heating all the methacrylic acid hydroxy polycaprolactone xylene solution prepared by A3 to 82-85 ℃ under the condition of introducing nitrogen, and keeping the temperature for 30-50 min under the condition; dropwise adding all the first initiator solution prepared in the step B1 for 10-15 min, heating to 82-100 ℃, and keeping the temperature for 60-80 min; dropwise adding all the second initiator solution prepared in the step B1 for 10-15 min, and keeping the temperature for 60-80 min; dropwise adding all the third initiator solution prepared in the step B1 for 10-15 min, and keeping the temperature for 90-120 min; cooling to 35-45 ℃ to obtain poly (methyl) acrylic acid hydroxy polycaprolactone;
C. synthesizing a poly (methyl) acrylate pressure-sensitive adhesive:
C1. adding 0.3kg of BPO (second initiator) with 20% of water into 7kg of dimethylbenzene, stirring, standing for 60-80 min, and removing water and impurities separated out after the solution is layered, clarified and transparent to obtain a fourth initiator solution; adding 1.2kg of BPO (second initiator) with 20% of water into 20kg of dimethylbenzene, stirring, standing for 60-80 min, and removing water and impurities separated out after the solution is layered, clarified and transparent to obtain a fifth initiator solution; adding 0.5kg of BPO (second initiator) with 20% of water content into 10kg of dimethylbenzene, stirring, standing for 60-80 min, and removing water and impurities separated out after the solution is layered, clarified and transparent to obtain a sixth initiator solution;
C2. mixing 60kg of isooctyl acrylate, 165kg of butyl acrylate, 9kg of hydroxyethyl acrylate, 3kg of acrylic acid and 63kg of EVA (polymerizable monomer) to obtain 300kg of monomer mixed solution;
C3. adding 400kg of ethyl acetate (organic solution) and all the fifth initiator solution prepared in the step C1 into 240kg of monomer mixed solution, and stirring for 5-10 min to prepare monomer dropping liquid;
C4. mixing the residual 60kg of monomer mixed solution with 100kg of ethyl acetate (organic solution) under the condition of introducing nitrogen, heating to 78-82 ℃, and refluxing for 10-20 min; dropwise adding all the fourth initiator solution prepared in the step C1 for 10-15 min; refluxing for 30-50 min; dropwise adding all the monomer dropwise added liquid prepared in the step C3 for 180-200 min; preserving the heat for 60-80 min; dropwise adding all the sixth initiator solution prepared in the step C1 for 10-15 min; refluxing for 120-160 min at 80-88 ℃; adding 20kg of ethyl acetate (organic solvent), and dripping for 5-10 min; cooling to 35-40 ℃ to obtain a pre-adhesive;
C5. filtering all the pre-adhesives obtained in the step C4, and hermetically storing to obtain a poly (methyl) acrylate pressure-sensitive adhesive with the solid content of 35%;
D. preparing an improved poly (methyl) acrylate pressure-sensitive adhesive coating liquid:
D1. mixing 10kg of poly (methyl) acrylic acid hydroxy polycaprolactone and 85kg of poly (methyl) acrylate pressure-sensitive adhesive to obtain improved poly (methyl) acrylate pressure-sensitive adhesive;
D2. mixing 1.1kg of TDI dimer (curing agent) and 10kg of ethyl acetate (organic solvent), and stirring to obtain a crosslinking agent diluent;
D3. adding 100kg of improved poly (methyl) acrylate pressure-sensitive adhesive into 34kg of ethyl acetate (organic solvent), and stirring for 30-50 min to obtain a glue diluent;
D4. adding all the cross-linking agent diluent obtained in the step D2 into the glue diluent obtained in the step D3, and stirring for 30-50 min to obtain an improved poly (methyl) acrylate pressure-sensitive adhesive coating liquid;
E. coating an improved poly (methyl) acrylate pressure-sensitive adhesive:
and D4, coating the improved poly (methyl) acrylate pressure-sensitive adhesive coating liquid prepared in the step D4 on the surface of a CPP substrate with the corona value not lower than 40mN/m, wherein the coating thickness is about 10 microns, drying for 1 minute by an oven at 100 ℃ to obtain an improved poly (methyl) acrylate pressure-sensitive adhesive coating, attaching a release film on the surface of the coating, and performing post-curing treatment at 50 ℃ for not lower than 48 hours to obtain the co-pelletizable protective film of the improved adhesive and the CPP substrate.
And E, taking the improved adhesive prepared in the step E and the CPP substrate co-pelletizable protective film to perform performance testing according to the standard in the table 2.
Item Unit of Reference value Test standard
Appearance of the product --- Smooth surface, no spot, impurity, dirt, scratch, and no adhesive migration Visualization
Total thickness of μm 85±3 GB/T 7125-2014
Thickness of the substrate μm 50±2 GB/T 7125-2014
Thickness of release film μm 25±1 GB/T 7125-2014
180 degree peel force gf/25mm 300±100 GB/T 2792-2014
Viscosity-holding property Hour(s) ≥120 GB/T 4851-2014
Temperature resistance 105℃/30min No crack, no residual glue, no falling off and no cracking Enterprise standard
TABLE 2
And E, performing a re-granulation test on the modified glue prepared in the used step E and the CPP base material co-granulable protective film, wherein the step E is as follows: cutting the improved glue and the CPP substrate co-pelletizable protective film into a specification with a proper size according to the feeding size of a screw extrusion pelletizer; setting parameters such as screw rotating speed, temperature and the like of an extruder, and granulating and recovering; and cutting the extruded molten material strip into plastic particles with specifications after water cooling and air cooling.
The basic performance of the improved adhesive and CPP substrate co-pelletizable protective film prepared in the embodiment 2 meets the use requirement of the protective film; the particles produced by re-granulation are light yellow, the surfaces are smooth, the mechanical strength is high, the compatibility of the CPP and the adhesive is good, the processing technology requirements of injection molding, extrusion molding, blow molding and the like are met, and the method can be used for further processing or selling.
Example 3
A. Preparation of modified polycaprolactone xylene solution:
A1. adding 1.4kg of triisopropoxyaluminum (catalyst) into 24kg of dimethylbenzene, stirring, standing for 60-80 min, filtering, and adjusting the concentration to obtain 25kg of a 5% triisopropoxyaluminum dimethylbenzene solution;
A2. mixing 47.1kg of dimethylbenzene, 70kg of epsilon-CL (polycaprolactone) and 4.76kg of hydroxyethyl methacrylate (first initiator) under the condition of introducing nitrogen, heating to 135-145 ℃, and refluxing for 30-50 min;
A3. dropwise adding all the triisopropoxyaluminum xylene solution prepared in the step A1 into the mixed solution prepared in the step A2 under the condition of introducing nitrogen, wherein the dropwise adding time is 20-30 min, and refluxing for 5-6 h at 135-145 ℃ to prepare a (methyl) acrylic acid hydroxy polycaprolactone xylene solution;
B. preparation of poly (meth) acrylic acid hydroxy polycaprolactone:
B1. adding 0.36kg of BPO (second initiator) with water content of 80% into 6kg of dimethylbenzene, stirring, standing for 60-80 min, removing water and impurities separated out after the solution is layered, clarified and transparent, and averagely dividing the rest solution into 3 parts, namely a first initiator solution, a second initiator solution and a third initiator solution;
B2. heating all (methyl) acrylic acid hydroxy polycaprolactone xylene solution prepared by A3 to 82-85 ℃ under the condition of introducing nitrogen, and keeping the temperature for 30-50 min under the condition; dropwise adding all the first initiator solution prepared in the step B1 for 10-15 min, heating to 82-100 ℃, and keeping the temperature for 60-80 min; dropwise adding all the second initiator solution prepared in the step B1 for 10-15 min, and keeping the temperature for 60-80 min; dropwise adding all the third initiator solution prepared in the step B1 for 10-15 min, and keeping the temperature for 90-120 min; cooling to 35-45 ℃ to obtain poly (methyl) acrylic acid hydroxy polycaprolactone;
C. synthesizing a poly (methyl) acrylate pressure-sensitive adhesive:
C1. adding 0.3kg of BPO (second initiator) with 20% of water into 7kg of dimethylbenzene, stirring, standing for 60-80 min, and removing water and impurities separated out after the solution is layered, clarified and transparent to obtain a fourth initiator solution; adding 1.2kg of BPO (second initiator) with 20% of water into 20kg of dimethylbenzene, stirring, standing for 60-80 min, and removing water and impurities separated out after the solution is layered, clarified and transparent to obtain a fifth initiator solution; adding 0.5kg of BPO (second initiator) with 20% of water content into 10kg of dimethylbenzene, stirring, standing for 60-80 min, and removing water and impurities separated out after the solution is layered, clarified and transparent to obtain a sixth initiator solution;
C2. mixing 60kg of isooctyl acrylate, 180kg of butyl acrylate, 9kg of hydroxyethyl acrylate, 30kg of EVA and 21kg of MMA ((meth) acrylate monomer) to obtain 300kg of monomer mixed solution;
C3. adding 400kg of ethyl acetate (organic solution) and all the fifth initiator solution prepared in the step C1 into 240kg of monomer mixed solution, and stirring for 5-10 min to prepare monomer dropping liquid;
C4. mixing the residual 60kg of monomer mixed solution with 100kg of ethyl acetate (organic solution) under the condition of introducing nitrogen, heating to 78-82 ℃, and refluxing for 10-20 min; dropwise adding all the fourth initiator solution prepared in the step C1 for 10-15 min; refluxing for 30-50 min; dropwise adding all the monomer dropwise added liquid prepared in the step C3 for 180-200 min; preserving the heat for 60-80 min; dropwise adding all the sixth initiator solution prepared in the step C1 for 10-15 min; refluxing for 120-160 min at 80-88 ℃; adding 20kg of ethyl acetate (organic solvent), and dripping for 5-10 min; cooling to 35-40 ℃ to obtain a pre-adhesive;
C5. filtering all the pre-adhesives obtained in the step C4, and hermetically storing to obtain a poly (methyl) acrylate pressure-sensitive adhesive with the solid content of 35%;
D. preparing an improved poly (methyl) acrylate pressure-sensitive adhesive coating liquid:
D1. mixing 10kg of poly (methyl) acrylic acid hydroxy polycaprolactone and 85kg of poly (methyl) acrylate pressure-sensitive adhesive to obtain improved poly (methyl) acrylate pressure-sensitive adhesive;
D2. 1.1kg of MDI dimer (curing agent) and 10kg of ethyl acetate (organic solvent) are mixed and stirred to obtain a cross-linking agent diluent;
D3. adding 100kg of improved poly (methyl) acrylate pressure-sensitive adhesive into 34kg of ethyl acetate (organic solvent), and stirring for 30-50 min to obtain a glue diluent;
D4. adding all the cross-linking agent diluent obtained in the step D2 into the glue diluent obtained in the step D3, and stirring for 30-50 min to obtain an improved poly (methyl) acrylate pressure-sensitive adhesive coating liquid;
E. coating an improved poly (methyl) acrylate pressure-sensitive adhesive:
and D4, coating the improved poly (methyl) acrylate pressure-sensitive adhesive coating liquid prepared in the step D4 on the surface of a BOPP substrate with the corona value not lower than 40mN/m, wherein the coating thickness is about 10 microns, drying for 1 minute by a 100 ℃ oven to obtain an improved poly (methyl) acrylate pressure-sensitive adhesive coating, attaching a release film on the surface of the coating, coating the other surface of the BOPP substrate with the coating thickness of about 10 microns, and performing postcuring treatment at 50 ℃ for not lower than 48 hours to obtain the co-granulation type protective film of the improved adhesive and the BOPP substrate.
And E, taking the improved adhesive prepared in the step E and the BOPP base material co-granulation type protective film to perform performance test according to the standard of the table 2.
Item Unit of Reference value Test standard
Appearance of the product --- Smooth surface, no spot, impurity, dirt, scratch, and no adhesive migration Visualization
Total thickness of μm 108±5 GB/T 7125-2014
Thickness of the substrate μm 38±2 GB/T 7125-2014
Thickness of release film μm 25±1 GB/T 7125-2014
180 degree peel force gf/25mm 150±30 GB/T 2792-2014
Viscosity-holding property Hour(s) ≥96 GB/T 4851-2014
Temperature resistance 105℃/30min No crack, no residual glue, no falling off and no cracking Enterprise standard
TABLE 3
And taking the improved adhesive prepared in the used step E and the BOPP base material co-granulation type protective film for carrying out a re-granulation test, wherein the steps are as follows: cutting the improved glue and the BOPP base material co-pelletizable protective film into a specification with a proper size according to the feeding size of a screw extrusion pelletizer; setting parameters such as screw rotating speed, temperature and the like of an extruder, and granulating and recovering; and cutting the extruded molten material strip into plastic particles with specifications after water cooling and air cooling.
The basic performance of the improved adhesive prepared in the embodiment 3 and the BOPP base material co-granulable protective film meets the use requirement of the protective film; the particles produced by re-granulation are light yellow, have smooth surfaces, higher mechanical strength and good compatibility of the BOPP and the adhesive, meet the processing technology requirements of injection molding, extrusion molding, blow molding and the like, and can be used for further processing or sale.
The invention has the beneficial effects that:
1. the pressure-sensitive adhesive and the protective film prepared by the invention have excellent adhesive property; 2. after the protective film is used, the plastic particles can be directly extruded and granulated by an extruder to obtain reusable novel plastic particles, so that the subsequent reutilization is facilitated; 3. the preparation method is simple and easy to implement, and has good bearing performance compared with the traditional protective film preparation process.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.

Claims (7)

1. A preparation method of an improved adhesive and polyolefin substrate co-granulable protective film is characterized by comprising the following steps:
A. preparation of modified polycaprolactone xylene solution:
A1. adding a catalyst into xylene, stirring, standing for 60-80 min, filtering, and adjusting the concentration to obtain a 5% catalyst and xylene mixed solution;
A2. mixing xylene, caprolactone and a first initiator, heating to 135-145 ℃, and refluxing for 30-50 min;
A3. dropwise adding all the mixed solution of the catalyst and the xylene prepared in the step A1 into the mixed solution in the step A2 for 20-30 min, and refluxing for 5-6 h at 135-145 ℃ to prepare a modified polycaprolactone xylene solution;
B. preparation of poly (meth) acrylic acid hydroxy polycaprolactone:
B1. adding a second initiator into dimethylbenzene, stirring, standing for 60-80 min, removing water and impurities separated from a solution after the solution is layered, clarified and transparent, and averagely dividing the remaining solution into 3 parts, namely a first initiator solution, a second initiator solution and a third initiator solution;
B2. heating all the modified polycaprolactone xylene solution prepared by A3 to 82-85 ℃, and keeping the temperature for 30-50 min; dropwise adding all the first initiator solution prepared in the step B1 for 10-15 min, heating to 82-100 ℃, and keeping the temperature for 60-80 min; dropwise adding all the second initiator solution prepared in the step B1 for 10-15 min, and keeping the temperature for 60-80 min; dropwise adding all the third initiator solution prepared in the step B1 for 10-15 min, and keeping the temperature for 90-120 min; cooling to 35-45 ℃ to obtain poly (methyl) acrylic acid hydroxy polycaprolactone;
C. synthesizing a poly (methyl) acrylate pressure-sensitive adhesive:
C1. adding a second initiator into dimethylbenzene, stirring, standing for 60-80 min, and removing water and impurities separated from a solution after the solution is layered, clarified and transparent to obtain a fourth initiator solution; adding a second initiator into dimethylbenzene, stirring, standing for 60-80 min, and removing water and impurities separated by layering after the solution is layered, clarified and transparent to obtain a fifth initiator solution; adding a second initiator into dimethylbenzene, stirring, standing for 60-80 min, and removing water and impurities separated by layering after the solution is layered, clarified and transparent to obtain a sixth initiator solution;
C2. mixing (methyl) acrylate monomers to obtain a monomer mixed solution;
C3. adding the organic solution and all the fifth initiator solution prepared in the step C1 into 75-80% of the total weight of the monomer mixed solution prepared in the step C2, and stirring for 5-10 min to prepare monomer dropping liquid;
C4. mixing the residual monomer mixed solution used in the step C3 with an organic solvent, heating to 78-82 ℃, and refluxing for 10-20 min; dropwise adding all the fourth initiator solution prepared in the step C1 for 10-15 min; refluxing for 30-50 min; dropwise adding all the monomer dropwise added liquid prepared in the step C3 for 180-200 min; preserving the heat for 60-80 min; dropwise adding all the sixth initiator solution prepared in the step C1 for 10-15 min; refluxing for 120-160 min at 80-88 ℃; adding an organic solvent, and dropwise adding for 5-10 min; cooling to 35-40 ℃ to obtain a pre-adhesive;
C5. filtering all the pre-adhesives obtained in the step C4, and hermetically storing to obtain a poly (methyl) acrylate pressure-sensitive adhesive with the solid content of 35%;
D. preparing an improved poly (methyl) acrylate pressure-sensitive adhesive coating liquid:
D1. mixing the poly (meth) acrylate polycaprolactone prepared in the step B2 and the poly (meth) acrylate pressure-sensitive adhesive prepared in the step C5 to obtain an improved poly (meth) acrylate pressure-sensitive adhesive;
D2. mixing and stirring a curing agent and an organic solvent to obtain a cross-linking agent diluent;
D3. adding the improved poly (methyl) acrylate pressure-sensitive adhesive obtained in the step D1 into an organic solvent, and stirring for 30-50 min to obtain an adhesive diluent;
D4. adding all the cross-linking agent diluent obtained in the step D2 into the glue diluent obtained in the step D3, and stirring for 30-50 min to obtain an improved poly (methyl) acrylate pressure-sensitive adhesive coating liquid;
E. coating an improved poly (methyl) acrylate pressure-sensitive adhesive:
and D4, coating the improved poly (methyl) acrylate pressure-sensitive adhesive coating liquid prepared in the step D to the surface of the polyolefin substrate, drying to obtain an improved poly (methyl) acrylate pressure-sensitive adhesive coating, attaching a release film to the surface of the coating, and performing post-curing treatment to obtain the co-pelletizable protective film of the improved adhesive and the polyolefin substrate.
2. The method for preparing the improved adhesive and polyolefin substrate pelletizable protective film according to claim 1, wherein: the steps A2, A3, B2 and C4 are all carried out under the condition of introducing nitrogen; in the step C4, the part of monomer mixed solution is stirred while the weight of the organic solution and the fifth initiator solution is 75-80% of the total weight of the monomer mixed solution; step D3, adding the improved poly (methyl) acrylate pressure-sensitive adhesive into the organic solvent and stirring the organic solvent at the same time; d4, adding the cross-linking agent diluent into the glue diluent and stirring the glue diluent at the same time; the operation of step C2 was performed in a stainless steel vessel; c4, before dripping, washing the dripping device by the organic solvent added in the last operation step; the caprolactone, the first initiator and all the xylene used in the preparation process in the step A2 are rectified and purified before use.
3. The method for preparing the improved adhesive and polyolefin substrate pelletizable protective film according to claim 1, wherein: in the step E, the surface of the base layer is subjected to corona treatment, and the corona value is not lower than 40 mN/m; the temperature of post-curing treatment is not lower than 50 ℃ and the time is not lower than 48 hours.
4. The method for preparing the improved adhesive and polyolefin substrate pelletizable protective film according to claim 1, wherein: the mass ratio of xylene mixed with the second initiator to the second initiator described in step B1 is at least 10: 1; the amount of the catalyst used in the step A1 is 1/500-1/50 of the mole number of the caprolactone used in the step A2.
5. The method for preparing the improved adhesive and polyolefin substrate pelletizable protective film according to claim 1, wherein: the catalyst in the step A1 is an alkoxy metal compound or Lewis acid; the first initiator in the step A2 is hydroxyethyl methacrylate or hydroxypropyl methacrylate; the caprolactone in the step A2 is epsilon-CL; the second initiator in step B1 is BPO; the organic solvent used in the preparation method of the modified glue and polyolefin substrate co-granulable protective film is ethyl acetate.
6. The method for preparing the improved adhesive and polyolefin substrate pelletizable protective film according to claim 1, wherein: the improved poly (methyl) acrylate pressure-sensitive adhesive comprises 60-95% of poly (methyl) acrylate polymers and 5-40% of modified polycaprolactone polymers; the poly (meth) acrylate-based polymer includes: 0-3% of acrylic acid, 20-50% of butyl acrylate, 10-40% of isooctyl acrylate, 1-3% of beta-hydroxyethyl acrylate, and 0-20% of MMA or EVA or a mixture of MMA and EVA.
7. A protective film characterized by: the protective film is prepared by the preparation method of any one of claims 1 to 6.
CN202011642932.8A 2020-12-31 2020-12-31 Preparation method of improved adhesive and polyolefin substrate co-granulable protective film and protective film Pending CN112724873A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107556936A (en) * 2017-09-08 2018-01-09 安徽明讯新材料科技股份有限公司 A kind of environmentally friendly diaphragm for touch-control glass screen and preparation method thereof
CN111171739A (en) * 2019-12-26 2020-05-19 安徽明讯新材料科技股份有限公司 Improved protective film capable of being co-granulated with PET (polyethylene terephthalate) base material and manufacturing method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107556936A (en) * 2017-09-08 2018-01-09 安徽明讯新材料科技股份有限公司 A kind of environmentally friendly diaphragm for touch-control glass screen and preparation method thereof
CN111171739A (en) * 2019-12-26 2020-05-19 安徽明讯新材料科技股份有限公司 Improved protective film capable of being co-granulated with PET (polyethylene terephthalate) base material and manufacturing method thereof

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