CN111040083A - Modified master batch for low surface energy polyethylene protective film and preparation method thereof - Google Patents
Modified master batch for low surface energy polyethylene protective film and preparation method thereof Download PDFInfo
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
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- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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Abstract
The invention provides a modified master batch for a low-surface-energy polyethylene protective film and a preparation method thereof, and relates to the technical field of high polymer materials. The modified master batch is prepared from the following raw materials in percentage by weight: 1 to 10 percent of organic silicon resin, 89 to 98 percent of polyethylene, 0.05 to 0.5 percent of initiator and 0.05 to 1 percent of antioxidant; the polyethylene is low density polyethylene and/or linear low density polyethylene. The modified master batch can endow the polyethylene protective film with ultra-low surface energy and stable anti-sticking performance, and is not easy to glue residue when in use.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a modified master batch for a low-surface-energy polyethylene protective film and a preparation method thereof.
Background
The polyethylene protective film is a polyethylene pressure-sensitive adhesive tape for protecting the surface of a material, can prevent the surface of the material from being scratched, polluted, corroded and the like in the processes of processing, transportation, storage and use, and is the variety with the largest use amount in the current surface protective films. Before the pressure-sensitive adhesive is coated on the adhesive-coated surface of the polyethylene substrate, the back surface of the substrate is usually subjected to corona treatment and coated with an anti-sticking layer or a release agent so as to reduce the adhesion force between the pressure-sensitive adhesive and the back surface of the substrate and facilitate the unwinding and the spreading of the PE protective film in the use process. However, the process is complicated to operate, prolongs the production period of products, is not beneficial to industrial production, and gradually fades down in the storage process, so that the adhesive force between the pressure-sensitive adhesive and the base material is reduced. Common anti-sticking agent materials are long-chain alkyl compounds, fluorine-containing polymers, acrylonitrile and vinylidene chloride copolymers and the like, and low molecular substances in the anti-sticking agent are easy to migrate, so that the phenomenon of adhesive residue is caused.
Disclosure of Invention
In view of the above, it is desirable to provide a modified master batch for a low surface energy polyethylene protective film, which can impart an ultra-low surface energy and stable anti-sticking property to the polyethylene protective film and is less likely to cause adhesive residue during use.
The modified master batch for the ultra-low surface energy polyethylene protective film is prepared from the following raw materials in percentage by weight:
the polyethylene is low density polyethylene and/or linear low density polyethylene.
Above-mentioned modified master batch adopts silicone resin and polyethylene graft copolymerization, helps reducing the surface tension of the antiseized face of polyethylene protection film, gives its ultralow surface energy, makes the antiseized face of protection film have good anti-sticking property, and the antiseized face of protection film is difficult for taking place the micromolecule migration phenomenon moreover, has prolonged the anti-sticking property of antiseized face to the life cycle of product has been prolonged.
In one embodiment, the silicone resin is selected from: one or more of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, and 3-methacryloxypropyltrimethoxysilane. Preferably, the organic silicon resin is selected from vinyltriethoxysilane and vinyltrimethoxysilane.
In one embodiment, the polyethylene is linear low density polyethylene; preferably, the polyethylene is selected from low density polyethylene and linear low density polyethylene.
In one embodiment, the low density polyethylene and the linear low density polyethylene each have a melt flow index of 1.7 to 2.8g/10 min. The polyethylene melt indexes are similar, and the composite effect of the material is better.
In one embodiment, the initiator is selected from: one or more of benzoyl peroxide, 1, 3-ditert-butyl dicumyl peroxide, ditert-butyl peroxide, tert-butyl benzoyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) acetylene and tert-butyl peroxybenzoate.
In one embodiment, the antioxidant is selected from: one or more than two of p-phenylenediamine, diarylsecondary amine, aldehyde amine, ketone amine, 2, 6-di-tert-butyl-4-methylphenol, dilauryl thiodipropionate, trisnonylphenyl phosphite, 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, isooctyl propionate alcohol and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
In one embodiment, the modified master batch is prepared from the following raw materials in percentage by weight;
in one embodiment, the modified master batch is prepared from the following raw materials in percentage by weight;
the invention also provides a preparation method of the modified master batch, which comprises the following steps:
mixing the organic silicon resin, the polyethylene, the initiator and the antioxidant in a mixer, melting and extruding, cooling, granulating and drying to obtain the functional master batch.
The preparation method does not need corona treatment and coating of an anti-sticking agent, simplifies the process flow, and the anti-sticking surface of the prepared polyethylene protective film can keep ultralow surface energy for a long time, thereby being beneficial to uncoiling and unfolding.
In one embodiment, the melt extrusion is carried out in a twin screw extruder with the temperature of each section of the screw being 170-190 ℃.
In one embodiment, the cooling temperature is 20-30 ℃.
In one embodiment, the preparation method of the modified master batch specifically comprises the following steps: and (2) placing the organic silicon resin, the polyethylene, the initiator and the antioxidant in a mixer, mixing for 10-15min, placing in a double-screw extruder, melting and extruding, wherein the temperature of each section of the screw is 170-190 ℃, cooling to 20-30 ℃ after extruding, granulating by a granulator, and drying to obtain the functional master batch.
Compared with the prior art, the invention has the following beneficial effects:
the modified master batch disclosed by the invention is beneficial to reducing the surface tension of the anti-sticking surface of the polyethylene protective film by graft copolymerization of the organic silicon resin and the polyethylene, and endows the anti-sticking surface with ultralow surface energy, so that the anti-sticking surface of the protective film has excellent anti-sticking performance, the anti-sticking surface of the protective film is not easy to generate a small molecule migration phenomenon, and the anti-sticking performance of the anti-sticking surface is prolonged, thereby prolonging the service life of the product.
The preparation method of the invention does not need corona treatment and coating of an anti-sticking agent, simplifies the process flow, and the anti-sticking surface of the prepared polyethylene protective film can keep ultra-low surface energy for a long time, thereby being beneficial to uncoiling and unfolding.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the preferred embodiments. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
In the following examples, the melt flow indices of the low density polyethylene and the linear low density polyethylene are each 1.7 to 2.8g/10 min.
Example 1
A modified master batch is prepared by the following method:
1 kg of vinyltriethoxysilane, 98 kg of low-density polyethylene, 0.3 kg of dicumyl peroxide and 0.7 kg of p-phenylenediamine are put into a mixer to be mixed for 10-15 minutes at a high speed, then the mixture is put into a double-screw extruder, the temperature of each section of a screw is 170-190 ℃, the mixture is melted, mixed uniformly, extruded, cooled to room temperature, granulated by a granulator and dried, and the functional master batch is obtained.
Example 2
A modified master batch is prepared by the following method:
4 kg of vinyl tri (2-methoxyethoxy) silane, 95 kg of linear low-density polyethylene, 0.2 kg of dicumyl peroxide and 0.8 kg of p-phenylenediamine are put into a mixer to be mixed for 10 to 15 minutes at a high speed, then the mixture is put into a double-screw extruder, the temperature of each section of a screw is 190 ℃, the mixture is melted, mixed and extruded evenly, cooled to room temperature, granulated by a granulator and dried, and the functional master batch is obtained.
Example 3
A modified master batch is prepared by the following method:
9 kg of 3-methacryloyl propyl trimethoxy silane, 60 kg of low density polyethylene, 30 kg of linear low density polyethylene, 0.5 kg of dicumyl peroxide and 0.5 kg of p-phenylenediamine are put into a mixer to be mixed for 10 to 15 minutes at high speed, then the mixture is put into a double-screw extruder, the temperature of each section of a screw is 170-190 ℃, the mixture is melted, mixed uniformly, extruded, cooled to room temperature, granulated by a granulator and dried, and the functional master batch is obtained.
Comparative example 1
A modified master batch differs from example 3 in that octadecyl methacrylate is used in place of 3-methacryloxypropyltrimethoxysilane.
Application example 1
A polyethylene protective film is prepared by the following method: respectively and uniformly mixing the raw materials of the inner layer of the base film, the middle layer of the base film and the outer layer of the base film, then respectively placing the mixture into three extruders at the temperature of 130-175 ℃, plasticizing and extruding, blow molding, cooling, drawing and rolling to obtain an original film, and coating the outer surface of the inner layer of the base film with polyacrylate pressure-sensitive adhesive to obtain the base film.
Wherein, the inner layer of the basement membrane comprises the following raw materials in percentage by weight: 20% of low-density polyethylene and 80% of linear low-density polyethylene;
the base film intermediate layer comprises the following raw materials in percentage by weight: 10% of low-density polyethylene, 40% of high-density polyethylene and 50% of metallocene linear low-density polyethylene;
the outer layer of the base film comprises the following raw materials in percentage by weight: 50% of low-density polyethylene, 30% of linear low-density polyethylene and 20% of modified master batch of example 1.
Application example 2
A polyethylene protective film, the preparation method is substantially the same as application example 1, except that the raw materials of the outer layer of the base film are: 50% of low-density polyethylene, 30% of linear low-density polyethylene and 20% of modified master batch in example 2.
Application example 3
A polyethylene protective film, the preparation method is substantially the same as application example 1, except that the raw materials of the outer layer of the base film are: 50% of low-density polyethylene, 30% of linear low-density polyethylene and 20% of modified master batch in example 3.
Application comparative example 1
A polyethylene protective film, the preparation method is substantially the same as application example 1, except that the raw materials of the outer layer of the base film are: 50% of low-density polyethylene, 30% of linear low-density polyethylene and 20% of modified master batch of comparative example 1.
Comparative application example 2
A polyethylene protective film, the preparation method is substantially the same as application example 1, except that the raw materials of the outer layer of the base film are: 75% of low-density polyethylene, 25% of linear low-density polyethylene and release agent coated on the outer layer of the base film.
Experimental example 1
The polyethylene protective films of the application examples and the application comparative examples were subjected to performance tests, the test methods were as follows:
(1) contact angle test: and (3) testing the contact angle of deionized water on the anti-sticking surface of the membrane by using a contact angle tester, sucking liquid into the needle tube, fixing the needle tube on an operation frame, placing the coating membrane on a sample table, dropwise adding liquid drops, and testing the angle between the liquid drops and an interface. The change of the surface energy of the polyethylene protective film is reflected by measuring the contact angle of deionized water on the surface of the film.
(2) And (3) testing residual bonding rate: the pressure-sensitive adhesive protective film with the 180-degree peel strength of 100g/25mm is uniformly adhered to the anti-sticking surface of the polyethylene film by certain pressure, and after the pressure-sensitive adhesive protective film is placed for a period of time under specified conditions, the pressure-sensitive adhesive protective film is peeled off from the anti-sticking layer and then is immediately stuck in a standard stuck test piece to test the 180-degree peel strength. And quantitatively reflecting the transfer degree of the anti-sticking layer through the ratio of the post-peeling strength value to the initial peeling strength value.
(3) And (3) testing mechanical properties: the mechanical property test is carried out according to the method GB/T1040.3-06.
The test results are shown in table 1 below:
table 1 results of performance testing
From the above table, the contact angles of the application examples and the application comparative examples are all above 110 °, and the contact angle of the polyethylene film is about 100 ° when the polyethylene is not modified, which indicates that the contact angle of the protective film is increased after the modification treatment, but the contact angle of the release surface of the polyethylene film modified by the modified master batch of the invention is obviously improved, which indicates that the surface energy of the protective film is low. As is clear from the results of the residual adhesion test, the residual adhesion of the application examples was maintained at 90% or more after leaving for 7 days, while the application comparative examples were all at 90% or less, and when the residual adhesion was 90% or more, it was considered that the release layer (outer layer of the base film) was not transferred, and it was seen that examples 1 to 3 effectively solved the problem of the transfer of the release layer. From the aspect of mechanical property indexes, the mechanical property of the protective film meets the use requirement.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The modified master batch for the ultra-low surface energy polyethylene protective film is characterized by being prepared from the following raw materials in percentage by weight:
the polyethylene is low density polyethylene and/or linear low density polyethylene.
2. The modified master batch for the ultra-low surface energy polyethylene protective film according to claim 1, wherein the silicone resin is selected from the group consisting of: one or more of vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, and 3-methacryloxypropyltrimethoxysilane.
3. The modified masterbatch for ultra-low surface energy polyethylene protective film according to claim 1, wherein the melt flow indexes of the low density polyethylene and the linear low density polyethylene are 1.7-2.8g/10 min.
4. The modified masterbatch for ultra-low surface energy polyethylene protective film according to claim 1, wherein the initiator is selected from the group consisting of: one or more of benzoyl peroxide, 1, 3-ditert-butyl dicumyl peroxide, ditert-butyl peroxide, tert-butyl benzoyl peroxide, 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) acetylene and tert-butyl peroxybenzoate.
5. The modified master batch for the ultra-low surface energy polyethylene protective film according to claim 1, wherein the antioxidant is selected from the group consisting of: one or more than two of p-phenylenediamine, diarylsecondary amine, aldehyde amine, ketone amine, 2, 6-di-tert-butyl-4-methylphenol, dilauryl thiodipropionate, trisnonylphenyl phosphite, 1,3, 5-trimethyl-2, 4,6- (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, isooctyl propionate alcohol and bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite.
6. The modified master batch for the ultra-low surface energy polyethylene protective film according to any one of claims 1 to 5, which is prepared from the following raw materials in percentage by weight;
7. the modified master batch for the ultra-low surface energy polyethylene protective film according to claim 6, which is prepared from the following raw materials in percentage by weight;
8. the preparation method of the modified master batch of any one of claims 1 to 7, which is characterized by comprising the following steps:
mixing the organic silicon resin, the polyethylene, the initiator and the antioxidant in a mixer, melting and extruding, cooling, granulating and drying to obtain the functional master batch.
9. The method for preparing the modified masterbatch of claim 8, wherein the melt extrusion is performed in a twin-screw extruder, and the temperature of each section of the screw is 170-190 ℃.
10. The preparation method of the modified masterbatch according to claim 8 or 9, wherein the cooling temperature is 20-30 ℃.
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| CN113136072A (en) * | 2021-04-09 | 2021-07-20 | 汕头市贝斯特科技有限公司 | Low-noise master batch for BOPP (biaxially-oriented polypropylene) adhesive tape base film and preparation method thereof |
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| CN109593163A (en) * | 2018-12-05 | 2019-04-09 | 佳易容相容剂江苏有限公司 | A kind of Polypropylene-based graft object and preparation method thereof |
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