CN115260707A - High-toughness heat-shrinkable battery label film and preparation method thereof - Google Patents
High-toughness heat-shrinkable battery label film and preparation method thereof Download PDFInfo
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- CN115260707A CN115260707A CN202210771187.XA CN202210771187A CN115260707A CN 115260707 A CN115260707 A CN 115260707A CN 202210771187 A CN202210771187 A CN 202210771187A CN 115260707 A CN115260707 A CN 115260707A
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- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000000155 melt Substances 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 238000001338 self-assembly Methods 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 12
- 238000009998 heat setting Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000004806 packaging method and process Methods 0.000 claims abstract description 7
- 238000005096 rolling process Methods 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 229920000742 Cotton Polymers 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 13
- 239000005995 Aluminium silicate Substances 0.000 claims description 12
- 235000012211 aluminium silicate Nutrition 0.000 claims description 12
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 12
- 229920001661 Chitosan Polymers 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- YAHBZWSDRFSFOO-UHFFFAOYSA-L dimethyltin(2+);2-(2-ethylhexoxy)-2-oxoethanethiolate Chemical group CCCCC(CC)COC(=O)CS[Sn](C)(C)SCC(=O)OCC(CC)CCCC YAHBZWSDRFSFOO-UHFFFAOYSA-L 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000002994 raw material Substances 0.000 abstract 1
- 238000007493 shaping process Methods 0.000 abstract 1
- 229920006257 Heat-shrinkable film Polymers 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- BPKGOZPBGXJDEP-UHFFFAOYSA-N [C].[Zn] Chemical compound [C].[Zn] BPKGOZPBGXJDEP-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000008863 intramolecular interaction Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/02—Cellulose; Modified cellulose
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- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08K9/00—Use of pretreated ingredients
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention relates to a high-toughness heat-shrinkable battery label film and a preparation method thereof, wherein the high-toughness heat-shrinkable battery label film comprises the following components in parts by weight: 60-80 parts of PETG slices, 20-30 parts of self-assembly powder, 3-5 parts of stabilizer and 1-3 parts of antioxidant; the preparation method comprises the following steps: s1: mixing the raw materials to obtain a mixture; s2: feeding the mixture into an extruder in vacuum for melt plasticization; dehumidifying and drying the melt; filtering the melt through a hyperfine filter after the melt is accurately measured; the melt enters a die head to carry out heat setting on the master slice; the master slice is cooled and shaped through a cooling roller for the second time; preheating and softening the master slice by a preheating roller, and longitudinally stretching the master slice into a film; cooling and shaping the film by a cooling roller; measuring the thickness of the film on line and controlling the thickness; and rolling and packaging to obtain the high-toughness heat-shrinkable battery label film. The product prepared by the invention has excellent mechanical strength and moderate heat shrinkage rate.
Description
Technical Field
The invention relates to the technical field of heat shrinkable film labels, in particular to a high-toughness heat shrinkable battery label film and a preparation method thereof.
Background
The heat shrinkable film label is a film label printed on a plastic film by using special ink, and when the label is heated (about 70 ℃) in the process of labeling, the heat shrinkable label can be quickly shrunk along the outer contour of an article and is tightly attached to the surface of the article, and the heat shrinkable film label mainly comprises a shrink sleeve type label and a shrink surrounding label. For example, the heat shrinkable film label can be used for a carbon zinc battery, an alkaline battery, a rechargeable battery, a mobile phone battery, a dry battery, a fuel cell, and the like.
The existing PET heat-shrinkable label film has the defects that due to the fact that the shrinkage rate is too high, printed marks on the surface of the label film are prone to being pulled and seriously deformed, the mark distinguishing effect is poor, the toughness is poor, cracks are prone to being generated, even the printed marks break away from a battery, and the using effect is poor.
Disclosure of Invention
In view of the above, the present invention provides a high-toughness heat-shrinkable battery label film having excellent mechanical strength and moderate heat shrinkage, and a method for preparing the same.
In order to achieve the purpose, the invention provides the following technical scheme:
a high-toughness heat-shrinkable battery label film is characterized by comprising the following components in parts by weight: 60-80 parts of PETG slices, 20-30 parts of self-assembly powder, 3-5 parts of stabilizer and 1-3 parts of antioxidant.
Preferably, the stabilizer is methyl tin mercaptide.
Preferably, the antioxidant is bisphenol a.
The invention also provides a preparation method of the high-toughness heat-shrinkable battery label film, which comprises the following steps:
s1: mixing the PETG slices, the self-assembly powder, the stabilizer and the antioxidant to obtain a mixture;
s2: firstly, feeding the mixture obtained in the step S1 into an extruder in vacuum, and plasticizing a melt at 200-280 ℃; then, dehumidifying and drying the melt; then, filtering the melt through a hyperfine filter after the melt is accurately metered; then, the melt enters a die head, and the heat setting of the master slice is carried out at 260-280 ℃; secondly, the heat-set master slice passes through a cooling roller for the second time and is cooled and set at the temperature of 30-50 ℃; then, the cold-formed master slice passes through a preheating roller to be preheated and softened at the temperature of 110-180 ℃, and is longitudinally stretched into a film with shrinkage rate at the stretching ratio of 2-6 times; then, the film with the shrinkage rate passes through a cooling roller, and is cooled and shaped at the temperature of 30-50 ℃; then, measuring the thickness of the film on line and controlling the thickness deviation within +/-1.5%; and finally, rolling and packaging to obtain the high-toughness heat-shrinkable battery label film.
Preferably, the method for preparing the self-assembled powder in the step S1 includes:
s11: preparing a silica sol;
s12: mixing the modified cotton fiber solution, the kaolin solution with the mass fraction of 55% and the silica sol, stirring for 1-2h, and standing for 2-4h to obtain an assembly solution;
s13: mixing chitosan, 30% by mass of acetic acid solution and the self-assembly solution obtained in the step S12, stirring for 1-2h, standing for 24-48h, washing, filtering, and vacuum drying at 60-70 ℃ for 12-24h to obtain the self-assembly powder.
Preferably, the weight ratio of the modified cotton fiber solution to the kaolin solution to the silica sol to the chitosan to the acetic acid solution is 3.
Preferably, the method for preparing the silica sol in step S11 includes: and mixing ethyl orthosilicate and absolute ethyl alcohol, stirring for 1-2h, adding a 65% nitric acid solution, and adjusting the pH to 3-4 to obtain the silicon dioxide sol.
Preferably, the weight part ratio of the tetraethoxysilane to the absolute ethyl alcohol is 1.
Preferably, the preparation method of the modified cotton fiber solution in the step S12 comprises
Mixing cotton fibers with a sulfuric acid solution with the volume fraction of 55%, and stirring at 40-50 ℃ for 1-2h to obtain the modified cotton fiber solution.
Preferably, the weight ratio of the cotton fiber to the 55% sulfuric acid solution by volume fraction is 1.
Preferably, the temperature of the extruder for melt plasticization in the step S2 is divided into 9 zones: first zone 200-220 ℃, second zone 220-240 ℃, third zone 240-260 ℃, fourth zone 240-260 ℃, fifth zone: 240-260 ℃, six zones: 240-260 ℃, seven zones: 240-260 ℃, eight zones: 260-280 ℃, nine zones: 260-280 ℃.
When the silicon dioxide sol is blended with the modified cotton fiber solution and the kaolin solution, the silicon dioxide sol can migrate and be embedded into a reticular interlayer space formed by interlayer crosslinking of cotton fibers and kaolin, so that an embedded structure is formed, intramolecular interaction and fiber chain bundles are enhanced, and internal ordering of the reticular interlayer structure is promoted.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious 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. In addition, the starting materials and equipment of the present invention are commercially available and are not specifically described, wherein the starting materials of the present invention are commercially available and are well known to those skilled in the art.
Example 1:
a high-toughness heat-shrinkable battery label film comprises the following components in parts by weight: 80 parts of PETG slices, 30 parts of self-assembly powder, 5 parts of stabilizer and 3 parts of antioxidant. Wherein the stabilizer is methyl tin mercaptide, and the antioxidant is bisphenol A.
A preparation method of a high-toughness heat-shrinkable battery label film comprises the following steps:
s1: mixing the PETG slices, the self-assembly powder, the stabilizer and the antioxidant to obtain a mixture;
s2: firstly, feeding the mixture obtained in the step S1 into an extruder in vacuum, and plasticizing a melt at 200-280 ℃, wherein the temperature is divided into 9 zones: first zone 200-220 ℃, second zone 220-240 ℃, third zone 240-260 ℃, fourth zone 240-260 ℃, fifth zone: 240-260 ℃, six zones: 240-260 ℃, seven zones: 240-260 ℃, eight zones: 260-280 ℃, nine zones: 260-280 ℃; then, dehumidifying and drying the melt; then, filtering the melt through a hyperfine filter after the melt is accurately metered; then, the melt enters a die head, and heat setting of the master slice is carried out at 280 ℃; secondly, the master slice after heat setting passes through a cooling roller for the second time, and is cooled and set at 50 ℃; then, the cold-formed master slice passes through a preheating roller to be preheated and softened at 180 ℃, and is longitudinally stretched into a film with shrinkage rate at the stretching ratio of 2-6 times (specifically determined by the thickness of the master slice and the thickness of the film); then, the film with the shrinkage rate passes through a cooling roller, and is cooled and shaped at 50 ℃; then, measuring the thickness of the film on line and controlling the thickness deviation within +/-1.5%; and finally, rolling and packaging to obtain the high-toughness heat-shrinkable battery label film.
The preparation method of the self-assembly powder in the step S1 comprises the following steps:
s11: mixing tetraethoxysilane and absolute ethyl alcohol according to the weight part ratio of 1;
mixing cotton fibers with a 55% volume fraction sulfuric acid solution according to a weight part ratio of 1;
s12: mixing the modified cotton fiber solution, the kaolin solution with the mass fraction of 55% and the silica sol, stirring for 2 hours, and standing for 4 hours to obtain an assembly solution;
s13: and (3) mixing chitosan, an acetic acid solution with the mass fraction of 30% and the self-assembly solution obtained in the step (S12), stirring for 2 hours, standing for 48 hours, washing, filtering, and drying in vacuum at 70 ℃ for 24 hours to obtain the self-assembly powder.
Wherein, the weight ratio of the modified cotton fiber solution to the kaolin solution to the silica sol to the chitosan to the acetic acid solution is 3.
Example 2:
a high-toughness heat-shrinkable battery label film comprises the following components in parts by weight: 60 parts of PETG slices, 20 parts of self-assembly powder, 3 parts of stabilizer and 1 part of antioxidant. Wherein the stabilizer is methyl tin mercaptide, and the antioxidant is bisphenol A.
A preparation method of a high-toughness heat-shrinkable battery label film comprises the following steps:
s1: mixing the PETG slices, the self-assembly powder, the stabilizer and the antioxidant to obtain a mixture;
s2: firstly, feeding the mixture obtained in the step S1 into an extruder in vacuum, and plasticizing a melt at 200-280 ℃, wherein the temperature is divided into 9 zones: first zone 200-220 ℃, second zone 220-240 ℃, third zone 240-260 ℃, fourth zone 240-260 ℃, fifth zone: 240-260 ℃, six zones: 240-260 ℃, seven regions: 240-260 ℃, eight zones: 260-280 ℃, nine zones: 260-280 ℃; then, dehumidifying and drying the melt; then, filtering the melt through a hyperfine filter after the melt is accurately metered; then, the melt enters a die head, and heat setting of the master slice is carried out at 260 ℃; secondly, the master slice after heat setting passes through a cooling roller for the second time, and is cooled and set at the temperature of 30 ℃; then, the cold-formed master slice passes through a preheating roller, is preheated and softened at the temperature of 110 ℃, and is longitudinally stretched into a film with the shrinkage rate at the stretching ratio of 2-6 times; then, the film with the shrinkage rate passes through a cooling roller, and is cooled and shaped at 30 ℃; then, measuring the thickness of the film on line and controlling the thickness deviation within +/-1.5%; and finally, rolling and packaging to obtain the high-toughness heat-shrinkable battery label film.
The preparation method of the self-assembly powder in the step S1 comprises the following steps:
s11: mixing tetraethoxysilane and absolute ethyl alcohol according to the weight part ratio of 1;
mixing cotton fibers with a 55% volume fraction sulfuric acid solution according to a weight part ratio of 1;
s12: mixing the modified cotton fiber solution, the kaolin solution with the mass fraction of 55% and the silica sol, stirring for 1 hour, and standing for 2 hours to obtain an assembly solution;
s13: and (3) mixing chitosan, an acetic acid solution with the mass fraction of 30% and the self-assembly solution obtained in the step (S12), stirring for 1h, standing for 24h, washing, filtering, and drying in vacuum at 60 ℃ for 12h to obtain the self-assembly powder.
Wherein the weight parts of the modified cotton fiber solution, the kaolin solution, the silica sol, the chitosan and the acetic acid solution are 3.
Example 3:
a high-toughness heat-shrinkable battery label film comprises the following components in parts by weight: 70 parts of PETG slices, 25 parts of self-assembly powder, 4 parts of stabilizer and 2 parts of antioxidant. Wherein the stabilizer is methyl tin mercaptide, and the antioxidant is bisphenol A.
A preparation method of a high-toughness heat-shrinkable battery label film comprises the following steps:
s1: mixing the PETG slices, the self-assembly powder, the stabilizer and the antioxidant to obtain a mixture;
s2: firstly, feeding the mixture obtained in the step S1 into an extruder in vacuum, and plasticizing a melt at 200-280 ℃, wherein the temperature is divided into 9 zones: the first zone is 200-220 ℃, the second zone is 220-240 ℃, the third zone is 240-260 ℃, the fourth zone is 240-260 ℃, and the fifth zone: 240-260 ℃, six zones: 240-260 ℃, seven regions: 240-260 ℃, eight zones: 260-280 ℃, nine zones: 260-280 ℃; then, dehumidifying and drying the melt; then, filtering the melt through a hyperfine filter after the melt is accurately measured; then, the melt enters a die head, and heat setting of the master slice is carried out at 270 ℃; secondly, the master slice after heat setting passes through a cooling roller for the second time, and is cooled and set at the temperature of 40 ℃; then, the cold-formed master slice passes through a preheating roller, is preheated and softened at the temperature of 150 ℃, and is longitudinally stretched into a film with the shrinkage rate at the stretching ratio of 2-6 times; then, the film with the shrinkage rate passes through a cooling roller, and is cooled and shaped at 40 ℃; then, measuring the thickness of the film on line and controlling the thickness deviation within +/-1.5%; and finally, rolling and packaging to obtain the high-toughness heat-shrinkable battery label film.
The preparation method of the self-assembly powder in the step S1 comprises the following steps:
s11: mixing tetraethoxysilane and absolute ethyl alcohol according to the weight part ratio of 1;
mixing cotton fibers with a 55% volume fraction sulfuric acid solution according to a weight part ratio of 1;
s12: mixing the modified cotton fiber solution, the kaolin solution with the mass fraction of 55% and the silica sol, stirring for 1.5 hours, and standing for 3 hours to obtain an assembly solution;
s13: and (3) mixing chitosan, an acetic acid solution with the mass fraction of 30% and the self-assembly solution obtained in the step S12, stirring for 1.5h, standing for 36h, washing, filtering, and drying in vacuum at 65 ℃ for 18h to obtain the self-assembly powder.
Wherein the weight parts of the modified cotton fiber solution, the kaolin solution, the silica sol, the chitosan and the acetic acid solution are 3.
Comparative example 1:
the preparation method of the comparative example 1 is basically the same as that of the example 1, except that the self-assembly powder is not used, specifically:
a heat-shrinkable battery label film comprises the following components in parts by weight: 80 parts of PETG slices, 5 parts of a stabilizer and 3 parts of an antioxidant. Wherein the stabilizer is methyl tin mercaptide, and the antioxidant is bisphenol A.
A preparation method of a heat-shrinkable battery label film comprises the following steps:
s1: mixing the PETG slices, the stabilizer and the antioxidant to obtain a mixture;
s2: firstly, feeding the mixture obtained in the step S1 into an extruder in vacuum, and plasticizing a melt at 200-280 ℃, wherein the temperature is divided into 9 zones: first zone 200-220 ℃, second zone 220-240 ℃, third zone 240-260 ℃, fourth zone 240-260 ℃, fifth zone: 240-260 ℃, six zones: 240-260 ℃, seven zones: 240-260 ℃, eight zones: 260-280 ℃, nine zones: 260-280 ℃; then, dehumidifying and drying the melt; then, filtering the melt through a hyperfine filter after the melt is accurately measured; then, the melt enters a die head, and the heat setting of the master slice is carried out at 280 ℃; secondly, the master slice after heat setting passes through a cooling roller for the second time and is cooled and set at the temperature of 50 ℃; then, the cold-formed master slice passes through a preheating roller, is preheated and softened at 180 ℃, and is longitudinally stretched into a film with shrinkage rate at the stretching ratio of 2-6 times; then, the film with the shrinkage rate passes through a cooling roller, and is cooled and shaped at 50 ℃; then, measuring the thickness of the film on line and controlling the thickness deviation within +/-1.5%; and finally, rolling and packaging to obtain the high-toughness heat-shrinkable battery label film.
The high toughness heat shrinkable battery label films obtained in examples 1 to 3 according to the present invention, the heat shrinkable battery label film obtained in comparative example 1, and a commercially available PET label film (available from ink-jet paper products packaging co., ltd, guan) were subjected to performance tests, and the test results are shown in table 1.
The longitudinal tensile strength, the transverse tensile strength, the longitudinal tearing strength, the transverse tearing strength, the longitudinal elongation at break and the transverse elongation at break of the heat shrinkable label film with the thickness of 40 mu m are measured by adopting a tensile tester, and the longitudinal heat shrinkage rate and the transverse heat shrinkage rate of the heat shrinkable label film are measured by adopting a heat shrinkage tester. The test is carried out according to the requirements of the recommended national standard GB/T34848-2017.
As can be seen from the above table, the heat-shrinkable label films of examples 1 to 3 of the present invention are superior in tensile strength, elongation at break and tear strength to those of comparative example 1 and commercially available heat-shrinkable label films, and have a moderate heat shrinkage rate, and thus have a good application prospect in the field of heat-shrinkable label films.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A high-toughness heat-shrinkable battery label film is characterized by comprising the following components in parts by weight: 60-80 parts of PETG slices, 20-30 parts of self-assembly powder, 3-5 parts of stabilizer and 1-3 parts of antioxidant.
2. The high toughness heat shrinkable battery label film of claim 1 wherein said stabilizer is methyl tin mercaptide and said antioxidant is bisphenol a.
3. A method for preparing a high toughness heat shrinkable battery label film according to claim 1, comprising the steps of:
s1: mixing the PETG slices, the self-assembly powder, the stabilizer and the antioxidant to obtain a mixture;
s2: firstly, feeding the mixture obtained in the step S1 into an extruder in vacuum, and plasticizing a melt at 200-280 ℃; then, dehumidifying and drying the melt; then, filtering the melt through a hyperfine filter after the melt is accurately measured; then, the melt enters a die head, and heat setting of the master slice is carried out at 260-280 ℃; secondly, the heat-set master slice passes through a cooling roller for the second time and is cooled and set at the temperature of 30-50 ℃; then, the cold-formed master slice passes through a preheating roller to be preheated and softened at the temperature of 110-180 ℃, and is longitudinally stretched into a film with shrinkage rate at the stretching ratio of 2-6 times; then, the film with the shrinkage rate passes through a cooling roller to be cooled and shaped at the temperature of 30-50 ℃; then, measuring the thickness of the film on line and controlling the thickness deviation within +/-1.5%; and finally, rolling and packaging to obtain the high-toughness heat-shrinkable battery label film.
4. The method for producing a high toughness heat shrinkable battery label film according to claim 3, wherein the method for producing the self-assembled powder in step S1 comprises:
s11: preparing silicon dioxide sol;
s12: mixing the modified cotton fiber solution, the kaolin solution with the mass fraction of 55% and the silica sol, stirring for 1-2h, and standing for 2-4h to obtain an assembly solution;
s13: mixing chitosan, 30% by mass of acetic acid solution and the self-assembly solution obtained in the step S12, stirring for 1-2h, standing for 24-48h, washing, filtering, and vacuum drying at 60-70 ℃ for 12-24h to obtain the self-assembly powder.
5. The method for preparing a high-toughness heat-shrinkable battery label film according to claim 4, wherein the weight ratio of the modified cotton fiber solution, the kaolin solution, the silica sol, the chitosan and the acetic acid solution is 3.
6. The method for preparing a high toughness heat shrinkable battery label film according to claim 4, wherein the method for preparing the silica sol in step S11 comprises: and mixing ethyl orthosilicate and absolute ethyl alcohol, stirring for 1-2h, adding a 65% nitric acid solution, and adjusting the pH to 3-4 to obtain the silicon dioxide sol.
7. The method for producing a high toughness heat shrinkable battery label film according to claim 6, wherein the weight ratio of the tetraethoxysilane to the absolute ethyl alcohol is 1.
8. The method for preparing a high toughness heat shrinkable battery label film according to claim 4, wherein the method for preparing the modified cotton fiber solution in step S12 comprises:
mixing cotton fibers with a sulfuric acid solution with the volume fraction of 55%, and stirring at 40-50 ℃ for 1-2h to obtain the modified cotton fiber solution.
9. The method for producing a high toughness heat shrinkable battery label film according to claim 8, wherein the weight ratio of the cotton fiber to the 55% by volume sulfuric acid solution is 1.
10. The method for producing a high toughness heat shrinkable battery label film according to claim 3, wherein the temperature at which the extruder performs melt plasticization in step S2 is divided into 9 zones: first zone 200-220 ℃, second zone 220-240 ℃, third zone 240-260 ℃, fourth zone 240-260 ℃, fifth zone: 240-260 ℃, six zones: 240-260 ℃, seven zones: 240-260 ℃, eight zones: 260-280 ℃, nine zones: 260-280 ℃.
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