CN108864627B - Polyvinyl alcohol film and preparation method thereof - Google Patents

Polyvinyl alcohol film and preparation method thereof Download PDF

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Publication number
CN108864627B
CN108864627B CN201810708730.5A CN201810708730A CN108864627B CN 108864627 B CN108864627 B CN 108864627B CN 201810708730 A CN201810708730 A CN 201810708730A CN 108864627 B CN108864627 B CN 108864627B
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film
polyvinyl alcohol
membrane
initial
rolling
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CN108864627A (en
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李承龙
吕新坤
谭海军
聂爽
陈玉仙
古文正
胡明源
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Chongqing spectrum New Material Technology Co.,Ltd.
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Chongqing Yuntianhua Hanen New Material Development Co ltd
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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
    • 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
    • C08J2329/00—Characterised by the use of 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
    • C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof

Abstract

The invention provides a preparation method of a polyvinyl alcohol film, which comprises the following steps: A) mixing polyvinyl alcohol resin, a plasticizer, a surfactant and a solvent to obtain a mixed solution of polyvinyl alcohol; B) extruding and casting the mixed solution to form an initial embryonic membrane, and drying to obtain the embryonic membrane; C) rolling out the embryonic membrane at the membrane surface temperature of 40-100 ℃ and the membrane surface tension of 1-50 N.m to obtain an initial membrane; D) and cooling the initial film to 5-30 ℃, and rolling when the film surface tension of the initial film is 1-50 N.m to obtain the polyvinyl alcohol film. The polyvinyl alcohol film has excellent surface hardness and strength, no embedded bubbles exist between the guide roller and the film in the winding process, and no wrinkle defect exists in the winding process; the film has no wrinkles in the process of rolling out of the unit and conveying.

Description

Polyvinyl alcohol film and preparation method thereof
Technical Field
The invention relates to the technical field of liquid crystal display, in particular to a polyvinyl alcohol film and a preparation method thereof.
Background
Polarizers are important components of Liquid Crystal Displays (LCDs) and are mainly used to control the optical rotation of light passing through the liquid crystal. In general, a polarizing film is formed by orienting and adsorbing iodine or a dichroic dye of a dichroic dye to a polyvinyl alcohol resin film. With the thinning of LCD products, the polarizer is also developing toward thinner and larger size, and the thinning of PVA film for polarizer becomes the problem to be solved. After the PVA film in the prior art is thinned, the surface hardness and the strength of the film are both deteriorated, and a series of production problems are generated, for example, in the winding process of the PVA film, air bubbles are easily embedded between a guide roller and the film to form printing marks, and the wrinkle defect frequently appears; meanwhile, the film is unstable and easy to form wrinkles during the film conveying and winding-out processes, and the quality of the film is further affected. The defects also affect the stability of the manufacturing process of downstream polarizer enterprises, and cause a series of problems of strip breakage in production, reduction of optical performance and the like.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a polyvinyl alcohol film and a preparation method thereof, and the polyvinyl alcohol film prepared by the preparation method provided by the present invention has superior surface hardness and strength. In the winding process, no bubble embedding phenomenon exists between the guide roller and the film, and no wrinkle defect occurs in the winding process; meanwhile, the film has no wrinkles in the processes of rolling-out unit and conveying.
The invention provides a preparation method of a polyvinyl alcohol film, which comprises the following steps:
A) mixing polyvinyl alcohol resin, a plasticizer, a surfactant and a solvent to obtain a mixed solution of polyvinyl alcohol;
B) extruding and casting the mixed solution to form an initial embryonic membrane, and drying to obtain the embryonic membrane;
C) rolling out the embryonic membrane at the membrane surface temperature of 40-100 ℃ and the membrane surface tension of 1-50 N.m to obtain an initial membrane;
D) and cooling the initial film to 5-30 ℃, and rolling when the film surface tension of the initial film is 1-50 N.m to obtain the polyvinyl alcohol film.
Preferably, in step a), the plasticizer is one or more selected from glycerol, ethylene glycol, propylene glycol and tetraethylene glycol.
Preferably, in the step A), the surfactant is selected from one or more of potassium laurate, dodecyl benzene sulfonate, octyl salicylate, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene laurate, polyoxyethylene lauryl amine ether, polyoxyethylene lauramide, polyoxyethylene polyoxypropylene ether, oleic acid diethanolamide and polyoxyalkylene allyl phenyl ether.
Preferably, in step a), the solvent is one selected from the group consisting of water, dimethyl sulfoxide, ethylene glycol, N-methylpyrrolidone, dimethylacetamide, trimethylolacetone and glycerol.
Preferably, in the step a), the mass ratio of the polyvinyl alcohol resin, the plasticizer, the surfactant and the solvent is 100: 3-15: 0.05-1: 134 to 997.
Preferably, in the step B), the extrusion temperature is 80-140 ℃.
Preferably, in step B), the drying is three-stage drying, including:
a) drying at 60-99 ℃ for 30-360 seconds;
b) drying at 50-99 ℃ for 60-240 s;
c) and finally drying the mixture for 5 to 240 seconds at the temperature of between 40 and 170 ℃.
Preferably, in the step C), the temperature of the film surface is maintained at 40-100 ℃ by hot roll heating, infrared radiation, auxiliary hot air drying, heat transfer or heat pulse treatment.
The invention also provides the polyvinyl alcohol film prepared by the preparation method.
The invention provides a preparation method of a polyvinyl alcohol film, which comprises the following steps: A) mixing polyvinyl alcohol resin, a plasticizer, a surfactant and a solvent to obtain a mixed solution of polyvinyl alcohol; B) extruding and casting the mixed solution to form an initial embryonic membrane, and drying to obtain the embryonic membrane; C) rolling out the embryonic membrane at the membrane surface temperature of 40-100 ℃ and the membrane surface tension of 1-50 N.m to obtain an initial membrane; D) and cooling the initial film to 5-30 ℃, and rolling when the film surface tension of the initial film is 1-50 N.m to obtain the polyvinyl alcohol film. The preparation method of the polyvinyl alcohol film provided by the invention is to roll out and roll up under the conditions of specific film surface temperature and film surface tension, so that the surface hardness and the strength of the polyvinyl alcohol film are excellent. During the rolling-out and rolling-up processes, no bubble embedding phenomenon exists between the guide roller and the film, and no wrinkle defect occurs during the rolling-up process; meanwhile, the film has no wrinkles in the processes of rolling-out unit and conveying. In addition, after the initial embryonic membrane is formed by casting, the thickness of the initial embryonic membrane can not be changed by a series of drying of rolling out and rolling.
Experimental results show that the yield strength of the polyvinyl alcohol film entering the unwinding section is 10-80N, the hardness of the film is larger than or equal to 2B, the solvent and plasticizer residues in the film are 3-20 wt% (the deviation is controlled within +/-0.5%), and the film has a good unwinding effect. The yield strength of the polyvinyl alcohol film entering the rolling section is 15-80N, the hardness of the film is more than or equal to 2B, the solvent and plasticizer residues in the film are 3-17 wt% (the deviation is controlled within +/-0.5%), and the film has a good rolling effect. The thickness of the polyvinyl alcohol film prepared by the preparation method provided by the invention is 20-90 mu m, no embedded air bubble phenomenon exists between the guide roller and the film in the winding-out and winding processes, and no wrinkle defect occurs in the winding process; meanwhile, the film has no wrinkles in the processes of rolling-out unit and conveying. In addition, after the initial embryonic membrane is formed by casting, the thickness of the initial embryonic membrane can not be changed by a series of drying of rolling out and rolling.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a polyvinyl alcohol film, which comprises the following steps:
A) mixing polyvinyl alcohol resin, a plasticizer, a surfactant and a solvent to obtain a mixed solution of polyvinyl alcohol;
B) extruding and casting the mixed solution to form an initial embryonic membrane, and drying to obtain the embryonic membrane;
C) rolling out the embryonic membrane at the membrane surface temperature of 40-100 ℃ and the membrane surface tension of 1-50 N.m to obtain an initial membrane;
D) and cooling the initial film to 5-30 ℃, and rolling when the film surface tension of the initial film is 1-50 N.m to obtain the polyvinyl alcohol film.
The invention firstly mixes polyvinyl alcohol resin, plasticizer, surfactant and solvent to obtain the mixed solution of polyvinyl alcohol.
In the invention, the polymerization degree of the polyvinyl alcohol resin is preferably less than or equal to 10000, and more preferably 1000-10000. The alcoholysis degree of the polyvinyl alcohol resin is preferably more than or equal to 80 percent; more preferably 99.99% or more.
The plasticizer is preferably one or more of glycerol, ethylene glycol, propylene glycol and tetraethylene glycol.
The surfactant is preferably one or more of a carboxylic acid type anionic surfactant, a sulfate type anionic surfactant, a sulfonic acid type anionic surfactant, an alkyl ether type nonionic surfactant, an alkyl benzene ether type nonionic surfactant, an alkyl ester type nonionic surfactant, an alkylamine type nonionic surfactant, an alkylamide type nonionic surfactant, a polypropylene glycol ether type nonionic surfactant, an alkanolamide type nonionic surfactant and an allylbenzene ether type nonionic surfactant; more preferably one or more of potassium laurate, dodecyl benzene sulfonate, octyl salicylate, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene laurate, polyoxyethylene lauryl amine ether, polyoxyethylene lauric acid amide, polyoxyethylene polyoxypropylene ether, oleic acid diethanolamide and polyoxyalkylene allyl phenyl ether.
The solvent is preferably one of water, dimethyl sulfoxide, ethylene glycol, N-methylpyrrolidone, dimethylacetamide, trimethylolacetone, and glycerol. The water is preferably deionized water.
In the present invention, the mass ratio of the polyvinyl alcohol resin, the plasticizer, the surfactant, and the solvent is preferably 100: 3-15: 0.05-1: 134 to 997. In certain embodiments of the present invention, the mass ratio of the polyvinyl alcohol resin, the plasticizer, the surfactant, and the solvent is 100: 4.9: 0.05: 700 or 100: 14.46: 1: 884.5 or 100: 3.1: 0.15: 146.7.
after the mixing, heating and stirring are preferably further included. The method of heating and stirring is not particularly limited in the present invention, and a method of heating and stirring known to those skilled in the art may be used. The heating and stirring temperature is preferably 90-140 ℃.
And after a mixed solution of polyvinyl alcohol is obtained, extruding and casting the mixed solution to form an initial embryonic membrane, and drying to obtain the embryonic membrane.
Before the extrusion, filtration is preferably also included. The method of filtration is not particularly limited in the present invention, and a filtration method known to those skilled in the art may be used.
The extrusion temperature is preferably 80-140 ℃. In certain embodiments of the invention, the temperature of the extrusion is 80 ℃, 100 ℃, or 140 ℃. The extrusion is preferably to a die. The invention has no special limitation on the model of the die and can be selected according to the actual requirement. In certain embodiments of the invention, the mold is a coat hanger mold.
The drying is preferably a three-stage drying, preferably comprising:
a) drying at 60-99 ℃ for 30-360 seconds;
b) drying at 50-99 ℃ for 60-240 s;
c) and finally drying the mixture for 5 to 240 seconds at the temperature of between 40 and 170 ℃.
In certain embodiments of the invention, the drying temperature of step a) is 60 ℃, 80 ℃ or 99 ℃. The drying time of step a) is 360s, 180s or 30 s. Said step a) is preferably carried out in casting rolls.
In certain embodiments of the invention, the drying temperature of step b) is 50 ℃, 75 ℃ or 99 ℃. The drying time of step b) is 240s, 180s or 60 s. Said step b) is preferably carried out in a guide roll.
In certain embodiments of the invention, the drying temperature of step c) is 40 ℃, 100 ℃ or 170 ℃. The drying time of said step c) is 240s, 120s or 5 s. Said step c) is preferably carried out in an oven.
In the three-stage drying, no embedded air bubbles exist between the guide roller and the film in the subsequent winding-out and winding processes, and no wrinkle defect occurs in the winding process; meanwhile, the film has no wrinkles in the processes of rolling-out unit and conveying, and has further promotion effect.
And rolling out the embryonic membrane at the membrane surface temperature of 40-100 ℃ and the membrane surface tension of 1-50 N.m to obtain an initial membrane.
The rolling-out temperature is 40-100 ℃. In certain embodiments of the invention, the temperature of the rollout is 80 ℃, 100 ℃ or 40 ℃. The film surface tension of the rolled-out film is 1-50 N.m. In certain embodiments of the invention, the unwound film surface tension is 1N · m, 15N · m, or 50N · m.
The film surface temperature is preferably maintained at 40-100 ℃ by hot roll heating, infrared radiation, auxiliary hot air drying, heat transfer or heat pulse treatment. The temperature of the film surface is maintained at 40-100 ℃, so that the normal operation of the film rolling-out process can be ensured.
The temperature of hot air in the auxiliary hot air drying is preferably 40-130 ℃.
The temperature of the heat pulse treatment is preferably 100-170 ℃. The film surface temperature is controlled by adopting heat pulse treatment, and the further promotion effect on finally improving the hardness and the yield strength of the film is achieved.
After the initial film is obtained, cooling the initial film to 5-30 ℃, and rolling when the film surface tension of the initial film is 1-50 N.m to obtain the polyvinyl alcohol film.
The temperature of the initial film after cooling is 5-30 ℃. In certain embodiments of the invention, the initial film is cooled to a temperature of 5 ℃, 20 ℃ or 30 ℃. The tension of the film surface of the winding is 1-50 N.m. In certain embodiments of the invention, the wound film surface tension is 1N · m, 10N · m, or 50N · m.
The cooling is preferably performed by cold air treatment. The temperature of the cold air is preferably 5-30 ℃. In certain embodiments of the invention, the cold air is at a temperature of 5 ℃, 20 ℃ or 30 ℃.
The invention rolls out and rolls under the conditions of specific membrane surface temperature and membrane surface tension, thereby leading the thickness of the obtained polyvinyl alcohol film to be thinner, simultaneously leading the surface hardness and the strength of the polyvinyl alcohol film to be better, leading no bubble embedding phenomenon between a guide roller and the film in the rolling process and leading no wrinkle defect to appear in the rolling process; meanwhile, the film has no wrinkles in the processes of rolling-out unit and conveying.
The invention also provides the polyvinyl alcohol film prepared by the preparation method.
In the invention, the thickness of the polyvinyl alcohol film is preferably 20-90 μm. In certain embodiments of the invention, the polyvinyl alcohol film has a thickness of 20 μm, 75 μm, or 90 μm.
The polyvinyl alcohol film has excellent surface hardness and strength. The yield strength of the polyvinyl alcohol film entering the rolling-out section is 10-80N, and preferably 30-80N; the hardness of the film is more than or equal to 2B, and preferably 2-5B; the residual amount of the solvent and the plasticizer in the film is 3 to 20 wt% (deviation is controlled within + -0.5%), preferably 3 to 10 wt% (deviation is controlled within + -0.5%); the film has good roll-out effect.
The yield strength of the polyvinyl alcohol film entering the rolling section is 15-80N, and preferably 40-80N; the hardness of the film is more than or equal to 2B, and preferably 2-4B; the residual amount of the solvent and the plasticizer in the film is 3 to 17 wt% (deviation is controlled within + -0.5%), preferably 3 to 8 wt% (deviation is controlled within + -0.5%); the film has good rolling effect.
In the rolling-out and rolling-up processes of the polyvinyl alcohol film, no bubble embedding phenomenon exists between the guide roller and the film, and no wrinkle defect occurs in the rolling-up process; meanwhile, the film has no wrinkles in the processes of rolling-out unit and conveying.
The source of the raw material components used in the present invention is not particularly limited, and may be generally commercially available.
The invention provides a preparation method of a polyvinyl alcohol film, which comprises the following steps: A) mixing polyvinyl alcohol resin, a plasticizer, a surfactant and a solvent to obtain a mixed solution of polyvinyl alcohol; B) extruding and casting the mixed solution to form an initial embryonic membrane, and drying to obtain the embryonic membrane; C) rolling out the embryonic membrane at the membrane surface temperature of 40-100 ℃ and the membrane surface tension of 1-50 N.m to obtain an initial membrane; D) and cooling the initial film to 5-30 ℃, and rolling when the film surface tension of the initial film is 1-50 N.m to obtain the polyvinyl alcohol film. The preparation method of the polyvinyl alcohol film provided by the invention is to roll out and roll up under the conditions of specific film surface temperature and film surface tension, so that the surface hardness and the strength of the polyvinyl alcohol film are excellent. During the rolling-out and rolling-up processes, no bubble embedding phenomenon exists between the guide roller and the film, and no wrinkle defect occurs during the rolling-up process; meanwhile, the film has no wrinkles in the processes of rolling-out unit and conveying.
Experimental results show that the yield strength of the polyvinyl alcohol film entering the unwinding section is 10-80N, the hardness of the film is larger than or equal to 2B, the solvent and plasticizer residues in the film are 3-20 wt% (the deviation is controlled within +/-0.5%), and the film has a good unwinding effect. The yield strength of the polyvinyl alcohol film entering the rolling section is 15-80N, the hardness of the film is more than or equal to 2B, the solvent and plasticizer residues in the film are 3-17 wt% (the deviation is controlled within +/-0.5%), and the film has a good rolling effect. The thickness of the polyvinyl alcohol film prepared by the preparation method provided by the invention is 20-90 mu m, no embedded air bubble phenomenon exists between the guide roller and the film in the winding-out and winding processes, and no wrinkle defect occurs in the winding process; meanwhile, the film has no wrinkles in the processes of rolling-out unit and conveying. In addition, after the initial embryonic membrane is formed by casting, the thickness of the initial embryonic membrane can not be changed by a series of drying of rolling out and rolling.
In order to further illustrate the present invention, the following examples are provided to describe the polyvinyl alcohol film and the preparation method thereof in detail, but should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all generally commercially available.
Example 1
100g of polyvinyl alcohol resin (with a polymerization degree of 2600 and an alcoholysis degree of 99.99%), 4.9g of glycerol, 0.05g of potassium laurate and 700g of deionized water were mixed to obtain a mixed solution of polyvinyl alcohol, and the mixed solution of polyvinyl alcohol was obtained after stirring uniformly at 130 ℃.
And filtering the mixed solution, extruding the mixed solution to a coat hanger type die at 100 ℃, and performing tape casting to form an initial embryonic membrane. The initial embryonic membrane was dried in a roller at 80 ℃ for 180s, in a guide roller at 75 ℃ for 180s, and in an oven at 100 ℃ for 120s to give an embryonic membrane. Through detection, the yield strength, hardness, solvent residue and plasticizer residue indexes of the embryonic membrane respectively reach: yield strength, 30N; hardness, 5B; solvent residue, 5.6%; plasticizer residue, 4.4%.
And heating the embryonic membrane to 80 ℃ by using hot air at 80 ℃, and rolling out the embryonic membrane under the condition of controlling the tension of the embryonic membrane to be 15 N.m to obtain an initial thin membrane.
And (3) treating the initial film by using cold air at 20 ℃ to reduce the temperature of the initial film to 20 ℃, and rolling when the film surface tension of the initial film is controlled to be 10 N.m to obtain the polyvinyl alcohol film with the thickness of 75 microns.
According to the standard of GB 13022-91 'test method for tensile property of plastic film', the yield strength of the polyvinyl alcohol film is detected to be 40N. The hardness of the polyvinyl alcohol film is detected to be 4B according to the standard of GB/T6739-. According to the GB/T687-94 Standard of chemical reagent glycerol, HB/T3558-.
The following are found in the experiment: in the winding process, no bubble embedding phenomenon exists between the guide roller and the film, and no wrinkle defect occurs in the winding process; meanwhile, the film has no wrinkles in the processes of rolling-out unit and conveying.
Example 2
100g of polyvinyl alcohol resin (with a polymerization degree of 1000 and an alcoholysis degree of 99.99%), 14.46g of ethylene glycol, 1g of dodecylbenzene sulfonate and 884.5g of deionized water were mixed to obtain a mixed solution of polyvinyl alcohol, and the mixed solution of polyvinyl alcohol was obtained after stirring uniformly at 90 ℃.
And filtering the mixed solution, extruding the mixed solution to a coat hanger type die at 140 ℃, and performing tape casting to form an initial embryonic membrane. The initial embryonic membrane was dried in a roller at 99 ℃ for 30s, in a guide roller at 99 ℃ for 60s, and in an oven at 170 ℃ for 5s to give an embryonic membrane. Through detection, the yield strength, hardness, solvent residue and plasticizer residue indexes of the embryonic membrane respectively reach: yield strength, 10N; hardness, 7B; residual solvent, 8.4%; plasticizer remained, 11.6%.
And (3) treating the embryonic membrane by a heat pulse at 170 ℃ until the membrane surface temperature is 100 ℃, and rolling out under the condition of controlling the membrane surface tension to be 1 N.m to obtain an initial membrane.
And treating the initial film by using cold air at 5 ℃ to reduce the temperature of the initial film to 5 ℃, and rolling when the film surface tension of the initial film is controlled to be 1 N.m to obtain the polyvinyl alcohol film with the thickness of 90 microns.
According to the standard of GB 13022-91 'test method for tensile property of plastic film', the yield strength of the polyvinyl alcohol film is detected to be 15N. The hardness of the polyvinyl alcohol film is detected to be 6B according to the standard of GB/T6739-. According to the GB/T4649-.
The following are found in the experiment: in the winding process, no bubble embedding phenomenon exists between the guide roller and the film, and no wrinkle defect occurs in the winding process; meanwhile, the film has no wrinkles in the processes of rolling-out unit and conveying.
Example 3
100g of polyvinyl alcohol resin (with a polymerization degree of 10000 and an alcoholysis degree of 99.99%), 3.1g of propylene glycol, 0.15g of polyoxyethylene oleyl ether and 146.7g of deionized water were mixed to obtain a mixed solution of polyvinyl alcohol, and the mixed solution of polyvinyl alcohol was obtained after stirring uniformly at 140 ℃.
And filtering the mixed solution, extruding the mixed solution to a coat hanger type die at 80 ℃, and performing tape casting to form an initial embryonic membrane. The initial embryonic film was dried in a roll at 60 ℃ for 360s, in a guide roll at 50 ℃ for 240s, and in an oven at 40 ℃ for 240s to give an embryonic film. Through detection, the yield strength, hardness, solvent residue and plasticizer residue indexes of the embryonic membrane respectively reach: yield strength, 80N; hardness, 2B; solvent residue, 0.5%; plasticizer residue, 3%.
And heating the embryonic membrane to 40 ℃ by hot air at 40 ℃, and rolling out the embryonic membrane under the condition of controlling the tension of the embryonic membrane to 50 N.m to obtain an initial thin membrane.
And treating the initial film by using cold air at 30 ℃ to reduce the temperature of the initial film to 30 ℃, and rolling when the film surface tension of the initial film is controlled to be 50 N.m to obtain the polyvinyl alcohol film with the thickness of 20 microns.
According to the standard of GB 13022-91 'test method for tensile property of plastic film', the yield strength of the polyvinyl alcohol film is detected to be 80N. The hardness of the polyvinyl alcohol film is detected to be 2B according to the standard of GB/T6739-. The polyvinyl alcohol film was tested to have a plasticizer residue of 3% and a solvent residue of 0.5% according to GB5009.251-2016 [ measurement of 1, 2-propanediol ], HB/T3558-.
The following are found in the experiment: in the winding process, no bubble embedding phenomenon exists between the guide roller and the film, and no wrinkle defect occurs in the winding process; meanwhile, the film has no wrinkles in the processes of rolling-out unit and conveying.
Comparative example 1
100g of polyvinyl alcohol resin (with a polymerization degree of 2600 and an alcoholysis degree of 99.99%), 4.9g of glycerol, 0.05g of potassium laurate and 700g of deionized water were mixed to obtain a mixed solution of polyvinyl alcohol, and the mixed solution of polyvinyl alcohol was obtained after stirring uniformly at 130 ℃.
And filtering the mixed solution, extruding the mixed solution to a coat hanger type die at 100 ℃, and performing tape casting to form an initial embryonic membrane. The initial embryonic membrane was dried in a roller at 80 ℃ for 180s, in a guide roller at 75 ℃ for 180s, and in an oven at 100 ℃ for 120s to give an embryonic membrane. Through detection, the yield strength, hardness, solvent residue and plasticizer residue indexes of the embryonic membrane respectively reach: yield strength, 30N; hardness, 5B; solvent residue, 5.6%; plasticizer residue, 4.4%.
And heating the embryonic membrane to 35 ℃ by hot air at 35 ℃, and rolling out the embryonic membrane under the condition of controlling the tension of the embryonic membrane to 15 N.m to obtain an initial thin membrane.
And (3) treating the initial film by using cold air at 20 ℃ to reduce the temperature of the initial film to 20 ℃, and rolling when the film surface tension of the initial film is controlled to be 10 N.m to obtain the polyvinyl alcohol film with the thickness of 75 microns.
According to the standard of GB 13022-91 'test method for tensile property of plastic film', the yield strength of the polyvinyl alcohol film is detected to be 12N. The hardness of the polyvinyl alcohol film is detected to be 7B according to the standard of GB/T6739-. According to the GB/T687-94 Standard of chemical reagent glycerol and the HB/T3558 Standard of 1988 Standard of film moisture content test, the plasticizer residue and the solvent residue of the polyvinyl alcohol film are respectively detected to be 8 percent and 10 percent.
The following are found in the experiment: when the polyvinyl alcohol film is in a roll-out unit, the film is soft and has no strength, and the phenomenon of continuous wrinkles appears in the conveying process, so that the film has indentations. Air bubbles are embedded between the guide roller and the film to form a print mark. Fold defects occur frequently in the winding process.
Comparative example 2
100g of polyvinyl alcohol resin (with a polymerization degree of 1000 and an alcoholysis degree of 99.99%), 14.46g of ethylene glycol, 1g of dodecylbenzene sulfonate and 884.5g of deionized water were mixed to obtain a mixed solution of polyvinyl alcohol, and the mixed solution of polyvinyl alcohol was obtained after stirring uniformly at 90 ℃.
And filtering the mixed solution, extruding the mixed solution to a coat hanger type die at 140 ℃, and performing tape casting to form an initial embryonic membrane. The initial embryonic membrane was dried in a roller at 99 ℃ for 30s, in a guide roller at 99 ℃ for 60s, and in an oven at 170 ℃ for 5s to give an embryonic membrane. Through detection, the yield strength, hardness, solvent residue and plasticizer residue indexes of the embryonic membrane respectively reach: yield strength, 10N; hardness, 7B; residual solvent, 8.4%; plasticizer remained, 11.6%.
And heating the embryonic membrane to the membrane surface temperature of 100 ℃ by using hot air at 170 ℃, and rolling out under the condition of controlling the membrane surface tension to be 1 N.m to obtain an initial membrane.
And (3) directly rolling the initial film when the film surface tension is 1 N.m to obtain the polyvinyl alcohol film with the thickness of 90 mu m.
According to the standard of GB 13022-91 'test method for tensile property of plastic film', the yield strength of the polyvinyl alcohol film is detected to be 13N. The hardness of the polyvinyl alcohol film is detected to be 7B according to the standard of GB/T6739-. According to the GB/T4649-.
The following are found in the experiment: fold defects occur frequently in the winding process.
Comparative example 3
100g of polyvinyl alcohol resin (with a polymerization degree of 2600 and an alcoholysis degree of 99.99%), 4.9g of glycerol, 0.05g of potassium laurate and 700g of deionized water were mixed to obtain a mixed solution of polyvinyl alcohol, and the mixed solution of polyvinyl alcohol was obtained after stirring uniformly at 130 ℃.
And filtering the mixed solution, extruding the mixed solution to a coat hanger type die at 100 ℃, and performing tape casting to form an initial embryonic membrane. The initial embryonic membrane was dried in a roller at 80 ℃ for 180s, in a guide roller at 75 ℃ for 180s, and in an oven at 100 ℃ for 120s to give an embryonic membrane. Through detection, the yield strength, hardness, solvent residue and plasticizer residue indexes of the embryonic membrane respectively reach: yield strength, 30N; hardness, 5B; solvent residue, 5.6%; plasticizer residue, 4.4%.
And heating the embryonic membrane to 80 ℃ by using hot air at 80 ℃, and rolling out the embryonic membrane under the condition of controlling the tension of the membrane surface to be 60 N.m to obtain an initial thin membrane.
And treating the initial film by using cold air at 20 ℃ to reduce the temperature of the initial film to 20 ℃, and rolling the initial film at 55 N.m to obtain the polyvinyl alcohol film with the thickness of 75 microns.
According to the standard of GB 13022-91 'test method for tensile property of plastic film', the yield strength of the polyvinyl alcohol film is detected to be 40N. The hardness of the polyvinyl alcohol film is detected to be 4B according to the standard of GB/T6739-. According to the GB/T687-94 Standard of chemical reagent glycerol and the HB/T3558 Standard of 1988 Standard of film moisture content test, the plasticizer residue and the solvent residue of the polyvinyl alcohol film are respectively detected to be 3.5% and 4.5%.
The following are found in the experiment: obvious wrinkles appear on the surface of a guide roller when the polyvinyl alcohol film is rolled out from the rolling-out unit, and the wrinkle defect of the film frequently appears during rolling.
As can be seen from the comparative examples and examples, the method for preparing the polyvinyl alcohol film provided by the present invention is to perform the rolling-out and the rolling-up under the conditions of the specific film surface temperature and the film surface tension, so that the polyvinyl alcohol film has excellent surface hardness and strength. During the rolling-out and rolling-up processes, no bubble embedding phenomenon exists between the guide roller and the film, and no wrinkle defect occurs during the rolling-up process; meanwhile, the film has no wrinkles in the processes of rolling-out unit and conveying. In addition, after the initial embryonic membrane is formed by casting, the thickness of the initial embryonic membrane can not be changed by a series of drying of rolling out and rolling.
Experimental results show that the yield strength of the polyvinyl alcohol film entering the unwinding section is 10-80N, the hardness of the film is larger than or equal to 2B, the solvent and plasticizer residues in the film are 3-20 wt% (the deviation is controlled within +/-0.5%), and the film has a good unwinding effect. The yield strength of the polyvinyl alcohol film entering the rolling section is 15-80N, the hardness of the film is more than or equal to 2B, the solvent and plasticizer residues in the film are 3-17 wt% (the deviation is controlled within +/-0.5%), and the film has a good rolling effect. The thickness of the polyvinyl alcohol film prepared by the preparation method provided by the invention is 20-90 mu m, no embedded air bubble phenomenon exists between the guide roller and the film in the winding-out and winding processes, and no wrinkle defect occurs in the winding process; meanwhile, the film has no wrinkles in the processes of rolling-out unit and conveying. In addition, after the initial embryonic membrane is formed by casting, the thickness of the initial embryonic membrane can not be changed by a series of drying of rolling out and rolling.
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 preparation method of a polyvinyl alcohol film comprises the following steps:
A) mixing polyvinyl alcohol resin, a plasticizer, a surfactant and a solvent to obtain a mixed solution of polyvinyl alcohol;
B) extruding and casting the mixed solution to form an initial embryonic membrane, and drying to obtain the embryonic membrane;
C) rolling out the embryonic membrane at the membrane surface temperature of 40-100 ℃ and the membrane surface tension of 1-50N/m to obtain an initial membrane;
D) and cooling the initial film to 5-30 ℃, and rolling when the film surface tension of the initial film is 1-50N/m to obtain the polyvinyl alcohol film.
2. The method according to claim 1, wherein in step a), the plasticizer is one or more selected from glycerol, ethylene glycol, propylene glycol and tetraethylene glycol.
3. The production method according to claim 1, wherein in step a), the surfactant is selected from one or more of potassium laurate, dodecylbenzene sulfonate, octylsalicylate, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene laurate, polyoxyethylene lauryl amine ether, polyoxyethylene lauramide, polyoxyethylene polyoxypropylene ether, oleic diethanolamide, and polyoxyalkylene allylphenyl ether.
4. The method according to claim 1, wherein the solvent in step a) is one selected from the group consisting of water, dimethylsulfoxide, ethylene glycol, N-methylpyrrolidone, dimethylacetamide, trimethylolacetone, and glycerol.
5. The production method according to claim 1, wherein in step a), the mass ratio of the polyvinyl alcohol resin, the plasticizer, the surfactant, and the solvent is 100: 3-15: 0.05-1: 134 to 997.
6. The method according to claim 1, wherein the temperature of the extrusion in step B) is 80 to 140 ℃.
7. The method according to claim 1, wherein the drying in step B) is a three-stage drying comprising:
a) drying at 60-99 ℃ for 30-360 seconds;
b) drying at 50-99 ℃ for 60-240 s;
c) and finally drying the mixture for 5 to 240 seconds at the temperature of between 40 and 170 ℃.
8. The method according to claim 1, wherein the film surface temperature is maintained at 40 to 100 ℃ by heat transfer in step C).
9. The production method according to claim 1, wherein in the step C), the film surface temperature is maintained at 40 to 100 ℃ by hot roll heating, infrared radiation, auxiliary hot air drying, or heat pulse treatment.
10. The polyvinyl alcohol film produced by the production method according to any one of claims 1 to 9.
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