CN114395157A - Hardened film and preparation method thereof - Google Patents
Hardened film and preparation method thereof Download PDFInfo
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- CN114395157A CN114395157A CN202111581126.9A CN202111581126A CN114395157A CN 114395157 A CN114395157 A CN 114395157A CN 202111581126 A CN202111581126 A CN 202111581126A CN 114395157 A CN114395157 A CN 114395157A
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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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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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- 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
- C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
-
- 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
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Abstract
The invention belongs to the field of films, and relates to a hardened film and a preparation method thereof. The hardened film comprises a base film and hardened layers positioned on any side of the base film; the coating liquid of the hardened layer comprises the following substances in parts by weight: 20-50 parts of high-Tg waterborne acrylic resin, 10-40 parts of waterborne resin, 35-39 parts of deionized water and 1-10 parts of closed-end isocyanate curing agent; the Tg of the high-Tg water-based acrylic resin is more than 80 ℃, and the Tg represents the glass transition temperature of the resin; the hardened film obtained by the technology of the application has certain hardness and good optical performance.
Description
Technical Field
The invention belongs to the field of films, and relates to a biaxially oriented online coated hardened film, in particular to a hardened film and a preparation method thereof.
Background
The polyethylene terephthalate (PET) film has the characteristics of high light transmittance, low haze, high brightness, no yellowing, good adhesion, good flatness, high temperature resistance, ultraviolet irradiation resistance, good stiffness, anti-burning crack, difficult damage and the like, and is widely applied to the aspects of industrial production, household daily use and the like. In recent years, with the progress of PET film manufacturing technology, optical grade PET films have been widely used in the fields of flat panel displays, in-mold Injection (IMD), solar cells, automotive film and window films.
PET is a high molecular polymer material, the surface hardness of the PET is low, the wear resistance is poor, and the defects of scratch, abrasion and the like are easily generated in the production and application processes, so that the product performance is reduced and the appearance quality is reduced. In order to solve the above problems, the most common method used at present is to form a scratch-resistant and abrasion-resistant hardened layer on the surface of the PET film, and the functional components of the hardened layer are mainly classified into silicone, polyurethane, and acrylic materials. For example, in patent publication No. CN 101384927A, a hard coat layer containing a fluorine-siloxane graft polymer and an ultraviolet-curable resin is applied to a substrate to form a cured film having a pencil hardness of 2H to 8H. Patent CN 102129090, at the coating such as the oligomer of a layer acrylic resin and hydroxyl or amino of substrate surface coating, after the UV solidification, form a layer sclerosis layer on the substrate surface, have higher hardness and good acid and alkali resistance, have high luminousness and solvent resistance simultaneously. Patent CN 102490429 a, by coating a first coating layer with refractive index of 1.57-1.69 on a substrate and coating a layer of polyurethane acrylic prepolymer with refractive index of 1.45-1.60 and 3 functionality on the first coating layer, a hardened film is made after photo-curing, which has extremely low interference fringes and hardness of more than 2H. In patent CN 102504625 a, UV acrylic resin oligomer, multifunctional UV acrylic monomer, photoinitiator, modified perfluoropolyether, leveling agent, and solvent are mixed in proportion, coated on a substrate, and photocured to form a hardened film with scratch resistance, wear resistance, and fingerprint contamination resistance.
At present, as mentioned above, the conventional hardened film is manufactured by adopting an off-line coating solvent formula and then performing UV curing, the off-line coating is manufactured by coating, drying and UV curing a finished film after a polyester film is manufactured by a biaxial stretching process, the solvent formula is formed by using an organic solvent as a main solvent of a coating liquid, a large amount of energy is consumed in the whole production process, and a large amount of volatile organic gas is generated in the production process of the solvent type coating liquid, so that the environment is not friendly.
With the increasing requirements of the society on environmental protection and energy conservation, the method of online coating is gradually paid attention, and the online coating refers to that after a polyester film is longitudinally stretched, an aqueous formula is coated on one surface or two surfaces of the film, and then the film with a coating liquid is subjected to transverse drawing section drying, stretching and curing to obtain the coating liquid. The coating liquid takes water as a main solvent, and is environment-friendly.
Compared with an off-line coating hardening film, the on-line coating has two obvious defects, firstly, the on-line coating is usually thermally cured by the temperature of a horizontal pulling section, the hardness of the currently thermally cured coating is difficult to break through 1H and is difficult to match with the hardness of UV cured coating with the hardness of more than 2H; secondly, after on-line coating, after the coating liquid volatilizes water in a drying section and is solidified to form a film, the film is transversely stretched by 3-4 times, the high-hardness resin and the curing agent react to form a film, a compact net structure is formed, then high stretching is carried out, and the coating generates tiny cracks, so that the light transmittance of the film is reduced, the haze is increased, the film is whitish and fogged, and the requirements of the application field with higher requirements on optical performance and coating appearance cannot be met.
Disclosure of Invention
The invention aims to provide a hardened film and a preparation method thereof, which have the advantages that the hardened film is coated on line in the PET biaxial stretching manufacturing process, has certain hardness and simultaneously has a PET film product with good optical performance.
In order to achieve the above purpose, the invention provides the following technical scheme: a hardening film comprises a base film and a hardening layer positioned on one side of the base film; the coating liquid of the hardened layer comprises the following substances in parts by weight:
20-50 parts of high-Tg water-based acrylic resin;
10-40 parts of water-based resin;
35-39 parts of deionized water;
1-10 parts of a closed-end isocyanate curing agent;
the Tg of the high Tg water-based acrylic resin is more than 80 ℃, and the Tg represents the glass transition temperature.
As an improved technical scheme of the application, the base film is formed by adopting a biaxial stretching process; the hardened layer is formed by coating a coating liquid of the hardened layer after the base film is longitudinally pulled up and before the base film is transversely stretched.
As an improvement of the present application, the base film is an optical-grade film; the thickness of the base film is between 30 and 300 mu m; the total light transmittance of the base film is more than or equal to 85 percent; the haze of the base film is less than or equal to 3.5 percent.
As an improved technical scheme, the base film is a polyethylene terephthalate film, the intrinsic viscosity of the polyethylene terephthalate film is between 0.6dL/g and 0.7dL/g, and the chroma b value is lower than 0.8.
As an improved technical scheme of the application, the waterborne resin comprises one or more of waterborne polyester resin and waterborne polyurethane resin, and the Tg range of the selected waterborne resin is between 40 ℃ and 90 ℃.
As an improved technical scheme of the application, the deblocking temperature of the blocked isocyanate curing agent is more than 140 ℃.
Another technical object of the present application is to provide a method of preparing a hardened film, comprising the steps of:
drying optical-grade polyester chips, performing melt extrusion through a screw extruder, and performing quenching on a casting roller to form a thick sheet;
preheating the thick polyester sheet in the previous step, and longitudinally stretching;
coating a layer of water-based hardening liquid on any surface of the longitudinally stretched membrane;
and drying the coated wet film sheet in an oven, transversely stretching, curing the coating, heat setting and cooling to obtain the polyester film with the surface hardening coating.
The coating method includes any one of slide coating, slot coating, bar coating and micro-gravure coating.
As an improved technical scheme of the application, the temperature of coating curing is higher than that of a transverse stretching stage.
As an improved technical scheme of the application, the temperature of the coating in the curing and heat setting stages is not lower than 140 ℃; the temperature of the transverse stretching stage is not higher than 140 ℃.
Has the advantages that:
the Tg value of the aqueous acrylic resin determines the hardness and tensile properties of the coating film formed therefrom. When the Tg value is higher, the coating film is harder, and the tensile property is weaker; conversely, the lower the Tg, the lower the film hardness and the better the tensile properties. The curing agent also has an effect on the hardness and tensile properties of the coating. The curing agent reacts with the resin at a proper temperature to form independent resin molecules into a high polymer network with a cross-linked network structure, so that the hardness of the coating is improved, and the tensile property is reduced. When the coating is applied to the online coating of a polyester film, the coating is dried and then transversely stretched together with the film, the selection of Tg becomes a contradiction, if high-Tg resin is selected to ensure the hardness of the coating, the stretching performance is weak, the coating is broken in the stretching process to generate tiny cracks, so that the light transmittance of the film is reduced, the haze is increased, the film is whitened and fogged, and the optical performance and the appearance of the product are influenced; the acrylic resin with lower Tg is selected, the hardness of a coating after film formation is difficult to ensure, the Tg value is low, and a coating film is easy to soften and tack back under a high-temperature condition, so that the interlayer adhesion of the film is caused, and the later use is influenced. In the invention, the high Tg water-based acrylic resin is adopted to be matched with the common water-based resin, so that the hardness and the tensile property of the coating are considered, the deblocking temperature of the isocyanate curing agent is more than 140 ℃, and the temperature of the preheating and stretching sections of the transverse drawing is controlled to be lower than the deblocking temperature of the curing agent, so that the coating does not generate crosslinking reaction in the preheating and stretching sections of the transverse drawing; after the uncrosslinked film-forming coating is stretched along with the film, the crosslinking reaction is carried out under the catalysis of high temperature (generally higher than 200 ℃) at the film shaping section to form a compact network structure, the hardness of the coating is further improved, the stretching performance of the coating is considered at the same time, and the appearance and the optical performance of a film product are ensured.
According to the technical scheme, the hardening film is produced in an online coating mode, namely, the hardening treatment of the PET film is completed while the biaxially oriented PET is produced, so that the secondary coating process is reduced, and the production cost is reduced. And the damage to the ecological environment is reduced due to the adoption of the aqueous formula.
It should be understood that all combinations of the foregoing concepts and additional concepts described in greater detail below can be considered as part of the inventive subject matter of this disclosure unless such concepts are mutually inconsistent.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present application will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention. Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
A hardening film comprises a base film and hardening layers positioned on any side of the base film; the base film is formed by adopting a biaxial stretching process; the hardened layer is formed by coating a coating liquid of the hardened layer after the base film is longitudinally pulled up and before the base film is transversely stretched.
The basement membrane is an optical-grade film; the thickness range is as follows: 30-300 μm; the total light transmittance is more than or equal to 85 percent; the haze is less than or equal to 3.5 percent. The base film is a polyethylene terephthalate (PET) film, the intrinsic viscosity of the PET film is between 0.6dL/g and 0.7dL/g, and the chroma b value is lower than 0.8.
In the hardened film, the hardness of the hardened layer is not lower than 1H. The coating liquid of the hardened layer comprises the following substances in parts by weight:
20-50 parts of high-Tg water-based acrylic resin;
10-40 parts of water-based resin;
35-39 parts of deionized water;
1-10 parts of a closed-end isocyanate curing agent;
the high Tg water-based acrylic resin is obtained by copolymerizing monomers by a known method, wherein on one hand, the resin has hardness and stretchability simultaneously through the collocation of soft and hard monomers; on the other hand, functional monomers, reactive emulsifiers, initiators and pH regulators are added to endow the polyester film with adhesion and hydrophilicity to the resin; preparing water-based acrylic resin; the monomer comprises the following substances in parts by weight:
the weight ratio range of the soft monomer and the hard monomer is as follows:
soft monomer/hard monomer: 1/10-1/2;
the soft monomer is one or any combination of ethyl acrylate, n-butyl acrylate and lauryl methacrylate;
the hard monomer is one or any combination of methyl methacrylate, styrene and acrylonitrile;
the functional monomer is one or any combination of acrylic acid, diacetone acrylamide, hydroxyethyl acrylate and isobornyl methacrylate;
the reactive emulsifier is one or any combination of 2-acrylamide-2, 2-dimethyl sodium ethanesulfonate and acrylamide sodium stearate;
the initiator is one or any combination of potassium persulfate and ammonium persulfate;
the pH regulator is one or any combination of sodium bicarbonate and ammonium bicarbonate;
the soft monomer and the hard monomer account for 80 percent of the total weight of the monomers, the functional monomer, the reactive emulsifier, the initiator and the pH regulator account for 20 percent of the total weight of the monomers, and the amount of each substance is determined according to actual requirements.
And (3) after the prepared acrylate emulsion is subjected to low-temperature solvent volatilization, testing the glass transition temperature of the solid resin by adopting Differential Scanning Calorimetry (DSC).
The waterborne resin comprises one or more of waterborne polyester resin and waterborne polyurethane resin, and the Tg range of the selected waterborne resin is between 40 ℃ and 90 ℃.
The deblocking temperature of the blocked-end isocyanate curing agent is more than 140 ℃, and the water-based polyisocyanate curing agent taking 3, 5-dimethylpyrazole, phenol, methyl ethyl ketoxime, ethylene glycol monobutyl ether and the like as the blocking agent is preferably adopted.
Another object of the present application is to provide a method for preparing the above hardening film coated on-line, comprising the steps of:
the raw material slices of the transparent base film are crystallized and dried at the temperature of 150-180 ℃, and then are sent into a corresponding extrusion system for melt extrusion to obtain a base film melt, wherein the melt extrusion temperature is 260-285 ℃;
passing the base film melt through a die head on a rotating cooling roller to obtain an unoriented cast thick sheet;
heating the cooled casting thick sheet to 80-120 ℃, and longitudinally stretching the casting thick sheet by 3.0-3.8 times to obtain a longitudinally stretched film;
coating the water-based hardening liquid on any surface of the longitudinally stretched film;
the film coated with the double-sided coating is heated and dried at 90-130 ℃, and then transversely stretched by 3.0-4.0 times, and in the step, the key point is that the temperature of the drying and stretching section is controlled not to be higher than the reaction temperature of the curing agent, so that the components in the coating liquid are not subjected to a crosslinking reaction before the stretching section. And then the stretched film is subjected to heat setting at 220-245 ℃, the temperature of a heat setting section needs to be controlled to be higher than the reaction temperature of a curing agent, so that the resin and the curing agent are subjected to a crosslinking reaction at the stage to form a reticular polymer structure. And (5) cooling and rolling to obtain the optical grade hardened film.
Example 1
Preparation of coating liquid:
coating liquid: a water-based acrylic resin synthesized with a soft monomer/hard monomer mass ratio of 1/10 (Tg measured by DSC: 130 ℃ C.): 30 parts of SENSHO CHEMICAL aqueous polyurethane resin WB-630 (Tg: 60 ℃): 30 parts of deionized water: 35 parts of ethylene glycol monobutyl ether blocked isocyanate curing agent (deblocking temperature is more than 140 ℃): 5 parts of the raw materials.
Preparation of thin film
Drying polyester chips at 150 ℃ for 4 hours, feeding the polyester chips into a screw extruder, extruding the polyester chips at 260 ℃ through a die head, quenching the polyester chips on a casting sheet roller to below 30 ℃ to form a thick sheet, drawing the thick sheet to a longitudinal drawing area through a guide roller, preheating the thick sheet through a preheating roller, heating the thick sheet to 85 ℃ through an infrared heater, longitudinally drawing the thick sheet by 3.1 times, cooling the thick sheet, carrying out corona treatment on two sides of the thin film, coating the hardened layer coating liquid and the bonding layer coating liquid on two surfaces of the thin film, feeding the coated wet sheet into a transverse drawing area, drying and curing the thin sheet at 110 ℃ in a transverse drawing preheating section, transversely drawing the thin sheet by 3.5 times at 130 ℃, carrying out heat setting at 240 ℃, cooling, cutting edges, and rolling to prepare the hardened film coated on line. The properties were measured (see Table 1).
Example 2
Preparation of coating liquid:
coating liquid: a water-based acrylic resin synthesized with a soft monomer/hard monomer mass ratio of 1/5 (Tg measured by DSC: 100 ℃ C.): 30 parts of SENSHO CHEMICAL aqueous polyurethane resin WB-630 (Tg: 60 ℃): 30 parts of deionized water: 35 parts of ethylene glycol monobutyl ether blocked isocyanate curing agent (deblocking temperature is more than 140 ℃): 5 parts of the raw materials.
Preparation of thin film
Drying polyester chips at the temperature of 170 ℃ for 4 hours, feeding the polyester chips into a screw extruder, extruding the polyester chips at the temperature of 270 ℃ through a die head, quenching the polyester chips on a casting sheet roller to below 30 ℃ to form a thick sheet, drawing the thick sheet to a longitudinal drawing area through a guide roller, preheating the thick sheet through a preheating roller, heating the thick sheet to 85 ℃ through an infrared heater, longitudinally drawing the thick sheet by 3.3 times, cooling the thick sheet, carrying out corona treatment on two sides of the thin film, coating the hardened layer coating liquid and the bonding layer coating liquid on two surfaces of the thin film, coating the wet sheet into a transverse drawing area, drying and curing the thin sheet at the transverse drawing preheating section at the temperature of 100 ℃, transversely drawing the thin sheet by 3.5 times at the temperature of 125 ℃, carrying out heat setting at the temperature of 245 ℃, cooling, cutting edges, and rolling to prepare the hardened film coated on line. The properties were measured (see Table 1).
Example 3
Preparation of coating liquid:
coating liquid: a water-based acrylic resin synthesized with a soft monomer/hard monomer mass ratio of 1/2 (Tg measured by DSC: 80 ℃ C.): 30 parts of SENSHO CHEMICAL aqueous polyurethane resin WB-630 (Tg: 60 ℃): 30 parts of deionized water: 35 parts of ethylene glycol monobutyl ether blocked isocyanate curing agent (deblocking temperature is more than 140 ℃): 5 parts of the raw materials.
Preparation of thin film
Drying polyester chips at 180 ℃ for 4 hours, feeding the polyester chips into a screw extruder, extruding the polyester chips at 285 ℃ through a die head, quenching the polyester chips on a casting roller to below 30 ℃ to form a thick sheet, drawing the thick sheet to a longitudinal drawing area through a guide roller, preheating the thick sheet through a preheating roller, heating the thick sheet to 85 ℃ through an infrared heater, longitudinally drawing the thick sheet by 3.6 times, cooling the thick sheet, carrying out corona treatment on two sides of the thin film, coating the hardened layer coating liquid and the bonding layer coating liquid on two surfaces of the thin film, feeding the coated wet sheet into a transverse drawing area, drying and curing the thin sheet at 110 ℃ in a transverse drawing preheating section, transversely drawing the thin sheet by 3.8 times at 130 ℃, carrying out heat setting at 260 ℃, cooling, cutting edges, and rolling to prepare the hardened film coated on line. The properties were measured (see Table 1).
Example 4
Preparation of coating liquid:
coating liquid: a water-based acrylic resin synthesized with a soft monomer/hard monomer mass ratio of 1/5 (Tg measured by DSC: 100 ℃ C.): 20 parts of SENSHO CHEMICAL aqueous polyurethane resin WB-630 (Tg: 60 ℃): 40 parts of deionized water: 35 parts of ethylene glycol monobutyl ether blocked isocyanate curing agent (deblocking temperature is more than 140 ℃): 5 parts of the raw materials.
Preparation of thin film
Drying polyester chips at 175 ℃ for 4 hours, feeding the polyester chips into a screw extruder, extruding the polyester chips at 255 ℃ through a die head, quenching the polyester chips on a casting sheet roller to below 30 ℃ to form a thick sheet, drawing the thick sheet to a longitudinal drawing area through a guide roller, preheating the thick sheet through a preheating roller, heating the thick sheet to 85 ℃ through an infrared heater, longitudinally drawing the thick sheet by 3.1 times, cooling the thick sheet, carrying out corona treatment on two sides of the thin film, coating the hardened layer coating liquid and the bonding layer coating liquid on two surfaces of the thin film, feeding the coated wet sheet into a transverse drawing area, drying and curing the thin sheet at 105 ℃ in a transverse drawing preheating section, transversely drawing the thin sheet by 3.7 times at 130 ℃, carrying out heat setting at 260 ℃, cooling, cutting edges, and rolling to prepare the hardened film coated on line. The properties were measured (see Table 1).
Example 5
Preparation of coating liquid:
coating liquid: a water-based acrylic resin synthesized with a soft monomer/hard monomer mass ratio of 1/5 (Tg measured by DSC: 100 ℃ C.): 50 parts of SENSHO CHEMICAL aqueous polyurethane resin WB-630 (Tg: 60 ℃): 10 parts of deionized water: 35 parts of ethylene glycol monobutyl ether blocked isocyanate curing agent (deblocking temperature is more than 140 ℃): 5 parts of the raw materials.
Preparation of thin film
Drying polyester chips at the temperature of 170 ℃ for 4 hours, feeding the polyester chips into a screw extruder, extruding the polyester chips at the temperature of 260 ℃ through a die head, quenching the polyester chips on a casting sheet roller to below 30 ℃ to form a thick sheet, drawing the thick sheet to a longitudinal drawing area through a guide roller, preheating the thick sheet through a preheating roller, heating the thick sheet to 85 ℃ through an infrared heater, longitudinally drawing the thick sheet by 3.8 times, cooling the thick sheet, carrying out corona treatment on two sides of the thin film, coating the hardened layer coating liquid and the bonding layer coating liquid on two surfaces of the thin film, coating the wet sheet into a transverse drawing area, drying and curing the thin sheet at the transverse drawing preheating section at the temperature of 110 ℃, transversely drawing the thin sheet by 4.0 times at the temperature of 130 ℃, carrying out heat setting at the temperature of 260 ℃, cooling, cutting edges, and rolling to prepare the hardened film coated on line. The properties were measured (see Table 1).
Example 6
Preparation of coating liquid:
coating liquid: a water-based acrylic resin synthesized with a soft monomer/hard monomer mass ratio of 1/5 (Tg measured by DSC: 100 ℃ C.): 30 parts of SENSHO CHEMICAL aqueous polyurethane resin WB-630 (Tg: 60 ℃): 30 parts of deionized water: 39 parts of ethylene glycol monobutyl ether blocked isocyanate curing agent (deblocking temperature is more than 140 ℃): 1 part.
Preparation of thin film
Drying polyester chips at the temperature of 170 ℃ for 4 hours, feeding the polyester chips into a screw extruder, extruding the polyester chips at the temperature of 260 ℃ through a die head, quenching the polyester chips on a casting sheet roller to below 30 ℃ to form a thick sheet, drawing the thick sheet to a longitudinal drawing area through a guide roller, preheating the thick sheet through a preheating roller, heating the thick sheet to 85 ℃ through an infrared heater, longitudinally drawing the thick sheet by 3.0 times, cooling the thick sheet, carrying out corona treatment on two sides of the thin film, coating the hardened layer coating liquid and the bonding layer coating liquid on two surfaces of the thin film, coating the wet sheet into a transverse drawing area, drying and curing the thin sheet at the transverse drawing preheating section at the temperature of 110 ℃, transversely drawing the thin sheet by 3.3 times at the temperature of 130 ℃, carrying out heat setting at the temperature of 260 ℃, cooling, cutting edges, and rolling to prepare the hardened film coated on line. The properties were measured (see Table 1).
Example 7
Preparation of coating liquid:
coating liquid: a water-based acrylic resin synthesized with a soft monomer/hard monomer mass ratio of 1/5 (Tg measured by DSC: 100 ℃ C.): 30 parts of SENSHO CHEMICAL aqueous polyurethane resin WB-630 (Tg: 60 ℃): 30 parts of deionized water: 35 parts of ethylene glycol monobutyl ether blocked isocyanate curing agent (deblocking temperature is more than 140 ℃): 10 parts.
Preparation of thin film
Drying polyester chips at the temperature of 170 ℃ for 4 hours, feeding the polyester chips into a screw extruder, extruding the polyester chips at the temperature of 260 ℃ through a die head, quenching the polyester chips on a casting sheet roller to below 30 ℃ to form a thick sheet, drawing the thick sheet to a longitudinal drawing area through a guide roller, preheating the thick sheet through a preheating roller, heating the thick sheet to 85 ℃ through an infrared heater, longitudinally drawing the thick sheet by 3.0 times, cooling the thick sheet, carrying out corona treatment on two sides of the thin film, coating the hardened layer coating liquid and the bonding layer coating liquid on two surfaces of the thin film, coating the wet sheet into a transverse drawing area, drying and curing the thin sheet at the transverse drawing preheating section at the temperature of 110 ℃, transversely drawing the thin sheet by 3.3 times at the temperature of 130 ℃, carrying out heat setting at the temperature of 260 ℃, cooling, cutting edges, and rolling to prepare the hardened film coated on line. The properties were measured (see Table 1).
Example 8
Preparation of coating liquid:
coating liquid: a water-based acrylic resin synthesized with a soft monomer/hard monomer mass ratio of 1/5 (Tg measured by DSC: 100 ℃ C.): 30 parts of SENSHO CHEMICAL waterborne polyester resin WB-730 (Tg: 46 ℃): 30 parts of deionized water: 35 parts of ethylene glycol monobutyl ether blocked isocyanate curing agent (deblocking temperature is more than 140 ℃): 5 parts of the raw materials.
Preparation of thin film
Drying polyester chips at the temperature of 170 ℃ for 4 hours, feeding the polyester chips into a screw extruder, extruding the polyester chips at the temperature of 260 ℃ through a die head, quenching the polyester chips on a casting sheet roller to below 30 ℃ to form a thick sheet, drawing the thick sheet to a longitudinal drawing area through a guide roller, preheating the thick sheet through a preheating roller, heating the thick sheet to 85 ℃ through an infrared heater, longitudinally drawing the thick sheet by 3.0 times, cooling the thick sheet, carrying out corona treatment on two sides of the thin film, coating the hardened layer coating liquid and the bonding layer coating liquid on two surfaces of the thin film, coating the wet sheet into a transverse drawing area, drying and curing the thin sheet at the transverse drawing preheating section at the temperature of 110 ℃, transversely drawing the thin sheet by 3.3 times at the temperature of 130 ℃, carrying out heat setting at the temperature of 260 ℃, cooling, cutting edges, and rolling to prepare the hardened film coated on line. The properties were measured (see Table 1).
Example 9
Preparation of coating liquid:
coating liquid: a water-based acrylic resin synthesized with a soft monomer/hard monomer mass ratio of 1/5 (Tg measured by DSC: 100 ℃ C.): 30 parts of SENSHO CHEMICAL aqueous polyurethane resin WB-630 (Tg: 60 ℃): 30 parts of deionized water: 35 parts of 3, 5-dimethylpyrazole blocked isocyanate curing agent (deblocking temperature is more than 140 ℃): 5 parts of the raw materials.
Preparation of thin film
Drying polyester chips at the temperature of 170 ℃ for 4 hours, feeding the polyester chips into a screw extruder, extruding the polyester chips at the temperature of 260 ℃ through a die head, quenching the polyester chips on a casting sheet roller to below 30 ℃ to form a thick sheet, drawing the thick sheet to a longitudinal drawing area through a guide roller, preheating the thick sheet through a preheating roller, heating the thick sheet to 85 ℃ through an infrared heater, longitudinally drawing the thick sheet by 3.0 times, cooling the thick sheet, carrying out corona treatment on two sides of the thin film, coating the hardened layer coating liquid and the bonding layer coating liquid on two surfaces of the thin film, coating the wet sheet into a transverse drawing area, drying and curing the thin sheet at the transverse drawing preheating section at the temperature of 110 ℃, transversely drawing the thin sheet by 3.3 times at the temperature of 130 ℃, carrying out heat setting at the temperature of 260 ℃, cooling, cutting edges, and rolling to prepare the hardened film coated on line. The properties were measured (see Table 1).
Comparative example 1
Preparation of coating liquid:
coating liquid: a water-based acrylic resin synthesized with a soft monomer/hard monomer mass ratio of 1/1 (Tg measured by DSC: 60 ℃ C.): 30 parts of SENSHO CHEMICAL aqueous polyurethane resin WB-630 (Tg: 60 ℃): 30 parts of deionized water: 35 parts of ethylene glycol monobutyl ether blocked isocyanate curing agent (deblocking temperature is more than 140 ℃): 5 parts of the raw materials.
Preparation of thin film
Drying polyester chips at the temperature of 170 ℃ for 4 hours, feeding the polyester chips into a screw extruder, extruding the polyester chips at the temperature of 270 ℃ through a die head, quenching the polyester chips on a casting sheet roller to below 30 ℃ to form a thick sheet, drawing the thick sheet to a longitudinal drawing area through a guide roller, preheating the thick sheet through a preheating roller, heating the thick sheet to 85 ℃ through an infrared heater, longitudinally drawing the thick sheet by 3.3 times, cooling the thick sheet, carrying out corona treatment on two sides of the thin film, coating the hardened layer coating liquid and the bonding layer coating liquid on two surfaces of the thin film, coating the wet sheet into a transverse drawing area, drying and curing the thin sheet at the transverse drawing preheating section at the temperature of 100 ℃, transversely drawing the thin sheet by 3.5 times at the temperature of 125 ℃, carrying out heat setting at the temperature of 245 ℃, cooling, cutting edges, and rolling to prepare the hardened film coated on line. The properties were measured (see Table 1).
Comparative example 2
Coating liquid: a water-based acrylic resin synthesized with a soft monomer/hard monomer mass ratio of 1/5 (Tg measured by DSC: 100 ℃ C.): 10 parts of SENSHO CHEMICAL aqueous polyurethane resin WB-630, (Tg: 60 ℃): 50 parts of deionized water: 35 parts of ethylene glycol monobutyl ether blocked isocyanate curing agent (deblocking temperature is more than 140 ℃): 5 parts of the raw materials.
Preparation of thin film
Drying polyester chips at the temperature of 170 ℃ for 4 hours, feeding the polyester chips into a screw extruder, extruding the polyester chips at the temperature of 270 ℃ through a die head, quenching the polyester chips on a casting sheet roller to below 30 ℃ to form a thick sheet, drawing the thick sheet to a longitudinal drawing area through a guide roller, preheating the thick sheet through a preheating roller, heating the thick sheet to 85 ℃ through an infrared heater, longitudinally drawing the thick sheet by 3.3 times, cooling the thick sheet, carrying out corona treatment on two sides of the thin film, coating the hardened layer coating liquid and the bonding layer coating liquid on two surfaces of the thin film, coating the wet sheet into a transverse drawing area, drying and curing the thin sheet at the transverse drawing preheating section at the temperature of 100 ℃, transversely drawing the thin sheet by 3.5 times at the temperature of 125 ℃, carrying out heat setting at the temperature of 245 ℃, cooling, cutting edges, and rolling to prepare the hardened film coated on line. The properties were measured (see Table 1).
Comparative example 3
Coating liquid: a water-based acrylic resin synthesized with a soft monomer/hard monomer mass ratio of 1/5 (Tg measured by DSC: 100 ℃ C.): 10 parts of SENSHO CHEMICAL aqueous polyurethane resin WB-630 (Tg: 60 ℃): 50 parts of deionized water: 35 parts of normal-temperature reaction type polycarbodiimide crosslinking agent: 5 parts of the raw materials.
Preparation of thin film
Drying polyester chips at the temperature of 170 ℃ for 4 hours, feeding the polyester chips into a screw extruder, extruding the polyester chips at the temperature of 270 ℃ through a die head, quenching the polyester chips on a casting sheet roller to below 30 ℃ to form a thick sheet, drawing the thick sheet to a longitudinal drawing area through a guide roller, preheating the thick sheet through a preheating roller, heating the thick sheet to 85 ℃ through an infrared heater, longitudinally drawing the thick sheet by 3.3 times, cooling the thick sheet, carrying out corona treatment on two sides of the thin film, coating the hardened layer coating liquid and the bonding layer coating liquid on two surfaces of the thin film, coating the wet sheet into a transverse drawing area, drying and curing the thin sheet at the transverse drawing preheating section at the temperature of 100 ℃, transversely drawing the thin sheet by 3.5 times at the temperature of 125 ℃, carrying out heat setting at the temperature of 245 ℃, cooling, cutting edges, and rolling to prepare the hardened film coated on line. The properties were measured (see Table 1).
Comparative example 4
Preparation of coating liquid:
coating liquid: a water-based acrylic resin synthesized with a soft monomer/hard monomer mass ratio of 1/5 (Tg measured by DSC: 100 ℃ C.): 70 parts of deionized water: 25 parts of ethylene glycol monobutyl ether blocked isocyanate curing agent (deblocking temperature is more than 140 ℃): 5 parts of the raw materials.
Preparation of thin film
Drying polyester chips at the temperature of 170 ℃ for 4 hours, feeding the polyester chips into a screw extruder, extruding the polyester chips at the temperature of 270 ℃ through a die head, quenching the polyester chips on a casting sheet roller to below 30 ℃ to form a thick sheet, drawing the thick sheet to a longitudinal drawing area through a guide roller, preheating the thick sheet through a preheating roller, heating the thick sheet to 85 ℃ through an infrared heater, longitudinally drawing the thick sheet by 3.3 times, cooling the thick sheet, carrying out corona treatment on two sides of the thin film, coating the hardened layer coating liquid and the bonding layer coating liquid on two surfaces of the thin film, coating the wet sheet into a transverse drawing area, drying and curing the thin sheet at the transverse drawing preheating section at the temperature of 100 ℃, transversely drawing the thin sheet by 3.5 times at the temperature of 125 ℃, carrying out heat setting at the temperature of 245 ℃, cooling, cutting edges, and rolling to prepare the hardened film coated on line. The properties were measured (see Table 1).
TABLE 1 test results
In comparative example 1, the aqueous acrylic resin contains more soft monomer components, the Tg value of the resin is lower, and the hardness of the formed coating is HB which is less than 1H when the resin is matched with the aqueous resin with low Tg.
In comparative example 2, the overall percentage of the aqueous acrylic resin is low, and the hardness of the formed coating is HB which is less than 1H when the aqueous acrylic resin is matched with the aqueous resin with low Tg.
In comparative example 3, a normal temperature reaction type polycarbodiimide crosslinking agent is adopted, the resin and the curing agent react in the drying and stretching stages of transverse drawing, a crosslinking network structure is formed prematurely, and the coating breaks in the stretching process to generate micro cracks, so that the light transmittance of the film is reduced and the haze of the film is increased.
In comparative example 4, only the aqueous acrylic resin was used, and although ethylene glycol monobutyl ether blocked isocyanate curing agent was used, the resin and the curing agent reacted only in the heat setting section of the cross-draw to form a coating having a hardness of 4H, the aqueous acrylic resin with a high Tg generated micro-cracks during the drawing process due to the absence of the aqueous resin with a low Tg, resulting in a decrease in the light transmittance and an increase in the haze of the film.
In Table 1, methods for detecting correlation properties
Light transmittance and haze: the execution standard is as follows: ISO 14782/13468-1, detection instrument: japanese electrochromic: NDH-2000N.
Hardness of pencil: the execution standard is as follows: ASTM D3363, test instrument: mitsubishi UNI hardness test pencil, uk yi high: elcometer 3086.
③ glass transition temperature of resin: the execution standard is as follows: ASTM D3418, test instrument: us TA instruments DSC 250.
Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the protection scope of the present invention should be determined by the appended claims.
Claims (9)
1. A hardening film is characterized by comprising a base film and a hardening layer positioned on one side of the base film; the coating liquid of the hardened layer comprises the following substances in parts by weight:
20-50 parts of high-Tg water-based acrylic resin;
10-40 parts of water-based resin;
35-39 parts of deionized water;
1-10 parts of a closed-end isocyanate curing agent;
the Tg of the high Tg water-based acrylic resin is more than 80 ℃, and the Tg represents the glass transition temperature of the resin.
2. The cured film according to claim 1, wherein the base film is formed by a biaxial stretching process; the hardened layer is formed by coating a coating liquid of the hardened layer after the base film is longitudinally stretched and before the base film is transversely stretched.
3. The cured film according to claim 1, wherein the base film is an optical-grade film; the thickness of the base film is between 30 and 300 mu m; the total light transmittance of the base film is more than or equal to 85 percent; the haze of the base film is less than or equal to 3.5 percent.
4. The cured film of claim 1, wherein the base film is a polyethylene terephthalate film having an intrinsic viscosity of 0.6dL/g to 0.7dL/g and a b-value of less than 0.8.
5. The hardened film of claim 1, wherein the aqueous resin comprises one or more of an aqueous polyester resin and an aqueous polyurethane resin, and the Tg of the aqueous resin is selected to be in the range of 40 ℃ to 90 ℃.
6. The cured film of claim 1, wherein the blocked isocyanate curing agent has a deblocking temperature of greater than 140 ℃.
7. A method for producing the cured film according to any one of claims 1 to 6, comprising the steps of:
drying optical-grade polyester chips, performing melt extrusion through a screw extruder, and performing quenching on a casting roller to form a thick sheet;
preheating the thick polyester sheet in the previous step, and longitudinally stretching;
coating a layer of water-based hardening liquid on any surface of the longitudinally stretched membrane;
and drying the coated wet film sheet in an oven, transversely stretching, solidifying and heat-setting the coating, and cooling to obtain the polyester film with the surface hardening coating.
8. The method of claim 7, wherein the temperature of the resin and the curing agent in the coating solution at which the crosslinking reaction occurs is higher than the temperature in the drying stage and the transverse stretching stage and lower than the temperature in the heat setting stage.
9. The method for preparing a hardened film according to claim 7, wherein the temperature of the coating curing and heat setting stage is not lower than 140 ℃; the temperature of the transverse stretching stage is not higher than 140 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275583A (en) * | 2013-06-20 | 2013-09-04 | 张家港康得新光电材料有限公司 | Water-based coating liquid for priming coat of polyester film use and polyester film |
| CN103692748A (en) * | 2013-12-13 | 2014-04-02 | 合肥乐凯科技产业有限公司 | Optical polyester thin film |
| CN108307665A (en) * | 2015-03-20 | 2018-07-20 | 杜邦帝人薄膜美国有限公司 | photovoltaic cell |
| CN112552543A (en) * | 2020-12-02 | 2021-03-26 | 合肥乐凯科技产业有限公司 | Optical-grade antifogging film and preparation method thereof |
| CN113088165A (en) * | 2021-03-30 | 2021-07-09 | 安徽国风塑业股份有限公司 | Online coating water-based primer coating and polyester film containing primer |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275583A (en) * | 2013-06-20 | 2013-09-04 | 张家港康得新光电材料有限公司 | Water-based coating liquid for priming coat of polyester film use and polyester film |
| CN103692748A (en) * | 2013-12-13 | 2014-04-02 | 合肥乐凯科技产业有限公司 | Optical polyester thin film |
| CN108307665A (en) * | 2015-03-20 | 2018-07-20 | 杜邦帝人薄膜美国有限公司 | photovoltaic cell |
| CN112552543A (en) * | 2020-12-02 | 2021-03-26 | 合肥乐凯科技产业有限公司 | Optical-grade antifogging film and preparation method thereof |
| CN113088165A (en) * | 2021-03-30 | 2021-07-09 | 安徽国风塑业股份有限公司 | Online coating water-based primer coating and polyester film containing primer |
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