CN114395150B - PET film and preparation method thereof, PET protective film and preparation method thereof - Google Patents

PET film and preparation method thereof, PET protective film and preparation method thereof Download PDF

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Publication number
CN114395150B
CN114395150B CN202111646745.1A CN202111646745A CN114395150B CN 114395150 B CN114395150 B CN 114395150B CN 202111646745 A CN202111646745 A CN 202111646745A CN 114395150 B CN114395150 B CN 114395150B
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pet
film
protective film
adhesive layer
weight
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CN114395150A (en
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郭修远
麦启波
纪亚洁
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Jiangsu Huangguan New Material Technology Co ltd
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Jiangsu Huangguan New Material Technology 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/50—Adhesives in the form of films or foils characterised by a primer layer between the carrier and the adhesive
    • 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
    • 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
    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2467/06—Unsaturated polyesters
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00—Presence of (meth)acrylic polymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

Abstract

The invention provides a PET film and a preparation method thereof, and a PET protective film and a preparation method thereof. At least one surface of the PET film is a non-smooth surface, the non-smooth surface is provided with granular bulges, the height of the bulges is 1-10 mu m, and the interval is 5-1000 mu m. The PET protective film prepared by taking the PET film as a substrate has good temperature resistance, can keep better dimensional stability under the high temperature condition, has lower heat shrinkage rate, and can solve the problem of overflow plating on the surface of glass after a PVD (physical vapor deposition) coating process.

Description

PET film and preparation method thereof, PET protective film and preparation method thereof
Technical Field
The invention relates to the technical field of high-temperature-resistant protective films, in particular to a PET film, a preparation method thereof, the PET film obtained by the preparation method, the PET protective film and the preparation method thereof.
Background
The protective film for electronic products is a film material which is applied to the production, processing and transportation processes of electronic devices and can prevent the surfaces of the electronic devices from being scratched or polluted in the processing process. After protection, the protective film is required to be torn off well, residues are not adhered to the surface of the glass, and the rear-stage manufacturing process of the electronic device is not affected. With the rapid development of electronic product production and processing technology, the requirements on the temperature resistance of the protective film are higher and higher. For example, in PVD (physical vapor deposition) process of the IR hole or the photosensitive hole of the cover glass of the mobile phone, the protective film is required to resist the temperature for 1-2 hours at the high temperature of 180-220 ℃ so as to meet the high temperature resistance requirement of glass electroplating, and the protective film is easy to tear off after being used, has no residue and has no overflow plating.
The current widely used temperature-resistant protective films are mainly made of PET materials and can be divided into a silica gel PET protective film and an acrylic gel PET protective film according to a gel system, wherein the silica gel PET protective film has the advantages of good temperature resistance, no residual gel and good air exhaust, but the problem of silicon transfer easily occurs after the process, the property of the bonded surface is influenced, the process of the later stage is influenced, and the method is basically rarely used. The acrylic adhesive PET protective film has the advantages of high transparency, simple process and large adjustable interval of viscosity, is widely used in the high temperature resistant process of electronic products at present, is limited by the temperature resistance of the PET film, and still cannot completely solve the overflow plating problem after the PVD process at present.
Therefore, developing a protective film with better temperature resistance is of great importance.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a PET film, a preparation method thereof and a PET film prepared by the PET film, and a PET protective film prepared by taking the PET film as a substrate and a preparation method of the PET protective film. The PET protective film has good temperature resistance, can keep better dimensional stability under high temperature conditions, has lower heat shrinkage rate, and can solve the problem of overflow plating on the surface of glass after a PVD coating process.
In order to achieve the above object, a first aspect of the present invention provides a PET film, at least one surface of which is a non-smooth surface having protrusions in the form of particles, the protrusions having a height of 1 μm to 10 μm and a pitch of 5 μm to 1000 μm.
The inventor of the invention finds that the particle-shaped bulges are arranged on the surface of the PET film, the heights and the intervals of the bulges are limited, so that the surface of the PET film can form certain roughness, and the surface of the PET film can counteract the stress of oriented shrinkage of a part of the film under the high-temperature condition, so that the thermal shrinkage rate of the PET film is lower, the dimensional stability is better, and the problem of overflow plating on the surface of glass after a PVD coating process can be effectively solved.
The present invention has enabled the PET film of the present invention to have a low heat shrinkage and a high dimensional stability by defining the height and pitch of the protrusions of the PET film as described above, and in order to further enhance the performance of the PET film, it is preferable that the height of the protrusions is 3 μm to 9 μm and the pitch is 6 μm to 800 μm; more preferably, the protrusions have a height of 5 μm to 8 μm and a pitch of 7 μm to 300 μm.
In the present invention, when the protrusions of the PET film are granular protrusions, the protruding particles are inorganic metal oxides.
The kind of the inorganic metal oxide is not particularly limited, and an inorganic metal oxide that is incompatible with the PET substrate conventionally used in the art may be selected.
Preferably, the inorganic metal oxide may be one or more of elements including silicon, titanium, zirconium, aluminum, calcium, magnesium, and the like.
Preferably, the inorganic metal oxide is selected from one or more of silica, titania, zirconia, alumina, calcium carbonate and magnesia.
Preferably, the particle size of the inorganic metal oxide is 1 μm to 10 μm. For better control of the protrusion height and protrusion pitch of the PET film, the particle diameter of the inorganic metal oxide is preferably 2 μm to 8 μm, more preferably 3 μm to 5 μm.
In the present invention, the term "particle size" refers to the geometric spherical diameter of individual particles rather than the average value, and when in range, refers to the particle size of such particles in the same material falling within that range; while the present invention allows for certain errors, i.e. when less than 5% of the total number of particles have a particle size outside the required range, it is also considered satisfactory. The particle size of the inorganic metal oxide in the present invention is measured by transmission electron microscopy.
Preferably, when the protrusions are granular protrusions, the glossiness of the PET film is 18-50% of 45 DEG, preferably 20-35% of 45 DEG. The glossiness of the PET film directly reflects the roughness of the film surface, and the lower the value of the glossiness, the higher the roughness.
In a second aspect, the present invention provides a process for preparing a PET film according to the first aspect of the present invention, the process comprising a blend film-forming and/or coating process:
the blend film making method comprises the following steps: mixing PET master batch and inorganic metal oxide, and melt-extruding to form a film;
the coating method comprises the steps of coating a photo-curing coating containing inorganic metal oxide on a PET substrate, and curing by light irradiation to form a photo-curing coating.
In the present invention, when the PET film is produced by a blend film-forming method, the inorganic metal oxide is contained in an amount of 5 to 30 wt%, preferably 10 to 25 wt%, and more preferably 15 to 20 wt%, based on the total weight of the PET film.
In one embodiment of the invention, the inorganic metal oxide is a combination of silica and calcium carbonate (weight ratio of 1:2-3), wherein the silica has a particle size of 1 μm to 3 μm and the calcium carbonate has a particle size of 3 μm to 5 μm. The inventor of the present invention found that the specific combination of two inorganic metal oxides, namely silicon dioxide and calcium carbonate, has lower heat shrinkage rate and better dimensional stability when being blended with PET master batch to prepare the PET film.
Preferably, the conditions for melt extrusion film formation include: the melting temperature is 255-285 ℃.
Preferably, the blend film-forming method further comprises the steps of cooling, biaxial stretching, heat setting and rolling after the melt extrusion.
The inventor of the invention researches and discovers that the addition of incompatible inorganic metal oxide to form granular protrusions in the production process of the PET film can enable the PET film to have a non-smooth surface and form a certain roughness, so that the PET film has lower heat shrinkage rate and better dimensional stability.
In the present invention, when the PET film is produced by a coating method, the content of the inorganic metal oxide is 5 to 20% by weight, preferably 8 to 18% by weight, and more preferably 10 to 15% by weight, based on the total weight of the photo-curable coating layer.
Preferably, the photocurable coating comprises a photocurable resin, an inorganic metal oxide, and a photoinitiator.
Preferably, the photo-curing resin is selected from one or more of polyester acrylic resin, epoxy acrylic resin and polyurethane modified acrylic resin.
Preferably, the photocurable resin is a polyester acrylic resin.
More preferably, the photocurable resin is a polyester acrylic resin having a functionality of 9.
Preferably, the inorganic metal oxide is selected from one or more of silica, titania, zirconia, alumina, calcium carbonate and magnesia.
Preferably, the particle size of the inorganic metal oxide is 1 μm to 10 μm; in order to enable better control of the protrusion height and protrusion pitch of the PET film after the photo-curable coating and the inorganic metal oxide are used in combination, the particle size of the inorganic metal oxide is preferably 2 μm to 8 μm, more preferably 3 μm to 5 μm.
Preferably, the photoinitiator may be selected from one or more of 184 (1-hydroxycyclohexyl phenyl ketone), TPO (2, 4, 6-trimethylbenzoyl-diphenyl phosphine oxide), and 1173 (2-hydroxy-2-methyl-1-phenylpropion).
In one embodiment of the present invention, the photo-curable coating layer is a polyester acrylic resin having a functionality of 9, and the inorganic metal oxide is a combination of silica and zirconium dioxide (weight ratio of 1:1-3), wherein the silica has a particle size of 3-5 μm and the titanium dioxide has a particle size of 5-8 μm. The inventor of the present invention found that the photo-curing coating formed by the specific combination of polyester acrylic resin with the functionality of 9, silicon dioxide and zirconium dioxide has lower heat shrinkage rate and better dimensional stability after coating PET base material.
Preferably, the photocurable coating further comprises an auxiliary agent and a solvent; the auxiliary agent preferably comprises a leveling agent and a dispersing agent.
Preferably, the leveling agent is selected from BYK-306, BYK358N, BYK-UV333.
Preferably, the dispersant is selected from the group consisting of DISPERBYK-110 and/or DISPERBYK-180.
Preferably, the solvent comprises one or more of ethyl acetate, propylene glycol dimethyl ether and butanone.
In one embodiment of the present invention, the polyester acrylic resin is contained in an amount of 50 to 80 wt%, the inorganic metal oxide is contained in an amount of 5 to 20 wt%, the photoinitiator is contained in an amount of 2 to 7 wt%, the leveling agent is contained in an amount of 1 to 5 wt%, the dispersant is contained in an amount of 1 to 5 wt%, and the solvent is contained in an amount of 10 to 40 wt%, based on the total weight of the photo-curable coating layer.
Wherein the conditions for the light irradiation include: the UV light energy is 200-1000mj/cm 2 。
Preferably, the thickness of the photo-cured coating is 2 μm to 6 μm. The thickness of the photo-curing coating is optimized, so that the prepared PET film has better bump height and bump spacing, and the effect of improving the overflow plating problem is better.
A third aspect of the present invention provides a PET film produced by the method for producing a PET film according to the second aspect of the present invention.
The PET film provided in the third aspect of the present invention has the same advantages as the PET film provided in the first aspect of the present invention, and will not be described here again.
According to a fourth aspect of the invention, there is provided a PET protective film comprising a substrate and an adhesive layer bonded to each other, the substrate being a PET film according to the first aspect of the invention and/or the third aspect of the invention, at least one non-smooth surface of the PET film being exposed.
The adhesive layer is not particularly limited, and a pressure-sensitive adhesive conventionally used in the art may be selected. In order to make the temperature resistance of the PET protective film better and to avoid the occurrence of residual glue, the thickness of the adhesive layer is preferably 15 μm to 135 μm, and the tackiness range is 5 to 85gf/25mm.
In one embodiment of the invention, the adhesive layer is a high temperature resistant pressure sensitive adhesive.
Preferably, the high temperature resistant pressure sensitive adhesive comprises polyacrylate resin, curing agent, heat stabilizer and solvent.
Wherein the weight average molecular weight of the polyacrylate resin is 20-80 ten thousand, preferably 30-50 ten thousand; the glass transition temperature is-60 ℃ to-35 ℃, preferably-55 ℃ to-45 ℃.
The curing agent is preferably an isocyanate system, and may be selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, and hexamethylene diisocyanate, for example.
The solvent is an organic solvent, preferably one or a mixture of ethyl acetate and toluene.
In the invention, the PET protective film further comprises a stripping layer covering the surface of the adhesive layer.
The material of the release layer is not particularly limited, and materials conventionally used in the art for release layers may be selected, for example, the materials of the release layer include, but are not limited to, one or more of PET, PE, OPP and PC.
Preferably, the thickness of the stripping layer is 25-75 μm, and the release force is 10-30g/25mm.
The PET protective film provided by the invention is obtained by taking a PET film with a non-smooth surface as a substrate and then attaching an adhesive layer and a stripping layer. The PET protective film is used in the high temperature resistant process of electronic products, can keep good dimensional stability under the high temperature condition, has low heat shrinkage rate, and can solve the problem of overflow plating on the surface of glass after the PVD coating process.
A fifth aspect of the present invention provides a method for preparing the PET protective film according to the fourth aspect of the present invention, comprising the steps of: applying an adhesive layer to a surface of a substrate and exposing at least one non-smooth surface of the substrate; the substrate is the PET film of the first aspect of the invention and/or the third aspect of the invention.
In one embodiment of the present invention, a method for preparing the PET protective film includes the steps of:
(a) Mixing PET master batch and inorganic metal oxide, melting and extruding, cooling, biaxially stretching, heat setting and rolling to obtain a PET film;
(b) Mixing polyacrylate resin, a curing agent, a heat stabilizer and a solvent to obtain an adhesive layer coating liquid, and coating the adhesive layer coating liquid on the surface of the PET film obtained in the step (a);
(c) And compounding the stripping layer on the surface of the adhesive layer, and curing to obtain the PET protective film.
In one embodiment of the present invention, a method for preparing the PET protective film includes the steps of:
(i) Mixing the photo-curing resin, inorganic metal oxide, photoinitiator and auxiliary agent, and uniformly dispersing to obtain photo-curing coating liquid;
(ii) Coating the photo-curing coating liquid obtained in the step (i) on a PET substrate, and curing by UV light irradiation to obtain a PET film;
(iii) Mixing polyacrylate resin, a curing agent, a heat stabilizer and a solvent to obtain an adhesive layer coating liquid, and coating the adhesive layer coating liquid on the surface of the PET film obtained in the step (ii);
(iv) And compounding the stripping layer on the surface of the adhesive layer, and curing to obtain the PET protective film.
The method for preparing the PET protective film provided by the invention has the advantages of simple process, easiness in operation, suitability for large-scale production and good application prospect.
The technical scheme adopted by the invention has the following beneficial effects:
(1) The PET film provided by the invention has the advantages of low heat shrinkage rate and good dimensional stability;
(2) The PET protective film provided by the invention has good temperature resistance, can keep better dimensional stability under high temperature conditions, has lower heat shrinkage rate, and can solve the problem of overflow plating on the surface of glass after a PVD coating process.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Drawings
Fig. 1 is a schematic view showing the structure of a PET protective film provided in example 1.
Fig. 2 is a schematic diagram showing the structure of the PET protective film provided in example 3.
Detailed Description
Unless defined otherwise, all scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention relates.
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
In the examples below, unless otherwise specified, all of the ingredients used were commercially available analytical grade. 1 part by weight represents 1g.
Example 1
(first) preparation of PET film
(1) Preparing materials:
PET master batch: 83 parts by weight of a copolyester masterbatch;
inorganic metal oxide: 5 parts by weight of silica having an average particle diameter of 4 μm; 12 parts by weight of calcium carbonate with an average particle size of 5 mu m;
(2) Mixing the PET master batch obtained in the step (1) with inorganic metal oxide, carrying out melt extrusion at 280 ℃, cooling, biaxially stretching and heat setting to obtain a PET film with the thickness of about 15 mu m;
the PET film has a non-smooth surface with granular protrusions, the height of the protrusions is 4-6 mu m, the distance is 150-200 mu m, and the glossiness is 45 DEG and 35%.
(II) preparation of PET protective film
(1) Preparing an adhesive layer coating liquid: 100 parts by weight of a polyacrylate resin (weight average molecular weight: 53 ten thousand, glass transition temperature: 56 ℃ below zero), 3 parts by weight of a curing agent (isocyanate system, trade name: D-100K, manufactured by DIC, japan), 0.5 part by weight of a heat stabilizer (antioxidant, trade name: 1010, manufactured by Basoff, germany) and 35 parts by weight of a solvent (ethyl acetate) were mixed to obtain an adhesive layer coating liquid;
(2) Coating the adhesive layer coating liquid obtained in the step (1) on one surface of the PET film obtained in the step (one);
(3) And compounding a PET material stripping film with the thickness of 50 mu m on the adhesive layer, and finally preparing the PET protective film after curing. The schematic structure of the PET protective film is shown in FIG. 1.
Example 2
(first) preparation of PET film
(1) Preparing materials:
PET master batch: 80 parts by weight of a copolyester masterbatch;
inorganic metal oxide: 5 parts by weight of silica having an average particle diameter of 3 μm; 15 parts by weight of calcium carbonate with an average particle size of 5 mu m;
(2) Mixing the PET master batch obtained in the step (1) with inorganic metal oxide, carrying out melt extrusion at 280 ℃, cooling, biaxially stretching and heat setting to obtain a PET film with the thickness of about 15 mu m;
the PET film has a non-smooth surface with granular protrusions, the heights of the protrusions are 4-6 mu m, the pitches are 100-200 mu m, and the glossiness is 45 DEG and 32%.
(II) preparation of PET protective film
(1) Preparing an adhesive layer coating liquid: 100 parts by weight of a polyacrylate resin (weight average molecular weight: 50 ten thousand, glass transition temperature: -50 ℃ C.), 3 parts by weight of a curing agent (isocyanate system, trade name: D-100K, manufactured by DIC, japan), 0.5 part by weight of a heat stabilizer (antioxidant, trade name: 1010, manufactured by Basoff, germany) and 35 parts by weight of a solvent (ethyl acetate) were mixed to obtain an adhesive layer coating liquid;
(2) Coating the adhesive layer coating liquid obtained in the step (1) on one surface of the PET film obtained in the step (one);
(3) And compounding a PET material stripping film with the thickness of 50 mu m on the adhesive layer, and finally preparing the PET protective film after curing.
Example 3
(first) preparation of PET film
(1) Preparing materials:
photo-curing resin: polyester acrylic resin (functionality 9), 55 parts by weight;
inorganic metal oxide: 2 parts by weight of silica having an average particle diameter of 4 μm; 8 parts by weight of zirconium dioxide with an average particle size of 5 mu m;
and (3) a photoinitiator: TPO,2 parts by weight; 184,3 parts by weight;
leveling agent: BYK-306,3 parts by weight;
dispersing agent: DISPRBYK-110,3 parts by weight;
solvent: ethyl acetate, 24 parts by weight;
(2) Mixing the photo-curing resin, the inorganic metal oxide, the photoinitiator, the leveling agent, the dispersing agent and the solvent in the step (1) to obtain photo-curing coating liquid;
(3) Coating the photo-curing coating liquid obtained in the step (2) on the surface of a PET substrate (PET substrate brand Ys/pt-10, manufacturer three-room lane) with the thickness of 15 mu m, wherein the UV light energy is 800mj/cm 2 And (3) irradiating, wherein the thickness of the photo-cured coating is about 6 mu m, so as to obtain the PET film layer.
The PET film has a non-smooth surface with granular protrusions, the height of the protrusions is 4-6 mu m, the distance is 200-300 mu m, and the glossiness is 45 DEG and 35%.
(II) preparation of PET protective film
(1) Preparing an adhesive layer coating liquid: 100 parts by weight of a polyacrylate resin (weight average molecular weight: 40 ten thousand, glass transition temperature: -45 ℃ C.), 3 parts by weight of a curing agent (isocyanate system, trade name: D-100K, manufactured by DIC, japan), 0.5 part by weight of a heat stabilizer (antioxidant, trade name: 1010, manufactured by Basoff, germany) and 35 parts by weight of a solvent (ethyl acetate) were mixed to obtain an adhesive layer coating liquid;
(2) Coating the adhesive layer coating liquid obtained in the step (1) on one surface of the PET film obtained in the step (one);
(3) And compounding a PET material stripping film with the thickness of 50 mu m on the adhesive layer, and finally preparing the PET protective film after curing. The schematic structure of the PET protective film is shown in FIG. 2.
Example 4
(one), preparing a PET film
(1) Preparing materials:
photo-curing resin: polyester acrylic resin (functionality 9), 52 parts by weight;
inorganic metal oxide: 3 parts by weight of silica having an average particle diameter of 3 μm; 10 parts by weight of zirconium dioxide with an average particle size of 5 mu m;
and (3) a photoinitiator: TPO,2 parts by weight; 184,3 parts by weight;
leveling agent: BYK-306,3 parts by weight;
dispersing agent: DISPRBYK-110,3 parts by weight;
solvent: ethyl acetate, 24 parts by weight;
(2) Mixing the photo-curing resin, the inorganic metal oxide, the photoinitiator, the leveling agent, the dispersing agent and the solvent in the step (1) to obtain a photo-curing coating liquid;
(3) Coating the photo-curing coating liquid obtained in the step (2) on the surface of a PET substrate (PET substrate brand Ys/pt-10, manufacturer three-room lane) with the thickness of 15 mu m, wherein the UV light energy is 800mj/cm 2 And (3) irradiating, wherein the thickness of the photo-cured coating is about 6 mu m, so as to obtain the PET film layer.
The PET film has a non-smooth surface with granular protrusions, the height of the protrusions is 4-6 mu m, the distance is 150-250 mu m, and the glossiness is 45 DEG and 30%.
(II) preparation of PET protective film
(1) Preparing an adhesive layer coating liquid: 100 parts by weight of a polyacrylate resin (weight average molecular weight: 60 ten thousand, glass transition temperature: -50 ℃ C.), 3 parts by weight of a curing agent (isocyanate system, trade name: D-100K, manufactured by DIC, japan), 0.5 part by weight of a heat stabilizer (antioxidant, trade name: 1010, manufactured by Basoff, germany) and 35 parts by weight of a solvent (ethyl acetate) were mixed to obtain an adhesive layer coating liquid;
(2) Coating the adhesive layer coating liquid obtained in the step (1) on one surface of the PET film obtained in the step (one);
(3) And compounding a PET material stripping film with the thickness of 50 mu m on the adhesive layer, and finally preparing the PET protective film after curing.
Example 5 group
The present set of examples is intended to illustrate the effects of the particle size of the raw materials and the proportions of the ingredients in the PET film.
This set of examples was performed as in example 1, except that the ratio of PET masterbatch to inorganic metal oxide was varied, the particle size of the inorganic metal oxide. Specifically:
example 5a: 75 parts by weight of a copolyester masterbatch; 10 parts by weight of silicon dioxide; 15 parts by weight of calcium carbonate;
example 5b: 88 parts by weight of a copolyester masterbatch; 4 parts by weight of silicon dioxide; 8 parts by weight of calcium carbonate;
example 5c: the average particle size of the silica was 6. Mu.m, and the average particle size of the calcium carbonate was 8. Mu.m.
Finally, PET protective films are respectively prepared.
Example 6 group
The present set of examples is intended to illustrate the effects of the particle size of the raw materials and the proportions of the ingredients in the PET film.
This set of examples was carried out as in example 3, except that the ratio of the photocurable resin to the inorganic metal oxide was changed, and the particle size of the inorganic metal oxide was changed. Specifically:
example 6a: a photo-curing resin, 57 parts by weight; 2 parts by weight of silicon dioxide; zirconium dioxide, 6 parts by weight;
example 6b: the average particle size of the silica was 6 μm and the average particle size of the zirconia was 8 μm;
finally, PET protective films are respectively prepared.
Example 7 group
This set of examples is intended to illustrate the effect of changing the raw material composition in PET films.
Example 7a: reference example 1 was performed, except that an equivalent amount of silica having a particle size of 5 μm was substituted for calcium carbonate;
example 7b: reference example 3 was made except that the polyester acrylic resin was replaced with an equivalent amount of polyurethane modified acrylic resin.
Finally, PET protective films are respectively prepared.
Comparative example 1
The process was performed with reference to example 3, except that the PET film was a conventional film purchased in three lanes of the manufacturer, under the trade name Ys/pt-10. Finally obtaining the PET protective film.
Comparative example 2
Reference example 3 was made, except that the photocurable resin, 61 parts by weight; 2 parts by weight of silicon dioxide; zirconium dioxide, 2 parts by weight; the final PET film has granular raised non-smooth surface with height of 4-6 microns and interval of 1100-1500 microns.
Finally obtaining the PET protective film.
Comparative example 3
Reference example 1 was performed except that the average particle diameter of silica was 12 μm and the average particle diameter of calcium carbonate was 12 μm; the final PET film has granular raised non-smooth surface with height of 12-20 microns and interval of 150-200 microns.
Finally obtaining the PET protective film.
Comparative example 4
Reference example 1 was performed except that the average particle diameter of silica was 100nm and the average particle diameter of calcium carbonate was 100nm; the final PET film has granular raised non-smooth surface with raised height of 0.1-0.5 microns and interval of 2-4 microns.
Finally obtaining the PET protective film.
Test case
(1) The thermal shrinkage of the PET protective films provided in examples and comparative examples was measured using or referring to GB/T38848-2017 standard, and the results are recorded in Table 1.
(2) And (3) after tearing off the stripping film of the sample, attaching the adhesive surface on plain glass, placing the plain glass in a constant-temperature blast drying oven for baking at 150 ℃/180 ℃, taking out the plain glass after baking, cooling the plain glass at room temperature for 20min, and tearing off the protective film to check whether residual adhesive is generated on the plain glass plate. The glass plate sticking condition of the PET protective films provided in examples and comparative examples was measured in the above-described manner, and the results are recorded in Table 1.
(3) The protective film is die-cut into the size of the front cover glass of the mobile phone, wherein the position of the photosensitive hole is reserved, the stripping layer of the die-cut protective film sheet is adhered to the front cover glass of the mobile phone after being torn off, the mobile phone is placed into an electroplating box, the electroplating box is vacuumized, PVD electroplating is carried out on the photosensitive hole at 180 ℃ for 1.5h, the front cover glass of the mobile phone is taken out after electroplating is finished, the protective film is torn off, and whether overflow plating occurs around the photosensitive hole is checked. The PET protective films provided in examples and comparative examples were measured for the case of changing the overflow plating in the above-described manner, and the results are recorded in Table 1.
(4) The tensile strength of the PET protective films provided in examples and comparative examples was measured with reference to GBT13022-1991, and the results are recorded in Table 1
TABLE 1
Note that: in order to meet the requirements of the customer process, the tensile strength of the PET protective film is usually more than 150MPa. PET protective films with tensile strength lower than 150MPa were not tested for overplating.
As can be seen from Table 1, the PET protective film prepared by the invention has good temperature resistance, can keep better dimensional stability under high temperature condition, has lower thermal shrinkage rate, and can solve the problem of overflow plating on the glass surface after PVD coating process.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is to be construed as including any modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (9)

1. A PET protective film, which is characterized by comprising a substrate and an adhesive layer which are mutually adhered, and a stripping layer which is covered on the surface of the adhesive layer;
the substrate is a PET film, the surface of the PET film is a non-smooth surface, the non-smooth surface is provided with granular bulges, the height of the bulges is 1-10 mu m, and the interval is 5-1000 mu m; the weight ratio of the raised particles is 1: the composition of silica and calcium carbonate of (2-3);
the glossiness of the PET film is 18-50% of 45 DEG;
the method for preparing the PET film comprises the following steps of blending film making method: the blend film making method comprises the following steps: mixing PET master batches, silicon dioxide in a mass ratio and a calcium carbonate composition, and carrying out melt extrusion to form a film;
the content of the composition of the silicon dioxide and the calcium carbonate is 10-25 percent based on the total weight of the PET film, the particle size of the silicon dioxide is 1-3 mu m, and the particle size of the calcium carbonate is 3-5 mu m.
2. The PET protective film according to claim 1, wherein the adhesive layer has a thickness of 15 μm to 135 μm and an adhesiveness ranging from 5 to 85gf/25mm.
3. The PET protective film according to claim 1 or 2, wherein the adhesive layer is a high temperature-resistant pressure-sensitive adhesive comprising a polyacrylate resin having a weight average molecular weight of 20 to 80 ten thousand, a curing agent having a glass transition temperature of-60 to-35 ℃, a heat stabilizer and a solvent, the curing agent being an isocyanate-based curing agent, and the heat stabilizer being an antioxidant 1010.
4. A PET protective film, which is characterized by comprising a substrate and an adhesive layer which are mutually adhered, and a stripping layer which is covered on the surface of the adhesive layer;
the substrate is a PET film, the surface of the PET film is a non-smooth surface, the non-smooth surface is provided with granular bulges, the height of the bulges is 1-10 mu m, and the interval is 5-1000 mu m; the weight ratio of the raised particles is 1: the silica-zirconia composition of (1-3);
the glossiness of the PET film is 18-50% of 45 DEG;
the method for preparing the PET film comprises the following steps: the coating method comprises the steps of coating a photo-curing coating containing a composition of silicon dioxide and zirconium dioxide on a PET substrate, and curing by light irradiation to form a photo-curing coating;
the photo-curing coating comprises polyester acrylic resin with the functionality of 9, a composition of silicon dioxide and zirconium dioxide and a photoinitiator, wherein the content of the composition of the silicon dioxide and the zirconium dioxide is 10-15% based on the total weight of the photo-curing coating, the particle size of the silicon dioxide is 3-5 mu m, and the particle size of the zirconium dioxide is 5-8 mu m.
5. The PET protective film according to claim 4, wherein the photo-curable coating further comprises a leveling agent, a dispersing agent, and a solvent.
6. The PET protective film according to claim 4 or 5, wherein the thickness of the photo-curable coating layer is 2-6 μm.
7. The PET protective film according to claim 4, wherein the photoinitiator is selected from one or more of 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, and 2-hydroxy-2-methyl-1-phenylpropion.
8. The PET protective film according to claim 4, wherein the adhesive layer has a thickness of 15 μm to 135 μm and an adhesiveness ranging from 5 to 85gf/25mm.
9. The PET protective film according to claim 4 or 8, wherein the adhesive layer is a high temperature-resistant pressure-sensitive adhesive comprising a polyacrylate resin having a weight average molecular weight of 20 to 80 ten thousand, a curing agent having a glass transition temperature of-60 to-35 ℃, a heat stabilizer and a solvent, the curing agent being an isocyanate-based curing agent, and the heat stabilizer being an antioxidant 1010.
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