CN110628346A - Ultrathin high-transparency PI film, protective film containing PI film and preparation method - Google Patents

Ultrathin high-transparency PI film, protective film containing PI film and preparation method Download PDF

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Publication number
CN110628346A
CN110628346A CN201810658699.9A CN201810658699A CN110628346A CN 110628346 A CN110628346 A CN 110628346A CN 201810658699 A CN201810658699 A CN 201810658699A CN 110628346 A CN110628346 A CN 110628346A
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China
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layer
transparent polyimide
transparent
film
protective film
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Inventor
李建辉
林志铭
杜伯贤
梅爱芹
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Asia Electronic Material Co Ltd
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Asia Electronic Material Co Ltd
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Priority to CN201810658699.9A priority Critical patent/CN110628346A/en
Priority to TW108105305A priority patent/TWI705093B/en
Publication of CN110628346A publication Critical patent/CN110628346A/en
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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
    • 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
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • 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
    • 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
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C09J2467/005—Presence of polyester in the release coating
    • 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
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

Abstract

The invention discloses an ultrathin high-transparency PI film, which comprises an anti-UV transparent polyimide layer, wherein the light transmittance of the anti-UV transparent polyimide layer is more than 88%, the haze is less than 1%, the L value of an Laab color system measured by an ultraviolet-visible spectrophotometer is 92-99, the a value is-2.0-2.0, the b value is-2.0-5.0, the surface hardness is more than 4H, and the thickness of the anti-UV transparent polyimide layer is 30-100 mu m; the anti-UV transparent polyimide layer comprises aromatic diamine, aromatic acid anhydride, imidization catalyst, dehydrating agent, anti-UV absorbent and organic solvent, and the weight percentage of each component is as follows in sequence: 30-40%, 2-3%, 2-5%, 1-3% and 9-30% of dehydrating agent. The protective film of the invention is composed of transparent polyimide varnish and an anti-UV transparent adhesive, and has extremely high penetration rate, extremely low haze, QUV irradiation resistance, high Tg, high flexibility, low bounce, voltage resistance and high heat dissipation.

Description

Ultrathin high-transparency PI film, protective film containing PI film and preparation method
Technical Field
The invention relates to the technical field of protective films for circuit boards or electronic products, in particular to a transparent PI (polyimide) film, a protective film and a preparation method, which are mainly applied to flexible mobile phones, AMOLED (active matrix organic light emitting diode), large-screen TVs, vehicle-mounted displays, circuit boards in the manufacturing process and the like.
Background
With the Organic Light Emitting Display (OLED) technology, compared with the conventional display technology, the OLED display has a series of advantages of ultra-light weight, ultra-thin property, wide viewing angle, high definition, low temperature resistance, good shock resistance, and the like. Therefore, organic light emitting display technology (OLED) has advanced greatly in the last 20 years, and various high-performance and long-life organic light emitting materials and devices have been continuously introduced. With the further development of organic light emitting display technology, active driving OLED displays with more abundant information, flexible OLED display screens and OLED light sources available for illumination will create a more colorful world for us in the near future. The OLED has very wide application prospect. In the display field, the OLED can be used in the civil product fields of mobile phones, MP3/MP4, digital cameras, GPS, PDA, 5G communication terminals, wall-mounted televisions, desktop and notebook computers, household appliances, industrial instruments and the like. The OLED is an ideal display and has wider application prospect. Meanwhile, the OLED is the only display technology capable of manufacturing a large-size, high-brightness and high-resolution soft screen in all the current display technologies, and the thickness of the device is only two layers of plastic sheets. At that time, "fantasy displays" such as screen televisions, rollable electronic newspapers, and the like are becoming increasingly practical. In the illumination field, the OLED can be used in the fields of indoor and outdoor general illumination, backlight source, decorative illumination and the like, and can even be used for preparing artistic flexible luminous wallpaper, windows capable of emitting light in single color or color, wearable luminous warning boards and other fantasy products.
The transparent PI is expected to replace glass to be applied to an OLED display screen, and the PI has the characteristic of being capable of being folded concavely, so that the PI can be used for preparing a flexible screen. The PI film on the market is golden yellow and not completely transparent, so that the material is limited in some fields of photoelectric field. Therefore, the demand for transparent PI and related transparent cover film products is on the move. The transparent covering film products on the market are mainly as follows:
firstly, a transparent PI film adopts biaxial extension and is difficult to manufacture an ultrathin film of 5-10 um;
secondly, the protective film made of the ultrathin PI film of 5-10um has poor operability at a downstream FPC end, is easy to tear, is difficult to align and the like;
the transparent PI film and the prepared protective film generally have no anti-UV absorbent, and can be yellowed and embrittled under long-time ultraviolet irradiation;
the transparent PET/PEN film is matched with transparent glue to manufacture a transparent product, but the PET/PEN film cannot resist high temperature (288 ℃) due to the melting point of 225-260 ℃.
Disclosure of Invention
In order to satisfy the market for high transmittance, low haze, high L-value, low a, b-value and small change in the above-mentioned optical properties after 240 hours of QUV irradiation; and transparent PI with high temperature resistance, high Tg, high flexibility, low rebound force, high surface hardness. The invention provides an ultrathin high-transparency PI film with high transmittance, low haze, high Tg and QUV irradiation resistance and a protective film containing the PI film, wherein the protective film provided by the invention is composed of transparent polyimide varnish and an anti-UV transparent adhesive, has extremely high transmittance, extremely low haze, QUV irradiation resistance, high Tg, high flexibility, low bounce, voltage resistance and high heat dissipation, and is ultrathin, and the thickness can be as low as 6-15 mu m.
In order to solve the technical problems, the invention adopts a technical scheme that: the invention provides an ultrathin high-transparency PI film, which comprises an anti-UV transparent polyimide layer, wherein the light transmittance of the anti-UV transparent polyimide layer is more than 88%, the haze of the anti-UV transparent polyimide layer is less than 1%, the L value of an LaAb color system measured by an ultraviolet-visible spectrophotometer is 92-99, the a value is-2.0-2.0, the b value is-2.0-5.0), the surface hardness of the anti-UV transparent polyimide layer is more than 4H, and the thickness of the anti-UV transparent polyimide layer is 30-100 mu m;
the anti-UV transparent polyimide layer comprises aromatic diamine, aromatic acid anhydride, imidization catalyst, dehydrating agent, anti-UV absorbent and organic solvent, and the weight percentage of each component is as follows: 30-40% of aromatic diamine, 30-40% of aromatic acid anhydride, 2-3% of imidization catalyst, 2-5% of dehydrating agent, 1-3% of anti-UV absorbent and 9-30% of organic solvent.
In order to solve the problems, the invention adopts the further technical scheme that:
the aromatic diamine is at least one of p-phenylenediamine, tetrafluoro diamine ether, 2-sulfuryl 1, 4-phenylenediamine and aliphatic diamine;
the aromatic acid anhydride is at least one of phthalic acid dianhydride, biphenyl tetracarboxylic dianhydride aromatic dianhydride, ketone tetracarboxylic dianhydride and dicarboxyphenyl dimethyl alkane dianhydride;
the dehydrating agent is at least one of aliphatic carboxylic anhydride, aromatic anhydride, ethanol, dioxane, n-butanol and tert-butanol;
the organic solvent is at least one of gamma-butyrolactone, cyclohexanone, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, pyridine, cyclohexane, dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, 1, 2-dichloroethane, trichloroethylene, triethylamine, 4-methyl-2-pentanone and xylene.
The imidization catalyst is at least one of aliphatic tertiary amine, N-hydroxyphthalimide, an oxidation catalyst, a cyclic imide immobilized catalyst, a free radical reaction accelerator, peracid, peroxide, an azo compound, acetophenone, a cyclic amine-N-oxyl compound, a component A, nitrogen dioxide and benzaldehyde;
the component A is at least one of nitric acid, nitrous acid, nitrate and nitrite;
the anti-UV absorbent is at least one of diphenyl ketone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4- (octyloxy) phenyl ketone, 2-hydroxy-4-octyloxy benzophenone, 2-hydroxy-4-n-octyloxy benzophenone, benzophenone-12, 2-hydroxy-4-n-octyloxy benzophenone, an ultraviolet absorbent BP-12, benzophenone-12 and an ultraviolet absorbent UV-531.
The ultrathin high-transparency PI film further comprises a release layer, the release layer is positioned on the outer side of the UV-resistant transparent polyimide layer, the release layer is an optical-grade PET release film subjected to pre-shrinking treatment, the light transmittance of the optical-grade PET release film is more than or equal to 88%, the haze of the optical-grade PET release film is less than or equal to 1%, and the heating shrinkage rate of the optical-grade PET release film is less than 0.5%
The invention also provides a protective film containing the ultrathin high-transparency PI film, which comprises the UV-resistant transparent polyimide layer and a UV-resistant transparent adhesive layer, wherein the UV-resistant transparent adhesive layer is positioned on the surface of the UV-resistant transparent polyimide layer; the thickness of the UV resistant transparent adhesive layer is 3-100 mu m; the total thickness of the stack of the anti-UV transparent polyimide layer and the anti-UV transparent polyimide layer is 6-200 μm;
the transmittance of light of a stack structure formed by the anti-UV transparent polyimide layer and the anti-UV transparent adhesive layer is more than or equal to 88%, the haze is less than or equal to 1%, the L value of an LaaBb color system of the stack structure measured by an ultraviolet visible spectrophotometer is 90-95, the a value is-2.0-2.0, and the b value is-2.0-2.0; glass transition temperature of the stack>360 DEG surface hardness>4H and thermal resistance, 0.3m2K/w and a breakdown voltage of 120kv/mm or more.
The protective film further comprises a release layer, the release layer is positioned on the outer side of the stack, the release layer is an optical-grade PET release film subjected to pre-shrinking treatment, the light transmittance of the optical-grade PET release film is more than or equal to 88%, the haze of the optical-grade PET release film is less than or equal to 1%, and the heating shrinkage rate of the optical-grade PET release film is less than 0.5%.
Further, it is two-layer and be the last layer of leaving type and lower layer of leaving type respectively to say from the type layer, go up from the type layer with it is located respectively from the type layer down the upper surface and the lower surface of superpose.
Further, each of the UV resistant transparent polyimide layers has a thickness of 3-5 μm, the UV resistant transparent adhesive layer has a thickness of 3-10 μm, and the total thickness of the stack of the UV resistant transparent polyimide layer and the UV resistant transparent polyimide layer is 6-15 μm.
Further, the anti-UV transparent adhesive layer is an acrylic adhesive layer, the acrylic adhesive layer comprises a component B, a low-temperature curing agent and an anti-UV absorbent, and the weight percentage of each component is as follows: the component B is 90-95%, the low-temperature curing agent is 1-3% and the anti-UV absorbent is 0.01-0.05%;
the component B is at least one of methyl acrylate, ethyl ester, polyphenyl methyl acrylate and polymethacrylic acid.
Further, the anti-UV absorbent is at least one of diphenyl ketone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4- (octyloxy) phenyl ketone, 2-hydroxy-4-octyloxy benzophenone, 2-hydroxy-4-n-octyloxy benzophenone, benzophenone-12, 2-hydroxy-4-n-octyloxy benzophenone, an ultraviolet absorbent BP-12, benzophenone-12 and an ultraviolet absorbent UV-531.
The low-temperature curing agent is at least one of 2-methylimidazole, RC526 powder curing agent and 2, 4, 6-tris (dimethylaminomethyl) phenol.
The invention also provides a preparation method of the protective film, which comprises the following steps:
s1, mixing the raw materials of the anti-UV transparent polyimide layer according to the proportion, and mixing the raw materials of the anti-UV transparent adhesive layer according to the proportion for later use;
s2, coating the precursor of the anti-UV transparent polyimide layer prepared in the step S1 on a release layer, curing at the low temperature of 100-150 ℃ for 3-10min to form a transparent composite PI semi-finished product, and rolling;
coating or transferring a precursor of the anti-UV transparent adhesive layer on the surface of the anti-UV transparent polyimide layer of the transparent composite PI semi-finished product, and baking to form a protective film;
wherein, the baking process parameters are as follows: the temperature is 60-90 ℃, and the rotating speed of a fan is as follows: 750-; the pressure during pressing is 0.8-1.5kgf/cm2；
S3, curing: and (5) curing the protective film prepared in the step (S2) at a low temperature of 45-55 ℃ for 1.5-2.5h to obtain the finished protective film.
The invention has the beneficial effects that:
the ultrathin high-transparency PI film is composed of transparent polyimide varnish, has the characteristics of extremely high transmittance, extremely low haze, QUV irradiation resistance, high Tg, high flexibility, low rebound force, high heat dissipation, voltage resistance and the like, wherein the transmittance of light is more than or equal to 88 percent, the haze is less than or equal to 1 percent, so the transparency is high, the mechanical strength is sufficient, the thickness range is wide and reaches 3-100 mu m, and more preferably, the thickness can be as low as 3-5 mu m, the ultrathin PI film can be ultrathin, and the PI film is particularly suitable for being used in an OLED display screen with high efficiency of a rigid-flexible board;
moreover, because the formula of the UV-resistant transparent polyimide layer is reasonable, the UV-resistant transparent polyimide layer can be formed in a coating mode, the thickness range is controllable, the thickness can be as low as 3-5 mu m, the ultra-thin film can be realized, and the ultra-thin film which is 5-10 mu m and is difficult to realize by adopting biaxial extension for the traditional PI film;
furthermore, the raw materials in the anti-UV transparent polyimide layer are reasonable in proportion, contain an anti-UV absorbent, can enhance the radiation yellowing resistance of the anti-UV transparent polyimide layer, and meanwhile, the precursor of the prepared anti-UV transparent polyimide layer can be directly coated on an optical-grade PET release film without dehydration and ring closure at a high temperature (200-;
moreover, the surface hardness of the PI film can reach 4H, and the PI film can prevent scratching and scuffing;
when the ultrathin high-transparency PI film contains the release layer, the ultrathin high-transparency PI film can be sold or used as a finished product, and when the ultrathin high-transparency PI film is used, the release film is only needed to be torn off and is pasted on the surface needing to be pasted, so that the use is convenient;
the protective film consists of transparent polyimide varnish and an anti-UV transparent adhesive, has the characteristics of extremely high transmittance, extremely low haze, QUV irradiation resistance, high Tg, high flexibility, low bounce and the like, wherein the transmittance of light is more than or equal to 88 percent, the haze is less than or equal to 1 percent, so the protective film has high transparency, enough mechanical strength and wide thickness range which can reach 6-200 mu m, can be designed into different thicknesses according to different electronic product requirements, and can be preferably as low as 6-15 mu m and can be ultrathin;
moreover, the surface hardness of the protective film can reach 4H, so that the protective film can prevent scratching and scratching, the scratching and scratching in the manufacturing process are reduced, the hardness of the protective film per se reaches 4H, the product requirements can be met, an additional evaporation coating or sputtering coating hard coating is not needed, the manufacturing process is reduced, the cost is reduced, the PI does not need to be subjected to high temperature in the evaporation coating or sputtering coating process, and the original mechanical property of the PI is not damaged;
moreover, the protective film has extremely low rebound force, and the rebound force of the ultrathin substrate (such as FPC) is less than or equal to 5 gf;
the proportion of the raw materials in the anti-UV transparent adhesive layer of the protective film is reasonable, the protective film also contains an anti-UV absorbent, the irradiation yellowing resistance of the protective film can be enhanced, and meanwhile, the precursor of the prepared anti-UV transparent adhesive layer can be directly coated on an optical-grade PET release film without dehydration and closed loop at high temperature (200-;
the preparation method of the protective film comprises the following steps: coating the precursor of the anti-UV transparent polyimide layer on the release layer, coating or transferring the precursor of the anti-UV transparent adhesive layer on the surface, and laminating the anti-UV transparent polyimide layer and the anti-UV transparent adhesive layer, wherein the anti-UV transparent polyimide layer and the anti-UV transparent adhesive layer are both formed in a coating or transferring mode, so that the thickness of each layer is controllable, the thickness range is wider and reaches 6-200 mu m, a traditional tape casting method or a film blowing method is not needed, a film can be formed by uniaxial or biaxial extension, and high-temperature dehydration closed-loop treatment at the temperature of 500-;
after the release layer can be torn off from the protective film, the UV-resistant transparent adhesive layer is a semi-cured adhesive layer, has activity, can be directly adhered with the FPC, has good operability in the downstream FPC manufacturing process due to better mechanical characteristics, is not easy to tear and fold, is easy to align and the like, reduces FPC working procedures, and saves labor and time;
the PI film and the protective film can also comprise release layers, the release layers are optical PET release films subjected to pre-shrinking treatment, the light transmittance of the optical PET release films is more than or equal to 88%, the haze of the optical PET release films is less than or equal to 1%, the heating shrinkage rate of the optical PET release films is less than 0.5%, the optical PET release films have the optical characteristics of high transmittance, low haze, high L value, low a value and low b value, and the change rate of the optical characteristics is small after QUV irradiation for 240 hours;
the PI film and the protective film have the characteristics of high temperature resistance, high Tg, high flexibility, low rebound force, high heat dissipation, voltage resistance, high surface hardness and the like, and can be bent for many times, cannot be bent, and have high transparency and the like due to the extremely low rebound force and the rebound force of the ultrathin substrate which is matched with the PI film can reach less than or equal to 5 gf;
the raw material of the anti-UV transparent polyimide layer of the protective film of the invention contains dehydrating agent, which has the advantages of dehydrating, cleaning and transparent functions, and can not cause the tissue to have defects of hardening and shrinking, the dehydrating process only needs to pass through each level of 30%, 70%, 90% and 100% and then enter paraffin, but the specific weight of the dehydrating agent is heavier than that of the dissolved paraffin, so the agent needs to be removed to the utmost before embedding, and the dehydrating agent is preferably passed through the procedure of xylene or chloroform once and then soaked in the paraffin, and the dehydrating agent is lighter than the dissolved paraffin, so the dehydrating agent can be easily removed in the tissue during embedding. The liquid can simplify dehydration and transparency, and improve the transparency of the prepared PI film.
The foregoing description of the present invention is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clear and clear, and to implement the technical solutions according to the content of the description, the following detailed description of the preferred embodiments of the present invention is provided with the accompanying drawings.
Drawings
FIG. 1 is a schematic structural view of a PI film of the present invention (without a release layer);
FIG. 2 is a schematic structural diagram of a PI film of the present invention (with a release layer);
FIG. 3 is a schematic structural diagram of the protective film of the present invention (without release layer);
FIG. 4 is a schematic structural diagram of the protective film according to the present invention (including a release layer);
the parts in the drawings are marked as follows:
a UV-resistant transparent polyimide layer 100, a UV-resistant transparent adhesive layer 200, an upper release layer 300, and a lower release layer 400.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and the present invention will be described in detail with reference to the accompanying drawings. The invention may be embodied in other different forms, i.e. it is capable of various modifications and changes without departing from the scope of the invention as disclosed.
Example 1: an ultra-thin high transparent PI film, as shown in fig. 1 and 2, comprising a UV resistant transparent polyimide layer 100 having a light transmittance of > 88% and a haze of < 1%, a value of L of la b color system of 92 to 99, a value of-2.0 to 2.0 and a value of b of-2.0 to 5.0, a surface hardness of >4H measured by UV-vis spectrophotometer, the thickness of the UV resistant transparent polyimide layer being 30 to 100 μm;
the anti-UV transparent polyimide layer 100 comprises aromatic diamine, aromatic acid anhydride, imidization catalyst, dehydrating agent, anti-UV absorbent and organic solvent, and the weight percentage of each component is as follows: 30-40% of aromatic diamine, 30-40% of aromatic acid anhydride, 2-3% of imidization catalyst, 2-5% of dehydrating agent, 1-3% of anti-UV absorbent and 9-30% of organic solvent.
The aromatic diamine is at least one of p-phenylenediamine, tetrafluoro diamine ether, 2-sulfuryl 1, 4-phenylenediamine and aliphatic diamine;
the aromatic acid anhydride is at least one of phthalic acid dianhydride, biphenyl tetracarboxylic dianhydride aromatic dianhydride, ketone tetracarboxylic dianhydride and dicarboxyphenyl dimethyl alkane dianhydride;
the dehydrating agent is at least one of aliphatic carboxylic anhydride (such as acetic anhydride, propionic anhydride, butyric anhydride, valeric anhydride and the like), aromatic acid anhydride (such as benzoic anhydride), ethanol, dioxane, n-butanol and tert-butanol;
the organic solvent is at least one of gamma-butyrolactone, cyclohexanone, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, pyridine, cyclohexane, dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, 1, 2-dichloroethane, trichloroethylene, triethylamine, 4-methyl-2-pentanone and xylene.
The imidization catalyst is at least one of aliphatic tertiary amines (such as trimethylamine and triethylenediamine, but not limited thereto), N-hydroxyphthalimides, oxidation catalysts (such as imide compounds and transition metal compounds, but not limited thereto), cyclic imide immobilization catalysts, radical reaction promoters (such as halogens, such as chlorine and bromine in halogens, and the like), peracids (such as peracetic acid and m-chloroperbenzoic acid, but not limited thereto), peroxides (such as hydroperoxides, but not limited thereto, such as hydrogen peroxide and t-butyl hydroperoxide), azo compounds (such as azobisisobutyronitrile), acetophenone compounds, cyclic amine-N-oxyl compounds, component a, nitrogen dioxide, and benzaldehyde;
the component A is at least one of nitric acid, nitrous acid, nitrate and nitrite;
the anti-UV absorbent is at least one of diphenyl ketone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4- (octyloxy) phenyl ketone, 2-hydroxy-4-octyloxy benzophenone, 2-hydroxy-4-n-octyloxy benzophenone, benzophenone-12, 2-hydroxy-4-n-octyloxy benzophenone, an ultraviolet absorbent BP-12, benzophenone-12 and an ultraviolet absorbent UV-531.
As shown in fig. 2, the ultrathin high-transparency PI film further includes a release layer, the release layer is located on the outer side of the UV-resistant transparent polyimide layer, the release layer is an optical-grade PET release film subjected to pre-shrinking treatment, the optical-grade PET release film has a light transmittance of not less than 88%, a haze of not more than 1%, and a heating shrinkage of less than 0.5%. In this embodiment, the release layer includes an upper release layer 300 and a lower release layer 400.
The preparation method of the ultrathin high-transparency PI film comprises the following steps: mixing the raw materials of the anti-UV transparent polyimide layer according to a ratio for later use; wherein, during mixing, defoaming and defoaming are carried out; and then coating the precursor of the prepared anti-UV transparent polyimide layer on a release layer, curing at the temperature of 100-150 ℃ for 3-10min to form a high-transparency PI film semi-finished product, and then laminating another release layer on the surface of the anti-UV transparent polyimide layer to obtain the finished ultrathin high-transparency PI film.
Example 2: a protective film comprising the ultra-thin high transparent PI film, as shown in fig. 3, comprises the UV-resistant transparent polyimide layer 100 and a UV-resistant transparent adhesive layer 200 on a surface of the UV-resistant transparent polyimide layer; the thickness of the UV resistant transparent adhesive layer is 3-100 mu m; the total thickness of the UV resistant transparent polyimide layer and the stack of UV resistant transparent polyimide layers is 6-200 μm
The transmittance of light of a stack structure formed by the anti-UV transparent polyimide layer and the anti-UV transparent adhesive layer is more than or equal to 88%, the haze is less than or equal to 1%, the L value of an LaaBb color system of the stack structure measured by an ultraviolet visible spectrophotometer is 90-95, the a value is-2.0-2.0, and the b value is-2.0-2.0; glass transition temperature of the stack>360 DEG surface hardness>4H and thermal resistance, 0.3m2K/w and a breakdown voltage of 120kv/mm or more.
As shown in fig. 4, the protective film further includes a release layer, the release layer is located on the outer side of the stack, the release layer is an optical-grade PET release film subjected to pre-shrinking treatment, the optical-grade PET release film has a light transmittance of not less than 88%, a haze of not more than 1%, and a heating shrinkage of less than 0.5%.
The release layer is two-layer and is last release layer 300 and lower release layer 100 respectively, go up from the release layer with the lower release layer is located respectively the upper surface and the lower surface of superpose.
Preferably, each of the UV resistant transparent polyimide layers has a thickness of 3-5 μm, and the UV resistant transparent adhesive layer has a thickness of 3-10 μm; the total thickness of the stack of the UV resistant transparent polyimide layer and the UV resistant transparent polyimide layer is 6-15 μm.
The anti-UV transparent adhesive layer is an acrylic adhesive layer, the acrylic adhesive layer comprises a component B, a low-temperature curing agent and an anti-UV absorbent, and the weight percentage of each component is as follows: the component B90-95%, the low-temperature curing agent is 1-3% and the anti-UV absorbent is 0.01-0.05%;
the component B is at least one of methyl acrylate, ethyl ester, polyphenyl methyl acrylate and polymethacrylic acid.
The anti-UV absorbent is at least one of diphenyl ketone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4- (octyloxy) phenyl ketone, 2-hydroxy-4-octyloxy benzophenone, 2-hydroxy-4-n-octyloxy benzophenone, benzophenone-12, 2-hydroxy-4-n-octyloxy benzophenone, an ultraviolet absorbent BP-12, benzophenone-12, an ultraviolet absorbent 531 and an ultraviolet absorbent UV-531.
The low-temperature curing agent is at least one of 2-methylimidazole, RC526 powder curing agent and 2, 4, 6-tris (dimethylaminomethyl) phenol.
A method for producing the protective film of embodiment 2, comprising the steps of:
s1, mixing the raw materials of the anti-UV transparent polyimide layer according to the proportion, and mixing the raw materials of the anti-UV transparent adhesive layer according to the proportion for later use; wherein, during mixing, defoaming and defoaming are carried out;
s2, coating the precursor of the anti-UV transparent polyimide layer prepared in the step S1 on a release layer, curing at the low temperature of 100-150 ℃ for 3-10min to form a transparent composite PI semi-finished product, and rolling;
coating or transferring a precursor of the anti-UV transparent adhesive layer on the surface of the anti-UV transparent polyimide layer of the transparent composite PI semi-finished product, and baking to form a protective film;
wherein, the baking process parameters are as follows: the temperature is 60-90 ℃, and the rotating speed of a fan is as follows: 750-; the pressure during pressing is 0.8-1.5kgf/cm2；
S3, curing: curing the protective film prepared in the step S2 at a low temperature of 45-55 ℃ for 1.5-2.5h by adopting a precise programmable oven to obtain a finished protective film;
s4, splitting: adopting Japanese import slitting equipment to slit the composite transparent PI finished product into widths required by customers;
s5, checking and warehousing: high-speed automatic inspection equipment is adopted, precise appearance measurement equipment is configured, ERP scanning code adjustment management is unified, and order is achieved.
The following is a comprehensive comparison of the performance indexes of samples 1 to 6 of example 2 of the present invention and samples of comparative examples, which are detailed in tables 1 and 2.
Table 1:
table 2:
note: 1. the reference example in table 2 indicates that the FPC is not attached with the protective film.
2. QUV irradiation conditions: exposure to 50. + -. 3 ℃ BPT,0.63W (m)2Nm) @340nm 240 hours.
Table 3 is the formulation of the UV resistant transparent polyimide layer and the UV resistant transparent adhesive layer of samples 1 to 6 of the examples.
Table 3:
note: 1. in table 3, the ultra-thin high transparent PI film of example 1 was formed when samples 1 to 6 were provided with only the UV resistant transparent polyimide layer;
2. UV resistant transparent polyimide layer: the aromatic diamine in samples 1 and 2 was phenylenediamine; the aromatic diamine in samples 3 and 4 was tetrafluorodiamine ether; in samples 5 and 6, the aromatic diamine is 2-sulfonyl 1.4-phenylenediamine and the aliphatic diamine, and the weight ratio of the aromatic diamine to the aliphatic diamine is 1: 1: 1; the aromatic anhydride in samples 1 to 3 was pyromellitic dianhydride; the aromatic acid anhydrides in samples 4 to 6 were methylotetracarboxylic dianhydride and dicarboxyphenyldimethylalkane dianhydride in a weight ratio of 1: 1; the imidization catalysts in samples 1 to 3 were trimethylamine and triethyldiamine; in samples 4 to 6, the imidization catalyst was azobisisobutyronitrile; the dehydrating agents in samples 1 to 3 were ethanol and dioxane in a weight ratio of 1: 1.5; the dehydrating agent in samples 4 to 6 was n-butanol; the anti-UV absorbers in samples 1 to 3 were 2-hydroxy-4-octyloxybenzophenone and 2-hydroxy-4-n-octyloxybenzophenone; the UV absorber in samples 4 to 6 was benzophenone-12; the organic solvent in samples 1 to 3 was butanone; the organic solvent in samples 4 to 6 was N, N-dimethylformamide;
3. anti-UV transparent adhesive layer: in sample 1 and sample 2, the component B is methyl acrylate and ethyl acrylate, and the weight ratio of the methyl acrylate to the ethyl acrylate is 2: 1; component B in samples 3 and 4 is polyphenylacrylate; component B in samples 5 and 6 is polymethacrylene; the low temperature curing agent in samples 1 to 3 was 2-methylimidazole; the low temperature curing agent in samples 4 to 6 was RC526 powder curing agent; the UV resistant absorbers in samples 1 to 3 were UV absorbers BP-12; the UV absorber in samples 4 to 6 was benzophenone-12.
As can be seen from Table 1, the protective film of the present invention has the advantages of high transmittance, low haze, high reflectivity, high temperature yellowing resistance, high Tg, QUV irradiation resistance, high flexibility, low rebound force, high heat dissipation, and voltage resistance, and has a surface hardness of 4H, and can prevent scratching and scratching.
As can be seen from table 2, the protective film of the present invention, in combination with the ultra-thin FPC, can obtain a product having a much smaller rebound force than that of the comparative example, and the rebound force is as low as <5.0 gf.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent structures made by using the contents of the specification and the drawings of the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.

Claims (10)

1. An ultra-thin high transparent PI membrane which characterized in that: comprising a UV resistant transparent polyimide layer having a light transmittance of > 88% and a haze of < 1%, a value of L of the Lab color system of 92 to 99, a value of-2.0 to 2.0 and a value of b of-2.0 to 5.0, as measured by an ultraviolet-visible spectrophotometer, a surface hardness of >4H, said UV resistant transparent polyimide layer having a thickness of 30 to 100 μm;
the anti-UV transparent polyimide layer comprises aromatic diamine, aromatic acid anhydride, imidization catalyst, dehydrating agent, anti-UV absorbent and organic solvent, and the weight percentage of each component is as follows: 30-40% of aromatic diamine, 30-40% of aromatic acid anhydride, 2-3% of imidization catalyst, 2-5% of dehydrating agent, 1-3% of anti-UV absorbent and 9-30% of organic solvent.
2. The ultra-thin high transparent PI film of claim 1, wherein: the aromatic diamine is at least one of p-phenylenediamine, tetrafluoro diamine ether, 2-sulfuryl 1, 4-phenylenediamine and aliphatic diamine;
the aromatic acid anhydride is at least one of phthalic acid dianhydride, biphenyl tetracarboxylic dianhydride aromatic dianhydride, ketone tetracarboxylic dianhydride and dicarboxyphenyl dimethyl alkane dianhydride;
the dehydrating agent is at least one of aliphatic carboxylic anhydride, aromatic anhydride, ethanol, dioxane, n-butanol and tert-butanol;
the organic solvent is at least one of gamma-butyrolactone, cyclohexanone, acetone, butanone, N-dimethylformamide, N-dimethylacetamide, pyridine, cyclohexane, dichloromethane, tetrahydrofuran, ethyl acetate, acetonitrile, 1, 2-dichloroethane, trichloroethylene, triethylamine, 4-methyl-2-pentanone and xylene.
The imidization catalyst is at least one of aliphatic tertiary amine, N-hydroxyphthalimide, an oxidation catalyst, a cyclic imide immobilized catalyst, a free radical reaction accelerator, peracid, peroxide, an azo compound, acetophenone, a cyclic amine-N-oxyl compound, a component A, nitrogen dioxide and benzaldehyde;
the component A is at least one of nitric acid, nitrous acid, nitrate and nitrite;
the anti-UV absorbent is at least one of diphenyl ketone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4- (octyloxy) phenyl ketone, 2-hydroxy-4-octyloxy benzophenone, 2-hydroxy-4-n-octyloxy benzophenone, benzophenone-12, 2-hydroxy-4-n-octyloxy benzophenone, an ultraviolet absorbent BP-12, benzophenone-12 and an ultraviolet absorbent UV-531.
3. The ultra-thin high transparent PI film of claim 1, wherein: the anti-UV transparent polyimide film is characterized by further comprising a release layer, wherein the release layer is positioned on the outer side of the anti-UV transparent polyimide layer, the release layer is an optical-grade PET release film subjected to pre-shrinking treatment, the light penetration rate of the optical-grade PET release film is more than or equal to 88%, the haze is less than or equal to 1%, and the heating shrinkage rate is less than 0.5%.
4. A protective film comprising the ultra-thin highly transparent PI film of claim 1, wherein: comprising the UV resistant transparent polyimide layer and a UV resistant transparent adhesive layer, the UV resistant transparent adhesive layer being located on a surface of the UV resistant transparent polyimide layer; the thickness of the UV resistant transparent adhesive layer is 3-100 μm, and the total thickness of the stack of the UV resistant transparent polyimide layer and the UV resistant transparent polyimide layer is 6-200 μm;
the transmittance of light of a stack structure formed by the anti-UV transparent polyimide layer and the anti-UV transparent adhesive layer is more than or equal to 88%, the haze is less than or equal to 1%, the L value of an LaaBb color system of the stack structure measured by an ultraviolet visible spectrophotometer is 90-95, the a value is-2.0-2.0, and the b value is-2.0-2.0; glass transition temperature of the stack>360 DEG surface hardness>4H and thermal resistance, 0.3m2K/w and a breakdown voltage of 120kv/mm or more.
5. The protective film according to claim 4, wherein: the release layer is positioned on the outer side of the stack structure, the release layer is an optical PET release film subjected to pre-shrinking treatment, the light penetration rate of the optical PET release film is more than or equal to 88%, the haze is less than or equal to 1%, and the heating shrinkage rate is less than 0.5%.
6. The protective film according to claim 5, wherein: the release layer is two-layer and is the last release layer and the lower release layer respectively, go up from the release layer with the lower release layer is located respectively the upper surface and the lower surface of folding structure.
7. The protective film according to claim 4, wherein: each of the UV resistant transparent polyimide layers has a thickness of 3-5 μm, the UV resistant transparent adhesive layer has a thickness of 3-10 μm, and the total thickness of the stack of the UV resistant transparent polyimide layers and the UV resistant transparent polyimide layers is 6-15 μm.
8. The protective film according to claim 4, wherein: the anti-UV transparent adhesive layer is an acrylic adhesive layer, the acrylic adhesive layer comprises a component B, a low-temperature curing agent and an anti-UV absorbent, and the weight percentage of each component is as follows: the component B is 90-95%, the low-temperature curing agent is 1-3% and the anti-UV absorbent is 0.01-0.05%;
the component B is at least one of methyl acrylate, ethyl ester, polyphenyl methyl acrylate and polymethacrylic acid.
9. The protective film according to claim 8, wherein: the anti-UV absorbent is at least one of diphenyl ketone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4- (octyloxy) phenyl ketone, 2-hydroxy-4-octyloxy benzophenone, 2-hydroxy-4-n-octyloxy benzophenone, benzophenone-12, 2-hydroxy-4-n-octyloxy benzophenone, an ultraviolet absorbent BP-12, benzophenone-12 and an ultraviolet absorbent UV-531.
The low-temperature curing agent is at least one of 2-methylimidazole, RC526 powder curing agent and 2, 4, 6-tris (dimethylaminomethyl) phenol.
10. A method for producing the protective film according to claim 5, characterized in that: the method comprises the following steps:
s1, mixing the raw materials of the anti-UV transparent polyimide layer according to the proportion, and mixing the raw materials of the anti-UV transparent adhesive layer according to the proportion for later use;
s2, coating the precursor of the anti-UV transparent polyimide layer prepared in the step S1 on a release layer, curing at the low temperature of 100-150 ℃ for 3-10min to form a transparent composite PI semi-finished product, and rolling;
coating or transferring a precursor of the anti-UV transparent adhesive layer on the surface of the anti-UV transparent polyimide layer of the transparent composite PI semi-finished product, and baking to form a protective film;
wherein, the baking process parameters are as follows: the temperature is 60-90 ℃, and the rotating speed of a fan is as follows: 750-; the pressure during pressing is 0.8-1.5kgf/cm2
S3, curing: and (5) curing the protective film prepared in the step (S2) at a low temperature of 45-55 ℃ for 1.5-2.5h to obtain the finished protective film.
CN201810658699.9A 2018-06-25 2018-06-25 Ultrathin high-transparency PI film, protective film containing PI film and preparation method Pending CN110628346A (en)

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