CN110626036A - High-transparency composite PI film and preparation method thereof - Google Patents
High-transparency composite PI film and preparation method thereof Download PDFInfo
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- CN110626036A CN110626036A CN201810658704.6A CN201810658704A CN110626036A CN 110626036 A CN110626036 A CN 110626036A CN 201810658704 A CN201810658704 A CN 201810658704A CN 110626036 A CN110626036 A CN 110626036A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/536—Hardness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/554—Wear resistance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
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Abstract
The invention discloses a high-transparency composite PI film, which comprises an anti-UV transparent polyimide layer and an anti-UV transparent adhesive layer, wherein the anti-UV transparent adhesive layer comprises two layers, and the anti-UV transparent adhesive layer is positioned between the two anti-UV transparent polyimide layers; the transmittance of light of a stack structure consisting of the upper anti-UV transparent polyimide layer, the anti-UV transparent adhesive layer and the upper anti-UV transparent polyimide layer is more than or equal to 88 percent, the haze is less than or equal to 1 percent, the L value of an LaAb 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; the glass transition temperature of the stack is >360 ° and the surface hardness is > 4H. The invention provides a high-transparency composite PI film with high transmittance, low haze, high reflectivity, high-temperature yellowing resistance, high Tg and QUV irradiation resistance.
Description
Technical Field
The invention relates to the technical field of PI (polyimide) films, in particular to a composite PI (polyimide) film and a preparation method thereof, which are mainly applied to flexible mobile phones, AMOLED (active matrix organic light emitting diode), large-screen TVs, vehicle-mounted displays and the like.
Background
It is a real bottleneck that prevents samsung from releasing a truly flexible display product?, which is not the display itself, but rather a flexible cover plate, in fact, the display part can be bent repeatedly with a certain curvature, which can meet the daily needs of the user, and the touch part can also meet the requirements using thin film metal grids or nano silver wires, except for the cover plate.
The scheme adopted in the method is a colorless transparent PI + hard coating scheme: manufacturers have screened PI, PMMA (polymethacrylate), PET (polyethylene terephthalate), PU (polyurethane) and some other organic polymeric materials. These materials are thin enough to be bent, but lack sufficient hardness, and all manufacturers also need a hard coating on them to increase their surface hardness. Since the hard coating layer is usually formed by sputtering or evaporation and needs to withstand higher process temperature, PI seems to be the preferred material and has the best high temperature resistance, so that the flexible cover plate scheme of PI + hard coating layer is actively developed for samsung display and LG display.
However, as a cover plate, PI also has a disadvantage in that it is opaque and ordinary PI appears yellowish. As a flexible AMOLED substrate material, yellowish is irrelevant, but is clearly not feasible as a cover plate. Therefore, colorless and transparent PI is the key for development, and manufacturers are trying to develop colorless and transparent PI with stable properties to meet the demand.
Some manufacturers try to mix various organic materials, such as PI, PMMA, PET and PU, to make a flexible cover plate, but the effect is not ideal and it is difficult to mass-produce. The end manufacturers have returned to the colorless clear PI + hard coat solution.
The transparent PI in the current market has the following defects:
1. the thickness of more than 3mil is not easy to prepare, the unit price is high, the Tg (glass transition temperature) point is low, the penetration rate is low and the haze is high;
2. the traditional PI film preparation method is a tape casting method or a film blowing method, then single-axis or double-axis extension is carried out, the requirement on equipment is high, and the process is complex because the high temperature of 500-800 ℃ dehydration closed-loop treatment is carried out.
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 a high-transparency composite PI film with high transmittance, low haze, high reflectivity, high-temperature yellowing resistance, high Tg and QUV irradiation resistance, which is composed of a transparent polyimide varnish and an anti-UV transparent adhesive, has extremely high transmittance, extremely low haze, QUV irradiation resistance, high Tg, high flexibility and low rebound force, and is particularly suitable for being used in an AMOLED display screen with high efficiency of a rigid-flexible board.
In order to solve the technical problems, the invention adopts a technical scheme that: the invention provides a high-transparency composite PI film, which comprises an anti-UV transparent polyimide layer and an anti-UV transparent adhesive layer, wherein the anti-UV transparent polyimide layer comprises two layers which are respectively an upper anti-UV transparent polyimide layer and a lower anti-UV transparent polyimide layer, and the anti-UV transparent adhesive layer is positioned between the upper anti-UV transparent polyimide layer and the lower anti-UV transparent polyimide layer;
the transmittance of light of a stack structure consisting of the upper UV-resistant transparent polyimide layer, the UV-resistant transparent adhesive layer and the upper UV-resistant transparent polyimide layer is more than or equal to 88%, the haze is less than or equal to 1%, the L value of an L a b color system of the stack structure measured by an ultraviolet-visible light photometer is 90-95, the a value is-2.0-2.0, and the b value is-2.0-2.0; the glass transition temperature of the stack is >360 ° and the surface hardness is > 4H;
the thickness of each UV resistant transparent polyimide layer is 3-100 mu m, and the thickness of each UV resistant transparent adhesive layer is 3-100 mu m; the total thickness of the stack is 9-300 μm.
In order to solve the technical problems, the invention adopts the further technical scheme that: the high-transparency composite PI 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 5-25 μm inclusive, and the UV resistant transparent adhesive layer has a thickness of 10-75 μm exclusive; the total thickness of the stack is 20.1-125 μm.
Further, 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.
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 accounts for 90-95%, the low-temperature curing agent accounts for 1-3% and the anti-UV absorbent accounts for 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.
Further, the imidization catalyst is at least one of aliphatic tertiary amine, N-hydroxyphthalimide, an oxidation catalyst, a cyclic imide immobilization catalyst, a radical reaction accelerator, peracid, peroxide, azo compounds, acetophenone compounds, cyclic amine-N-oxyl compounds, a component A, nitrogen dioxide and benzaldehyde;
the component A is at least one of nitric acid, nitrous acid, nitrate and nitrite.
The invention also provides a preparation method of the high-transparency composite PI 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 winding the semi-finished product into 2 rolls;
coating or transferring a precursor of the anti-UV transparent adhesive layer on the surface of the anti-UV transparent polyimide layer of one roll of the transparent composite PI semi-finished product, baking, laminating with the other roll of the transparent composite PI semi-finished product, and rolling to form a transparent composite PI film;
wherein the parameters of the baking process are as follows: the temperature is 60-90 ℃, and the rotating speed of the fan is 750-800 rpm; the pressure during pressing is 0.8-1.5kgf/cm2
S3, curing: and (5) curing the transparent composite PI film prepared in the step (S2) at a low temperature of 45-55 ℃ for 1.5-2.5h to obtain the finished high-transparency composite PI film.
The invention has the beneficial effects that:
the high-transparency composite PI film provided by the invention is composed 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 deflection, low rebound force and the like, wherein the transmittance of light is more than or equal to 88%, the haze is less than or equal to 1%, so the transparency is high, the mechanical strength is sufficient, the thickness range is wide and reaches 9-300 mu m, different thicknesses can be designed according to different electronic product requirements, and the high-transparency composite PI film is suitable for different flexible cover plates, and is particularly suitable for being used in high-efficiency AMOLED display screens of soft and hard combined plates;
moreover, the surface hardness of the high-transparency composite PI film can reach 4H, so that the high-transparency composite PI film can be prevented from being scratched or scratched, the scratching and scratching in the manufacturing process are reduced, the attractiveness of a finished product is improved, the finished product is not easy to scratch or scratch in the using process, the hardness of the high-transparency composite PI film reaches 4H, the product requirement 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 or sputtering process, and the original mechanical performance of the PI is not damaged;
the raw materials in the anti-UV transparent polyimide layer and the anti-UV transparent adhesive layer are reasonable in proportion, and both contain anti-UV absorbers, so that the irradiation yellowing resistance of the anti-UV transparent polyimide layer can be enhanced, and meanwhile, the precursor of the prepared anti-UV transparent polyimide layer can be directly coated on an optical-grade PET release film without high-temperature (200-;
thirdly, the preparation method of the PI film comprises the following steps: coating the precursor of the anti-UV transparent polyimide layer on a release layer, rolling the release layer into two rolls, coating the precursor of the anti-UV transparent adhesive layer on the surface of one roll, and laminating the release layer and the roll, wherein the anti-UV transparent polyimide layer and the anti-UV transparent adhesive layer are both formed in a coating mode, so that the thickness of each layer is controllable, the thickness range is wider and reaches 9-300 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-;
the PI film also comprises a release layer, the release layer is an optical PET release film subjected to pre-shrinking treatment, the light transmittance of the release layer is more than or equal to 88%, the haze of the release layer is less than or equal to 1%, and the heating shrinkage rate of the release layer is less than 0.5%, the optical PET release film has 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;
fifthly, the high-transparency composite PI film can be sold or used as a finished product, when in use, the release film is only needed to be torn off and adhered to the surface needing to be adhered, and the use is convenient;
sixth, the high transparent compound PI film of the invention has high temperature resistant, high Tg, high flexibility, low bounce, high heat dissipation, withstand voltage, high surface hardness, etc. characteristics, because of having extremely low bounce, match the ultra-thin base plate bounce and can be up to less than or equal to 5gf, therefore can buckle many times, will not deflect, high transparency, especially suitable for using in the soft or hard combination plate high-efficient AMOLED display screen;
the raw material of the UV-resistant transparent polyimide layer contains dehydrating agent, which has the advantages of dehydrating, cleaning and transparent effects, and no defects of hardening and shrinking of tissues, wherein the dehydrating agent only needs to pass through each stage of 30%, 70%, 90% and 100% and then enter paraffin, but the specific weight of the dehydrating agent is heavier than that of dissolved paraffin, so that the agent needs to be removed to the greatest extent before embedding, and the dehydrating agent is preferably passed through a procedure of xylene or chloroform once and then soaked in wax, so that the dehydrating agent is easily removed from the tissues during embedding because the dehydrating agent is lighter than the dissolved paraffin. 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 example 1 of the present invention (without release layer);
FIG. 2 is a schematic structural view (including a release layer) of example 2 of the present invention;
the parts in the drawings are marked as follows:
an upper UV resistant transparent polyimide layer 100, a lower UV resistant transparent polyimide layer 200, a UV resistant transparent adhesive layer 300, an upper release layer 400, and a lower release layer 500.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
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.
The terms "upper" and "lower" in the present invention are used only for distinction and do not limit the scope of protection of the present invention; for example, the upper UV resistant transparent polyimide layer and the lower UV resistant transparent polyimide layer are merely for the purpose of distinguishing and not the same UV resistant transparent polyimide layer.
Example 1: a high-transparent composite PI film comprising an anti-UV transparent polyimide layer comprising two layers, respectively an upper anti-UV transparent polyimide layer 100 and a lower anti-UV transparent polyimide layer 300, and an anti-UV transparent adhesive layer 300 between the upper anti-UV transparent polyimide layer and the lower anti-UV transparent polyimide layer;
the transmittance of light of a stack structure consisting of the upper UV-resistant transparent polyimide layer, the UV-resistant transparent adhesive layer and the upper UV-resistant transparent polyimide layer is more than or equal to 88%, the haze is less than or equal to 1%, the L value of an L a b color system of the stack structure measured by an ultraviolet-visible light photometer is 90-95, the a value is-2.0-2.0, and the b value is-2.0-2.0; the glass transition temperature of the stack is >360 ° and the surface hardness is > 4H;
the thickness of each UV resistant transparent polyimide layer is 3-100 mu m, and the thickness of each UV resistant transparent adhesive layer is 3-100 mu m; the total thickness of the stack is 9-300 μm.
In this embodiment, it is preferable that each of the UV-resistant transparent polyimide layers has a thickness of 5 to 25 μm inclusive, and the UV-resistant transparent adhesive layer has a thickness of 10 to 75 μm inclusive; the total thickness of the stack is 20.1-125 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.
Wherein the aromatic diamine is at least one of p-phenylenediamine, tetrafluorodiamine 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 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 accounts for 90-95%, the low-temperature curing agent accounts for 1-3% and the anti-UV absorbent accounts for 0.01-0.05%; the component B is at least one of methyl acrylate, ethyl ester, polyphenyl methyl acrylate and polymethacrylic acid.
The low-temperature curing agent is at least one of 2-methylimidazole, RC526 powder curing agent and 2, 4, 6-tris (dimethylaminomethyl) phenol.
The anti-UV absorber in the anti-UV transparent polyimide layer and the anti-UV transparent adhesive layer 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 absorber BP-12, benzophenone-12 and an ultraviolet absorber UV-531.
Example 2: the utility model provides a compound PI film of high transparency, still includes from the type layer, it is optics level PET that passes through preshrinking processing from the type layer to leave the type film, optics level PET is from the light penetration rate of type film its characterized in that: the laminated glass is characterized by further comprising a release layer, wherein the release layer is positioned on the outer side of the laminated structure, the release layer is larger than or equal to 88%, the haze is smaller than or equal to 1%, and the heating shrinkage rate is smaller than 0.5%.
In this embodiment, it is two-layer and be the upper release layer 400 and leave the layer 500 down respectively to leave the type layer, go up to leave the type layer with it is located respectively to leave the type layer down the upper surface and the lower surface of superpose.
The preparation method of the high-transparency composite PI film of the embodiment includes 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; 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 winding the semi-finished product into 2 rolls;
coating or transferring a precursor of the anti-UV transparent adhesive layer on the surface of the anti-UV transparent polyimide layer of one roll of the transparent composite PI semi-finished product, baking, laminating with the other roll of the transparent composite PI semi-finished product, and rolling to form a transparent composite PI film;
wherein the parameters of the baking process are as follows: the temperature is 60-90 ℃, and the rotating speed of the fan is 750-800 rpm; the pressure during pressing is 0.8-1.5kgf/cm2
S3, curing: curing the transparent composite PI film prepared in the step S2 at a low temperature of 45-55 ℃ for 1.5-2.5h by adopting a precise programmable control oven to obtain a finished high-transparency composite PI 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, and ERP scanning code adjustment management is unified.
The following are the comprehensive comparisons of the performance indexes of the samples 1 to 5 of example 1 of the present invention and the samples of the comparative example, and the detailed results are shown in Table 1, and Table 2 is the test method of each performance index.
Table 1:
in sample 1: the upper and lower UV-resistant transparent polyimide layers are both 6 μm, and the UV-resistant transparent adhesive layer is 13 μm;
in sample 2: the upper and lower UV-resistant transparent polyimide layers are 13 μm, and the UV-resistant transparent adhesive layer is 12 μm;
in sample 3: the upper and lower anti-UV transparent polyimide layers are 15 μm, and the anti-UV transparent adhesive layer is 20 μm;
in sample 4: the upper anti-UV transparent polyimide layer, the anti-UV transparent adhesive layer and the upper anti-UV transparent polyimide layer are all 3 micrometers;
in sample 5: the upper UV resistant transparent polyimide layer, the UV resistant transparent adhesive layer and the upper UV resistant transparent polyimide layer were all 100 μm.
Table 2:
note: 1. the performance index in table 1 is measured for the performance index without the release layer and for the performance index of the stack of the upper UV resistant transparent polyimide layer, the UV resistant transparent adhesive layer and the upper UV resistant transparent polyimide layer.
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 5 of the examples.
Table 3:
note: 1. 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 sample 5, the aromatic diamine is 2-sulfonyl 1, 4-phenylenediamine and 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; in samples 4 to 5, the aromatic acid anhydrides 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 5, 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 5 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 5 was benzophenone-12; the organic solvent in samples 1 to 3 was butanone; the organic solvent in samples 4 to 5 was N, N-dimethylformamide;
2. 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 sample 5 was polymethacrylene; the low temperature curing agent in samples 1 to 3 was 2-methylimidazole; the low temperature curing agent in samples 4 to 5 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 5 was benzophenone-12.
As can be seen from table 1, the high-transparency composite PI film of the invention has the performance advantages of high transmittance, low haze, high reflectivity, high resistance to high temperature yellowing, high Tg, QUV irradiation resistance, high deflection and low bounce, has a surface hardness of 4H, can prevent scratches and scratches, and is particularly suitable for use in a high-performance AMOLED display screen of a rigid-flexible board.
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. A high-transparency composite PI film is characterized in that: comprising an anti-UV transparent polyimide layer comprising two layers, an upper anti-UV transparent polyimide layer and a lower anti-UV transparent polyimide layer, respectively, and an anti-UV transparent adhesive layer between the upper anti-UV transparent polyimide layer and the lower anti-UV transparent polyimide layer;
the transmittance of light of a stack structure consisting of the upper UV-resistant transparent polyimide layer, the UV-resistant transparent adhesive layer and the upper UV-resistant transparent polyimide layer is more than or equal to 88%, the haze is less than or equal to 1%, the L value of an L a b color system of the stack structure measured by an ultraviolet-visible light photometer is 90-95, the a value is-2.0-2.0, and the b value is-2.0-2.0; the glass transition temperature of the stack is >360 ° and the surface hardness is > 4H;
the thickness of each UV resistant transparent polyimide layer is 3-100 mu m, and the thickness of each UV resistant transparent adhesive layer is 3-100 mu m; the total thickness of the stack is 9-300 μm.
2. The high-transparency composite PI film according to claim 1, 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%.
3. The highly transparent composite PI film according to claim 2, 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.
4. The high-transparency composite PI film according to claim 1, wherein: each UV resistant transparent polyimide layer is 5-25 μm thick and does not contain an end value of 5, and the UV resistant transparent adhesive layer is 10-75 μm thick and does not contain an end value of 10; the total thickness of the stack is 20.1-125 μm.
5. The high-transparency composite PI film according to claim 1, wherein: 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.
6. The high-transparency composite PI film according to claim 1, 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 accounts for 90-95%, the low-temperature curing agent accounts for 1-3% and the anti-UV absorbent accounts for 0.01-0.05%;
the component B is at least one of methyl acrylate, ethyl ester, polyphenyl methyl acrylate and polymethacrylic acid.
7. The highly transparent composite PI film according to claim 5 or 6, 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.
8. The highly transparent composite PI film as claimed in claim 5, wherein: 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.
9. The highly transparent composite PI film as claimed in claim 5, 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.
10. A method for preparing a high-transparency composite PI film according to claim 3, wherein the method comprises the following steps: 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 winding the semi-finished product into 2 rolls;
coating or transferring a precursor of the anti-UV transparent adhesive layer on the surface of the anti-UV transparent polyimide layer of one roll of the transparent composite PI semi-finished product, baking, laminating with the other roll of the transparent composite PI semi-finished product, and rolling to form a transparent composite PI film;
wherein the parameters of the baking process are as follows: the temperature is 60-90 ℃, and the rotating speed of the fan is 750-800 rpm; the pressure during pressing is 0.8-1.5kgf/cm2；
S3, curing: and (5) curing the transparent composite PI film prepared in the step (S2) at a low temperature of 45-55 ℃ for 1.5-2.5h to obtain the finished high-transparency composite PI film.
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| US10144847B2 (en) * | 2014-05-30 | 2018-12-04 | Lg Chem, Ltd. | Polyimide-based solution and polyimide-based film produced using same |
| TWI557180B (en) * | 2015-05-27 | 2016-11-11 | 台虹科技股份有限公司 | Composition for forming dissolvable polyimide, coverlayer, and manufacturing method thereof |
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| CN205112572U (en) * | 2015-10-19 | 2016-03-30 | 昆山雅森电子材料科技有限公司 | Coloured cover membrane of high frequency |
| WO2017175869A1 (en) * | 2016-04-07 | 2017-10-12 | 株式会社カネカ | Polyimide resin, polyimide solution, film, and method for producing same |
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