KR20160082478A - Polyimide Substrate And Display Substrate Module Including The Same - Google Patents
Polyimide Substrate And Display Substrate Module Including The Same Download PDFInfo
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- KR20160082478A KR20160082478A KR1020150189009A KR20150189009A KR20160082478A KR 20160082478 A KR20160082478 A KR 20160082478A KR 1020150189009 A KR1020150189009 A KR 1020150189009A KR 20150189009 A KR20150189009 A KR 20150189009A KR 20160082478 A KR20160082478 A KR 20160082478A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
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- C08J7/047—
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/12—Mountings, e.g. non-detachable insulating substrates
- H01L23/14—Mountings, e.g. non-detachable insulating substrates characterised by the material or its electrical properties
- H01L23/145—Organic substrates, e.g. plastic
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- H01L51/0097—
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- H01L51/5284—
Abstract
Description
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide substrate and a display substrate module including the polyimide substrate. More particularly, the present invention relates to a polyimide substrate useful as a cover substrate of a flexible electronic device, .
Flexible electronic devices such as flexible OLEDs, lightweight displays, flexible encapsulants, color EPDs, plastic LCDs, TSPs, and OPVs have attracted attention as electronic devices that can bend or bend into one of the next generation displays have. Flexible type display capable of such bending or rolling is possible, and a new type of flexible cover substrate is required to replace the conventional glass cover substrate in order to protect the lower element. In addition, such a substrate needs to maintain high hardness, low moisture permeability, chemical resistance and light transmittance in order to protect the parts included in the display device.
As such flexible display cover substrate materials, various high-hardness plastic substrates have been studied as candidates, and a transparent polyimide film capable of realizing a thinner thickness and a higher hardness has been considered as a major candidate. However, since the transparent plastic substrate has a lower surface hardness than the glass, there is a limit in securing the abrasion resistance. For this purpose, high hardness coating, that is, hard coating technology, has been an important issue for improving the surface hardness of the polymer film.
For the purpose of improving the surface hardness of a plastic substrate, Korean Patent Laid-Open Publication No. 2010-0041992 discloses a hard hard coating film composition comprising an ultraviolet ray curable polyurethane acrylate oligomer, and disclosed in International Patent Publication No. WO2013-187699 There has been proposed a high hardness siloxane resin composition containing an alicyclic epoxy group, a process for producing the same, and an optical film containing the cured product.
Thus, conventionally, a method of directly forming an acrylic or epoxy organic cured film on the surface of a transparent film has been used in order to improve most of the hardness. However, when a hard coating layer having a large difference in strength from a plastic substrate such as an acrylic or epoxy based organic cured film is directly formed on a plastic substrate, not only the flexibility of the plastic substrate is deteriorated but also the coating layer is not flexible, When the impact resistance and the like were evaluated, the surface was cracked.
Accordingly, it is an object of the present invention to provide a polyimide substrate which can improve the optical characteristics and moisture barrier property while maintaining the bending property, the surface hardness and the chemical resistance, as compared with the substrate in which the hard coating layer is directly formed on the polyimide film.
According to a first aspect of the present invention, there is provided a semiconductor device comprising: a polyimide layer; And an optical primer layer comprising a silazane-siloxane compound represented by the following formula (1) on at least one surface of the polyimide layer.
≪ Formula 1 >
Wherein R is a Urethane group having at least one bonding structure selected from the group consisting of hydroxyl, vinyl, acryl, epoxy and amin, and R 'is selected from the group consisting of hydroxyl, vinyl, acryl, epoxy and amin A cyanate group containing at least one type of bonding structure, and m and n are integers of 1 to 10.
The polyimide substrate according to the first embodiment may further include a hard coating layer.
Further, a second preferred embodiment of the present invention is a display substrate module comprising a transparent adhesive layer, a black metal layer, and the polyimide substrate of the first embodiment.
According to the present invention, it is possible to provide a transparent polyimide substrate having excellent solvent resistance, optical characteristics, moisture barrier properties and scratch resistance, while having excellent bending property and impact resistance. The transparent polyimide substrate according to the present invention can be usefully used as a cover substrate of a flexible electronic device, thereby providing a flexible display substrate module having excellent bending properties and impact resistance.
1 is a structural view showing an example of a display substrate module including a polyimide substrate of the present invention.
According to one aspect of the present invention there is provided a polyimide layer; And an optical primer layer comprising a silazane-siloxane compound on at least one side of the polyimide layer.
In the present invention, the polyimide layer is made of a polyimide film, and may be a conventional polyimide film obtained by polymerizing a diamine and an acid dianhydride followed by imidization. The polyimide layer of the present invention can be applied to any colorless transparent polyimide film which has inherent heat resistance of a polyimide resin and does not appear yellow, and can be applied to a film having a thickness of 10 to 100 μm by a UV spectrophotometer If the measured average transmittance at 350 to 700 nm is 85% or more, the yellowness is 5 or less, and the average linear expansion coefficient (CTE) measured at 50 to 250 ° C according to the TMA-Method is 50.0 ppm / May be more preferable.
If the average transmittance of the polyimide film is less than 85% based on the thickness of the polyimide film of 10 to 100 占 퐉 or the yellowness exceeds 5, the transparency becomes poor and it can not be applied to displays or optical elements. (CTE) exceeds 50.0 ppm / 占 폚, the thermal expansion coefficient difference with the plastic substrate becomes large, so that the device may be overheated or short-circuited if the temperature is high.
In the present invention, the silazane-siloxane compound may be represented by the following general formula (1), and has a weight average molecular weight measured by gel permeation chromatography (GPC) of 500 to 500,000 g / mol.
≪ Formula 1 >
Wherein R is a Urethane group having at least one bonding structure selected from the group consisting of hydroxyl, vinyl, acryl, epoxy and amin, and R 'is selected from the group consisting of hydroxyl, vinyl, acryl, epoxy and amin A cyanate group containing at least one type of bonding structure, and m and n are integers of 1 to 10.
When the weight average molecular weight of the silazane-siloxane compound represented by the formula (1) is less than 500 g / mol, the effect of improving the solvent resistance, heat resistance and moisture barrier property is insignificant, and when it exceeds 50,000 g / mol, It may lack adhesion with other compounds. The silazane-siloxane compound has a high-density structure and improves the chemical resistance of the substrate. Since the refractive index of the silazane-siloxane compound is lower than that of the substrate, the optical characteristics of the polyimide film can be improved Can be improved.
In the present invention, the silazane-siloxane compound is dissolved and dissolved in an organic solvent, and the organic solvent is selected from the group consisting of isopropyl alcohol (IPA), propylene glycol monomethyl ether (PGME), and propylene glycol monomethyl ether acetate PGMEA), N-butanol, Pentanol, Methyl ethyl ketone (MEK), Acetone, Methyl alchol and Ethyl alchol. At this time, the amount of the organic solvent may be selected according to the thickness to be applied, preferably 0.5 to 90 wt%, more preferably 1 to 50 wt%, and most preferably 1 to 50 wt% 20% by weight. If the amount of the organic solvent is less than 0.5% by weight, the coating may not be uniformly formed at the time of coating, resulting in a thickness variation on the surface of the substrate, and if it exceeds 90% by weight,
In the present invention, the optical primer layer containing the silazane-siloxane compound preferably has a thickness of 0.1 탆 or more in order to secure solvent resistance and optical properties and to improve moisture barrier properties, It is preferable to set the thickness to 3 탆 or less in order to prevent occurrence of curling and curling. The optical primer layer may be formed on the lower surface or the upper surface of the polyimide film, but may be formed on both surfaces of the polyimide film. According to the present invention, the polyimide substrate including the optical primer layer can exhibit excellent optical characteristics with a CM-3700D measurement standard, a yellowness value of 2.5 or less and a light transmittance of 85 to 93% at 350 to 700 nm.
In the present invention, the optical primer layer may be coated by a suitable method selected from a variety of methods such as spray coating, bar coating, spin coating and dip coating. But is not limited thereto as long as it is applicable. The optical primer layer is thermally cured by heat treatment at a temperature of 200 to 300 ° C to have an intramolecular network structure, and it can make the film properties more rigid, and thus can provide excellent chemical resistance and heat resistance.
According to a preferred embodiment of the present invention, the polyimide substrate further includes a hard coat layer to ensure chemical resistance and impact resistance, and can exhibit surface hardness of 5H to 10H according to JIS K56000 measurement standard. However, by forming both the optical primer layer and the hard coat layer on the polyimide layer, the hard coat layer must be formed on the surface of the substrate. As compared with the polyimide substrate having only the hard coat, the transmittance and the yellowness At the same time as the optical properties are maintained, the ASTM E96BW measurement moisture permeability can fall from 0.001 to 10 g / m 2 * day. In particular, the polyimide substrate of the present invention may be more advantageous in protecting TFTs and OLED devices from external humid environments by exhibiting a low water permeability in the above range
In this case, the hard coating layer may be formed from a siloxane resin containing a chemical reactant or a mixture of an alkoxysilane represented by the following Chemical Formula 2 and an alkoxy metal represented by the following Chemical Formula 3.
(2)
(3)
Wherein R 1 is a linear, branched, alicyclic or aromatic organic compound containing an epoxy, acryl or isocyanate, and R 2 and R 3 are linear, branched or cyclic organic compounds containing a hetero compound such as oxygen or nitrogen, Branched or alicyclic C 1 to C 8 alkyl group, and n is an integer of 1 to 3. M is a metal element including a transition metal, and m is an integer of 1 to 10.
In the present invention, the siloxane resin may be prepared from the polymerization reaction of the alkoxysilane of formula (2) alone or may be prepared as a siloxane resin in which the chemical bond of the metal element is present by introducing the alkoxy metal of formula (2) . The reaction of forming the siloxane resin may proceed at room temperature, but may be stirred at 50 to 120 ° C for 1 to 120 hours to promote the reaction.
As a catalyst for carrying out the hydrolysis and condensation reaction during the reaction, an acid catalyst such as hydrochloric acid, acetic acid, hydrogen fluoride, nitric acid, and sulfuric acid iodic acid, a base such as ammonia, potassium hydroxide, sodium hydroxide, barium hydroxide, imidazole A catalyst, and an amberite. These catalysts may be used alone or in combination. The amount of the catalyst is not particularly limited, but 0.0001 to about 10 parts by weight based on 100 parts by weight of the siloxane resin may be added.
When the hydrolysis and condensation reaction proceeds, alcohol as a by-product is produced. By eliminating it, the reverse reaction can be reduced and the reaction can proceed more quickly, and the reaction rate can be controlled through the reaction. After completion of the reaction, the by-product may be removed by decompression and heating.
The siloxane resin synthesized by the condensation reaction can control the viscosity and the curing rate by the monomers added during the reaction, thereby providing an optimal resin composition suitable for the application. In addition, the siloxane resin obtained through the above reaction can prevent the curling due to curing shrinkage because intermolecular space is secured during crosslinking, and it is possible to realize high surface hardness by crosslinking and metal elements.
According to a preferred embodiment of the present invention, the resin composition for hard coating may further include an initiator for the polymerization of the siloxane resin. For example, a photopolymerization initiator such as an organic metal salt and a thermal polymerization initiator such as an amine or imidazole Can be used. In this case, the amount of the initiator to be added is not particularly limited, but about 0.01 to 10 parts by weight may be added to about 100 parts by weight of the siloxane resin.
In addition, the resin composition for hard coating of the present invention may further include an organic solvent for controlling the viscosity of the siloxane resin to facilitate workability and adjusting the thickness of the coating film. The amount of the organic solvent to be added is not particularly limited and examples of usable organic solvents include ketones such as acetone, methyl ethyl ketone, methyl butyl ketone and cyclohexanone, cellosolves such as methyl cellosolve and butyl cellosolve, Or alcohols such as ethers such as ethyl ether and dioxane, isobutyl alcohol, isopropyl alcohol, butanol and methanol, halogenated hydrocarbons such as dichloromethane, chloroform and trichlorethylene, and halogenated hydrocarbons such as n-hexane, And solvents composed of hydrocarbons and the like.
The siloxane resin of the present invention may further include an antioxidant to inhibit the oxidation reaction resulting from the polymerization reaction, and may further include a leveling agent or a coating aid, but the present invention is not limited thereto.
The resin composition for hard coating of the present invention can be prepared by hardening a hard coat by photopolymerization or thermal polymerization after molding such as coating, casting or molding. For the photopolymerization it is possible to obtain a uniform surface over the light article pre-heat treatment, which can be carried out at a temperature below about 300 ℃ than 40 ℃, if the irradiation light amount performed under the conditions of 50mJ / cm 2 or more 20000mJ / cm 2 or less But is not limited thereto. Further, in the case of thermal polymerization, it may be carried out at a temperature of 40 ° C or more and about 300 ° C or less, but is not limited thereto.
In the present invention, the hard coat layer formed as described above preferably has a dry thickness of 10 탆 or more in order to obtain excellent surface hardness, impact resistance and chemical resistance, and is preferably formed to be less than 50 탆 in order to prevent warpage and excessive rigidity .
Further, the present invention can provide a display substrate module including a transparent adhesive layer , a black matrix, and a polyimide substrate of the above-described characteristics. Although not limited thereto, the display substrate module of the present invention may include a polyimide substrate having a structure in which an optical primer layer 20, a polyimide layer 10 and a
Example
Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for the purpose of illustrating the present invention more specifically, and the present invention is not limited thereto.
< Manufacturing example 1. Production of polyimide film>
1-1: Preparation of polyimide powder
832 g of N, N-dimethylacetamide (DMAc) was charged into a 1 L reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a condenser while nitrogen was passed through the reactor. 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was dissolved and the solution was maintained at 25 占 폚. Thereto were added 31.09 g (0.07 mol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropanedioanhydride (6FDA) and 8.83 g (0.03 mol) of biphenyltetracarboxylic dianhydride (BPDA) ) Was added and stirred for a certain period of time to dissolve and react. The temperature of the solution was maintained at 25 占 폚. Then, 20.302 g (0.1 mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution having a solid content of 13 wt%.
25.6 g of pyridine and 33.1 g of acetic anhydride were added to the polyamic acid solution, stirred for 30 minutes, and further stirred at 70 ° C for 1 hour. The mixture was cooled to room temperature and precipitated with 20 L of methanol. The precipitated solid was filtered and pulverized And then dried at 100 DEG C under vacuum for 6 hours to obtain 111 g of a solid powdery polyimide.
1-2: Production of polyimide film
0.03 g (0.03 wt%) of OH group-bonded amorphous silica particles was added to N, N-dimethylacetamide (DMAc) at a dispersion concentration of 0.1% and ultrasonic treatment was performed until the solvent became transparent. 100 g of the obtained polyimide powder as a solid powder was dissolved in 670 g of N, N-dimethylacetamide (DMAc) to obtain a 13 wt% solution. The solution thus obtained was applied to a stainless steel plate, cast to 340 占 퐉 and dried with hot air at 130 占 폚 for 30 minutes, and then the film was peeled off from the stainless plate and fixed to the frame with a pin.
The frame with the film fixed therein was placed in a vacuum oven, slowly heated from 100 ° C to 300 ° C for 2 hours, cooled gradually and separated from the frame to obtain a polyimide film. Thereafter, the substrate was subjected to heat treatment at 300 ° C for 30 minutes as a final heat treatment process. The prepared polyimide film had a thickness of 80 μm, an average light transmittance of 87%, a haze of 4.5, and an average coefficient of linear thermal expansion (CTE) measured at 50 to 250 ° C. according to the TMA-Method was 20 ppm / ° C. .
< Manufacturing example 2. Manufacture of hard coating resin>
The mixture was mixed with KBM-303 (Shinetsu), Titanium isopropoxide (Sigma-Aldrich) and H 2 O at a ratio of 227.96 mL: 1.94 mL: 21.61 mL and put into a 500 mL flask. 0.2 g of sodium hydroxide was added as a catalyst to 60 0.0 > C < / RTI > for 24 hours. Thereafter, 0.45um be collected by filtration using a Teflon filter-average molecular weight of 7245, weight hyeonggyun a molecular weight of 20146 and a polydispersity index (PDI, M w / M n) is to obtain a siloxane resin of 2.78 (the molecular weight by GPC Measure). 3 parts by weight of IRGACURE 250 (BASF) as a photoinitiator relative to 100 parts by weight of the resin was added to finally obtain a resin for hard coating.
Example One
A solution obtained by dissolving 3 wt% of a polysilazane-siloxane compound (DCT Co.) having a weight average molecular weight of 2,000 g / mol in PGME (manufactured by Daehwa Fine Chemical Co., Ltd.) was coated on one surface of a colorless transparent polyimide film, And then dried at a temperature of 80 캜 to form a polysilazane siloxane compound film having a thickness of 0.1 탆. Thereafter, the substrate was left to stand at room temperature for about 5 minutes, and thermally cured at a temperature of about 250 ° C to prepare a polyimide substrate having an optical primer layer having a thickness of 0.1 μm.
Example 2
A solution obtained by dissolving 10 wt% of a polysilazane siloxane compound (DCT Co.) having a weight average molecular weight of 2,000 g / mol in PGME (manufactured by Daehwa Fine Chemical Co., Ltd.) was applied onto one surface of a colorless transparent polyimide film prepared by the above- And dried at a temperature of 80 캜 to form a polysilazane siloxane compound film having a thickness of 0.5 탆. Thereafter, the film was allowed to stand at room temperature for about 5 minutes, and then thermally cured at a temperature of about 250 ° C to prepare a polyimide substrate having an optical primer layer having a thickness of 0.5 μm.
Example 3
A solution obtained by dissolving 20 wt% of a polysilazane siloxane compound (DCT) having a weight average molecular weight of 2,000 g / mol in PGME (manufactured by Daehwa Fine Chemical Co., Ltd.) was applied to one surface of a colorless transparent polyimide film prepared in the above Production Example by wire , And dried at a temperature of 80 캜 to form a polysilazane siloxane compound film having a thickness of 1.0 탆. Thereafter, the substrate was left to stand at room temperature for about 5 minutes, and thermally cured at a temperature of about 250 ° C to prepare a polyimide substrate having an optical primer layer having a thickness of 1.0 탆.
Example 4
A solution obtained by dissolving 20 wt% of a polysilazane siloxane compound (DCT) having a weight average molecular weight of 2,000 g / mol in PGME (manufactured by Daehwa Fine Chemical Co., Ltd.) was applied to one surface of a colorless transparent polyimide film prepared in the above Production Example by wire And dried at a temperature of 80 캜 to form a polysilazane siloxane compound film having a thickness of 3.0 탆. Thereafter, the substrate was left to stand at room temperature for about 5 minutes, and thermally cured at a temperature of about 250 ° C to prepare a polyimide substrate having an optical primer layer having a thickness of 3.0 μm.
Example 5
An optical primer layer was formed in the same manner as in Example 1, and an optical primer layer was formed on both sides of the polyimide substrate.
Example 6
A polyimide substrate having an optical primer layer formed thereon was prepared in the same manner as in Example 1 except that the resin for hard coating of Production Example 2 was coated on one surface of the polyimide layer opposite to the surface on which the optical primer layer was formed And then exposed to an ultraviolet lamp having a wavelength of 315 nm for 30 seconds to form a hard coat layer.
Example 7
A hard coat layer was additionally formed on the upper surface of the optical primer layer on one side of the optical primer layers formed on both sides in Example 5, in the same manner as in Example 6. [
Example 8
A polyimide substrate was prepared in the same manner as in Example 1 except that the polysilazane-siloxane compound (DCT) having a weight average molecular weight of 1,000,000 g / mol was used.
Comparative Example One
The polyimide film prepared in Production Example 1 was prepared as it was and was designated as Comparative Example 1. [
Comparative Example 2
The optical primer layer was omitted from the polyimide film of Production Example 1 and only the hard coat layer was formed in the same manner as in Example 6 to prepare a polyimide substrate.
Comparative Example 3
The hard coat layer was formed in the same manner as in Example 6 except that acrylic resin was used instead of the hard coat resin of Preparation Example 2, but the shrinkage ratio was not suitable, and curl was severely generated during curing, and surface cracks were visually confirmed.
Comparative Example 4
The polyimide substrate was prepared in the same manner as in Example 1 except that the thickness of the optical primer layer was changed to 3.5 탆. However, it was confirmed that the polyimide substrate was difficult to produce due to cracking during curing.
< Measurement example >
Subsequently, physical properties were measured by the following methods in the above-mentioned Examples and Comparative Examples, except for Comparative Examples 3 and 4, in which the analysis was impossible due to the occurrence of crake in the naked eyes. The results are shown in Tables 1 and 2 Respectively.
(1) Average light transmittance (%): The optical transmittance at 350 to 700 nm was measured using a spectrophotometer (CM-3700D, KONICA MINOLTA) according to the standard specification ASTM E313.
(2) Yellowness: Yellowness was measured using a spectrophotometer (CM-3700D, KONICA MINOLTA) according to ASTM E313.
(3) Water Permeability (g / m 2 * day): Water permeability (WVTR) was measured using a standard ASTM E69BW using a water-based transient (MOCON / US / Aquatran-model-1).
(4) Pencil hardness: Standard of 50 mm at a rate of 180 mm / min under a load of 1 kg using a pencil hardness tester (Mitsubishi Evaluation Pencil (UNI) with ASTM D3363) After the spinning, the pencil hardness at which no scratches were generated on the surface was measured.
(5) Adhesion (detachment after detachment with tape): Measured by tapping after cross cutting according to standard (ASTM D3359).
(6) Flexural characteristics: The substrate was wound around a circular tool having a diameter of 2 mm, and the substrate was wound. The film was repeated 200,000 times to observe the film with a naked eye or a microscope. If there was any cracking, the film was marked as 'Failed' 'OK'.
(7) Chemical resistance measurement: 2.38% of tetramethylammonium hydroxide (TMAH), dimethylacetamide (DMAc), N-methyl-2-pyrrolidone ), Sodium hydroxide (KOH) 1%, acetone, isopropyl alcohol (IPA), methylethylketone (MEK) and MASO 2 (sodium sulfate) for 1 hour, X "when white turbidity or abnormality occurs, and" ○ "when the weight change rate after drying is within 0.01%.
(%)
(g / m 2 * day)
As is clear from the results of Tables 1 and 2, in the case of Examples 1 to 5 in which an optical primer layer containing silazansiloxane was formed on the surface of the polyimide film, as compared with Comparative Example 1, The optical properties such as light transmittance and yellowness as well as chemical resistance were improved. However, it was confirmed that the surface hardness and adhesiveness were somewhat lowered and the flexural characteristics were slightly observed in the case of Example 8 in which the weight average molecular weight of the silazanosiloxane was higher than those of Examples 1 to 5.
On the other hand, Examples 6 and 7 in which the optical primer layer and the hard coat layer were formed showed little change in physical properties such as chemical resistance and pencil hardness as compared with Comparative Example 2 in which only the hard coating was formed by omitting the optical primer layer, And the optical characteristics and the water permeability were found to be significantly improved as compared with Comparative Example 2.
These results indicate that the polyimide substrate according to the present invention is suitable for a display substrate module of a flexible electronic device because of its excellent surface hardness, chemical resistance, and warp characteristics as well as optical characteristics. Particularly, And to protect the OLED device.
10: polyimide layer 20: optical primer layer
30: hard coating layer 40: transparent adhesive layer
50: Black mattress layer
Claims (10)
And an optical primer layer comprising a silazane-siloxane compound represented by the following formula (1) on at least one surface of the polyimide layer.
≪ Formula 1 >
Wherein R is a Urethane group having at least one bonding structure selected from the group consisting of hydroxyl, vinyl, acryl, epoxy and amin, and R 'is selected from the group consisting of hydroxyl, vinyl, acryl, epoxy and amin A cyanate group containing at least one type of bonding structure, and m and n are integers of 1 to 10.
(2)
(3)
Wherein R 1 is a linear, branched, alicyclic or aromatic organic compound containing an epoxy, acryl or isocyanate, and R 2 and R 3 are linear, branched or cyclic organic compounds containing a hetero compound such as oxygen or nitrogen, Branched or alicyclic C 1 to C 8 alkyl group, and n is an integer of 1 to 3. M is a metal element including a transition metal, and m is an integer of 1 to 10.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW104144514A TWI556962B (en) | 2014-12-31 | 2015-12-30 | Polyimide substrate and display substrate module including the same |
| PCT/KR2015/014497 WO2016108629A1 (en) | 2014-12-31 | 2015-12-30 | Polyimide substrate and display substrate module comprising same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140196057 | 2014-12-31 | ||
| KR20140196057 | 2014-12-31 |
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| TW (1) | TWI556962B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190090300A (en) * | 2018-01-24 | 2019-08-01 | 주식회사 동진쎄미켐 | Polyimide film and method for producing the same |
| WO2023101176A1 (en) * | 2021-11-30 | 2023-06-08 | 삼성전자주식회사 | Protective film structure and electronic device comprising same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5840848B2 (en) * | 2011-03-01 | 2016-01-06 | メルクパフォーマンスマテリアルズＩｐ合同会社 | Composition for forming low refractive index film, method for forming low refractive index film, and low refractive index film and antireflection film formed by the forming method |
| KR101489959B1 (en) * | 2012-05-21 | 2015-02-04 | 제일모직주식회사 | Gas barrier film, method for preparing thereof and display display member comprising the same |
| KR101537845B1 (en) * | 2012-12-12 | 2015-07-17 | 코오롱인더스트리 주식회사 | Transparent Polyimide Substrate and method for producing the same |
| KR101519559B1 (en) * | 2013-04-29 | 2015-05-13 | 이근수 | Modified polysilazane-based polymer, coating composition comprising the same, coated plastic substrate obtainable using the same and its preparing method, and method of preparing the modified polysilazane-based polymer |
-
2015
- 2015-12-29 KR KR1020150189009A patent/KR20160082478A/en not_active Application Discontinuation
- 2015-12-30 TW TW104144514A patent/TWI556962B/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190090300A (en) * | 2018-01-24 | 2019-08-01 | 주식회사 동진쎄미켐 | Polyimide film and method for producing the same |
| WO2023101176A1 (en) * | 2021-11-30 | 2023-06-08 | 삼성전자주식회사 | Protective film structure and electronic device comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201627163A (en) | 2016-08-01 |
| TWI556962B (en) | 2016-11-11 |
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