TW201109355A - Release layer materials, substrate structures comprising the same and fabrication method thereof - Google Patents

Abstract

A release layer material of cyclic olefin copolymers (COC) applied in flexible electrical devices represented by Formula (I) or (II) is provided. The invention also provides a substrate structure including the release layer. The substrate structure includes a carrier, a release layer overlying the carrier with one or more blocks with a first area, wherein the release layer includes cyclic olefin copolymers (COC) represented by the disclosed Formula (I) or (II), and a flexible substrate overlying the release layer and the carrier with a second area, wherein the second area is larger than the first area and the flexible substrate has a greater adhesion force than that of the release layer to the carrier. The invention further provides a method for fabricating the substrate structure. In Formula (I) or (II), X is 30-70, X+Y is 100 and R is -H, -CH3 or -C2H5.

Description

201109355 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a release layer material, and more particularly to a cyclic olefin copolymer release layer material and a substrate structure including the release layer. [Prior Art] Soft display has become the development trend of the new generation of new displays, and the development of active soft display is the mainstream trend. The world's major R&D companies are all from the current heavy and fragile glass substrate into the non-glass. The light and soft plastic substrate material is developed and moves towards the active full color tft display panel. At present, technologies for developing active flexible displays include a-Si TFT, LPTS TFT, and 0TFT, and the components of the display medium include EPD, ECD, LCD, and EL. In the choice of manufacturing methods can be divided into batch type and roll t〇r〇u two ways, if you choose the batch type method for tft component manufacturing, you can use the existing TFT s support for production, has considerable advantages, but must develop the § stomach Substrate Transfer or Film Release Technology 'Transfers the flexible display from the glass to other plastic substrates or removes it. The roll to r〇ll method must be carried out with new equipment and must overcome the problems caused by the rotation and contact. There are three main ways to manufacture TFT structures in batch type. One is SEC using PES to transfer the substrate onto the germanium wafer, and the 7" VGA (640x480) piastic LCD is developed using low temperature a-Si TFT technology. This method requires a high temperature resistance. High transparent substrate material with low thermal expansion coefficient, low light hysteresis and good chemical resistance, combined with appropriate rubber and good release technology. 5 201109355 Second, Seiko Epson develops TFT backplane with LPTS transfer technology. The LPTS TFT backplane is fabricated on the glass substrate. After completion, Seiko Epson uses laser igniting. The main advantage of the transfer technology is that the TFT component process temperature is not limited by the plastic substrate. Therefore, there is a better Characteristics, so generally high-transparency plastic substrate can be used, but its transfer mechanism and transfer technology is more important. In addition, 'the third is Philips using poly-liminamide (PI) coated on glass, Developed a-Si TFT-EPD display and removed the PI substrate on the glass by transfer technology. This technology has high resistance to the use of traditional PI plastic substrates. The temperature characteristics are directly applied to the glass, not only the process temperature can exceed 300 ° C. The step of transferring can be omitted, but the glass substrate must still be removed by laser. Due to the mismatch with the flexible substrate material and low thermal resistance, Therefore, the conventional release layer material is not suitable for use in a TFT process. SUMMARY OF THE INVENTION One embodiment of the present invention provides a cyclic olefin copolymer release layer material for use in a flexible electronic component, having the following chemical formula (I) or ( II): 201109355

γ (II) fluorenyl or ii(i) or (η), χ is 30~7〇, χ+γ is i〇〇, r is hydrogen, one of the substrate structures of the present invention, - a cover of the soft electronic component of the support = two bodies; a release layer U an area of a ring olefin copolymer / i or a plurality of commissions 'where the release layer is coated with a chemical formula (1) Or (n); and a soft base on both sides of the cover of the release layer and the support carrier, wherein the first material is applied to the _ layer and the cut-off ±, (4) into - (four) substrate sister suitable for application purity Base_separation. According to an embodiment of the present invention, there is provided a method of manufacturing a substrate structure comprising: providing a n-cover for supporting a carrier 3; and a release layer on the (four) body to form one or a plurality of t-blocks, wherein the _-type layer comprises a ring-diffusing copolymer having the above chemical formula (1) or 3: covering a flexible substrate in the release layer and the branch bud in a two-two area, wherein the second area is larger than the first area and the soft raft 7 201109355 The degree of adhesion to the support carrier is greater than the adhesion of the release layer to the support carrier. The invention provides a substrate structure which can be applied to a flexible electronic component by using a conventional semiconductor device, which utilizes the difference in adhesion between the two release layers and the support carrier, and firstly makes the release layer with poor adhesion less The area is formed on the support carrier, and the release layer (such as a flexible display substrate) having a better adhesion to the support carrier is overlaid on the release layer of the poor adhesion with a large area and is in contact with the support carrier. The substrate structure produced in this way can ensure that it does not fall off during the TFT process, and after the process is completed, the portion of the release layer which is not densely attached to the outside is removed, and the adhesion degree can be easily separated. Release layer and support carrier. After separation, the release layer (e.g., the flexible display substrate) with better adhesion can remain intact without damage. The above described objects, features and advantages of the present invention will become more apparent and understood. A cyclic olefin copolymer release layer material applied to a flexible electronic component having the following chemical formula (1) or (Π). r 1 r Η Η 1 inch ch2-ch2—]~~——C——C---

201109355

γ (ΐΐ) In the formula (1) or (II), X may be 30 to 70, Χ+Υ may be 100, and R may be hydrogen, decyl or ethyl. In order to achieve process uniformity, the above release layer material is soluble in an organic solvent. Referring to Fig. 1, a substrate structure of a soft electronic component according to one embodiment of the present invention will be described. The substrate structure 10 includes a support carrier 12, a release layer 14, and a flexible substrate 16. The release layer 14 covers the support carrier 12 with a first area A1 to form one or more blocks (as shown in Figure 1A). The release layer 14 comprises a cyclic olefin copolymer having a soft substrate of the above formula (I) or (II) and covering the release layer 14 and the support carrier 12 with a second area Λ2. It is to be noted that the second area A2 is larger than the first area A1 and the adhesion of the flexible substrate 16 to the support carrier 12 is greater than the adhesion of the release layer 14 to the support carrier 12. The invention does not limit the size, shape and configuration of the release layer block. The support carrier 12 can include a glass or germanium wafer. The adhesion of the release layer 14 to the support carrier 12 is 0B to 1B (100-gauge adhesion test). The release layer 14 may have a solid content of 1 to 20%. The release layer 14 may have a thickness of 0.2 to 20 μm, preferably 0.5 to 5 μm. The flexible substrate 16 can be a flexible display substrate, such as an active flexible display substrate, which has a adhesion to the support carrier 12 of 1 to 5 B (100 knives 201109355 adhesion test). The flexible substrate 16 may be, for example, polyimide (PI), polycarbonate (PC), polyethersulfone (PES), polyacrylate (PA), polynorbornene (polynorbornene, PNB), polyethylene terephthalate (PET), polyetheretherketone (PEEK), polyethylene naphthalate (PEN) or polyetherimide ( Polyetherimide, PEI) is composed of materials. If the flexible substrate 16 is a transparent polyiminamide (PI), it may have the following chemical formula (III):

Sulfhydryl, trifluoromethyl, meridine, -OR (R can be a carbon number of 1 to 18), desert, gas or moth, Z can be ·〇-, -CH2-, -C(CH3)2 -, -S〇2_, - Ar_〇-Ar-, -Ar-CH2-Ar--Ar-C(CH3)2-Ar- or -Ar-S〇2_Ar- (Ar can be benzene

ring). B may include □, 201109355 σΌ, or V ν, and Χ and γ may be hydrogen, fluorenyl, trifluoromethyl, hydroxy, -〇R (R may be an alkyl group having 1 to 18 carbon atoms), bromine, chlorine or Iodine, Z can be -0-, -CH2-, -C(CH3)2-, -S02-, -Ar-0-Ar-, -Ar-CH2-Ar-, -Ar_C(CH3)2-Ar- Or -Ar-S〇2-Ar- (Ar can be a benzene ring). η can be an integer greater than one. Further, a siloxane compound or cerium oxide may be added to the flexible substrate 16 to increase the adhesion of the flexible substrate 16 to the support carrier 12. The cyclic olefin copolymer release layer material of the present invention is coated on a support carrier (e.g., a glass substrate) to form one or more blocks. Thereafter, a soft base material is applied to the release layer and the support carrier to form a two-layer substrate structure suitable for separation of the flexible substrate. The second to second embodiments illustrate an embodiment of the present invention, and a method of manufacturing a substrate structure for a flexible electronic component. Referring to Figure 2, first, a support carrier 12 having a release layer 14 coated thereon is provided. The release layer 14 is applied to the support carrier 12 to form one or more blocks (as shown in Figure 1). The coated area is a first area Α1. The release layer 14 comprises a cyclic olefin copolymer having the above formula (I) or (II). The invention does not limit the size, shape and configuration of the release layer block. Next, referring to Fig. 2, a flexible substrate 16 is coated on the release layer 14 and the support carrier 12, for example, by coating. The flexible substrate 16 covers the area of the release layer 14 and the support carrier 12 to a second area Α2. It is worth noting that the second area Α2 is greater than the first area Α1 and the adhesion of the flexible substrate 16 to the support carrier 12 is greater than the adhesion of the release layer 14 to the support carrier 12. Next, referring to FIG. 2C, the two ends of the release layer 14 are cut off 201109355 points (c, c'), and the partial flexible substrate 16 and the support cut-type layer 14, the flexible substrate 16 and the support carrier 12 are cut off. As is the case, the separation provided by the present invention can be illustrated by the prior art. The substrate structure of the flexible electronic component utilizes the difference of the adhesion degree of the two kinds of applications, firstly, the release layer with poor adhesion is cut into the support carrier by 1 and the support, and then the support carrier is dense. A relatively small and small-area molded flexible display substrate) is covered with a relatively large area on a relatively dense two-type layer (for example, and is in contact with the branch #_. The base layer produced in this way is protected from the TFT). The process will not be removed, and in the completion of the system ^ 确 : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : : The degree is better than that of a flexible display substrate) and remains intact. , the type of the layer (examples of the embodiment of the present invention is to first use the glass for the TFT 5cm I5cm) to make the release layer, in which the hollow sheet can be used to control the area of the release layer (such as 8cm) *8cm), and then molding the substrate material over the release layer area (such as l〇cm*l〇cm) on the glass containing the release layer to form a substrate structure for manufacturing flexible electronic components, and then using this structure After all the processes of the flexible electronic component are performed, the partial substrate and the release layer can be easily cut along both ends of the release layer or the inside thereof, and the flexible electronic component can be separated on the glass. [Example 1] Polyimide B1317-BAPPm (BB)/Topas (X=50, Y=50)/glass 201109355 Production of glass substrate structure First, different solid contents (1%, 3%, 6%, 7%, 8%) of Topas solution. Thereafter, the above Topas solution was applied to different glass support supports to form a wet Topas film. The thickness of the wet Topas film was 30 μm, 60 μm, 90 μm, and 120 μm, respectively. After baking at 50 ° C for 5 minutes and baking at 300 ° C for 1 hour, a polyimide substrate material (containing 1% adhesion promoter) was applied to the Topas film. After baking again, the release test was carried out, and the results are shown in Table 1. Table I

Topas solid content is completely dissolved. The adhesion of the glass support carrier is 1% of the release of the polyimide substrate. Yes 0B Completely removed, no damage 3% Yes 0B Completely removed, no damage 6% Yes 0B Completely removed , No breakage 7% Yes 0B Completely taken, No broken 8% No, Forming colloid - [Example 2] Polybendamine B1317-BAPPm (BB)/Arton (χ=5〇, Y=50, 201109355 R=H)/Production of Glass Substrate Structure First, Arton solutions of different solid contents (5%, 10%, 15%, 20%, 25%) were prepared. The above Arton solution was then coated onto a different glass support carrier to form a wet Arton film. The thickness of the wet Arton film is

30 μm, 60 μm, 90 μm, 120 μm. After baking at 50 ° C for 5 minutes and 300 ° C for 1 hour, a polyimide substrate material (containing 1% adhesion promoter) was applied to the Arton film. After baking again, the release test was carried out, and the results are shown in Table 2. Table II

Is the solid content of Arton completely dissolved------- The release of the dense polyimide substrate of the glass support carrier is 5% Yes 0B Completely removed, no damage 10% Yes ~---- 0B Complete Next, no damage 15% Yes '' 0B Completely removed, no damage 20% Yes 0B Completely removed, no damage 25% No, forming colloid L_ [Example 3] Preparation of parylene release layer 201109355 Put the parylene dimer into the hot-steaming equipment, and put the pre-washed glass (15cm*15cm) into the sample chamber, covering it with a hollow (8cm*8cm) gasket. On the glass, after vacuuming, heat to 150 ° C to vaporize the polyethylene terephthalate precursor, then heat to 650 ° C, lyse it, open the door to the sample chamber, and polymerize and deposit at room temperature. The glass area not covered by the spacer forms an 8 cm*8 cm release film. [Embodiment 4]

Arton, Topas, Zeonor release layer production, Arton, Topas, Zeonor were dissolved in benzene in a solid content of 10%, coated on glass by doctor blade, placed in an oven at 80 ° C and 150 ° C Baking was carried out for 0.5 hours to form a release film of 8 cm * 8 cm. [Example 5] Preparation of polybendamine B1317-BAPPm (BB)/parylene/glass substrate structure ~Ο'°ΌΉΟ~0Ό·{Χίΐ^Ν- 0 0 First, at room temperature, using a three-necked bottle 0.0147 moles of BAPPm diphenylamine was dissolved in 32.94 grams of cresol solvent under nitrogen. After BAPPm was completely dissolved, 0_015 mol of B1317 dianhydride was added until B1317 was completely dissolved, and stirring was continued for 1 hour to form a viscous polyfluorene 201109355 amine acid solution. Thereafter, the mixture was heated to 220 ° C for 3 hours of the amidoximation reaction, and the water was removed simultaneously using a water removal device during the reaction. Finally, the reaction was dropped into decyl alcohol to immerse the polyamine, and dried in a vacuum oven for 12 hours. After drying, the polymethyleneamine was dissolved in DMAc at a solid content of 20% to form a polymethyleneamine solution. Then, the polyamidamine solution was coated on a glass plated with 8 cm*8 cm of paryiene by a doctor blade method in an area of 10 cm*10 cm and placed in an oven at 80 ° C and 150 ° C for drying. After baking for 1 hour, a substrate structure containing polyamine (BB) can be obtained. [Example 6] Preparation of cerium oxide/polyiminamide B1317-BAPPm (Si〇2/BB37)/parylene/glass substrate structure First, 3 g of a solid content of 20% was dissolved in DMAc at room temperature. Ceria (Si〇2) and 7 g of B1317-BAPPm (BB) dissolved in DMAc at a solid content of 20% were placed in a sample vial. Next, 3 g of an amine-containing oxirane was added and stirred at room temperature for 30 minutes. Thereafter, it is applied to a glass plated with parylene by a doctor blade, and baked in an oven at 80 ° C and 150 ° C for 1 hour to obtain a cerium oxide/polymer. Substrate structure of arsenamide B1317-BAPPm (Si02/BB37). [Example 7] Preparation of cerium oxide/polyiminamide B1317-BAPPm (Si〇2/BB55)/parylene/glass substrate structure First, 5 g of a solid content of 20% was dissolved in DMAc at room temperature. Cerium oxide (SiO 2 ) was placed in a sample vial with 5 g of 201109355 B1317-BAPPm (BB) dissolved in DMAc at a solid content of 20%. Next, 2 g of an amine-containing azepine was added and the mixture was stirred at room temperature for 30 minutes. Thereafter, it is applied to a glass plated with parylene by a doctor blade, and baked in an oven at 80 ° C and 150 ° C for 1 hour to obtain a silica dioxide containing day. Substrate structure of polybendamine B1317-BAPPm (Si02/BB55). [Example 8] Preparation of oxidized hair/polyimide amine B1317-BAPPm (Si02/BB73)/parylene/glass substrate structure First, 7 g of a solid content of 20% solid solution was dissolved in DMAc at room temperature.矽 (SiOJ and 3 g of B1317-BAPPm (BB) dissolved in DMAc at a solid content of 20% were placed in a sample vial. Then, 0.12 g of an amine-containing oxirane was added and stirred at room temperature for 30 minutes. Thereafter, It is coated on a glass of parylene with a doctor blade and baked in an oven at 80 ° C and 150 ° C for 1 hour to obtain cerium oxide/polyarylene. Substrate structure of amine B1317-BAPPm (Si02/BB73) [Example 9] Preparation of tetraethoxy decane/polyiminamide B1317-BAPPm (TEOS/BB)/Topas/glass substrate structure First, at room temperature 0.2 g of tetraethoxysilane (TEOS) and 10 g of B1317-BAPPm (BB) dissolved in DMAc at a solid content of 20% were placed in a sample vial. Then, it was applied by a spatula to Topas On the glass, and baked in an oven at 80 ° C and 150 ° C for 1 hour, you can get tetraethoxy decane / polyamido 201109355 B1317-BA The substrate structure of PPm (TEOS/ΒΒ). [Example 10] Preparation of amino decane/polyimide B1317-BAPPm (amino silane/BB)/Zeonor/glass substrate structure First, at room temperature, 0.2 g The amino silane is placed in a vial with 10 g of B1317-BAPPm (BB) dissolved in DMAc at a solid content of 20%. Then, it is applied to the Zeonor-coated glass by a doctor blade and placed. After baking in an oven at 80 ° C and 150 ° C for 1 hour, a substrate structure containing amino decane/polyimide B1317-BAPPm (amino silane/BB) can be obtained. [Example 11] 3-( Preparation of methacryloxy)propyltrimethoxy decane/polyamidoamine B1317-BAPPm (MPMS/BB)/Arton/glass substrate structure First, at room temperature, 0.2 g of 3-(fluorenyl) 3-(methacryloxy) propyl trimethoxy silane (MPMS) was placed in a vial with 10 g of B1317-BAPPm (BB) dissolved in DMAc at a solid content of 20%. It is coated on Arton-coated glass by a doctor blade, and baked in an oven at 80 ° C and 150 ° C for 1 hour to obtain 3-(mercaptopropoxy)propyltriazine. Yl Silane / polyalkylene Amides B1317-BAPPm (MPMS / BB) of the substrate structure. After the substrate structure is completed, as long as the electronic component is fabricated in the range containing the release layer, after the entire component is completed, a part of the substrate and the release layer are cut off at the boundary or inside of the release layer, and the substrate and the substrate can be easily Electronic component 18 201109355 is separated from the glass. Table 3 and Table 4 show the adhesion of the release layer and the flexible substrate to the support carrier of the present invention. Table 3 Material Adhesion (B) Parylene (Example 3) 0 Topas (Example 4) 0 Zeonor (Example 4) 0 Arton (Example 4) 0 Polyiminide (Example 5) 1 Polyaluminium Amine + cerium oxide (Examples 6 to 8) 2 to 5 Polyimide + TEOS (Example 9) 5 Polyiminide + Aminodecane (Example 10) 5 Polyiminide + MPMS (Example 11) 5 Table IV cerium oxide content (%) Tightness (B) 0 (Example 5) 1 30 (Example 6) 5 50 (Example 7) 3 70 (Example 8) 2 Although the present invention has The present invention is disclosed in the above preferred embodiments, but it is not intended to limit the present invention to 19 201109355. Any person skilled in the art can change and refine the present invention without departing from the spirit and scope of the present invention. This is subject to the definition of the scope of the patent application. 20 201109355 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing a structure of a substrate for a flexible electronic component according to an embodiment of the present invention. Fig. 1A is a top view of a substrate structure applied to a flexible electronic component according to an embodiment of the present invention. 2A to 2D are diagrams showing a cross-sectional view of a method of manufacturing a flexible electronic component substrate structure according to an embodiment of the present invention. [Main component symbol description] 10~substrate structure; 12~ support carrier; 14~release layer; 16~soft substrate;

Al, A2 ~ coverage area; C, C' ~ cut-off point. twenty one

Claims (1)

201109355 VII. Patent application scope: 1. A cyclic olefin copolymer release layer material for soft electronic components, having the following chemical formula (1) or (II): Wherein X is from 30 to 70, X + Y is 100, and R is hydrogen, decyl or ethyl. 2. The cyclic olefin copolymer release layer material for use in a soft electronic component according to claim 1, wherein the release layer material is soluble in an organic solvent. 3. A substrate structure for a flexible electronic component, comprising: a support carrier; a release layer covering the support #carrier with a first area to form one or more blocks, wherein the release layer comprises a ring An olefin copolymer having the following chemical formula (I) or (II): 22 201109355 (ιι) wherein X is 30 to 70, Χ+Υ is 100, R is hydrogen, fluorenyl or ethyl; and a flexible substrate covering the release layer and the support carrier with a second area, wherein the second The area is larger than the first area and the adhesion of the flexible substrate to the support carrier is greater than the adhesion of the release layer to the support carrier. 4. The substrate structure for a flexible electronic component according to claim 3, wherein the support carrier comprises a glass or germanium wafer. 5. The substrate structure applied to the flexible electronic component according to claim 3, wherein the release layer has a density of 0B to 1B 〇6 to the support carrier. The substrate structure is applied to a flexible electronic component, wherein the release layer has a solid content of 1 to 20%. 7. The substrate structure for a flexible electronic component according to claim 3, wherein the release layer has a thickness of 0.2 to 20 μm. The method of claim 3, wherein the thickness of the release layer is between 0 and 5 micrometers. 9. The substrate structure for a flexible electronic component according to claim 3, wherein the flexible substrate has a adhesion to the support carrier of 1 to 5 B 〇 10 as described in claim 3 The substrate structure is applied to a flexible electronic device, wherein the flexible substrate comprises polyimide (PI), polycarbonate (PC), polyethersulfone (PES), polyacrylate (polyacrylate). PA), polynorbornene (PNB), polyethylene terephthalate (PET), polyetheretherketone (PEEK), polyethylene naphthalate , PEN) or polyetherimide (PEI) 0. The substrate structure for soft electronic components according to claim 10, wherein the polyamidomine has the following chemical formula (III): 24 201109355 Or wherein Y and Y are hydrogen, fluorenyl, trifluoromethyl, hydroxy, -OR (R is an alkyl group having 1 to 18 carbon atoms), bromine, chlorine or iodine, and Ζ is -0-, -CH. , -C(CH3)2_, -S〇2_, -Ar-0-Ar_, -Ar-CH^-Ar-, -Ar-C(CH3)2-Ar- or -Ar-S02-Ar- (Ar Is a benzene ring); β includes LI], Wherein X and Y are hydrogen, fluorenyl, trifluoromethyl, hydroxy, -OR (R is an alkyl group having 1 to 18 carbon atoms), bromine, chlorine or iodine, and hydrazine is -0-, -CH2-, - C(CH3)2_, _S〇2_, _Ar-0-Ar-, -Ar-CH2_Ar-, -Ar-C(CH3)2_Ar- or -Ar-S02-Ar- (Ar is a benzene ring); and n is An integer greater than one. 12. The substrate structure for a flexible electronic component according to claim 10, wherein the flexible substrate further comprises a siloxane compound. 13. The substrate structure for a flexible electronic component according to claim 12, wherein the flexible substrate further comprises ruthenium oxide. 14. A method of fabricating a substrate structure for a flexible electronic component, comprising: providing a support carrier; covering a release layer on the support carrier with a first area to form one or more blocks, wherein the release type The layer comprises a cyclic olefin copolymer having the following chemical formula (I) or (II): 25 (i) (i) 201109355 Wherein X is 30 to 70, X+Y is 100, R is hydrogen, sulfhydryl or ethyl; and a soft substrate is coated on the release layer and the support carrier by a second area, wherein the second area is greater than The first area and the adhesion of the flexible substrate to the support carrier is greater than the adhesion of the release layer to the support carrier. 15. The method of fabricating a substrate structure for a flexible electronic component according to claim 14, wherein the flexible substrate is coated on the release layer and the support carrier. 16. The method for manufacturing a substrate structure for a flexible electronic component according to claim 14, further comprising cutting a portion of the flexible substrate and the support by using a point of the two ends of the release layer or an inner side thereof as a cut-off point. a carrier to separate the release layer, the flexible substrate, and the support carrier. 26