TWI690545B - Composition for forming peeling layer - Google Patents
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- TWI690545B TWI690545B TW108111742A TW108111742A TWI690545B TW I690545 B TWI690545 B TW I690545B TW 108111742 A TW108111742 A TW 108111742A TW 108111742 A TW108111742 A TW 108111742A TW I690545 B TWI690545 B TW I690545B
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- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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Abstract
依據本發明時,可提供可維持與設置有剝離層之玻璃基板之密著性,且在與玻璃基板之界面不會產生剝離,此外,形成於比剝離層更上部之層或層群,可簡單由剝離層剝離之形成該剝離層用的組成物。本發明係提供一種剝離層形成用組成物,其係含有:含有50莫耳%以上之式(1)表示之單體單位,且重量平均分子量為10,000以上的聚醯胺酸及有機溶劑。在此,式(1)中,X1表示4價有機基,Y1表示下述式(P)表示之2價基。 According to the present invention, it is possible to provide adhesion to a glass substrate provided with a peeling layer without peeling at the interface with the glass substrate. In addition, the layer or layer group formed above the peeling layer can The composition for forming the peeling layer is simply peeled from the peeling layer. The present invention provides a composition for forming a peeling layer, which contains a polyamic acid containing 50 mol% or more of monomer units represented by formula (1) and having a weight average molecular weight of 10,000 or more and an organic solvent. Here, in formula (1), X 1 represents a tetravalent organic group, and Y 1 represents a divalent group represented by the following formula (P).
Description
本發明係有關設置於玻璃基板正上方之剝離層形成用的組成物。 The present invention relates to a composition for forming a peeling layer provided directly above a glass substrate.
近年,電子裝置要求賦予彎曲的機能或薄型化及輕量化等的性能。因此,要求使用輕量的軟性塑膠基板取代以往重且脆弱,無法彎曲的玻璃基板。又,新世代顯示器則要求開發一種使用輕量之軟性塑膠基板的主動全彩(active full-color)TFT顯示器面板。 In recent years, electronic devices have been required to impart bending performance, thinness, and weight reduction. Therefore, it is required to use a light-weight flexible plastic substrate to replace the glass substrate which is heavy and fragile and cannot be bent in the past. In addition, the new generation of displays requires the development of an active full-color TFT display panel using a lightweight flexible plastic substrate.
因此,開始檢討各種以樹脂薄膜作為基板之電子裝置的製造方法,正進行檢討可轉用既有之TFT設備的製程來製造新世代顯示器。 Therefore, reviews of various electronic device manufacturing methods using resin films as substrates are underway, and reviews are being made to switch to existing TFT device manufacturing processes to manufacture new-generation displays.
專利文獻1、2及3揭示在玻璃基板上形成非晶矽薄膜層,該薄膜層上形成塑膠基板後,由玻璃面側照射雷射,藉由伴隨非晶矽之結晶化所產生之氫氣體,將塑膠基板由玻璃基板上剝離的方法。 Patent Documents 1, 2 and 3 disclose that an amorphous silicon thin film layer is formed on a glass substrate. After a plastic substrate is formed on the thin film layer, a laser is irradiated from the glass surface side, and hydrogen gas generated by crystallization of the amorphous silicon is accompanied by , The method of peeling the plastic substrate from the glass substrate.
又,專利文獻4揭示使用專利文獻1~3所揭示的技術,將被剝離層(專利文獻4中,記載為「被轉印層」) 黏貼於塑膠薄膜,完成液晶顯示裝置的方法。 In addition, Patent Document 4 discloses that the technique disclosed in Patent Documents 1 to 3 is used to separate the layer to be peeled (in Patent Document 4, it is described as "transferred layer") A method of sticking to a plastic film to complete a liquid crystal display device.
但是專利文獻1~4揭示的方法,特別是專利文獻4揭示的方法,必須使用透光性高的基板,使基板通過,為了釋出非晶質矽所含的氫,而提供充分的能量,因此必須照射較大的雷射光,有對於被剝離層造成損傷的問題。又,雷射處理需要長時間,難以剝離具有大面積之被剝離層,故也有難以提高裝置製作之生產性的問題。 However, the methods disclosed in Patent Documents 1 to 4, especially the method disclosed in Patent Document 4, must use a substrate with high light transmittance to pass the substrate to provide sufficient energy in order to release hydrogen contained in amorphous silicon. Therefore, a large amount of laser light must be irradiated, which may cause damage to the peeled layer. In addition, laser processing requires a long time, and it is difficult to peel off the peeled layer having a large area, so there is also a problem that it is difficult to improve the productivity of device manufacturing.
[專利文獻1]日本特開平10-125929號公報。 [Patent Document 1] Japanese Patent Laid-Open No. 10-125929.
[專利文獻2]日本特開平10-125931號公報。 [Patent Document 2] Japanese Patent Laid-Open No. 10-125931.
[專利文獻3]WO2005/050754號小冊子。 [Patent Document 3] WO2005/050754 pamphlet.
[專利文獻4]日本特開平10-125930號公報。 [Patent Document 4] Japanese Patent Laid-Open No. 10-125930.
因此,本發明之目的係解決上述課題者。 Therefore, the object of the present invention is to solve the above-mentioned problems.
具體而言,本發明之目的係提供不會對於適用於軟性電子裝置之基板造成損傷,使剝離用之剝離層形成用的組成物。 Specifically, an object of the present invention is to provide a composition for forming a peeling layer for peeling without causing damage to a substrate suitable for a flexible electronic device.
又,本發明之目的除上述目的,或上述目的 外,提供可維持與設置有剝離層之玻璃基板之密著性,且在與玻璃基板之界面不會產生剝離,此外,形成於比剝離層更上部之層或層群,可簡單由剝離層剝離之形成該剝離層用的組成物。 Moreover, the object of the present invention is in addition to the above object, or the above object In addition, it can maintain the adhesion with the glass substrate provided with the peeling layer, and there is no peeling at the interface with the glass substrate. In addition, the layer or layer group formed above the peeling layer can be easily formed by the peeling layer. The composition for forming the peeling layer is peeled off.
本發明人發現以下的發明。亦即,本發明人意外發現使用具有含有50莫耳%以上之特定結構之單體單位,且重量平均分子量為一定值以上的聚醯胺酸及有機溶劑的組成物,形成剝離層時,該層具有對於被適用於軟性電子裝置等之基板,不會造成損傷,且可使剝離之較佳的特性。此層可維持與設置有剝離層之玻璃基板之密著性,且在與玻璃基板之界面不會產生剝離,此外,形成於比與玻璃基板相反側之剝離層更上部所形成之層或層群,可簡單由剝離層剝離者。本發明係依據此見解的發明。 The inventor found the following invention. That is, the present inventor unexpectedly discovered that when a composition having a polyamide unit and an organic solvent having a monomer unit having a specific structure of 50 mol% or more and a weight average molecular weight of a certain value or more is used to form a peeling layer, the The layer has a characteristic that it does not cause damage to a substrate applied to a flexible electronic device or the like, and can be peeled off. This layer can maintain the adhesion to the glass substrate provided with the peeling layer, and there is no peeling at the interface with the glass substrate. In addition, the layer or layer formed above the peeling layer opposite to the glass substrate Group, can be easily peeled by the peeling layer. The present invention is based on this knowledge.
<1>一種剝離層形成用組成物,其係含有:含有50莫耳%以上之下述式(1)表示之單體單位,且重量平均分子量為10,000以上的聚醯胺酸及有機溶劑,
<2>前述<1>中,前述Y1可為以下述式(P1)~(P3)之任一表示之2價基。 <2> In the aforementioned <1>, the aforementioned Y 1 may be a divalent group represented by any of the following formulas (P1) to (P3).
<3>前述<2>中,前述Y1可為至少含有式(P1)表示之2價基。 <3> In the aforementioned <2>, the aforementioned Y 1 may contain at least a divalent group represented by the formula (P1).
<4>前述<1>~<3>之任一者中,聚醯胺酸可進一步含有下述式(2)表示之單體單位。 <4> In any of the aforementioned <1> to <3>, the polyamic acid may further contain a monomer unit represented by the following formula (2).
<5>前述<1>~<4>之任一者中,X1可為4價芳香族基。 <5> In any of the aforementioned <1> to <4>, X 1 may be a tetravalent aromatic group.
<6>前述<5>中,前述4價芳香族基可為具有選自苯骨架、萘骨架及聯苯骨架之至少1種者。 <6> In the aforementioned <5>, the tetravalent aromatic group may be at least one selected from the group consisting of a benzene skeleton, a naphthalene skeleton, and a biphenyl skeleton.
<7>前述<1>~<6>之任一者中,前述有機溶劑可為以下述式(A)或(B)表示之溶劑。 <7> In any of the aforementioned <1> to <6>, the organic solvent may be a solvent represented by the following formula (A) or (B).
<8>前述<1>~<7>之任一者中,前述聚醯胺酸中之前述式(1)表示之單體單位之含量可為60莫耳%以 上。 <8> In any of the aforementioned <1> to <7>, the content of the monomer unit represented by the aforementioned formula (1) in the polyamide may be 60 mol% or less on.
<9>前述<1>~<8>之任一者中,本發明之剝離層形成用組成物,可為用於形成設置於玻璃基板正上方之剝離層者。 <9> In any of the aforementioned <1> to <8>, the composition for forming a peeling layer of the present invention may be used to form a peeling layer provided directly above a glass substrate.
<10>一種剝離層,其係形成於被適用於軟性電子裝置之軟性基板與基礎基板之間的剝離層,使用前述<1>~<9>之任一之剝離層形成用組成物所製作。 <10> A peeling layer formed between a flexible substrate and a base substrate applied to a flexible electronic device, and produced using the composition for forming a peeling layer according to any one of the above <1> to <9> .
<11>一種基板構造,其係適用於軟性電子裝置的基板構造,其係含有:基礎基板;以1或2以上的區域,覆蓋前述基礎基板的剝離層,且藉由如前述<1>~<9>之任一之剝離層形成用組成物所形成的剝離層;及覆蓋前述基礎基板與前述剝離層之軟性基板;前述軟性基板與前述剝離層之密著力,大於前述剝離層與前述基礎基板之密著力。 <11> A substrate structure suitable for a flexible electronic device, which includes: a base substrate; a peeling layer covering the base substrate with an area of 1 or 2 or more, and by the above-mentioned <1>~ <9> the peeling layer formed by the peeling layer forming composition; and the flexible substrate covering the base substrate and the peeling layer; the adhesion between the flexible substrate and the peeling layer is greater than the peeling layer and the foundation The tightness of the substrate.
<12>前述<11>中,基礎基板可為含有玻璃者。 <12> In the aforementioned <11>, the base substrate may contain glass.
<13>一種剝離層之製造方法,其係使用前述<1>~<9>之任一之剝離層形成用組成物。其中一個較佳的態樣中,前述剝離層之製造方法,包含將前述剝離層形成用樹脂組成物塗佈於基板,進行加熱的步驟。 <13> A method for manufacturing a peeling layer, which uses the composition for forming a peeling layer according to any one of the above <1> to <9>. In one preferred aspect, the method for manufacturing the peeling layer includes the steps of applying the resin composition for forming the peeling layer to the substrate and heating.
<14>一種製作方法,其係適用於軟性電子裝置之基板構造之製作方法,其係含有以下步驟: 準備基礎基板之步驟;使用前述<1>~<9>之任一之剝離層形成用組成物來製作以1或2以上的區域,覆蓋前述基礎基板的剝離層的步驟;及在前述基礎基板與前述剝離層上形成軟性基板的步驟;前述軟性基板與前述剝離層之密著力,大於前述剝離層與前述基礎基板之密著力。 <14> A manufacturing method, which is a manufacturing method suitable for a substrate structure of a flexible electronic device, which includes the following steps: The step of preparing the base substrate; the step of using the peeling layer forming composition of any one of the above <1> to <9> to prepare a peeling layer covering the base substrate with an area of 1 or more; and the base substrate The step of forming a flexible substrate on the peeling layer; the adhesion between the flexible substrate and the peeling layer is greater than the adhesion between the peeling layer and the base substrate.
藉由本發明可解決上述課題。 The above-mentioned problems can be solved by the present invention.
具體而言,藉由本發明可提供對於被適用於軟性電子裝置等之基板,不會造成損傷,且可使剝離之剝離層形成用的組成物。 Specifically, the present invention can provide a composition for forming a peeling layer that can be peeled without causing damage to a substrate applied to a flexible electronic device or the like without causing damage.
又,藉由本發明,除上述目的,或上述目的外,提供可維持與設置有剝離層之玻璃基板之密著性,且在與玻璃基板之界面不會產生剝離,此外,形成於比剝離層更上部之層或層群,可簡單由剝離層剝離之形成該剝離層用的組成物。 In addition, according to the present invention, in addition to the above objects, or in addition to the above objects, it is possible to provide adhesion to a glass substrate provided with a peeling layer without peeling at the interface with the glass substrate. The upper layer or layer group can be easily peeled from the peeling layer to form the composition for the peeling layer.
以下詳細說明本發明。 The present invention will be described in detail below.
本發明之剝離層形成用組成物如前述,其係含有:含 有50莫耳%以上之式(1)表示之單體單位的聚醯胺酸,且其重量平均分子量為10,000以上的聚醯胺酸及有機溶劑者。 The composition for forming a peeling layer of the present invention is as described above, which contains: There are more than 50 mole% of the polyamic acid in the monomer unit represented by the formula (1), and the polyamic acid and organic solvent having a weight average molecular weight of 10,000 or more.
又如前述,式(1)中,X1表示4價有機基,Y1表示下述式(P)表示之2價基。 As also described above, in formula (1), X 1 represents a tetravalent organic group, and Y 1 represents a divalent group represented by the following formula (P).
又,式(P)中,R表示F、Cl、或碳數1~3之烷基、或苯基,較佳為表示F、Cl。同樣地,前述之式(P)中,m表示0~4之整數,較佳為表示0~2,更佳為表示0~1,特佳為表示0。又,前述式(P)中,r表示1~3之整數。 Moreover, in formula (P), R represents F, Cl, or a C1-C3 alkyl group, or a phenyl group, Preferably it represents F and Cl. Similarly, in the aforementioned formula (P), m represents an integer of 0 to 4, preferably 0 to 2, more preferably 0 to 1, and particularly preferably 0. In addition, in the aforementioned formula (P), r represents an integer of 1 to 3.
碳數1~3之烷基,包含甲基、乙基、n-丙基、及i-丙基,較佳為碳數1~3之烷基為甲基,更佳為甲基。 The alkyl group having 1 to 3 carbons includes methyl, ethyl, n-propyl, and i-propyl groups. Preferably, the alkyl group having 1 to 3 carbons is methyl, and more preferably methyl.
本發明使用之具有式(1)表示之單體單位之聚醯胺酸的重量平均分子量,必須為10,000以上,較佳為15,000以上、更佳為20,000以上、又更佳為30,000以 上。此外,本發明使用之聚醯胺酸之重量平均分子量的上限值,通常為2,000,000以下,但是若考慮抑制樹脂組成物之黏度變得過高或再現性良好得到柔軟性高的樹脂薄膜時,較佳為1,000,000以下、更佳為200,000以下。 The weight average molecular weight of the polyamic acid having the monomer unit represented by formula (1) used in the present invention must be 10,000 or more, preferably 15,000 or more, more preferably 20,000 or more, and still more preferably 30,000 or more. on. In addition, the upper limit of the weight average molecular weight of the polyamic acid used in the present invention is usually 2,000,000 or less. However, when it is considered that the viscosity of the resin composition becomes excessively high or the reproducibility is good, a resin film with high flexibility is obtained. It is preferably 1,000,000 or less, and more preferably 200,000 or less.
本發明使用之聚醯胺酸,含有50莫耳%以上、較佳為60莫耳%以上、更佳為70莫耳%以上、又更佳為80莫耳%以上、再更佳為90莫耳%以上之式(1)表示之單體單位。藉由使用這種單體單位之含量的聚醯胺酸,可再現性良好得到具有適合剝離膜之特性的樹脂薄膜。 The polyamic acid used in the present invention contains 50 mol% or more, preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 80 mol% or more, and even more preferably 90 mol The monomer unit represented by formula (1) above the ear %. By using polyamide having such a monomer unit content, a resin film having characteristics suitable for a release film can be obtained with good reproducibility.
依據本發明之較佳的態樣時,本發明之剝離層形成用組成物所含的聚醯胺酸係僅由式(1)表示之單體單位所構成之聚合物,亦即,式(1)表示之單體單位含有100莫耳%的聚合物。此時,這種聚醯胺酸中之單體單位,只要是式(1)表示時,可為僅特定1種,也可為2種以上。後者的情形,聚醯胺酸所含之式(1)之單體單位之數,較佳為2~4,更佳為2~3。 According to a preferred aspect of the present invention, the polyamic acid contained in the composition for forming a peeling layer of the present invention is a polymer composed of only monomer units represented by formula (1), that is, formula ( 1) The indicated monomer unit contains 100 mol% of polymer. At this time, as long as the monomer unit in such a polyamic acid is represented by formula (1), only one kind may be specified, or two or more kinds may be used. In the latter case, the number of monomer units of the formula (1) contained in the polyamic acid is preferably 2 to 4, more preferably 2 to 3.
本發明中,式(P)表示之基,較佳為含有式(P1)~(P3)之任一表示之2價基,更佳為含有式(P1)或(P3)表示之2價基,又更佳為含有式(P3)表示之2價基。 In the present invention, the group represented by formula (P) preferably contains a divalent group represented by any of formulas (P1) to (P3), and more preferably contains a divalent group represented by formula (P1) or (P3) , And more preferably, contains a divalent group represented by formula (P3).
前述式(P1)、式(P2)及式(P3)中,R1、R2、R3、R4、R5及R6可相同或相異,表示F、Cl、碳數1~3之烷基、或苯基,較佳為表示F、或Cl。 In the above formula (P1), formula (P2) and formula (P3), R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be the same or different, indicating F, Cl, carbon number 1~3 The alkyl group or phenyl group preferably represents F or Cl.
同樣地,此等式中,m1、m2、m3、m4、m5及m6可相同或相異,表示0~4之整數,較佳為表示0~2,更佳為表示0~1,特佳為表示0。 Similarly, in this equation, m1, m2, m3, m4, m5, and m6 may be the same or different, and represent integers of 0~4, preferably 0-2, more preferably 0-1, and particularly preferably Is 0.
本發明使用之聚醯胺酸,除了式(1)表示之單體單位外,也可含有其他的單體單位。這種其他之單體單位的含量,必須未達50莫耳%,較佳為未達40莫耳%,更佳為未達30莫耳%,又更佳為未達20莫耳%,再更佳為未達10莫耳%。 The polyamic acid used in the present invention may contain other monomer units in addition to the monomer unit represented by formula (1). The content of this other monomer unit must be less than 50 mol%, preferably less than 40 mol%, more preferably less than 30 mol%, and still more preferably less than 20 mol%, and then More preferably, it is less than 10 mol%.
這種其他的單體單位,可列舉例如式(2)之單體單位。 Examples of such other monomer units include monomer units of formula (2).
式(2)中,X1表示4價之有機基,Y2表示前述的式(P4)表示之基。 In formula (2), X 1 represents a tetravalent organic group, and Y 2 represents a group represented by the aforementioned formula (P4).
式(P4)中,R7、及R8可相同或相異,表示F、Cl、碳數1~3之烷基、或苯基。R7較佳為表示F、或Cl。R8較佳為表示F、或Cl。 In formula (P4), R 7 and R 8 may be the same or different, and represent F, Cl, a C 1-3 alkyl group, or a phenyl group. R 7 preferably represents F or Cl. R 8 preferably represents F or Cl.
R’表示氫原子、碳數1~3之烷基、或苯基,較佳為表示氫原子、或碳數1~3之烷基,更佳為表示氫原子。 R'represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a phenyl group, preferably represents a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms, and more preferably represents a hydrogen atom.
此外,l及m可相同或相異,表示0~4之整數,較佳為表示0~2,更佳為表示0~1,特佳為表示0。 In addition, l and m may be the same or different, and represent integers of 0 to 4, preferably represent 0 to 2, more preferably represent 0 to 1, and particularly preferably represent 0.
這種其他的單體單位,除前述式(2)之單體單位外,可列舉o-苯二胺、m-苯二胺、p-苯二胺、2-甲基-1,4-苯二胺、5-甲基-1,3-苯二胺、4-甲基-1,3-苯二胺、2-(三氟甲基)-1,4-苯二胺、2-(三氟甲基)-1,3-苯二胺及4-(三氟甲基)-1,3-苯二胺、聯苯胺、2,2’-二甲基聯苯胺、3,3’-二甲基聯苯胺、2,3’-二甲基聯苯胺、2,2’-雙(三氟甲基)聯苯胺、3,3’-雙(三氟甲基)聯苯胺、2,3’-雙(三氟甲基)聯苯胺、4,4’-二苯基醚、4,4’-雙(4-胺基苯氧基)聯苯、4,4’-二胺基苯甲醯苯胺(benzanilide)、5-胺基-2-(3-胺基苯基)-1H-苯並咪唑、9,9-雙(4-胺基苯基)茀等之二胺與偏苯三甲酸酐(PMDA)、2,3,6,7-萘四 羧酸二酐、4,4’-氧二鄰苯二甲酸酐、3,3’、4,4’-二苯甲酮四羧酸酐等之酸二酐所衍生之結構等。 Such other monomer units include, in addition to the monomer unit of the aforementioned formula (2), o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2-methyl-1,4-benzene Diamine, 5-methyl-1,3-phenylenediamine, 4-methyl-1,3-phenylenediamine, 2-(trifluoromethyl)-1,4-phenylenediamine, 2-(tri (Fluoromethyl)-1,3-phenylenediamine and 4-(trifluoromethyl)-1,3-phenylenediamine, benzidine, 2,2'-dimethylbenzidine, 3,3'-di Methyl benzidine, 2,3'-dimethyl benzidine, 2,2'-bis (trifluoromethyl) benzidine, 3,3'-bis (trifluoromethyl) benzidine, 2,3' -Bis(trifluoromethyl)benzidine, 4,4'-diphenyl ether, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-diaminobenzyl Diamine and trimellitic anhydride of aniline (benzanilide), 5-amino-2-(3-aminophenyl)-1H-benzimidazole, 9,9-bis(4-aminophenyl) stilbene, etc. (PMDA), 2,3,6,7-naphthalene tetra Structure derived from acid dianhydride such as carboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3', 4,4'-benzophenone tetracarboxylic anhydride, etc.
式(1)及式(2)中,如前述,X1表示4價之有機基,較佳為4價之芳香族基。 In formula (1) and formula (2), as described above, X 1 represents a tetravalent organic group, preferably a tetravalent aromatic group.
X1可採用之4價的芳香族基,在製作本發明使用的聚醯胺酸時,藉由使用如以下的芳香族四羧酸二酐,可製作。 The tetravalent aromatic group that can be used for X 1 can be produced by using the following aromatic tetracarboxylic dianhydride when producing the polyamic acid used in the present invention.
亦即,偏苯三甲酸二酐、3,3’,4,4’-聯苯基四羧酸二酐、3,3’,4,4’-二苯甲酮四羧酸二酐、2,3,3’,4’-聯苯基四羧酸二酐、3,3’,4,4’-二苯基碸四羧酸二酐、1,4,5,8-萘四羧酸二酐、1,2,5,6-萘四羧酸二酐、4,4’-氧二鄰苯二甲酸酐、3,3’,4,4’-二甲基二苯基矽烷四羧酸二酐、3,3’,4,4’-四苯基矽烷四羧酸二酐、1,2,3,4-呋喃四羧酸二酐、4,4’-雙(3,4-二羧基苯氧基)二苯基丙烷二無水物、4,4’-六氟異亞丙基二苯二甲酸酐、對伸苯基二苯二甲酸二酐、2,2-雙-((3,4-二羧基苯基)-六氟丙烷二無水物、9,9-雙(3,4-二羧基苯基)茀二無水物、9,9‘-雙[4-(3,4-二羧基苯氧基)苯基]茀二無水物、3,3’,4,4’-聯苯基醚四羧酸二酐、2,3,5,6-吡啶四羧酸二酐、3,4,9,10-苝四羧酸二酐、4,4’-磺醯基二苯二甲酸二酐、對三聯苯基-3,4,3’,4’-四羧酸二酐、間三聯苯基(Meta terphenyl)-3,3’,4,4’-四羧酸二酐、3,3’,4,4’-二苯基醚四羧酸二酐、1,3-雙(3,4-二羧基苯基)-1,1,3,3-四甲基二矽氧烷二無水物、1-(2,3-二羧基苯基)-3-(3,4-二羧基苯基)-1,1,3,3-四甲基二矽氧 烷二無水物、3,3’,4,4’-氫醌二苯甲酸酯四羧酸二酐、2,2’-雙(4-羥基苯基)丙烷二苯甲酸酯-3,3’,4,4’-四羧酸等。 That is, trimellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2 ,3,3',4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid Dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic acid Acid dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4- Dicarboxyphenoxy) diphenylpropane dianhydrate, 4,4'-hexafluoroisopropylidene phthalic anhydride, p-phenylene phthalic dianhydride, 2,2-bis-(( 3,4-dicarboxyphenyl)-hexafluoropropane dianhydrate, 9,9-bis(3,4-dicarboxyphenyl) stilbene anhydrate, 9,9'-bis(4-(3,4 -Dicarboxyphenoxy)phenyl] stilbene dihydrate, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-Perylenetetracarboxylic dianhydride, 4,4'-sulfonyl diphthalic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride 、Meta terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 1,3- Bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisilaxane dihydrate, 1-(2,3-dicarboxyphenyl)-3-(3,4 -Dicarboxyphenyl)-1,1,3,3-tetramethyldisilazane Alkane dianhydrate, 3,3',4,4'-hydroquinone dibenzoate tetracarboxylic dianhydride, 2,2'-bis(4-hydroxyphenyl)propane dibenzoate-3, 3',4,4'-tetracarboxylic acid, etc.
較佳為在此較佳的芳香族四羧酸二酐係選自由下述化合物群者。 Preferably, the preferred aromatic tetracarboxylic dianhydride here is selected from the group consisting of the following compounds.
因此,依據本發明之較佳態樣時,X1可採用之4價的芳香族基係具有苯骨架、萘骨架、聯苯骨架、三聯苯基骨架之任一者,更佳為具有苯骨架、萘骨架、聯苯骨架之任一者,又更佳為具有苯骨架、聯苯骨架之任一者。 Therefore, according to the preferred aspect of the present invention, the tetravalent aromatic group that X 1 can adopt has any one of a benzene skeleton, a naphthalene skeleton, a biphenyl skeleton, and a terphenyl skeleton, more preferably a benzene skeleton , Any of the naphthalene skeleton and the biphenyl skeleton is more preferably any one having a benzene skeleton and a biphenyl skeleton.
依據本發明之較佳態樣時,本發明使用之聚醯胺酸係使作為酸二酐之3,3’、4,4’-聯苯基四羧酸二酐(BPDA)(式(4))與作為二胺之p-苯二胺(pPDA)(式(5))及4,4”-二胺基-p-三聯苯基(DATP)(式(6))、或作為酸二酐之偏苯三甲酸二酐(PMDA)(式(7))與作為二胺之pPDA(式(5))進行反應可得。 According to the preferred aspect of the present invention, the polyamic acid used in the present invention is 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) (formula (4 )) with p-phenylenediamine (pPDA) (formula (5)) and 4,4”-diamino-p-terphenyl (DATP) (formula (6)) as diamines, or as acid di Anhydride trimellitic dianhydride (PMDA) (formula (7)) and pPDA (formula (5)) as a diamine can be obtained by reacting.
上述反應中,3,3’、4,4’-聯苯基四羧酸二酐(BPDA)與由p-苯二胺(pPDA)及4,4”-二胺基-p-三聯苯基(DATP)所構成之二胺、或偏苯三甲酸二酐(PMDA)與pPDA之投入比(莫耳比),考慮所望之聚 醯胺酸之分子量或單體單位之比例等,可適宜設定,但是相對於胺成分1,通常酸酐成分可設為0.7~1.3左右,較佳為0.8~1.2左右。 In the above reaction, 3,3', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) and p-phenylenediamine (pPDA) and 4,4"-diamino-p-terphenyl (DATP) The input ratio of diamine, trimellitic dianhydride (PMDA) and pPDA (mol ratio), consider the desired polymerization The molecular weight of the amide acid, the ratio of monomer units, and the like can be appropriately set, but the acid anhydride component is usually set to about 0.7 to 1.3, preferably about 0.8 to 1.2 relative to the amine component 1.
此外,二胺的pPDA與DATP之投入比,當DATP之物質量(m2)設定為1的情形,pPDA之物質量(m1)通常可設為1.7~20左右,較佳為2.1~20、更佳為2.2~20、又更佳為2.3~19、再更佳為2.3~18。亦即,m1與m2通常為m1/m2=1.7~20,較佳為2.1~20,更佳為2.2~20,又更佳為2.3~19,再更佳為2.3~18。 In addition, for the input ratio of pPDA and DATP of the diamine, when the material mass (m 2 ) of DATP is set to 1, the material mass (m 1 ) of pPDA can usually be set to about 1.7-20, preferably 2.1-20 , Better is 2.2~20, yet better is 2.3~19, and even better is 2.3~18. That is, m 1 and m 2 are usually m 1 /m 2 =1.7 to 20, preferably 2.1 to 20, more preferably 2.2 to 20, still more preferably 2.3 to 19, and even more preferably 2.3 to 18.
上述反應係在有機溶劑中進行。亦即,本發明之剝離層形成用組成物含有此有機溶劑。在此可使用之有機溶劑,只要是對於前述反應不會產生不良影響者,即可使用各種溶劑。 The above reaction is carried out in an organic solvent. That is, the composition for peeling layer formation of this invention contains this organic solvent. The organic solvent that can be used here can be any solvent as long as it does not adversely affect the aforementioned reaction.
具體例可列舉例如m-甲酚、2-吡咯烷酮(pyrrolidone)、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、N-乙烯基-2-吡咯烷酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、3-甲氧基-N,N-二甲基丙基醯胺、3-乙氧基-N,N-二甲基丙基醯胺、3-丙氧基-N,N-二甲基丙基醯胺、3-異丙氧基-N,N-二甲基丙基醯胺、3-丁氧基-N,N-二甲基丙基醯胺、3-sec-丁氧基-N,N-二甲基丙基醯胺、3-tert-丁氧基-N,N-二甲基丙基醯胺、γ-丁內酯等之質子性溶劑等。此等可單獨使用或組合2種以上使用。 Specific examples include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethyl Ethylacetamide, N,N-dimethylformamide, 3-methoxy-N,N-dimethylpropylamide, 3-ethoxy-N,N-dimethylpropylamide Amine, 3-propoxy-N,N-dimethylpropylamide, 3-isopropoxy-N,N-dimethylpropylamide, 3-butoxy-N,N-di Methylpropylamide, 3-sec-butoxy-N,N-dimethylpropylamide, 3-tert-butoxy-N,N-dimethylpropylamide, γ-butane Protic solvents such as lactones. These can be used alone or in combination of two or more.
依據本發明之較佳態樣時,有機溶劑係以式(A)或(B)表示之溶劑。 According to a preferred aspect of the present invention, the organic solvent is a solvent represented by formula (A) or (B).
式(A)及式(B)中,Ra及Rb可相同或相異,表示碳數1~4之烷基,較佳為碳數1~3。在此,h表示自然數,較佳為1~3。 In, R a and R b may be the same as the formula (A) and formula (B) or different and represent an alkyl group having 1 to 4 carbon atoms, the carbon atoms preferably 1 to 3. Here, h represents a natural number, preferably 1 to 3.
反應溫度只要在使用之溶劑的熔點至沸點為止的範圍內適宜設定即可,通常為0~100℃左右,但是為了防止所得之聚醯胺酸之醯亞胺化,維持聚醯胺酸單位之高含量時,較佳為0~70℃左右,更佳為0~60℃左右,又更佳為0~50℃左右。 The reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent used, and is usually about 0 to 100°C. However, in order to prevent the imidization of the resulting polyamic acid, the unit of the polyamic acid is maintained At a high content, it is preferably about 0 to 70°C, more preferably about 0 to 60°C, and still more preferably about 0 to 50°C.
反應時間係依存於反應溫度或原料物質之反應性,故無法一概限定,通常為1~100小時左右。 The reaction time depends on the reaction temperature or the reactivity of the raw materials, so it cannot be limited in general, but is usually about 1 to 100 hours.
藉由以上說明的方法,可得到含有作為目標之聚醯胺酸的反應溶液。 By the method described above, a reaction solution containing the target polyamic acid can be obtained.
本發明通常將上述反應溶液進行過濾後,該濾液直接或經稀釋或濃縮,作為剝離層形成用組成物使用。如此,不僅可減低可能成為所得之樹脂薄膜之耐熱性、柔軟性或線膨脹係數特性惡化之原因的雜質混入,可有效率得到組成物。 In the present invention, after the above reaction solution is filtered, the filtrate is directly or diluted or concentrated and used as a composition for forming a peeling layer. In this way, not only can impurities that may cause deterioration of the heat resistance, flexibility, or linear expansion coefficient characteristics of the resulting resin film be reduced, and the composition can be obtained efficiently.
稀釋或濃縮所用的溶劑,無特別限定,可列舉例如與上述反應之反應溶劑之具體例同樣者,彼等可單獨使用或組合2種以上使用。 The solvent used for dilution or concentration is not particularly limited, and examples thereof include the same as specific examples of the reaction solvent in the above reaction, and these can be used alone or in combination of two or more kinds.
此等之中,考慮再現性良好得到平坦性高的樹脂薄膜時,使用的溶劑,較佳為N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮、1,3-二甲基-2-咪唑啉酮、N-乙基-2-吡咯烷酮、γ-丁內酯。 Among these, the solvent used when obtaining a resin film with high flatness and good reproducibility is preferably N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, γ-butyrolactone.
聚醯胺酸相對於剝離層形成用組成物總質量之濃度係考慮製作之薄膜(剝離層)之厚度或組成物黏度等,來適宜設定者,但是通常為0.5~30質量%左右,較佳為5~25質量%左右。 The concentration of the polyamic acid with respect to the total mass of the composition for forming the peeling layer is suitably set considering the thickness of the film (peeling layer) produced or the viscosity of the composition, but it is usually about 0.5 to 30% by mass, preferably It is about 5-25% by mass.
又,剝離層形成用組成物之黏度也考慮製作之薄膜之厚度等,來適宜設定者,特別是再現性良好得到0.05~5μm左右之厚度之樹脂薄膜之目的時,通常於25℃下為10~10,000mPa.s左右,較佳為20~1000mPa.s左右,更佳為20~200mPa.s左右。 In addition, the viscosity of the composition for forming the peeling layer is also suitably set considering the thickness of the film to be produced, especially when the resin film with a thickness of about 0.05 to 5 μm is obtained with good reproducibility, usually 10 at 25°C ~10,000mPa. Around s, preferably 20~1000mPa. Around s, more preferably 20~200mPa. s or so.
在此,剝離層形成用組成物之黏度,使用市售之液體之黏度測量用黏度計,例如參照JIS K7117-2所記載的步驟,剝離層形成用組成物可在溫度25℃的條件測量。較佳為黏度計使用圓錐平板型(cone-plate)迴轉黏度計,較佳為以同型的黏度計,使用標準錐形轉子(cone Rotor)1° 34‘×R24,剝離層形成用組成物可在溫度25℃之條件測量。這種迴轉黏度計,可列舉例如東機產業股份有限公司製TVE-25H。 Here, the viscosity of the composition for peeling layer formation can be measured at a temperature of 25°C using a commercially available viscometer for measuring the viscosity of liquids, for example, referring to the procedure described in JIS K7117-2. It is preferable to use a cone-plate rotary viscometer for the viscometer, preferably to use a standard cone rotor 1° 34'×R24 with the same type of viscometer, and the composition for forming the peeling layer may be Measured at 25°C. Examples of such a rotary viscometer include TVE-25H manufactured by Toki Industries Co., Ltd.
又,本發明之組成物除了聚醯胺酸與有機溶劑外,也可含有各種成分。可列舉例如交聯劑(以下也稱為交聯性化合物),但是不受此限定。 In addition, the composition of the present invention may contain various components in addition to polyamic acid and an organic solvent. For example, a crosslinking agent (hereinafter also referred to as a crosslinkable compound) may be mentioned, but it is not limited thereto.
前述交聯性化合物可列舉例如含有2個以上之環氧基的化合物、具有胺基之氫原子經羥甲基、烷氧基甲基或其兩者取代之基的三聚氰胺衍生物、苯胍胺衍生物或甘脲等,但是不受此限定。 Examples of the aforementioned crosslinkable compound include compounds containing two or more epoxy groups, melamine derivatives having a hydrogen atom having an amine group substituted with a methylol group, an alkoxymethyl group, or both, benzoguanamine Derivatives, glycolurils, etc., but not limited to this.
以下可列舉交聯性化合物之具體例,但是不限於此。 Specific examples of the cross-linkable compound are listed below, but it is not limited thereto.
含有2個以上之環氧基的化合物,可列舉例如Epolead GT-401、Epolead GT-403、Epolead GT-301、Epolead GT-302、Celloxide 2021、Celloxide 3000(以上為股份公司Daicel製)等具有環氧環己烯結構之環氧化合物;Epikote 1001、Epikote 1002、Epikote 1003、Epikote 1004、Epikote 1007、Epikote 1009、Epikote 1010、Epikote 828(以上為Japan Epoxy Resin(股)製(現:三菱化學股份公司製、jER(註冊商標)系列))等之雙酚A型環氧化合物;Epikote 807(Japan Epoxy Resin(股)製)等之雙酚F型環氧化合物;Epikote 152、Epikote 154(以上為Japan Epoxy Resin(股)製)、EPPN201、EPPN202(以上為日本化藥(股)製)等之酚醛清漆型環氧化合物;EOCN-102、EOCN-103S、EOCN-104S、EOCN-1020、EOCN-1025、EOCN-1027(以上為日本化藥(股)製)、Epikote 180S75(Japan Epoxy Resin(股)(現:三菱化學股份公司製、jER(註冊商標)系列))製)等之酚醛清漆型環氧化合物;V8000-C7(DIC股份公司製)等之萘型環氧化合物;Denacol EX-252 (NagaseChemtex(股)製)、CY175、CY177、CY179、Araldite CY-182、Araldite CY-192、Araldite CY-184(以上為BASF公司製)、Epiclon 200、Epiclon 400(以上為DIC(股)製)、Epikote 871、Epikote 872(以上為Japan Epoxy Resin(股)製(現:三菱化學股份公司製、jER(註冊商標)系列))製)、ED-5661、ED-5662(以上為Celanese coating(股)製)等之脂環式環氧化合物;Denacol EX-611、Denacol EX-612、Denacol EX-614、Denacol EX-622、Denacol EX-411、Denacol EX-512、Denacol EX-522、Denacol EX-421、Denacol EX-313、Denacol EX-314、Denacol EX-312(以上為NagaseChemtex(股)製)等之脂肪族聚縮水甘油醚化合物。 Compounds containing two or more epoxy groups include, for example, Epolead GT-401, Epolead GT-403, Epolead GT-301, Epolead GT-302, Celloxide 2021, Celloxide 3000 (above manufactured by Daicel Corporation), etc. Epoxy compound with oxycyclohexene structure; Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (above are manufactured by Japan Epoxy Resin Co., Ltd. (now: Mitsubishi Chemical Corporation) System, jER (registered trademark) series)), etc. bisphenol A epoxy compound; Epikote 807 (manufactured by Japan Epoxy Resin Co., Ltd.) bisphenol F epoxy compound; Epikote 152, Epikote 154 (above Japan Epoxy resin (made by Epoxy Resin), EPPN201, EPPN202 (the above is made by Nippon Kayaku (made by Japan)) and other novolak epoxy compounds; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 , EOCN-1027 (the above is manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S75 (Japan Epoxy Resin (share) (now: manufactured by Mitsubishi Chemical Corporation, jER (registered trademark) series), etc., novolak type rings Oxygen compounds; naphthalene-type epoxy compounds such as V8000-C7 (manufactured by DIC Corporation); Denacol EX-252 (Made by Nagase Chemtex), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above manufactured by BASF), Epiclon 200, Epiclon 400 (above manufactured by DIC (share)) , Epikote 871, Epikote 872 (the above is Japan Epoxy Resin (share) system (now: Mitsubishi Chemical Corporation, jER (registered trademark) series)), ED-5661, ED-5662 (the above is Celanese coating (share) ))) alicyclic epoxy compound; etc.; Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522, Denacol EX- Aliphatic polyglycidyl ether compounds such as 421, Denacol EX-313, Denacol EX-314, Denacol EX-312 (above are manufactured by Nagase Chemtex Co., Ltd.), etc.
具有胺基之氫原子經羥甲基、烷氧基甲基或其兩者取代之基的三聚氰胺衍生物、苯胍胺衍生物或甘脲,可列舉例如1個三嗪環中,經甲氧基甲基平均3.7個取代的MX-750、1個三嗪環中,經甲氧基甲基平均5.8個取代的MW-30(以上為股份公司三和化學製);Cymel 300、Cymel 301、Cymel 303、Cymel 350、Cymel 370、Cymel 771、Cymel 325、Cymel 327、Cymel 703、Cymel 712等之甲氧基甲基化三聚氰胺;Cymel 235、Cymel 236、Cymel 238、Cymel 212、Cymel 253、Cymel 254等之甲氧基甲基化丁氧基甲基化三聚氰胺;Cymel 506、Cymel 508等之丁氧基甲基化三聚氰胺;如Cymel 1141之 含有羧基之甲氧基甲基化異丁氧基甲基化三聚氰胺;如Cymel 1123之甲氧基甲基化乙氧基甲基化苯胍胺;如Cymel 1123-10之甲氧基甲基化丁氧基甲基化苯胍胺;如Cymel 1128之丁氧基甲基化苯胍胺;如Cymel 1125-80之含有羧基之甲氧基甲基化乙氧基甲基化苯胍胺;如Cymel 1170之丁氧基甲基化甘脲;如Cymel 1172之羥甲基化甘脲(以上為三井Cyanamid股份有限公司製(現:日本CytecIndustries股份公司)等。 A melamine derivative, benzoguanamine derivative, or glycoluril having a hydrogen atom of an amine group substituted with a methylol group, an alkoxymethyl group, or both of them, for example, a triazine ring, through methoxy MX-750 with an average of 3.7 substituted methyl groups and MW-30 with an average of 5.8 substituted with methoxymethyl groups in one triazine ring (the above is manufactured by Sanwa Chemical Co., Ltd.); Cymel 300, Cymel 301 Cymel 303, Cymel 350, Cymel 370, Cymel 771, Cymel 325, Cymel 327, Cymel 703, Cymel 712, etc. methoxymethylated melamine; Cymel 235, Cymel 236, Cymel 238, Cymel 212, Cymel 253, Cymel 254 Methoxymethylated butoxymethylated melamine; Cymel 506, Cymel 508, etc. butoxymethylated melamine; such as Cymel 1141 Methoxymethylated isobutoxymethylated melamine containing carboxyl groups; such as methoxymethylated ethoxymethylated benzoguanamine of Cymel 1123; methoxymethylated such as Cymel 1123-10 Butoxymethylated benzoguanamine; such as Cymel 1128 butoxymethylated benzoguanamine; such as Cymel 1125-80 containing carboxyl-containing methoxymethylated ethoxymethylated benzoguanamine; such as Cymel 1170's butoxymethylated glycoluril; such as Cymel 1172's hydroxymethylated glycoluril (above manufactured by Mitsui Cyanamid Co., Ltd. (now: Japan Cytec Industries Co., Ltd.), etc.
將以上說明之本發明之剝離層形成用組成物塗佈於基體,藉由加熱可得到由具有高的耐熱性、適度的柔軟性、適度的線膨脹係數之聚醯亞胺所構成的薄膜(剝離層)。 By applying the composition for forming a peeling layer of the present invention described above to a substrate, a film made of polyimide having high heat resistance, moderate flexibility, and moderate linear expansion coefficient can be obtained by heating ( Peel layer).
基礎基板(基材)可列舉例如玻璃、塑膠(聚碳酸酯、聚甲基丙烯酸酯、聚苯乙烯、聚酯、聚烯烴、環氧、三聚氰胺、三乙醯基纖維素、ABS、AS、降莰烯系樹脂等)、金屬(矽晶圓等)、木材、紙、石棉等。 The base substrate (substrate) includes, for example, glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triethyl cellulose, ABS, AS, Camphene resins, etc.), metals (silicon wafers, etc.), wood, paper, asbestos, etc.
塗佈的方法無特別限定,可列舉例如澆鑄塗佈法、旋轉塗佈法、刮刀塗佈法、浸漬塗佈法、輥塗法、棒塗法、模具塗佈法、噴墨法、印刷法(凸版、凹版、平版、網版印刷等)等。 The coating method is not particularly limited, and examples thereof include a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an inkjet method, and a printing method (Relief, gravure, lithography, screen printing, etc.) etc.
又,使本發明之剝離層形成用組成物中所含有的聚醯胺酸產生醯亞胺化的方法,可列舉例如將塗佈於基板上之組成物直接加熱的熱醯亞胺化、及在組成物中添加觸媒,進行加熱的觸媒醯亞胺化。 In addition, the method for producing imidate in the polyamic acid contained in the composition for forming a peeling layer of the present invention includes, for example, thermal imidate in which the composition applied on the substrate is directly heated, and A catalyst is added to the composition, and the heated catalyst is imidized.
聚醯胺酸之觸媒醯亞胺化係在本發明之剝離層形成用組成物中,添加觸媒,藉由調製觸媒添加組成物後,塗佈於基板,藉由加熱可得到樹脂薄膜(剝離層)。觸媒的量為醯胺酸基之0.1~30莫耳倍,較佳為1~20莫耳倍。又,觸媒添加組成物中,可添加作為脫水劑的乙酸酐等,其量為醯胺酸基之1~50莫耳倍、較佳為3~30莫耳倍。 Polyimide acid catalyst imidization is added to the composition for forming a peeling layer of the present invention, a catalyst is added, and after adding the composition by preparing the catalyst, it is coated on a substrate and a resin film can be obtained by heating (Peeling layer). The amount of catalyst is 0.1 to 30 mole times of the amide acid group, preferably 1 to 20 mole times. In addition, in the catalyst addition composition, acetic anhydride or the like as a dehydrating agent may be added, and the amount thereof is 1 to 50 mole times of the amide acid group, preferably 3 to 30 mole times.
醯亞胺化觸媒,較佳為使用三級胺。三級胺較佳為吡啶、取代吡啶類、咪唑、取代咪唑類、甲基吡啶(picoline)、喹啉、異喹啉等。 The amide imidization catalyst preferably uses a tertiary amine. The tertiary amine is preferably pyridine, substituted pyridines, imidazole, substituted imidazoles, picoline, quinoline, isoquinoline and the like.
熱醯亞胺化及觸媒醯亞胺化時之加熱溫度,較佳為450℃以下。超過450℃時,所得之樹脂薄膜變脆,有時無法得到適合目的之用途的樹脂薄膜的情形。 The heating temperature during thermal imidization and catalyst imidization is preferably 450°C or lower. When the temperature exceeds 450°C, the resulting resin film becomes brittle, and a resin film suitable for the intended use may not be obtained.
又,考慮所得之樹脂薄膜之耐熱性與線膨脹係數特性時,將塗佈後的組成物,於50℃~100℃下加熱5分鐘~2小時後,該狀態下,階段性加熱使溫度上昇,最終以超過375℃~450℃下加熱30分鐘~4小時為佳。 In addition, when considering the heat resistance and linear expansion coefficient characteristics of the resulting resin film, the coated composition is heated at 50°C to 100°C for 5 minutes to 2 hours. In this state, stepwise heating increases the temperature Finally, it is better to heat at more than 375℃~450℃ for 30 minutes~4 hours.
特別是塗佈後的組成物,在50℃~100℃下加熱5分鐘~2小時後,於超過100℃~200℃下加熱5分鐘~2小時,接著,以超過200℃~375℃下加熱5分鐘~2小時,最後於超過375℃~450℃下,加熱30分鐘~4小時較佳。 In particular, the coated composition is heated at 50°C to 100°C for 5 minutes to 2 hours, then heated at more than 100°C to 200°C for 5 minutes to 2 hours, and then heated at more than 200°C to 375°C 5 minutes to 2 hours, and finally at more than 375 ℃ ~ 450 ℃, it is better to heat for 30 minutes to 4 hours.
加熱所用的器具,可列舉例如加熱板、烤箱等。加熱環境可為空氣下,也可為惰性氣體下,又可為常壓下,或減壓下。 Examples of appliances used for heating include hot plates and ovens. The heating environment can be under air, under inert gas, under normal pressure, or under reduced pressure.
樹脂薄膜之厚度,特別是作為剝離層使用的情形,通常為0.01~10μm左右,較佳為0.05~5μm左右,調整加熱前之塗膜的厚度,形成所望之厚度的樹脂薄膜。 The thickness of the resin film, especially when used as a peeling layer, is usually about 0.01 to 10 μm, preferably about 0.05 to 5 μm, and the thickness of the coating film before heating is adjusted to form a resin film of a desired thickness.
以上說明的薄膜,最適合作為對於適用於軟性電子裝置的基板不會造成損傷而使其剝離用的剝離層使用。 The film described above is most suitable for use as a peeling layer for peeling a substrate suitable for a flexible electronic device without causing damage.
藉由本案之組成物,可形成被設置於適用於軟性電子裝置之軟性基板與基礎基板之間的剝離層。基礎基板較佳為含有玻璃或矽晶圓者,更佳為含有玻璃者。 With the composition of this case, a peeling layer provided between a flexible substrate and a base substrate suitable for flexible electronic devices can be formed. The base substrate preferably contains glass or silicon wafers, and more preferably contains glass.
例如在玻璃基板上,藉由以往公知的手法塗佈本案之組成物,將所得之塗佈膜藉由以特定的溫度加熱,可形成剝離層。 For example, the composition of this case is applied to a glass substrate by a conventionally known method, and the resulting coating film is heated at a specific temperature to form a peeling layer.
又,被剝離體層可形成於剝離層上。被剝離體層可為一層,也可為複數層。製作各種裝置時,現實上為複數層者。 In addition, the layer to be peeled may be formed on the peeling layer. The layer to be peeled may be one layer or plural layers. When making various devices, there are actually multiple layers.
被剝離體層之中,剝離層正上方的層係依存於使用的剝離層,但是可使用與該剝離層之剝離性較佳者,換言之,與使用之剝離層之密著性不佳者。 Among the layers to be peeled, the layer directly above the peeling layer depends on the peeling layer used, but those having better peelability with the peeling layer can be used, in other words, those with poor adhesion to the peeling layer used.
本案之其他方面為提供被剝離體之製造方法。 The other aspect of this case is to provide a method for manufacturing the stripped body.
該方法為藉由具有下述步驟可得到被剝離體。 In this method, the peeled body can be obtained by having the following steps.
a)將本案之組成物塗佈於玻璃基板上後,形成剝離層的步驟;b)於該剝離層上形成被剝離體的步驟;及 c)在剝離層與被剝離體之界面,將被剝離體剝離的步驟;b)步驟中,「被剝離體」可為一層,也可為複數層。 a) the step of forming a peeling layer after applying the composition of the present invention on a glass substrate; b) the step of forming a peeled body on the peeling layer; and c) The step of peeling off the peeled body at the interface between the peeling layer and the peeled body; in step b), the "stripped body" may be one layer or plural layers.
又,「被剝離體」之中,剝離層正上方的層係依存於使用的剝離層,但是可使用與該剝離層之剝離性較佳者,換言之,與使用之剝離層之密著性不佳者。 In addition, in the "removed body", the layer directly above the peeling layer depends on the peeling layer used, but the peelability of the peeling layer can be used better, in other words, the adhesion with the peeling layer used is not The best.
依據本發明之其他之較佳態樣時,可提供一種基板構造,其係適用於軟性電子裝置的基板構造,其係含有:基礎基板;以1或2以上的區域內,覆蓋前述基礎基板的剝離層,且藉由本發明之剝離層形成用組成物所形成的剝離層;及覆蓋前述基礎基板與前述剝離層之軟性基板,前述軟性基板與前述剝離層之密著力,大於前述剝離層與前述基礎基板之密著力。在此所謂的密著力之大小,例如可藉由本案之實施例所示之方格試驗來確認。 According to other preferred aspects of the present invention, a substrate structure may be provided, which is suitable for flexible electronic device substrate structures, and includes: a base substrate; and an area of 1 or more, covering the aforementioned base substrate A peeling layer, and a peeling layer formed by the peeling layer forming composition of the present invention; and a flexible substrate covering the base substrate and the peeling layer, the adhesion of the flexible substrate and the peeling layer is greater than that of the peeling layer and the above Dense focus on the base substrate. The magnitude of the adhesion force here can be confirmed by, for example, the grid test shown in the embodiment of the present invention.
以下依據實施例說明本發明,但是本發明不限於該實施例者。 The present invention will be described below based on embodiments, but the present invention is not limited to those of the embodiments.
本實施例所用的簡稱,列舉如下並說明。 The abbreviations used in this embodiment are listed and explained below.
NMP:N-甲基吡咯烷酮。 NMP: N-methylpyrrolidone.
p-PDA:p-苯二胺。 p-PDA: p-phenylenediamine.
APAB:2-(3-胺基苯基)-5-胺基苯並咪唑。 APAB: 2-(3-aminophenyl)-5-aminobenzimidazole.
DATP:4,4’-二胺基-p-三聯苯。 DATP: 4,4'-diamino-p-terphenyl.
6FAP:2,2-雙(3-胺基-4-羥基苯基)六氟丙烷。 6FAP: 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane.
BPDA:3,3’-4,4’-聯苯基四羧酸二酐。 BPDA: 3,3'-4,4'-biphenyltetracarboxylic dianhydride.
BA-TME:4,4-亞聯苯基(Biphenylene)雙(苯均四酸單酯酸酐)。 BA-TME: 4,4-Biphenylene bis (pyromellitic acid monoester anhydride).
PMDA:偏苯三甲酸二酐。 PMDA: trimellitic dianhydride.
IPHA:間苯二甲醛(isophthalaldehyde)。 IPHA: isophthalaldehyde.
聚合物之重量平均分子量(以下簡稱「Mw」)與分子量分布,使用日本分光股份有限公司製GPC裝置(Shodex(註冊商標)管柱KF803L及KF805L),在作為溶出溶劑之二甲基甲醯胺,以流量1ml/分鐘、管柱溫度 50℃的條件下進行測量。又,Mw為聚苯乙烯換算值。 The weight-average molecular weight of the polymer (hereinafter referred to as "Mw") and molecular weight distribution were determined using a GPC device (Shodex (registered trademark) columns KF803L and KF805L) manufactured by Nippon Spectroscopy Co., Ltd., and dimethylformamide as the elution solvent , Flow rate 1ml/min, column temperature The measurement is performed under the condition of 50°C. In addition, Mw is a polystyrene conversion value.
將p-PDA 17.8g(0.164莫耳)、DATP 2.38g(0.009莫耳)及APAB 2.05g(0.009莫耳)溶解於NMP 425g中,同時添加BPDA 52.8g(0.179莫耳)後,再度添加NMP 7.4g,在氮環境下,使於23℃反應24小時。所得之聚醯亞胺前驅物P1之Mw為63000、分子量分布為9.9。 After dissolving p-PDA 17.8g (0.164 mol), DATP 2.38g (0.009 mol) and APAB 2.05g (0.009 mol) in NMP 425g, and adding BPDA 52.8g (0.179 mol), add NMP again Under a nitrogen environment, 7.4g was allowed to react at 23°C for 24 hours. The obtained polyimide precursor P1 had an Mw of 63000 and a molecular weight distribution of 9.9.
使DATP 30.8g(0.118莫耳)溶解於NMP 425g中,同時添加BPDA 34.1g(0.116莫耳)後,再度添加NMP 10g,氮環境下,使於23℃反應24小時。所得之聚醯亞胺前驅物P2之Mw為70700、分子量分布為9.7。 After dissolving 30.8 g (0.118 mol) of DATP in 425 g of NMP and simultaneously adding 34.1 g (0.116 mol) of BPDA, 10 g of NMP was added again, and the reaction was performed at 23° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polyimide precursor P2 was 70,700, and the molecular weight distribution was 9.7.
使p-PDA 20.261g(0.1875莫耳)與TPDA 12.206g(0.0469莫耳)溶解於NMP 617.4g中,冷卻至15℃後,添加PMDA 50.112g(0.2298莫耳),氮環境下,使於50℃反應48小時。所得之聚醯亞胺前驅物P3之Mw為 82,100、分子量分布為2.7。 P-PDA 20.261g (0.1875 mol) and TPDA 12.206g (0.0469 mol) were dissolved in NMP 617.4g, and after cooling to 15°C, PMDA 50.112g (0.2298 mol) was added under nitrogen atmosphere at 50 React for 48 hours at ℃. The Mw of the obtained polyimide precursor P3 is 82,100, molecular weight distribution is 2.7.
使p-PDA 9.66g(0.089莫耳)與APAB 1.05g(0.005莫耳)溶解於NMP 440g中,添加BP-TME 49.2g(0.092莫耳),氮環境下,使於室溫反應24小時。所得之聚醯亞胺前驅物P4之Mw為57000、分子量分布為9.3。 9.66 g (0.089 mol) of p-PDA and 1.05 g (0.005 mol) of APAB were dissolved in 440 g of NMP, 49.2 g (0.092 mol) of BP-TME was added, and the mixture was allowed to react at room temperature for 24 hours under a nitrogen atmosphere. The obtained polyimide precursor P4 had an Mw of 57,000 and a molecular weight distribution of 9.3.
使p-PDA 3.176g(0.02937莫耳)溶解於NMP 88.2g中,添加BPDA 8.624g(0.02931莫耳)後,氮環境下,使於23℃反應24小時。所得之聚醯亞胺前驅物P5之Mw為107,300、分子量分布為4.6。 After dissolving 3.176 g (0.02937 mol) of p-PDA in 88.2 g of NMP and adding 8.624 g (0.02931 mol) of BPDA, the reaction was carried out at 23° C. for 24 hours under a nitrogen atmosphere. The obtained polyimide precursor P5 had an Mw of 107,300 and a molecular weight distribution of 4.6.
使6FAP 3.18g(0.059莫耳)溶解於NMP 70g中,添加IPHA 7.92g(0.060莫耳)後,氮環境下,使於23℃反應24小時。所得之聚合物之Mw為107,300、分子量分布為4.6。 After dissolving 3.18 g (0.059 mol) of 6FAP in 70 g of NMP and adding 7.92 g (0.060 mol) of IPHA, the reaction was carried out at 23° C. for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 107,300 and the molecular weight distribution was 4.6.
使p-PDA 10.078g(93mmol)溶解於NMP 220.0g中。所得之溶液中添加PMDA 19.922g(91mmol),氮環境下,使於23℃反應24小時。所得之聚合物之Mw為55,900、分子量分布為3.1。 10.078 g (93 mmol) of p-PDA was dissolved in 220.0 g of NMP. To the resulting solution, 19.922 g (91 mmol) of PMDA was added, and the reaction was carried out at 23°C for 24 hours under a nitrogen atmosphere. The Mw of the obtained polymer was 55,900 and the molecular weight distribution was 3.1.
將上述合成例1~7所得之P1~P7,以NMP稀釋成4wt%,使用旋轉塗佈機塗佈於100mm×100mm之玻璃基板(OA-10G無鹼玻璃)或矽晶圓上後,於硬化條件A~C下,以烤箱進行燒成,製作剝離層。 P1~P7 obtained in the above Synthesis Examples 1~7 were diluted with NMP to 4wt%, and then applied on a 100mm×100mm glass substrate (OA-10G alkali-free glass) or silicon wafer using a spin coater. Under hardening conditions A to C, it is baked in an oven to produce a peeling layer.
硬化條件A:120℃下,維持30分鐘→昇溫→300℃下,維持60分鐘→昇溫→400℃下,維持60分鐘。又,昇溫速度為10℃/分鐘。 Hardening condition A: 120°C, 30 minutes → temperature rise → 300°C, 60 minutes → temperature rise → 400°C, 60 minutes. In addition, the temperature increase rate is 10°C/min.
硬化條件B:120℃下,維持30分鐘→昇溫→180℃下,維持20分鐘→昇溫→240℃下,維持20分鐘→昇溫→300℃下,維持20分鐘→昇溫→400℃下,維持20分鐘→昇溫→450℃下,維持60分鐘。又,昇溫速度為10℃/分鐘。 Hardening condition B: 120°C, 30 minutes → temperature rise → 180°C, 20 minutes → temperature rise → 240°C, 20 minutes → temperature rise → 300°C, 20 minutes → temperature rise → 400°C, 20 Minutes → temperature rise → 450°C for 60 minutes. In addition, the temperature increase rate is 10°C/min.
硬化條件C:80℃下,維持10分鐘→昇溫→300℃下,維持30分鐘→昇溫→400℃下,維持30分鐘。又,昇溫速度為10℃/分鐘。 Hardening condition C: at 80°C, 10 minutes → temperature rise → 300°C, 30 minutes → temperature rise → 400°C, 30 minutes. In addition, the temperature increase rate is 10°C/min.
所得之塗佈膜之膜厚係使用接觸式膜厚測量器(股份公司ULVAC製Dektak 3ST)進行測量。 The film thickness of the obtained coating film was measured using a contact film thickness measuring device (Dektak 3ST manufactured by ULVAC Co., Ltd.).
表1表示使用之P1~P7之前驅物、塗佈基板、硬化條件、及製作之剝離層之膜厚。 Table 1 shows the used P1~P7 precursors, coated substrates, curing conditions, and the film thickness of the produced release layer.
對於表1所示之實施例1~5及比較例1~3之具備剝離層的基板,以方格試驗I確認基板(玻璃或矽晶圓)/剝離層之密著力。 For the substrates with peeling layers of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, the adhesive force of the substrate (glass or silicon wafer)/peeling layer was confirmed by the square test I.
方格試驗I係如下述進行。 The grid test I was performed as follows.
(1)薄膜上製作100個1mm四方的正方形。 (1) Make 100 squares of 1mm square on the film.
(2)然後,以黏著膠帶(賽路玢膠帶(註冊商標))黏貼於上述正方形,然後進行剝離步驟。 (2) Then, stick the adhesive tape (Selicate tape (registered trademark)) to the above square, and then perform the peeling step.
(3)剝離步驟後,計算殘存於基板之上述正方形。 (3) After the peeling step, the square remaining on the substrate is calculated.
以下述指標表示方格試驗之結果、剝離之程度。 The results of the grid test and the degree of peeling are indicated by the following indicators.
5B:未剝離。 5B: No peeling.
4B:5%以下之剝離。 4B: Peel below 5%.
3B:5~15%之剝離。 3B: 5~15% peeling.
2B:15~35%之剝離。 2B: 15~35% peeling.
1B:35~65%之剝離。 1B: 35~65% peeling.
0B:65%~80%之剝離。 0B: 65%~80% peeling.
B:80%~95%之剝離。 B: 80%~95% peeling.
A:95%~未達100%之剝離。 A: 95%~less than 100% peeling.
AA:100%之剝離。 AA: 100% peeling.
與上述方格試驗I不同,針對表1所示之實施例1~5及比較例1~3之具備剝離層的基板,測量構成該剝離層之成分之特性、亦即,(1)顯示加熱時之重量變化減少1%重量的溫度、(2)於波長1000nm之折射率、(3)於波長1000nm之雙折射、及(4)表面能量。又,各特性之測量條件等如以下所示。 Unlike the above-mentioned grid test I, for the substrates with peeling layers of Examples 1 to 5 and Comparative Examples 1 to 3 shown in Table 1, the characteristics of the components constituting the peeling layer were measured, that is, (1) showed heating The weight change at the time reduces the temperature by 1% by weight, (2) the refractive index at a wavelength of 1000 nm, (3) the birefringence at a wavelength of 1000 nm, and (4) the surface energy. The measurement conditions of each characteristic are shown below.
使用bruker股份有限公司製TD-DTA2000ST,氮環境下進行熱重量(TG)測量,求重量減少1%的溫度。 Using TD-DTA2000ST manufactured by Bruker Co., Ltd., thermogravimetric (TG) measurement was carried out in a nitrogen environment, and the temperature at which the weight was reduced by 1% was determined.
使用高速分光橢圓測厚儀M-2000(J.A.Woollam Japan股份公司製),測量折射率及雙折射率。又,折射率係1000nm之值之面內折射率,而雙折射率為面內折射率與面外折射率之差。 Using a high-speed spectroscopic elliptical thickness gauge M-2000 (manufactured by J.A. Woollam Japan Co., Ltd.), the refractive index and birefringence were measured. In addition, the refractive index is the in-plane refractive index at a value of 1000 nm, and the birefringence is the difference between the in-plane refractive index and the out-of-plane refractive index.
使用全自動接觸角計DM-701(共和界面科學股份公司製),測量各構件之表面能量。又,測量所用的溶劑為水與碘化亞甲基,由此等之溶劑的接觸角計算得到。 Using a fully automatic contact angle meter DM-701 (made by Kyowa Interface Science Co., Ltd.), the surface energy of each component is measured. In addition, the solvent used for the measurement is water and methylene iodide, and the contact angle of the solvent is calculated.
於實施例1~5及比較例1~3之具備有剝離層之基板上,形成被剝離體,以方格試驗II確認其剝離的程度。 On the substrates provided with the peeling layers of Examples 1 to 5 and Comparative Examples 1 to 3, the object to be peeled was formed, and the degree of peeling was confirmed by the square test II.
於具備有剝離層之基板之該剝離層上,形成作為被剝離體之聚醯亞胺層。 On the peeling layer of the substrate provided with the peeling layer, a polyimide layer as a peeled body is formed.
具體而言,如表1所示,於實施例1~5及比較例1~3之具備剝離層之基板之剝離層上,以塗佈棒塗佈上述合成例5或合成例1所得之前驅物P5或P1。然後,以烤箱在120℃下,維持30分鐘→昇溫→180℃下,維持20分鐘→昇溫→240℃/維持20分鐘→昇溫→300℃下,維持20分鐘→昇溫→400℃下,維持20分鐘→昇溫→450℃下,維持60分鐘(任一的昇溫速度為10℃/分鐘)進行硬化,製作由聚醯亞胺所構成之膜厚15μm的被剝離體層。 Specifically, as shown in Table 1, the precursor obtained in Synthesis Example 5 or Synthesis Example 1 above was coated with a coating bar on the peeling layers of the substrates having peeling layers in Examples 1 to 5 and Comparative Examples 1 to 3.物P5 or P1. Then, the oven is maintained at 120°C for 30 minutes → temperature rise → 180°C for 20 minutes → temperature rise → 240°C/maintain 20 minutes → temperature rise → 300°C for 20 minutes → temperature rise → 400°C for 20 Minutes → temperature rise → 450° C., maintaining for 60 minutes (any temperature rise rate is 10° C./minute) and hardening, to produce a 15 μm-thick peeled body layer composed of polyimide.
對於上述所得之具備被剝離體層及剝離層之基板,以 方格試驗II確認被剝離體層/剝離層間之密著力。 For the substrate with peeled body layer and peeling layer obtained above, The square test II confirmed the adhesion between the peeled body layer and the peeled layer.
方格試驗II係與方格試驗I同樣進行。 The grid test II was conducted in the same way as the grid test I.
表2中表示(1)表示加熱時之重量變化之減少1%重量的溫度(表2中,「以(1)」表示)、(2)波長1000nm之折射率(表2中,「以(2)」表示)、(3)該(2)之折射率與雙折射之差(表2中,「以(3)」表示)、(4)表面能量(表2中,以「(4)」表示。但是單位為dyne/cm)、被剝離體層使用的聚醯亞胺前驅物、及方格試驗I及II之結果。 Table 2 shows (1) the temperature at which the weight change during heating is reduced by 1% by weight (in Table 2, "denoted by (1)"), and (2) the refractive index at a wavelength of 1000 nm (in Table 2, "denoted by ( 2)"), (3) the difference between the refractive index and birefringence of (2) (in Table 2, "denoted by (3)"), (4) surface energy (in Table 2, denoted by "(4) "Means. However, the unit is dyne/cm), the polyimide precursor used in the peeled body layer, and the results of grid tests I and II.
*:比較例2之雙折射無法測量。 *: The birefringence of Comparative Example 2 cannot be measured.
**:比較例1及比較例3之方格試驗II係因與剝離層及基板之密著性低,故無法測量。 **: The square test II of Comparative Example 1 and Comparative Example 3 was unable to measure because of the low adhesion to the peeling layer and the substrate.
由表2得知以下的情形。實施例1~5之剝離層之試驗I的結果為5B,故得知剝離層不會自基板剝離,而試驗II之結果為AA,因此,得知僅被剝離體層自 剝離層剝離。換言之,得知由本發明之剝離層用組成物所形成的剝離層,產生所期望的剝離結果。 Table 2 shows the following situation. The result of the test I of the peeling layer of Examples 1 to 5 is 5B, so it is known that the peeling layer will not peel off from the substrate, and the result of the test II is AA, so it is known that only the peeling layer The peeling layer peels off. In other words, it is known that the peeling layer formed from the composition for peeling layer of the present invention produces a desired peeling result.
另外,比較例1及比較例3之試驗I的結果為AA,故得知剝離層可自基板剝離。換言之,得知比較例1及比較例3無法得到所期望的剝離結果。又,比較例2之試驗I及試驗II均為5B,故得知即使在剝離層與基板之界面,或剝離層與被剝離體層之界面,也不會剝離,也無法得到所期望之剝離結果。 In addition, the result of Test I of Comparative Example 1 and Comparative Example 3 is AA, so it is known that the peeling layer can be peeled off from the substrate. In other words, it is understood that Comparative Example 1 and Comparative Example 3 cannot obtain the desired peeling result. In addition, since both Test I and Test II of Comparative Example 2 are 5B, it is understood that even at the interface between the peeling layer and the substrate, or the interface between the peeling layer and the object layer to be peeled off, the desired peeling result cannot be obtained .
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KR20160142331A (en) | 2016-12-12 |
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TW201927861A (en) | 2019-07-16 |
CN108690494B (en) | 2021-04-06 |
CN106133077B (en) | 2018-11-06 |
CN106133077A (en) | 2016-11-16 |
KR102467104B1 (en) | 2022-11-14 |
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TWI669356B (en) | 2019-08-21 |
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