TW200925171A - Unsaturated carboxylic acid-grafted polyolefin and its manufacturing method - Google Patents
Unsaturated carboxylic acid-grafted polyolefin and its manufacturing method Download PDFInfo
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200925171 九、發明說明 【發明所屬之技術領域】 本發明係關於不飽和羧酸接枝聚烯烴、其製造方法及 其用途。 【先前技術】 聚烯烴因爲機械強度、透明性、成形性、衛生性等優 異,故使用於廣泛的領域,但在作爲層合物利用’因爲聚 烯烴是無極性的聚合物,故會有與各種的極性物質的接著 性低之材料固有的問題。爲了改良此問題點’目前爲止嘗 試了各種改良,但其接著性稱不上充分,爲更進一步地改 良接著性,例如提議接枝不飽和羧酸、或其衍生物之改性 聚烯烴樹脂。 舉例來說,已知藉由使聚烯烴溶解於溶劑使不飽和羧 酸接枝化而製造不飽和羧酸接枝聚烯烴,作爲此溶劑係使 用脂肪族烴、芳香族烴,可列舉例如苯、甲苯、二甲苯等 之芳香族烴、或戊烷、己烷、庚烷等之脂肪族烴(專利文 獻1)。 惟,因爲此等的芳香族烴係沸點比較高,反應溫度亦 高至160°C,故會有不僅熱能成本變高,於回收步驟中亦 有成本變高之虞,此外,由苯等爲致癌性物質之毒性的觀 點而言,希望不要使用,另一方面,己烷等之脂肪族烴, 聚烯烴的溶解性稱不上充分,故必須提高溶解溫度,而熱 能成本亦高。亦即,將不飽和羧酸於溶液中接枝於聚烯烴 -5- 200925171200925171 IX. Description of the Invention [Technical Field] The present invention relates to an unsaturated carboxylic acid grafted polyolefin, a process for producing the same, and use thereof. [Prior Art] Polyolefin is used in a wide range of fields because it is excellent in mechanical strength, transparency, formability, hygiene, etc., but it is used as a laminate because 'polyolefin is a non-polar polymer, so there will be A problem inherent in materials with low adhesion of various polar substances. In order to improve this problem, various improvements have been tried so far, but the adhesion is not sufficient, and the adhesion is further improved. For example, a modified polyolefin resin in which an unsaturated carboxylic acid or a derivative thereof is grafted is proposed. For example, it is known that an unsaturated carboxylic acid grafted polyolefin is produced by dissolving a polyolefin in a solvent to graft an unsaturated carboxylic acid, and an aliphatic hydrocarbon or an aromatic hydrocarbon is used as the solvent, and benzene is exemplified. An aromatic hydrocarbon such as toluene or xylene or an aliphatic hydrocarbon such as pentane, hexane or heptane (Patent Document 1). However, since these aromatic hydrocarbons have a relatively high boiling point and a reaction temperature of 160 ° C, there is a problem that not only the heat energy cost is high but also the cost is high in the recovery step, and benzene or the like is used. From the viewpoint of the toxicity of the carcinogenic substance, it is desirable not to use it. On the other hand, the solubility of the aliphatic hydrocarbon such as hexane and the polyolefin is not sufficient. Therefore, it is necessary to increase the dissolution temperature and the heat cost is also high. That is, the unsaturated carboxylic acid is grafted to the polyolefin in solution -5 - 200925171
Ο 之先前技術的製造技術,對於聚合物的離析,不得不變成 爲了去除溶劑而浪費熱能之高成本製程。如上述,在將芳 香族烴使用於溶劑將酸酐接枝於聚烯烴之反應中,爲了將 所使用的高沸點的芳香族烴溶劑自反應器去除,使用了利 用添加水使水與芳香族烴溶劑共沸,而去除溶劑之製程。 惟,因爲此方法中使用水,故此去除需要大量的熱能,因 而稱不上在經濟上爲優異的製程,故尋求此改善方式。而 且,於聚合物的溶液中添加水,去除有機溶劑之該製程, 因爲最後聚合物變成塊狀,故之後需要煩雜且花費成本之 製程,將聚合物賦形爲易成形加工的形狀,亦即顆粒等的 形狀。 此外,藉由此等的反應所得到的生成物,被指摘出會 有熱安定性差、經常凝膠產生之問題。 因此,期望不使用上述的溶劑、凝膠產生受到抑制之 不飽和羧酸接枝聚烯烴的更低成本的製造法。 此外,如上述作法所製造的酸改性聚烯烴樹脂組成物 ,雖然具有接著性的改良效果,但隨著對於接著性聚合物 要求的高度化,依然要求接著性的改良。 另一方面,作爲不使用溶劑之不飽和羧酸接枝聚烯烴 的製造方法,一般已知在使聚烯烴溶融的狀態下接枝不飽 和羧酸之熔融法,此熔融法係基於經濟上理由一般使用不 使用反應器而使用擠壓機之方法,可列舉例如使用具有排 氣口之二軸擠壓機之方法(專利文獻2)。 惟,熔融法因爲擠壓機内的滯留時間比較短’無法確 -6- 200925171 保接枝反應時間,與使用反應器之接枝反應比較下,一般 而言不僅是提高不飽和羧酸的反應量有困難,接枝反應亦 爲局部性,具有生成物的品質易變不均勻之本質上的缺點 。因此,會有所得到的生成物含有凝膠,加工成薄膜時發 生魚眼等之應改良的課題。此外,反應時,因爲必須使樹 脂熔融,故反應溫度變成例如250 °C的高溫,結果因爲引 起不飽和羧酸的揮發•蒸發,不僅是必須裝入過剩的不飽 0 和羧酸,由前述的反應時間的問題而言,此方法所得到的 不飽和羧酸接枝聚烯烴會有未接枝充分量的不飽和羧酸, 例如與金屬材料或無機物質等異種材料的接著性低之問題 。由此等的背景而言,期望用於得到接著性受到改善的不 飽和羧酸接枝聚烯烴之製造法、及與異種材料的接著性優 異、不含凝膠或凝膠的含量少之不飽和羧酸接枝聚烯烴。 另一方面,作爲適用於需要絕緣保護被覆的金屬基材 之被覆材,已知有塡充劑摻合的聚矽氧烷組成物、聚偏氟 Q 乙烯組成物、環氧樹脂組成物等之熱硬化性樹.脂組成物。 惟,此等的熱硬化性樹脂組成物,一般而言因爲硬化 反應需要數十分單位的硬化時間,故作業性差、聚矽氧烷 組成物(聚矽氧烷系硬化材)爲高成本,此外,環氧樹脂 組成物雖然廉價,但會對環境溫度的變化弱,因爲熱衝撃 破壞材料,與被黏著物發生剝離等之問題。 此外,金屬絕緣體使用聚醯亞胺等步驟塑膠等時,極 難同時滿足絕緣性、與金屬的接著強度、彎折、衝撃等力 學強度’此外,亦不及與環氧樹脂組成物同樣地熱衝擊等 200925171 激烈的溫度變化,會發生接著層裂開、作爲電子零件的機 能受損等問題。 因此,需要製造比較容易,此外,以藉由連續層壓等 手段可輕易地自動化之簡單的方法,而且不需要以比較低 溫、短時間對金屬表面施加特別的處理下可簡便且堅固地 熱接著於金屬基材之絕緣性的彈性層,亦即彈性薄片、彈 性薄膜或彈性膠帶等。 0 作爲電絕緣性優異的廉價素材,以聚烯烴較適合,但 於作爲層合物的利用中,因爲聚烯烴爲無極性的聚合物, 故會有與各種極性物質的接著性低、對於金屬的接著性亦 極低的問題。 因此,爲了利用廉價且成形性優異的聚烯烴作爲熱接 著性的絕緣材料,而進行了爲了改良其接著性的各種檢討 。其中之一方法,提議例如經接枝不飽和羧酸或其衍生物 的改性聚烯烴樹脂(專利文獻1 )。 Q 但是,以此等先前技術的製造製程所得到的不飽和羧 酸接枝聚烯烴,會有熱安定性低、含有凝膠的問題。此外 ’雖然作爲金屬絕緣用樹脂的接著性提高,但作爲用於層 合不同的2種材料,例如層合金屬與塑膠之接著層使用時 ,所得到層合板經不起熱衝撃,而尋求彈性更豐富、接著 性優異的絕緣性樹脂。 另一方面’家具、室内壁、汽車的内裝零件、鍵盤樂 器的裝飾等廣泛使用重現木材的高級感與質感之氯乙烯、 苯乙烯系樹脂、丙烯酸系樹脂等之成形體、或薄片、薄膜 -8- 200925171 等(例如專利文獻3):但是,無法重現真正的木材所具 有的高級感、質感,故利用木材本身作爲裝飾材料的期望 提高,爲了重現木材的質感、及重量感,將木材直接接著 於金屬的期望變強。 〇先前 Prior art manufacturing techniques have necessitated a high-cost process for wasting heat energy in order to remove the solvent. As described above, in the reaction in which an aromatic hydrocarbon is used in a solvent to graft an acid anhydride to a polyolefin, in order to remove the high-boiling aromatic hydrocarbon solvent to be used from the reactor, water and aromatic hydrocarbons are added by using added water. The solvent is azeotropic and the solvent is removed. However, since water is used in this method, the removal requires a large amount of heat energy, and thus it cannot be called an economically excellent process, so this improvement method is sought. Moreover, the process of adding water to the solution of the polymer to remove the organic solvent, because the polymer becomes a block in the end, requires a complicated and costly process to shape the polymer into a shape suitable for forming, that is, The shape of the particles, etc. Further, the product obtained by such a reaction is referred to as having a problem that the thermal stability is poor and the gel is often generated. Therefore, it is desirable to produce a lower cost manufacturing method of the unsaturated carboxylic acid grafted polyolefin which is inhibited without using the above solvent or gel. Further, the acid-modified polyolefin resin composition produced by the above-described method has an effect of improving the adhesion, but it is required to improve the adhesion as the thickness of the adhesive polymer is required. On the other hand, as a method for producing an unsaturated carboxylic acid grafted polyolefin which does not use a solvent, a melting method of grafting an unsaturated carboxylic acid in a state in which a polyolefin is melted is generally known, and the melting method is based on economic reasons. A method of using an extruder without using a reactor is generally used, and a method of using a two-axis extruder having an exhaust port is exemplified (Patent Document 2). However, the melting method is relatively short because of the short residence time in the extruder. It is not possible to confirm the grafting reaction time. Compared with the grafting reaction using the reactor, it is generally not only to increase the reaction amount of the unsaturated carboxylic acid. Difficulties, the grafting reaction is also local, and has the inherent disadvantage of the quality of the product becoming uneven. Therefore, there is a problem that the obtained product contains a gel, and when a film is formed into a film, fish eye or the like is improved. Further, in the reaction, since the resin must be melted, the reaction temperature becomes a high temperature of, for example, 250 ° C, and as a result, volatilization and evaporation of the unsaturated carboxylic acid are caused, not only the excess of the unsaturated and the carboxylic acid must be charged, In terms of reaction time, the unsaturated carboxylic acid grafted polyolefin obtained by this method may have a non-grafted sufficient amount of unsaturated carboxylic acid, for example, low adhesion to a dissimilar material such as a metal material or an inorganic substance. . From the background of the above, it is desirable to produce a method for producing an unsaturated carboxylic acid grafted polyolefin having improved adhesion, and excellent adhesion to a dissimilar material, and no gel or gel content. Saturated carboxylic acid grafted polyolefin. On the other hand, as a coating material suitable for a metal substrate requiring an insulating protective coating, a polyfluorene oxide composition, a polyvinylidene fluoride Q ethylene composition, an epoxy resin composition, etc., which are blended with a lubricant, are known. Thermosetting tree. Fat composition. However, these thermosetting resin compositions generally require a hardening time of several tenths of a unit of the hardening reaction, so that the workability is poor and the polyoxane composition (polyoxyalkylene-based hardened material) is high in cost. Further, although the epoxy resin composition is inexpensive, it has a weak change in the environmental temperature, and the heat is washed and destroyed, and the adhesive is peeled off from the adherend. In addition, when the metal insulator is made of a plastic such as polyimide or the like, it is extremely difficult to satisfy both the insulating property, the bonding strength with the metal, the mechanical strength such as bending and punching, and the thermal shock similar to that of the epoxy resin composition. 200925171 Intense temperature changes can cause problems such as cracking of the underlying layer and damage to the function of electronic parts. Therefore, it is relatively easy to manufacture, and further, a simple method which can be easily automated by means of continuous lamination or the like, and it is not necessary to apply a special treatment to the metal surface at a relatively low temperature and for a short time, and it is easy and strong to heat up. An insulating elastic layer of a metal substrate, that is, an elastic sheet, an elastic film, an elastic tape, or the like. 0 As a cheap material with excellent electrical insulation, polyolefin is suitable. However, in the use of a laminate, since polyolefin is a non-polar polymer, it has low adhesion to various polar substances and is suitable for metals. The adhesion is also extremely low. Therefore, in order to utilize a polyolefin which is inexpensive and excellent in moldability as a thermally conductive insulating material, various reviews for improving the adhesion are performed. One of the methods proposes, for example, a modified polyolefin resin grafted with an unsaturated carboxylic acid or a derivative thereof (Patent Document 1). Q However, the unsaturated carboxylic acid-grafted polyolefin obtained by such a prior art manufacturing process has a problem of low heat stability and gelation. In addition, although the adhesion as a resin for metal insulation is improved, when used as a laminate for two different materials, for example, a laminate of a metal and a plastic, the obtained laminate cannot withstand heat and seek elasticity. An insulating resin that is more abundant and excellent in adhesion. On the other hand, 'forms, sheets, and the like, such as vinyl chloride, styrene resin, and acrylic resin, which reproduce the high-grade feeling and texture of wood, such as the furniture, the interior wall, the interior parts of the automobile, and the decoration of the keyboard instrument. Film -8- 200925171, etc. (for example, Patent Document 3): However, it is impossible to reproduce the high-grade feeling and texture of real wood, so the use of wood itself as a decorative material is expected to be improved, in order to reproduce the texture and weight of wood. The desire to bring the wood directly to the metal is stronger. 〇
惟,本材與金屬的接著使用液狀接著劑時,要於整個 廣面積上均勻地塗佈液狀接著劑,而且從塗佈至接著爲止 的間隔時間内完成接著,接著後確保接著層的均勻性很這 點很困難。此外,木材與金屬因爲其材料的極性差異很大 ,故要堅固地地黏著此等異種素材並不容易。 因此,需要以比較的低溫、短時間在不需要對金屬、 木材施加特別的表面處理下簡便且堅固地接著之薄膜、及 、藉由此薄膜使木材與金屬接著之層合物。 另一方面,電子機器的電子電路,現狀一般爲使用由 接著了銅箔與聚醯亞胺薄膜之銅箔/接著劑/聚醯亞胺所成 的三層可撓貼銅層合板。此可撓貼銅層合板中,接著上述 的銅箔與聚醯亞胺薄膜時,將熱硬化型的環氧樹脂使用於 接著(例如專利文獻4)。此外,亦已知不使用環氧系的 熱硬化型接著劑下於銅箔塗佈聚醯亞胺清漆於加熱下與聚 醯亞胺貼合,由金屬箔/聚醯亞胺所成的二層可撓貼銅層 合板(例如專利文獻5 )。此等方法,爲了使聚醯亞胺硬 化,最後以超過3 00 °C的溫度進行熱處理。 如上述,先前技術的三層可撓貼銅層合板,因爲在其 製造步驟中與銅箔的接著使用環氧樹脂,此硬化反應需要 數十分單位的硬化時間,故作業性差。此外,環氧樹脂組 -9 - 200925171 成物雖然廉價’但會有經不起環境溫度的變化,因爲熱衝 撃而材料破壞,與被黏著物發生剝離等問題。 此外,二層層合板,在此製造步驟中不僅是需要塗佈 聚醯亞胺清漆,一邊慢慢地提高一邊熱處理之步驟,亦需 要在最後以300°C所謂的高溫處理,需要煩雜且熱能消耗 型的製造方法。However, when the liquid material is subsequently applied to the metal and the metal, the liquid adhesive is uniformly applied over the entire area, and the coating is completed from the application to the subsequent interval, and then the subsequent layer is ensured. Uniformity is very difficult. In addition, because wood and metal have very different polarities, it is not easy to firmly adhere these different materials. Therefore, it is necessary to laminate a wood and a metal by a thin film at a relatively low temperature and for a short period of time without requiring a special surface treatment for metal or wood. On the other hand, the electronic circuit of an electronic device is generally a three-layer flexible copper laminate which is formed of a copper foil/adhesive/polyimine which is followed by a copper foil and a polyimide film. In the flexible copper clad laminate, a thermosetting epoxy resin is used in the case of the copper foil and the polyimide film described above (for example, Patent Document 4). Further, it is also known that a polyethylene-based thermosetting type adhesive is used in which a copper foil-coated polyimide pigment varnish is bonded to a polyimide under heating, and a metal foil/polyimine is used. The layer is flexible with a copper laminate (for example, Patent Document 5). In order to harden the polyimine, these methods are finally heat-treated at a temperature exceeding 300 °C. As described above, the prior art three-layer flexible copper laminate has a work hardness because it requires an epoxy resin for the subsequent use of the epoxy resin in the manufacturing step thereof, and the hardening reaction requires several tenths of hardening time. In addition, although the epoxy resin group -9 - 200925171 is inexpensive, it may not be able to withstand changes in the ambient temperature, because the material is destroyed by heat and the article is peeled off from the adherend. In addition, the two-layer laminate, in this manufacturing step, not only needs to coat the polyimide varnish, but also slowly increases the heat treatment step, and also needs to be treated at a high temperature of 300 ° C at the end, which requires cumbersome and thermal energy. Consumable manufacturing method.
因此,尋求可藉由以連續層壓等之簡便、且經濟的方 法進行製造之耐彎折性、耐寒性、柔軟性、熱衝撃性優異 的可撓配線板。 另一方面,薄膜天線係在具有透明性的塑膠薄膜上藉 由印刷、蒸鍍等方法形成天線電路之薄膜狀的天線,因爲 厚度薄、輕量而廣泛地被利用於各種攜帶終端、汽車窗戶 、個人電腦等之情報終端、住宅用窗玻璃等,亦可應用於 IC TAG 等之 RFID ( Radio Frequency Identification)。 惟,先前技術的薄膜天線,因爲薄膜天線本身不具有接著 Q 性,故採取於薄膜的單面塗佈黏著劑(例如專利文獻6 ) ,或者使用黏著膠帶(例如專利文獻7),而接著於被黏 著物之方法。 但是,此方法因爲需要在薄膜天線塗佈黏著劑,或貼 合黏著膠帶之步驟,故尋求可更簡便地接著於被黏著物之 薄膜天線。 另一方面,半導體裝置、平面型顯示器、記錄媒介物 等所使用的薄膜的形成,現在工業上廣泛地使用濺鍍法’ 濺鍍法所使用的薄膜材料(成對標靶本體)’在濺鍍薄膜 -10-Therefore, a flexible wiring board which is excellent in bending resistance, cold resistance, flexibility, and thermal punchability by being manufactured by a simple and economical method such as continuous lamination is sought. On the other hand, a film antenna is a film-shaped antenna in which an antenna circuit is formed on a plastic film having transparency by printing, vapor deposition, or the like, and is widely used in various portable terminals and automobile windows because of its thin thickness and light weight. Information terminals such as personal computers and window glass for residential use can also be applied to RFID (Radio Frequency Identification) such as IC TAG. However, the prior art film antenna has a single-sided coating adhesive (for example, Patent Document 6) or an adhesive tape (for example, Patent Document 7) because the film antenna itself does not have the Q property. The method of being glued. However, since this method requires a step of applying an adhesive to the film antenna or attaching the adhesive tape, a film antenna which can be more easily adhered to the adherend is sought. On the other hand, the formation of thin films used in semiconductor devices, flat-panel displays, recording media, etc., is now widely used in the industry by sputtering methods used to sputter the film materials (paired target bodies). Plating film -10-
❹ 200925171 形成步驟中,雖然必須固定於真空室裝置 作爲電極使用之背板接合後使用爲一般的 ,成對標靶本體與背板的接合,主要是使 例如專利文獻8),而且此接合中必須接 的全側面與背板,但因爲此接合步驟比較 廉價且簡便的接合方法。 另一方面,先前技術,於基材上形成 ,一直是使用藉由微影術之方法。此方法 殘留所望的導體圖型後藉由蝕刻而去除其 、在未層合銅的基材上生成負型圖型的抗 解電鍍形成導體圖型之加成法。因爲此等 法需要煩雜的步驟,大量的處理廢液產生 刷應用於電子零件的製造之稱爲可印刷電 意,作爲製造電路基板或電子零件之方法 性油墨或導電性膏等直接印刷於基板之方 藉由可印刷電子之方法,與先前技術 方法比較下,由遮罩製成變不需要等、電 中製造步驟大寬度地簡單化方面,與藉由 較下,蝕刻液等的廢液不會產生,亦可期 具有大的效果。例如作爲藉由導電性油墨 檢討了照相凹版印刷、膠版印刷、噴墨印 ,但噴墨印刷因爲在必要處塗佈必要的量 墨的浪費,成爲省熱能的製造製程,此外 、網版印刷印刷中,可高速印刷,故可達 内,但此時,與 作法。先前技術 用高價的焊銦( 合成對標靶本體 煩雜,故尋求更 電路圖型之方法 已知有在基板上 他部分之移除法 鏟敷,藉由無電 的電路圖型形成 ,故近年,將印 子之技術受到注 ,檢討了將導電 法。 之藉由微影術之 路基板等的作製 微影術之方法比 待廢棄物的削減 之印刷方法,已 刷、網版印刷等 的油墨,故無油 ,照相凹版印刷 到熱能削減。 -11 - 200925171 由如此背景而言,檢討了可印刷的導電性油墨,例如 揭示使用十二烷胺等之低分子量的分散劑等使銀的奈米粒 子分散於有機溶劑中之導電性油墨等的技術(例如專利文 獻9) 〇❹ 200925171 In the forming step, although it is necessary to fix it to the vacuum chamber device as a backing plate used as an electrode, it is used in general, and the bonding of the paired target body and the backing plate is mainly made, for example, in Patent Document 8), and in this bonding The full side and back plate that must be connected, but because of this bonding step is a relatively inexpensive and simple joining method. On the other hand, the prior art, formed on a substrate, has been using a method by lithography. This method removes the desired conductor pattern and then removes it by etching, and forms a negative pattern of the anti-deposition plating to form a conductor pattern on the unlaminated copper substrate. Since these methods require complicated steps, a large amount of processing waste liquid generating brush is applied to the manufacture of electronic parts, which is called printable electric power, and is directly printed on the substrate as a method ink or a conductive paste for manufacturing a circuit board or an electronic part. By means of printable electronics, compared with the prior art method, the mask is made unnecessary, the manufacturing steps in the electricity are simplified in a large width, and the waste liquid such as the etching liquid is used. Will not produce, but also have a large effect. For example, gravure printing, offset printing, and inkjet printing have been reviewed by conductive inks, but inkjet printing has become a manufacturing process for saving heat energy because it wastes the necessary amount of ink where necessary, and in addition, screen printing In the middle, it can be printed at high speed, so it can be reached inside, but at this time, and practice. The prior art uses high-priced solder indium (the synthesis of the target body is cumbersome, so the method of seeking a more circuit pattern is known to have a partial removal method on the substrate, which is formed by an electroless circuit pattern, so in recent years, the ink is printed. The technology has been investigated, and the conductive method has been reviewed. The method of making lithography by using a lithography substrate or the like is a printing method based on the reduction of waste, and inks such as brushing and screen printing are not used. Oil, gravure printing to thermal energy reduction. -11 - 200925171 From this background, the printable conductive ink was reviewed, for example, by dispersing silver nanoparticles using a low molecular weight dispersant such as dodecylamine. A technique such as a conductive ink in an organic solvent (for example, Patent Document 9) 〇
惟,因爲該溶液例如僅由有機溶劑、低分子量的分散 劑、及金屬粒子而成,故將該溶液塗佈於基材,使溶劑揮 發時,會有由低分子量的分散劑、及金屬粒子所成的皮膜 與塑膠等基材的密著性或接著性低的問題。因此,使用導 電性油墨,例如在絕緣性塑膠薄膜上進行電路形成時,發 生所形成的電路剝離等問題。 此外,雖然揭示添加苯二甲酸酐等之酸酐及/或十二 烷胺等之烷胺、及熱硬化型之酚樹脂之銀粒子分散膏(例 如專利文獻10),此技術中,在基材上所形成的皮膜的 硬化需要費時1小時左右,會有生產性低的問題。 作爲爲了保護或加飾塑膠表面而於塑膠表面形成金屬 膜之方法,已揭示藉由鍍敷之方法(例如專利文獻11) 、或藉由金屬的蒸鍍之方法(例如專利文獻12),但此 等的方法被指出會有需要樹脂表面的前處理等製造步驟煩 雜’此外蒸鍍時間長而生產性低等的問題。 作爲進行如此的塑膠成型體的保護、加飾之方法,已 知於塑膠成型體上蒸鍍金屬之方法,但稱不上是生產性、 成本的雙面皆優異的方法。 因爲以上的理由,一直以來尋求可在堅固地接著於各 種的塑膠、玻璃、矽晶圓、金屬等基材的狀態下形成皮膜 -12- 200925171 ,而且,經由短時間的熱處理可形成安定的皮膜之無機微 粒子分散液。However, since the solution is formed of, for example, only an organic solvent, a low molecular weight dispersant, and metal particles, the solution is applied to a substrate, and when the solvent is volatilized, a low molecular weight dispersant and metal particles are present. The adhesion between the formed film and the substrate such as plastic is low. Therefore, when a conductive ink is used, for example, when a circuit is formed on an insulating plastic film, problems such as peeling of the formed circuit occur. In addition, a silver particle dispersion paste containing an acid anhydride such as phthalic anhydride or an alkylamine such as dodecylamine or a thermosetting type phenol resin (for example, Patent Document 10) is disclosed. The hardening of the film formed thereon takes about one hour, and there is a problem that productivity is low. As a method of forming a metal film on a plastic surface for protecting or decorating a plastic surface, a method of plating (for example, Patent Document 11) or a method of vapor deposition of a metal (for example, Patent Document 12) has been disclosed. These methods have been pointed out that there are problems in that the manufacturing steps such as the pretreatment of the resin surface are complicated, and the vapor deposition time is long and the productivity is low. As a method of protecting and adoring such a plastic molded body, a method of vapor-depositing a metal on a plastic molded body is known, but it is not a method which is excellent in both productivity and cost. For the above reasons, it has been sought to form a film -12-200925171 in a state of being firmly adhered to various substrates of plastic, glass, enamel wafer, metal, etc., and a stable film can be formed by heat treatment for a short period of time. Inorganic fine particle dispersion.
〔專利文獻1〕 特開平9-3138號公報 〔專利文獻2〕 特開2002-1 87914號公報 〔專利文獻3〕 特開2004-268373號公報 〔專利文獻4〕 特開平7-1 54〇42號公報 〔專利文獻5〕 特開2005-313380號公報 〔專利文獻6〕 特許第2594224號公報 〔專利文獻7〕 特開2001-313508號公報 〔專利文獻8〕 特開平11-200028號公報 〔專利文獻9〕 特開2002-299833號公報 〔專利文獻10〕 特許第3900248號公報 〔專利文獻11〕 特開平5-222578號公報 〔專利文獻12〕 特開平5-275828號公報 【發明內容】 〔發明所欲解決之課題〕 本發明係鑑於上述的課題而完成者,其目的係提供不 僅是與塑膠材料’與異種材料的接著性亦優異,具有廣泛 有用性之不飽和羧酸接枝聚烯烴。 〔用以解決課題之手段〕 本發明者等人,爲了解決上述的課題而經過精心硏討 的結果,而達成本發明。亦即,本發明係關於其特徵爲於 -13- 200925171 加熱至140 °C的二甲苯中不溶的凝膠的含量爲低於0.02重 量%,而且,不飽和羧酸的接枝量爲0.1〜10重量%之不飽 和羧酸接枝聚烯烴、其製造法、及其用途。具體的而言, 本發明具有以下的構成。 (1) 一種不飽和羧酸接枝聚烯烴,其特徵係於加熱 至140t的二甲苯中不溶的凝膠的含量爲低於0.02重量% ,而且,不飽和羧酸的接枝量爲0.1〜10重量%。 0 (2)如上述(1)所記載之不飽和羧酸接枝聚烯烴, 其係於加熱至140°c的二甲苯中不含不溶的凝膠。 (3) —種上述(1)或(2)所記載之不飽和羧酸接 枝聚烯烴的製造法,其特徵係於溶劑中使不飽和羧酸接枝 反應於聚烯烴時,使用經去除1,1,2-三氯乙烷中所含有的 醇化合物及/或環氧基化合物雜質之1,1,2-三氯乙烷作爲 溶劑,且,反應溫度爲40〜130 °C,反應壓力爲1 MPa以下 〇 Q (4) 一種上述(1)或(2)所記載之不飽和羧酸接 枝聚烯烴的製造法,其特徵係由在於常壓下沸點爲120°C 以下的鹵素系溶劑中,使不飽和羧酸接枝反應於聚烯烴之 接枝反應步驟;藉由將接枝反應後的反應溶液供給至鼓式 乾燥機使該溶劑揮發去除;離析反應生成物的不飽和羧酸 接枝聚烯烴之離析步驟所成。 (5) —種熱熔著性薄膜,其特徵係由上述(1)或( 2)所記載之不飽和羧酸接枝聚烯烴所成。 (6) —種多層層合物,其係由金屬層及樹脂層的至 -14- 200925171 少1層、與彈性電絕緣層所構成,而金屬層及/或樹脂層 與彈性電絕緣層經接著之多層層合物,其特徵係彈性電絕 緣層,由上述(1)或(2)所記載之不飽和羧酸接枝聚烯 烴所成。 (7) 如上述(6)所記載之多層層合物,其係金屬層 及/或樹脂層與彈性電絕緣層,藉由加熱壓黏而接著。 (8) 如上述(6)或(7)所記載之多層層合物,其 0 係相對於不飽和羧酸接枝聚烯烴1〇〇重量份,再含有 20〜40重量份的難燃劑。 (9) 一種可撓配線薄膜,其特徵係在由上述(1)或 (2)所記載之不飽和羧酸接枝聚烯烴所成的薄膜的至少 單面上,具有以金屬所形成的導電電路。 (1 0 ) —種導電性薄膜,其特徵係由含有導電性微粒 子之上述(1)或(2)所記載之不飽和羧酸接枝聚烯烴所 成。 Q ( 11)如上述(1 〇)所記載之導電性薄膜,其中導電 性微粒子係由金、銀、銅、鉬、鎳、碳、錫、銦、鈀、铑 、餓、釕、銥、鋁、鐵、銦、鎂、鉑、矽、錫、鋅、鈷、 鉻、鈦、鉬、鎢、碳黑所選出的1種以上的微粒子。 (1 2 )如上述(1 〇 )或(1 1 )所記載的導電性薄膜, 其係相對於不飽和羧酸接枝聚烯烴100重量份,含有 3 0〜9 9重量份的導電性微粒子。 (13) —種濺鍍標靶,其特徵係將成對標靶本體與背 板使用上述(1 〇 )〜(1 2 )中任一項所記載之導電性薄膜 -15- 200925171 進行接著而成。 (14) 一種無機微粒子分散液,其特徵係含有上述( 1)或(2)所記載之不飽和羧酸接枝聚烯烴、無機微粒子 及溶劑。 (15) 如上述(14)所記載之無機微粒子分散液,其 中無機微粒子係由金、銀、銅、鈀、铑、餓、釕、銥、鋁 、鐵、銦、鎂、鉑、矽、錫、鋅、鈷、鎳、鉻、鈦、鉅、 鎢、碳黑所選出的至少1種類的微粒子。 〔發明的效果〕[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. OBJECTS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to provide an unsaturated carboxylic acid graft polyolefin which is excellent not only in adhesion to a plastic material and a dissimilar material but also has wide usefulness. [Means for Solving the Problem] The present inventors have achieved the present invention by carefully examining the above-mentioned problems in order to solve the above problems. That is, the present invention relates to a gel which is characterized in that the gel which is insoluble in xylene heated to 140 ° C at -13 to 200925171 is less than 0.02% by weight, and the graft amount of the unsaturated carboxylic acid is 0.1~ 10% by weight of unsaturated carboxylic acid grafted polyolefin, a process for the production thereof, and uses thereof. Specifically, the present invention has the following constitution. (1) An unsaturated carboxylic acid grafted polyolefin characterized in that the content of the gel insoluble in xylene heated to 140 t is less than 0.02% by weight, and the graft amount of the unsaturated carboxylic acid is 0.1~ 10% by weight. (2) The unsaturated carboxylic acid grafted polyolefin according to (1) above, which is in the form of an insoluble gel in xylene heated to 140 °C. (3) A process for producing an unsaturated carboxylic acid grafted polyolefin according to the above (1) or (2), which is characterized in that, when a unsaturated carboxylic acid is graft-reacted to a polyolefin in a solvent, it is removed. 1,1,2-trichloroethane contained in the 1,1,2-trichloroethane and/or the impurity of the epoxy compound as a solvent, and the reaction temperature is 40 to 130 ° C. The pressure is 1 MPa or less 〇Q (4) A method for producing an unsaturated carboxylic acid grafted polyolefin according to the above (1) or (2), which is characterized in that it has a boiling point of 120 ° C or less at normal pressure. In the solvent, the unsaturated carboxylic acid is grafted into the grafting reaction step of the polyolefin; the solvent is removed by supplying the reaction solution after the grafting reaction to a drum dryer; the unsaturated product is isolated from the reaction product. The separation step of the carboxylic acid grafted polyolefin. (5) A heat-fusible film characterized by comprising the unsaturated carboxylic acid grafted polyolefin described in the above (1) or (2). (6) A multilayer laminate consisting of a metal layer and a resin layer to a layer of -14 to 200925171, and an elastic electrically insulating layer, and the metal layer and/or the resin layer and the elastic electrically insulating layer are The multilayer laminate, which is characterized by an elastic electrically insulating layer, is formed from the unsaturated carboxylic acid grafted polyolefin described in the above (1) or (2). (7) The multilayer laminate according to (6) above, wherein the metal layer and/or the resin layer and the elastic electrically insulating layer are bonded by heating and pressure bonding. (8) The multilayer laminate according to the above (6) or (7), wherein the 0 layer is further contained in an amount of 20 to 40 parts by weight based on 1 part by weight of the unsaturated carboxylic acid graft polyolefin. . (9) A flexible wiring film characterized by having a conductive layer formed of a metal on at least one side of a film formed of the unsaturated carboxylic acid grafted polyolefin described in the above (1) or (2) Circuit. (10) A conductive film characterized by comprising the conductive fine particles of the unsaturated carboxylic acid grafted polyolefin described in the above (1) or (2). (11) The conductive film according to the above (1), wherein the conductive fine particles are gold, silver, copper, molybdenum, nickel, carbon, tin, indium, palladium, rhodium, samarium, bismuth, antimony, aluminum. One or more kinds of fine particles selected from iron, indium, magnesium, platinum, rhodium, tin, zinc, cobalt, chromium, titanium, molybdenum, tungsten, and carbon black. (1) The conductive film according to the above (1) or (1), which contains 30 to 99 parts by weight of conductive fine particles with respect to 100 parts by weight of the unsaturated carboxylic acid graft polyolefin. . (13) A sputtering target, characterized in that the pair of target bodies and the back sheet are subjected to the conductive film -15-200925171 described in any one of the above (1 〇) to (1 2). to make. (14) An inorganic fine particle dispersion containing the unsaturated carboxylic acid graft polyolefin, the inorganic fine particles, and a solvent described in the above (1) or (2). (15) The inorganic fine particle dispersion according to the above (14), wherein the inorganic fine particles are gold, silver, copper, palladium, rhodium, samarium, bismuth, antimony, aluminum, iron, indium, magnesium, platinum, rhodium, tin. At least one type of fine particles selected from zinc, cobalt, nickel, chromium, titanium, giant, tungsten, and carbon black. [Effects of the Invention]
藉由本發明所得到的不飽和羧酸接枝聚烯烴,因爲凝 膠的含量少,且,接著性提高,具有可簡便且堅固地熱接 著包括金屬材料之廣泛的材料之特性,故在產業上可應用 至極廣泛的範圍;而且,由熱能成本的觀點而言,提供不 使用芳香族烴或脂肪族烴,提高與異種材料的接著性之低 成本的不飽和羧酸接枝聚烯烴的製造方法;此外,可展現 於活用本發明的不飽和羧酸接枝聚烯烴所有的特性的廣泛 的用途。 〔實施發明之最佳形態〕 以下詳細說明關於本發明。 本發明的不飽和羧酸接枝聚烯烴,於加熱至14(TC的 二甲苯中不溶的凝膠的含量爲低於〇·〇2重量%。即使於加 熱至l4〇°C的二甲苯中含有不溶的凝膠,其含量低於〇.〇2 -16- 200925171 重量%時,雖然與異種材料的接著性優異,但爲了使接著 性更優異,於加熱至i4〇°c的二甲苯中不含有不溶的凝膠 較佳。於加熱至140°C的二甲苯中不溶的凝膠的含量爲 0.02重量%以上’會發生不僅是大寬度損傷薄膜化時的製 品外觀,亦因爲凝膠的量而使作爲接著劑之接著強度、耐 久性等之力學特性降低,剝離等的問題。 而且,本發明的不飽和羧酸接枝聚烯烴,係不飽和羧 0 酸的接枝量爲0.1〜10重量%,較佳爲0.5~8重量%。低於 〇 · 1重量%,則無充分的接著性、缺乏實用性。此外,超 過1〇重量%時,聚合物的熔融黏度高而損及成形性以外 ,因爲作爲接著層的靭性亦差而缺乏實用性。 本發明中作爲不飽和羧酸,可列舉例如不飽和單羧酸 類及其衍生物、不飽和二羧酸類及其衍生物、不飽和二羧 酸的酸酐類及其衍生物等。作爲不飽和單羧酸類,可列舉 丙烯酸、甲基丙烯酸、巴豆酸、異巴豆酸等;作爲不飽和 〇 單羧酸類的衍生物,可列舉甲基(甲基)丙烯酸酯、乙基 (甲基)丙烯酸酯、η-丙基(甲基)丙烯酸酯、異丙基( 甲基)丙嫌酸醋、丁基丙稀酸酯等。作爲不飽和二竣酸類 ’可列舉馬來酸、富馬酸、衣康酸、檸康酸、四氫苯二甲 酸等;作爲不飽和二羧酸類的衍生物,可列舉馬來酸單甲 酯、馬來酸二甲酯、馬來酸單乙酯、馬來酸二乙酯、富馬 酸單甲酯、富馬酸二甲酯、富馬酸單乙酯、富馬酸二乙醋 等。作爲不飽和二羧酸的酸酐類及其衍生物,可列舉馬來 酸酐、衣康酸酐、檸康酸酐、四氫苯二甲酸酐等。此等可 -17- 200925171 單獨使用或2種類以上倂用,特別是由接著性的觀點而言 ,以馬來酸酐單獨或馬來酸酐與(甲基)丙烯酸酯類的組 合。The unsaturated carboxylic acid-grafted polyolefin obtained by the present invention has industrial properties as long as the content of the gel is small and the adhesion is improved, and the properties of a wide range of materials including a metal material can be easily and firmly heated. It is applied to a wide range of applications; and, in view of thermal energy cost, a method for producing a low-cost unsaturated carboxylic acid grafted polyolefin which does not use an aromatic hydrocarbon or an aliphatic hydrocarbon and improves adhesion to a dissimilar material; Furthermore, it can be exhibited in a wide range of applications in which all of the properties of the unsaturated carboxylic acid grafted polyolefin of the present invention are utilized. [Best Mode for Carrying Out the Invention] The present invention will be described in detail below. The unsaturated carboxylic acid grafted polyolefin of the present invention has a gel content of less than 〇·〇2% by weight in the xylene heated to 14 (TC), even in xylene heated to 14 ° C. Containing an insoluble gel, when the content is less than 〇.〇2 -16- 200925171% by weight, although it is excellent in adhesion to a dissimilar material, it is heated to i4 〇 °c in order to make the adhesion more excellent. It is preferred that the gel is not contained insoluble, and the content of the gel which is insoluble in xylene heated to 140 ° C is 0.02% by weight or more 'the appearance of the product not only when the film is damaged by a large width but also because of the gel The amount of the unsaturated carboxylic acid-grafted polyolefin of the present invention, the amount of grafting of the unsaturated carboxylic acid is 0.1 to 0.1%, and the mechanical properties such as adhesion strength and durability of the adhesive are lowered. 10% by weight, preferably 0.5 to 8% by weight, and less than 〇·1% by weight, there is no sufficient adhesion and lack of practicality. Further, when it exceeds 1% by weight, the melt viscosity of the polymer is high and is damaged. In addition to formability, the toughness as the adhesive layer is also poor. In the present invention, examples of the unsaturated carboxylic acid include unsaturated monocarboxylic acids and derivatives thereof, unsaturated dicarboxylic acids and derivatives thereof, acid anhydrides of unsaturated dicarboxylic acids, and derivatives thereof. Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, and isocrotonic acid; and examples of the unsaturated fluorinated monocarboxylic acid derivative include methyl (meth) acrylate and ethyl (methyl). Acrylate, η-propyl (meth) acrylate, isopropyl (methyl) propylene sulphuric acid vinegar, butyl acrylate, etc. As the unsaturated diterpenic acid, 'maleic acid, Fuma Examples of the unsaturated dicarboxylic acid derivatives include monomethyl maleate, dimethyl maleate, and monoethyl maleate. Diethyl maleate, monomethyl fumarate, dimethyl fumarate, monoethyl fumarate, diethyl fumarate, etc. as anhydrides and derivatives of unsaturated dicarboxylic acids, Examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, and tetrahydrophthalic anhydride. -17-200925171 used singly or two kinds or more Merger with, in particular of the viewpoint of adhesive property, the maleic anhydride alone or maleic anhydride with (meth) acrylates combination.
本發明中作爲聚烯烴,可列舉例如高密度聚乙烯( HDPE )、中密度聚乙烯(MDPE )、低密度聚乙烯( LDPE )、線狀低密度聚乙烯(L-LDPE )、超低密度聚乙 烯(V-LDPE)等。作爲線狀低密度聚乙烯(L-LDPE ), 可列舉乙烯-1-丁烯共聚物、乙烯-1-己烯共聚物、乙烯-1-辛烯共聚物等之乙烯-α-烯烴共聚物;其他可列舉乙烯-4-甲基戊烯-1樹脂、乙烯-乙酸乙烯酯共聚物(EVA )及其 鹼化物、乙烯-乙烯醇樹脂(EVOH )、乙烯-丙烯共聚物 (EPM)等之乙烯系共聚物、聚丙烯均聚物、聚丙烯嵌段 共聚物、聚丙烯無規共聚物等,而且,此等的聚烯烴的氯 化物亦可同樣地使用。 用於合成此等的聚烯烴之聚合方法,可爲一般已知的 Q 方法,亦可列舉高壓自由基聚合、中低壓聚合、溶液聚合 、淤漿聚合等,使用觸媒可列舉過氧化物系觸媒、齊格 靭-納塔觸媒、芳環烯金屬衍生物觸媒等,可使用以此等 的觸媒被聚合的聚烯烴。 成爲本發明的原料之聚烯烴的分子量的簡單標準之熔 體流動速率(MFR ),並沒特別的限制,但爲了使對溶劑 的溶解性即使於加溫時亦優良,此外,維持最後的接枝反 應物的材料強度,較佳爲 0.01〜50000 (g/ΙΟ分鐘),更 佳爲0.01〜100 (g/10分鐘)。 "18- 200925171In the present invention, examples of the polyolefin include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), and ultra low density poly. Ethylene (V-LDPE) and the like. Examples of the linear low-density polyethylene (L-LDPE) include an ethylene-α-olefin copolymer such as an ethylene-1-butene copolymer, an ethylene-1-hexene copolymer, and an ethylene-1-octene copolymer. Other examples include ethylene-4-methylpentene-1 resin, ethylene-vinyl acetate copolymer (EVA) and its alkali compound, ethylene-vinyl alcohol resin (EVOH), ethylene-propylene copolymer (EPM), and the like. A vinyl copolymer, a polypropylene homopolymer, a polypropylene block copolymer, a polypropylene random copolymer, etc., and the chloride of these polyolefins can also be used similarly. The polymerization method for synthesizing such polyolefins may be a generally known Q method, and may also be a high pressure radical polymerization, a medium pressure polymerization, a solution polymerization, a slurry polymerization, etc., and a catalyst may be used as the peroxide system. A catalyst, a sigma-tano-nata catalyst, an aromatic ring-olefin metal derivative catalyst, or the like can be used, and a polyolefin polymerized by such a catalyst can be used. The melt flow rate (MFR) of a simple standard of the molecular weight of the polyolefin which is a raw material of the present invention is not particularly limited, but is excellent even in the case of heating in order to improve the solubility in a solvent, and further, the last connection is maintained. The material strength of the branched reactant is preferably from 0.01 to 50,000 (g/min), more preferably from 0.01 to 100 (g/10 min). "18- 200925171
聚烯烴的氯化方法爲習知,例如已揭示將使其溶解於 四氯化碳等之鹵素系溶劑的溶液,在紫外線照射下與含氯 的氣體接觸而氯化聚烯烴之方法(例如特開昭47-8643號 公報);於使聚烯烴的粉末懸濁於水中的淤漿中吹入氯氣 而氯化烯烴之方法(例如特公昭3 6 - 4 7 4 5號公報);不使 用溶劑,將聚烯烴加熱至其熔點以上,在熔融的狀態下與 氯氣接觸’在未使用自由基產生劑、紫外線照射等下氯化 聚烯烴之方法(例如特開平3 - 1 9 9 2 0 6號公報)。本發明 所用的經氯化的聚烯烴,可使此等的任一方法製造,對於 氯化聚烯烴的製造方法並沒任何制限。 本發明的不飽和羧酸接枝聚烯烴,依前述的原料聚烯 烴的種類,可列舉例如不飽和羧酸接枝聚乙烯、不飽和羧 酸接枝乙烯•丙烯共聚物、不飽和羧酸接枝乙烯· 丁烯共 聚物、不飽和羧酸接枝乙烯•己烯共聚物、不飽和羧酸接 枝乙烯•乙酸乙烯酯共聚物、不飽和羧酸接枝聚丙烯等。 作爲本發明的不飽和羧酸接枝聚烯烴的製造法,可列 舉例如以下所揭示的2種方法。 本發明的不飽和羧酸接枝聚烯烴的第一製造法,係在 溶劑中對聚烯烴接枝反應不飽和羧酸時,作爲溶劑係使用 去除1,1,2-三氯乙烷中以雜質被含有的醇化合物及/或環 氧基化合物之1,1,2 -三氯乙烷。 不飽和羧酸的接枝化反應,係藉由以自由基產生劑作 爲觸媒,在去除1,1,2-三氯乙烷以雜質被含有的醇化合物 及/或環氧基化合物之1,1,2-三氯乙烷中使聚烯烴與不飽 -19-A method of chlorinating a polyolefin is known, for example, a method of dissolving a solution in a halogen-based solvent such as carbon tetrachloride, and contacting a chlorine-containing gas under ultraviolet irradiation to chlorinate a polyolefin (for example, JP-A-47-8643); a method of chlorinating an olefin by blowing chlorine gas into a slurry in which a powder of a polyolefin is suspended in water (for example, Japanese Patent Publication No. 3-6-47); a method of heating a polyolefin to a temperature above the melting point and contacting it with chlorine gas in a molten state 'chlorinating the polyolefin without using a radical generating agent, ultraviolet irradiation or the like (for example, special opening 3 - 1 9 9 2 06) Bulletin). The chlorinated polyolefin used in the present invention can be produced by any of these methods, and the method for producing the chlorinated polyolefin is not limited. The unsaturated carboxylic acid graft polyolefin of the present invention may, for example, be an unsaturated carboxylic acid grafted polyethylene, an unsaturated carboxylic acid grafted ethylene/propylene copolymer, or an unsaturated carboxylic acid, depending on the kind of the raw material polyolefin. Branch ethylene·butene copolymer, unsaturated carboxylic acid grafted ethylene/hexene copolymer, unsaturated carboxylic acid grafted ethylene/vinyl acetate copolymer, unsaturated carboxylic acid grafted polypropylene, etc. As a method for producing the unsaturated carboxylic acid grafted polyolefin of the present invention, two methods as disclosed below can be listed. The first production method of the unsaturated carboxylic acid grafted polyolefin of the present invention is carried out by grafting an unsaturated carboxylic acid to a polyolefin in a solvent, and removing 1,1,2-trichloroethane as a solvent system. The impurity is contained in the alcohol compound and/or the epoxy compound 1,1,2-trichloroethane. The grafting reaction of an unsaturated carboxylic acid is carried out by using a radical generating agent as a catalyst to remove 1,1,2-trichloroethane as an impurity and an alcohol compound and/or an epoxy compound. , 1,2-trichloroethane, polyolefin and unsaturated-19-
200925171 和羧酸進行反應而進行。 而且,本發明的不飽和羧酸接枝聚烯烴 ,係反應溫度爲40〜13 0°C,反應溫度低於 枝充分量的不飽和羧酸,變成品質上差者而 溫度超過130°C,由因爲凝膠的產生而使品 能成本之雙面而言較不佳,反應溫度較佳爲 反應壓力,因爲高壓反應除了需要特殊 外,反應操作亦變煩雜,與製造成本的_ IMPa以下爲佳,較佳爲0〜0.7MPa。本反應 、及、反應的聚烯烴的種類,會有從均勻的 濁狀態下進行接枝反應的狀況,但儘可能在 態下進行接枝反應,故依聚烯烴的種類適當 較佳。 作爲自由基產生劑,使用偶氮系化合物 物等,作爲偶氮系化合物,可列舉α,α-偶氮 氮雙環己烷腈、2,2’-偶氮雙(2,4-二甲基戊 有機過氧化物,可列舉過酸化苯甲醯、過酸 化t-丁基、過苯甲酸t-丁基等。 偶氮系化合物或有機過氧化物的添加量 限制,但爲了維持不飽和羧酸的接枝量,此 樹脂的熔融黏度的增加來防止成形性的降低 質,相對於聚烯烴100重量份較佳爲0.05-佳爲0.05~3重量份。 不飽和羧酸接枝聚烯烴的製造法所使用 的第一製造法 4 0 °C,則未接 較不佳,反應 質降低,及熱 6 0~13 0。(: ° 的反應裝置之 匕昇有關,故 中依反應溫度 溶液狀態至懸 均勻的溶液狀 選擇反應溫度 或有機過氧化 雙異丁腈、偶 腈)等;作爲 化乙醯、過酸 並沒有特別的 外,藉由防止 而維持製品品 _5重量份,更 的不飽和羧酸 -20- 200925171 、聚烯烴,與上述相同。 接枝反應結束後,必要時添加安定劑,添加安定劑是 爲了消除接枝反應時所產生的自由基、使接枝反應停止。 通常使用於聚烯烴中所添加抗氧化劑較佳,例如酚系抗氧 化劑、磷系抗氧化劑、硫系抗氧化劑、此等的複合系抗氧 化劑較適合使用。200925171 is carried out by reacting with a carboxylic acid. Further, the unsaturated carboxylic acid grafted polyolefin of the present invention has a reaction temperature of 40 to 130 ° C, a reaction temperature lower than a sufficient amount of the unsaturated carboxylic acid, and the quality is inferior and the temperature exceeds 130 ° C. The reaction temperature is preferably the reaction pressure because the production of the gel is relatively low on both sides, and the reaction temperature is preferably the reaction pressure. Because the high pressure reaction requires special handling, the reaction operation becomes complicated, and the manufacturing cost is below _ IMPa. Preferably, it is preferably 0 to 0.7 MPa. The type of the polyolefin to be reacted and reacted may be grafted in a uniform turbid state. However, the grafting reaction is carried out as much as possible in the state of the polyolefin. Therefore, the type of the polyolefin is preferably as appropriate. As the radical generator, an azo compound or the like is used, and examples of the azo compound include α,α-azozabicyclohexanecarbonitrile and 2,2'-azobis(2,4-dimethyl group). Examples of the pentyl organic peroxide include peracidified benzamidine, peracidified t-butyl, perbenzoic acid t-butyl, etc. The amount of the azo compound or the organic peroxide added is limited, but in order to maintain the unsaturated carboxylic acid The amount of grafting of the acid, the increase in the melt viscosity of the resin to prevent deterioration of formability, is preferably 0.05 to preferably 0.05 to 3 parts by weight based on 100 parts by weight of the polyolefin. Unsaturated carboxylic acid grafted polyolefin The first manufacturing method used in the manufacturing method is 40 °C, the poor connection is not good, the reaction quality is lowered, and the heat is 60 to 130. (: ° The reaction device is soaring, so the reaction temperature solution From the state to the suspension, the solution temperature is selected as the reaction temperature or the organic peroxide bisisobutyronitrile, the acrylonitrile, etc.; as the acetamidine and the peracid, there is no special, and the product is kept _5 parts by weight, and more Unsaturated carboxylic acid-20- 200925171, polyolefin, same as above. After completion, if necessary, a stabilizer is added, and the stabilizer is added to eliminate the radical generated during the grafting reaction and to stop the grafting reaction. It is generally preferred to use an antioxidant added to the polyolefin, such as a phenolic antioxidant. Phosphorus-based antioxidants, sulfur-based antioxidants, and such composite antioxidants are suitable for use.
接枝反應所使用的反應容器,一般可使用分批式(間 歇式)反應所使用的容器,只要是可承受上述反應溫度、 反應壓力者即可,材質通常使用不鏽鋼製,必要時可使用 内面施以玻璃襯裏、氟塗覆處理者。 使接枝反應所生成的不飽和羧酸接枝聚烯烴與溶劑分 離之方法,藉由水蒸氣蒸餾、附有排氣口的擠壓機、鼓式 乾燥機等一般使用的方法分離兩者。 本發明中作爲反應溶劑使用的1,1,2-三氯乙烷,從 1,1,2-三氯乙烷去除醇化合物及/或環氧基化合物後進行反 Q 應這點很重要,市售的1,1,2-三氯乙烷,經常以雜質含有 0_5〜2.0重量%的醇化合物及/或環氧基化合物,此處所謂 的醇化合物之意,係指具有羥基的化合物,可列舉例如乙 基醇或丁醇等,此外,此處所謂的環氧基化合物之意,係 指具有環氧基的化合物,可列舉例如1,2-環氧基丙烷或 1,2-環氧基丁烷等。 以雜質含有醇化合物及/或環氧基化合物之1,1,2-三 氯乙烷作爲溶劑所合成的不飽和羧酸接枝聚烯烴係著色爲 淡黃色,又熱安定性差、凝膠發生的傾向強,亦即,使用 -21 - 200925171 於薄膜用途時,因爲色調、透明性差而會有不易著色的問 題’此外,凝膠因爲在薄膜化時會產生魚眼,而顯著地損 及薄膜表面外觀的結果,此商品價値喪失。作爲接著劑的 原料使用時,亦因爲凝膠成分未溶解於溶劑,而事實上無 法作爲接著劑原料利用。 以經去除醇化合物及/或環氧基化合物的1,1,2-三氯 乙烷作爲溶劑所合成的不飽和羧酸接枝聚烯烴爲無色透明 Q ’熱安定性優良且無凝膠的發生,故成爲不僅是與塑膠材 料,與異種材料的接著性優異,在商業上具有價値的不飽 和羧酸接枝聚烯烴。 本發明的不飽和羧酸接枝聚烯烴的第二製造法,係由 以下一連串的步驟所成,以下說明關於各步驟。 (步驟1 )於常壓下的沸點爲1 2(TC以下的鹵素系溶 劑中使不飽和羧酸接枝反應於聚烯烴之接枝反應步驟 (步驟2 )藉由將接枝反應後的反應溶液供給至鼓式 0 乾燥機而揮發去除常壓下的沸點爲120 °C以下的鹵素系溶 劑,離析反應生成物之不飽和羧酸接枝聚烯烴之離析步驟 此方法雖然是藉由聚合物的.離析需要大量熱能之溶液 法對聚烯烴進行不飽和羧酸的接枝反應,但發現使用低沸 點且不燃性的鹵素系溶劑,藉由使用鼓式乾燥機作爲從聚 合物溶液離析出聚合物之方法,可用低成本且安全、並且 輕易地離析聚合物。 (步驟1 )接枝反應步驟 -22- 200925171 不飽和羧酸的接枝反應步驟,係藉由以自由基產生劑 作爲觸媒,使不飽和羧酸,在常壓下的沸點爲120°C以下 的鹵素系溶劑中與聚烯烴進行反應而進行。 作爲反應溶劑使用之常壓下的沸點爲120 °C以下的鹵 素系溶劑,可列舉例如1,1-二氯乙烷、1,2-二氯乙烷、二 氯甲烷、氯仿、三氯乙烷、1,1,2 -三氯乙烷、四氯化 碳、三氯乙烯、全氯乙烯等之氯系溶劑,溴化乙烷等之溴 0 系溶劑、單氟苯、1,4-二氟苯、全氟庚烷、全氟辛烷、二 氯五氟丙烷等之氟系溶劑、溴氯甲烷、1,2-二溴-1,1-二氟 乙烷等之含有溴與氟之溶劑等,但由沸點、聚烯烴的溶解 性而言,以1,1,2 -三氯乙烷、氯仿較適合使用。作爲溶劑 使用1,1,2-三氯乙烷時,去除此溶劑中所含有的雜質,亦 即醇化合物、及/或環氧基化合物後使用較佳。 反應溫度並沒有特別的限制,但爲了提高接枝反應的 效率,防止不飽和羧酸接枝聚烯烴的著色、及交聯等,較 〇 佳爲40〜130°C,更佳爲60〜130°C,反應壓力依所使用的 溶劑的種類、及反應溫度而決定,並沒有特別的限制,但 爲了不需要用到特殊的反應裝置,較佳爲0〜1 MPa,更佳 爲0〜0_7MPa。本反應中依反應溫度、及、反應的聚嫌烴 的種類,會有從均勻的溶液狀態至懸濁狀態下進行接枝反 應的狀況,但儘可能在均勻的溶液狀態下進行接枝反應, 故依聚烯烴的種類適當選擇反應溫度較佳。 作爲自由基產生劑,使用偶氮系化合物或有機化酸化 物等。作爲偶氮系化合物,可列舉α,α -偶氮雙異丁腊、偶 -23- 200925171 氮雙環己烷腈、2,2’-偶氮基雙(2,4-二甲基戊腈)等,作 爲有機化酸化物,可列舉過酸化苯甲醯、過酸化乙醯、過 酸化t-丁基、過苯甲酸t-丁基等。The reaction vessel used for the grafting reaction can generally be used in a batch (intermittent) reaction, as long as it can withstand the above reaction temperature and reaction pressure. The material is usually made of stainless steel, and the inner surface can be used if necessary. Glass lining, fluorine coated processor. The method of separating the unsaturated carboxylic acid grafted polyolefin formed by the graft reaction from the solvent is carried out by a method generally used for steam distillation, an extruder equipped with a vent, a drum dryer or the like. It is important that the 1,1,2-trichloroethane used as the reaction solvent in the present invention is subjected to an anti-Q reaction after removing the alcohol compound and/or the epoxy compound from 1,1,2-trichloroethane. The commercially available 1,1,2-trichloroethane often contains 0-5 to 2.0% by weight of an alcohol compound and/or an epoxy compound as an impurity. The term "alcohol compound" herein means a compound having a hydroxyl group. For example, ethyl alcohol or butanol may be mentioned, and the term "epoxy compound" as used herein means a compound having an epoxy group, and examples thereof include 1,2-epoxypropane or 1,2-ring. Oxybutane and the like. The unsaturated carboxylic acid grafted polyolefin synthesized by using 1,1,2-trichloroethane containing an alcohol compound and/or an epoxy compound as a solvent is colored yellowish, and has poor thermal stability and gelation. The tendency is strong, that is, when using -21, 2009,171, for film use, there is a problem that it is difficult to color due to poor color tone and transparency. In addition, the gel significantly damages the film because it causes fish eyes during film formation. As a result of the appearance of the surface, the price of this commodity is lost. When used as a raw material for an adhesive, the gel component is not dissolved in a solvent, and in fact cannot be utilized as an adhesive material. The unsaturated carboxylic acid grafted polyolefin synthesized by using 1,1,2-trichloroethane as a solvent to remove the alcohol compound and/or the epoxy compound is colorless and transparent, and has excellent thermal stability and no gelation. When it occurs, it is an unsaturated carboxylic acid grafted polyolefin which is excellent not only in adhesiveness with a plastic material but also a dissimilar material, and is commercially expensive. The second production method of the unsaturated carboxylic acid grafted polyolefin of the present invention is carried out by the following series of steps, and the respective steps will be described below. (Step 1) a grafting reaction step (step 2) of grafting an unsaturated carboxylic acid to a polyolefin in a halogen-based solvent having a boiling point of 1 or less under normal pressure (step 2) by a reaction after grafting The solution is supplied to a drum 0 dryer to volatilize and remove a halogen-based solvent having a boiling point of 120 ° C or lower at normal pressure, and the separation step of the unsaturated carboxylic acid-grafted polyolefin of the reaction product is obtained by a polymer. Isolation requires a large amount of thermal energy solution method to carry out the graft reaction of the unsaturated carboxylic acid on the polyolefin, but it is found that the use of a low-boiling and non-combustible halogen-based solvent is used to separate the polymerization from the polymer solution by using a drum dryer. The method of the material can be used to isolate the polymer at a low cost and safely and easily. (Step 1) Grafting reaction step -22-200925171 The grafting reaction step of the unsaturated carboxylic acid is carried out by using a radical generating agent as a catalyst. The unsaturated carboxylic acid is reacted with a polyolefin in a halogen-based solvent having a boiling point of 120 ° C or less under normal pressure. The halogen solvent having a boiling point of 120 ° C or less at normal pressure used as a reaction solvent is used. Examples thereof include 1,1-dichloroethane, 1,2-dichloroethane, dichloromethane, chloroform, trichloroethane, 1,1,2-trichloroethane, carbon tetrachloride, and three. Chlorine solvent such as vinyl chloride or perchloroethylene, bromine 0 solvent such as brominated ethane, monofluorobenzene, 1,4-difluorobenzene, perfluoroheptane, perfluorooctane, dichloropentafluoropropane a solvent containing bromine and fluorine, such as a fluorine-based solvent, bromochloromethane or 1,2-dibromo-1,1-difluoroethane, but the boiling point and the solubility of the polyolefin are 1, 1,2-trichloroethane and chloroform are preferably used. When 1,1,2-trichloroethane is used as a solvent, impurities contained in the solvent, that is, alcohol compounds, and/or epoxy compounds are removed. The reaction temperature is not particularly limited, but in order to improve the efficiency of the graft reaction, the coloring and crosslinking of the unsaturated carboxylic acid grafted polyolefin are prevented, and it is preferably 40 to 130 ° C, more preferably It is preferably 60 to 130 ° C, and the reaction pressure is determined depending on the type of the solvent to be used and the reaction temperature, and is not particularly limited, but in order to eliminate the need for a special reaction device, Preferably, it is 0 to 1 MPa, more preferably 0 to 0_7 MPa. In the present reaction, depending on the reaction temperature and the type of polyorganic hydrocarbon to be reacted, a graft reaction may be carried out from a uniform solution state to a suspension state. However, the grafting reaction is carried out in a uniform solution state as much as possible, so that the reaction temperature is preferably selected depending on the type of the polyolefin. As the radical generating agent, an azo compound or an organic acid compound or the like is used as the azo compound. Examples thereof include α,α-azobisisobutylidene, even-23-200925171 nitrogen bicyclohexanecarbonitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and the like. Examples of the acid compound include peracid benzamidine, peracetate acetamidine, peracidified t-butyl group, and perbenzoic acid t-butyl group.
偶氮系化合物或有機過氧化物的添加量並沒有特別的 限制,但爲了維持不飽和羧酸的接枝量,此外,藉由防止 樹脂的熔融黏度的增加來防止成形性的降低而維持製品品 質,相對於聚烯烴100重量份較佳爲0.05〜5重量份,更 佳爲0.05〜3重量份。 不飽和羧酸接枝聚烯烴的製造法所使用的不飽和羧酸 、聚烯烴,與上述相同。 接枝反應結束後,必要時添加安定劑,添加安定劑是 爲了消除接枝反應時所產生的自由基、使接枝反應停止。 通常使用於聚烯烴中所添加抗氧化劑較佳,例如酚系抗氧 化劑、磷系抗氧化劑、硫系抗氧化劑、此等的複合系抗氧 化劑較適合使用。 接枝反應所使用的反應容器,一般可使用分批式(間 歇式)反應所使用的容器,只要是可承受上述反應溫度、 反應壓力者即可,材質通常使用不鏽鋼製,必要時可使用 内面施以玻璃襯裏、氟塗覆處理者。 (步驟2)離析步驟 作爲從經接枝以接枝反應步驟所得到的不飽和羧酸之 聚烯烴的反應溶液分離溶劑之方法,使用鼓式乾燥機,結 束反應步驟後,將此反應溶液從反應器送料至經加熱的鼓 -24- 200925171 式乾燥機,從聚合物溶液離析生成物。藉由使用鼓式乾燥 機,不需要藉由加熱將反應溶劑去除至反應器外之煩雜的 步驟,可用比較的低溫、連續的且短時間下,經濟地離析 聚合物。此時的鼓式乾燥機的溫度並沒有特別的限制,但 爲了在持續促進乾燥下,抑制聚合物的著色、熱劣化、交 聯,較佳爲120〜200°C的範圍,更佳爲150〜165°C,聚合 物係以薄膜狀從轉筒剝離後離析。The amount of the azo compound or the organic peroxide to be added is not particularly limited, but in order to maintain the graft amount of the unsaturated carboxylic acid, the product is prevented from being lowered by preventing an increase in the melt viscosity of the resin. The quality is preferably 0.05 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, per 100 parts by weight of the polyolefin. The unsaturated carboxylic acid or polyolefin used in the production method of the unsaturated carboxylic acid grafted polyolefin is the same as described above. After completion of the graft reaction, a stabilizer is added as necessary, and a stabilizer is added to eliminate the radical generated during the graft reaction and to stop the graft reaction. The antioxidant to be added to the polyolefin is usually used. For example, a phenolic antioxidant, a phosphorus antioxidant, a sulfur-based antioxidant, or a composite antioxidant is preferably used. The reaction vessel used for the grafting reaction can generally be used in a batch (intermittent) reaction, as long as it can withstand the above reaction temperature and reaction pressure. The material is usually made of stainless steel, and the inner surface can be used if necessary. Glass lining, fluorine coated processor. (Step 2) Separation step As a method of separating a solvent from a reaction solution of a polyolefin grafted with an unsaturated carboxylic acid obtained by a graft reaction step, using a drum dryer, after the reaction step is finished, the reaction solution is removed from the reaction solution. The reactor was fed to a heated drum-24-200925171 dryer to isolate the product from the polymer solution. By using a drum dryer, there is no need for a complicated step of removing the reaction solvent to the outside of the reactor by heating, and the polymer can be economically separated by a comparatively low temperature, continuous and short time. The temperature of the drum dryer at this time is not particularly limited. However, in order to suppress coloring, thermal deterioration, and crosslinking of the polymer while continuously promoting drying, it is preferably in the range of 120 to 200 ° C, more preferably 150. At ~165 ° C, the polymer was isolated from the drum in the form of a film and isolated.
藉由鼓式乾燥機從聚合物溶液去除溶劑所需要的時間 ,依所使用的溶劑的種類、及鼓式乾燥機的溫度而不同, 可適當的選擇,但通常爲10秒〜5分鐘。 此外,藉由鼓式乾燥機經揮發之常壓下的沸點爲 120°C以下的鹵素系溶劑之氯仿、1,1,2-三氯乙烷等,使用 被設置在鼓式乾燥機上部的回收線,進行回收,可再度使 用於反應。 經離析的聚合物必要時可加工成軟線狀、薄片狀、股 線狀或片狀,將此等經1次賦形的聚合物,再供給至1軸 ,或必要時供給至2軸擠壓機,使聚合物熔融後擠壓,單 股切割、或亦可在水中切割而顆粒化。此時的擠壓溫度並 沒有特別的限制,但爲了使所使的聚烯烴充分地熔融後順 利地擠壓,而且抑制聚烯烴的分解、著色等,較佳爲 100〜300°C,更佳爲 150〜2 5 0°C。 藉由此方法,不僅是與塑膠材料,與異種材料的接著 性優異、以及色相等之品質優異的不飽和羧酸接枝聚烯烴 ,可以低成本、簡便、且安全地獲得。 -25- 200925171 本發明的不飽和羧酸接枝聚烯烴中,可摻合其他樹脂 。作爲其他樹脂,例如不僅是未施加接枝反應的上述聚烯 烴樹脂,可列舉聚苯乙烯、聚-α-甲基苯乙烯、聚苯乙烯-丙烯腈共聚物、苯乙烯-丙烯腈-丁二烯樹脂等之苯乙烯系 樹脂、聚丙烯酸、聚甲基丙烯酸-甲基等之丙烯酸系樹脂 、聚氯乙烯系樹脂、聚偏氯乙烯樹脂、聚醯胺、聚酯、聚 碳酸酯樹脂、氟系樹脂、聚矽氧烷系樹脂、聚苯醚樹脂( 0 ΡΡΟ )、聚苯硫醚樹脂(PPS)、聚醯亞胺、聚颯、聚醚 颯、聚醚醚酮、聚對苯二甲酸丁二醇酯樹脂(ΡΒΤ )、聚 甲醛(polyoxymethylen)樹脂(ΡΟΜ)、環氧樹脂、聚胺 基甲酸乙酯、尿素樹脂、酚樹脂、三聚氰胺樹脂、纖維素 、石油樹脂等。必要時可使具有反應性的官能基、或末端 基之其他樹脂與本發明的不飽和羧酸基進行化學反應,或 可利用此等官能基之間的物理的相互作用進行摻合。而且 可添加矽烷偶合劑、鈦偶合劑等之偶合劑作爲第三成分, Q 提高與其他樹脂的相溶性,或提高接著性。 本發明的不飽和羧酸接枝聚烯烴中,可摻合彈性體或 橡膠成分,作爲彈性體或橡膠成分,可列舉例如天然橡膠 、異戊二烯橡膠、丁二烯橡膠、苯乙烯-丁二烯橡膠、丁 基橡膠、乙烯-丙烯橡膠、氯丁二烯橡膠、氯磺化聚乙烯 、氯化聚乙烯、環氧氯丙烷橡膠、腈橡膠、丙烯酸橡膠、 胺基甲酸乙酯橡膠、聚矽氧烷橡膠、氟橡膠等。此外,作 爲熱可塑性彈性體(TPE),可列舉SBS、SIS等之苯乙 烯系TPE ( SBC )、聚烯烴系TPE ( TPO )、胺基甲酸乙 -26- 200925171 酯系ΤΡΕ ( TPU )、聚酯系彈性體(ΤΡΕΕ )、聚醯胺系彈 性體(TPA)、聚矽氧烷系TPE、氟系TPE。 不飽和羧酸接枝聚烯烴中,可摻合以下的各種添加劑 ;作爲抗氧化劑,可列舉酚系抗氧化劑、磷系抗氧化劑、 硫系抗氧化劑 '此等的複合系抗氧化劑等;作爲其他安定 劑,可列舉有機亞磷酸酯系安定劑、硫醚系安定劑、阻胺 系光安定劑等;此外,作爲塡充劑,可列舉例如球狀塡充 0 劑、板狀塡充劑、纖維狀塡充劑等;作爲接著劑,可列舉 例如液體及固體雙酚A環氧樹脂、環氧甲酚酚醛清漆、 環氧酚酚醛清漆及雙酚A環氧樹脂與環氧甲酚酚醛清漆 或與環氧酚酚醛清漆之混合物 '雙酚F環氧樹脂、脂肪族 環氧樹脂等;作爲環氧交聯劑,可列舉三氟化硼的錯化合 物、二氰二醯胺、聚醯胺類、聚胺類等;作爲難燃劑,可 列舉例如乙烯雙四溴苯二甲醯亞胺、十溴二苯基氧化物、 S A YTEX 8010、十四溴二苯氧基苯等之溴化系難燃劑、三 Q 氧化銻、五氧化銻、硼酸鋅、FIREBRAKE ZB等之難燃助 劑、DECLORANE PLUS等之氯化系難燃劑等;作爲滑劑 ,使用高級脂肪酸金屬鹽之例如硬脂酸、油酸、月桂酸等 之高級脂肪酸的鎂鹽、鈣鹽、鋇鹽等之鹼土類金屬鹽、鎘 鹽、鋅鹽、鉛鹽,且鈉鹽、鉀鹽、鋰鹽等之鹼金屬鹽等; 作爲此其他添加劑,可列舉防靜電劑、著色劑、天然油、 合成油、蠟、可塑劑、造核劑、重金屬不活性化劑、加工 助劑、蠟類、弧抑制劑、氧化鋁、經矽烷處理的滑石、雲 母、長石及硅灰石之滴下抑制劑等。添加劑的添加量並沒 -27- 200925171 有特別的限制,但爲了表現出添加劑的添加效果、且維持 接著性,相對於不飽和羧酸接枝聚烯烴1 0 0重量份以 20~40重量份較佳。 此外,本發明的不飽和羧酸接枝聚烯烴,亦可含有導 電性微粒子。作爲導電性微粒子,可列舉例如金、銀、銅 、鉬、鎳、碳、錫、銦、鈀、鍺、餓、釕、銥、鋁、鐵、 銦、鎂、鉑、矽、錫、鋅、鈷、鉻、鈦、鉅、鎢、碳黑等 本發明的不飽和羧酸接枝聚烯烴與其他樹脂、彈性體 或橡膠成分、各種添加劑、導電性微粒子之混合,可使用 溶液混合或通常所使用的混練方法,作爲混練方,可列舉 單軸擠壓機、二軸擠壓機、布拉本德型密練機、班伯里混 練機、滾筒、捏合機、亨雪莉混練機、V摻合機、轉鼓混 練機等。 本發明的不飽和羧酸接枝聚烯烴可藉由習知的方法成 0 形爲薄膜,作爲薄膜成形法,除了熔融擠壓法以外,可使 用溶液流延法。使用熔融成形方法時,可使用加工一般的 聚烯烴樹脂之成形方法,可列舉吹塑薄膜成形、流延成形 、擠壓層壓成形、壓延成形、薄片成形、纖維成形、吹塑 成形、射出成形、旋轉成形、被覆成形。於各種薄膜成形 中,可爲於至少單側一層上使用本發明的不飽和羧酸接枝 聚烯烴之共擠壓成形或多層層合成形,另一方面,亦可爲 使用溶劑之流延薄膜成形。 作爲多層化的基材,不僅爲聚醯胺、聚酯、乙烯-乙 -28- 200925171 烯醇樹脂等之樹脂製薄膜,亦可爲與紙、鋁箔、不鏽鋼箱 、銅箔等之金屬箔、玻璃等之異種素材的層合。 使用溶液流延法時,例如可將使本發明的不飽和羧酸 接枝聚烯烴溶解於l,i,2-三氯乙烷、氯仿、甲基乙基酮等 之溶劑之溶液流延於聚對苯二甲酸乙二醇酯薄膜上’藉由 揮發去除溶劑而成膜。 可列製造本發明的不飽和羧酸接枝聚烯烴之單層薄膜 0 、或使單層薄片與其他樹脂、或含有無機、金屬材料之其 他的素材層合之多層薄膜、多層薄片、多層擠壓層壓成形 體、多層吹塑容器、多層2色成形體、多層異形擠壓成形 體、與金屬構件的嵌入式射出成形體等。具體而言,可列 舉使阻擋層之EVOH薄膜或薄片多層化之食品包裝薄膜、 食品容器、或汽油槽、多層纖維、鋼管被覆、不鏽鋼板、 彩鋼板、貼銅層合薄膜、銅線的表面接著劑、銅線被覆等 爲代表的金屬素材的表面或内面以本發明的不飽和羧酸接 〇 枝聚烯烴進行塗佈之被覆製品、或内層具有樹脂及此等的 發泡體而表面爲金屬之多層成形體中表面金屬層與内層樹 脂層之中間接著層、無機玻璃彼此間的接著所使用之夾層 玻璃用中間薄膜、光學薄膜與玻璃的接著所使用的中間層 薄膜、提高各種樹脂與無機充塡材、奈米塡充劑或顏料的 親和性之相溶化劑、塗料、墨水等。 此外’本發明的不飽和羧酸接枝聚烯烴,可作爲熱溶 著性薄膜使用,此熱溶著性薄膜適合作爲各種熱可塑性樹 脂與金屬所成的層合物的中間接著層、或絕緣性中間接著 -29- 200925171 層使用。此用途中可將本發明的樹脂成形爲薄膜狀,於作 爲熱熔著性薄膜上可使用。作爲可接著的樹脂,可列舉聚 醯亞胺、聚苯硫醚、聚碳酸酯、聚醯胺、聚對苯二甲酸乙 二醇酯等之聚酯所代表的縮合系聚合物、藉由EVOH等之 自由基聚合所衍生的聚合物、藉由芳環烯金屬衍生物觸媒 、齊格勒觸媒等之配位聚合所得到的各種聚烯烴等,適合 作爲以玻璃、金屬等爲基材層所形成的各種層合物的中間 0 接著層使用。而且必要時在由金屬素材、樹脂素材所形成 的多層層合板上、或多層層合薄膜上,將本發明的樹脂藉 由熱溶著法再層合,可簡便地於製造可裝置於金屬素材、 或各種樹脂素材上之多層層合板、或多層層合薄膜。 以下詳細地說明關於使用本發明的不飽和羧酸接枝聚 烯烴之具體的用途。 1)作爲第1具體的用途,說明關於由金屬層及樹脂 層的至少1層,與彈性電絕緣層所構成,金屬層及/或樹 Q 脂層與彈性電絕緣層經接著的多層層合物,彈性電絕緣層 爲由本發明的不飽和羧酸接枝聚烯烴所成的多層層合物。 發現此仍可提供由本發明的不飽和羧酸接枝聚烯烴所 製造的層狀物,亦即,利用薄膜、薄片或膠帶藉由以短時 間、加壓下、比較的低溫進行加熱與金屬層等堅固地接著 ,具有優異的彈性的性質,可製造由金屬層及樹脂層的至 少1層、與彈性電絕緣層所構成的多層層合物,因爲此多 層層合物係金屬層及/或樹脂層與彈性電絕緣層接著,故 可提供具有熱硬化性樹脂難以達成的優異熱衝撃性之多層 -30- 200925171 層合物。 本發明的多層層合物,只要是由金屬層及樹脂層的至 少1層、與彈性電絕緣層所構成,金屬層及/或樹脂層與 彈性電絕緣層經接著者即可,並沒任何限制,可構成活用 彈性電絕緣層對金屬層的堅固的接著性,由金屬層及樹脂 層的至少1層所構成之多層層合物。The time required for removing the solvent from the polymer solution by the drum dryer may be appropriately selected depending on the type of the solvent to be used and the temperature of the drum dryer, but it is usually 10 seconds to 5 minutes. In addition, chloroform, 1,1,2-trichloroethane, or the like, which is a halogen solvent having a boiling point of 120 ° C or less under normal pressure, which is volatilized by a drum dryer, is used in the upper portion of the drum dryer. The recovery line is recycled and can be reused in the reaction. The isolated polymer can be processed into a soft line, a flake, a strand or a sheet as necessary, and the polymer which has been shaped once is supplied to the 1 axis or, if necessary, to the 2 axis extrusion. The machine is extruded after the polymer is melted, cut in a single strand, or cut in water to pelletize. The extrusion temperature at this time is not particularly limited. However, in order to allow the polyolefin to be sufficiently melted and then smoothly extruded, and to suppress decomposition, coloring, and the like of the polyolefin, it is preferably 100 to 300 ° C, more preferably It is 150~2 5 0 °C. By this method, not only a plastic material, but also an unsaturated carboxylic acid graft polyolefin excellent in adhesion to a dissimilar material and excellent in color, can be obtained at low cost, easily, and safely. -25- 200925171 In the unsaturated carboxylic acid graft polyolefin of the present invention, other resins may be blended. As the other resin, for example, not only the above polyolefin resin to which no graft reaction is applied, but also polystyrene, poly-α-methylstyrene, polystyrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene Acrylic resin such as olefin resin, acrylic resin such as polyacrylic acid or polymethacrylic acid-methyl group, polyvinyl chloride resin, polyvinylidene chloride resin, polyamide, polyester, polycarbonate resin, fluorine Resin, polyoxyalkylene resin, polyphenylene ether resin (0 ΡΡΟ), polyphenylene sulfide resin (PPS), polyimine, polyfluorene, polyether oxime, polyetheretherketone, polyterephthalic acid Butylene glycol ester resin (ΡΒΤ), polyoxymethylene resin (ΡΟΜ), epoxy resin, polyurethane, urea resin, phenol resin, melamine resin, cellulose, petroleum resin, and the like. If necessary, the reactive functional group or other resin of the terminal group may be chemically reacted with the unsaturated carboxylic acid group of the present invention, or may be blended by physical interaction between the functional groups. Further, a coupling agent such as a decane coupling agent or a titanium coupling agent may be added as the third component, and Q may improve compatibility with other resins or improve adhesion. In the unsaturated carboxylic acid graft polyolefin of the present invention, an elastomer or a rubber component may be blended, and examples of the elastomer or rubber component include natural rubber, isoprene rubber, butadiene rubber, and styrene-butylene. Diene rubber, butyl rubber, ethylene-propylene rubber, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin rubber, nitrile rubber, acrylic rubber, urethane rubber, poly Alkane rubber, fluororubber, etc. Further, examples of the thermoplastic elastomer (TPE) include styrene-based TPE (SBC) such as SBS and SIS, polyolefin-based TPE (TPO), and urethane formate B-26-200925171 ester system (TPU). Ester-based elastomer (ΤΡΕΕ), polyamine-based elastomer (TPA), polyoxyalkylene-based TPE, and fluorine-based TPE. In the unsaturated carboxylic acid-grafted polyolefin, the following various additives may be blended; examples of the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant such as a composite antioxidant; Examples of the stabilizer include an organic phosphite stabilizer, a thioether stabilizer, and a hindered amine light stabilizer; and examples of the chelating agent include a spherical ruthenium-filling agent and a plate-like chelating agent. As the adhesive, for example, liquid and solid bisphenol A epoxy resin, epoxy cresol novolac, epoxy phenol novolac, bisphenol A epoxy resin and epoxy cresol novolac Or a mixture with epoxy phenol novolacs bis bisphenol F epoxy resin, aliphatic epoxy resin, etc.; as the epoxy crosslinking agent, a wrong compound of boron trifluoride, dicyandiamide, polyamine Examples, polyamines, etc.; as a flame retardant, for example, bromination of ethylene bistetrabromophthalimide, decabromodiphenyl oxide, SA YTEX 8010, tetradecbromodiphenoxybenzene, etc. Flame retardant, tri-Q cerium oxide, antimony pentoxide, boric acid , a flame retardant such as FIREBRAKE ZB, a chlorinated flame retardant such as DECLORANE PLUS, etc.; as a slip agent, a magnesium salt of a higher fatty acid such as stearic acid, oleic acid or lauric acid of a higher fatty acid metal salt; An alkaline earth metal salt such as a calcium salt or a barium salt, a cadmium salt, a zinc salt or a lead salt, and an alkali metal salt such as a sodium salt, a potassium salt or a lithium salt; and examples of the other additives include an antistatic agent and a colorant. , natural oils, synthetic oils, waxes, plasticizers, nucleating agents, heavy metal inactivating agents, processing aids, waxes, arc inhibitors, alumina, decane-treated talc, mica, feldspar and wollastonite Drop inhibitors and the like. The amount of the additive to be added is not particularly limited to -27 to 200925171, but in order to exhibit the additive effect of the additive and to maintain the adhesion, it is 20 to 40 parts by weight based on 100 parts by weight of the unsaturated carboxylic acid graft polyolefin. Preferably. Further, the unsaturated carboxylic acid graft polyolefin of the present invention may contain conductive fine particles. Examples of the conductive fine particles include gold, silver, copper, molybdenum, nickel, carbon, tin, indium, palladium, ruthenium, osmium, iridium, osmium, aluminum, iron, indium, magnesium, platinum, rhodium, tin, and zinc. Cobalt, chromium, titanium, giant, tungsten, carbon black, and the like, the unsaturated carboxylic acid grafted polyolefin of the present invention is mixed with other resins, elastomers or rubber components, various additives, and conductive fine particles, and may be mixed with a solution or a conventional one. The kneading method used, as a kneading party, can be exemplified by a single-axis extruder, a two-axis extruder, a Brabender-type compacting machine, a Banbury kneading machine, a drum, a kneading machine, a Henry Shirley kneading machine, and a V Blending machine, drum mixing machine, etc. The unsaturated carboxylic acid-grafted polyolefin of the present invention can be formed into a film by a conventional method, and as a film forming method, a solution casting method can be used in addition to the melt extrusion method. When a melt forming method is used, a general processing method of a polyolefin resin can be used, and examples thereof include blown film forming, tape casting, extrusion lamination molding, calender molding, sheet molding, fiber molding, blow molding, and injection molding. , rotational molding, and coating. In various film forming, the co-extrusion or multi-layer synthesis of the unsaturated carboxylic acid grafted polyolefin of the present invention may be used on at least one side layer, and on the other hand, a cast film using a solvent may be used. Forming. The multilayered substrate is not only a resin film made of polyamine, polyester, or ethylene-B-28-200925171 enol resin, but also a metal foil such as paper, aluminum foil, stainless steel case, or copper foil. Lamination of different materials such as glass. When the solution casting method is used, for example, a solution in which the unsaturated carboxylic acid graft polyolefin of the present invention is dissolved in a solvent such as 1,1,2-trichloroethane, chloroform or methyl ethyl ketone may be cast. On the polyethylene terephthalate film, a film is formed by volatilization to remove the solvent. A single layer film 0 of the unsaturated carboxylic acid grafted polyolefin of the present invention, or a multilayer film, a multilayer sheet, a multi-layered film in which a single layer sheet is laminated with other resins or other materials containing inorganic or metallic materials. A press-molded molded body, a multilayer blow molded container, a multilayered 2-color molded body, a multi-layered shaped extruded body, an embedded injection molded body of a metal member, or the like. Specifically, a food packaging film, a food container, or a gasoline tank, a multilayer fiber, a steel pipe coating, a stainless steel plate, a color steel plate, a copper-clad laminate film, or a copper wire surface in which a EVOH film or a sheet of a barrier layer is multilayered may be mentioned. a coated article coated with the unsaturated carboxylic acid-bonded lychee polyolefin of the present invention on the surface or the inner surface of the metal material represented by the coating agent, the copper wire coating, or the like, or the inner layer having a resin and a foam thereof, and the surface is In the multilayer molded body of metal, the intermediate layer of the surface metal layer and the inner resin layer, the intermediate film for laminated glass used for the inorganic glass, the intermediate film for the optical film and the glass, and the various resins and A compatibilizing agent, a paint, an ink, or the like of an affinity of an inorganic filler, a nanofiller, or a pigment. Further, the unsaturated carboxylic acid grafted polyolefin of the present invention can be used as a heat-soluble film which is suitable as an intermediate layer or a layer of a laminate of various thermoplastic resins and metals. Sexuality is then used in the -29-200925171 layer. In this application, the resin of the present invention can be formed into a film shape and used as a heat-fusible film. Examples of the recyclable resin include a condensed polymer represented by a polyester such as polyimide, polyphenylene sulfide, polycarbonate, polyamine or polyethylene terephthalate, and EVOH. A polymer derived by radical polymerization, a polyolefin obtained by coordination polymerization of an aromatic cycloolefin metal derivative catalyst or a Ziegler catalyst, etc., and is suitable as a substrate made of glass or metal. The middle 0 of the various laminates formed by the layers is used in the next layer. Further, if necessary, the resin of the present invention is laminated by a hot-melting method on a multilayer laminate formed of a metal material or a resin material, or a multilayer laminated film, so that it can be easily fabricated into a metal material. , or a multilayer laminate on various resin materials, or a multilayer laminate film. The specific use of the unsaturated carboxylic acid grafted polyolefin of the present invention is explained in detail below. 1) As a first specific use, it is explained that at least one layer of a metal layer and a resin layer is formed of an elastic electrically insulating layer, and the metal layer and/or the Q-lipid layer and the elastic electrically insulating layer are laminated by a subsequent multilayer. The elastic electrically insulating layer is a multilayer laminate formed from the unsaturated carboxylic acid grafted polyolefin of the present invention. It has been found that this can still provide a layer made from the unsaturated carboxylic acid grafted polyolefin of the present invention, that is, heating and metal layer by means of a film, sheet or tape by a short time, under pressure, and at a relatively low temperature. Sturdy and then, with excellent elastic properties, it is possible to manufacture a multilayer laminate composed of at least one layer of a metal layer and a resin layer and an elastic electrically insulating layer, since the multilayer laminate is a metal layer and/or The resin layer is followed by the elastic electrically insulating layer, so that a multilayer -30-200925171 laminate having excellent thermal repellency which is difficult to achieve with a thermosetting resin can be provided. The multilayer laminate of the present invention may be composed of at least one layer of a metal layer and a resin layer and an elastic electrically insulating layer, and the metal layer and/or the resin layer and the elastic electrically insulating layer may be passed through without any The restriction may constitute a multilayer laminate composed of at least one of a metal layer and a resin layer, which is a strong adhesive property of the elastic electrically insulating layer to the metal layer.
作爲本發明的多層層合物的構成,可列舉例如金屬層 /彈性電絕緣層、樹脂層/彈性電絕緣層之2層的層合物, 金屬層/彈性電絕緣層/樹脂層、金屬層/彈性電絕緣層/金 屬層等之3層的層合物、金屬層/彈性電絕緣層/金屬層/彈 性電絕緣層、金屬層/彈性電絕緣層/樹脂層/彈性電絕緣層 、樹脂層/彈性電絕緣層/金屬層/彈性電絕緣層等之4層的 層合物等,但此等的例子並不能限制本發明,可構成更多 層的層合物。 此外,只要是可熱接著,各層的厚度沒有限制,對於 金屬層、或樹脂層非平坦,層合由金屬材料所形成的電路 之具有凹凸者亦可同樣地適用。而且,金屬層並非爲層的 表面整體被覆金屬層的狀態,具有由樹脂層與金屬層所構 成的表面之層同樣地亦可爲層合物。 本發明的多層構造體中金屬層之意,係指由金屬所成 的箔、薄膜、薄片、板狀物等之平坦的平面狀金屬成形體 、及、將具有此等的成形體再經2次加工的立體的形狀之 3次元成形體的總稱,此等2次元、或3次元的成形體可 爲矩形形狀者,亦可形成爲如電子電路之複雜的平面形狀 -31 - 200925171 ,因此,層並非平面時可具有持有特定且非一定的曲率之 面。其中,金屬係可列舉例如鋼、銅、鋁、錫鍍敷鋁、銀 鍍敷銅、經硏磨的不鏽鋼、經噴射(blasting )處理的鋼 等,而且,表面以異種金屬鎪敷的金屬等亦同樣地可適用 〇 本發明的多層構造體中樹脂層之意,係指以由熱可塑 性樹脂、熱硬化性樹脂等所成的薄膜、薄膜、薄片、板狀 0 物等之平坦的平面狀成形體爲首,藉由射出成形、擠壓成 形、注型成形等之一般樹脂的成形所使用的方法等所得到 的3次元形狀的各種成形體的總稱,此等成形體的形狀並 沒有制限,包括任何形狀者,因此,層並非平面時可具有 持有特定且非一定的曲率之面。其中,熱可塑性樹脂係可 列舉例如聚醯亞胺、聚醯胺、聚碳酸酯、聚苯硫醚等,熱 硬化性樹脂係可列舉例如環氧樹脂、酚樹脂、聚矽氧烷系 樹脂等。 〇 本發明的多層層合物中彈性電絕緣層,係與金屬層等 可熱熔融接著之層,由本發明的不飽和羧酸接枝聚烯烴所 成。藉由使彈性電絕緣層由不飽和羧酸接枝聚烯烴所成, 可製造絕緣性、熱衝撃性、接著強度優異的層合物。 於接枝反應中所生成的不飽和羧酸接枝聚烯烴與溶劑 之分離,可使用鼓式乾燥機、水蒸氣蒸餾、附有排氣口的 擠壓機等一般常用的方法,但使用鼓式乾燥機由經濟的利 用面而言特別佳。 於反應步驟中使不飽和羧酸接枝聚烯烴與溶劑分離之 -32- 200925171 方法,使用鼓式乾燥機時,係在結束反應步驟後,將此反 應溶液由反應器連續地送料至經加熱的鼓式乾燥機,將生 成物從聚合物溶液離析出來。此時的鼓式乾燥機的溫度, 爲了在持續促進乾燥下’抑制聚合物的著色、熱劣化、交 聯’較佳爲120〜20CTC的範圍,更佳爲i50~165t:,聚合 物係以薄膜狀從轉筒剝離後離析。 此外,藉由鼓式乾燥機經揮發的1,1,2-三氯乙烷,係 0 可使用被設置於鼓式乾燥機上部的回收線進行回收,再度 使用於反應。 藉由鼓式乾燥機從聚合物溶液去除溶劑所需要的時間 ’依所使用的溶劑的種類、及鼓式乾燥機的溫度而不同, 可適當的選擇,但通常爲10秒〜5分鐘。 經離析的聚合物必要時可加工成軟線狀、薄片狀、股 線狀或片狀,將此等經1次賦形的聚合物,再供給至1軸 ’或必要時供給至2軸擠壓機,使聚合物熔融後擠壓,單 〇 股切割、或亦可在水中切割而顆粒化。此時的擠壓溫度並 沒有特別的限制,但爲了使所使的聚烯烴充分地熔融後順 利地擠壓,而且抑制聚烯烴的分解、著色等,較佳爲 100~300°C,更佳爲 150~2 5 0°C。 本發明的多層層合物中電氣彈性絕緣層,可將不飽和 羧酸接枝聚烯烴藉由一般加工聚烯烴樹脂之成形方法而薄 膜化,可列舉吹塑薄膜成形、流延成形 '擠壓層壓成形、 壓延成形、薄片成形、纖維成形、吹塑成形、射出成形、 旋轉成形、被覆成形。此外,必要時於薄膜成形中,可爲 -33- 200925171 將本發明之經接枝不飽和羧酸的聚烯烴使用於至少單側一 層之共擠壓成形或多層層合成形。The composition of the multilayer laminate of the present invention may, for example, be a laminate of a metal layer/elastic electrically insulating layer, a resin layer/elastic electrically insulating layer, a metal layer/elastic electrically insulating layer/resin layer, a metal layer. /Layer of three layers of elastic electrical insulating layer / metal layer, metal layer / elastic electric insulating layer / metal layer / elastic electric insulating layer, metal layer / elastic electric insulating layer / resin layer / elastic electric insulating layer, resin A laminate of four layers of a layer/elastic electrically insulating layer/metal layer/elastic electrically insulating layer or the like, but such examples do not limit the invention, and may constitute a laminate of more layers. Further, as long as it is heat-receivable, the thickness of each layer is not limited, and the metal layer or the resin layer is not flat, and the unevenness of the circuit formed of the metal material may be similarly applied. Further, the metal layer is not in a state in which the entire surface of the layer is coated with the metal layer, and the layer may be a layer similarly to the layer formed of the resin layer and the metal layer. The term "metal layer" in the multilayer structure of the present invention means a flat planar metal molded body of a foil, a film, a sheet, a plate or the like formed of a metal, and a molded body having such a shape. The generalized name of the three-dimensional shaped body of the three-dimensional shape of the secondary processing, and the two-dimensional or three-dimensional molded body may have a rectangular shape, or may be formed into a complicated planar shape such as an electronic circuit -31 - 200925171, and therefore, When the layer is not planar, it may have a face that holds a specific and non-constant curvature. The metal system may, for example, be steel, copper, aluminum, tin-plated aluminum, silver-plated copper, honed stainless steel, blasted steel, or the like, and a metal coated with a dissimilar metal. The same applies to the resin layer in the multilayer structure of the present invention, and is a flat planar shape of a film, a film, a sheet, or a plate-like material formed of a thermoplastic resin or a thermosetting resin. The molded article is a general term for various molded bodies of a three-dimensional shape obtained by a method used for molding a general resin such as injection molding, extrusion molding, or injection molding, and the shape of these molded bodies is not limited. , including any shape, therefore, the layer may have a face with a specific and non-constant curvature when it is not planar. In addition, examples of the thermoplastic resin include, for example, polyimine, polyamine, polycarbonate, and polyphenylene sulfide, and examples of the thermosetting resin include an epoxy resin, a phenol resin, and a polyoxyalkylene resin. .弹性 The elastic electrically insulating layer of the multilayer laminate of the present invention is a layer which is thermally fused with a metal layer or the like, and is formed of the unsaturated carboxylic acid grafted polyolefin of the present invention. By forming the elastic electrically insulating layer from the unsaturated carboxylic acid grafted polyolefin, it is possible to produce a laminate having excellent insulating properties, thermal repellency, and adhesion strength. The separation of the unsaturated carboxylic acid grafted polyolefin formed in the grafting reaction and the solvent can be carried out by a commonly used method such as a drum dryer, steam distillation, or an extruder equipped with a vent, but using a drum. Dryers are particularly good at economical use. In the reaction step, the unsaturated carboxylic acid grafted polyolefin is separated from the solvent by the method of -32-200925171. When the drum dryer is used, the reaction solution is continuously fed from the reactor to the heated after the end of the reaction step. A drum dryer that separates the product from the polymer solution. The temperature of the drum dryer at this time is preferably in the range of 120 to 20 CTC, more preferably i50 to 165 t in order to suppress the coloring, thermal deterioration, and crosslinking of the polymer while continuously promoting drying. The film shape was separated from the drum and separated. Further, the 1,1,2-trichloroethane which is volatilized by the drum dryer can be recovered by using a recovery line provided on the upper portion of the drum dryer, and used again for the reaction. The time required for removing the solvent from the polymer solution by the drum dryer can be appropriately selected depending on the type of the solvent to be used and the temperature of the drum dryer, but it is usually 10 seconds to 5 minutes. The isolated polymer can be processed into a soft line, a flake, a strand or a sheet as necessary, and the polymer which has been shaped once is supplied to the 1 axis 'or, if necessary, to the 2 axis extrusion The machine is used to melt the polymer and then extrude it, cut it in a single strand, or cut it in water to pelletize it. The extrusion temperature at this time is not particularly limited. However, in order to sufficiently melt the polyolefin to be melted and to suppress decomposition and coloring of the polyolefin, it is preferably 100 to 300 ° C, more preferably It is 150~2 50 °C. The electroelastic insulating layer in the multilayer laminate of the present invention can be obtained by thinning the unsaturated carboxylic acid grafted polyolefin by a general processing method for processing a polyolefin resin, and can be exemplified by blown film forming and cast forming. Lamination molding, calendering, sheet molding, fiber molding, blow molding, injection molding, rotational molding, and coating molding. Further, in the film formation as necessary, the polyolefin of the graft-unsaturated carboxylic acid of the present invention may be used in a co-extrusion or multi-layered form of at least one side layer in the range of -33 to 200925171.
作爲多層化的基材,不僅是聚醯胺、聚酯、乙烯-乙 烯醇樹脂等之樹脂製薄膜,亦可與紙、鋁箔、不鏽鋼箔、 銅箔等之金屬箔、鋁板、不鏽鋼板、銅板、玻璃等之異種 素材層合。此外,若必須爲厚度薄的層,可將經接枝不飽 和羧酸的聚烯烴溶解於有機溶劑後,將此溶液流延至PET 等之基材上,使溶劑揮發後剝離之方法,亦即,藉由可溶 劑流延法進行薄膜化。而且,將使上述的聚烯烴溶解於有 機溶劑的溶液以一定的膜厚直接地塗佈於前述的金屬箔、 金屬薄片、金屬板等、或、各種的樹脂、各種的玻璃、紙 等之異種材料之層上,之後使溶劑揮發,可得到經賦予接 著性、絕緣性、熱熔著性之2層構造的金屬箔層合物、金 屬薄片層合物、金屬板層合物、樹脂薄膜層合物、樹脂板 層合物、樹脂薄片層合物、玻璃層合物、紙層合物。 另一方面,使用溶劑之流延薄膜成形亦可,使用溶液 流延法時,例如可藉由將使本發明的樹脂溶解於1,1,2-三 氯乙烷、氯仿、甲基乙基酮等之溶劑的溶液流延於聚對苯 二甲酸乙二醇酯薄膜上,揮發去除溶劑而成膜。 可製造本發明的不飽和羧酸接枝聚烯烴之單層薄膜、 或使單層薄片與其他樹脂、或含有無機、金屬材料之其他 的素材層合之多層薄膜、多層薄片、多層擠壓層壓成形體 、多層吹塑容器、多層2色成形體、多層異形擠壓成形體 、與金屬構件的嵌入式射出成形體等。具體而言,可列舉 -34- 200925171 使阻擋層之EVOH薄膜或薄片多層化之食品包裝薄膜、食 品容器、或汽油槽、多層纖維、鋼管被覆、不鏽鋼板、彩 鋼板、貼銅層合薄膜、銅線的表面接著劑、銅線被覆等爲 代表的金屬素材的表面或内面以本發明的不飽和羧酸接枝 聚烯烴進行塗佈之被覆製品、或内層具有樹脂及此等的發 泡體而表面爲金屬之多層成形體中表面金屬層與内層樹脂 層之中間接著層、無機玻璃彼此間的接著所使用之夾層玻 0 璃用中間薄膜、光學薄膜與玻璃的接著所使用的中間層薄 膜、提高各種樹脂與無機充塡材、奈米塡充劑或顏料的親 和性之相溶化劑、塗料、墨水等。 本發明的多層層合物中,可、將彈性電絕緣層使用自動 化製程接著於薄膜、薄片或膠帶之金屬層進行絕緣被覆。 例如使其通過使薄膜接著金屬層的層壓用滾筒而使其接著 之方法,可藉由將金屬層於彈性薄膜的熔融溫度附近預熱 備用之方法而接著,另一方面,在不預熱金屬層下藉由層 〇 壓機進行加熱壓黏之方法同樣亦可,只要是可加熱至彈性 電絕緣層表現出接著性之溫度即可,不限制於任何層合方 法,預熱金屬時,可使用熱風的噴吹或誘導加熱。在任何 情況中,皆可活用本發明的樹脂爲熱可塑性這點’使層合 物製造的自動化輕易達到。 本發明的多層層合物中彈性電絕緣層的熔融接著溫度 係40~25(TC,低於40°C時’會有彈性電絕緣層的熔解不 充分、接著強度降低的情況’此外超過250 °c時,會有因 爲彈性電絕緣層的熱劣化等看到著色之情況,此外,會有 -35- 200925171 因爲彈性電絕緣層的劣化而導致接著強度的降低的情況, 較佳爲80〜200 °C。The multilayered substrate is not only a resin film such as polyamide, polyester or ethylene-vinyl alcohol resin, but also a metal foil such as paper, aluminum foil, stainless steel foil or copper foil, aluminum plate, stainless steel plate or copper plate. Lamination of different materials such as glass. Further, if it is necessary to form a layer having a small thickness, a method in which a polyolefin grafted with an unsaturated carboxylic acid is dissolved in an organic solvent, and the solution is cast onto a substrate such as PET to volatilize the solvent and then peeled off, that is, Thin film formation by solvent casting method. Further, the solution in which the above polyolefin is dissolved in an organic solvent is directly applied to the above-mentioned metal foil, metal foil, metal plate, or the like, or various resins, various kinds of glass, paper, or the like, with a constant film thickness. On the layer of the material, the solvent is then volatilized to obtain a metal foil laminate, a metal foil laminate, a metal sheet laminate, and a resin film layer having a two-layer structure imparting adhesion, insulation, and thermal fusion properties. Compound, resin sheet laminate, resin sheet laminate, glass laminate, paper laminate. On the other hand, casting film using a solvent may be formed by using a solution casting method, for example, by dissolving the resin of the present invention in 1,1,2-trichloroethane, chloroform, methylethyl group. A solution of a solvent such as a ketone is cast on a polyethylene terephthalate film, and a solvent is removed by evaporation to form a film. A single layer film of the unsaturated carboxylic acid grafted polyolefin of the present invention, or a multilayer film, a multilayer sheet, a multilayer extrusion layer which laminates a single layer sheet with other resins or other materials containing inorganic or metallic materials A press-formed body, a multilayer blow-molded container, a multilayer two-color molded body, a multi-layer shaped extruded body, an embedded injection molded body of a metal member, or the like. Specifically, a food packaging film, a food container, or a gasoline tank, a multilayer fiber, a steel pipe coating, a stainless steel plate, a color steel plate, a copper-clad laminate film, which is a multilayered EVOH film or sheet, may be cited as -34-200925171. A coated article coated with the unsaturated carboxylic acid grafted polyolefin of the present invention on the surface or inner surface of a metal material represented by a surface line of a copper wire, a copper wire coating, or the like, or an inner layer having a resin and a foam thereof The intermediate layer of the surface metal layer and the inner resin layer in the multilayer molded body of the metal, the interlayer film for the laminated glass used for the inorganic glass, and the intermediate film for the optical film and the glass. A compatibilizing agent, a coating material, an ink, etc., which improve the affinity of various resins with inorganic fillers, nano-fillers or pigments. In the multilayer laminate of the present invention, the elastic electrically insulating layer may be subjected to an insulating coating using an automatic process followed by a metal layer of a film, a sheet or a tape. For example, by subjecting the film to the lamination of the metal layer by a roller, the method of preheating the metal layer near the melting temperature of the elastic film can be followed by, on the other hand, without preheating. The method of heating and pressure-bonding under the metal layer by a layer rolling machine is also possible, as long as it can be heated to a temperature at which the elastic electrical insulating layer exhibits adhesion, and is not limited to any lamination method, when preheating the metal, Hot air blowing or induction heating can be used. In any case, the use of the resin of the present invention as a thermoplastic means that the automation of the manufacture of the laminate is easily achieved. In the multilayer laminate of the present invention, the elastic electrically insulating layer is melted at a temperature of 40 to 25 (TC, when the temperature is lower than 40 ° C, the melting of the elastic electrical insulating layer is insufficient, and the subsequent strength is lowered) At °c, there is a case where coloring is observed due to thermal deterioration of the elastic electric insulating layer, and in addition, there is a case where the strength of the elastic electric insulating layer is deteriorated due to deterioration of the elastic electric insulating layer, preferably 80~. 200 °C.
本發明的多層層合物中彈性電絕緣層的熔融接著所使 用的壓力,只要電絕緣層熔著即可,並沒有特別的限制, 但爲了維持接著界面的密著性,且,抑制因爲彈性電絕緣 層的流動抑制層厚度的降低,較佳爲0.01〜20MPa,再更 佳爲0.01〜5MPa,接著時的壓力可依被黏著物的種類而適 當選擇。 本發明中彈性電絕緣層適用於經閃鏟錫鍍敷鋁或銀之 銅等的金屬層時,形成與金屬層堅固地接著的彈性電絕緣 層。具有藉由取代溶融接著環氧粉末,使用彈性電絕緣層 ,可以低於如錫鍍敷的低熔點金屬軟化的溫度之溫度進行 接著之特徵。此外,因爲所得到的彈性電絕緣層具有彈性 ,可適應溫度的急速變化、基板的彎曲等。此等的特性係 大寬度降低對金屬鍍敷層帶來損傷的危險,與流動層塗佈 技術等比較下操作性亦優異。 本發明的多層層合物,與先前技術用一直以來所使用 之對熱衝撃弱的熱硬化性樹脂不同,藉由利用彈性電絕緣 層,成爲熱衝撃強、接著性優異的層合物。而且,本發明 藉由利用不飽和羧酸接枝聚烯烴作爲此彈性電絕緣層,藉 由以4 0〜2 5 0 °C之比較的低溫的條件下進行加熱壓黏,可短 時間且連續地製造多層層合物,提供在產業上適用範圍極 廣的層合物及其製造方法。 2)作爲第2具體的用途,說明關於以金屬層、接著 -36- 200925171 層及木材的順序所構成,金屬層與木材以接著層經接著之 多層層合物,其係接著層爲由本發明的不飽和羧酸接枝聚 烯烴所成的多層層合物。 發現此仍可提供由本發明的不飽和羧酸接枝聚烯烴所 製造的薄膜、薄片或膠帶,藉由以短時間、加壓下、比較 的低溫進行加熱,使金屬層與木材等堅固地接著,可製造 由由金屬層/接著層/木材所成的層合物。The pressure used in the melting of the elastic electrically insulating layer in the multilayer laminate of the present invention is not particularly limited as long as the electrically insulating layer is fused, but in order to maintain the adhesion of the interface, and to suppress the elasticity The thickness of the flow-inhibiting layer of the electrically insulating layer is preferably from 0.01 to 20 MPa, more preferably from 0.01 to 5 MPa, and the pressure at the subsequent pressure can be appropriately selected depending on the kind of the adherend. In the present invention, the elastic electrically insulating layer is suitable for forming a resiliently electrically insulating layer which is firmly adhered to the metal layer when a metal layer such as aluminum or silver copper is plated by flashing tin. It is characterized by a temperature at which the epoxy resin is replaced by melting, and the elastic electrically insulating layer is used, which can be lower than the temperature at which the low melting point metal such as tin plating is softened. Further, since the obtained elastic electrically insulating layer has elasticity, it can be adapted to rapid changes in temperature, bending of the substrate, and the like. These characteristics are such that the large width reduces the risk of damage to the metal plating layer, and is excellent in operability compared with the flow layer coating technique. The multilayer laminate of the present invention is a laminate which is excellent in thermal strength and excellent in adhesion by utilizing an elastic electrically insulating layer, unlike the thermosetting resin which has been conventionally used for heat-shrinking. Moreover, the present invention can be used for the short time and continuous by using the unsaturated carboxylic acid grafted polyolefin as the elastic electrically insulating layer by heating and pressing at a low temperature of 40 to 250 ° C. The multilayer laminate is produced to provide a laminate which is widely used in the industry and a method for producing the same. 2) As a second specific use, it is explained that the metal layer and the layer of -36-200925171 and the wood are sequentially formed, and the metal layer and the wood are successively laminated with the multilayer layer, and the subsequent layer is the present invention. A multilayer laminate of an unsaturated carboxylic acid grafted polyolefin. It has been found that this can still provide a film, sheet or tape made of the unsaturated carboxylic acid grafted polyolefin of the present invention, and the metal layer and the wood are firmly adhered by heating in a short time, under pressure, and at a relatively low temperature. A laminate formed of a metal layer/attach layer/wood can be produced.
本發明的多層層合物,係以金屬層、接著層及木材的 順序所構成,金屬層與木材以接著層經接著者。 本發明的多層構造體中金屬層之意,係指由金屬所成 的箔、薄膜、薄片、板狀物等之平坦的平面狀金屬成形體 、及、具有的立體的形狀之3次元成形體的總稱。上述的 平面狀金屬成形體中,對其厚度並沒有特別的限制,此外 此處所謂的3次元的成形體,包括具有如切削金屬塊後所 得到的特定的立體形狀者。其中,金屬係可列舉例如鋼、 銅、鋁、錫鍍敷鋁、銀鍍敷銅、不鏽鋼等,本發明並非限 定於此等,任何金屬皆可使用,而且,表面以異種金屬鑪 敷的金屬等亦同樣地可適用。 本發明的多層層合物中木材之意,係指將木材切成薄 片所得到的薄片狀物、使天然木本身成形爲特定的形狀之 成形體、將經粉碎的木材以黏合劑凝固而成形爲薄片、薄 膜、板、塊狀之成形材等,此等的成形體必要時可進行曲 面加工等之2次加工’此外’爲薄片、薄膜狀時,例如藉 由適切的方法以和紙、洋紙、纖維素系聚合物、合成樹脂 -37- 200925171 薄膜等補強薄片、薄膜的裏面亦可。其中,木材之意’可 列舉白樺、竹、橡樹、斑木樹、沙貝梨、楓、鳥眼楓、紫 檀、黑檀、木瓜、樱、大葉桉、刺楸、杉、合桃、非洲紫 壇等,但本發明並非限定於此等,只要是可成爲上述所示 形狀的成形體即可,並沒有任何限制皆可使用。 ΟThe multilayer laminate of the present invention is composed of a metal layer, an adhesive layer and a wood in the order of the metal layer and the wood. The metal layer in the multilayer structure of the present invention means a flat planar metal molded body of a foil, a film, a sheet, a plate or the like made of a metal, and a three-dimensional shaped body having a three-dimensional shape. The general term. In the above-mentioned planar metal molded body, the thickness thereof is not particularly limited, and the so-called three-dimensional molded body includes a specific three-dimensional shape obtained by cutting a metal block. In addition, examples of the metal system include steel, copper, aluminum, tin-plated aluminum, silver-plated copper, and stainless steel. The present invention is not limited thereto, and any metal can be used, and the metal coated on the surface is made of a dissimilar metal. The same applies to the same. The term "wood" in the multilayer laminate of the present invention means a sheet obtained by cutting wood into a sheet, a shaped body in which natural wood itself is formed into a specific shape, and solidification of the pulverized wood by a binder. In the case of a sheet, a film, a sheet, a block-shaped material, or the like, these molded bodies can be subjected to secondary processing such as curved surface processing as needed. When the film is in the form of a sheet or a film, for example, a paper or a paper is used by a suitable method. , Cellulose-based polymer, synthetic resin -37- 200925171 It is also possible to use a reinforcing sheet such as a film or a film. Among them, the meaning of wood can be listed as white birch, bamboo, oak, sapling, sand pear, maple, bird eye maple, red sandalwood, ebony, papaya, cherry, big leafhopper, hedgehog, cedar, peach, African purple The altar or the like is not limited thereto, and may be any shape as long as it can be a molded body having the above-described shape, and can be used without any limitation. Ο
本發明的多層層合物中接著層,係接著金屬層、木材 之層,由本發明的不飽和羧酸接枝聚烯烴所成者。藉由使 接著層由不飽和羧酸接枝聚烯烴所成,可製造絕緣性、熱 衝撃性、接著強度優異的層合物。 於接枝反應所生成的不飽和羧酸接枝聚烯烴與溶劑的 分離、於反應步驟使不飽和羧酸接枝聚烯烴與溶劑分離之 方法、此外,藉由鼓式乾燥機經揮發的1,1,2-三氯乙烷的 回收、藉由鼓式乾燥機從聚合物溶液去除溶劑所需要的時 間、經離析的聚合物的加工,如前述。 本發明的多層層合物中接著層,可將不飽和羧酸接枝 聚烯烴藉由一般加工聚烯烴樹脂之成形方法而薄膜化,可 列舉吹塑薄膜成形、流延成形、擠壓層壓成形、壓延成形 、薄片成形、纖維成形、吹塑成形、射出成形、旋轉成形 、被覆成形。此外,必要時於薄膜成形中,可爲將本發明 之經接枝不飽和羧酸的聚烯烴使用於至少單側一層之共擠 壓成形或多層層合成形。 本發明的多層層合物的製造中,構成多層層合物之金 屬層、接著層、木材的層合順序並沒有特別的限制,但可 列舉將接著層之不飽和羧酸接枝聚烯烴的薄膜藉由加熱壓 -38- 200925171 黏法經層合於金屬層後,於此層合物接著木材之方法,將 接著層之不飽和羧酸接枝聚烯烴的薄膜藉由加熱壓黏法經 層合於木材的裏面,製造加熱壓黏性的木材後’將此熱壓 黏性的木材加熱壓黏於金屬層之方法,在以金屬層、接著 層、木材的順序重疊的狀態下,同時加熱壓黏此等之方法 ,但由施工性的觀點而言,製造於金屬層或木材的單側上 預先加熱壓黏不飽和羧酸接枝聚烯烴的薄膜之金屬或木材 0 ,之後使此金屬/聚烯烴薄膜層合物與木材接著,或使木 材/聚烯烴薄膜層合物與金屬接著之2階段的層合方法較 適用。 使金屬層或木材爲薄片、箔、薄膜等之平坦的形狀時 ,將成爲接著層之不飽和羧酸接枝聚烯烴薄膜使用自動化 製程連續地接著於金屬層或木材,可製造滾筒形狀的熱接 著性金屬薄片、熱接著性金屬薄膜、熱接著性木材薄片等 。例如使其通過使薄膜接著於金屬層之層壓用滾筒而使其 Q 接著之方法,可藉由將金屬層於接著層的熔融溫度附近預 熱備用之方法進行接著。另一方面,在不預熱金屬層下藉 由層壓機進行加熱壓黏之方法同樣亦可’只要是可加熱至 接著層表現出接著性之溫度即可,不限制於任何層合方法 ,預熱金屬時,可使用熱風的噴吹或誘導加熱。在任何情 況中,皆可活用不飽和羧酸接枝聚烯烴爲熱可塑性這點’ 使層合物製造的自動化輕易達到。與金屬層同樣,即使爲 木材,在與不飽和羧酸接枝聚烯烴薄膜的接著中可預熱木 材備用,但此時,因爲從木材揮發出水分、經燃燒而變色 -39- 200925171 等成爲問題,故預熱溫度僅可能爲低溫較佳,50~150°C較 適合使用。 本發明的多層層合物中接著層的熔融接著溫度係 40~250°C,低於40°C時,會有接著層的熔解不充分、接著 強度降低的情況,此外超過25 0°C時,會有因爲接著層的 熱劣化等看到著色之情況,此外,會有因爲接著層的劣化 而導致接著強度的降低的情況,較佳爲80〜200°C。The adhesive layer in the multilayer laminate of the present invention is a layer of a metal layer or a layer of wood, which is composed of the unsaturated carboxylic acid grafted polyolefin of the present invention. By forming the subsequent layer from a polyolefin grafted with an unsaturated carboxylic acid, a laminate having excellent insulating properties, thermal repellency, and strength can be produced. Separation of the unsaturated carboxylic acid grafted polyolefin formed by the grafting reaction with a solvent, separation of the unsaturated carboxylic acid grafted polyolefin with a solvent in a reaction step, and further, volatilization by a drum dryer The recovery of 1,2-trichloroethane, the time required to remove the solvent from the polymer solution by a drum dryer, the processing of the isolated polymer, as described above. In the multilayer laminate of the present invention, the unsaturated carboxylic acid grafted polyolefin can be thinned by a general processing method for processing a polyolefin resin, and examples thereof include blown film forming, tape casting, and extrusion lamination. Molding, calendering, sheet forming, fiber forming, blow molding, injection molding, rotational molding, and coating molding. Further, in the film formation as necessary, the polyolefin obtained by grafting the unsaturated carboxylic acid of the present invention may be used in a co-extrusion molding or a multi-layer composite molding of at least one side. In the production of the multilayer laminate of the present invention, the order of laminating the metal layer, the subsequent layer, and the wood constituting the multilayer laminate is not particularly limited, but an unsaturated carboxylic acid grafted polyolefin having an adhesive layer may be mentioned. After the film is laminated to the metal layer by a heat-pressure-38-200925171 adhesive method, the film of the unsaturated carboxylic acid grafted polyolefin of the adhesive layer is heated by a pressure-bonding method. After laminating the inside of the wood, after manufacturing the heat-pressed wood, the method of heating and pressing the hot-pressed wood to the metal layer is in the state of overlapping the metal layer, the subsequent layer, and the wood, while simultaneously Heating and pressure bonding, etc., but from a construction point of view, the metal or wood 0 of the film of the pressure-bonded unsaturated carboxylic acid grafted polyolefin is preheated on one side of the metal layer or wood, and then The metal/polyolefin film laminate is then applied to the wood, or a two-stage lamination process in which the wood/polyolefin film laminate and the metal are subsequently applied. When the metal layer or the wood is in a flat shape such as a sheet, a foil, a film, or the like, the unsaturated carboxylic acid grafted polyolefin film which becomes an adhesive layer is continuously adhered to the metal layer or wood using an automated process, and the heat of the roll shape can be manufactured. A subsequent metal foil, a thermal adhesive metal film, a thermal adhesive wood sheet, or the like. For example, the method of causing the film to follow the lamination of the metal layer by the step of laminating the metal layer may be followed by preheating the metal layer in the vicinity of the melting temperature of the subsequent layer. On the other hand, the method of heating and pressure-bonding by a laminator without preheating the metal layer can also be used as long as it can be heated to a temperature at which the adhesive layer exhibits adhesion, and is not limited to any lamination method. When preheating the metal, hot air blowing or induction heating can be used. In any case, the use of unsaturated carboxylic acid grafted polyolefins for thermoplasticity is readily achieved by automated automation of laminate manufacture. Like the metal layer, even in the case of wood, the wood can be preheated in the subsequent step of grafting the polyolefin film with the unsaturated carboxylic acid, but at this time, the water is volatilized from the wood, and the color is changed by burning - 39-200925171 The problem, so the preheating temperature is only possible for low temperature, 50~150 °C is more suitable for use. In the multilayer laminate of the present invention, the subsequent layer is melted at a temperature of 40 to 250 ° C. When the temperature is lower than 40 ° C, the subsequent layer may be insufficiently melted, and the subsequent strength may be lowered. Further, when the temperature exceeds 25 ° C. There is a case where coloring is observed due to thermal deterioration of the adhesive layer or the like, and there is a case where the strength of the adhesive layer is deteriorated due to deterioration of the adhesive layer, and it is preferably 80 to 200 °C.
〇 本發明的多層層合物中接著層的熔融接著所使用的壓 力,只要接著層熔著即可,並沒有特別的限制,但爲了維 持接著界面的密著性,且,抑制因爲接著層的流動抑制層 厚度的降低,較佳爲〇.〇1〜20MPa,再更佳爲0.01~5MPa ,接著時的壓力可依被黏著物的種類而適當選擇。 本發明的多層層合物,藉由以可與金屬、木材堅固地 接著之不飽和羧酸接枝聚烯烴作爲接著層,可提供金屬與 木材堅固地經接著之具有質感、重量感、高級感的多層層 合物。 3)作爲第3具體的用途,說明關於由本發明的不飽 和羧酸接枝聚烯烴所成的薄膜的至少單面上具有以金屬所 形成的導電電路之可撓配線薄膜。 發現此仍可提供由本發明的不飽和羧酸接枝聚烯烴所 製造的電絕緣性薄膜與金屬堅固地接著,而且,與此金屬 接著的薄膜,於微影術及蝕刻中使用,對於藥劑顯示出安 定性,耐彎折性、耐寒性、柔軟性、耐熱衝撃性優異的可 撓配線薄膜。 -40-In the multilayer laminate of the present invention, the pressure of the subsequent layer is melted, and the pressure used is not particularly limited as long as the subsequent layer is fused, but in order to maintain the adhesion of the interface, and to suppress the adhesion of the layer. The thickness of the flow suppressing layer is preferably reduced from 〜1 to 20 MPa, more preferably from 0.01 to 5 MPa, and the pressure at the time may be appropriately selected depending on the type of the adherend. The multi-layered laminate of the present invention can provide a strong texture of the metal and the wood with a texture, a sense of weight and a high-grade feeling by using a polyolefin grafted with an unsaturated carboxylic acid which can be firmly adhered to metal or wood as an adhesive layer. Multilayer laminate. 3) As a third specific use, a flexible wiring film having a conductive circuit formed of a metal on at least one side of a film formed of the unsaturated carboxylic acid-grafted polyolefin of the present invention will be described. It has been found that this still provides that the electrically insulating film made of the unsaturated carboxylic acid grafted polyolefin of the present invention is firmly adhered to the metal, and the film followed by the metal is used in lithography and etching for the drug display. A flexible wiring film which is excellent in stability, bending resistance, cold resistance, flexibility, and heat resistance. -40-
200925171 本發明的可撓配線薄膜,係於由本發 接枝聚烯烴所成的薄膜的至少單面上具有 導電電路者。作爲此構成,可列舉具有於 枝聚烯烴所成的薄膜的單面上具有以金屬 路的2層的構造之可撓配線薄膜、或具有 接枝聚烯烴所成的薄膜的雙面上具有導電 造之可撓配線薄膜。具有3層的構造之可 形成於由不飽和羧酸接枝聚烯烴所成的薄 可不同。 本發明的可撓配線薄膜所使用的金屬 制,可列舉例如銅、鋁、鐵、金、銀等, 經濟且導電性優異的銅較佳。此等之金屬 及板,但由電路形成容易而言,使用箔較 所使用的製品適當地選擇,但100 μιη以下 箔,可列舉例如壓延銅箔、電解銅箔等,銅 Q 操作性、銅箔的破裂之關係而言,通常使用 範圍者,特別是以5〜50μηι者較適合。此夕1 以表面粗度小者較適用,Rz (十點平均高5 下者較佳,5μιη以下者更佳。 於接枝反應所生成的不飽和羧酸接枝靠 分離、於反應步驟使不飽和羧酸接枝聚烯烴 方法、此外,藉由鼓式乾燥機經揮發的1,1 回收、藉由鼓式乾燥機從聚合物溶液去除淫 間、經離析的聚合物的加工,如前述。 的不飽和羧酸 金屬所形成的 不飽和羧酸接 形成的導電電 由不飽和羧酸 路的3層的構 配線薄膜中, 的雙面之電路 沒有特別的限 等之中,使用 形狀可列舉箔 。其厚度可依 較佳,作爲銅 箔的厚度,由 15~100μιη 的 ,作爲銅箔, ί )爲 7μιη以 烯烴與溶劑的 與溶劑分離之 ,2-三氯乙烷的 劑所需要的時 -41 - 200925171 不飽和羧酸接枝聚烯烴的薄膜可藉由一般熟知的樹脂 的成形加工法製造,可列舉例如吹塑薄膜成形、流延成形 、擠壓層壓成形、壓延成形、薄片成形、吹塑成形。此外 ,必要時於薄膜成形中,可爲將本發明之經接枝不飽和羧 酸的聚烯烴使用於至少單側一層之共擠壓成形或多層層合 成形,此外,使用溶劑之流延薄膜成形亦可。使用溶液流 延法時,例如可將使本發明的不飽和羧酸接枝聚烯烴溶解 0 於1,1,2-三氯乙烷、氯仿、甲基乙基酮等之溶劑之溶液流 延於聚對苯二甲酸乙二醇酯薄膜上,藉由揮發去除溶劑而 成膜。 此外,不飽和羧酸接枝聚烯烴的薄膜,必要時亦可藉 由加熱、紫外線、電子線等之照射使其交聯。 本發明的可撓配線薄膜,由不飽和羧酸接枝聚烯烴所 成的薄膜與金屬經接著後,可藉由微影術形成導電電路而 製造。 Q 不飽和羧酸接枝聚烯烴的薄膜與金屬之接著方法並沒 有特別的限制,可藉由雙帶式加壓、熱加壓、擠壓層壓、 滾筒層壓成形等習知的方法進行,可使用自動化製程而以 薄膜、薄片或膠帶接著於金屬。例如使其通過使薄膜接著 於金屬層之層壓用滾筒而使其接著之方法,可藉由將金屬 層於不飽和羧酸接枝聚烯烴的薄膜的熔融溫度附近預熱備 用之方法進行接著’此時,以金屬的軟化溫度以下進行加 熱這點很重要。 另一方面’藉由層壓機進行加熱壓黏之方法同樣亦可 -42- 200925171 ,只要是可加熱至不飽和羧酸接枝聚烯烴的薄膜表現出接 著性之溫度即可,不限制於任何層合方法,預熱金屬時, 可使用熱風的噴吹或誘導加熱。在任何情況中,皆可活用 不飽和羧酸接枝聚烯烴的薄膜爲熱可塑性這點,使金屬經 層合的薄膜更容易以自動地製造。 本發明的可撓配線薄膜中不飽和羧酸接枝聚烯烴的薄 膜的熔融接著溫度係40~2 5 0°C,低於40°C時,會有薄膜 0 的熔解不充分、接著強度降低的情況,此外超過250 °C時 ,會有因爲薄膜的熱劣化等看到著色之情況,此外,會有 因爲薄膜的劣化而導致接著強度的降低的情況,較佳爲 80〜20CTC 0 本發明的可撓配線薄膜中不飽和羧酸接枝聚烯烴的薄 膜的熔融接著所使用的壓力,只要不飽和羧酸接枝聚烯烴 的薄膜熔著即可,並沒有特別的限制,但爲了維持接著界 面的密著性,且,抑制因爲接著層的流動抑制層厚度的降 〇 低,較佳爲 0.01〜20MPa,再更佳爲 0.01〜5MPa,接著時 的壓力可依被黏著物的種類而適當選擇。 藉由以上所述的方法,從金屬箔的滾筒及不飽和羧酸 接枝聚烯烴的薄膜的滾筒,捲出金屬箔及不飽和羧酸接枝 聚烯烴的薄膜,藉由加熱壓黏,必要時藉由冷卻,可以滾 筒卷撓的狀態連續地得到金屬經層合的薄膜,所得到的薄 膜必要時可依所定的大小進行切斷或穿鑿作爲配線薄膜利 用。 由此薄膜藉由微影術可製造可撓配線薄膜,例如使用 -43- 200925171 正型光阻時,可列舉形成保護配線圖型經形成的部分的金 屬表面之蝕刻光阻的配線圖型後,使用此本身蝕刻液藉由 蝕刻去除配線未被形成的部分之金屬,去除蝕刻光阻之方 法。此外,使用負型光阻時,可列舉與使用正型光阻時相 反,在將欲形成的配線圖型以外遮住的形狀下曝光,用光 阻保護配線圖型部的金屬,使用蝕刻液藉由蝕刻去除配線 未被形成的部分的金屬,去除蝕刻光阻之方法。使用印刷 0 法時,並非金屬經層合的薄膜的全面上塗佈光阻,可列舉 例如將正型光阻直接印刷如配線圖型的形狀,然後,曝光 、藉由蝕刻去除光阻之方法等。印刷法係不浪費光阻,而 且,以適合量產之經濟的方法,大量生產可撓配線基板, 故較適用。作爲正型光阻劑,可使用例如重氮萘醌等之光 分解型光阻;作爲負型光阻劑,可使用例如環化聚異戊二 烯等之光增感型光阻;曝光光源的波長,依電路的線寬適 宜地選擇,可列舉例如g線、i線、KrF步進機、ArF步 〇 進機等;此外,作爲光阻可使用液狀光阻、薄膜狀的乾薄 膜光阻、電沈積光阻等。光阻的塗佈後,必要時亦可進行 用於去除溶劑之預烘烤亦可,作爲顯影方法,可使用浸漬 顯影、或噴霧顯影的任一種。 對於所使用的顯影劑,並沒有特別的限制,可使用一 般所使用的顯影劑。例如正型光阻,因爲藉由曝光經光照 射的部分分解後成爲鹼可溶性之酸,此顯影液未使用鹼水 溶液’作爲驗性顯影液可列舉偏砂酸鈉、氫氧化鈉、磷酸 鈉等爲主體的水溶液、作爲非金屬鹼之四級銨鹽、胺、醇 -44 - 200925171 混合物等之有機鹼水溶液。此外,作爲可顯影負型光 可列舉鹼性化合物,例如氫氧化鈉、氫氧化鉀、碳酸 矽酸鈉、偏矽酸鈉、氨水等之無機鹼類、或乙基胺、 基胺等之第一級胺、二乙基胺、二-η-丙基胺等之第 胺、三乙基胺、甲基二乙基胺等之第三級胺、二甲基 胺、三乙醇胺等之胺基醇、氫氧化四甲基銨、氫氧化 基銨、氫氧化四丙基鉸等之氫氧化四級銨等之有機鹼 0 水溶液。 對於顯影溫度並沒有特別的限制,只要是金屬經 的薄膜產生熱變形的溫度以下即可,可毫無問題地使 顯影後進行水洗,充分地洗淨顯影液,乾燥後剝 阻較佳。剝離劑,可列舉一般所使用之丙酮、甲基乙 等之酮類,甲醇、乙醇、異丙醇等之醇類。此外,顯 去除光阻中的溶劑、水分,亦可進行用於提高與基板 著性之後烘烤,其條件係依所選擇的光阻適當地選擇 度、時間較佳。 對於飩刻所使用的鈾刻液,並沒有特別的限制, 用氯化鐵水溶液等。 作爲蝕刻方法,可使用乾蝕刻、濕蝕刻、電解蝕 〇 本發明的可撓配線薄膜,可使用於例如IC TAG 磁誘導電路、感應電路、平面天線等。特別是可有效 用於將可撓配線薄膜熱熔著於非平面形狀的樹脂構件 金屬構件時,此時,可活用可撓配線薄膜的柔軟性、 阻, 鈉、 η-丙 二級 乙醇 四乙 類的 層合 用。 離光 基酮 影後 的密 其溫 可使 刻等 、電 地使 、或 及加 -45- 200925171 壓接著性,在可撓配線薄膜的單面上形成電路時,例如可 作爲接著至携帶電話、電腦等之携帶情報終端内部的薄膜 狀電子電路零件使用。此外,雙面上經形成電路時,在電 路的機能未受到阻礙的範圍,可接著於其他的樹脂零件, 例如聚碳酸酯、聚苯硫醚樹脂製零件等。 依據本發明,接著金屬與薄膜,藉由微影術形成電路 圖型可製造可撓配線薄膜,可提供耐彎折性、耐寒性、'柔 ^ 軟性、耐熱衝撃性優異的可撓配線薄膜。 4)作爲第4具體的用途,說明關於由本發明的不飽 和羧酸接枝聚烯烴所成的薄膜的至少單面上具有以金屬所 形成的導電電路之薄膜天線。 發現此仍由本發明的接枝不飽和羧酸之聚烯烴所成之 具有電絕緣性的薄膜與金屬堅固地接著,而且,與金屬接 著的薄膜對於在微影術及蝕刻中所使用的藥劑表現出安定 性,可提供耐彎折性、耐寒性、柔軟性、耐熱衝撃性優異 Q 的薄膜天線。 本發明的薄膜天線,由本發明的不飽和羧酸接枝聚烯 烴所成的薄膜上,不使用先前技術用所使用的接著劑、或 黏著劑等,而使金屬製的導電電路的薄膜經層合者,此薄 膜天線,具有更容易地熱接著於各種的熱可塑性樹脂、金 屬等之特徵。 本發明的薄膜天線,係由本發明的不飽和羧酸接枝聚 烯烴所成的薄膜的至少單面上具有以金屬所形成的導電電 路者。由此不飽和羧酸接枝聚烯烴所成的薄膜,因爲具有 -46- 200925171 電絕緣性,故可作爲天線使用。作爲本發明的薄膜天線的 構成,可列舉具有在由不飽和羧酸接枝聚烯烴所成的薄膜 的單面上具有導電電路之2層的構造之薄膜天線、具有由 不飽和羧酸接枝聚烯烴所成的薄膜的雙面上導電電路之3 層的構造之薄膜天線等。具有3層的構造之薄膜天線中, 在由不飽和羧酸接枝聚烯烴所成的薄膜的雙面上所形成的 電路可不同。200925171 The flexible wiring film of the present invention is a conductive circuit formed on at least one side of a film formed of the present grafted polyolefin. In this configuration, a flexible wiring film having a structure in which two layers of a metal path are formed on one surface of a film made of a branched polyolefin, or a film formed of a grafted polyolefin is electrically conductive on both sides. Made of flexible wiring film. The structure having a three-layer structure may be formed in a thin form formed by grafting a polyolefin with an unsaturated carboxylic acid. The metal used for the flexible wiring film of the present invention may, for example, be copper, aluminum, iron, gold or silver, and copper which is economical and excellent in conductivity is preferable. Although the metal and the plate are easily formed by a circuit, the foil is used as appropriate as the product to be used, but a foil of 100 μm or less may be, for example, a rolled copper foil or an electrolytic copper foil, copper Q handleability, copper. In terms of the relationship of the fracture of the foil, it is generally suitable for use in a range of 5 to 50 μm. This eve 1 is more suitable for surface roughness, Rz (10 points average height is better than 5, and 5μηη or less is better. The unsaturated carboxylic acid formed by grafting reaction is separated by separation, in the reaction step The method for grafting a polyolefin with an unsaturated carboxylic acid, and further, recovering from the polymer solution by a drum dryer by a volatile 1,1, and removing the polymer from the polymer solution by a drum dryer, as described above. The conductive electric charge formed by the unsaturated carboxylic acid metal formed by the unsaturated carboxylic acid metal is composed of a three-layered wiring film of an unsaturated carboxylic acid path, and the double-sided circuit is not particularly limited, and the shape can be used. The thickness of the foil may be preferably as the thickness of the copper foil, from 15 to 100 μm, as copper foil, ί) is 7 μm, and the solvent is separated from the solvent by the olefin and the solvent, and the 2-trichloroethane agent is required. The film of the unsaturated carboxylic acid grafted polyolefin can be produced by a molding process of a generally known resin, and examples thereof include blown film forming, tape casting, extrusion lamination forming, calendering, and the like. Sheet forming, blow molding shape. Further, in the film formation as necessary, the polyolefin of the grafted unsaturated carboxylic acid of the present invention may be used in a co-extrusion or multi-layered form of at least one side layer, and further, a cast film using a solvent. Forming is also possible. When the solution casting method is used, for example, a solution in which the unsaturated carboxylic acid graft polyolefin of the present invention is dissolved in a solvent of 1,1,2-trichloroethane, chloroform, methyl ethyl ketone or the like can be cast. On the polyethylene terephthalate film, a solvent is removed by evaporation to form a film. Further, the film of the unsaturated carboxylic acid-grafted polyolefin may be crosslinked by irradiation with heat, ultraviolet rays, electron beams or the like as occasion demands. In the flexible wiring film of the present invention, a film made of an unsaturated carboxylic acid grafted polyolefin and a metal are subsequently formed by forming a conductive circuit by lithography. The film of the Q-unsaturated carboxylic acid-grafted polyolefin and the method of bonding the metal are not particularly limited, and can be carried out by a conventional method such as double-belt pressurization, hot pressurization, extrusion lamination, roll lamination molding, or the like. It can be attached to the metal with a film, sheet or tape using an automated process. For example, by subjecting the film to a subsequent lamination of the metal layer, the method of subsequently preheating the metal layer near the melting temperature of the film of the unsaturated carboxylic acid grafted polyolefin can be carried out. At this time, it is important to heat the metal below the softening temperature. On the other hand, the method of heating and pressing by a laminating machine can also be -42-200925171, as long as the film which can be heated to the unsaturated carboxylic acid grafted polyolefin exhibits an adhesive temperature, and is not limited thereto. Any lamination method, when preheating the metal, may be performed by hot air blowing or induction heating. In any case, the film of the unsaturated carboxylic acid grafted polyolefin can be used for the thermoplasticity, so that the metal laminated film can be more easily manufactured automatically. In the flexible wiring film of the present invention, the film of the unsaturated carboxylic acid grafted polyolefin is melted at a temperature of 40 to 250 ° C, and when it is lower than 40 ° C, the film 0 is insufficiently melted and the strength is lowered. In the case of more than 250 ° C, the coloring may be observed due to thermal deterioration of the film or the like, and the strength may be lowered due to deterioration of the film, and preferably 80 to 20 CTC 0. The pressure of the film of the unsaturated carboxylic acid grafted polyolefin in the flexible wiring film is followed by the pressure of the film of the unsaturated carboxylic acid grafted polyolefin, and is not particularly limited, but in order to maintain the subsequent The adhesion of the interface is suppressed, and since the thickness of the flow suppressing layer of the adhesive layer is low, it is preferably 0.01 to 20 MPa, more preferably 0.01 to 5 MPa, and the pressure at the subsequent pressure may be appropriately selected depending on the type of the adhesive. select. By the method described above, a film of a metal foil and an unsaturated carboxylic acid grafted polyolefin is rolled out from a roll of a metal foil and a film of a film of a non-saturated carboxylic acid grafted polyolefin, and is heated and pressed. At the time of cooling, the metal laminated film can be continuously obtained in a state where the roll is curled, and the obtained film can be cut or punctured as a wiring film according to a predetermined size. Thus, a flexible wiring film can be produced by lithography of the film. For example, when a positive resist of -43 to 200925171 is used, a wiring pattern for forming an etching resist of a metal surface of a portion where the wiring pattern is formed can be cited. A method of removing the etching photoresist by etching the metal of the portion where the wiring is not formed by etching using the etching liquid itself. In addition, when a negative-type photoresist is used, as opposed to the case of using a positive-type photoresist, it is exposed in a shape which is shielded from the wiring pattern to be formed, and the metal of the wiring pattern portion is protected by a photoresist, and an etching solution is used. A method of removing an etched photoresist by etching a metal in a portion where wiring is not formed. When the printing 0 method is used, the photoresist is not coated on the entire surface of the metal laminated film, and for example, a method of directly printing a positive photoresist such as a wiring pattern, and then exposing and removing the photoresist by etching may be mentioned. Wait. The printing method does not waste light resistance, and is more suitable for mass production of a flexible wiring substrate in an economical manner suitable for mass production. As the positive photoresist, a photodegradable photoresist such as diazonaphthoquinone or the like can be used; as the negative photoresist, a photo-sensitized photoresist such as cyclized polyisoprene can be used; The wavelength of the circuit is appropriately selected depending on the line width of the circuit, and examples thereof include a g line, an i line, a KrF stepper, an ArF step boring machine, and the like; in addition, a liquid photoresist or a film-like dry film can be used as the photoresist. Photoresist, electrodeposited photoresist, etc. After the application of the photoresist, pre-baking for removing the solvent may be carried out as necessary, and as the developing method, either immersion development or spray development may be used. The developer to be used is not particularly limited, and a developer which is generally used can be used. For example, a positive-type resist is used as an alkali-soluble acid by decomposing a portion irradiated with light, and the developer is not used as an aqueous solution. As an organic developer, sodium metasilicate, sodium hydroxide, sodium phosphate, etc. may be mentioned. It is an aqueous solution of a main body, an aqueous solution of an organic base which is a quaternary ammonium salt of a non-metal base, an amine, an alcohol-44-200925171 mixture or the like. Further, examples of the developable negative light include basic compounds such as inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium metasilicate, and aqueous ammonia, or ethylamines and amines. Amines such as a primary amine such as a primary amine, a diethylamine or a di-n-propylamine; a tertiary amine such as a triethylamine or a methyldiethylamine; an amine group such as a dimethylamine or a triethanolamine; An aqueous solution of an organic base 0 such as an alcohol, tetramethylammonium hydroxide, ammonium hydroxide or tetrapropylammonium hydroxide. The developing temperature is not particularly limited as long as it is at least the temperature at which the metal film is thermally deformed, and the developing solution can be washed with water without any problem, and the developing solution is sufficiently washed, and the peeling after drying is preferred. Examples of the release agent include ketones such as acetone and methyl ethyl which are generally used, and alcohols such as methanol, ethanol and isopropyl alcohol. Further, it is also possible to remove the solvent and moisture in the photoresist, and to perform baking after the substrate is improved, and the conditions are preferably selected in accordance with the selected photoresist. There is no particular limitation on the uranium engraving used for engraving, and an aqueous solution of ferric chloride or the like is used. As the etching method, the flexible wiring film of the present invention can be used for dry etching, wet etching, or electrolytic etching, and can be used for, for example, an IC TAG magnetic induction circuit, an induction circuit, a planar antenna, or the like. In particular, it can be effectively used for thermally fusing a flexible wiring film to a non-planar-shaped resin member metal member. In this case, the flexibility and resistance of the flexible wiring film can be utilized, sodium, η-propyl secondary ethanol tetra The lamination of classes. The temperature of the light-based ketone can be used to etch, etc., or to add -45-200925171, and when the circuit is formed on one side of the flexible wiring film, for example, it can be used as a portable telephone. Use of film-shaped electronic circuit components inside the information terminal such as a computer. Further, when the circuit is formed on both sides, in the range where the function of the circuit is not hindered, it can be followed by other resin parts such as polycarbonate or polyphenylene sulfide resin parts. According to the present invention, a flexible wiring film can be produced by forming a circuit pattern by lithography with a metal and a film, and a flexible wiring film excellent in bending resistance, cold resistance, softness, and heat resistance can be provided. 4) As a fourth specific use, a film antenna having a conductive circuit formed of a metal on at least one side of a film formed of the unsaturated carboxylic acid grafted polyolefin of the present invention will be described. It has been found that the electrically insulating film which is still formed by the polyolefin of the graft unsaturated carboxylic acid of the present invention is firmly adhered to the metal, and the film with the metal is used for the performance of the agent used in lithography and etching. It provides stability and provides a film antenna with excellent bending resistance, cold resistance, flexibility, and thermal shock resistance. In the film antenna of the present invention, the film of the conductive circuit of the present invention is laminated on the film of the unsaturated carboxylic acid grafted polyolefin of the present invention without using an adhesive or an adhesive used in the prior art. Further, this film antenna has characteristics that it is more easily thermally bonded to various thermoplastic resins, metals, and the like. The film antenna of the present invention is a conductive circuit formed of a metal on at least one side of a film formed of the unsaturated carboxylic acid grafted polyolefin of the present invention. The film obtained by grafting a polyolefin with an unsaturated carboxylic acid can be used as an antenna because it has an electrical insulating property of -46 to 200925171. The configuration of the film antenna of the present invention includes a film antenna having a structure in which two layers of a conductive circuit are formed on one surface of a film formed by grafting a polyolefin with an unsaturated carboxylic acid, and having a graft by an unsaturated carboxylic acid. A thin film antenna having a three-layer structure of a conductive circuit on both sides of a film made of a polyolefin. In the film antenna having a three-layer structure, the circuit formed on both sides of the film made of the unsaturated carboxylic acid grafted polyolefin may be different.
本發明的薄膜天線所使用的金屬,並沒有特別的限制 ,可列舉例如銅、鋁、鐵、金、銀等’此等中,使用經濟 具導電性優異的銅較佳。此等的金屬的形狀可列舉箱及板 ,但因爲電路形成容易,故使用箔較佳。其厚度可依所使 用的製品適當地選擇,但ΙΟΟμιη以下較佳,作爲銅箔, 可列舉例如壓延銅箔、電解銅箔等,銅箔的厚度依操作性 、銅箔的破裂的關係,一般使用15〜ΙΟΟμιη的範圍者,但 特別是以5〜50μηι者較適合。此外,作爲銅箱,以表面粗 度小者較適用,Rz (十點平均高度)爲7μιη以下者較佳 ,5μιη以下者更佳。 於接枝反應所生成的不飽和羧酸接枝聚烯烴與溶劑的 分離、於反應步驟使不飽和羧酸接枝聚烯烴與溶劑分離之 方法、此外,藉由鼓式乾燥機經揮發的1,1,2-三氯乙烷的 回收、藉由鼓式乾燥機從聚合物溶液去除溶劑所需要的時 間、經離析的聚合物的加工,如前述。 由不飽和羧酸接枝聚烯烴所成的的薄膜可藉由一般熟 知的樹脂的成形加工法製造,可列舉例如吹塑薄膜成形、 -47- 200925171 流延成形、擠壓層壓成形、壓延成形、薄片成形、吹塑成 形。此外,必要時於薄膜成形中,可爲將不飽和羧酸接枝 聚烯烴使用於至少單側一層之共擠壓成形或多層層合成形 ,此外,使用溶劑之流延薄膜成形亦可。使用溶液流延法 時,例如可將使不飽和羧酸接枝聚烯烴溶解於1,1,2-三氯 乙烷、氯仿、甲基乙基酮等之溶劑之溶液流延於聚對苯二 甲酸乙二醇酯薄膜上,藉由揮發去除溶劑而成膜。 0 此外,不飽和羧酸接枝聚烯烴的薄膜,必要時亦可藉 由加熱、紫外線、電子線等之照射使其交聯。 本發明的薄膜天線,由不飽和羧酸接枝聚烯烴所成的 薄膜與金屬箔經熱接著而層合後,可藉由微影術等之手法 形成導電電路而製造。 由不飽和羧酸接枝聚烯烴所成的薄膜與金屬之接著方 法並沒有特別的限制,可藉由雙帶式加壓、熱加壓、擠壓 層壓、滾筒層壓成形等習知的方法進行,可使用自動化製 Q 程而以薄膜、薄片或膠帶接著於金屬箔。例如使其通過使 薄膜接著於金屬箔之層壓用滾筒而使其接著之方法,可藉 由必要時將金屬於不飽和羧酸接枝聚烯烴的薄膜的熔融溫 度附近預熱備用之方法進行接著,此時,以金屬箔的軟化 溫度以下進行加熱這點很重要。 另一方面,藉由層壓機進行加熱壓黏之方法同樣亦可 ,只要是可加熱至由不飽和羧酸接枝聚烯烴所成的的薄膜 表現出接著性之溫度即可,不限制於任何層合方法,預熱 金屬時,可使用熱風的噴吹或誘導加熱。在任何情況中, -48- 200925171 皆可活用由不飽和羧酸接枝聚烯烴所成的的薄膜爲熱可塑 性這點,使金屬經層合的薄膜更容易以自動地製造。 接著由不飽和羧酸接枝聚烯烴所成的薄膜時的溫度係 40〜250°C,低於40°C時,會有薄膜的熔解不充分、接著強 度降低的情況,此外超過250°C時,會有因爲薄膜的熱劣 化等看到著色之情況,此外,會有因爲薄膜的劣化而導致 接著強度的降低的情況,較佳爲80〜20 0°C。 由不飽和羧酸接枝聚烯烴所成的薄膜的接著所使用的 壓力,只要由不飽和羧酸接枝聚烯烴所成的薄膜熔著即可 ,並沒有特別的限制,但爲了維持接著界面的密著性,且 ,抑制因爲接著層的流動抑制層厚度的降低,較佳爲 0.0 l~20MPa,再更佳爲0 · 0 1 ~5 MPa,接著時的壓力可依被 黏著物的種類而適當選擇。 藉由以上所述的方法,從金屬箔的滾筒及不飽和羧酸 接枝聚烯烴的薄膜的滾筒,捲出金屬箔及不飽和羧酸接枝 聚烯烴的薄膜,藉由加熱壓黏,必要時藉由冷卻,可以滾 筒卷撓的狀態連續地得到金屬經層合的薄膜,所得到的薄 膜必要時可依所定的大小進行切斷或穿鑿作爲配線薄膜利 用。 由此薄膜藉由微影術可製造薄膜天線,例如使用正型 光阻時,可列舉形成天線圖型經形成的部分的金屬表面之 蝕刻光阻的天線圖型後,使用此本身蝕刻液藉由蝕刻去除 天線未被形成的部分之金屬,去除鈾刻光阻之方法。此外 ,使用負型光阻時,可列舉與使用正型光阻時相反,在將 -49- 200925171The metal used in the film antenna of the present invention is not particularly limited, and examples thereof include copper, aluminum, iron, gold, silver, etc. In the above, it is preferable to use copper which is economical and excellent in conductivity. The shape of such a metal may be a case and a plate. However, since the circuit is easy to form, it is preferable to use a foil. The thickness can be appropriately selected depending on the product to be used, and it is preferably ΙΟΟμηη or less. Examples of the copper foil include a rolled copper foil and an electrolytic copper foil. The thickness of the copper foil depends on the handling property and the crack of the copper foil. Use a range of 15~ΙΟΟμιη, but especially suitable for 5~50μηι. Further, as the copper box, those having a small surface roughness are preferable, and Rz (ten-point average height) is preferably 7 μm or less, and 5 μm or less is more preferable. Separation of the unsaturated carboxylic acid grafted polyolefin formed by the grafting reaction with a solvent, separation of the unsaturated carboxylic acid grafted polyolefin with a solvent in a reaction step, and further, volatilization by a drum dryer The recovery of 1,2-trichloroethane, the time required to remove the solvent from the polymer solution by a drum dryer, the processing of the isolated polymer, as described above. The film formed by grafting a polyolefin with an unsaturated carboxylic acid can be produced by a molding process of a generally known resin, and examples thereof include blown film forming, -47-200925171 tape casting, extrusion lamination forming, calendering Forming, sheet forming, blow molding. Further, in the film formation, if necessary, the unsaturated carboxylic acid grafted polyolefin may be used in a co-extrusion or a multi-layered form of at least one side, and may be formed by casting a film using a solvent. When the solution casting method is used, for example, a solution in which an unsaturated carboxylic acid grafted polyolefin is dissolved in a solvent such as 1,1,2-trichloroethane, chloroform or methyl ethyl ketone can be cast to polyparaphenylene. On the ethylene glycol diester film, a solvent is removed by evaporation to form a film. Further, the film of the unsaturated carboxylic acid-grafted polyolefin may be crosslinked by irradiation with heat, ultraviolet rays, electron beams or the like as necessary. In the film antenna of the present invention, a film made of an unsaturated carboxylic acid grafted polyolefin and a metal foil are laminated by heat, and then a conductive circuit can be formed by a method such as lithography. The method of bonding a film and a metal formed by grafting a polyolefin with an unsaturated carboxylic acid is not particularly limited, and may be conventionally carried out by double-belt pressurization, hot pressurization, extrusion lamination, roll lamination molding, and the like. The method can be carried out by using an automated process to adhere to the metal foil with a film, sheet or tape. For example, by subjecting the film to the subsequent lamination of the metal foil, the method of subsequently preheating the metal to the vicinity of the melting temperature of the film of the unsaturated carboxylic acid grafted polyolefin may be carried out. Next, at this time, it is important to heat the metal foil at a softening temperature or lower. On the other hand, the method of heating and pressure-bonding by a laminator may be as long as it is heated to a temperature at which the film formed of the unsaturated carboxylic acid-grafted polyolefin exhibits adhesion, and is not limited to Any lamination method, when preheating the metal, may be performed by hot air blowing or induction heating. In any case, -48-200925171 can utilize the film formed of the unsaturated carboxylic acid grafted polyolefin as the thermoplasticity, making the metal laminated film easier to manufacture automatically. Next, when the film formed by grafting the polyolefin with an unsaturated carboxylic acid has a temperature of 40 to 250 ° C, when the temperature is lower than 40 ° C, the film may be insufficiently melted and the bonding strength may be lowered, and further than 250 ° C may be exceeded. In the case of coloring, the film may be colored due to thermal deterioration of the film, and the film may be deteriorated due to deterioration of the film, and is preferably 80 to 20 °C. The pressure to be used in the film formed of the unsaturated carboxylic acid grafted polyolefin is not particularly limited as long as it is fused by the film of the unsaturated carboxylic acid grafted polyolefin, but in order to maintain the subsequent interface The adhesion is suppressed, and the thickness of the flow inhibiting layer of the adhesive layer is preferably reduced from 0.01 to 20 MPa, more preferably from 0. 0 to 5 MPa, and the pressure may be depending on the type of the adhesive. And choose the right one. By the method described above, a film of a metal foil and an unsaturated carboxylic acid grafted polyolefin is rolled out from a roll of a metal foil and a film of a film of a non-saturated carboxylic acid grafted polyolefin, and is heated and pressed. At the time of cooling, the metal laminated film can be continuously obtained in a state where the roll is curled, and the obtained film can be cut or punctured as a wiring film according to a predetermined size. Therefore, the film can be manufactured by lithography, for example, when a positive type photoresist is used, an antenna pattern of an etched photoresist which forms a metal surface of the formed portion of the antenna pattern can be cited, and the etching liquid is used. A method of removing the metal of the portion where the antenna is not formed by etching, and removing the uranium engraved photoresist. In addition, when a negative photoresist is used, it can be enumerated as opposed to when a positive photoresist is used, in the case of -49- 200925171
Ο 欲形成的天線圖型以外遮住的形狀下曝光,用光阻保護天 線圖型部的金屬,使用蝕刻液藉由蝕刻去除天線未被形成 的部分的金屬,去余蝕刻光阻之方法。使用印刷法時,並 非金屬經層合的薄膜的全面上塗佈光阻,可列舉例如將正 型光阻直接印刷如天線圖型的形狀,然後,曝光、藉由蝕 刻去除光阻之方法等。印刷法係不浪費光阻,而且,以適 合量產之經濟的方法,大量生產薄膜天線,故較適用。作 爲正型光阻劑,可使用例如重氮萘醌等之光分解型光阻; 作爲負型光阻劑,可使用例如環化聚異戊二烯等之光增感 型光阻;曝光光源的波長,依電路的線寬適宜地選擇,可 列舉例如g線、i線、KrF步進機、ArF步進機等;此外 ,作爲光阻可使用液狀光阻、薄膜狀的乾薄膜光阻、電沈 積光阻等。光阻的塗佈後,必要時亦可進行用於去除溶劑 之預烘烤亦可,作爲顯影方法,可使用浸漬顯影、或噴霧 顯影的任一種。 對於所使用的顯影劑,並沒有特別的限制,可使用一 般所使用的顯影劑。例如正型光阻,因爲藉由曝光經光照 射的部分分解後成爲鹼可溶性之酸,此顯影液未使用鹼水 溶液,作爲鹼性顯影液可列舉偏矽酸鈉、氫氧化鈉、磷酸 鈉等爲主體的水溶液、作爲非金屬鹼之四級銨鹽、胺、醇 混合物等之有機鹼水溶液。此外,作爲可顯影負型光阻, 可列舉鹼性化合物,例如氫氧化鈉、氫氧化鉀、碳酸鈉、 矽酸鈉、偏矽酸鈉、氨水等之無機鹼類、或乙基胺、η-丙 基胺等之第一級胺、二乙基胺、二-η-丙基胺等之第二級 -50- 200925171 胺、三乙基胺、甲基二乙基胺等之第三級胺、二甲基乙醇 胺、三乙醇胺等之胺基醇、氫氧化四甲基銨、氫氧化四乙 基銨、氫氧化四丙基銨等之氫氧化四級銨等之有機鹼類的 水溶液。 對於顯影溫度並沒有特別的限制,只要是金屬經層合 的薄膜產生熱變形的溫度以下即可,可毫無問題地使用。 顯影後進行水洗,充分地洗淨顯影液,乾燥後剝離光 0 阻較佳。剝離劑,可列舉一般所使用之丙酮、甲基乙基酮 等之酮類,甲醇、乙醇、異丙醇等之醇類。此外,顯影後 去除光阻中的溶劑、水分,亦可進行用於提高與基板的密 著性之後供烤,其條件係依所選擇的光阻適當地選擇其溫 度、時間較佳。 對於蝕刻所使用的蝕刻液,並沒有特別的限制,可使 用氯化鐵水溶液等。 作爲蝕刻方法,可使用乾蝕刻、濕蝕刻、電解蝕刻等 〇 。 本發明的薄膜天線,可有效地使用於熱熔著於非平面 形狀的樹脂構件、或金屬構件時,此時,活用薄膜天線的 柔軟性、及加壓接著性,在薄膜天線的單面上形成電路時 ’例如可作爲接著至携帶電話、電腦等之携帶情報終端内 部的薄膜狀電子電路零件使用。此外,雙面上經形成電路 時’在電路的機能未受到阻礙的範圍,可接著於其他的樹 脂零件’例如聚碳酸酯、聚苯硫醚樹脂製零件等,必要時 亦可接著於鋁、銅、不鏽鋼製的金屬零件。 -51 - 200925171 依據本發明,可提供耐彎折性、耐寒性、柔軟性、耐 熱衝撃性優異、可熱接著於各種樹脂之薄膜天線。 5)作爲第5具體的用途,說明關於由含有導電性微 粒子之本發明的不飽和羧酸接枝聚烯烴所成的導電性薄膜 、濺鍍標靶。曝光 Exposure to the shape of the antenna pattern to be formed, the metal of the antenna pattern portion is protected by a photoresist, and the metal of the portion where the antenna is not formed is removed by etching using an etching solution to remove the photoresist. When the printing method is used, the photoresist is not coated on the entire surface of the metal laminated film, and for example, a positive resist is directly printed in the shape of an antenna pattern, and then exposed, and the photoresist is removed by etching. . The printing method does not waste light resistance, and it is more suitable for mass production of film antennas in an economical manner suitable for mass production. As the positive photoresist, a photodegradable photoresist such as diazonaphthoquinone or the like can be used; as the negative photoresist, a photo-sensitized photoresist such as cyclized polyisoprene can be used; The wavelength is appropriately selected depending on the line width of the circuit, and examples thereof include a g line, an i line, a KrF stepper, an ArF stepper, and the like. Further, as the photoresist, a liquid photoresist or a film-like dry film light can be used. Resistance, electrodeposition photoresist, etc. After the application of the photoresist, prebaking for removing the solvent may be carried out as necessary, and as the developing method, either immersion development or spray development may be used. The developer to be used is not particularly limited, and a developer which is generally used can be used. For example, a positive-type resist is an alkali-soluble acid which is decomposed by exposure to light, and an alkali aqueous solution is not used as the developing solution. Examples of the alkaline developing solution include sodium metasilicate, sodium hydroxide, sodium phosphate, and the like. It is an aqueous solution of a main body, an aqueous solution of an organic alkali which is a quaternary ammonium salt of a non-metal base, an amine, an alcohol mixture or the like. Further, examples of the developable negative photoresist include basic compounds such as inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and aqueous ammonia, or ethylamine and η. a second stage of a first-stage amine such as a propylamine, a diethylamine, a di-n-propylamine or the like, and a third stage such as an amine, a triethylamine or a methyldiethylamine. An aqueous solution of an organic base such as an amine group such as an amine, dimethylethanolamine or triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide or tetrapropylammonium hydroxide. The development temperature is not particularly limited as long as it is at most a temperature at which the metal laminated film is thermally deformed, and can be used without any problem. After the development, the water is washed, the developer is sufficiently washed, and the light is removed after drying. Examples of the release agent include ketones such as acetone and methyl ethyl ketone which are generally used, and alcohols such as methanol, ethanol and isopropyl alcohol. Further, after the development, the solvent and moisture in the photoresist are removed, and the adhesion to the substrate can be improved, and then the baking can be performed. The conditions are preferably selected according to the selected photoresist, and the temperature is preferably selected. The etching liquid used for the etching is not particularly limited, and an aqueous solution of ferric chloride or the like can be used. As the etching method, dry etching, wet etching, electrolytic etching, or the like can be used. The film antenna of the present invention can be effectively used for heat-melting a resin member or a metal member having a non-planar shape. In this case, the flexibility and pressure adhesion of the film antenna are utilized on one side of the film antenna. When the circuit is formed, it can be used, for example, as a film-shaped electronic circuit component inside a portable information terminal such as a mobile phone or a computer. In addition, when the circuit is formed on both sides, the range in which the function of the circuit is not hindered can be followed by other resin parts such as polycarbonate or polyphenylene sulfide resin parts, and if necessary, aluminum, Metal parts made of copper and stainless steel. -51 - 200925171 According to the present invention, it is possible to provide a film antenna which is excellent in bending resistance, cold resistance, flexibility, and heat repellency, and which can be thermally bonded to various resins. 5) As a fifth specific use, a conductive thin film or a sputtering target made of the unsaturated carboxylic acid grafted polyolefin of the present invention containing conductive fine particles will be described.
發現此仍與金屬堅固地接著,而且,不飽和羧酸接枝 聚烯烴有效地作爲經分散有導電性微粒子的媒介物,而且 ,藉由將含有導電性微粒子之不飽和羧酸接枝聚烯烴薄膜 化,可輕易地加熱接著成對標靶本體與背板,此外,可確 保成對標靶本體與背板間的導電性。 本發明的導電性薄膜,係由含有導電性微粒子的不飽 和羧酸接枝聚烯烴所形成者。 不飽和羧酸接枝聚烯烴,在以本發明的導電性薄膜接 著成對標靶本體與背板接著時的接著面内中爲了維持薄膜 的電傳導性及熱傳導性的均勻性,該不飽和羧酸接枝聚烯 烴不含有於加熱至140 °C的二甲苯中不溶的凝膠較佳。 作爲不飽和羧酸接枝聚烯烴所含有的導電性微粒子, 只要是在無損及薄膜表面的平滑性下,接著後表現導電性 者即可,並沒有任何的限制,但可列舉例如金、銀、銅、 鉬、鎳、碳、錫、銦、鈀、铑、餓、釕、銥、鋁、鐵、銦 、鎂、鉑、矽、錫、鋅、鈷、鉻、鈦、鉬、鎢、碳黑等, 較佳者爲金、銀、銅 '鈀、铑、釕、銥、鈾、鈷、鎳、碳 黑。以選自此等粒子的1種以上的微粒子爲例,本發明所 謂的微粒子係指平均粒徑爲0.5nm〜50μιη。 -52- 200925171 導電性微粒子的平均粒徑,依用途適當選擇即可,並 沒有特別的限制,賦予導電性時,使用奈米粒子較佳,平 均粒徑爲l~50nm較適合使用,必要時可混合不同平均粒 徑的粒子後使用’特別是已知平均粒徑爲奈米尺寸的金屬 粒子,因爲熔點下降現象而引起自發的融合,亦可依目的 .選擇平均粒徑小的金屬粒子。 不飽和羧酸接枝聚烯烴中導電性微粒子的含量,可依 Q 目的適當地變更,爲了維持導電性及接著強度,相對於不 飽和羧酸接枝聚烯烴100重量份,導電性微粒子爲30〜99 重量份較佳。 不飽和羧酸接枝聚烯烴,亦可依提高接著性等之特性 的目的,含有上述的其他樹脂、彈性體或橡膠成分、各種 添加劑。此外,本發明的導電性薄膜,可依提高接著性等 之特性之目的,提高上述的其他樹脂、彈性體或橡膠成分 、各種添加劑。 〇 本發明的導電性薄膜中含有上述的其他樹脂、彈性體 或橡膠成分、各種添加劑時,在無損及導電性及接著性的 範圍內含有,並沒特別的限制,但其含量係相對於不飽和 竣酸接枝聚烯烴100重量份而言0.1〜10重量份較佳’ 0.1〜5重量份更佳,此外,其含量相對於本發明的導電性 薄膜100重量份而言0.13〜20.9重量份較佳,0.13~10.45 重量份爲更佳。 於接枝反應所生成的不飽和羧酸接枝聚烯烴與溶劑的 分離、於反應步驟使不飽和羧酸接枝聚烯烴與溶劑分離之 -53- 200925171 方法、此外,藉由鼓式乾燥機經揮發的1,1,2-三氯乙烷的 回收、藉由鼓式乾燥機從聚合物溶液去除溶劑所需要的時 間、經離析的聚合物的加工,如前述。 本發明的含有導電性薄膜所使用的導電性微粒子之不 飽和羧酸接枝聚烯烴的製造,可使用各種的方法。亦即, 可使用將不飽和羧酸接枝聚烯烴與導電性微粒子使用習知 的方法,例如使用2軸擠壓機進行熔融混練之方法之外, 0 將該聚烯烴溶解於前述的溶劑,於所得到的溶液中添加導 電性微粒子,從室溫較佳爲溶劑的沸點以下的溫度範圍內 ,使溶液攪拌分散之方法等。可藉由使用前述的方法從所 得到的溶液去除溶劑而製造含有導電性微粒子的不飽和羧 酸接枝聚烯烴。 本發明的導電性薄膜,將含有導電性微粒子的不飽和 羧酸接枝聚烯烴的顆粒,藉由熔融擠壓法在熔融狀態下薄 膜化之流延成形、吹塑成形等方法之外,亦可藉由熱加壓 〇 等進行薄膜化,此外,可將該顆粒溶解於前述的有機溶劑 後,藉由溶液流延法進行薄膜化。此時,溶液調製可使用 具備攪拌機的反應器等進行,但亦可使用均漿器等之機械 進行。此時,溶解溫度並沒有特別的限制,但一般在室溫 至所使用的溶劑的沸點以下進行較佳。所得到的聚烯烴溶 液中添加導電性微粒子,使用超音波洗淨器、均漿器等使 導電性微粒子分散,此時的溫度只要是不會揮發溶劑的溫 度即可並沒有特別的限制,從室溫至溶劑的沸點以下。此 外’可使用耐壓容器以溶劑的沸點以上的溫度進行導電性 -54- 200925171 微粒子的分散。 本發明的濺鍍標靶,係使用本發明的導電性薄膜接著 成對標靶本體與背板而成者。It was found that this was still firmly adhered to the metal, and the unsaturated carboxylic acid grafted polyolefin was effectively used as a medium in which the conductive fine particles were dispersed, and by grafting the unsaturated carboxylic acid-containing polyolefin containing conductive fine particles. The film is thinned and can be easily heated to the pair of target bodies and the back plate, and further, the conductivity between the pair of target bodies and the back plate can be ensured. The conductive film of the present invention is formed of an unsaturated carboxylic acid-grafted polyolefin containing conductive fine particles. The unsaturated carboxylic acid grafted polyolefin is unsaturated in order to maintain the uniformity of electrical conductivity and thermal conductivity of the film in the subsequent surface of the conductive film of the present invention in the subsequent bonding of the target body and the backing plate. The carboxylic acid grafted polyolefin is preferably one which does not contain a gel which is insoluble in xylene heated to 140 °C. The conductive fine particles contained in the unsaturated carboxylic acid-grafted polyolefin are not particularly limited as long as they are non-destructive and smooth on the surface of the film, and are not limited in any way, and examples thereof include gold and silver. , copper, molybdenum, nickel, carbon, tin, indium, palladium, rhodium, bismuth, antimony, bismuth, aluminum, iron, indium, magnesium, platinum, rhodium, tin, zinc, cobalt, chromium, titanium, molybdenum, tungsten, carbon Black, etc., preferably gold, silver, copper 'palladium, rhodium, ruthenium, osmium, uranium, cobalt, nickel, carbon black. The microparticles of the present invention are exemplified by one or more kinds of fine particles selected from the above particles, and the average particle diameter of the present invention is from 0.5 nm to 50 μm. -52- 200925171 The average particle diameter of the conductive fine particles is not particularly limited as long as it is appropriately selected depending on the application. When the conductivity is imparted, it is preferred to use nanoparticles, and the average particle diameter is preferably from 1 to 50 nm. It is possible to mix particles having different average particle diameters, and in particular, it is known that metal particles having an average particle diameter of a nanometer size cause spontaneous fusion due to a decrease in melting point, and metal particles having a small average particle diameter can be selected depending on the purpose. The content of the conductive fine particles in the unsaturated carboxylic acid-grafted polyolefin can be appropriately changed according to the purpose of Q, and the conductive fine particles are 30 parts by weight with respect to 100 parts by weight of the unsaturated carboxylic acid graft polyolefin in order to maintain conductivity and adhesion strength. It is preferably -99 parts by weight. The unsaturated carboxylic acid-grafted polyolefin may contain the above-mentioned other resin, elastomer or rubber component, and various additives for the purpose of improving the properties such as adhesion. Further, the conductive film of the present invention can improve the above-mentioned other resin, elastomer or rubber component, and various additives for the purpose of improving the properties such as adhesion. When the conductive film of the present invention contains the above-mentioned other resin, elastomer or rubber component, and various additives, it is contained in the range of non-destructiveness, conductivity, and adhesion, and is not particularly limited, but the content thereof is relative to More preferably, 0.1 to 10 parts by weight of the saturated citric acid-grafted polyolefin is 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, and further, the content is 0.13 to 20.9 parts by weight based on 100 parts by weight of the conductive film of the invention. Preferably, 0.13 to 10.45 parts by weight is more preferred. Separation of the unsaturated carboxylic acid grafted polyolefin formed by the grafting reaction with a solvent, separation of the unsaturated carboxylic acid grafted polyolefin and the solvent in the reaction step - 53 - 200925171, and further, by a drum dryer Recovery of volatilized 1,1,2-trichloroethane, time required to remove solvent from the polymer solution by a drum dryer, processing of the isolated polymer, as described above. Various methods can be used for the production of the unsaturated carboxylic acid graft polyolefin containing the conductive fine particles used for the conductive film of the present invention. That is, a method in which the unsaturated carboxylic acid grafted polyolefin and the conductive fine particles are used, for example, a method of melt-kneading using a 2-axis extruder, may be used, and the polyolefin is dissolved in the solvent described above. The conductive fine particles are added to the obtained solution, and the solution is stirred and dispersed in a temperature range of room temperature or lower, preferably at a temperature equal to or lower than the boiling point of the solvent. The unsaturated carboxylic acid-grafted polyolefin containing conductive fine particles can be produced by removing the solvent from the obtained solution by the aforementioned method. In the conductive film of the present invention, the particles of the unsaturated carboxylic acid-grafted polyolefin containing the conductive fine particles are formed by a melt extrusion method in which a film is formed by melt-molding in a molten state, and a method such as blow molding. The film formation can be carried out by hot pressurization or the like, and the particles can be dissolved in the organic solvent described above and then thinned by a solution casting method. In this case, the solution preparation may be carried out using a reactor equipped with a stirrer or the like, but it may be carried out using a machine such as a homogenizer. In this case, the dissolution temperature is not particularly limited, but it is usually preferably from room temperature to the boiling point of the solvent to be used. The conductive fine particles are added to the obtained polyolefin solution, and the conductive fine particles are dispersed by using an ultrasonic cleaner or a homogenizer. The temperature at this time is not particularly limited as long as it is a temperature at which the solvent is not volatilized. From room temperature to below the boiling point of the solvent. Further, it is possible to use a pressure-resistant container to conduct conductivity at a temperature equal to or higher than the boiling point of the solvent. -54 - 200925171 Dispersion of fine particles. The sputtering target of the present invention is obtained by using the conductive film of the present invention and then pairing the target body and the back sheet.
本發明的濺銨標靶,可藉由使用本發明的導電性薄膜 接著成對標靶本體與背板而製造。成對標靶本體與背板的 接著方法,只要是可確保兩者的電氣導電性即可,並沒任 何的限制,可列舉此接著方法的其中一例,將背板、本發 明的導電性薄膜、及成對標靶本體依此順序層合後,必要 時在加壓下放進加熱室内而熔融接著之方法。此時的溫度 只要是背板與成對標靶本體可接著即可,並沒有特別的限 制,通常爲90~3 00°C,更佳爲120〜250 °C,可依接著溫度 所使用的導電性薄膜的熔點而適當變更,但若爲薄膜的熔 融溫度以上較佳,此外若爲該薄膜的熱分解溫度以下較佳 。爲了確保充分的接著強度,例如該接著溫度係薄膜的溶 點加上1 〇〇°C的溫度以下進行較佳,接著時間只要是背板 與成對標靶本體具有均勻且實用上充分的接著強度即可, 並沒有特別的限制,通常爲1〜60分鐘,較佳爲1〜30分鐘 ,再更佳爲1〜10分鐘。當接著時,可預先將背板與成對 標靶本體加熱至接著溫度備用,此時可縮短接著時間;接 著時的壓力只要背板與成對標靶本體具有均勻且實用上充 分的接著強度即可,並沒有特別的限制,通常0.2〜lOMPa ,較佳0·2〜5MPa,更佳爲0.2〜3MPa。爲了得到充分的濺 鍍性能,在本發明的導電性薄膜熔融時未流出至接著面外 之上述的壓力條件下接著較佳。 -55- 200925171 藉由本發明,可提供導電性薄膜,特別是簡便地熱接 著成對標靶本體與背板,於兩者間可賦予電氣導電性之導 電性薄膜,背板經接著的經濟性優異的濺鍍標靶、及其製 造方法。 本發明的不飽和羧酸接枝聚烯烴,此狀態直接,但亦 可以含有本發明的不飽和羧酸接枝聚烯烴、無機微粒子及 溶劑的無機微粒子分散液。 ΟThe ammonium splash target of the present invention can be produced by using the conductive film of the present invention in conjunction with the pair of target bodies and the back sheet. The method of attaching the pair of target bodies and the back sheet is not limited as long as it can ensure electrical conductivity of both, and an example of the following method is used, and the back sheet and the conductive film of the present invention are used. And the paired target bodies are laminated in this order, and if necessary, placed in a heating chamber under pressure and melted. The temperature at this time may be followed by the back plate and the pair of target bodies, and is not particularly limited, and is usually 90 to 300 ° C, more preferably 120 to 250 ° C, which can be used according to the temperature. The melting point of the conductive film is appropriately changed, but it is preferably at least the melting temperature of the film, and more preferably at least the thermal decomposition temperature of the film. In order to ensure sufficient adhesion strength, for example, it is preferable to add a melting point of the temperature-based film to a temperature of 1 〇〇 ° C or less, and then the time is as long as the back plate and the pair of target bodies are uniform and practically sufficient. The strength is not particularly limited and is usually from 1 to 60 minutes, preferably from 1 to 30 minutes, and more preferably from 1 to 10 minutes. When subsequently, the backing plate and the pair of target bodies can be heated in advance to the subsequent temperature standby, in which case the bonding time can be shortened; the subsequent pressure is as long as the backing plate and the paired target body have uniform and practically sufficient bonding strength. There is no particular limitation, and it is usually 0.2 to 10 MPa, preferably 0 to 2 MPa, more preferably 0.2 to 3 MPa. In order to obtain sufficient sputtering performance, it is preferable to carry out the above-described pressure conditions which do not flow out to the outside of the surface when the conductive film of the present invention is melted. -55- 200925171 According to the present invention, it is possible to provide a conductive film, in particular, a conductive film which can be electrically connected to a target body and a back sheet in a simple manner, and which can impart electrical conductivity therebetween, and the back sheet is excellent in economical efficiency. Sputter target, and its manufacturing method. The unsaturated carboxylic acid grafted polyolefin of the present invention may be in this state as it is, but may also contain the inorganic fine particle dispersion liquid of the unsaturated carboxylic acid grafted polyolefin, inorganic fine particles and solvent of the present invention. Ο
發現此仍作爲使無機微粒子分散的媒介物,以不飽和 羧酸接枝聚烯烴溶解於有機溶劑的聚合物溶液較有效,而 且,將該溶液中分散無機微粒子之液以適當的方法塗佈於 金屬、塑膠等之基材後,揮發溶劑,而且藉由加熱處理, 形成由該聚合物與無機微粒子所成的皮膜,此皮膜堅固地 黏著於金屬、塑膠等之基材。 本發明的無機微粒子分散液,係含有本發明的不飽和 羧酸接枝聚烯烴、無機微粒子及溶劑,使不飽和羧酸接枝 聚烯烴溶解於溶劑的聚合物溶液中分散有無機微粒子。 不飽和羧酸接枝聚烯烴,係將本發明的無機微粒子分 散液塗佈或印刷於基材上後,使溶劑揮發時在與基材接著 的狀態下形成皮膜’使製品外觀良好,特別是進行電路形 成時爲了提局電傳導性,不含有於加熱至140 °c的二甲苯 中不溶的凝膠較佳。 本發明的無機微粒子分散液中作爲無機微粒子,只要 是從該無機微粒子分散液揮發溶劑時所形的由無機微粒子 與不飽和羧酸接枝聚烯烴所成的皮膜爲平滑即可,並沒有 -56- 200925171 特別的限制,可列舉例如金、銀、銅、鈀、鍺、餓、釕、 銥、鋁、鐵、銦、鎂、鉑、矽、錫、鋅、鈷、鎳、鉻、鈦 、钽、鎢、碳黑等,可列舉選自此等粒子的至少1種的微 粒子。本發明所謂微粒子之意,係指平均粒徑爲lnm〜5 Ομιη 者。 賦予導電性時,以金、銀、銅等之微粒子較適合使用 ,此外,對加飾用途以鋁、銅、銀等之微粒子較適用。無 0 機微粒子的平均粒徑可依用途適當選擇,並沒有特別的限 制,賦予導電性時使用奈米粒子較佳,作爲平均粒徑以 1〜50nm較適合使用,此外,加飾用途則以50ηηι~50μιη的 平均粒徑較適合使用,而且,在任何的用途中,必要時亦 可混合不同平均粒徑的粒子後使用。特別是已知平均粒徑 爲奈米尺寸的金屬粒子,因爲熔點下降現象而引起自發的 融合,由此觀點而言,對形成電路的用途而言,儘可能使 用平均粒徑小的金屬粒子較佳。 〇 本發明中,無機微粒子的含量可依目的適當變更,但 爲了表現出導電性或表面保護的機能,而且,防止皮膜強 度的降低,相對於不飽和羧酸接枝聚烯烴1重量份,無機 微粒子爲1〜50重量份較佳,5〜40重量份爲更佳。 本發明的無機微粒子分散液中作爲溶劑,只要是不飽 和羧酸接枝聚烯烴產生溶解的溶劑,並沒有任何的限制皆 可使用,依不飽和羧酸接枝聚烯烴的種類適當選擇。作爲 溶劑,可列舉甲基乙基酮、甲基異丁基酮等之酮系溶劑、 苯、甲苯、二甲苯等之芳香族烴,或戊烷、已烷、環己烷 -57- 200925171 、庚烷等之脂肪族烴、環己醇、葱品醇等之醇類、i1-二 氯乙烷、1,2 -二氯乙烷、二氯甲烷、氯仿、Ι,Ι,1·三氯乙 烷、1,1,2-三氯乙烷、四氯化碳、三氯乙烯、全氯乙烯等 之氯系溶劑、溴化乙烷等之溴系溶劑、單氟苯、1,4-二氟 苯、全氟庚烷、全氟辛烷、二氯五氟丙烷等之氟系溶劑、 溴氯甲烷、1,2-二溴-1,1-二氟乙烷等之含有溴及氟之溶劑 等,但爲了抑制因爲溶劑的揮發產生分散液的黏度變化, 0 溶劑的沸點爲1 〇〇°c以上者較適用,此等溶劑可單獨使用 ,必要時混合複數的溶劑使用亦可。 本發明的無機微粒子分散液的黏度,可依塗佈、印刷 該分散液之方法適當選擇,但噴墨印刷係該分散液的黏度 爲l~50mPa · s較適合,照相凹版印刷、膠版印刷、及網 版印刷印刷時,以1〜500Pa · s的範圍較適合。 本發明的無機微粒子分散液,亦可含有前述的其他樹 脂、彈性體或橡膠成分、各種添加劑。 〇 此等的其他樹脂、彈性體或橡膠成分、各種添加劑, 可在不損及本發明所提供的導電性的皮膜或表面保護皮膜 的機能的範圍內含有,其含量相對於不飽和羧酸接枝聚烯 烴100重量份而言爲0.1〜10重量份較佳,更佳爲0 重量份。 於接枝反應中所生成的不飽和羧酸接枝聚烯烴與溶劑 之分離’可使用鼓式乾燥機'水蒸氣蒸餾、附有排氣口的 擠壓機等一般常用的方法’但使用鼓式乾燥機由經濟的利 用面而S特別佳。另一方面,製造本發明的無機微粒子分 -58- 200925171 散液所使用的溶劑與上述的接枝反應的溶劑相同時,不需 要從反應溶液離析該不飽和羧酸接枝聚烯烴,藉由添加反 應溶劑、或濃縮反應溶液等之方法,調整該不飽和羧酸接 枝聚烯烴的濃度,在此狀態下使用於無機微粒子分散液的 製造。 於接枝反應所生成的不飽和羧酸接枝聚烯烴與溶劑的 分離、藉由鼓式乾燥機經揮發的1,1,2-三氯乙烷的回收、 0 藉由鼓式乾燥機從聚合物溶液去除溶劑所需要的時間、經 離析的聚合物的加工,如前述。 作爲塗佈或印刷本發明的無機微粒子分散液的對象之 基材,可列舉聚碳酸酯、聚烯烴、環狀聚烯烴、聚對苯二 甲酸乙二醇酯、聚乙嫌萘酸酯(polyethylenenaphtalate ) 、丙烯腈·苯乙烯共聚物、聚甲基甲基丙烯酸酯、聚甲基 戊烯-1、聚苯硫醚、聚醯亞胺、聚氯乙烯等之樹脂成形體 、鋁、銅、不鏽鋼等之金屬成型體、玻璃的成型體、矽晶 Q 圓等。 作爲本發明的無機微粒子分散液的製造方法,可使用 各種的方法,以列舉出其中一例。 將所製造的不飽和羧酸接枝聚烯烴溶解於前述的有機 溶劑而調製聚烯烴溶液,此溶液調製可使用具備攪拌機之 反應器等,但亦可使用均漿器等之機械進行。此時,溶解 溫度並沒有特別的限制,但通常在室溫至所使用的溶劑的 沸點以下進行較佳。於所得到的聚烯烴溶液中添加無機微 粒子’使用超音波洗淨器、均漿器等使無機微粒子分散, -59- 200925171 此時的溫度只要是溶劑不揮發的溫度,並沒有特別的限制 ,爲室溫至溶劑的沸點以下。此外,可使用耐壓容器以溶 劑的沸點以上的溫度進行無機微粒子的分散。 本發明的無機微粒子分散液係藉由既存的照相凹版印 刷、膠版印刷、網版印刷印刷、噴墨印刷、含浸、旋轉塗 佈等之技術,以簡便、經濟的、且高生產性形成於塑膠、 金屬、玻璃、矽晶圓等之各種基材上形成導電性電路之表 面保護膜,或可用於使用前述的各種基材在經成型的成型 體表面上賦予圖案性。 依據本發明,可於各種的塑膠、玻璃、矽晶圓、金屬 等之基材上以堅固地接著的狀態形成皮膜,而且,可提供 經由短時間的熱處理可形成安定的皮膜之無機微粒子分散 液。 【實施方式】It has been found that as a vehicle for dispersing inorganic fine particles, it is effective to dissolve a polymer solution in which an unsaturated carboxylic acid grafted polyolefin is dissolved in an organic solvent, and a solution in which inorganic fine particles are dispersed in the solution is applied in an appropriate manner. After the base material of metal or plastic, the solvent is volatilized, and a film formed of the polymer and the inorganic fine particles is formed by heat treatment, and the film is firmly adhered to a substrate such as metal or plastic. The inorganic fine particle dispersion liquid of the present invention contains the unsaturated carboxylic acid graft polyolefin of the present invention, inorganic fine particles and a solvent, and inorganic fine particles are dispersed in a polymer solution in which an unsaturated carboxylic acid grafted polyolefin is dissolved in a solvent. The unsaturated carboxylic acid-grafted polyolefin is obtained by coating or printing the inorganic fine particle dispersion of the present invention on a substrate, and then forming a film in a state in which the solvent is volatilized in a state in which the solvent is volatilized. In order to improve electrical conductivity when forming a circuit, it is preferred that the gel is not contained in xylene heated to 140 ° C. In the inorganic fine particle dispersion liquid of the present invention, as the inorganic fine particles, the film formed by the inorganic fine particles and the unsaturated carboxylic acid grafted polyolefin which is formed when the solvent is volatilized from the inorganic fine particle dispersion liquid may be smooth, and there is no - 56- 200925171 Specific restrictions include, for example, gold, silver, copper, palladium, rhodium, samarium, bismuth, antimony, aluminum, iron, indium, magnesium, platinum, rhodium, tin, zinc, cobalt, nickel, chromium, titanium, Examples of the ruthenium, tungsten, carbon black, and the like include fine particles selected from at least one of these particles. The term "microparticles" as used in the present invention means an average particle diameter of 1 nm to 5 Ομιη. When conductivity is imparted, fine particles such as gold, silver, or copper are preferably used, and fine particles such as aluminum, copper, and silver are preferably used for decorative purposes. The average particle diameter of the zero-particle-free fine particles can be appropriately selected depending on the use, and is not particularly limited. It is preferable to use a nanoparticle for imparting conductivity, and it is preferably used as an average particle diameter of 1 to 50 nm, and in addition, for decorative use, The average particle diameter of 50 ηηι to 50 μιη is preferably used, and in any application, if necessary, particles having different average particle diameters may be mixed and used. In particular, it is known that metal particles having an average particle diameter of a nanometer size cause spontaneous fusion due to a decrease in melting point. From the viewpoint of the use of a circuit, the use of metal particles having a small average particle diameter is used as much as possible. good. In the present invention, the content of the inorganic fine particles may be appropriately changed depending on the purpose, but in order to exhibit the function of conductivity or surface protection, and to prevent the decrease in the strength of the film, 1 part by weight of the unsaturated carboxylic acid grafted polyolefin is inorganic. The fine particles are preferably 1 to 50 parts by weight, more preferably 5 to 40 parts by weight. The solvent for the inorganic fine particle dispersion of the present invention is not particularly limited as long as it is a solvent which does not saturate the carboxylic acid grafted polyolefin, and is appropriately selected depending on the type of the unsaturated carboxylic acid grafted polyolefin. Examples of the solvent include a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, an aromatic hydrocarbon such as benzene, toluene or xylene, or pentane, hexane or cyclohexane-57-200925171. An aliphatic hydrocarbon such as heptane, an alcohol such as cyclohexanol or onion alcohol, i1-dichloroethane, 1,2-dichloroethane, dichloromethane, chloroform, hydrazine, hydrazine, and tri-chloro a chlorine solvent such as ethane, 1,1,2-trichloroethane, carbon tetrachloride, trichloroethylene or perchloroethylene, a bromine solvent such as brominated ethane, monofluorobenzene or 1,4- Fluorine-based solvents such as difluorobenzene, perfluoroheptane, perfluorooctane, dichloropentafluoropropane, bromochloromethane, 1,2-dibromo-1,1-difluoroethane, etc. In order to suppress the change in the viscosity of the dispersion due to the volatilization of the solvent, the boiling point of the solvent of 0 is preferably 1 〇〇 ° C or more. These solvents may be used singly or in combination with a plurality of solvents if necessary. The viscosity of the inorganic fine particle dispersion of the present invention can be appropriately selected according to the method of coating and printing the dispersion, but the inkjet printing system has a viscosity of 1 to 50 mPa·s, and is suitable for gravure printing, offset printing, In the case of screen printing, it is suitable for a range of 1 to 500 Pa·s. The inorganic fine particle dispersion of the present invention may contain the above-mentioned other resin, elastomer or rubber component, and various additives. The other resin, elastomer or rubber component, and various additives may be contained in a range that does not impair the function of the conductive film or surface protective film provided by the present invention, and the content thereof is relative to the unsaturated carboxylic acid. The amount of the polyolefin of the branched polyolefin is preferably 0.1 to 10 parts by weight, more preferably 0 part by weight. The separation of the unsaturated carboxylic acid grafted polyolefin formed in the grafting reaction from the solvent can be carried out by using a drum dryer, steam distillation, an extruder equipped with a vent, etc. The dryer is particularly advantageous from the economical use surface. On the other hand, when the solvent used in the production of the inorganic fine particles of the present invention is the same as the solvent for the above grafting reaction, it is not necessary to isolate the unsaturated carboxylic acid grafted polyolefin from the reaction solution by The concentration of the unsaturated carboxylic acid grafted polyolefin is adjusted by adding a reaction solvent or a method of concentrating the reaction solution, etc., and is used in the production of the inorganic fine particle dispersion. Separation of the unsaturated carboxylic acid grafted polyolefin formed by the grafting reaction with a solvent, recovery of 1,1,2-trichloroethane which is volatilized by a drum dryer, and 0 by a drum dryer The time required for the polymer solution to remove the solvent, the processing of the isolated polymer, as described above. Examples of the substrate to be coated or printed with the inorganic fine particle dispersion of the present invention include polycarbonate, polyolefin, cyclic polyolefin, polyethylene terephthalate, and polyethylenenaphtalate. ), acrylonitrile-styrene copolymer, polymethyl methacrylate, polymethylpentene-1, polyphenylene sulfide, polyimide, polyvinyl chloride, etc., resin molded body, aluminum, copper, stainless steel Such as a metal molded body, a molded body of glass, a twinned Q circle, or the like. As a method for producing the inorganic fine particle dispersion of the present invention, various methods can be used, and an example thereof can be cited. The produced unsaturated carboxylic acid-grafted polyolefin is dissolved in the above-mentioned organic solvent to prepare a polyolefin solution. The solution can be prepared by using a reactor equipped with a stirrer or the like, but it can also be carried out using a machine such as a homogenizer. In this case, the dissolution temperature is not particularly limited, but it is usually preferably from room temperature to the boiling point of the solvent to be used. The inorganic fine particles are added to the obtained polyolefin solution. The inorganic fine particles are dispersed by using an ultrasonic cleaner or a homogenizer. The temperature at this time is not particularly limited as long as the temperature at which the solvent does not volatilize. It is from room temperature to below the boiling point of the solvent. Further, the pressure-resistant container can be used to disperse the inorganic fine particles at a temperature equal to or higher than the boiling point of the solvent. The inorganic fine particle dispersion of the present invention is formed into a plastic in a simple, economical, and high-productivity by existing technologies such as gravure printing, offset printing, screen printing, inkjet printing, impregnation, spin coating, and the like. A surface protective film for forming a conductive circuit on various substrates such as metal, glass, germanium wafer, or the like, or can be used to impart patterning on the surface of the molded body using the various substrates described above. According to the present invention, a film can be formed in a solid state on a substrate of various plastics, glass, germanium wafers, metals, etc., and an inorganic fine particle dispersion capable of forming a stable film by a short-time heat treatment can be provided. . [Embodiment]
接著基於實施例詳細地說明本發明,但此等實施例爲 幫助本發明的理解之例,本發明並不受到此等的實施例的 任何限制。 再者,此等的實施例所使用的値係依以下的測量法所 得到。 <原料> 本發明的實施例使用下記的原料。 -60- 200925171The invention is described in detail below based on the embodiments, but these examples are examples of the understanding of the invention, and the invention is not limited by the examples. Further, the oxime used in the examples is obtained by the following measurement method. <Materials> The examples of the present invention use the raw materials described below. -60- 200925171
(1 ) EVA 乙烯•乙酸乙烯酯共聚物:東曹股份有限公司製烏 魯投拉仙(登錄商標)751 (乙酸乙烯酯含量=28重量%、 MFR = 5.7g/10 分鐘、密度=952kg/m3)(1) EVA ethylene/vinyl acetate copolymer: Ulutou Laxian (registered trademark) 751 manufactured by Tosoh Corporation (vinyl acetate content = 28% by weight, MFR = 5.7g/10 minutes, density = 952kg/ M3)
(2) L-LDPE(2) L-LDPE
乙烯•己烯-1共聚物:東曹股份有限公司製 NIPOLON-Z (登錄商標)ZF230 ( MFR = 2.0g/10 分鐘、密 度=920kg/m3)Ethylene/hexene-1 copolymer: manufactured by Tosoh Corporation NIPOLON-Z (registered trademark) ZF230 (MFR = 2.0g/10 min, density = 920kg/m3)
(3 ) PP 均聚丙烯:CHISSO石油化學股份有限公司製 CHISSO POLYPRO XF181 1 ( MFR = 2.5g/10 分鐘、密度 =900kg/m3)(3) PP homopolypropylene: CHISSO POLYPRO XF181 1 manufactured by CHISSO Petrochemical Co., Ltd. (MFR = 2.5g/10 min, density = 900kg/m3)
(4 ) HDPE 高密度聚乙烯:東曹股份有限公司製 NIPOLON HARD (登錄商標)4000 ( MFR = 5.0g/10分鐘、密度(4) HDPE high-density polyethylene: manufactured by Tosoh Corporation, NIPOLON HARD (registered trademark) 4000 (MFR = 5.0g/10 minutes, density
(5) 鹼化EVA (乙烯•乙酸乙烯酯共聚物的鹼化物(5) alkalized EVA (alkaline of ethylene/vinyl acetate copolymer)
1 )鹼化EVA-1 :東曹股份有限公司製H-6410M1) Alkaline EVA-1: H-6410M manufactured by Tosoh Corporation
2) 鹼化EVA-2:東曹股份有限公司製H-605 1 K 3) 鹼化EVA-3:東曹股份有限公司製H-6960 (6) 苯甲醯過氧化物(BPO)2) Alkali EVA-2: H-605 1 K manufactured by Tosoh Corporation 3) Alkaline EVA-3: H-6960 (6) Benzoyl peroxide (BPO) manufactured by Tosoh Corporation
日本油脂股份有限公司製NYPER B (7) 二(2-t-丁基過氧化丙基)苯(DBPIB) -61 - 200925171NYPER B (7) bis(2-t-butylperoxypropyl)benzene (DBPIB) -61 - 200925171
曰本油脂股份有限公司製PERBUTYL P (8) 2,6-二-tert-丁基-p-甲酚(ΒΗΤ) 股份有限公司API YOSHINOX ΒΗΤ (9) 馬來酸酐、丙烯酸、丙烯酸乙基、丙烯酸丁酯 、1,1,2 -三氯乙烷、二甲苯、甲醇、二甲基甲醯胺、ΒΗΤ 、四氫呋喃(THF )、苯基咪唑、26%硫酸水溶液、百里 香酚藍指示藥、Ν/20的ΚΟΗ溶液、甲基六氫苯二甲酸酐 0 爲使用關東化學股份有限公司製的1級試藥。 (10) 鋁板 東洋鋁股份有限公司製支數:Α1Ν30Η-Η18厚度: 1 0 0 μπι (11 )不鏽鋼 (股)NILACO 製 SUS304 753 5 1 3 (1 2 )木材 FLOWER ART夢大陸製黑檀薄片、木瓜薄片、鳥眼 〇 楓薄片、橡樹薄片、斑木樹薄片厚度:0.3mmPERBUTYL P (8) 2,6-di-tert-butyl-p-cresol (ΒΗΤ) Co., Ltd. API YOSHINOX ΒΗΤ (9) Maleic anhydride, acrylic acid, ethyl acrylate, acrylic acid Butyl ester, 1,1,2-trichloroethane, xylene, methanol, dimethylformamide, hydrazine, tetrahydrofuran (THF), phenylimidazole, 26% aqueous sulfuric acid, thymol blue indicator, Ν/ The hydrazine solution of 20 and the methyl hexahydrophthalic anhydride 0 were used as the first-stage reagents manufactured by Kanto Chemical Co., Ltd. (10) Aluminum plate Toyo Aluminum Co., Ltd. Count: Α1Ν30Η-Η18 Thickness: 1 0 0 μπι (11) Stainless steel (share) NILACO SUS304 753 5 1 3 (1 2 ) Wood FLOWER ART Dream ebony flakes, Papaya flakes, bird's eye maple leaf flakes, oak flakes, porphyra tree flakes thickness: 0.3mm
(1 3 )環氧樹脂A(1 3 ) Epoxy resin A
曰本環氧樹脂(股)jER (登錄商標)807 (1 4 )環氧樹脂B 日本環氧樹脂(股)jER (登錄商標)191P (1 5 )環氧樹脂硬化劑 明和化成社製酚酚醛清漆型硬化劑Η-1 (1 6 )聚醯亞胺薄膜 宇部興產股份有限公司製 UPILEX (登錄商標)755 -62- 200925171 (17)聚碳酸酯薄膜 帝人化成股份有限公司製 panlite (登錄商標)PC- 21 5 1 (1 8 )聚苯硫醚薄片 東曹股份有限公司製 SULTEEL (登錄商標)G10 (19) 聚-(苯乙烯·丁二烯-苯乙烯)嵌段共聚物 Shell化學(股)製、商品名TR-1150 (20) 銅箔 股份有限公司NILACO製 CU-113253厚度:40μιη (2 1 )聚醯亞胺膠帶 住友3Μ股份有限公司製聚醯亞胺膠帶5412 (22)顯影液曰本 epoxy resin (share) jER (registered trademark) 807 (1 4) epoxy resin B Japan epoxy resin (share) jER (registered trademark) 191P (1 5) epoxy resin hardener Minghe Chemical Co., Ltd. phenol phenolic Varnish type hardener Η-1 (1 6 ) Polyimide film UPILEX (registered trademark) 755 -62- 200925171 (17) Polycarbonate film Teijin Chemical Co., Ltd. made panlite (Login trademark ) PC- 21 5 1 (1 8 ) Polyphenylene sulfide sheet SULTEEL (registered trademark) G10 (19) Poly-(styrene-butadiene-styrene) block copolymer Shell chemistry ( Co., Ltd., trade name TR-1150 (20) CU-113253 Manufactured by NILACO, Copper Foil Co., Ltd. Thickness: 40μιη (2 1 ) Polyimide Tape Polyurethane Tape 5412 (22) Developed by Sumitomo 3 Co., Ltd. liquid
ROHM&HAAS製 Μ IC R Ο Ρ 0 SIΤ (磷酸鹽系顯影液) DEVELOPPER (23 )導電性微粒子ROHM&HAAS Μ IC R Ο Ρ 0 SIΤ (phosphate developer) DEVELOPPER (23) conductive microparticles
1) 銅微粒子:(股)高純度化學硏究所製CUE0 8PB 平均粒徑1 μ m1) Copper microparticles: (stock) High purity chemical research institute CUE0 8PB Average particle size 1 μ m
2) 碳黑:三菱化學股份有限公司製 KETJENBLACK2) Carbon black: manufactured by Mitsubishi Chemical Corporation KETJENBLACK
EC (24)無機微粒子 1) 銀粒子:(股)高純度化學硏究所製還原銀粒 子AGE08PB平均粒徑Ιμιη 2) 鋁粒子:(股)高純度化學硏究所製ALE 11ΡΒ平 均粒徑3μ -63- 200925171 3) 銅粒子:(股)高純度化學硏究所製CUE08PB平 均粒徑1 μηι 4) 金粒子:(股)高純度化學硏究所製平均粒徑 1 μηι 5) 酸化第二鐵鐵粒子:(股)高純度化學硏究所製 FEO02PB平均粒徑1 μιη 6) 銀奈米膏:ULVAC Materials股份有限公司製平EC (24) Inorganic fine particles 1) Silver particles: (Stock) High-purity chemical research institute Reduced silver particles AGE08PB Average particle size Ιμιη 2) Aluminum particles: (Shares) High-purity chemical research institute ALE 11ΡΒ Average particle size 3μ -63- 200925171 3) Copper particles: (C) high-purity chemical research institute CUE08PB average particle size 1 μηι 4) Gold particles: (stock) high-purity chemical research institute average particle size 1 μηι 5) Acidification second Ferro-iron particles: FEO02PB average particle size 1 μιη produced by the High Purity Chemical Research Institute 6) Silver Nano Paste: Flattened by ULVAC Materials Co., Ltd.
7)碳黑:三菱化學股份有限公司製KETJENBLACK EC (2 5 )葱品醇(不飽和脂肪族環式酚) 曰本萜烯化學股份有限公司 <接著試驗> 接著試驗係使用下記的樹脂、金屬。7) Carbon black: KETJENBLACK EC manufactured by Mitsubishi Chemical Co., Ltd. (2 5 ) Onion alcohol (unsaturated aliphatic cyclic phenol) 曰本萜烯化学股份有限公司<Next test> Next, the test system uses the following resin ,metal.
(1 )聚醯亞胺薄膜 宇部興產股份有限公司製UP ILEX (登錄商標)75 5 (2)聚碳酸酯薄膜 帝人化成股份有限公司製panlite (登錄商標)ΡΟΖ 1 5 1 (3 )聚苯硫醚(PPS ) 東曹股份有限公司製SULTEEL (登錄商標)GS40 (4)聚對苯二甲酸乙二醇酯薄膜 東麗股份有限公司製RUMIRER #1 00 -64- 200925171 (5 )銅板 股份有限公司NILACO製CU-113328 0.10m (6)鋁板 東洋鋁股份有限公司製支數:A1N30H-H18厚度: 1 0 0 μπι <酸價> 0 秤量聚合物試樣lg,使其加熱溶解於甲苯1 0 0ml後 ’加入甲醇l〇ml、二甲基甲醯胺i〇ml、水〇.5ml,接著 ’加入百里香酚藍指示藥lml,用N/2 0的KOH溶液(n- 丙醇/苯溶液)滴定,計算出藍紫色持續〗分鐘以上的時 間點作爲終點。 <熔體流動速率(MFR) > 熔體流動速率(MFR)係聚乙烯依據JISK6 922-1、乙 〇 燃乙酸乙烯酯共聚物依據JISK6924-1、聚丙烯依據 JISK6921-2 ’使用寶工業(股)製的 MELT INDEXER L244 ’以測量溫度1 9 〇 Ό、荷重2.1 6kgf的條件進行測量 <凝膠分率的測量> 將聚合物50mg添加於二甲苯50ml中,以140。(:使其 進行1 2小時溶解後’將此溶液用2〇〇網眼的不鏽鋼製的 網眼(75μιη)進行過濾,進行105 °C、5小時乾燥後計算 -65- 200925171 出金網上的未熔融成分。 <黃色指數(YI)的測量> 依據Jis K71 05 ( 1 98 1年版),將使用(股) 屬工業所製的復動式壓縮成形機WFA-50,以加 150°C、壓力 lOMPa、10分鐘、冷卻溫度 30°C 1 OMPa、5分鐘的條件加壓之厚度ΙΟΟμιη的薄膜的 用SUGA試驗機(股)製 SM彩色電腦進行測量。(1) UP ILEX (registered trademark) 75 5 (2) Polycarbonate film manufactured by Teijin Chemicals Co., Ltd. panlite (registered trademark) ΡΟΖ 1 5 1 (3) Polyphenylene Sulfide (PPS) SULTEEL (registered trademark) GS40 (4) Polyethylene terephthalate film manufactured by Toray Co., Ltd. RUMIRER #1 00 -64- 200925171 (5) Limited copper plate shares Company NILACO CU-113328 0.10m (6) Aluminum plate Toyo Aluminum Co., Ltd. Count: A1N30H-H18 Thickness: 1 0 0 μπι <acid price> 0 Weigh the polymer sample lg and heat it to dissolve in toluene After adding 100 ml of '100 ml of methanol, dimethylformamide i〇ml, hydrazine. 5 ml, then 'add thymol blue indicator lml, use N/2 0 KOH solution (n-propanol / The benzene solution was titrated, and the time point above which the blue-violet continuation was counted as the end point was calculated. <Melt flow rate (MFR) > Melt flow rate (MFR) based on polyethylene according to JIS K6 922-1, acetonitrile vinyl acetate copolymer according to JIS K6924-1, polypropylene according to JIS K6921-2 'Use Bao industry MELT INDEXER L244 'made by (stock) was measured under the conditions of a temperature of 19 Torr and a load of 2.1 6 kgf. <Measurement of gel fraction> 50 mg of the polymer was added to 50 ml of xylene to 140. (: After it was dissolved for 12 hours, 'this solution was filtered with a stainless steel mesh (75 μm) of 2 mesh mesh, and dried at 105 ° C for 5 hours. -65-200925171 Unmelted component. <Measurement of yellow index (YI)> According to Jis K71 05 (1 98 1st edition), the double-action compression molding machine WFA-50 manufactured by the company will be used to add 150°. C, a pressure of 10 MPa, 10 minutes, a cooling temperature of 30 ° C 1 OMPa, a condition of 5 minutes of pressure, and a film of thickness ΙΟΟμηη was measured by a SU color tester (s).
神藤金 熱溫度 '壓力 YI,使 用裝置 製之長 裝置( <1,1,2-三氯乙烷中的1-丁醇及1,2-環氧基丁烷量> 用微量注射器採取出1,1,2-三氯乙烷0.5μ1, GC 毛細管柱 DB-1301 (Agilent Technologies 公司 度30m、内徑〇.25mm、膜厚〇·25μπι)之氣相層析 島津製作所製GC-1 4 A ),用以下的條件進行測量< 注射溫度:40°C 注射溫度保持時間:4分鐘 昇溫程式1 : 5°C/分鐘(40〜90°C) 昇溫程式2: 10°C/分鐘(90~190°C) 最終溫度:190°C 最終溫度保持時間:20分 載氣:氦 <接著試驗> 成形機 使用(股)神藤金屬工業所製的復動式壓縮 -66 - 200925171Shentan Gold Hot Temperature 'Pressure YI, using a device made of long device ( <1,1,2-trichloroethane in 1-butanol and 1,2-epoxybutane amount> Take with a micro syringe GC-1, manufactured by Gas Chromatography Shimadzu Corporation, with 1,1,2-trichloroethane 0.5 μl, GC capillary column DB-1301 (Agilent Technologies, Inc., 30 m, inner diameter 〇.25 mm, film thickness 〇·25 μπι) 4 A ), measured with the following conditions < Injection temperature: 40 ° C Injection temperature retention time: 4 minutes Heating program 1: 5 ° C / minute (40 ~ 90 ° C) Heating program 2: 10 ° C / minute (90~190°C) Final temperature: 190°C Final temperature retention time: 20 minutes carrier gas: 氦<Next test> Forming machine used (share) Shendu Metal Industry's double-acting compression-66 - 200925171
WFA-50作爲加壓成形機,以加熱溫度 15(TC、壓力 lOMPa、1〇分鐘、冷卻溫度30°C、壓力l〇MPa、5分鐘的 加壓條件得到厚度1 ΟΟμηι的加壓薄膜。將該成形爲 ΙΟΟμιη厚度的薄膜與被黏著物使用TESTER產業股份有限 公司製的 Heat Seal TESTERTP-701,以 180〇C、60 秒 ' 0.2MPa的條件進行加熱接著。使用(股)ORIENTEC製 Tensilon萬能試驗機RTE-1210作爲拉伸試驗機,用拉伸 速度(剝離速度)3 00mm/分鐘的條件藉由T型剝離試驗 ,評估其接著強度。 <熔融擠壓> 使用具有排氣口的NAKATANI機械工業製的區段數 10、2 軸擠壓機(115ιηιηφ、L/D = 50)。 <熱循環試驗> 使用ESPEC股份有限公司製的冷熱衝撃裝置TSA-7 1L-A,以85°C30分鐘、常溫5分鐘、-40°C30分鐘作爲 1個循環,對接著試驗片施加熱衝撃,觀察接著片的剝離 等。 <旋轉塗佈> 使用MIKASA旋轉塗佈機1H-360S。 <耐彎折性> -67- 200925171 耐彎折性的評價(MIT試驗),係依據JIS-C5016使 用股份有限公司Mitutoyo製MIT試驗器,使用R = 〇.38的 治具評估層合物的破裂次數、或剝離次數。 <導電性微粒子的混練> 使用東洋精機(股)製的laboplastomill R30,以旋 轉數60rpm的條件於不飽和羧酸接枝聚烯烴中添加導電性 0 微粒子,於熔融狀態下混練,得到含有導電性微粒子之不 飽和羧酸接枝聚烯烴。 <薄膜的成形> 使用(股)神藤金屬工業所製的復動式壓縮成形機 WFA-50作爲加壓成形機,以加熱溫度 150°C、壓力 lOMPa、10分鐘、冷卻溫度30°C'壓力lOMPa、5分鐘的 加壓條件得到厚度1 〇 〇 μηι的加壓薄膜。 〇 <Τ型剝離試驗> 使用(股)ORIENTEC製Tensilon萬能試驗機RTE-1210,用拉伸速度(剝離速度)3 00mm/分鐘的條件用T 型剝離試驗,評估其接著強度。 <膠帶剝離試驗> 於基材上藉由網版印刷進行印刷5 mm X 5 mm的正方形 的圖型100個,乾燥後、以210 °C經熱處理,於此圖型上 -68- 200925171 貼上膠帶,膠帶剝離時調查圖型從基材剝離的個數。 實施例1WFA-50 was used as a press molding machine to obtain a pressurized film having a thickness of 1 ΟΟμηι under heating conditions of a heating temperature of 15 (TC, a pressure of 10 MPa, a pressure of 30 ° C, a pressure of 10 ° C, and a pressure of 5 MPa for 5 minutes). The film formed into a thickness of ΙΟΟμηη and the adherend were heated by a Heat Seal TESTERTP-701 manufactured by TESTER Industries, Inc., and heated at 180 〇C, 60 sec '0.2 MPa. The Tensilon universal test using ORIENTEC was used. RTE-1210 was used as a tensile tester and its adhesion strength was evaluated by a T-peel test at a tensile speed (peeling speed) of 300 mm/min. <Fused extrusion> Using NAKATANI with a vent The number of sections made by the mechanical industry is 10 and 2 axis extruders (115 ιηιηφ, L/D = 50). <Heat cycle test> Using the hot and cold blasting apparatus TSA-7 1L-A manufactured by ESPEC Co., Ltd., 85 °C for 30 minutes, normal temperature for 5 minutes, and -40 °C for 30 minutes as one cycle, heat treatment was applied to the subsequent test piece, and peeling of the adhesive sheet was observed. <Rot Coating> A MIKASA spin coater 1H-360S was used. <Bending resistance> -67 - 200925171 Evaluation of bending resistance (MIT test), using the MIT tester manufactured by Mitutoyo Co., Ltd. according to JIS-C5016, using the jig of R = 〇.38 to evaluate the number of breaks or the number of peeling of the laminate. (Kneading of conductive fine particles) Using a laboroplastomill R30 manufactured by Toyo Seiki Co., Ltd., conductive 0 microparticles were added to the unsaturated carboxylic acid grafted polyolefin at a rotation number of 60 rpm, and kneaded in a molten state to obtain a conductive material. Unsaturated carboxylic acid grafted polyolefin of fine particles. <Forming of film> Using a double-action compression molding machine WFA-50 manufactured by Shinto Metal Industry as a press molding machine at a heating temperature of 150 ° C , pressure lOMPa, 10 minutes, cooling temperature 30 ° C 'pressure lOMPa, 5 minutes of pressurization conditions to obtain a pressure film of thickness 1 〇〇 μηι. 〇 < Τ type peel test> Use (stock) ORIENTEC Tensilon versatile The test machine RTE-1210 was evaluated for its adhesion strength by a T-peel test using a tensile speed (peeling speed) of 300 mm/min. < Tape peeling test> by screen printing on a substrate 100 patterns of 5 mm X 5 mm squares were printed, and after drying, heat treatment was carried out at 210 °C. On this pattern, tape was attached to -68-200925171. When the tape was peeled off, the pattern was peeled off from the substrate. number. Example 1
將關東化學股份有限公司製的三氯乙烷5 000 重量份與26 %硫酸水溶液2500重量份’放進附有下口的 10升燒瓶中激烈地攪拌,靜置後取出下層的有機層’接 著將取出的有機層與蒸餾水5000重量份,放進附有下口 的10升燒瓶中激烈地攪拌,靜置後取出下層的有機層之 操作藉由重覆3次,去除雜質的1-丁醇及1,2-環氧基丁烷 ,更藉由於取出的有機層中添加150重量份的分子篩4A 、用攪拌器攪拌而脫水。 於2升的玻璃製反應容器中裝入經由上述的操作經去 除1-丁醇及1,2-環氧基丁烷的1,1,2-三氯乙烷1 250重量 份、EVA 100重量份、及馬來酸酐2_0重量份,藉由將反 應器昇溫至80°C,然後以80°C保持3小時而均勻地溶解 EVA。此外在此期間,於反應器中以5升/分鐘的流速導 入氮氣,排除混入反應器的空氣,接下來將反應器從80 °C 昇溫至ll〇°C,將作爲接枝反應的觸媒(自由基產生劑) 之使0.8重量份的BPO溶解於經去除1-丁醇及1,2-環氧 基丁烷的1,1,2-三氯乙烷50重量份之觸媒溶液,在用3 小時連續地持續添加至反應器下進行接枝反應,接著以同 溫度繼續2小時反應,反應器的壓力係透過反應保持在 1 MPa以下,反應結束後,回到常壓使反應器的溫度降低 至70°C爲止,然後,添加作爲安定劑之0.03重量份的 -69- 200925171 BHT後’藉由甲醇使此溶液再沈澱,從溶劑分離出們 成物的不飽和羧酸接枝EVA。 已知生成物係具有分析的結果1.8重量%的不ti 酸,凝膠爲〇重量%,YI爲2且色相優良,此外,劈 鋁、聚醯亞胺、聚碳酸酯' PPS的接著強度各爲52、 39、35、3 6N/15 mm,強固地接著於各種的被黏著转 量凝膠、色相、接著強度的結果列示於表1。 爲生 和羧 銅、 60、 ,測5 000 parts by weight of trichloroethane manufactured by Kanto Chemical Co., Ltd. and 2500 parts by weight of a 26% aqueous sulfuric acid solution were placed in a 10-liter flask with a lower mouth and vigorously stirred, and after standing, the lower organic layer was taken out. The extracted organic layer and 5000 parts by weight of distilled water were placed in a 10-liter flask with a lower opening and vigorously stirred, and the operation of removing the organic layer of the lower layer was carried out after standing, and the 1-butanol of the impurity was removed by repeating three times. Further, 1,2-epoxybutane was further dehydrated by adding 150 parts by weight of molecular sieve 4A to the taken-out organic layer and stirring with a stirrer. 1 liter of glass reaction vessel was charged with 1,1,2-trichloroethane 1 -1,2-trichloroethane 1 -butoxyl and 1 ,2-epoxybutane removed by the above operation, and EVA 100 weight A portion and 2 to 0 parts by weight of maleic anhydride were uniformly dissolved in EVA by raising the temperature of the reactor to 80 ° C and then maintaining at 80 ° C for 3 hours. In addition, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liters/min to remove the air mixed into the reactor, and then the reactor was heated from 80 ° C to ll 〇 ° C, which was used as a catalyst for the graft reaction. (Free Radical Generating Agent) 0.8 parts by weight of BPO is dissolved in a catalyst solution of 50 parts by weight of 1,1,2-trichloroethane from which 1-butanol and 1,2-epoxybutane are removed, The grafting reaction was carried out continuously continuously for 3 hours to the reactor, and then the reaction was continued at the same temperature for 2 hours, and the pressure of the reactor was maintained below 1 MPa through the reaction. After the reaction was completed, the reactor was returned to atmospheric pressure. The temperature was lowered to 70 ° C, and then 0.03 parts by weight of -69-200925171 BHT as a stabilizer was added, and then the solution was reprecipitated by methanol to separate the unsaturated carboxylic acid grafted from the solvent. EVA. It is known that the resultant product has a result of analysis of 1.8% by weight of non-ti ci, the gel is 〇% by weight, YI is 2 and the hue is excellent, and the subsequent strengths of yttrium aluminum, polyimine, and polycarbonate 'PPS are each The results for gel, hue, and strength of 52, 39, 35, and 3 6 N/15 mm, which are strongly adhered to various adhesive rotations, are shown in Table 1. For life and carboxy copper, 60, measured
〇 -70- 200925171 ο Ο 〔Is 實施例7 & Ο νΜ ο ΟΝ Η 〇 (N 〇 〇 〇 »Ti <N T—^ Ο ο 00 ο in 〇 (Ν (Ν 〇 <N cn (N 實施例6 HDPE Ο Ό ΟΝ in 〇 〇 2200 ο ο s ο ο 00 〇 tn as (N 〇\ o 寸 實施例5 L-LDPE ο Ο <Ν 〇\ (Ν 〇 (N 〇 〇 ο W-) (S ο ο 00 ο iTi 〇 CN m 00 CN 00 CN <N 實施例4 EVA ο CN Ον 卜 〇 〇 0 1 ο ο ν〇 ο ο <r! 〇 Γ〇 g 〇 ON m Ο 寸 實施例3 EVA ο <Ν κη 〇\ 卜 〇\ 〇 〇 o <rj (N ο ο ο ΓΟ η 〇 S v〇 m cn Ο 寸 實施例2 EVA ο <s 〇\ 〇 (N 〇 〇 (N ο ο νο ο 〇 04 m P; iTi m CN 實施例1 EVA ο (Ν ^Ti Ο 〇 (N 〇 〇 o in cs ο ο 00 ο 00 〇 CN) in § ON cn νο cn CN 障量份 m曰 丨g/io分鐘 重量份 重量份 重量份 重量份 重量份 重量份 重量份 重量% _ ώπΐ] ΡΤη N/15mm N/15mm N/15mm N/15mm 1 N/15mm j m MFR 馬來酸酐 丙烯酸 丙烯酸丁酯 1,1,2-三氯乙烷 擀 η 拼 ο CU CQ 酸改性量 凝膠 骠 聚醯亞胺 聚碳酸酯 GO (X 筠 Μ嵌 遐氍 K·您 溶劑 自由基產生劑 改性聚合物 接著強度 YU色調) -71 - 200925171 實施例2 除了將自由基產生劑的添加量變更爲0.16重量份以 外,與實施例1使用同樣方法進行反應,接著分離生成物 〇 已知生成物係分析結果爲具有1 _5重量%的不飽和羧 酸,凝膠爲〇重量%,YI爲2且色相優良,此外’與銅、 鋁、聚醯亞胺、聚碳酸酯、PPS的接著強度各爲42、53、 37、37、3 5N/15mm,強固地接著於各種的被黏著物,測 量凝膠、色相、接著強度的結果列示於表1。 實施例3 除了將馬來酸酐的添加量變更爲9.7重量份、BPO的 添加量變更爲3.0重量份以外,與實施例1使用同樣方法 進行反應,接著分離生成物。 已知生成物係分析結果爲具有2.1重量%的不飽和羧 酸,凝膠爲〇重量%,YI爲4且色相優良,此外,與銅、 鋁、聚醯亞胺、聚碳酸酯、PPS的接著強度各爲60、66、 36、35、40N/1 5mm,強固地接著於各種的被黏著物,測 量凝膠、色相、接著強度的結果列示於表1。 實施例4 除了將馬來酸酐的添加量變更爲20重量份、1,1,2 -三 氯乙烷的添加量變更爲2000重量份、BPO的添加量變更 爲0 . 1 6重量份以外,與實施例1使用同樣方法進行反應 -72- 200925171 ,接著分離生成物。 已知生成物係分析結果爲具有3·0重量%的不飽和殘 酸,凝膠爲〇重量%’ YI爲4且色相優良,此外’與銅、 鋁、聚醯亞胺、聚碳酸酯、pps的接著強度各爲73、80、 40、39、40N/15mm,強固地接著於各種的被黏著物’測 量凝膠、色相、接著強度的結果列示於表1。 0 實施例5~7 除了將實施例1與基礎聚合物由EVA變更爲L-LDPE 、HDPE、PP,而且將馬來酸酐的添加量變更爲30重量份 、1,1,2 -三氯乙烷的添加量變更爲2200重量份、BPO的添 加量變更爲0.03重量份(實施例6 )以外,與實施例1使 用同樣方法進行反應,接著分離生成物。測量凝膠、色相 、接著強度的結果列示於表1。無凝膠,色相、接著強度 皆優異。 〇 實施例8〜1 1 除了變更1,1,2 -三氯乙烷、不飽和羧酸、βρο的添加 量以外’藉由與實施例4~7同樣的手法進行反應,分離生 成物’測量凝膠、色相、接著強度的結果列示於表2。無 凝膠,色相、接著強度皆優異。 -73- 200925171〇-70- 200925171 ο Ο [Is Example 7 & Ο νΜ ο ΟΝ Η 〇 (N 〇〇〇»Ti <NT—^ Ο ο 00 ο in 〇 (Ν (Ν 〇<N cn (N implementation Example 6 HDPE Ο Ό ΟΝ in 〇〇 2200 ο ο s ο ο 00 〇 tn as (N 〇 \ o inch embodiment 5 L-LDPE ο Ο <Ν 〇\ (Ν 〇 (N 〇〇ο W-) ( S ο ο 00 ο iTi 〇CN m 00 CN 00 CN <N Embodiment 4 EVA ο CN Ον 〇〇 〇〇 0 1 ο ο ν〇ο ο <r! 〇Γ〇g 〇ON m Ο 实施 Example 3 EVA ο <Ν κη 〇\ 卜〇 \ 〇〇o <rj (N ο ο ο ΓΟ η 〇S v〇m cn 寸 实施 实施 实施 实施 实施 E E E E ο νο ο 〇 04 m P; iTi m CN Example 1 EVA ο (Ν ^Ti Ο 〇(N 〇〇o in cs ο ο 00 ο 00 〇CN) in § ON cn νο cn CN Barrier m曰丨g/io minute parts by weight parts by weight parts by weight parts by weight parts by weight _ ώπΐ] ΡΤη N/15mm N/15mm N/15mm N/15mm 1 N/15mm jm MFR Maleic anhydride butyl acrylate 1 , 1,2-trichloroethane 擀η οο CU CQ acid change Amount of gel 骠 polyimine polycarbonate GO (X 筠Μ 遐氍 K · your solvent radical generator modified polymer followed by strength YU tone) -71 - 200925171 Example 2 In addition to the free radical generator The reaction was carried out in the same manner as in Example 1 except that the amount of addition was changed to 0.16 parts by weight, and then the product was separated. The product was analyzed to have an unsaturated carboxylic acid having a content of 1 to 5% by weight, and the gel was 〇% by weight. YI is 2 and the hue is excellent. In addition, the adhesion strength to copper, aluminum, polyimine, polycarbonate, and PPS is 42, 53, 37, 37, 3 5 N/15 mm, and is firmly adhered to various types. The results of measuring the gel, hue, and subsequent strength are shown in Table 1. Example 3 Example 1 was changed except that the amount of maleic anhydride added was changed to 9.7 parts by weight, and the amount of BPO added was changed to 3.0 parts by weight. The reaction was carried out in the same manner, followed by separation of the product. It is known that the product analysis result is 2.1% by weight of an unsaturated carboxylic acid, the gel is 〇% by weight, YI is 4 and the hue is excellent, and further, with copper, aluminum, polyimine, polycarbonate, PPS The strengths were then 60, 66, 36, 35, 40 N/1 5 mm, and the results were as follows. The results of measuring the gel, hue, and strength of the various adherends are shown in Table 1. Example 4 The amount of addition of maleic anhydride was changed to 20 parts by weight, the amount of addition of 1,1,2-trichloroethane was changed to 2,000 parts by weight, and the amount of BPO added was changed to 0.16 parts by weight. The reaction was carried out in the same manner as in Example 1 -72 to 200925171, followed by separation of the product. It is known that the product analysis results in an unsaturated residual acid of 3.0% by weight, and the gel has a 〇% by weight 'YI of 4 and excellent hue, and 'with copper, aluminum, polyimine, polycarbonate, The adhesive strengths of pps were each 73, 80, 40, 39, 40 N/15 mm, and the results of measuring gel, hue, and subsequent strength in various adherends are shown in Table 1. 0 Examples 5 to 7 except that the first embodiment and the base polymer were changed from EVA to L-LDPE, HDPE, and PP, and the amount of maleic anhydride added was changed to 30 parts by weight, 1,1,2-trichloroethane. The reaction was carried out in the same manner as in Example 1 except that the amount of the added amount of the alkane was changed to 2,200 parts by weight and the amount of the BPO was changed to 0.03 part by weight (Example 6), and then the product was separated. The results of measuring gel, hue, and subsequent strength are shown in Table 1. No gel, excellent hue and strength. Example 8 to 1 1 In addition to the addition amount of 1,1,2-trichloroethane, unsaturated carboxylic acid, and βρο, the reaction was carried out by the same method as in Examples 4 to 7, and the product was measured to measure The results of gel, hue, and subsequent strength are shown in Table 2. No gel, excellent hue and strength. -73- 200925171
實施例 17 900 in <N 〇 (N 〇 r-H 1195 〇 〇 〇 m οό 〇 (Ν cn Ο m 實施例 16 EVA CN in ON 卜 〇 (N 〇 1665 〇 〇 to rn ο σν 〇 m MD Ο (Ν ^Τ) 寸 CO 實施例 15 HDPE Ο 1—Η VO G\ 〇 〇 〇 1250 〇 〇 ο CN 〇 Ο 1-Η vn <Ν CN tN <N 實施例 14 & Ο 900 CN 〇 〇 (N 〇 1250 〇 〇 ο ▼—Η 〇 菩 in (Ν 〇\ CN <N m cn 實施例 13 L-LDPE ο 920 CN o 〇 CN 〇 1250 〇 〇 ο ΟΟ 〇 § Ο m (N 们 m CN 實施例 12 EVA Ο 952 卜 o 〇 <N 〇 1250 〇 〇 ο α; 〇 ON in % <Ν m m ο (N 實施例 11 Ο Τ*-Η 900 ^T) <N o m 〇 〇 2200 〇 〇 οο ο <Ν 00 〇 沄 卜 CN § 實施例 10 HDPE Ο r—Η ν〇 ON 〇 〇 2200 〇 〇 οο ο ο 卜·· 〇 CN 们 VO οο in 實施例 9 L-LDPE Ο r-^ 〇 (N as CN 〇 〇 2200 〇 〇 οο ο ι> 〇 in in (N Ό cn 等 萃 實施例 8 EVA Ο CN V% ON 卜 ο 〇 〇 2200 〇 〇 οο ο ο 〇 <N Ό ΟΟ jrj σ\ CN (N 重量份 1 g/io分鐘 1重量份 重量份 重量份 重量份 重量份 重量份 重量份 重量% 重量% N/15mm N/15mm N/15mm N/15mm 丨 N/15mm 丨 密度 MFR 馬來酸酐 丙烯酸 丙烯酸丁酯 1,1,2-三氯乙烷 浒 fi ll ΒΡΟ 酸改性量 凝膠 tio7 瑕 聚醯亞胺 聚碳酸酯 PPS 原料 聚烯烴 不飽和 羧酸 溶劑 自由基產生劑 改性聚合物 接著強度 1 _______ 一— ί YU色調) -74-Example 17 900 in <N 〇(N 〇rH 1195 〇〇〇m οό 〇(Ν cn Ο m Example 16 EVA CN in ON 〇 (N 〇1665 〇〇to rn ο σν 〇m MD Ο (Ν ^Τ) Inch CO Example 15 HDPE Ο 1—Η VO G\ 〇〇〇1250 〇〇ο CN 〇Ο 1-Η vn <Ν CN tN <N Example 14 & Ο 900 CN 〇〇(N 〇1250 〇〇ο ▼—Η 〇 in in (Ν 〇\ CN <N m cn Example 13 L-LDPE ο 920 CN o 〇CN 〇1250 〇〇ο ΟΟ 〇§ Ο m (N us m CN embodiment 12 EVA Ο 952 卜o 〇<N 〇1250 〇〇ο α; 〇ON in % <Ν mm ο (N Example 11 Ο Τ*-Η 900 ^T) <N om 〇〇2200 〇〇οο ο <Ν 00 〇沄 CNCN § Example 10 HDPE Ο r—Η ν〇ON 〇〇2200 〇〇οο ο ο 卜·· 〇CN VO οο in Example 9 L-LDPE Ο r-^ 〇 ( N as CN 〇〇2200 〇〇οο ο ι> 〇in in (N Ό cn et al. 8 EVA Ο CN V% ON οο 〇〇 2200 〇〇οο ο ο 〇 <N Ό ΟΟ jrj σ\ CN (N weight Parts 1 g / io minutes 1 part by weight parts by weight parts by weight parts by weight parts by weight % by weight % N / 15mm N / 15mm N / 15mm N / 15mm 丨 N / 15mm 丨 density MFR Maleic anhydride acrylic acid butyl Ester 1,1,2-trichloroethane 浒fi ll ΒΡΟ acid-modified gel tio7 瑕polyimine polycarbonate PPS raw material polyolefin unsaturated carboxylic acid solvent free radical generator modified polymer bonding strength 1 _______ one — ί YU tone) -74-
200925171 實施例12〜15200925171 Examples 12-15
除 了使用 EVA、L-LDPE、PP、HDPE 烯烴,將馬來酸酐變更爲丙烯酸,又變更 以外,藉由與實施例1同樣的手法進行反月 ,測量凝膠、色相、接著強度的結果列示方 ,色相、接著強度皆優異。 實施例16~17 除了將馬來酸酐變更爲馬來酸酐/丙烯 ,變更BPO的添加量以外,藉由與實施例 進行反應。分離生成物,測量凝膠、色相、 果列示於表2。無凝膠,色相、接著強度皆 實施例1 8 將關東化學股份有限公司製的 Q 重量份與26%硫酸水溶液2500重量份,放 1 〇升燒瓶中激烈地攪拌,靜置後取出下層 著將取出的有機層與蒸餾水5 000重量份, 的10升燒瓶中激烈地攪拌,靜置後取出下 操作重複3次,去除1-丁醇及1,2-環氧基丁 的有機層中添加150重量份的分子篩4A, 而脫水。The results of gel, hue, and subsequent strength were measured by the same method as in Example 1 except that EVA, L-LDPE, PP, and HDPE olefin were used, and the maleic anhydride was changed to acrylic acid. The hue and the strength are excellent. Examples 16 to 17 Reactions were carried out in the same manner as in the examples except that the maleic anhydride was changed to maleic anhydride/propylene and the amount of BPO added was changed. The product was separated, and the gel, hue, and fruit were measured and shown in Table 2. No gel, hue, and subsequent strength. Example 1 8 parts by weight of Kanto Chemical Co., Ltd. and 2500 parts by weight of a 26% aqueous solution of sulfuric acid were placed in a 1 liter flask and stirred vigorously. After standing, the lower layer was taken out. The taken-out organic layer was vigorously stirred in a 10 liter flask of 5,000 parts by weight of distilled water, and after standing, the operation was repeated three times, and the organic layer of 1-butanol and 1,2-epoxy butyl was added and 150 was added. Part by weight of molecular sieve 4A, and dehydrated.
於2升的玻璃製反應容器中裝入經由上 除1-丁醇及1,2-環氧基丁烷的1,1,2-三氯Z 作爲原料的聚 B P 〇的添加量 (。分離生成物 ‘表 2。無凝膠 酸丁酯混合物 1同樣的手法 接著強度的結 優異。 三氯乙烷5000 進附有下口的 的有機層。接 放進附有下口 層的有機層之 烷。更於取出 用攪拌器攪拌 述的操作經去 烷1 250重量 -75- 200925171A 2 liter glass reaction vessel was charged with a polyBP hydrazine added as a raw material by using 1-butanol and 1,2-epoxybutane as a raw material. The product 'Table 2. The gel-free butyl ester mixture 1 was excellent in the same strength and the strength of the knot. The trichloroethane 5000 was fed with the organic layer of the lower mouth, and was placed in the organic layer with the lower layer. Alkane. More than the operation of agitating with a stirrer, de-alkane 1 250 wt-75- 200925171
份、EVA100重量份、及馬來酸酐2.0重量份,將反應器 昇溫至80°C,然後以80°C保持3小時而均勻地溶解EVA 。此外在此期間,於反應器中以5升/分鐘的流速導入氮 氣,排除混入反應器的空氣,接下來將反應器從80 °C昇溫 至110 °C,將作爲接枝反應的觸媒(自由基產生劑)之使 1.0重量份的BPO溶解於經去除1-丁醇及1,2-環氧基丁烷 的1,1,2-三氯乙烷50重量份之觸媒溶液,一倂投入反應 器中進行接枝反應。接著以同溫度繼續2小時反應,反應 器的壓力係透過反應保持在1 MPa以下,反應結束後,回 到常壓使反應器的溫度降低至70°C爲止,然後,添加作爲 安定劑之〇.〇3重量份的BHT後,藉由甲醇使此溶液再沈 澱,從溶劑分離出作爲生成物的不飽和羧酸接枝EVA。 已知生成物係具有分析的結果1.8重量%的不飽和羧 酸,凝膠爲0.010重量%,YI爲3且色相優良,此外,與 銅、鋁、聚醯亞胺、聚碳酸酯、PPS的接著強度各爲48、 55、33、30、30N/15mm,強固地接著於各種的被黏著物 ,測量凝膠、色相、接著強度的結果列示於表3。 -76- 200925171 ο ΟThe solution, EVA 100 parts by weight, and 2.0 parts by weight of maleic anhydride, the reactor was heated to 80 ° C, and then kept at 80 ° C for 3 hours to uniformly dissolve the EVA. In addition, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liters/min to remove the air mixed into the reactor, and then the reactor was heated from 80 ° C to 110 ° C to serve as a catalyst for the graft reaction ( a free radical generator), wherein 1.0 part by weight of BPO is dissolved in a catalyst solution of 50 parts by weight of 1,1,2-trichloroethane from which 1-butanol and 1,2-epoxybutane are removed, The crucible is put into the reactor for grafting reaction. Then, the reaction was continued at the same temperature for 2 hours, and the pressure of the reactor was maintained at 1 MPa or less through the reaction. After the reaction was completed, the pressure was returned to normal pressure to lower the temperature of the reactor to 70 ° C, and then, as a stabilizer, it was added. After 3 parts by weight of BHT, the solution was reprecipitated by methanol, and the unsaturated carboxylic acid grafted EVA as a product was separated from the solvent. It is known that the resultant product has an analytical result of 1.8% by weight of an unsaturated carboxylic acid, a gel of 0.010% by weight, a YI of 3 and excellent hue, and further, with copper, aluminum, polyimine, polycarbonate, PPS. The strengths were then 48, 55, 33, 30, 30 N/15 mm, and were firmly adhered to various adherends. The results of measuring gel, hue, and subsequent strength are shown in Table 3. -76- 200925171 ο Ο
US 實施例 24 Ο τ—^ Ο 04 〇 cs 〇 〇 (S ν·Η 〇 〇 〇 0.015 m ο m yn CN CN CN 實施例 23 HDPE Ο Η νο ΟΝ in 沄 〇 〇 2200 〇 〇 〇 ο 00 0.012 oo 00 S 寸 寸 實施例 22 L-LDPE Ο 1-Η 宕 CN o CN 〇 〇 〇 in cs — 〇 〇 〇 r-H 0.013 寸 r-H o cn (N <S 實施例 21 EVA Ο CA νη α\ 卜 tr! 〇 〇 ο 1 〇 〇 〇 00 0.014 〇 oo 寸 Ο] 寸 實施例 20 EVA Ο Τ—Η CN ΟΝ 卜 卜 OS 〇 〇 ο v-i CN 〇 〇 〇 rn ο ΓΟ 0.011 § 〇 00 cn 00 m 寸 實施例 19 EVA Ο (Ν ΙΤ) ΟΝ o (N 〇 〇 (N r-~< 〇 〇 〇 yn 0.016 〇〇 m 00 r^ m ο (N 實施例 18 EVA ο (Ν 〇\ 卜 o CN 〇 〇 ο Ό (Ν 〇 〇 P r—Η 00 0.010 κη ο cn m 重量份 m日 g/io分鐘 重量份 重量份 重量份 重量份 重量份 重量份 重量份 雷量% 重量% N/15mm N/15mm N/15mm N/15mm N/15mm MFR 馬來酸酐 丙烯酸 丙烯酸丁酯 U,2-三氯乙烷 拼 fr Π ο Oh 03 酸改性量 凝膠 i Πρ7 <Μ 聚醯亞胺 聚碳酸酯 X/l CL, 國 Μ鉍 κ·您 溶劑 自由基產生劑 改性聚合物 接著強度 _____-__1 YU色調) -77- 200925171 實施例1 9 除了將自由基產生劑的添加量變更爲0.16重量份以 外’與實施例18同樣的方法進行反應,接著分離生成物 〇 已知生成物係分析結果爲具有1.5重量%的不飽和羧 酸,凝膠爲0.016重量%,YI爲2且色相優良,此外,與 銅、鋁、聚醯亞胺、聚碳酸酯、PPS的接著強度各爲38、 48、38、37、4 ON/15 mm’強固地接著於各種的被黏著物 ,測量凝膠、色相、接著強度的結果列示於表3。 實施例20 除了將馬來酸酐的添加量變更爲9.7重量份、且BPO 的添加量變更爲3.0重量份以外,與實施例18同樣的方 法進行反應,接著分離生成物。US Embodiment 24 Ο τ—^ Ο 04 〇cs 〇〇(S ν·Η 〇〇〇0.015 m ο m yn CN CN CN Example 23 HDPE Ο Η νο ΟΝ in 沄〇〇2200 〇〇〇ο 00 0.012 oo 00 S inch embodiment 22 L-LDPE Ο 1-Η 宕CN o CN 〇〇〇in cs — 〇〇〇rH 0.013 inch rH o cn (N <S Example 21 EVA Ο CA νη α\ 卜tr! 〇 〇ο 1 〇〇〇00 0.014 〇oo 寸Ο] inch embodiment 20 EVA Τ Τ—Η CN ΟΝ 卜卜 OS 〇〇ο vi CN 〇〇〇rn ο ΓΟ 0.011 § 〇00 cn 00 m inch Example 19 EVA Ο (Ν ΙΤ) ΟΝ o (N 〇〇(N r-~< 〇〇〇yn 0.016 〇〇m 00 r^ m ο (N Example 18 EVA ο (Ν 〇\ 卜o CN 〇〇ο Ό ( Ν 〇〇P r—Η 00 0.010 κη ο cn m Parts by weight m day g/io minutes parts by weight parts by weight parts by weight parts by weight parts by weight parts by weight % by weight N/15mm N/15mm N/15mm N /15mm N/15mm MFR Maleic anhydride acrylic acid butyl acrylate U,2-trichloroethane paste fr Π ο Oh 03 acid modified amount gel i Πρ7 <Μ Imine polycarbonate X/l CL, Μ铋 · · your solvent radical generator modified polymer adhesion strength _____-__1 YU tone) -77- 200925171 Example 1 9 In addition to the addition of free radical generator The reaction was carried out in the same manner as in Example 18 except that the amount was changed to 0.16 parts by weight, and then the product was separated. The product was analyzed to be 1.5% by weight of an unsaturated carboxylic acid, and the gel was 0.016% by weight, and YI was 2 and excellent hue, in addition, the bonding strength with copper, aluminum, polyimine, polycarbonate, PPS is 38, 48, 38, 37, 4 ON / 15 mm 'strongly followed by various adherends The results of measuring gel, hue, and subsequent strength are shown in Table 3. Example 20 Example 18 was changed except that the amount of maleic anhydride added was changed to 9.7 parts by weight and the amount of BPO added was changed to 3.0 parts by weight. The reaction was carried out in the same manner, followed by separation of the product.
已知生成物係分析結果爲具有3.0重量%的不飽和羧 酸,凝膠爲0.011重量%,YI爲4且色相優良,此外,與 銅、鋁、聚醯亞胺、聚碳酸酯、PPS的接著強度各爲60、 64、40、38、3 8N/15 mm,強固地接著於各種的被黏著物 ,測量凝膠、色相、接著強度的結果列示於表3。 實施例2 1 除了馬來酸酐的添加量變更爲20重量份,1,1,2-三氯 乙烷的添加量變更爲2000重量份’ BPO的添加量變更爲 1.0重量份以外,與實施例18同樣的方法進行反應,接著 -78- 200925171 分離生成物。 已知生成物係具有分析的結果1.8重量%的不飽和羧 酸,凝膠爲〇_〇14重量°/。,YI爲4且色相優良,此外,與 銅、鋁、聚醯亞胺、聚碳酸酯、PPS的接著強度各爲70、 78、42、43、42N/15mm,強固地接著於各種的被黏著物 ’測量凝膠、色相、接著強度的結果列示於表3。 0 實施例22〜24 將實施例18與基礎聚合物由EVA變更爲L-LDPE、 HDPE、PP’而且,馬來酸酐的添加量變更爲3〇重量份、 1,1,2 -三氯乙烷的添加量變更爲2200重量份(實施例23 )以外,與實施例1 8同樣的方法進行反應,接著分離生 成物。測量凝膠、色相、接著強度的結果列示於表3。含 有凝膠但其含量爲低於0.02重量%,色相、接著強度皆優 異。 ❹ 實施例25〜2 8 除了變更1,1,2 -三氯乙烷、不飽和羧酸、BPO的添加 量以外,藉由與實施例2 1〜24同樣的手法進行反應。分離 生成物’測量凝膠、色相、接著強度的結果列示於表4。 含有凝膠但其含量爲低於0.02重量%,色相、接著強度皆 優異。 -79- 200925171It is known that the product analysis result is 3.0% by weight of an unsaturated carboxylic acid, the gel is 0.011% by weight, the YI is 4, and the hue is excellent, and further, with copper, aluminum, polyimine, polycarbonate, PPS. The strengths were then 60, 64, 40, 38, 38 N/15 mm, and were firmly adhered to various adherends. The results of measuring gel, hue, and subsequent strength are shown in Table 3. Example 2 1 The amount of addition of 1,1,2-trichloroethane was changed to 2000 parts by weight, and the amount of addition of BPO was changed to 1.0 part by weight, except that the amount of maleic anhydride added was changed to 20 parts by weight. In the same manner, the reaction was carried out, and then the product was separated from -78 to 200925171. It is known that the resultant has an analytical result of 1.8% by weight of unsaturated carboxylic acid, and the gel has a 〇_〇14 weight °/. YI is 4 and the hue is excellent. In addition, the bonding strength with copper, aluminum, polyimine, polycarbonate, and PPS is 70, 78, 42, 43, and 42 N/15 mm, respectively, and is firmly adhered to various adhesives. The results of the measurement of gel, hue, and subsequent strength are shown in Table 3. 0 Examples 22 to 24 The example 18 and the base polymer were changed from EVA to L-LDPE, HDPE, and PP', and the amount of maleic anhydride added was changed to 3 parts by weight, 1,1,2-trichloroethane. The reaction was carried out in the same manner as in Example 18 except that the amount of the alkane added was changed to 2200 parts by weight (Example 23), and the product was separated. The results of measuring gel, hue, and subsequent strength are shown in Table 3. It contains a gel but its content is less than 0.02% by weight, and the hue and the strength are excellent.实施 Examples 25 to 2 8 The reaction was carried out in the same manner as in Examples 21 to 24 except that the amounts of 1,1,2-trichloroethane, unsaturated carboxylic acid and BPO were changed. Separation of the product The results of measuring the gel, hue, and subsequent strength are shown in Table 4. It contains a gel but its content is less than 0.02% by weight, and is excellent in hue and strength. -79- 200925171
!實施例 34 & 900 in oi Ο oi 〇 1195 〇 〇 〇 cn 〇6 0.013 〇 m 3 00 m Ο Ο m m 實施例 33 EVA g 952 卜 ο ri 〇 1665 〇 〇 m" On 0.013 in ο οο m m 丨實施例 32 lHDPE Ο νο ο 〇 (Ν 〇 1250 〇 〇 〇 CN ν—Η 0.012 00 卜 (N 丨實施例 31 ο Η 900 in Η ο 〇 (Ν 〇 1250 〇 〇 〇 r-H 0.010 (Ν ο m cn 實施例 30 L-LDPE Ο 920 CN ο 〇 (Ν 〇 1250 〇 〇 1—Η 00 0.012 〇 m ο cn (N 實施例 29 EVA ο 952 ο 〇 CN 〇 1250 〇 〇 r—Η Ο O) 0.016 m <N 實施例 28 & ο Τ-Η Ο Ο oi 〇 〇 2200 〇 〇 00 ο (N oo 0.014 in ΟΟ ίη § (N 實施例 27 ,HDPE Ο in νο Os 〇 〇 2200 〇 〇 00 ο O 0.012 (N m in m \〇 實施例 26 L-LDPE Ο 920 (Ν 〇 〇 2200 〇 〇 οο 0.011 m S 實施例 25 EVA ο fN 卜 ο ΓΛ 〇 〇 2200 〇 〇 οο ο o \〇 0.013 s JO 3 寸 00 (Ν (N 重量份 Ϊ g/io分鐘 重量份 重量份 重量份 重量份 重量份 重量份 重量份 重量% 重量% N/15mm N/15mm N/15mm N/15mm N/15mm 密度 MFR 馬來酸酐 丙烯酸 丙烯酸丁酯 1,1,2-三氯乙烷 二甲苯 1 ΒΡΟ 酸改性量 凝膠 TTp7 箱 聚醯亞胺 聚碳酸酯 PPS 原料 聚烯烴 不飽和 羧酸 溶劑 自由基產生劑 改性聚合物 接著強度 YI (色調) -80- 200925171 實施例29~32 除了使用EVA、L-LDPE、PP、HDPE作爲原料的聚 烯烴,將馬來酸酐變更爲丙烯酸,又變更BPO的添加量 以外,與實施例18同樣的手法進行反應。分離生成物, 測量凝膠、色相、接著強度的結果列示於表4。含有凝膠 但其含量爲低於0.02重量%,色相、接著強度皆優異。Example 34 & 900 in oi Ο oi 〇 1195 〇〇〇cn 〇6 0.013 〇m 3 00 m Ο Ο mm Example 33 EVA g 952 ο ri 〇 1665 〇〇m" On 0.013 in ο οο mm 丨Example 32 lHDPE Ο νο ο 〇 (Ν 〇1250 〇〇〇CN ν—Η 0.012 00 卜 (N 丨Example 31 ο Η 900 in Η ο 〇 (Ν 〇1250 〇〇〇rH 0.010 (Ν ο m cn implementation Example 30 L-LDPE 920 920 CN ο 〇 (Ν 〇1250 〇〇1—Η 00 0.012 〇m ο cn (N Example 29 EVA ο 952 ο 〇CN 〇1250 〇〇r—Η Ο O) 0.016 m < N Example 28 & ο Τ-Η Ο Ο oi 〇〇 2200 〇〇 00 ο (N oo 0.014 in ΟΟ ίη § (N Example 27, HDPE Ο in νο Os 〇〇2200 〇〇00 ο O 0.012 (N m in m \〇Example 26 L-LDPE Ο 920 (Ν 〇〇 2200 〇〇οο 0.011 m S Example 25 EVA ο fN 卜 ΓΛ 〇〇 2200 〇〇οο ο o \〇0.013 s JO 3 inch 00 ( Ν (N parts by weight Ϊ g / io minutes by weight parts by weight parts by weight parts by weight parts by weight Quantity % Weight % N/15mm N/15mm N/15mm N/15mm N/15mm Density MFR Maleic anhydride butyl acrylate 1,1,2-trichloroethane xylene 1 ΒΡΟ Acid modified gel TTp7 box Polyimide Polycarbonate PPS Raw Material Polyolefin Unsaturated Carboxylic Acid Solvent Free Radical Producer Modified Polymer Strength YI (Hue) -80- 200925171 Examples 29~32 In addition to using EVA, L-LDPE, PP, HDPE The polyolefin was used as a raw material, and the reaction was carried out in the same manner as in Example 18 except that the maleic anhydride was changed to acrylic acid, and the amount of the BPO was changed. The product was separated, and the results of measuring the gel, the hue, and the subsequent strength were shown in the table. 4. It contains a gel but its content is less than 0.02% by weight, and is excellent in hue and strength.
實施例33~34 除了將馬來酸酐變更爲馬來酸酐/丙烯酸丁酯混合物 ,變更BPO的添加量以外,與實施例18同樣的手法進行 反應。分離生成物,測量凝膠、色相、接著強度的結果列 示於表4。含有凝膠但其含量爲低於0.02重量%,色相、 接著強度皆優異。 比較例1 在將 EVA100重量份、馬來酸酐 4.0重量份、 DBPIB0.03重量份使用亨雪莉混練機事先均勻地混合的狀 態下,供給至二軸擠壓機(東洋精機製、laboplastomill L/D = 25 ' <i>=20mm),以旋轉數30rpm的條件,第1機桶 以140°C、第2機桶以200°C、第3機桶以20〇°C進行反應 ,得到馬來酸酐改性EVA。 生成物的分析結果係凝膠存在0.1重量%、YI亦高至 15、黃色度亦高。此外,與銅、鋁、聚醯亞胺、聚碳酸酯 、PPS的接著強度,相對於以實施例所得到的聚合物明顯 地較差,測量凝膠、色相、接著強度的結果列示於表5。 -81 - 200925171Examples 33 to 34 Reactions were carried out in the same manner as in Example 18 except that the maleic anhydride was changed to a maleic anhydride/butyl acrylate mixture and the amount of BPO added was changed. The results of separating the product and measuring the gel, hue, and subsequent strength are shown in Table 4. It contains a gel but its content is less than 0.02% by weight, and is excellent in hue and subsequent strength. Comparative Example 1 In a state in which 100 parts by weight of EVA, 4.0 parts by weight of maleic anhydride, and 0.03 parts by weight of DBPIB were uniformly mixed in advance using a Henschel mixer, the product was supplied to a two-axis extruder (Toyo Seiki, laboroplastomill L/). D = 25 ' <i>=20mm), the first barrel is reacted at 140 ° C, the second barrel is 200 ° C, and the third barrel is 20 ° ° C at a rotation number of 30 rpm. Maleic anhydride modified EVA. The analysis result of the product was that the gel was present in an amount of 0.1% by weight, the YI was also as high as 15, and the yellowness was also high. Further, the adhesion strength to copper, aluminum, polyimine, polycarbonate, and PPS was significantly inferior to that of the polymer obtained in the examples, and the results of measuring gel, hue, and subsequent strength are shown in Table 5. . -81 - 200925171
-82- 200925171 比較例2 除了將改性所使用的樹脂由EVA變更爲L-LDPE以 外,藉由與比較例1同樣的手法得到馬來酸酐改性L-LDPE。-82-200925171 Comparative Example 2 Maleic anhydride-modified L-LDPE was obtained by the same method as in Comparative Example 1, except that the resin used for the modification was changed from EVA to L-LDPE.
生成物的分析結果係凝膠存在0.08重量%、YI亦高 至13、黃色度亦高。此外,與銅、鋁、聚醯亞胺、聚碳 酸酯、PPS的接著強度,相對於以實施例所得到的聚合物 明顯地較差,測量凝膠、色相、接著強度的結果列示於表 比較例3 除了將改性所使用的樹脂由EVA變更爲PP以外,藉 由與比較例1同樣的手法得到馬來酸酐改性PP。 生成物的分析結果係凝膠存在〇·〇4重量% ' YI亦高 至11、黃色度亦高。此外,與銅、鋁、聚醯亞胺、聚碳 〇 酸酯、PPS的接著強度,相對於以實施例所得到的聚合物 明顯地較差,測量凝膠、色相、接著強度的結果列示於表 比較例4 除了將改性所使用的樹脂由EVA變更爲HDPE以外 ,藉由與比較例1同樣的手法得到馬來酸酐改性HDPE。 生成物的分析結果係凝膠存在〇· 〇6重量%、YI亦高 至11、黃色度亦高。此外,與銅、鋁、聚醯亞胺、聚碳 -83- 200925171 酸酯、PPS的接著強度,相對於以實施例所得到的聚合物 明顯地較差’測量凝膠、色相、接著強度的結果列示於表 比較例5〜8The analysis result of the product was 0.08% by weight of the gel, YI was also as high as 13, and the yellowness was also high. Further, the adhesion strength to copper, aluminum, polyimine, polycarbonate, and PPS was significantly inferior to that of the polymer obtained in the examples, and the results of measuring gel, hue, and subsequent strength are shown in the table comparison. Example 3 Maleic anhydride-modified PP was obtained by the same method as Comparative Example 1, except that the resin used for the modification was changed from EVA to PP. The analysis result of the product was that the gel was present in 凝胶·〇 4% by weight, 'YI was also as high as 11, and the yellowness was also high. Further, the adhesion strength to copper, aluminum, polyimine, polycarbonate, and PPS was significantly inferior to that of the polymer obtained in the examples, and the results of measuring gel, hue, and subsequent strength are shown in Table Comparative Example 4 Maleic anhydride-modified HDPE was obtained by the same method as in Comparative Example 1, except that the resin used for the modification was changed from EVA to HDPE. The analysis result of the product was that the gel was present in an amount of 重量·〇6 wt%, YI was also as high as 11, and yellowness was also high. Further, the adhesion strength to copper, aluminum, polyimine, polycarb-83-200925171 acid ester, and PPS was significantly inferior to that of the polymer obtained in the examples, and the results of measuring gel, hue, and strength were measured. Listed in Table Comparative Examples 5 to 8
除了將反應溶劑由1,1,2-三氯乙烷變更爲二甲苯,而 且變更馬來酸酐的添加量、及BPO的添加量以外,藉由 與實施例1同樣的手法得到接枝不飽和羧酸的聚合物。被 導入至基礎聚合物的不飽和羧酸量少,此外,色相亦優異 ,但相對於實施例所得到的聚合物,接著性明顯地較差。 測量凝膠、色相、接著強度的結果列示於表5。 比較例9~12 除了將馬來酸酐變更爲丙烯酸以外,藉由與比較例 1〜4同樣的手法得到接枝丙烯酸的聚合物。生成物含有凝 Q 膠,相對於藉由實施例所得到的聚合物,色相、接著性的 雙面明顯地較差。測量凝膠、色相、接著強度的結果列示 於表6。 -84- 200925171Grafting is not obtained by the same method as in Example 1 except that the reaction solvent was changed from 1,1,2-trichloroethane to xylene, and the amount of maleic anhydride added and the amount of BPO added were changed. a polymer of carboxylic acid. The amount of the unsaturated carboxylic acid introduced into the base polymer was small, and the hue was also excellent, but the adhesion was remarkably inferior to the polymer obtained in the examples. The results of measuring gel, hue, and subsequent strength are shown in Table 5. Comparative Examples 9 to 12 A polymer of grafted acrylic acid was obtained by the same method as Comparative Examples 1 to 4 except that maleic anhydride was changed to acrylic acid. The resultant contained a Q-gel, and the both sides of the hue and the adhesion were remarkably inferior to the polymer obtained by the examples. The results of measuring gel, hue, and subsequent strength are shown in Table 6. -84- 200925171
比較例 19 EVA Ο (Ν On 卜 in 〇 (N 〇 〇 〇 tr> CN 〇 〇 〇 00 ο ο 〇 vn 卜 m m CN cn (N 比較例 18 EVA ο (Ν 〇\ r- 〇 (N 〇 〇 〇 CN 1—Η 〇 〇 〇 οο ο ο S ο 〇 Η m H CN <N 比較例 17 EVA ο 1—Η CS ΟΝ 卜 in 〇 (N 〇 〇 〇 〇 VO (Ν 〇 〇 00 ο ο 〇 〇 οο (Ν m Os (N o m vo (N 比較例 16 HOPE ο ΙΤί νο Ον IT) <N 〇 〇 〇 〇 〇 〇 〇 κη (Ν S ο ο ο 〇 ο oo <N m m 寸 比較例 15 g: ο 1-^ Ο U-i rN c> 〇 〇 〇 〇 〇 ο CN S ο ο g CD 〇 ο oo to oo m m 比較例 14 L-LDPE ο Ο CS Ον <N <N 〇 〇 〇 〇 〇 〇 ο (Ν S ο ο s ο 〇 ο 寸 寸 m 比較例 13 EVA ο CS 〇\ r- iri CN 〇 〇 〇 〇 〇 〇 ο *Τ) <Ν S ο ο ο 〇 V£) oo VO 卜 m 比較例 HOPE ο os o P — 〇 〇 〇 〇 ο ο S ο (Ν ο S 〇 o § o 比較例 11 ο 1—^ ο as to oi o P 〇 〇 〇 〇 ο ο S ο ΠΊ ο S 〇 卜 os 比較例 L-LDPE ο 宕 Os o P 〇 〇 〇 〇 ο ο S ο V-) ο S 〇 On 1—H 比較例 9 EVA ο cs IT) Os r- tr! o 〇 寸· 〇 〇 〇 〇 ο ο S ο ν〇 ο 〇〇 Ρ 〇 ο ON CN 对 os On 丨重量份 m 4 g/l〇分鐘 重量份 重量份 重量份 重量份 重量份 重量份 重量份 重量份 重量份 重量% 重量% N/15mm N/15mm N/15mm N/15mm N/15mm 俟 MFR 馬來酸酐 丙烯酸 丙烯酸丁酯 1,1,2_三氯乙烷(純化) 1,1,2-三氯乙烷(未純化) 浒 fi ll £ ο 〇Η PQ DBPIB 酸改性量 凝膠 m 聚醯亞胺 聚碳酸酯 Oh 蚝嵌 不飽和 羧酸 1 自由基 產生劑 改性 聚合物 接著強度 |yu色調) -85- 200925171 比較例1 3 ~ 1 6 除了將反應溶劑由1,1,2-三氯乙烷變更爲甲苯,而且 ,將馬來酸酐變更爲馬來酸酐及丙烯酸丁酯的混合物,變 更其添加量以外,藉由與實施例1〜4同樣的手法得到接枝 不飽和羧酸的聚合物。被導入至基礎聚合物的不飽和羧酸 量少,相對於實施例所得到的聚合物,接著性明顯地較差 。測量凝膠、色相、接著強度的結果列示於表6。 〇 比較例1 7 除了將反應溶劑由經純化的1,1,2 -三氯乙烷變更爲未 純化的1,1,2-三氯乙烷以外,藉由與實施例1同樣的手法 將馬來酸酐接枝於EVA。所得到的聚合物的分析結果、 及接著試驗結果列示於表6。生成物係含有凝膠、YI値亦 高、看見著色、製品外觀差。 Q 比較例18 除了將反應溫度從110°c降至35t以外,藉由與實施 例1同樣的手法將馬來酸酐接枝於EVA。反應溫度低, EVA未完全地溶解於溶劑,反應溶液整體成爲果凍狀, 無法均勻地進行反應。此外’因爲反應後的溶液爲果凍狀 而流動性低,故無法用鼓式乾燥機處理,使其沈澱於甲醇 後,甲醇洗淨、過瀘後’以40 °C進行一天一夜減壓乾燥後 離析聚合物,所得到的聚合物的分析結果、及接著試驗結 果列示於表6’其接著強度差。 -86- 200925171 比較例1 9 除了將反應溫度由110 °C提高至135 °C以外,藉由與 實施例1同樣的手法將馬來酸酐接枝於EVA。所得到的 聚合物的分析結果、及接著試驗結果列示於表6,生成物 係含有凝膠、Y1値亦高、看見著色、製品外觀差。Comparative Example 19 EVA Ο (Ν On in in 〇(N 〇〇〇tr> CN 〇〇〇00 ο ο 〇vn 卜mm CN cn (N Comparative Example 18 EVA ο (Ν 〇\r- 〇(N 〇〇〇 CN 1—Η 〇〇〇οο ο ο S ο 〇Η m H CN <N Comparative Example 17 EVA ο 1—Η CS ΟΝ 卜 in 〇 (N 〇〇〇〇VO (Ν 〇〇00 ο ο 〇〇οο (Ν m Os (N om vo (N Comparative Example 16 HOPE ο ΙΤί νο Ον IT) <N 〇〇〇〇〇〇〇κη (Ν S ο ο ο 〇ο oo < N mm inch Comparative Example 15 g: ο 1-^ Ο Ui rN c> 〇〇〇〇〇ο CN S ο ο g CD 〇ο oo to oo mm Comparative Example 14 L-LDPE ο Ο CS Ον <N <N 〇〇〇〇〇〇ο (Ν S ο ο s ο 〇ο inch inch m Comparative Example 13 EVA ο CS 〇\ r- iri CN 〇〇〇〇〇〇ο *Τ) <Ν S ο ο ο 〇V£) oo VO 卜 m Comparative example HOPE ο os o P — 〇〇〇〇ο ο S ο (Ν ο S 〇o § o Comparative Example 11 ο 1—^ ο as to oi o P 〇〇〇〇ο ο S ο ΠΊ ο S 〇 os Comparison Example L-LDPE ο 宕Os o P 〇 〇〇〇ο ο S ο V-) ο S 〇On 1—H Comparative Example 9 EVA ο cs IT) Os r- tr! o 〇 inch · 〇〇〇〇ο ο S ο ν〇ο 〇〇Ρ 〇ο ON CN to os On 丨 by weight m 4 g/l 〇 min parts by weight parts by weight parts by weight parts by weight parts by weight parts by weight parts by weight % by weight N/15mm N/15mm N/15mm N/15mm N /15mm 俟MFR Maleic anhydride butyl acrylate 1,1,2_trichloroethane (purified) 1,1,2-trichloroethane (unpurified) 浒fi ll £ ο 〇Η PQ DBPIB acid modification Amount of gel m Polyimine polycarbonate Oh 蚝 Imprinted unsaturated carboxylic acid 1 Free radical generator Modified polymer Strength | yu tone) -85- 200925171 Comparative Example 1 3 ~ 1 6 In addition to the reaction solvent by 1 The 1,2-trichloroethane was changed to toluene, and the maleic anhydride was changed to a mixture of maleic anhydride and butyl acrylate, and the addition amount was changed, and the same method as in Examples 1 to 4 was used. A polymer of a branched unsaturated carboxylic acid. The amount of the unsaturated carboxylic acid introduced into the base polymer was small, and the adhesion was remarkably inferior to the polymer obtained in the examples. The results of measuring gel, hue, and subsequent strength are shown in Table 6. 〇Comparative Example 1 7 The same procedure as in Example 1 was carried out except that the reaction solvent was changed from the purified 1,1,2-trichloroethane to unpurified 1,1,2-trichloroethane. Maleic anhydride is grafted to EVA. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 6. The resulting product contained a gel, YI was also high, coloration was observed, and the appearance of the product was poor. Q Comparative Example 18 Maleic anhydride was grafted to EVA by the same method as in Example 1 except that the reaction temperature was lowered from 110 ° C to 35 t. The reaction temperature was low, EVA was not completely dissolved in the solvent, and the entire reaction solution became jelly-like, and the reaction could not be performed uniformly. In addition, since the solution after the reaction is jelly-like and has low fluidity, it cannot be treated with a drum dryer, and after it is precipitated in methanol, it is washed with methanol and dried, and then dried at 40 ° C for one day and one night under reduced pressure. The polymer was isolated, and the analysis results of the obtained polymer and the results of subsequent tests are shown in Table 6', which is the difference in strength. -86-200925171 Comparative Example 1 9 Maleic anhydride was grafted to EVA by the same method as in Example 1 except that the reaction temperature was raised from 110 °C to 135 °C. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 6. The resulting product contained a gel, Y1 was also high, coloration was observed, and the appearance of the product was poor.
比較例20~23 除了將反應溶劑由1,1,2-三氯乙烷變更爲二甲苯,而 且變更馬來酸酐的添加量、及BPO的添加量以外,藉由 與實施例1 8同樣的手法得到接枝不飽和羧酸的聚合物。 雖然色相優異,但被導入至基礎聚合物的不飽和羧酸量少 ,而且,凝膠存在多量,相對於實施例所得到的聚合物, 接著性明顯地較差,測量凝膠、色相、接著強度的結果列 示於表7。Comparative Examples 20 to 23 The same procedure as in Example 18 except that the reaction solvent was changed from 1,1,2-trichloroethane to xylene, and the amount of maleic anhydride added and the amount of BPO added were changed. A polymer obtained by grafting an unsaturated carboxylic acid is obtained by a method. Although the hue is excellent, the amount of the unsaturated carboxylic acid introduced into the base polymer is small, and the gel is present in a large amount, which is remarkably inferior to the polymer obtained in the examples, and the gel, hue, and subsequent strength are measured. The results are shown in Table 7.
-87- 200925171-87- 200925171
US 比較例 30 EVA ο CN Ον 卜 〇 <N 〇 〇 1250 〇 Ο ο οο ο ο 'Ο 0.05 〇 Ό (N (N 比較例 29 ί EVA ο <Ν 〇\ 卜 tri 〇 (N 〇 〇 1250 〇 ο ο 00 ο ο 0.02 0.09 〇 〇 <N 比較例 28 EVA Ο 1 952 卜 in 〇 oi 〇 〇 〇 1250 ο ο 00 ο ο 0.05 VO (N 艺 v〇 CN 比較例 27 HDPE ο ν〇 OS CN o 〇 〇 〇 〇 ο 1250 0.03 ο 0.06 0.11 Ο VO ί—^ 寸 比較例 26 g: ο 1 900 <N <N o 〇 〇 〇 〇 ο 1250 0.03 ο 0.06 〇 ο m ν〇 们 比較例 25 L-LDPE ο ο CS ΟΝ (N (N 〇 〇 〇 〇 〇 ο 1250 0.03 ο 0.05 0.09 ο (N 00 CN (N m 比較例 24 EVA ο 1 952 卜 <ri (N 〇 〇 〇 〇 〇 ο 1250 0.03 ο 0.07 〇 寸 〇〇 兮 寸 比較例 23 HDPE ο «"Η ιη ν〇 〇\ iTi o 〇 〇 〇 〇 1250 Ο 0.03 ο 0.01 0.06 ο 卜 CN rN m 比較例 22 ο ί—^ ο § CN in c> 〇 〇 〇 〇 1250 Ο 0.03 ο 0.02 0.06 ο m cn (N 寸 比較例 21 L-LDPE ο 1 920 <N 〇 〇 〇 〇 〇 1250 ο 0.03 ο 0.04 0.08 ο ΓΟ 卜 ro 寸 比較例 20 EVA ο 1 952 r*- 〇 〇 〇 〇 〇 1250 ο 0.03 ο 0.03 0.09 寸 1—Η κη κη :重量份 1 |g/i〇分鐘1 雷景份 重量份 重量份 重量份 _ 酬 重量份 重量份 重量份 重量份 重量% _ _ N/15mm N/15mm N/15mm N/15mm N/15mm Μ Β MFR 馬來酸酐 丙烯酸 丙烯酸丁酯 |1,1,2-三氯乙烷(純化) $ m 遯 K1 U Π1 (N 二甲苯 ΒΡΟ ΡΒΡΙΒ 酸改性量 凝膠 疆 聚醯亞胺 聚碳酸酯 PPS 原料 聚烯烴 不飽和 羧酸 溶劑 自由基 產生劑 改性 聚合物 接著強度 γι (色調) -88- 200925171 比較例24〜27US Comparative Example 30 EVA ο CN Ον 〇 〇 <N 〇〇1250 〇Ο ο οο ο ο 'Ο 0.05 〇Ό (N (N Comparative Example 29 ί EVA ο <Ν 〇\ 卜tri 〇 (N 〇〇1250 〇ο ο 00 ο ο 0.02 0.09 〇〇<N Comparative Example 28 EVA Ο 1 952 卜 in 〇oi 〇〇〇1250 ο ο 00 ο ο 0.05 VO (N 艺 v〇CN Comparative Example 27 HDPE ο ν〇OS CN o 〇〇〇〇ο 1250 0.03 ο 0.06 0.11 Ο VO ί—^ Inch Comparative Example 26 g: ο 1 900 <N <N o 〇〇〇〇ο 1250 0.03 ο 0.06 〇ο m ν〇Comparative Example 25 L-LDPE ο ο CS ΟΝ (N (N 〇〇〇〇〇ο 1250 0.03 ο 0.05 0.09 ο (N 00 CN (N m Comparative Example 24 EVA ο 1 952 卜<ri (N 〇〇〇〇〇ο 1250 0.03 ο 0.07 〇 inch 比较 Comparative Example 23 HDPE ο «"Η ιη ν〇〇\ iTi o 〇〇〇〇1250 Ο 0.03 ο 0.01 0.06 ο 卜 CN rN m Comparative Example 22 ο ί—^ ο § CN In c> 〇〇〇〇1250 Ο 0.03 ο 0.02 0.06 ο m cn (N inch Comparative Example 21 L-LDPE ο 1 920 <N 〇〇〇〇〇1250 ο 0.03 ο 0.04 0.08 ο ΓΟ 卜 比较 20 20 E E E E E E E E E E E E E E E E E E E E 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 景 景 景 景 景 景 景Parts by weight parts by weight _% by weight parts by weight parts by weight _ _ N/15mm N/15mm N/15mm N/15mm N/15mm Μ Β MFR Maleic anhydride butyl acrylate|1,1, 2-trichloroethane (purification) $ m 遁K1 U Π1 (N-xylene ΒΡΟ ΡΒΡΙΒ acid modified amount of gel polyimine polycarbonate PPS raw material polyolefin unsaturated carboxylic acid solvent free radical generator modification Polymer strength γι (hue) -88- 200925171 Comparative Example 24~27
除了將反應溶劑由1,1,2 -三氯乙烷變更爲甲苯’而且 ,將馬來酸酐變更爲馬來酸酐及丙烯酸丁酯的混合物’變 更其添加量以外,藉由與實施例18〜21同樣的手法得到接 枝不飽和羧酸的聚合物。被導入至基礎聚合物的不飽和羧 酸量少,而且,凝膠存在多量,相對於實施例所得到的聚 合物,接著性明顯地較差,測量凝膠、色相、接著強度的 結果列示於表7。 比較例2 8 除了將反應溶劑由經純化的1,1,2-三氯乙烷,變更爲 未純化的1,1,2-三氯乙烷以外,藉由與實施例18同樣的 手法將馬來酸酐接枝於EVA。所得到的聚合物的分析結 果、及接著試驗結果列示於表7。生成物係含有凝膠、YI 値亦高、看見著色、製品外觀差。 比較例2 9 除了將反應溫度從ll〇°C降至35t以外,藉由與實施 例18同樣的手法將馬來酸酐接枝於EVA。反應溫度低, EVA未完全地溶解於溶劑,反應溶液整體成爲果凍狀, 無法均勻地進行反應。此外,因爲反應後的溶液爲果凍狀 而流動性低,故無法用鼓式乾燥機處理,使其沈澱於甲醇 後,甲醇洗淨、過濾後,以40 °C進行一天一夜減壓乾燥後 離析聚合物,所得到的聚合物的分析結果、及接著試驗結 果列示於表7,其接著強度差。 -89- 200925171 比較例3 0 除了將反應溫度由110 °C提高至135 °C以外,藉由與 實施例1 8同樣的手法將馬來酸酐接枝於EVA。所得到的 聚合物的分析結果、及接著試驗結果列示於表7,生成物 係含有凝膠、YI値亦高、看見著色、製品外觀差。In addition to changing the reaction solvent from 1,1,2-trichloroethane to toluene', and changing the maleic anhydride to a mixture of maleic anhydride and butyl acrylate, the amount of addition was changed, and Example 18~ 21 The same procedure was used to obtain a polymer grafted with an unsaturated carboxylic acid. The amount of the unsaturated carboxylic acid introduced into the base polymer was small, and the gel was present in a large amount, and the adhesion was remarkably inferior to the polymer obtained in the examples. The results of measuring the gel, the hue, and the subsequent strength are shown in Table 7. Comparative Example 2 8 The same procedure as in Example 18 was carried out except that the reaction solvent was changed from purified 1,1,2-trichloroethane to unpurified 1,1,2-trichloroethane. Maleic anhydride is grafted to EVA. The analysis results of the obtained polymer and the results of subsequent tests are shown in Table 7. The resulting product contained a gel, and the YI 値 was also high, and the coloration was observed, and the appearance of the product was poor. Comparative Example 2 9 Maleic anhydride was grafted to EVA by the same procedure as in Example 18 except that the reaction temperature was lowered from ll 〇 °C to 35 Torr. The reaction temperature was low, EVA was not completely dissolved in the solvent, and the entire reaction solution became jelly-like, and the reaction could not be performed uniformly. In addition, since the solution after the reaction is jelly-like and has low fluidity, it cannot be treated with a drum dryer, precipitated in methanol, washed with methanol, filtered, and then dried at 40 ° C for one day and one night under reduced pressure. The polymer, the analysis results of the obtained polymer, and the subsequent test results are shown in Table 7, which was followed by the difference in strength. -89-200925171 Comparative Example 3 0 Maleic anhydride was grafted to EVA by the same procedure as in Example 18 except that the reaction temperature was raised from 110 °C to 135 °C. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 7. The resulting product contained a gel, and the YI was also high, and the coloration was observed, and the appearance of the product was poor.
❹ 製造例1 :氯化聚丙烯(CPP )的製造例 於附有攪拌機、UV照射裝置、回流冷卻器之1 0L可 分離燒瓶中,裝入MFR2.5、密度9 0 0kg/m3的聚丙烯500 重量份、離子交換水8L、及0.23重量份的烷基磺酸鈉, 調製懸濁液,一邊對此懸濁液照射UV,一邊連續地導入 氯氣,以l〇〇°C進行6小時反應,得到氯含量20%的氯化 聚丙烯(CPP)。 製造例2:氯化聚乙烯(CPE )的製造例 除了將聚丙烯變更爲MFR2、密度 920kg/m3的ΙΕ D P E 以外, 藉由與 製造例 1 同 樣的手 法得到 氯含量 1 6 % 的氯化聚乙烯(CPE )。 實施例3 5 將關東化學股份有限公司製的1,1,2-三氯乙烷10000 重量份與2 6 %硫酸水溶液5 0 0 0重量份,放進附有下口的 20升燒瓶中,激烈地攪拌’靜置後取出下層的有機層。 接著將取出的有機層與蒸餾水10000重量份放進附有下口 -90- 200925171 的20升燒瓶中,激烈地攪拌,靜置後取出下層的有機層 之操作重複3次,去除1-丁醇及1,2-環氧基丁烷’更於取 出的有機層中添加40 0重量份的分子篩4A’用攪拌器攪 拌而脫水。 於5升的玻璃製反應容器中裝入藉由上述的操作經去 除1-丁醇及1,2-環氧基丁烷的1,1,2-三氯乙烷25 00重量 份、EVA20 0重量份、及馬來酸酐4重量份。❹ Production Example 1: Production Example of Chlorinated Polypropylene (CPP) In a 10 L separable flask equipped with a stirrer, a UV irradiation device, and a reflux condenser, polypropylene having MFR 2.5 and a density of 9000 kg/m 3 was charged. 500 parts by weight, 8 L of ion-exchanged water, and 0.23 part by weight of sodium alkyl sulfonate, and a suspension was prepared, and while the suspension was irradiated with UV, chlorine gas was continuously introduced, and the reaction was carried out at 100 ° C for 6 hours. A chlorinated polypropylene (CPP) having a chlorine content of 20% was obtained. Production Example 2: Production Example of Chlorinated Polyethylene (CPE) A chlorinated polymer having a chlorine content of 16% was obtained by the same method as in Production Example 1 except that the polypropylene was changed to MFR2 and ΙΕDPE having a density of 920 kg/m3. Ethylene (CPE). Example 3 5 10000 parts by weight of 1,1,2-trichloroethane manufactured by Kanto Chemical Co., Ltd. and 500 parts by weight of a 20% aqueous sulfuric acid solution were placed in a 20-liter flask with a lower opening. Stir vigorously' After standing, remove the lower organic layer. Next, 10,000 parts by weight of the taken-out organic layer and distilled water were placed in a 20-liter flask equipped with a lower mouth of -90-200925171, stirred vigorously, and the operation of removing the organic layer of the lower layer was repeated three times after the standing, to remove 1-butanol. And 1,2-epoxybutane' was added to the taken-out organic layer, and 40 parts by weight of molecular sieve 4A' was added and stirred with a stirrer to dehydrate. A 5 liter glass reaction vessel was charged with 25 parts by weight of 1,1,2-trichloroethane of 1-butanol and 1,2-epoxybutane by the above operation, and EVA20 0 Parts by weight and 4 parts by weight of maleic anhydride.
❹ 將反應器昇溫至80°C,然後以80°C保持3小時而均 勻地溶解EVA,此外在此期間,於反應器中以5升/分鐘 的流速導入氮氣,排除混入反應器的空氣,接下來將反應 器從80°C昇溫至1 l〇°C,將作爲接枝反應的觸媒之使1.6 重量份的BPO溶解於經去除1-丁醇及1,2-環氧基丁烷的 1,1,2-三氯乙烷100重量份之觸媒溶液,在用3小時連續 地持續添加至反應器下進行接枝反應後,以同溫度繼續2 小時反應,在此期間,使反應器的壓力保持在IMPa以下。 反應終了後,使反應器的壓力回復常壓後,將反應器 的溫度降低至70°C,添加作爲安定劑之0.06重量份的 BHT後,將此溶液送進加熱至16〇t之鼓式乾燥機中,將 生成物的改性E V A從溶劑分離出。 已知生成物係分析結果爲具有1.3重量%的馬來酸酐 ,無凝膠,YI爲2,色相亦優良。此外,與銅、鋁、聚醯 亞胺、聚碳酸酯、PET、PPS皆堅固地接著,顯示出作爲 接著性聚合物之優異的特性。 所得到的聚合物的分析結果、及接著試驗結果列示於 表8。 -91 - 200925171 Qο 〔8撇〕 實施例 42 CPP 200 1 p 寸 2500 I 0.16 I 〇 〇 in CN cn 寸 實施例 41 EVA 200 952 〇 寸’ 2500 0.16 〇 〇 (N O m as (Ν VO (Ν ΓΟ 實施例 40 EVA 200 1 L-952 .1 〇 寸 2500 1 0.16 CN 〇 〇 m 卜 (N CN m 實施例 39 EVA 200 CN ON Ο 2500 1 0.16 <Ti 〇 c> CN ON <N CM (N (N m 實施例 38 HDPE 200 965 ο 2500 〇 ΓΠ CN (N 〇 〇 〇〇 κη m (N m CN m 實施例 37 200 900 ο — 2500 〇〇 〇 〇 T—Η cn ΓΛ CN m ΓΝΪ m 實施例 36 L-LDPE 200 920 ο ¥ [2500 00 〇 〇 〇 (Ν 00 CN <N (N 實施例 35 EVA 200 952 ο 寸· 「2500 1 [0.16 cn 〇 〇 (Ν Ο cn o CO CN (N 重量份 m日 |g/i〇分鐘1 !重量份 重量份 重量份 重量份 :重量份 重量份 重量份 重量份 重量份 重量% 重量% 兄/15mm S/15mni1 N/15mm ^/15mni| S/15mm 1 密度 馬來酸酐 丙烯酸 丙烯酸丁酯 丙烯酸乙酯 1,1,2-三氯乙烷 氯仿 四氯化碳 單氟苯 1,2-二溴-1,1-二氟乙烷 過氧化苯甲醯 酸改性量 凝膠 骠 聚醯亞胺 聚碳酸酯 PPS 原料聚烯烴 不飽和羧酸 溶劑 自由基產生劑 改性聚合物 接著強度 YI (色動 -92- 200925171 實施例36 . 除了使用經純化的1,1,2-三氯乙烷,將EVA變更爲 L-LDPE以外,藉由與實施例35同樣的手法,進行接枝於 L-LDPE之馬來酸酐的接枝反應。所得到的聚合物的分析 結果、及接著試驗結果列示於表8。 實施例37❹ The reactor was heated to 80 ° C, then kept at 80 ° C for 3 hours to uniformly dissolve the EVA, and during this time, nitrogen was introduced into the reactor at a flow rate of 5 liter / minute to remove the air mixed into the reactor. Next, the reactor was heated from 80 ° C to 1 l ° ° C, and 1.6 parts by weight of BPO was dissolved as a catalyst for the graft reaction to remove 1-butanol and 1,2-epoxybutane. 100 parts by weight of the 1,1,2-trichloroethane catalyst solution was continuously added to the reactor for 3 hours for grafting reaction, and then continued at the same temperature for 2 hours, during which time The pressure of the reactor was kept below IMPa. After the completion of the reaction, after the pressure of the reactor was returned to normal pressure, the temperature of the reactor was lowered to 70 ° C, 0.06 parts by weight of BHT as a stabilizer was added, and the solution was heated to a drum of 16 〇t. In the dryer, the modified EVA of the product is separated from the solvent. It is known that the product analysis results are 1.3% by weight of maleic anhydride, no gel, YI of 2, and excellent hue. Further, it is strongly adhered to copper, aluminum, polyimide, polycarbonate, PET, and PPS, and exhibits excellent characteristics as a secondary polymer. The analysis results of the obtained polymer and the results of subsequent tests are shown in Table 8. -91 - 200925171 Qο [8撇] Example 42 CPP 200 1 p inch 2500 I 0.16 I 〇〇in CN cn inch embodiment 41 EVA 200 952 〇 inch ' 2500 0.16 〇〇 (NO m as (Ν VO (Ν ΓΟ Example 40 EVA 200 1 L-952 .1 2 2500 1 0.16 CN 〇〇m 卜 (N CN m Example 39 EVA 200 CN ON Ο 2500 1 0.16 <Ti 〇c> CN ON <N CM (N (N m embodiment 38 HDPE 200 965 ο 2500 〇ΓΠ CN (N CNκη m (N m CN m embodiment 37 200 900 ο — 2500 〇〇〇〇T-Η cn ΓΛ CN m ΓΝΪ m embodiment 36 L-LDPE 200 920 ο ¥ [2500 00 〇〇〇 (Ν 00 CN <N (N Example 35 EVA 200 952 ο inch · "2500 1 [0.16 cn 〇〇 (Ν Ο cn o CO CN (N weight Parts m day|g/i〇minute 1 ! parts by weight parts by weight parts by weight: parts by weight parts by weight parts by weight parts by weight% by weight Brother/15mm S/15mni1 N/15mm ^/15mni| S/15mm 1 density maleic anhydride acrylic acid butyl acrylate ethyl 1,1,2-trichloro Alkanol chloroform monochlorobenzene monofluorobenzene 1,2-dibromo-1,1-difluoroethane benzoic acid modified amount gel 骠polyimine polycarbonate PPS raw material polyolefin unsaturated carboxylic acid Acid solvent free radical generator modified polymer followed by strength YI (color shift -92- 200925171 Example 36. In addition to using purified 1,1,2-trichloroethane, EVA was changed to L-LDPE, borrowed The grafting reaction of maleic anhydride grafted to L-LDPE was carried out in the same manner as in Example 35. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 8. Example 37
除了使用經純化的1,1,2 -三氯乙烷,將EVA變更爲 PP以外,藉由與實施例35同樣的手法,進行接枝於pp 之馬來酸酐的接枝反應,所得到的聚合物的分析結果、及 接著試驗結果列示於表8。 實施例3 8 除了使用經純化的1,1,2-三氯乙烷,將EVA變更爲 HDPE以外,藉由與實施例35同樣的手法,進行接枝於 〇 HDPE之馬來酸酐的接枝反應。所得到的聚合物的分析結 果、及接著試驗結果列示於表8。 實施例39 除了將反應溶劑由經純化的1,1,2 -三氯乙烷變更氯仿 以外,藉由與實施例3 5同樣的手法將馬來酸酐接枝於 EVA。所得到的聚合物的分析結果、及接著試驗結果列示 於表8。 -93- 200925171 實施例40 除了將反應溶劑由經純化的1,1,2 -三氯乙烷變更爲四 氯化碳以外’藉由與實施例35同樣的手法將丙烯酸接枝 於EVA。所得到的聚合物的分析結果、及接著試驗結果 列示於表8。 實施例4 1 除了將反應溶劑由經純化的1,1,2-三氯乙烷變更爲單 氟苯以外’藉由與實施例35同樣的手法將丙烯酸丁酯接 枝於EVA。所得到的聚合物的分析結果、及接著試驗結 果列示於表8。 實施例42 除了將反應溶劑由經純化的1,1,2-三氯乙烷變更爲 1,2-二溴-1,1-二氟甲烷、將改性的聚烯烴由EVA變更爲 製造例1所製造的氯化聚丙烯(CPP )以外,藉由與實施 例35同樣的手法將馬來酸酐接枝於CPP。所得到的聚合 物的分析結果、及接著試驗結果列示於表8° 實施例43 除了將改性的聚烯烴由EVA變更爲製造例2所製造 的氯化聚乙烯(CPE)以外,藉由與實施例35同樣的手 法將馬來酸酐接枝於CPE。所得到的聚合物的分桁結果、 及接著試驗結果列示於表9。 -94- 200925171 〔6S 實施例 48 CPE 200 1 〇 (N 〇 oi 2500 0.16 〇 〇 ON (N (N m CN 實施例 47 CPP 200 > 〇 寸_ 2500 0.16 ΓΟ 〇 〇 00 (N m 〇 o (N 00 (N 實施例 46 HDPE 200 ON 〇 CN 〇 (N 2500 0.16 00 t-η 〇 〇 in 寸 寸 卜 V〇 實施例 45 & 200 900 〇 (N 〇 CN 2500 0.16 〇 (N 〇 〇 r-H 卜 〇 CN oo cn 實施例 44 LDPE 1 200 〇 <N On 〇 — 2500 0.16 \〇 〇 <d> 宕 Ό m <N m 實施例 1__43 — CPE 200 1 〇 寸· 2500 0.16 in 〇 〇 (N m 00 (N 寸 丨重量份 m日 |g/i〇分鐘Ί 重量份 重量份 重量份 重量份 重量份 重量份 重量份 重量份 重量份 _ tlrml 糊 重量% |N/15mm , N/15mm | S/15mm N/15mm N/15mm j 侧 馬來酸酐 丙烯酸 丙烯酸丁酯 丙烯酸乙酯 U,2-三氯乙烷 氯仿 四氯化碳 單氟苯 1,2-二溴-1,1-二氟乙烷 過氧化苯甲醯 酸改性量 凝膠 聚醯亞胺 聚碳酸酯 PPS 原料聚烯烴 不飽和羧酸 溶劑 自由基產生劑 改性聚合物 接著強度 YU色調) -95- 200925171 實施例44 除了將改性的聚烯烴由EVA變更爲LDPE、將不飽和 羧酸由馬來酸酐變更丙烯酸以外,藉由與實施例35同樣 的手法將丙烯酸接枝於LDPE。所得到的聚合物的分析結 果、及接著試驗結果列示於表9。 實施例45The grafting reaction of maleic anhydride grafted to pp was carried out in the same manner as in Example 35 except that the purified 1,1,2-trichloroethane was changed to PP. The analysis results of the polymer and the results of the subsequent tests are shown in Table 8. Example 3 8 Grafting of maleic anhydride grafted to 〇HDPE was carried out by the same method as in Example 35 except that purified 1,1,2-trichloroethane was used and EVA was changed to HDPE. reaction. The analysis results of the obtained polymer and the results of subsequent tests are shown in Table 8. Example 39 Maleic anhydride was grafted to EVA by the same procedure as in Example 35 except that the reaction solvent was changed from purified 1,1,2-trichloroethane to chloroform. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 8. -93-200925171 Example 40 Acrylic acid was grafted to EVA by the same method as in Example 35 except that the reaction solvent was changed from purified 1,1,2-trichloroethane to carbon tetrachloride. The analysis results of the obtained polymer and the results of subsequent tests are shown in Table 8. Example 4 1 Butyl acrylate was grafted to EVA by the same procedure as in Example 35 except that the reaction solvent was changed from purified 1,1,2-trichloroethane to monofluorobenzene. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 8. Example 42 except that the reaction solvent was changed from purified 1,1,2-trichloroethane to 1,2-dibromo-1,1-difluoromethane, and the modified polyolefin was changed from EVA to a production example. Maleic anhydride was grafted to CPP in the same manner as in Example 35 except for the chlorinated polypropylene (CPP) produced. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 8 ° Example 43 except that the modified polyolefin was changed from EVA to chlorinated polyethylene (CPE) produced in Production Example 2, Maleic anhydride was grafted to CPE in the same manner as in Example 35. The results of the classification of the obtained polymer and the results of the subsequent tests are shown in Table 9. -94- 200925171 [6S Example 48 CPE 200 1 〇 (N 〇 oi 2500 0.16 〇〇 ON (N (N m CN Example 47 CPP 200 > 〇 inch _ 2500 0.16 ΓΟ 〇〇00 (N m 〇o ( N 00 (N Example 46 HDPE 200 ON 〇CN 〇 (N 2500 0.16 00 t-η 〇〇in inch 卜V V 〇 Example 45 & 200 900 〇 (N 〇CN 2500 0.16 〇 (N 〇〇rH 〇 CN oo cn Example 44 LDPE 1 200 〇<N On 〇-2500 0.16 \〇〇<d> 宕Ό m <N m Example 1__43 — CPE 200 1 inch · 2500 0.16 in 〇〇 (N m 00 (N inch 丨 part by weight m day | g / i 〇 minute 重量 parts by weight parts by weight parts by weight parts by weight parts by weight _ tlrml paste weight % | N / 15mm , N / 15mm | S / 15mm N/15mm N/15mm j side maleic anhydride acrylic acid butyl acrylate ethyl acrylate U, 2-trichloroethane chloroform carbon tetrachloride monofluorobenzene 1,2-dibromo-1,1-difluoroethane Benzoyl phthalate modified amount gel polyimine polycarbonate PPS raw material polyolefin unsaturated carboxylic acid Agent free radical generator modified polymer strength YU tone) -95- 200925171 Example 44 In addition to changing the modified polyolefin from EVA to LDPE, and changing the unsaturated carboxylic acid from maleic anhydride to acrylic acid, In the same manner as in Example 35, acrylic acid was grafted to LDPE. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 9. Example 45
除了將改性的聚烯烴由EVA變更爲PP、將不飽和羧 酸由馬來酸酐變更爲馬來酸酐及丙烯酸丁酯的混合物以外 ,藉由與實施例35同樣的手法將不飽和羧酸接枝於PP。 所得到的聚合物的分析結果、及接著試驗結果列示於表9 實施例4 6 除了將改性的聚烯烴由EVA變更爲HDPE、將不飽和 〇 羧酸由馬來酸酐變更爲馬來酸酐及丙烯酸乙基的混合物以 外’藉由與實施例35同樣的手法將不飽和羧酸接枝於 HDPE。所得到的聚合物的分析結果、及接著試驗結果列 示於表9。 實施例47 除了將改性的聚烯烴由EVA變更爲製造例1所製造 的氯化聚丙烯(CPP )、將不飽和羧酸由馬來酸酐變更爲 丙烯酸以外,藉由與實施例35同樣的手法將丙烯酸接枝 -96- 200925171 於CPP。所得到的聚合物的分析結果、及接著試驗結果列 示於表9。 實施例4 8The unsaturated carboxylic acid was grafted in the same manner as in Example 35 except that the modified polyolefin was changed from EVA to PP and the unsaturated carboxylic acid was changed from maleic anhydride to a mixture of maleic anhydride and butyl acrylate. Branched in PP. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 9. Example 4 6 except that the modified polyolefin was changed from EVA to HDPE, and the unsaturated hydrazine carboxylic acid was changed from maleic anhydride to maleic anhydride. The unsaturated carboxylic acid was grafted to HDPE by the same method as in Example 35 except that a mixture of ethyl acrylate was used. The analysis results of the obtained polymer and the results of subsequent tests are shown in Table 9. Example 47 The same procedure as in Example 35 except that the modified polyolefin was changed from EVA to chlorinated polypropylene (CPP) produced in Production Example 1, and the unsaturated carboxylic acid was changed from maleic anhydride to acrylic acid. The graft is grafted with acrylic acid -96-200925171 in CPP. The analysis results of the obtained polymer and the results of subsequent tests are shown in Table 9. Example 4 8
除了將改性的聚烯烴由EVA變更爲製造例2所製造 的氯化聚乙烯(CPE)、將不飽和殘酸由馬來酸酐變更爲 馬來酸酐及丙嫌酸丁酯的混合物以外,藉由與實施例35 同樣的手法將馬來酸酐接枝於CPE。所得到的聚合物的分 析結果、及接著試驗結果列示於表9。 比較例3 1 除了將反應溶劑由經純化的1,1,2-三氯乙烷,變更爲 常壓下的沸點爲132°C之單氯苯以外,藉由與實施例35同 樣的手法將馬來酸酐接枝於EVA。將反應後的聚合物溶 液導入至鼓式乾燥機中,藉由與實施例35同樣的手法嘗 〇 試聚合物的離析,但聚合物薄膜黏著於轉筒上,薄膜無法 剝離,無法連續地離析聚合物。因此,藉由用甲醇再沈澱 操作無法使聚合物溶液離析。 所得到的聚合物的分析結果、及接著試驗結果列示於 表1 〇,接著強度降低。 -97- 200925171 οο 〔01 撇〕 比較例 33 EVA 200 I 952 〇 — 2500 0.16 (N 〇 〇 νο 3 in (N 比較例 :―J2— _ EVA 200 952 〇 τί- 2500 0.16 寸· 〇 〇 00 (Ν CM m CN (N 比較例 31 EVA 200 (N in ON q — 2500 0.16 p 〇 CN (Ν 00 (Ν (N 寸 1重量份 m 盤 丨g/10分鐘 丨重量份 重量份 雷量份 |重量份 重量% ιΐτπΐΐ _ N/15mm N/15mm N/15mm N/15mm N/15mm 馬來酸酐 1,1,2-三氯乙烷 單氯苯 1 過氧化苯甲醯 酸改性量 凝膠 騷 聚醯亞胺 聚碳酸酯 PPS 原料聚烯烴 不飽和羧酸 溶劑 自由基產生劑 改性聚合物 接著強度 YU色調) -98-In addition to changing the modified polyolefin from EVA to chlorinated polyethylene (CPE) manufactured in Production Example 2, and changing the unsaturated residual acid from maleic anhydride to a mixture of maleic anhydride and butyl citrate, Maleic anhydride was grafted to the CPE by the same procedure as in Example 35. The analysis results of the obtained polymer and the results of subsequent tests are shown in Table 9. Comparative Example 3 1 The same procedure as in Example 35 was carried out except that the reaction solvent was changed from purified 1,1,2-trichloroethane to monochlorobenzene having a boiling point of 132 ° C under normal pressure. Maleic anhydride is grafted to EVA. The polymer solution after the reaction was introduced into a drum dryer, and the segregation of the test polymer was tasted by the same method as in Example 35, but the polymer film adhered to the drum, the film could not be peeled off, and the continuous separation could not be performed. polymer. Therefore, the polymer solution could not be isolated by re-precipitation with methanol. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 1, and the strength was lowered. -97- 200925171 οο [01 撇] Comparative Example 33 EVA 200 I 952 〇—2500 0.16 (N 〇〇νο 3 in (N Comparative Example: “J2— _ EVA 200 952 〇τί- 2500 0.16 inch· 〇〇00 ( CM CM m CN (N Comparative Example 31 EVA 200 (N in ON q — 2500 0.16 p 〇CN (Ν 00 (Ν N (N inch 1 part by weight m 丨 g/10 minutes 丨 parts by weight parts by weight | parts by weight | weight Parts by weight ιΐτπΐΐ _ N/15mm N/15mm N/15mm N/15mm N/15mm Maleic anhydride 1,1,2-trichloroethane monochlorobenzene 1 benzoic acid modified gel germination醯imine polycarbonate PPS raw material polyolefin unsaturated carboxylic acid solvent free radical generator modified polymer strength YU color tone) -98-
〇 200925171 比較例3 2 除了變更不飽和羧酸的接枝反應後的聚合物離 以外,藉由實施例35所表示的方法將馬來酸酐 EVA。 反應終了後,使反應器的壓力回復常壓後,將5 的溫度降低至70°c,添加作爲安定劑之BHT 0.06 I 後,於反應系内供給水,將反應器的溫度再度携 1〇〇°C,使水與1,1,2-三氯乙烷共沸而將1,1,2-三氯z 除至反應器外,將計2 0 0 0重量份的水供給於反應暑 到高濃度的聚合物溶液分散於水中的懸濁液。將此持 入於使300 0ml的甲醇循環的粉碎機,得到與聚合电 的同時經粉碎的淤漿,將此淤漿過濾過、用甲醇5L 後,以4 0 °C經由一天一夜減壓乾燥而得到經乾燥的赛 。如上述,此方法與實施例所表示的方法比較下,海 耗時間及成本之缺乏經濟性的方法。 所得到的聚合物的分析結果、及接著試驗結果歹 表1 0,但接著強度降低。 比較例33 除了將反應溶劑由經純化的1,1,2-三氯乙烷,丨 常壓下的沸點爲1 l〇.6°C之甲苯以外,藉由與實施例 樣的手法將馬來酸酐接枝於EVA。因爲將反應後E 物溶液導入至鼓式乾燥機中’與不燃性的三: 不同,經揮發的甲苯蒸氣會有引火爆炸的危險,雖; 操作 枝於 應器 量份 高至 院去 ,得 液導 沈澱 洗淨 合物 雜且 示於 :更爲 3 5同 聚合 ,乙烷 :藉由 -99- 200925171 與比較例31同樣的手法離析聚合物’但其係非常地煩雜 且耗時間及成本之欠缺經濟性的方法。 所得到的聚合物的分析結果、及接著試驗結果列不於 表1 〇,接著強度降低。 實施例49 <不飽和羧酸接枝聚烯烴的製造> 0 將5000重量份的1,1,2-三氯乙烷與25 00重量份的 26%硫酸水溶液,放進附有下口的1 〇升燒瓶中激烈地攪 拌,靜置後取出下層的有機層。接著’將經取出的有機層 與蒸餾水5kg放進附有下口的1〇升燒瓶中激烈地攪拌’ 靜置後取出下層的有機層之操作重複3次’去除卜丁醇 及1,2-環氧基丁烷。更藉由於取出的有機層中添加150重 量份的分子篩4A、使用攪拌器攪拌進行脫水’得到經純 化的1,1,2-三氯乙烷(以下,記爲純化TCE)。 〇 於4升的玻璃製反應容器中裝入純化2480重量份的 TCE與200重量份的EVA、及4.1重量份的馬來酸酐,將 反應器昇溫至80°C,然後藉由以80°C保持4小時均勻地 溶解EVA,此外在此期間,於反應器中以5升/分鐘的流 速導入氮氣,排除混入反應器的空氣,作爲接枝反應的觸 媒之使1 .5重量份的BPO溶解於純化TCE 100重量份, 將此溶液連續地持續添加至反應器,將反應器的壓力保持 在1 MPa的狀態下,進行3小時接枝反應。反應結束後, 使壓力回復至常壓,將反應器的溫度提高至70°C爲止,添 -100- 200925171 加作爲安定劑之0.06重量份的BHT,將此溶液注入至大 量的甲醇中,使生成物的馬來酸酐接枝EVA從溶劑分離 出。 已知生成物係分析結果爲具有1.5重量%的不飽和羧 酸(馬來酸酐),凝膠爲〇重量%,YI爲2及色相優良。 <不飽和羧酸接枝聚烯烴薄膜的製造>〇 200925171 Comparative Example 3 2 Maleic anhydride EVA was obtained by the method shown in Example 35 except that the polymer after the graft reaction of the unsaturated carboxylic acid was changed. After the completion of the reaction, after the pressure of the reactor was returned to normal pressure, the temperature of 5 was lowered to 70 ° C, and BHT 0.06 I as a stabilizer was added, and water was supplied to the reaction system to carry the temperature of the reactor again. 〇°C, the water is azeotroped with 1,1,2-trichloroethane, and 1,1,2-trichloroz is removed to the outside of the reactor, and 200 parts by weight of water is supplied to the reaction heat. A suspension of the high concentration polymer solution dispersed in water. This was held in a pulverizer which circulated 300 ml of methanol to obtain a slurry which was pulverized at the same time as the polymerization. The slurry was filtered, and 5 L of methanol was used, and then dried under reduced pressure at 40 ° C overnight. And get a dried game. As described above, this method is compared with the method represented by the embodiment, and the method of economical cost and cost is lacking. The analysis results of the obtained polymer and the subsequent test results are shown in Table 10, but the strength was subsequently lowered. Comparative Example 33 A horse was prepared by a method similar to that of the example except that the reaction solvent was purified from 1,1,2-trichloroethane and a toluene having a boiling point of 1 l〇.6 ° C under normal pressure. The anhydride is grafted to EVA. Because the E solution after the reaction is introduced into the drum dryer 'different from the non-combustible three: the volatilized toluene vapor may have a risk of igniting and exploding, although the operation branch is high in the hospital, the liquid is obtained. The precipitated washing compound was mixed and shown in: more homopolymerized, ethane: the polymer was isolated by the same method as in Comparative Example 31 by -99-200925171' but it was very complicated and time consuming and costly. Lack of economics. The analysis results of the obtained polymer and the results of the subsequent tests are shown in Table 1 and the strength was lowered. Example 49 <Production of Unsaturated Carboxylic Acid-Grafted Polyolefin> 0 5000 parts by weight of 1,1,2-trichloroethane and 2500 parts by weight of a 26% aqueous sulfuric acid solution were placed in the lower mouth. The 1 liter flask was vigorously stirred, and after standing, the lower organic layer was taken out. Then, 'the extracted organic layer and 5 kg of distilled water were placed in a 1-liter flask equipped with a lower mouth and stirred vigorously'. The operation of removing the organic layer of the lower layer was repeated 3 times to remove the butanol and 1,2- Epoxy butane. Further, by adding 150 parts by weight of the molecular sieve 4A to the taken-out organic layer and dehydrating by stirring with a stirrer, purified 1,1,2-trichloroethane (hereinafter referred to as purified TCE) was obtained. Purifying 2480 parts by weight of TCE and 200 parts by weight of EVA, and 4.1 parts by weight of maleic anhydride in a 4 liter glass reaction vessel, heating the reactor to 80 ° C, and then by 80 ° C The EVA was uniformly dissolved for 4 hours, and during this time, nitrogen gas was introduced into the reactor at a flow rate of 5 liters/min to remove the air mixed into the reactor, and 1.5 parts by weight of BPO was used as a catalyst for the graft reaction. The solution was dissolved in 100 parts by weight of purified TCE, and this solution was continuously continuously added to the reactor, and the pressure of the reactor was maintained at 1 MPa, and grafting reaction was carried out for 3 hours. After the completion of the reaction, the pressure was returned to normal pressure, the temperature of the reactor was raised to 70 ° C, and 0.06 part by weight of BHT as a stabilizer was added to add -100 to 200925171, and this solution was poured into a large amount of methanol to make The product of maleic anhydride grafted EVA was separated from the solvent. The result of the analysis of the product was found to be 1.5% by weight of an unsaturated carboxylic acid (maleic anhydride), the gel was 〇% by weight, the YI was 2, and the hue was excellent. <Production of unsaturated carboxylic acid grafted polyolefin film>
藉中使用復動式壓縮成形機WFA-50,使上述所得到 的不飽和羧酸接枝EVA,以加熱溫度150°C、壓力l〇MPa 、加熱時間1〇分鐘、冷卻溫度30°C、壓力lOMPa、冷卻 時間5分鐘的條件進行加壓成形,得到尺寸 5 Omm X 1 00mm 、厚度100 μιη的薄膜(薄膜1),所得到的薄膜的外觀、 性狀爲優良,未看到魚眼等之缺點。 <銅薄片的絕緣被覆> Q 將所得到的尺寸50mmxlO〇mm、厚度100μιη的薄膜 (薄膜1)、未進灯表面處理之尺寸lOOmmxlOOmm、厚 度0.5mm的銅薄片(薄片1)、尺寸lOOmmxlOOmm厚度 100 μιη的聚醯亞胺薄膜(薄膜2),以薄片1/薄膜1/薄膜 2的構成進行層合’以壓力〇.2MPa、溫度180°C、時間1 分鐘的條件,得到銅薄片、及聚醯亞胺薄膜的一半的面積 經接著的餍合物。將由所得到的層合物切割出長度 100mm、寬度15111111的薄長方狀試料,使其成爲一半的面 積被接著、一半的面積未被接著的狀態,以以拉伸速度 -101 - 200925171 〇By using the double-action compression molding machine WFA-50, the above-mentioned unsaturated carboxylic acid grafted EVA is heated at a temperature of 150 ° C, a pressure of 10 MPa, a heating time of 1 〇 minutes, a cooling temperature of 30 ° C, Pressure molding was carried out under the conditions of a pressure of 10 MPa and a cooling time of 5 minutes to obtain a film (film 1) having a size of 5 Omm X 1 00 mm and a thickness of 100 μm, and the obtained film was excellent in appearance and properties, and no fisheye or the like was observed. Disadvantages. <Insulation coating of copper flakes> Q A film (film 1) having a size of 50 mm x 10 mm, a thickness of 100 μm, a size of 100 mm x 100 mm of a surface which is not subjected to lamp treatment, a copper sheet having a thickness of 0.5 mm (sheet 1), and a size of 100 mm x 100 mm A polyimide film (film 2) having a thickness of 100 μm was laminated by the composition of the sheet 1 / film 1 / film 2 to obtain a copper sheet under the conditions of a pressure of 2 MPa, a temperature of 180 ° C, and a time of 1 minute. And half of the area of the polyimide film is passed through the subsequent composition. A thin rectangular sample having a length of 100 mm and a width of 15111111 was cut out from the obtained laminate so that half of the area was followed, and half of the area was not followed, at a stretching speed of -101 - 200925171 〇
3 00mm/分鐘的條件進行T型剝離試驗的結果,本層合物 顯示出4〇Ν/1 5 mm的優異的剝離強度。此外,可確認本試 驗片經過200次的熱循環試驗,在構成層合物的各材料間As a result of the T-peel test under conditions of 30,000 mm/min, the laminate exhibited excellent peel strength of 4 Å / 15 mm. In addition, it can be confirmed that the test piece has undergone 200 thermal cycle tests between the materials constituting the laminate.
未產生剝離、破壞,係對於熱衝撃爲堅強的層合物,其結 果列示於表1 1。 Q -102- 200925171 ο Ο 〔11¥ 實施例56 LDPE 馬來酸酐 1 (N 〇 寸 銅薄片 馬來酸酐 接枝EVA ^ m 鱷激 m 1 1 1 200以上 實施例55 EVA 馬來酸酐 1 00 〇 鋁薄片 馬來酸酐 接枝EVA PPS薄片 1 1 1 200以上 實施例54 EVA 馬來酸酐 1 〇 cn 鋁薄片 馬來酸酐 接枝EVA 聚碳酸酯 薄膜 1 1 1 200以上 實施例53 EVA 丙烯酸 1 〇 鋁薄片 丙烯酸接 枝EVA 鹽嫩 m 1 1 1 200以上 實施例52 EVA 馬來酸酐 丙烯酸乙酯 〇 cn 鋁薄片 ^ K! w 长i赵 睡裝 PPS薄片 _1 馬來酸酐/丙 烯酸乙酯 接枝EVA 銅薄片 1—Η 200以上 實施例51 EVA 馬來酸酐 丙烯酸丁酯 〇 (N 〇 m 銅薄片 經fc ω ^ f t< 聚碳酸酯 薄膜 馬來酸酐/丙 烯酸丁酯 接枝EVA 銅薄片 Ό ro 200以上 實施例50 EVA 丙烯酸 1 〇〇 〇 (N 銅薄片 丙烯酸接 枝EVA 鋁薄片 1 1 00 1 200以上 實施例49 EVA 馬來酸酐 1 〇 CN 銅薄片 馬來酸酐 接枝EVA 鱷嫩 嵌 1 1 ο 1 200以上 聚烯烴 不飽和羧酸1 不飽和羧酸2 重量% 重量% 1 幽 CN 幽 m 寸 幽 yri 幽 N/15mm 1 N/15mm ι 酸改性量 凝膠 YI (色調) 層1/層3 層3層5 剝離次數 原料 改性聚合物 被黏著物 接著強度 熱循環試驗 -103- 200925171 實施例5 0 藉由與實施例49同樣的手法製造經接枝丙烯酸的 EVA,進行經薄膜化後接著試驗。除了被黏著物爲銅薄片 、及、鋁薄片以外,藉由與實施例4 9同樣的手法得到層 合物。實施此層合物的剝離試驗的結果’本層合物顯示出 3 8N/1 5mm之非常強的剝離強度,此外,可確認本試驗片 經由200次的熱循環試驗,構成層合物的各材料間不會產 生剝離、破壞,係對於熱衝撃爲堅強的層合物。其結果列 示於表1 1。 實施例5 1No peeling or breakage occurred, and it was a laminate which was strong for hot stamping, and the results are shown in Table 11. Q -102- 200925171 ο Ο [11¥ Example 56 LDPE maleic anhydride 1 (N 〇 inch copper flakes maleic anhydride grafted EVA ^ m crocodile m 1 1 1 200 or more Example 55 EVA maleic anhydride 1 00 〇 Aluminum flakes Maleic anhydride grafted EVA PPS flakes 1 1 1 200 Above Example 54 EVA Maleic anhydride 1 〇cn Aluminum flakes Maleic anhydride grafted EVA Polycarbonate film 1 1 1 200 Above Example 53 EVA Acrylic acid 1 〇 aluminum Sheet acrylic graft EVA salt tender m 1 1 1 200 or more Example 52 EVA Maleic anhydride ethyl acrylate cncn aluminum sheet ^ K! w long i Zhao sleeping PPS sheet _1 maleic anhydride / ethyl acrylate graft EVA Copper flakes 1 - Η 200 Above Example 51 EVA Maleic anhydride butyl acrylate N (N 〇m copper flakes via fc ω ^ f t < polycarbonate film maleic anhydride / butyl acrylate graft EVA copper flakes Ό ro 200 Example 50 above EVA acrylic acid 1 〇〇〇 (N copper foil acrylic grafted EVA aluminum foil 1 1 00 1 200 or more Example 49 EVA maleic anhydride 1 〇CN copper foil maleic anhydride graft EVA crocodile tender embedded 1 1 ο More than 1,200 polyolefins Unsaturated Carboxylic Acid 1 Unsaturated Carboxylic Acid 2% by Weight Weight % 1 幽CN 幽m 寸幽yri 幽 N/15mm 1 N/15mm ι Acid Modified Gel YI (Hue) Layer 1 / Layer 3 Layer 3 Layer 5 The number of times of peeling of the raw material-modified polymer was adhered to the strength and thermal cycle test. -103 - 200925171. Example 5 EVA of grafted acrylic acid was produced by the same method as in Example 49, followed by thinning and subsequent tests. The laminate was obtained by the same method as that of Example 49 except that the adhesive was a copper foil and an aluminum foil. The result of the peeling test of the laminate was carried out. 'The laminate showed 3 8 N/1 5 mm. The peeling strength was very strong, and it was confirmed that the test piece passed through 200 heat cycle tests, and the laminates were not peeled or broken between the materials constituting the laminate, and were strong laminates for hot stamping. Shown in Table 1 1. Example 5 1
藉由與實施例49同樣的手法製造經接枝馬來酸酐及 丙烯酸丁酯之EVA,進行經薄膜化後接著試驗。藉由與 實施例4 9同樣的手法,得到由銅薄片/經接枝馬來酸酐及 丙烯酸丁酯之EVA薄膜/聚碳酸酯薄膜/經接枝馬來酸酐及 丙烯酸丁酯之EVA薄膜/銅薄片所成的5層的層合物,實 施此層合物的剝離試驗的結果,本層合物係層1 /層3間@ 剝離強度爲 4 2 N /1 5 m m、層 3 /層 5間的剝離強度爲 3 6N/1 5 mm,顯示出非常強的剝離強度。此外,可確認本 試驗片經由200次的熱循環試驗,構成層合物的各材料胃 不會產生剝離、破壞,係對於熱衝撃爲堅強的層合物。其 結果列示於表1 1。 實施例52 -104- 200925171 藉由與實施例49同樣的手法製造經接枝馬來酸酐及 丙烯酸乙基之EVA,進行經薄膜化後接著試驗。藉由與 實施例49同樣的手法,得到由鋁薄片/經接枝馬來酸酐及 丙烯酸乙基之EVA薄膜/PPS薄片/經接枝馬來酸酐及丙烯 酸乙基之EVA薄膜/銅薄片所成的5層的層合物。實施此 層合物的剝離試驗的結果,本層合物係顯示出層1 /層3間 的剝離強度爲 50N/1 5mm、層3/層 5間的剝離強度爲 4 1 N/1 5mm之非常強的剝離強度,此外,可確認本試驗片 經由200次的熱循環試驗,構成層合物的各材料間不會產 生剝離、破壞,係對於熱衝撃爲堅強的層合物,其結果列 示於表11。 實施例5 3 藉由與實施例49同樣的手法製造經接枝丙烯酸的 EVA ’進行經薄膜化後接著試驗。除了使實施例49與被 〇 黏著物爲厚度〇.5mm的鋁薄片、及、厚度1〇〇μηι的聚酿 亞胺薄膜以外’藉由與實施例49同樣的手法得到層合物 。實施此層合物的剝離試驗的結果,本層合物係顯示出 5 1Ν/1 5mm之非常強的剝離強度,此外,可確認本試驗片 經由200次的熱循環試驗’構成層合物的各材料間不會產 生剝離、破壞,係對於熱衝撃爲堅強的層合物,其結果列 示於表1 1。 實施例54 -105-The EVA grafted with maleic anhydride and butyl acrylate was produced by the same method as in Example 49, and thinned and then tested. An EVA film/polycarbonate film/grafted maleic anhydride and butyl acrylate EVA film/copper obtained from copper flakes/grafted maleic anhydride and butyl acrylate was obtained by the same method as in Example 49. The laminate of the five layers formed by the sheet was subjected to the peeling test of the laminate, and the laminate layer 1 / layer 3 had a peel strength of 4 2 N /1 5 mm, and the layer 3 / layer 5 The peel strength between the sheets was 3 6 N/1 5 mm, showing a very strong peel strength. Further, it was confirmed that the test piece was subjected to a heat cycle test for 200 times, and the material constituting the laminate did not cause peeling or breakage of the stomach, and was a strong laminate for hot stamping. The results are shown in Table 11. Example 52 -104-200925171 EVA grafted with maleic anhydride and ethyl acrylate was produced by the same procedure as in Example 49, followed by thinning and subsequent tests. By the same method as in Example 49, an EVA film/PPS sheet/grafted maleic anhydride and an ethyl acrylate-based EVA film/copper sheet of aluminum flakes/grafted maleic anhydride and ethyl acrylate were obtained. A 5-layer laminate. As a result of performing the peeling test of this laminate, the present laminate showed a peel strength between layer 1 / layer 3 of 50 N / 15 mm, and a peel strength between layer 3 / layer 5 of 4 1 N / 15 mm Very strong peeling strength, and it was confirmed that the test piece passed through 200 thermal cycle tests, and the laminates were not peeled or broken between the materials, and the laminates were strong laminates. Shown in Table 11. Example 5 3 EVA of grafted acrylic acid was produced by the same method as in Example 49, followed by thinning and subsequent tests. A laminate was obtained by the same method as in Example 49 except that Example 49 and an aluminum foil having a thickness of 〇5 mm and a polyimide film having a thickness of 1 μm were used. As a result of performing the peeling test of this laminate, the present laminate exhibited a very strong peel strength of 5 1 Ν / 15 mm, and further, it was confirmed that the test piece was subjected to 200 thermal cycle tests 'constituting the laminate. There was no peeling or breakage between the materials, and it was a strong laminate for hot stamping, and the results are shown in Table 11. Example 54 - 105-
200925171 藉由與實施例49同樣的手法製造經接枝馬來酸酉干 EVA,進行經薄膜化後接著試驗。除了使實施例49與 黏著物爲厚度0.5mm的鋁薄片、及、厚度1〇〇μιη的聚 酸酯薄膜以外,藉由與實施例49同樣的手法得到層合 。實施此層合物的剝離試驗的結果,本層合物係顯示 53Ν/1 5mm之非常強的剝離強度,此外,可確認本試驗 經由200次的熱循環試驗,構成層合物的各材料間不會 生剝離、破壞,係對於熱衝撃爲堅強的層合物,其結果 示於表1 1。 實施例5 5 藉由與實施例49同樣的手法製造經接枝馬來酸酐 EVA,進行經薄膜化後接著試驗。除了使實施例49與 黏著物爲厚度〇.5mm的鋁薄片、及、厚度1mm的PPS 外,藉由與實施例49同樣的手法得到層合物。實施此 合物的剝離試驗的結果,本層合物係顯示出55 N/15 mm 非常強的剝離強度,此外,可確認本試驗片經由200次 熱循環試驗,構成層合物的各材料間不會產生剝離、破 ,係對於熱衝撃爲堅強的層合物,其結果列示於表1 1。 實施例5 6 除了將聚烯烴變更爲LDPE以外,藉由與實施例 同樣的手法製造經接枝馬來酸酐之LDPE,薄膜化後進 接著試驗,其結果列示於表i i。 之 被 碳 物 出 片 產 列 之 被 以 層 之 的 壞 4 9 行 -106- 200925171 實施例5 7 除了將聚烯烴變更爲HD PE以外,藉由與實施例49 同樣的手法製造經接枝馬來酸酐之HDPE,薄膜化後進行 接著試驗,除了使聚醯亞胺薄膜爲厚度〇.5mm的鋁薄片 以外’藉由與實施例49同樣的手法得到層合物,實施此 層合物的剝離試驗,其結果列示於表12。 〇 -107 200925171 ο〇 〔(Nls 實施例63 EVA 1 馬來酸酐 1 00 Ο m 鋁薄片 馬來酸酐 接枝EVA 銅薄片 馬來酸酐 接枝EVA 1 1 1 薄膜破裂 200以上 實施例62 EVA 丙烯酸 1 〇 m 鋁薄片 丙烯酸接 枝EVA 1 1 1 1 薄膜破裂 1 1 200以上 實施例61 馬來酸酐 1 〇 ΓΟ 鋁薄片 馬來酸酐 接枝PP 聚醯亞胺薄膜 馬來酸酐 接枝PP 1 1 〇〇 1 1 1 200以上 1實施例60 L-LDPE 馬來酸酐 丙烯酸丁酯 〇 m 鋁薄片 11 s 1^3 随® 聚醯亞胺薄膜 |1 a Iap3 鋁薄片 〇 1 1 1—Η 200以上 實施例56 CPP 馬來酸酐 1 〇 銅薄片 馬來酸酐 接枝CPP 聚醯亞胺薄膜 馬來酸酐 接枝CPP 銅薄片 1 1 200以上 實施例55 L-LDPE 馬來酸酐 丙烯酸 Ο) 〇 銅薄片 馬來酸酐/ 丙烯酸接枝 L-LDPE 聚碳酸酯薄膜 馬來酸酐/Η 烯酸接枝 L-LDPE 1 ο 1 1 1 200以上 實施例57 HDPE 馬來酸酐 1 〇 寸 銅薄片 馬來酸酐接 枝 HDPE 1鋁薄片 1 1 1 1 1 200以上 聚烯烴 不飽和羧酸1 !不飽和羧酸2 雷量% !重量0/〇 * 幽 (N 13^ 寸 幽 幽 N/15mm N/15mm N/15mm N/15mm 酸改性量 丨凝膠 YI (色調) 層1/層3 層1/層2 層3/層4 層3/層5 剝離次數 原料 改性聚合物 被黏著物 接著強度 熱循環試驗 -108- 200925171 實施例5 8 除了將聚烯烴變更爲L-LDPE以外,藉由與實施例49 同樣的手法製造經接枝馬來酸酐及丙烯酸之L-LDPE,薄 膜化後進行接著試驗。藉由與實施例49同樣的手法、得 到由銅薄片/經接枝馬來酸酐及丙烯酸之L-LDPE薄膜/聚 碳酸酯薄膜/經接枝馬來酸酐及丙烯酸之L-LDPE薄膜所 成的4層的層合物,實施此層合物的剝離試驗,其結果列200925171 A grafted maleic acid EVA was prepared by the same method as in Example 49, followed by thinning and subsequent tests. Lamination was carried out in the same manner as in Example 49 except that the Example 49 and the adhesive were an aluminum flake having a thickness of 0.5 mm and a polyacrylate film having a thickness of 1 μm. As a result of performing the peeling test of this laminate, the present laminate exhibited a very strong peel strength of 53 Å / 15 mm, and it was confirmed that the test was conducted between the materials of the laminate through 200 heat cycle tests. It is not peeled or broken, and is a strong laminate for hot stamping. The results are shown in Table 11. Example 5 5 Grafted maleic anhydride EVA was produced by the same procedure as in Example 49, followed by thinning and subsequent tests. A laminate was obtained in the same manner as in Example 49 except that Example 49 and an aluminum foil having a thickness of 〇5 mm and a PPS having a thickness of 1 mm were used. As a result of the peeling test of this compound, the present laminate exhibited a very strong peel strength of 55 N/15 mm, and it was confirmed that the test piece was subjected to 200 heat cycle tests to constitute a laminate material. There is no peeling or breaking, and it is a laminate which is strong for hot stamping, and the results are shown in Table 11. Example 5 6 A LDPE grafted with maleic anhydride was produced by the same method as in the Example except that the polyolefin was changed to LDPE, and the film was further subjected to a test, and the results are shown in Table i i. The bad layer of the carbonaceous material produced by the layer 4-9-106-200925171 Example 5 7 The grafted horse was produced by the same method as in Example 49 except that the polyolefin was changed to HD PE. The HDPE of the anhydride was subjected to a subsequent test after the film formation, and the laminate was obtained by the same method as in Example 49 except that the polyimide film was made of an aluminum foil having a thickness of 55 mm. The results of the tests are shown in Table 12. 〇-107 200925171 ο〇 [(Nls Example 63 EVA 1 Maleic anhydride 1 00 Ο m Aluminum flakes Maleic anhydride grafted EVA Copper flakes Maleic anhydride grafted EVA 1 1 1 Film rupture 200 or more Example 62 EVA Acrylic acid 1 〇m aluminum foil acrylic graft EVA 1 1 1 1 film cracking 1 1 200 or more Example 61 maleic anhydride 1 〇ΓΟ aluminum flake maleic anhydride graft PP polyimine film maleic anhydride graft PP 1 1 〇〇 1 1 1 200 or more 1 Example 60 L-LDPE Maleic anhydride butyl acrylate 〇m Aluminum sheet 11 s 1^3 With ® Polyimine film | 1 a Iap3 Aluminum sheet 〇 1 1 1 - Η 200 or more Examples 56 CPP maleic anhydride 1 beryllium copper flakes maleic anhydride grafted CPP polyimine film maleic anhydride grafted CPP copper flakes 1 1 200 above Example 55 L-LDPE maleic anhydride acrylic acid bismuth copper bismuth copper maleate / Acrylic acid grafted L-LDPE polycarbonate film maleic anhydride / decanoic acid grafted L-LDPE 1 ο 1 1 1 200 above Example 57 HDPE maleic anhydride 1 〇 inch copper flake maleic anhydride graft HDPE 1 aluminum Sheet 1 1 1 1 1 200 or more polyolefin is not full Carboxylic acid 1 ! Unsaturated carboxylic acid 2 Thunder %! Weight 0 / 〇 * 幽 (N 13^ inch 幽 N / 15mm N / 15mm N / 15mm N / 15mm acid modified amount 丨 gel YI (hue) Layer 1 /layer 3 layer 1 / layer 2 layer 3 / layer 4 layer 3 / layer 5 peeling times raw material modified polymer adherent strength thermal cycle test -108- 200925171 Example 5 8 In addition to changing the polyolefin to L-LDPE A graft of maleic anhydride and L-LDPE of acrylic acid was produced by the same method as in Example 49, and the film was subjected to a subsequent test. The same procedure as in Example 49 was carried out to obtain a copper flake/graft. A four-layer laminate of maleic anhydride and acrylic acid L-LDPE film/polycarbonate film/grafted maleic anhydride and acrylic acid L-LDPE film, and the peeling test of the laminate was carried out, and the result was as follows. Column
實施例59 於附有攪拌機、UV照射裝置、回流冷卻器之10L可 分離燒瓶中,裝入MFR2.5、密度900kg/m3的聚丙烯500 重量份、離子交換水8L、及〇·23重量份的烷基磺酸鈉, 調製懸濁液,一邊對此懸濁液照射UV,一邊連續地導入 氯氣,以1 〇 〇 °C進行6小時反應,得到氯含量2 0 %的氯化 聚丙稀。 使用所得到的氯化P P藉由與實施例4 9同樣的手法, 得到經接枝馬來酸酐之CPP後,薄膜化後實施接著試驗 。藉由與實施例4 9同樣的手法,得到由銅薄片/經接枝馬 來酸酐之CPP薄膜/聚醯亞胺薄膜/經接枝馬來酸酐之CPP 薄膜/銅薄片所成的5層的層合物、實施此層合物的剝離 試驗,其結果列示於表12。 實施例60 -109- 200925171Example 59 In a 10 L separable flask equipped with a stirrer, a UV irradiation apparatus, and a reflux cooler, 500 parts by weight of polypropylene having MFR 2.5, density of 900 kg/m 3 , ion-exchanged water of 8 L, and 〇·23 parts by weight were charged. The sodium alkylsulfonate was prepared, and the suspension was irradiated with UV gas, and chlorine gas was continuously introduced thereto, and the mixture was reacted at 1 ° C for 6 hours to obtain a chlorinated polypropylene having a chlorine content of 20%. Using the obtained chlorinated P P, a CPP obtained by grafting maleic anhydride was obtained by the same method as in Example 49, and then subjected to a subsequent test after film formation. By the same method as in Example 49, a 5-layer layer of a copper foil/grafted maleic anhydride CPP film/polyimine film/grafted maleic anhydride CPP film/copper sheet was obtained. The laminate and the peel test for carrying out the laminate were shown in Table 12. Example 60 -109- 200925171
除了變更爲MFR2、密度920kg/m3的L-LDPE以外, 藉由與實施例49同樣的手法製造經接枝馬來酸酐及丙烯 酸丁酯之L-LDPE,此外,將所得到的改性L-LDPE藉由 與實施例49同樣的手法薄膜化,實施接著試驗。藉由與 實施例49同樣的手法得到由鋁薄片/經接枝馬來酸酐及丙 烯酸丁酯之L-LDPE薄膜/聚醯亞胺薄膜/經接枝馬來酸酐 及丙烯酸丁醋之L-LDPE薄膜/銘薄片所成的5層的層合 物,實施此層合物的剝離試驗,其結果列示於表12。 實施例6 1 除了將聚烯烴變更爲PP以外,藉由與實施例49同樣 的手法製造經接枝馬來酸酐之PP,薄膜化後進行接著試 驗。藉由與實施例49同樣的手法,得到由銅薄片/經接枝 馬來酸酐之PP薄膜/聚醯亞胺薄膜/經接枝馬來酸酐之PP 薄膜所成的4層的層合物,實施此層合物的剝離試驗,其 Q 結果列示於表12。 實施例62 使用藉由與實施例49同樣的手法製造經接枝丙烯酸 的EVA,於厚度0.5mm的鋁薄片的單面上接著經接枝丙 烯酸之EVA薄膜,此時,將與鋁薄片接著的面相反側之 面用聚對苯二甲酸乙二醇酯薄膜保護之丙烯酸接枝EVA 的薄膜,藉由與實施例49同樣的手法得到層合物。實施 此層合物的剝離試驗的結果,因爲EVA薄膜與鋁薄片的 -110- 200925171 接著強度強,故EVA薄膜先破裂,此外,可確認本試驗 片經由200次的熱循環試驗,構成層合物的各材料間不會 發生剝離,係對於熱衝撃爲堅強的層合物,其結果列示於 表12。 實施例63 藉由與實施例49同樣的手法得到由厚度〇.5mm的鋁 薄片、厚度〇.5mm的銅薄片、厚度ΙΟΟμιη的馬來酸酐接 枝EVA薄膜所成之由鋁薄片/馬來酸酐接枝EVA薄膜/銅 薄片/馬來酸酐接枝EVA薄膜所構成的4層的層合物。實 施此層合物的接著試驗的結果列示於表12。 實施例64 <不飽和羧酸接枝聚烯烴的製造>L-LDPE grafted with maleic anhydride and butyl acrylate was produced by the same method as in Example 49 except that LFR was changed to MFR2 and had a density of 920 kg/m3. Further, the obtained modified L- The LDPE was subjected to the same method as in Example 49 to carry out a subsequent test. L-LDPE film/polyimine film/grafted maleic anhydride and butyl acrylate L-LDPE obtained from aluminum flakes/grafted maleic anhydride and butyl acrylate were obtained by the same method as in Example 49. A peel test of the laminate was carried out on the laminate of the five layers of the film/Ming sheet, and the results are shown in Table 12. Example 6 1 PP which was grafted with maleic anhydride was produced by the same method as in Example 49 except that the polyolefin was changed to PP, and the film was subjected to a subsequent test. A four-layer laminate of a copper foil/grafted maleic anhydride PP film/polyimine film/grafted maleic anhydride PP film was obtained by the same method as in Example 49. A peel test of this laminate was carried out, and the Q results thereof are shown in Table 12. Example 62 An EVA film grafted with acrylic acid was produced by the same method as in Example 49, followed by grafting an acrylic EVA film on one side of an aluminum foil having a thickness of 0.5 mm, at which time, it was followed by an aluminum foil. The film of the acrylic grafted EVA protected with a polyethylene terephthalate film on the opposite side was obtained by the same method as in Example 49. As a result of the peeling test of this laminate, since the EVA film and the aluminum foil were strong in strength from -110 to 200925171, the EVA film was first broken, and further, it was confirmed that the test piece was subjected to thermal cycling test for 200 times to constitute lamination. No peeling occurred between the materials of the material, which was a strong laminate for hot stamping, and the results are shown in Table 12. Example 63 An aluminum flake/maleic anhydride was obtained by the same procedure as in Example 49, from an aluminum flake having a thickness of 〇5 mm, a copper flake having a thickness of 55 mm, and a maleic anhydride grafted EVA film having a thickness of ΙΟΟμηη. A four-layer laminate composed of a grafted EVA film/copper sheet/maleic anhydride grafted EVA film. The results of the subsequent tests for carrying out this laminate are shown in Table 12. Example 64 <Production of Unsaturated Carboxylic Acid-Grafted Polyolefin>
將5 000重量份的1,1,2-三氯乙烷與2500重量份的 26%硫酸水溶液放進附有下口的10升燒瓶中激烈地攪拌 ,靜置後取出下層的有機層,接著,將取出的有機層與 5kg蒸餾水放進附有下口的10升燒瓶中激烈地攪拌,靜 置後取出下層的有機層之操作重複3次,去除1-丁醇及 1,2-環氧基丁烷,更藉由於取出的有機層中添加150重量 份的分子篩4A、用攪拌器攪拌而脫水,得到經純化的 1,1,2-三氯乙烷(以下,記爲純化1^£)。 於4升的玻璃製反應容器中裝入2480重量份的純化 TCE與200重量份的EVA、及4.1重量份的馬來酸酐,將 -111 - 200925171 反應器昇溫至80 °C,然後藉由以80 °C保持4小時均勻地 溶解EVA ’此外在此期間,於反應器中以5升/分鐘的流 速導入氮氣,排除混入反應器的空氣,作爲接枝反應的觸 媒之使1.5重量份的BPO溶解於純化TCE 100重量份中 ,將此溶液用1小時添加至反應器後,在反應器的壓力保 持在1 MPa狀態下,進行3小時接枝反應,反應終了後, 使壓力回復至常壓,將反應器的溫度提高至70 °C爲止,添 加作爲安定劑之〇·〇6重量份的BHT,將此溶液注入至大 量的甲醇中,將生成物的馬來酸酐接枝EVA從溶劑分離 出。 已知生成物係分析結果爲具有1.5重量%的不飽和羧 酸(馬來酸酐),凝膠爲0.011重量%,YI爲2及色相爲 優良。 <不飽和羧酸接枝聚烯烴薄膜的製造>5 000 parts by weight of 1,1,2-trichloroethane and 2500 parts by weight of a 26% aqueous solution of sulfuric acid were placed in a 10-liter flask with a lower mouth and stirred vigorously, and after standing, the lower organic layer was taken out, followed by The removed organic layer and 5 kg of distilled water were placed in a 10-liter flask with a lower mouth and vigorously stirred. After standing, the operation of taking out the lower organic layer was repeated three times to remove 1-butanol and 1,2-epoxy. Butane, by adding 150 parts by weight of molecular sieve 4A to the extracted organic layer, and dehydrating with a stirrer to obtain purified 1,1,2-trichloroethane (hereinafter, referred to as purification 1) ). A 4 liter glass reaction vessel was charged with 2480 parts by weight of purified TCE and 200 parts by weight of EVA, and 4.1 parts by weight of maleic anhydride, and the -111 - 200925171 reactor was heated to 80 ° C, and then EVA was uniformly dissolved at 80 ° C for 4 hours. Further, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liters / minute to remove air mixed into the reactor, and 1.5 parts by weight as a catalyst for the graft reaction was used. BPO was dissolved in 100 parts by weight of purified TCE. After adding this solution to the reactor for 1 hour, the grafting reaction was carried out for 3 hours while the pressure of the reactor was maintained at 1 MPa. After the reaction was completed, the pressure was returned to normal. Pressurize, increase the temperature of the reactor to 70 ° C, add 6 parts by weight of BHT as a stabilizer, and inject this solution into a large amount of methanol to form a product of maleic anhydride grafted EVA from the solvent. Separated. The result of the analysis of the product was found to be 1.5% by weight of an unsaturated carboxylic acid (maleic anhydride), the gel was 0.011% by weight, the YI was 2, and the hue was excellent. <Production of unsaturated carboxylic acid grafted polyolefin film>
藉由使用復動式壓縮成形機WFA-50,將上述所得到 的不飽和羧酸接枝EVA,以加熱溫度150 °C、壓力lOMPa 、加熱時間1〇分鐘、冷卻溫度30°C、壓力lOMPa、冷卻 時間5分鐘的條件進行加壓成形,得到尺寸50mmxl00mm 、厚度100 μιη的薄膜(薄膜1),所得到的薄膜的外觀、 性狀爲優良,看不到魚眼等之缺點。 <銅薄片的絕緣被覆> 將所得到的尺寸50mmxl00mm'厚度ΙΟΟμιη的薄膜 -112- 200925171 (薄膜1)、未進行表面處理尺寸1 OOmmx 1 00mm、厚度 0.5mm的銅薄片(薄片1 )、尺寸loommxlOOmm厚度 100μιη的聚醯亞胺薄膜(薄膜2),以薄片w薄膜w薄膜 2的構成進行層合,以壓力〇.2Mpa、溫度18(TC、時間1 分鐘的條件’得到銅薄片、及聚醯亞胺薄膜的一半面積經 接著之層合物。將由所得到的層合物切割出長度100mm 、寬度15mm的薄長方狀試料,使其成爲—半的面積被接 著、一半的面積未被接著的狀態,以拉伸速度300mm/分 鐘的條件進行T型剝離試驗的結果,本層合物係顯示出 42N/15mm之優異的剝離強度。此外,可確認本試驗片經 由200次的熱循環試驗,構成層合物的各材料間不會產生 剝離、破壞’係對於熱衝撃爲堅強的層合物’其結果列示 於表1 3。The above-mentioned unsaturated carboxylic acid was grafted with EVA by using a double-action compression molding machine WFA-50 at a heating temperature of 150 ° C, a pressure of 10 MPa, a heating time of 1 Torr, a cooling temperature of 30 ° C, and a pressure of 10 MPa. The film was formed by press molding under the conditions of a cooling time of 5 minutes to obtain a film (film 1) having a size of 50 mm x 100 mm and a thickness of 100 μm. The obtained film was excellent in appearance and properties, and the defects such as fish eyes were not observed. <Insulation coating of copper sheet> Film of the obtained size 50 mm x 100 mm 'thickness ΙΟΟμηη-112-200925171 (film 1), copper sheet (sheet 1) having a surface treatment size of 1 OO mm x 100 mm and a thickness of 0.5 mm, A polyimine film (film 2) having a size of loommxlOOmm and a thickness of 100 μm was laminated by a composition of a sheet w film w film 2, and a copper sheet was obtained under the conditions of a pressure of M2 Mpa and a temperature of 18 (TC, time of 1 minute). Half of the area of the polyimide film was passed through the laminate. A thin rectangular sample having a length of 100 mm and a width of 15 mm was cut out from the obtained laminate, so that the area of the half was followed by half of the area. As a result of performing a T-type peeling test under the conditions of a tensile speed of 300 mm/min, the present laminate exhibited excellent peel strength of 42 N/15 mm. Further, it was confirmed that the test piece was heated by 200 times. In the cycle test, no peeling or breakage was observed between the materials constituting the laminate, and the results were shown in Table 13.
-113- 200925171 ο Ο 〔Π撇〕 實施例71 LDPE 馬來酸酐 1 (N 0.010 寸 銅薄片 馬來酸酐 接枝EVA 聚醯亞胺 薄膜 1 1 5 1 200以上 實施例70 EVA 馬來酸酐 1 00 0.014 鋁薄片 馬來酸酐 接枝EVA PPS薄片 1 1 CN 1 200以上 實施例69 EVA 馬來酸酐 诵 0.011 m 鋁薄片 馬來酸酐 接枝EVA 餵 m m ϋ概 嵌 1 1 1 200以上 實施例68 EVA 丙烯酸 1 ! 0.011 m 鋁薄片 丙烯酸接 枝EVA 鱷嫩 1 1 1 200以上 實施例67 EVA 馬來酸酐 丙烯酸乙酯 Η 0.014 m 鋁薄片 經Κ] ω 恢g怒 uf SI PPS薄片 馬來酸酐/丙 烯酸乙酯 接枝EVA 銅薄片 〇 200以上 實施例66 EVA 馬來酸酐 丙烯酸丁酯 〇 r-i 0.013 m 銅薄片 經t w 保i您 聚碳酸酯 薄膜 馬來酸酐炳 烯酸丁酯 接枝EVA 銅薄片 〇 m 200以上 實施例65 EVA 丙烯酸 1 oo 0.013 fN 銅薄片 丙烯酸接 枝EVA 鋁薄片 1 1 〇 1 200以上 實施例64 丨EVA 馬來酸酐 1 0.011 (N 銅薄片 馬來酸酐 接枝EVA )¾ m 磐嫩 m 1 1 1 200以上 I聚烯烴 !不飽和羧酸1 不飽和羧酸2 1重量% 重量% 1 幽 <N cn is 寸 幽 _ N/15mm N/15mm 酸改性量 凝膠 YU色調) 層1/層3 層3/層5 剝離次數 原料 改性聚合物 被黏著物 接著強度 熱循環試驗 -114- 200925171 實施例65 藉由與實施例64同樣的手法製造經接枝丙烯酸的 EVA ’進行經薄膜化後接著試驗,除了使被黏著物爲銅薄 片、及、鋁薄片以外,藉由與實施例6 4同樣的手法得到 層合物。實施此層合物的剝離試驗的結果,本層合物顯示 出40N/15mm之非常強的剝離強度,此外,可確認本試驗 片經由200次的熱循環試驗,構成層合物的各材料間不會 產生剝離、破壞,係對於熱衝撃爲堅強的層合物,其結果 列示於表1 3。 實施例66 藉由與實施例64同樣的手法製造經接枝馬來酸酐及 丙烯酸丁酯之EVA,進行經薄膜化後接著試驗,藉由與 實施例64同樣的手法,得到由銅薄片/經接枝馬來酸酐及 丙烯酸丁酯之EVA薄膜/聚碳酸酯薄膜/經接枝馬來酸酐及 Q 丙烯酸丁酯之EVA薄膜/銅薄片所成的5層的層合物。實 施此層合物的剝離試驗的結果,本層合物顯示出層Η層3 間的剝離強度爲40Ν/1 5mm、層3/層5間的剝離強度爲 35N/15mm之非常強的剝離強度,此外’可確認本試驗片 經由200次的熱循環試驗,構成層合物的各材料間不會產 生剝離、破壞,係對於熱衝撃爲堅強的層合物’其結果列 示於表13。 實施例67 -115- 200925171-113- 200925171 ο Ο [Π撇] Example 71 LDPE Maleic Anhydride 1 (N 0.010 inch copper flake maleic anhydride grafted EVA polyimine film 1 1 5 1 200 or more Example 70 EVA maleic anhydride 1 00 0.014 Aluminum flakes Maleic anhydride grafted EVA PPS flakes 1 1 CN 1 200 Above Example 69 EVA Maleic anhydride 诵 0.011 m Aluminum flakes Maleic anhydride grafted EVA Feeding mm ϋ 嵌 1 1 1 200 200 Above E 68 Acrylic acid 1 ! 0.011 m Aluminium foil Acrylic grafted EVA crocodile 1 1 1 200 or more Example 67 EVA Maleic anhydride ethyl acrylate Η 0.014 m Aluminum flakes Κ ω g 怒 uf SI PPS flakes Maleic anhydride / ethyl acrylate Grafted EVA copper flakes 〇 200 above Example 66 EVA Maleic anhydride butyl acrylate 〇 0.013 m Copper flakes tw Protected by your polycarbonate film Maleic anhydride butyl acrylate graft EVA Copper flakes 〇 m 200 or more Example 65 EVA Acrylic acid 1 oo 0.013 fN Copper flakes Acrylic grafted EVA Aluminum flakes 1 1 〇 1 200 Above Example 64 丨 EVA Maleic anhydride 1 0.011 (N copper flake maleic anhydride grafted EVA) 3⁄4 m 磐 tender m 1 1 1 200 or more I polyolefin! Unsaturated carboxylic acid 1 Unsaturated carboxylic acid 2 1% by weight % by weight 1 幽<N cn is inch _ N/15mm N/15mm acid-modified gel YU tone) Layer 1 / layer 3 layer 3/layer 5 peeling times raw material modified polymer adherend followed by strength heat cycle test-114-200925171 Example 65 by grafting acrylic acid-containing EVA' in the same manner as in Example 64, after thinning Next, a laminate was obtained by the same method as in Example 64 except that the adherend was a copper foil and an aluminum foil. As a result of performing the peeling test of the laminate, the laminate exhibited a very strong peel strength of 40 N/15 mm, and further, it was confirmed that the test piece was subjected to a thermal cycle test of 200 times to constitute a laminate material. There is no peeling or damage, and it is a strong laminate for hot stamping, and the results are shown in Table 13. Example 66 EVA obtained by grafting maleic anhydride and butyl acrylate was produced by the same method as in Example 64, followed by film formation and subsequent test, and the same procedure as in Example 64 was carried out to obtain a copper foil/wafer. EVA film/polycarbonate film grafted with maleic anhydride and butyl acrylate/5 layer laminate of grafted maleic anhydride and Q-butyl acrylate EVA film/copper sheet. As a result of performing the peeling test of this laminate, the present laminate showed a very strong peel strength of a peel strength of 40 Å/15 5 mm between layers 3 and 5 and a peel strength of 35 N/15 mm between layers 3 and 5. In addition, it was confirmed that the test piece was subjected to 200 thermal cycle tests, and the laminates were not peeled or broken between the materials constituting the laminate, and the laminates were strong for thermal pulverization. The results are shown in Table 13. Example 67 -115- 200925171
藉由與實施例64同樣的手法製造經接枝馬來酸酐及 丙烯酸乙基之EVA,進行經薄膜化後接著試驗。藉由與 實施例64同樣的手法,得到由鋁薄片/經接枝馬來酸酐及 丙烯酸乙基之EVA薄膜/PPS薄片/經接枝馬來酸酐及丙烯 酸乙基之EVA薄膜/銅薄片所成的5層的層合物。實施此 層合物的剝離試驗的結果,本層合物顯示出層1/層3間的 剝離強度爲 48N/1 5mm、層 3/層 5間的剝離強度爲 40N/1 5mm之非常強的剝離強度,此外,可確認本試驗片 經由2 0 0次的熱循環試驗,構成層合物的各材料間不會產 生剝離、破壞,係對於熱衝撃爲堅強的層合物,其結果列 7K於表1 3。 實施例6 8 藉由與實施例64同樣的手法製造經接枝丙烯酸的 EVA,進行經薄膜化後接著試驗。除了使實施例64與被 〇 黏著物爲厚度〇.5mm的鋁薄片、及、厚度Ι00μιη的聚酿 亞胺薄膜以外,藉由與實施例64同樣的手法得到層合物 。實施此層合物的剝離試驗的結果,本層合物顯示出 54Ν/15 mm之非常強的剝離強度。此外,可確認本試驗片 經由200次的熱循環試驗,構成層合物的各材料間不會產 生剝離、破壞,係對於熱衝撃爲堅強的層合物。其結果歹IJ 示於表13。 實施例69 -116- 200925171 藉由與實施例64同樣的手法製造經接枝馬來酸酐之 EVA,進行經薄膜化後接著試驗。除了使實施例64與被 黏著物爲厚度〇.5mm的鋁薄片、及、厚度ΙΟΟμιη的聚碳 酸酯薄膜以外,藉由與實施例64同樣的手法得到層合物 。實施此層合物的剝離試驗的結果,本層合物顯示出 50N/15mm之非常強的剝離強度,此外,可確認本試驗片 經由200次的熱循環試驗,構成層合物的各材料間不會產 生剝離、破壞,係對於熱衝撃爲堅強的層合物,其結果列 示於表1 3。 實施例7 0 藉由與實施例64同樣的手法製造經接枝馬來酸酐之 EVA,進行經薄膜化後接著試驗。除了使實施例64與被 黏著物爲厚度〇.5mm的鋁薄片、及、厚度1mm的PPS以 外,藉由與實施例64同樣的手法得到層合物。實施此層 〇 合物的剝離試驗的結果,本層合物顯示出52N/1 5mm之非 常強的剝離強度,此外,可確認本試驗片經由200次的熱 循環試驗,構成層合物的各材料間不會產生剝離、破壞, 係對於熱衝撃爲堅強的層合物,其結果列示於表13。 實施例7 1 除了將聚烯烴變更爲LDPE以外,藉由與實施例64 同樣的手法製造經接枝馬來酸酐之LDPE,薄膜化後進行 接著試驗,其結果列示於表1 3。 117- 200925171The EVA grafted with maleic anhydride and ethyl acrylate was produced in the same manner as in Example 64, and subjected to film formation followed by a test. By the same method as in Example 64, an EVA film/PPS sheet/grafted maleic anhydride and an ethyl acrylate-based EVA film/copper sheet of aluminum flake/grafted maleic anhydride and ethyl acrylate were obtained. A 5-layer laminate. As a result of performing the peeling test of this laminate, the present laminate showed a peel strength between layer 1/layer 3 of 48 N/15 5 mm, and a peel strength between layer 3/layer 5 of very strong 40 N/1 5 mm. In addition, it was confirmed that the test piece was subjected to a thermal cycle test of 200 times, and no peeling or breakage occurred between the materials constituting the laminate, and it was a strong laminate for hot stamping, and the result was 7K. In Table 13. Example 6 8 EVA of grafted acrylic acid was produced by the same method as in Example 64, followed by thinning and subsequent tests. A laminate was obtained in the same manner as in Example 64 except that the Example 64 and the adherend were an aluminum flake having a thickness of 〇5 mm and a polyimide film having a thickness of Ι00 μm. As a result of the peeling test of this laminate, the laminate exhibited a very strong peel strength of 54 Å / 15 mm. Further, it was confirmed that the test piece passed through the thermal cycle test for 200 times, and the laminates were not peeled or broken between the materials constituting the laminate, and were strong laminates for hot stamping. The results 歹IJ are shown in Table 13. Example 69 - 116 - 200925171 EVA of grafted maleic anhydride was produced by the same procedure as in Example 64, followed by thinning and subsequent tests. A laminate was obtained in the same manner as in Example 64 except that the Example 64 and the adherend were an aluminum foil having a thickness of 〇5 mm and a polycarbonate film having a thickness of ΙΟΟμηη. As a result of performing the peeling test of the laminate, the laminate exhibited a very strong peel strength of 50 N/15 mm, and further, it was confirmed that the test piece was subjected to 200 heat cycle tests to constitute a laminate material. There is no peeling or damage, and it is a strong laminate for hot stamping, and the results are shown in Table 13. Example 70 An EVA grafted with maleic anhydride was produced by the same procedure as in Example 64, followed by thinning and subsequent tests. A laminate was obtained in the same manner as in Example 64 except that the Example 64 and the adherend were an aluminum foil having a thickness of 55 mm and a PPS having a thickness of 1 mm. As a result of the peeling test of this layer of the composition, the laminate exhibited a very strong peel strength of 52 N/1 5 mm, and it was confirmed that the test piece was subjected to 200 cycles of heat cycle test to constitute each of the laminates. There was no peeling or breakage between the materials, and it was a strong laminate for hot stamping, and the results are shown in Table 13. Example 7 1 A LDPE grafted with maleic anhydride was produced by the same procedure as in Example 64 except that the polyolefin was changed to LDPE, and the film was subjected to a subsequent test. The results are shown in Table 13. 117- 200925171
實施例72 除了將聚烯烴變更爲HDPE以外’藉由與實施例64 闻樣的手法製造經接枝馬來酸酐之HDPE,薄膜化後進行 接著試驗。除了使聚醯亞胺薄膜爲厚度〇.5mm的鋁薄片 以外,藉由與實施例64同樣的手法得到層合物,實施此 餍合物的剝離試驗’其結果列示於表14。 -118- 200925171 〔寸1¥ 實施例78 EVA 馬來酸酐 1 〇〇 0.015 m 鋁薄片 馬來酸酐 接枝EVA 銅薄片 馬來酸酐 接枝EVA 1 1 1 薄膜破裂 200以上 實施例77 EVA 丙烯酸 1 0.011 m 鋁薄片 丙烯酸接 枝EVA 1 1 1 1 薄膜破裂 1 1 200以上 實施例76 & 馬來酸酐 1 寸· 0.012 m 銅薄片 馬來酸酐 接枝PP 聚醯亞胺薄膜 馬來酸酐 接枝PP 1 〇 1 1 1 200以上 實施例75 L-LDPE 馬來酸酐 丙烯酸丁酯 0.015 m 鋁薄片 1^3 聚醯亞胺薄膜 1^3 鋁薄片 1 1 〇 200以上 實施例74 Ah P-. ο 馬來酸酐 I m fN 0.016 m 銅薄片 & 氍^ HU谢 聚醯亞胺薄膜 溢& 氍u 嵌尨 n谢 銅薄片 1 r 200以上 實施例73 L-LDPE 馬來酸酐 丙烯酸 1_ 〇\ 1-H 0.013 m 銅薄片 馬來酸酐/ 丙烯酸接枝 L-LDPE 聚碳酸酯薄膜 馬來酸酐/丙 烯酸接枝 L-LDPE 1 1 1 1 200以上 實施例72 HDPE 馬來酸酐 1 (N 0.011 寸 銅薄片 馬來酸酐接 枝 HDPE 鋁薄片 1 1 1 1 1 200以上 聚烯烴 丨不飽和羧酸1 不飽和羧酸2 雷量% |重量% 隹 (N _ m 幽 寸 i; 幽 N/15mm N/15mm N/15mm N/15mm 酸改性量 凝膠 YU色調) 層1/層3 層1/層2 層3/層4 層3/層5 剝離次數 原料 改性聚合物 被黏著物 接著強度 熱循環試驗 119- 200925171 實施例73 除了將聚烯烴變更爲L-LDPE以外,藉由與實施例64 同樣的手法製造經接枝馬來酸酐及丙烯酸之L-LDPE,薄 膜化後進行接著試驗。藉由與實施例64同樣的手法,得 到由銅薄片/經接枝馬來酸酐及丙烯酸L-LDPE薄膜/聚碳 酸酯薄膜/經接枝馬來酸酐及丙烯酸L-LDPE薄膜所成的4 層的層合物,實施此層合物的剝離試驗,其結果列示於表 實施例74 於附有攪拌機、UV照射裝置、回流冷卻器之10L可 分離燒瓶中,裝入MFR2.5、密度900kg/m3的聚丙烯500 重量份、離子交換水8L、及0.23重量份的烷基磺酸鈉, 調製懸濁液,一邊對此懸濁液照射UV,一邊連續地導入 氯氣,以l〇〇°C進行6小時反應,得到氯含量2〇%的氯化 Q 聚丙烯。 使用所得到的氯化PP藉由與實施例64同樣的手法, 得到經接枝馬來酸酐之CPP後,薄膜化後實施接著試驗 。藉由與實施例6 4同樣的手法,得到由銅薄片/經接枝馬 來酸酐之CPP薄膜/聚醯亞胺薄膜/經接枝馬來酸酐之CPP 薄膜/銅薄片所成的5層的層合物,實施此層合物的剝離 試驗,其結果列示於表14。 實施例75 -120- 200925171 除了變更爲MFR2、密度920kg/m3的L-LDPE以外, 藉由與實施例64同樣的手法製造經接枝馬來酸酐及丙烯 酸丁酯之L-LDPE ’此外’將所得到的改性L-LDPE藉由 與實施例64同樣的手法薄膜化,實施接著試驗。藉由與 實施例64同樣的手法得到由鋁薄片/經接枝馬來酸酐及丙 烯酸丁酯之L-LDPE薄膜/聚醯亞胺薄膜/經接枝馬來酸酐 及丙烯酸丁酯之L_LDPE薄膜/鋁薄片所成的5層的層合 物,實施此層合物的剝離試驗,其結果列示於表14。 實施例7 6 除了將聚烯烴變更爲PP以外,藉由與實施例64同樣 的手法製造經接枝馬來酸酐之PP,薄膜化後進行接著試 驗。藉由與實施例64同樣的手法,得到由銅薄片/經接枝 馬來酸酐之PP薄膜/聚醯亞胺薄膜/經接枝馬來酸酐之PP 薄膜所成的4層的層合物,實施此層合物的剝離試驗,其 〇 結果列示於表1 4。 實施例7 7 使用藉由與實施例64同樣的手法製造經接枝丙烯酸 的EVA,於厚度0.5mm的鋁薄片的單面上,接著經接枝 丙烯酸之EVA薄膜,此時,將與鋁薄片接著的面相反側 之面用聚對苯二甲酸乙二醇酯薄膜保護之丙烯酸接枝 EVA的薄膜,藉由與實施例64同樣的手法得到層合物。 實施此層合物的剝離試驗的結果,因爲EVA薄膜與鋁薄 -121 - 200925171 片的接著強度強,故EVA薄膜先破裂,此外,可確認本 試驗片經由200次的熱循環試驗,構成層合物的各材料間 不會發生剝離,係對於熱衝撃爲堅強的層合物,其結果列 示於表14。 實施例78Example 72 In addition to the modification of the polyolefin to HDPE, HDPE grafted with maleic anhydride was produced by the method of the sample of Example 64, and the film was subjected to the subsequent test. A laminate test was conducted in the same manner as in Example 64 except that the polyimide film was made of an aluminum foil having a thickness of 55 mm, and the peel test of the composition was carried out. The results are shown in Table 14. -118- 200925171 [Inch 1 ¥ Example 78 EVA Maleic anhydride 1 〇〇 0.015 m Aluminum flakes Maleic anhydride grafted EVA Copper flakes Maleic anhydride grafted EVA 1 1 1 Film rupture 200 or more Example 77 EVA Acrylic acid 1 0.011 m Aluminium foil acrylic grafted EVA 1 1 1 1 Film cracked 1 1 200 or more Example 76 & Maleic anhydride 1 inch · 0.012 m Copper flakes Maleic anhydride grafted PP Polyimine film Maleic anhydride grafted PP 1 〇1 1 1 200 or more Example 75 L-LDPE Maleic anhydride butyl acrylate 0.015 m Aluminum flakes 1^3 Polyimide film 1^3 Aluminum flakes 1 1 〇200 or more Example 74 Ah P-. ο Malay Anhydride I m fN 0.016 m Copper flakes & 氍 ^ HU 醯 醯 醯 薄膜 薄膜 & & 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 谢 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 以上 1- 1- 1- 1- 1- 1- 1- 1- 1- 1- Copper flake maleic anhydride / acrylic acid grafted L-LDPE polycarbonate film maleic anhydride / acrylic acid grafted L-LDPE 1 1 1 1 200 or more Example 72 HDPE maleic anhydride 1 (N 0.011 inch copper flake maleic anhydride Branch HDPE aluminum sheet 1 1 1 1 1 200 or more polyolefin Unsaturated Carboxylic Acid 1 Unsaturated Carboxylic Acid 2 Thunder Amount % |% by Weight 隹(N _ m 寸i; 幽N/15mm N/15mm N/15mm N/15mm Acid Modified Gel YU Tone) Layer 1 Layer 3 Layer 1 / Layer 2 Layer 3 / Layer 4 Layer 3 / Layer 5 Stripping Times Raw Material Modified Polymer Adhesive Next Strength Thermal Cycle Test 119 - 200925171 Example 73 In addition to changing the polyolefin to L-LDPE, L-LDPE grafted with maleic anhydride and acrylic acid was produced in the same manner as in Example 64, and the film was subjected to a subsequent test. The same procedure as in Example 64 was carried out to obtain a copper flake/grafted maleic anhydride. And a laminate of four layers of an L-LDPE film/polycarbonate film/grafted maleic anhydride and an L-LDPE film of acrylic acid, and a peeling test of the laminate was carried out, and the results are shown in the table. Example 74 In a 10 L separable flask equipped with a stirrer, a UV irradiation apparatus, and a reflux cooler, 500 parts by weight of polypropylene having MFR 2.5, density of 900 kg/m 3 , 8 L of ion-exchanged water, and 0.23 parts by weight of an alkyl group were charged. Sodium sulfonate, a suspension is prepared, and the suspension is continuously introduced with chlorine while irradiating UV to the suspension. In the reaction for 6 hours l〇〇 ° C, a chlorine content of chlorinated Q 2〇% polypropylene. Using the obtained chlorinated PP, a CPP obtained by grafting maleic anhydride was obtained by the same method as in Example 64, and then a film was formed and subjected to a subsequent test. By the same method as in Example 64, a 5-layer layer of a copper foil/grafted maleic anhydride CPP film/polyimine film/grafted maleic anhydride CPP film/copper sheet was obtained. The laminate was subjected to a peel test of this laminate, and the results are shown in Table 14. Example 75 - 120 - 200925171 L-LDPE 'addition' of grafted maleic anhydride and butyl acrylate was produced by the same procedure as in Example 64 except that LFR was changed to MFR 2 and a density of 920 kg/m 3 . The obtained modified L-LDPE was thinned by the same method as in Example 64, and the subsequent test was carried out. An L-LDPE film/polyimine film/a grafted maleic anhydride and butyl acrylate L_LDPE film obtained from aluminum flakes/grafted maleic anhydride and butyl acrylate was obtained by the same method as in Example 64. The laminate of the five layers of the aluminum foil was subjected to a peel test of the laminate, and the results are shown in Table 14. Example 7 6 PP which was grafted with maleic anhydride was produced by the same method as in Example 64 except that the polyolefin was changed to PP, and the film was subjected to a subsequent test. A four-layer laminate of a copper foil/grafted maleic anhydride PP film/polyimine film/grafted maleic anhydride PP film was obtained by the same method as in Example 64. The peel test of this laminate was carried out, and the results are shown in Table 14. Example 7 7 EVA of grafted acrylic acid was produced by the same method as in Example 64 on one side of an aluminum foil having a thickness of 0.5 mm, followed by grafting an EVA film of acrylic acid, at this time, with an aluminum foil A laminate of acrylic acid-grafted EVA film protected with a polyethylene terephthalate film on the opposite side of the surface was obtained in the same manner as in Example 64. As a result of the peeling test of this laminate, since the EVA film and the aluminum thin-121 - 200925171 sheet had strong adhesive strength, the EVA film was first broken, and further, it was confirmed that the test piece was subjected to 200 thermal cycle tests to form a layer. The peeling of each material of the compound did not occur, and it was a strong laminate for hot stamping, and the results are shown in Table 14. Example 78
藉由與實施例64同樣的手法由厚度0.5 mm的鋁薄片 、厚度〇.5mm的銅薄片、厚度ΙΟΟμιη的馬來酸酐接枝 EVA薄膜所成之鋁薄片/馬來酸酐接枝EVA薄膜/銅薄片/ 馬來酸酐接枝EVA薄膜所構成的4層的層合物。實施此 層合物的接著試驗的結果列示於表14。 比較例3 4 使用NAKATANI製的 115機械工業mm φ 、L/D = 5〇 的2軸擠壓機,將區段Cl、C2、C3設定在150、180、 200°C,將區段C4〜CIO、A、D設定在220°C,以旋轉數 1 1 Orpm,從C6~C7間的排氣口去除未反應的不飽和羧酸 ,進行接枝反應。亦即、以EVA1 〇〇重量份、馬來酸酐4 重量份、BP02重量份的比例,使用亨雪莉混練機被均勻 地混合的預摻合物供給至二軸擠壓機’進行接枝反應得到 經接枝馬來酸酐之EVA。確認所得到的EVA係含有分析 結果爲含有0.6重量%的馬來酸酐,含有0.1 5重量%的凝Aluminum flake/maleic anhydride grafted EVA film/copper formed by aluminum flakes having a thickness of 0.5 mm, copper flakes having a thickness of 55 mm, and a maleic anhydride grafted EVA film having a thickness of ΙΟΟμηη by the same method as in Example 64. A four-layer laminate of a sheet/maleic anhydride grafted EVA film. The results of the subsequent tests for carrying out this laminate are shown in Table 14. Comparative Example 3 4 Sections Cl, C2, and C3 were set at 150, 180, and 200 ° C using a two-axis extruder of 115 mechanical industry mm φ and L/D = 5 制 manufactured by NAKATANI, and the section C4 was CIO, A, and D were set at 220 ° C, and the unreacted unsaturated carboxylic acid was removed from the exhaust port between C6 and C7 at a number of revolutions of 1 1 O rpm to carry out a graft reaction. That is, in a ratio of EVA1 〇〇 by weight, 4 parts by weight of maleic anhydride, and BP02 parts by weight, a preblend uniformly mixed using a Henschel mixer is supplied to a two-axis extruder for grafting reaction. An EVA grafted with maleic anhydride was obtained. It was confirmed that the obtained EVA-containing analysis analysis contained 0.6% by weight of maleic anhydride and contained 0.15% by weight of coagulum.
-122- 200925171 <不飽和羧酸接枝聚烯烴薄膜的製造> 使用復動式壓縮成形機WFA-50,使所得到的馬來酸 酐接枝EVA,以加熱溫度l5〇°C、壓力l〇MPa、加熱時間 10分鐘、冷卻溫度30°C、壓力l〇MPa、冷卻時間5分鐘 的條件進行加壓成形,得到厚度1 〇〇μιη的薄膜。所得到 的薄膜出現魚眼,外觀與實施例所得到的薄膜比較下明顯 地較差。-122- 200925171 <Production of Unsaturated Carboxylic Acid-Grafted Polyolefin Film> Using the double-action compression molding machine WFA-50, the obtained maleic anhydride was grafted with EVA at a heating temperature of 15 ° C, pressure Pressurization molding was carried out under the conditions of 〇 MPa, heating time of 10 minutes, cooling temperature of 30 ° C, pressure of 10 MPa, and cooling time of 5 minutes to obtain a film having a thickness of 1 μm. The obtained film appeared fish eyes, and the appearance was remarkably inferior to that of the film obtained in the examples.
Ο 將所得到的尺寸50mmxl00mm、厚度ΙΟΟμιη的薄膜 (薄膜 3)、未進行表面處理尺寸 lOOmmxlOOmm、厚度 0.5mm的銅薄片(薄片 1)、尺寸 lOOmmxlOOmm厚度 100 μιη的聚醯亞胺薄膜(薄膜2),以薄片1/薄膜3/薄膜 2的構成進行層合,以壓力〇.2MPa、溫度180°C、時間1 分鐘的條件,得到經接著箔1、及聚醯亞胺薄膜的一半面 積之層合物。將由所得到的層合物切割出長度1 〇〇mm、 寬度15mm的薄長方狀試料,使其成爲一半的面積被接著 、一半的面積未被接著的狀態,以以拉伸速度300mm/分 鐘的條件進行 T型剝離試驗的結果,本層合物顯示出 13N/15mm之剝離強度低的値,此外,本試驗片經由20 次的熱循環試驗,構成層合物之各材料間發生剝離,與實 施例所得到的層合物比較下,係對於熱衝撃爲弱的層合物 ,其結果列示於表1 5。 -123- 200925171 Q o 〔SIS 比較例42 Ρη 〇 馬來酸酐 1 m Ο I銅薄片1 馬來酸酐 接枝CPP 廳漉 嵌 & m ^ 长蹈 υί|逝 1 00 t 比較例41 Ah Oh u 馬來酸酐 1 ο c5 m 丨銅薄片I 馬來酸酐 接枝CPP mm 馬來酸酐 接枝CPP 1 00 v〇 1 比較例40 EVA 馬來酸酐 1 寸 ο S o r-H l鋁薄片」 馬來酸酐 接枝EVA PPS薄片 馬來酸酐 接枝EVA 1 00 卜 1 比較例39 EVA 馬來酸酐 1 寸 ο g o 1鋁薄片1 馬來酸酐 接枝EVA 聚碳酸酯 薄膜 馬來酸酐 接枝EVA 1 〇〇 ( (N CO ί匕較例38 EVA 馬來酸酐 1 rn s o rs 1鋁薄片I 馬來酸酐 接枝EVA 跬鹤 mm 馬來酸酐 接枝EVA 1 ON 卜 1 沄 比較例37 EVA 馬來酸酐 1_ 1 Οί o’ s o 1鋁薄片Ί 馬來酸酐 接枝EVA PPS薄片 馬來酸酐 接枝EVA 1銅薄片Ί 〇 1 m 比較例36 EVA 馬來酸酐 丙烯酸 丁酯 cn 〇 s o ON 1銅薄片1 馬來酸酐/ 丙烯酸丁 酯接枝 EVA 聚碳酸酯 薄膜 馬來酸酐/ 丙烯酸丁 酯接枝 EVA 「銅薄片I 〇 1 CN oo r-H 比較例35 EVA 馬來酸酐 丙烯酸 1_ o s o o 1—H 1銅薄片I 馬來酸酐/ 丙烯酸接 枝EVA 鋁薄片 1 1 1 1 比較例34 EVA 馬來酸酐 1 o c5 CN 1銅薄片I 馬來酸酐 接枝EVA 聚醯亞胺 薄膜 1 1 ΓΛ 1 1 I聚烯烴 i不飽和羧酸1 不飽和羧酸2 _ \Μ\ 重量% 1 幽 (N m _ 寸 幽 |N/15mm| N/15mm N/15mm 酸改性量 凝膠 |yu色調)1 層1/層3 J 丨層3/層4 | 層3/層5 J 剝離次數 原料 改性聚合物 被黏著物 ... .^1 接著強度 熱循環試驗 -124- 200925171 比較例3 5 除了藉由與比較例34同樣的手法製造經接枝馬來酸 酐及丙烯酸的EVA,使比較例34的被黏著物爲銅薄片、 及、鋁薄片以外,藉由與實施例49同樣的手法得到層合 物。實施此層合物的剝離試驗的結果,本層合物顯示出 15N/15mm之低剝離強度,此外,本試驗片經由50次的 熱循環試驗,構成層合物之各材料間發生剝離,與實施例 所得到的層合物比較下,係對於熱衝撃爲弱的層合物,其 結果列示於表1 5。 比較例3 6 藉由與比較例34同樣的手法製造經接枝馬來酸酐及 丙烯酸丁酯之EVA,使比較例34的被黏著物爲銅薄片( 層1)、聚碳酸酯薄膜(層3)、銅薄片(層5)的構造 以外,藉由與實施例49同樣的手法得到層合物。實施此 Q 層合物的剝離試驗的結果,本層合物顯示出層1/層3間的 剝離強度l〇N/15mm、層3/層5間的剝離強度12N/15mm 之低的値,此外,本試驗片經由1 8次的熱循環試驗,構 成層合物之各材料間發生剝離,與實施例所得到的層合物 比較下,係對於熱衝撃爲弱的層合物。其結果列示於表 15 » 比較例3 7 除了藉由與比較例34同樣的手法製造經接枝馬來酸 -125- 200925171薄膜 The obtained film (film 3) having a size of 50 mm×100 mm and a thickness of ΙΟΟμη, a copper foil (sheet 1) having a surface treatment size of 100 mm×100 mm and a thickness of 0.5 mm, and a polyimide film (film 2) having a thickness of 100 μm and a thickness of 100 μm Lamination was carried out in the form of sheet 1 / film 3 / film 2, and a layer of half area of the foil 1 and the polyimide film was obtained under the conditions of a pressure of 2 MPa, a temperature of 180 ° C, and a time of 1 minute. Compound. A thin rectangular sample having a length of 1 mm and a width of 15 mm was cut out from the obtained laminate so that half of the area was followed, and half of the area was not followed, at a stretching speed of 300 mm/min. As a result of the T-peel test, the laminate exhibited a ruthenium having a low peel strength of 13 N/15 mm, and the test piece was peeled off between the materials constituting the laminate through 20 thermal cycle tests. Compared with the laminate obtained in the examples, it was a laminate which was weak for hot stamping, and the results are shown in Table 15. -123- 200925171 Q o [SIS Comparative Example 42 Ρη 〇 Maleic anhydride 1 m Ο I Copper flakes 1 Maleic anhydride grafted CPP Hall && m ^ Long υ | 逝 1 00 t Comparative Example 41 Ah Oh u Maleic anhydride 1 ο c5 m Beryllium copper sheet I Maleic anhydride grafted CPP mm Maleic anhydride grafted CPP 1 00 v〇1 Comparative Example 40 EVA Maleic anhydride 1 inch ο S o rH l aluminum sheet” Maleic anhydride Branch EVA PPS sheet Maleic anhydride graft EVA 1 00 Bu 1 Comparative Example 39 EVA Maleic anhydride 1 inch ο go 1 Aluminum sheet 1 Maleic anhydride grafted EVA polycarbonate film Maleic anhydride grafted EVA 1 〇〇 ( N CO 匕 匕 38 EVA maleic anhydride 1 rn so rs 1 aluminum flakes I maleic anhydride graft EVA 跬 crane mm maleic anhydride graft EVA 1 ON 卜 1 沄 Comparative Example 37 EVA maleic anhydride 1_ 1 Οί o ' so 1 aluminum flakes Ί maleic anhydride graft EVA PPS flakes maleic anhydride graft EVA 1 copper flakes Ί 1 m Comparative Example 36 EVA maleic anhydride butyl acrylate 〇 so ON 1 copper flakes 1 maleic anhydride / acrylic acid Butyl Ester Grafted EVA Polycarbonate Film Maleic Anhydride / Butyl Acrylate Graft EVA "Copper Sheet I 1 CN oo rH Comparative Example 35 EVA Maleic Anhydride Acrylic Acid 1_ osoo 1-H 1 Copper Sheet I Maleic Anhydride / Acrylic Graft EVA Aluminum Sheet 1 1 1 1 Comparative Example 34 EVA Maleic Anhydride 1 o c5 CN 1 Copper Sheet I Maleic anhydride grafted EVA polyimine film 1 1 ΓΛ 1 1 I polyolefin i unsaturated carboxylic acid 1 unsaturated carboxylic acid 2 _ \Μ\ wt% 1 幽 (N m _ inch 幽|N/15mm| N /15mm N/15mm acid modified gel | yu tone) 1 layer 1 / layer 3 J 丨 layer 3 / layer 4 | layer 3 / layer 5 J stripping times raw material modified polymer is adhered ... . 1 Intensity Thermal Cycling Test - 124 - 200925171 Comparative Example 3 5 The adhesive of Comparative Example 34 was made into a copper foil, and the EVA of the grafted maleic anhydride and acrylic acid was produced by the same method as that of Comparative Example 34. A laminate was obtained by the same method as in Example 49 except for the aluminum foil. As a result of the peeling test of the laminate, the laminate exhibited a low peel strength of 15 N/15 mm, and further, the test piece was passed through 50. The second thermal cycle test, the peeling occurred between the materials constituting the laminate, compared with the laminate obtained in the examples, For laminates which are weakly hot, the results are shown in Table 15. Comparative Example 3 6 The EVA of the grafted maleic anhydride and butyl acrylate was produced by the same method as that of Comparative Example 34, and the adherend of Comparative Example 34 was a copper foil (layer 1) and a polycarbonate film (layer 3). The laminate was obtained in the same manner as in Example 49 except for the structure of the copper foil (layer 5). As a result of performing the peeling test of the Q laminate, the laminate showed a peel strength of 10 N/15 mm between the layers 1 and 3 and a peel strength of 12 N/15 mm between the layers 3 and 5. Further, this test piece was peeled off between the respective materials constituting the laminate by the thermal cycle test of 18 times, and was a laminate which was weak against thermal pulverization as compared with the laminate obtained in the examples. The results are shown in Table 15 » Comparative Example 3 7 A grafted maleic acid was produced by the same method as Comparative Example 34 -125-200925171
酐之EVA,使比較例34的被黏著物爲鋁薄片(層i)、 PPS薄片(層2)、銅薄片(層3)以外,藉由與實施例 49同樣的手法5層的層合物。實施此層合物的剝離試驗 的結果’本層合物顯示出層1/層3間的剝離強度 1 ON/1 5mm、層3/層5間的剝離強度1 1N/1 5mm之低的値 ’此外,本試驗片經由35次的熱循環試驗,構成層合物 之各材料間發生剝離,與實施例所得到的層合物比較下, 係對於熱衝撃爲弱的層合物,其結果列示於表1 5。 比較例38 除了藉由與比較例34同樣的手法製造經接枝馬來酸 酐之EVA,使比較例34的被黏著物爲鋁薄片、及、聚醯 亞胺薄膜以外,藉由與實施例49同樣的手法得到表丨5所 表示的4層的層合物。實施此層合物的剝離試驗的結果, 本層合物顯示出層1/層3間的剝離強度爲9N/1 5 m m之低 〇 的値’層3/層4間的剝離強度亦爲7N/1 5 m m之低的値, 此外’本試驗片經由30次的熱循環試驗,構成層合物之 各材料間發生剝離,與實施例所得到的層合物比較下,係 對於熱衝撃爲弱的層合物,其結果列示於表15。 比較例3 9 除了藉由與比較例34同樣的手法製造經接枝馬來酸 酐之EVA,使比較例34的被黏著物爲鋁薄片、及、聚碳 酸酯以外,藉由與實施例49同樣的手法得到表15所表示 -126- 200925171 的4層的層合物。實施此層合物的剝離試驗的結果,本層 合物顯示出層1 /層3間的剝離強度爲1 1 n /1 5 m m之低的値 、層3/層4間的剝離強度亦爲8N/1 5mm之低的値,此外 ,本試驗片經由32次的熱循環試驗,構成層合物之各材 料間發生剝離,與實施例所得到的層合物比較下,係對於 熱衝撃爲弱的層合物,其結果列示於表1 5。The EVA of the anhydride was such that the adherend of Comparative Example 34 was an aluminum foil (layer i), a PPS sheet (layer 2), and a copper sheet (layer 3), and the same method as in Example 49 was carried out. . As a result of the peeling test of the laminate, the laminate showed a peel strength of 1 ON/1 5 mm between the layers 1 and 3, and a peel strength of 1 1 N/1 5 mm between the layers 3 and 5. In addition, this test piece was peeled off between the materials constituting the laminate through 35 heat cycle tests, and compared with the laminate obtained in the example, the laminate was weak to heat, and the result was as follows. Listed in Table 15. Comparative Example 38 An EVA of the grafted maleic anhydride was produced by the same method as that of Comparative Example 34, and the adherend of Comparative Example 34 was an aluminum flake and a polyimide film, and Example 49 was used. The same method was used to obtain a four-layer laminate represented by Table 5. As a result of the peeling test of the laminate, the laminate showed a peel strength of 〇' layer 3/layer 4 having a peel strength of 9 N/1 5 mm between layer 1 and layer 3 of 7 N. /1 5 mm low enthalpy, in addition, the test piece was peeled off between the materials constituting the laminate through 30 thermal cycle tests, and compared with the laminate obtained in the example, it was The weak laminates are shown in Table 15. Comparative Example 3 9 The same procedure as in Comparative Example 34 was carried out to produce EVA grafted with maleic anhydride, and the adherend of Comparative Example 34 was an aluminum flake and polycarbonate, and the same as in Example 49. The four-layer laminate of -126-200925171 represented by Table 15 was obtained. As a result of performing the peeling test of the laminate, the laminate showed a peel strength of 1 1 n /1 5 mm between the layers 1 / 3 and a peel strength between the layers 3 / 4 8N/1 5mm low enthalpy, in addition, this test piece was peeled off between the materials constituting the laminate through 32 heat cycle tests, compared with the laminate obtained in the example, The weak laminates are shown in Table 15.
比較例4 0 除了藉由與比較例34同樣的手法製造經接枝馬來酸 酐之EVA,使比較例34的被黏著物爲鋁薄片、及、PPS 以外’藉由與實施例4 9同樣的手法得到表1 5所表示的4 層的層合物。實施此層合物的剝離試驗的結果,本層合物 顯示出層1/層3間的剝離強度8N/1 5mm之低的値、層3/ 層4間的剝離強度亦爲7N/l5mm之低的値,此外,本試 驗片經由26次的熱循環試驗,構成層合物之各材料間發 生剝離,與實施例所得到的層合物比較下,係對於熱衝撃 爲弱的層合物,其結果列示於表1 5。 比較例4 1 使用實施例59所得到的CPP,藉由與比較例34同樣 的手法製造經接枝馬來酸酐之CPP,使所得到的聚合物薄 膜化後,製造銅薄片/經接枝馬來酸酐之CPP薄膜/聚醒亞 胺薄膜/經接枝馬來酸酐之CPP薄膜的4層的層合物,進 行其接著試驗的結果,列示於表15。接著試驗的結果, -127- 200925171 層合物係關於接著強度、色相、熱衝撃的任一物性,皆比 實施例所得到的層合物差,其結果列示於表1 5。 比較例42Comparative Example 40 The EVA of the grafted maleic anhydride was produced by the same method as that of Comparative Example 34, and the adherend of Comparative Example 34 was an aluminum flake and the same as PPS, by the same as Example 49. The four layer laminates shown in Table 15 were obtained by the method. As a result of performing the peeling test of this laminate, the laminate showed a peel strength of 8 N/15 mm between layers 1/layer 3, and a peel strength between layer 3/layer 4 of 7 N/l 5 mm. In addition, the test piece was peeled off between the materials constituting the laminate by the 26th thermal cycle test, and was a weak laminate for hot stamping as compared with the laminate obtained in the example. The results are shown in Table 15. Comparative Example 4 1 Using the CPP obtained in Example 59, CPP of grafted maleic anhydride was produced by the same method as Comparative Example 34, and the obtained polymer was thinned to prepare a copper flake/grafted horse. The results of the subsequent tests of the CPP film of the anhydride anhydride/the polyamidide film/the four-layered layer of the CPP film grafted with maleic anhydride are shown in Table 15. As a result of the test, the -127-200925171 laminate was inferior to any of the properties of the subsequent strength, hue, and hot stamping, and the results are shown in Table 15. Comparative Example 42
使用實施例74所得到的CPP,藉由與比較例34同樣 的手法製造經接枝馬來酸酐之CPP,使所得到的聚合物薄 膜化後,製造銅薄片/經接枝馬來酸酐之CPP薄膜/聚醯亞 胺薄膜/經接枝馬來酸酐之CPP薄膜的4層的層合物,進 行其接著試驗的結果,列示於表15。接著試驗的結果, 層合物係關於接著強度、色相、熱衝撃的任一物性,皆比 實施例所得到的層合物差,其結果列示於表1 5。 實施例79 <不飽和羧酸接枝聚烯烴的製造> 將5000重量份的1,1,2-三氯乙烷與2500重量份的 Q 26%硫酸水溶液放進附有下口的1〇升燒瓶中激烈地攪拌 ,靜置後取出下層的有機層。接著、將被取出的有機層與 5kg蒸餾水放進附有下口的1〇升燒瓶中激烈地攪拌,靜 置後取出下層的有機層之操作重複3次,去除1-丁醇及 1,2-環氧基丁烷。更藉由於取出的有機層中添加15〇重量 份的分子篩4A,用攪拌器攪拌而脫水,得到經純化的 1,1,2-三氯乙烷(以下,記爲純化TCE )。 於4升的玻璃製反應容器中裝入3〇〇〇重量份的純化 TCE與200重量份的EVA、及5重量份的馬來酸酐,將 -128- 200925171Using the CPP obtained in Example 74, CPP of grafted maleic anhydride was produced by the same method as Comparative Example 34, and the obtained polymer was thinned to prepare a copper flake/CPP of grafted maleic anhydride. A laminate of a film/polyimine film/a four-layer laminate of a CPP film grafted with maleic anhydride was subjected to the subsequent test, and is shown in Table 15. As a result of the test, the laminate was inferior to any of the properties of the subsequent strength, hue, and hot stamping, and the results are shown in Table 15. Example 79 <Production of Unsaturated Carboxylic Acid-Grafted Polyolefin> 5000 parts by weight of 1,1,2-trichloroethane and 2500 parts by weight of a Q 26% sulfuric acid aqueous solution were placed in the lower mouth 1 The stirred flask was vigorously stirred, and after standing, the lower organic layer was taken out. Next, the taken-out organic layer and 5 kg of distilled water were placed in a 1-liter flask equipped with a lower mouth and vigorously stirred, and the operation of removing the organic layer of the lower layer was repeated 3 times to remove 1-butanol and 1,2. - Epoxybutane. Further, 15 parts by weight of molecular sieve 4A was added to the extracted organic layer, and the mixture was stirred and dehydrated to obtain purified 1,1,2-trichloroethane (hereinafter referred to as purified TCE). A 4 liter glass reaction vessel was charged with 3 parts by weight of purified TCE and 200 parts by weight of EVA, and 5 parts by weight of maleic anhydride, and -128-200925171
反應器昇溫至,然後藉由以80°C保持4小時均勻地 溶解EVA,此外在此期間,於反應器中以5升/分鐘的流 速導入氮氣,排除混入反應器的空氣,作爲接枝反應的觸 媒之使1.55重量份的BPO溶解於純化TCE 100重量份, 將此溶液連續地持續添加至反應器,在反應器的壓力保持 在1 MPa狀態下,進行3小時接枝反應。反應終了後、使 壓力回復至常壓,將反應器的溫度提高至70 °C爲止,添加 作爲安定劑之0.06重量份的BHT,將此溶液注入至大量 的甲醇中,將生成物的馬來酸酐接枝EVA從溶劑分離出 已知生成物係分析結果爲具有1.6重量%的不飽和羧 酸(馬來酸酐),凝膠爲〇重量%。 <不飽和羧酸接枝聚烯烴薄膜的製造> 使用復動式壓縮成形機WFA-50,將上述所得到的不 飽和羧酸接枝EVA,以加熱溫度15(TC、壓力lOMPa、加 熱時間10分鐘、冷卻溫度30°C、壓力lOMPa、冷卻時間 5分鐘的條件進行加壓成形,得到尺寸lOOmmxlOOmm、 厚度ΙΟΟμπι的薄膜,所得到的薄膜的外觀、性狀爲優良 ,看不到魚眼等之缺點。 <多層層合物的製造> 將所得到的尺寸1 OOmmx 1 00mm、厚度1 ΟΟμπι的薄膜 與以和紙補強裏面的厚度0.3mm的黑檀薄片,以壓力 -129- 200925171 O.IMPa、溫度180°C、1分鐘的條件進行加熱壓黏,得到 具有熱熔著性之黑檀薄片。將所得到的黑檀薄片重疊於未 進行表面處理的尺寸lOOmmxlOOmm、厚度1mm的錯板, 以壓力O.IMPa、溫度180°C、1分鐘的條件進行加熱壓黏 ,得到多層層合物。將所得到的層合物的各層堅固地接著 ,雖然加熱至40~80°C,但未看到剝離,製成與此層合物 同一構成的剝離試驗片,以以拉伸速度300mm/分鐘的條 件進行T型剝離試驗的結果,金屬層與接著層之間的剝離 強度爲50N/15mm之優異値,木材與接著層之間的剝離強 度係超過木材自體的破裂強度,此外,確認此層合物以-4 0 °C彎折並未見到剝離,低溫特性亦優異。此外,本層合 物經由200次的熱循環試驗後亦未見到剝離,爲接著強度 高的層合物。 實施例8 0The reactor was heated to a temperature, and then EVA was uniformly dissolved by maintaining at 80 ° C for 4 hours. Further, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liter / minute to remove air mixed into the reactor as a graft reaction. The catalyst was dissolved in 1.55 parts by weight of BPO in 100 parts by weight of purified TCE, and this solution was continuously continuously added to the reactor, and the graft reaction was carried out for 3 hours while maintaining the pressure of the reactor at 1 MPa. After the completion of the reaction, the pressure was returned to normal pressure, the temperature of the reactor was raised to 70 ° C, 0.06 parts by weight of BHT as a stabilizer was added, and the solution was poured into a large amount of methanol to form a product of Malay. The acid anhydride-grafted EVA was separated from the solvent by a known product system and found to have 1.6% by weight of an unsaturated carboxylic acid (maleic anhydride) and the gel was 〇% by weight. <Production of unsaturated carboxylic acid grafted polyolefin film> The above-obtained unsaturated carboxylic acid was grafted with EVA at a heating temperature of 15 (TC, pressure 10 MPa, heating using a double-action compression molding machine WFA-50) The film was subjected to press molding under the conditions of a time of 10 minutes, a cooling temperature of 30° C., a pressure of 10 MPa, and a cooling time of 5 minutes to obtain a film having a size of 100 mm×100 mm and a thickness of ΙΟΟμπι, and the obtained film was excellent in appearance and properties, and no fisheye or the like was observed. Disadvantages. <Manufacturing of Multilayer Laminate> The obtained film having a size of 1 OOmm x 1 00 mm and a thickness of 1 ΟΟμπι and a ebony sheet having a thickness of 0.3 mm in the reinforced paper were pressed at a pressure of -129 to 200925171 O. IMPa, temperature and temperature of 180 ° C, 1 minute conditions were heated and pressure-bonded to obtain a blister sheet having heat fusibility. The obtained ebony sheet was superposed on a non-surface-treated sheet of a size of 100 mm x 100 mm and a thickness of 1 mm. The mixture was heated and pressure-bonded under the conditions of a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute to obtain a multilayer laminate. The layers of the obtained laminate were firmly followed by heating to 40 to 80 ° C, but not Seeing peeling The release test piece having the same structure as the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 50 N/15 mm.値, the peeling strength between the wood and the adhesive layer exceeded the breaking strength of the wood itself. Further, it was confirmed that the laminate was not peeled off at -40 ° C, and the low-temperature characteristics were excellent. The compound did not show peeling after 200 cycles of thermal cycling, and was a laminate having high strength. Example 8 0
將實施例 79所得到的尺寸 lOOmmxlOOmm、厚度 ΙΟΟμιη的薄膜與以和紙補強裏面之厚度〇.3mm的木瓜薄 片,以壓力O.IMPa、溫度180 °C ' 1分鐘的條件進行加熱 壓黏,得到具有熱熔著性之木瓜薄片。將所得到的木瓜薄 片重疊於未進行表面處理之尺寸10〇mmxlOOmm、厚度 1mm的鋁板,壓力O.IMPa、溫度180 °C、1分鐘的條件進 行加熱壓黏,得到多層層合物。所得到的層合物的各層係 堅固地接著,雖然加熱至4 0 ~ 8 0 °C但未見到剝離’製成與 此層合物同一構成的剝離試驗片,以以拉伸速度3 0 0mm/ -130- 200925171 分鐘的條件進行τ型剝離試驗的結果,金屬層與接著層之 間的剝離強度爲55Ν/15mm之優異値,木材與接著層之間 的剝離強度超過木材自體的破裂強度,此外,確認此層合 物以-4 0°C彎折並未見到剝離,低溫特性亦優異,此外, 本層合物經由2 0 0次的熱循環試驗後亦未見到剝離,爲接 著強度高的層合物。The film having a size of 100 mm×100 mm and a thickness of ΙΟΟμηη obtained in Example 79 and a papaya sheet having a thickness of 3.3 mm reinforced with a paper were heated and pressure-bonded under the conditions of a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute to obtain Hot-melt papaya flakes. The obtained papaya sheet was overlaid on an aluminum plate having a size of 10 mm×100 mm and a thickness of 1 mm which was not subjected to surface treatment, and was pressure-bonded under the conditions of a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute to obtain a multilayer laminate. The layers of the obtained laminate were firmly adhered to each other, and although it was heated to 40 to 80 ° C, no peeling test piece was formed which was formed into the same composition as the laminate to obtain a tensile speed of 3 0. 0mm/ -130- 200925171 minutes As a result of the τ-type peeling test, the peel strength between the metal layer and the adhesive layer was excellent at 55 Ν / 15 mm, and the peel strength between the wood and the adhesive layer exceeded the rupture of the wood itself. In addition, it was confirmed that the laminate was not peeled off at -40 ° C, and the low-temperature characteristics were excellent. Further, the laminate did not show peeling after the thermal cycle test of 200 times. It is a laminate with high strength.
實施例8 1 於4升的玻璃製反應容器中裝入3 000重量份的純化 TCE與200重量份的L-LDPE、及6重量份的丙烯酸,將 反應器昇溫至80°C,然後藉由以80 °C保持4小時均句地 溶解L-LDPE。此外在此期間,於反應器中以5升/分鐘的 流速導入氮氣,排除混入反應器的空氣,作爲接枝反應的 觸媒之使1.4重量份的BPO溶解於純化TCE 100重量份 。將此溶液連續地持續添加至反應器,在反應器的壓力保 持在1 MPa狀態下,進行3小時接枝反應。反應終了後、 使壓力回復至常壓,將反應器的溫度提高至70°C爲止,添 加作爲安定劑之0.06重量份的BHT。將此溶液注入至大 量的甲醇中,將生成物的丙烯酸接枝L-LDPE從溶劑分離 出。已知生成物係分析結果爲具有1.8重量%的丙烯酸, 凝膠爲〇重量%。 將所得到的丙烯酸接枝L-LDPE藉由與實施例79同 樣的手法薄膜化後,以壓力〇· IMPa、溫度1 80°C、1分鐘 的條件與鳥眼楓薄片進行加熱壓黏,而且,重疊於未進行 -131 - 200925171 表面處理尺寸lOOmmxlOOmm、厚度lmm的銘板,以壓力 0.1 MPa、溫度180 °C、4〇秒的條件進行加熱壓黏,得到多 層層合物。 製成與此層合物同一構成的剝離試驗片,以拉伸速度 3 00mm/分鐘的條件進行T型剝離試驗的結果,金屬層與 接著層之間的剝離強度爲52N/15mm之優異値,木材與接 著層之間的剝離強度超過木材自體的破裂強度,此外,確 認此層合物以-40°C彎折並未見到剝離,低溫特性亦優異 ,此外,本層合物經由200次的熱循環試驗後亦未見到剝 離,爲接著強度高的層合物。 實施例82Example 8 1 A 3 liter glass reaction vessel was charged with 3,000 parts by weight of purified TCE and 200 parts by weight of L-LDPE, and 6 parts by weight of acrylic acid, and the reactor was heated to 80 ° C, and then by The L-LDPE was dissolved uniformly at 80 ° C for 4 hours. Further, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liter / minute to exclude air mixed into the reactor, and 1.4 parts by weight of BPO was dissolved as 100 parts by weight of the purified TCE as a catalyst for the graft reaction. This solution was continuously continuously added to the reactor, and the graft reaction was carried out for 3 hours while maintaining the pressure of the reactor at 1 MPa. After the completion of the reaction, the pressure was returned to normal pressure, and the temperature of the reactor was raised to 70 ° C, and 0.06 part by weight of BHT as a stabilizer was added. This solution was poured into a large amount of methanol, and the resultant acrylic grafted L-LDPE was separated from the solvent. It is known that the result of the analysis of the product system was 1.8% by weight of acrylic acid, and the gel was 〇% by weight. The obtained acrylic grafted L-LDPE was thinned by the same method as in Example 79, and then heat-pressed with a bird's eye maple leaf under the conditions of pressure 〇 IMPa, temperature of 180 ° C, and 1 minute. , superimposed on the -131 - 200925171 surface treatment size lOOmmxlOOmm, thickness lmm of the nameplate, pressure 0.1 MPa, temperature 180 ° C, 4 〇 second conditions of heating and pressure bonding, to obtain a multilayer laminate. A peeling test piece having the same structure as the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 52 N/15 mm. The peeling strength between the wood and the adhesive layer exceeded the breaking strength of the wood itself. Further, it was confirmed that the laminate was not peeled off at -40 ° C, and the low-temperature characteristics were excellent. Further, the laminate was passed through 200. No peeling was observed after the secondary heat cycle test, and the laminate was high in strength. Example 82
於4升的玻璃製反應容器中裝入3 000重量份的純化 TCE與200重量份的L-LDPE、及5重量份的馬來酸酐, 將反應器昇溫至80°C,然後藉由以80°C保持4小時均勻 地溶解L-LDPE。此外在此期間,於反應器中以5升/分鐘 的流速導入氮氣,排除混入反應器的空氣,作爲接枝反應 的觸媒之使1.8重量份的BPO溶解於純化TCE 100重量 份,將此溶液連續地持續添加至反應器,在反應器的壓力 保持在1 MPa狀態下,進行3小時接枝反應。反應終了後 、使壓力回復至常壓,將反應器的溫度提高至7〇 °C爲止, 添加作爲安定劑之〇.〇6重量份的BHT。將此溶液注入至 大量的甲醇中,將生成物的馬來酸酐接枝L-LDPE從溶劑 分離出,已知生成物係分析結果爲具有1.4重量%的馬來 -132- 200925171 酸酐,凝膠爲〇重量%。 將所得到的馬來酸酑接枝L-LDPE藉由與實施例79 同樣的手法薄膜化後,與斑木樹薄片以壓力〇.lMPa、溫 度15(TC、30秒的條件進行加熱壓黏,而且,與厚度1mm 的不鏽鋼板以壓力O.IMPa、溫度180°C、60秒的條件進 行加熱壓黏,得到多層層合物。A 4 liter glass reaction vessel was charged with 3,000 parts by weight of purified TCE and 200 parts by weight of L-LDPE, and 5 parts by weight of maleic anhydride, and the reactor was heated to 80 ° C, and then by 80 The L-LDPE was uniformly dissolved at °C for 4 hours. Further, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liters/min to remove air mixed into the reactor, and 1.8 parts by weight of BPO was dissolved in 100 parts by weight of purified TCE as a catalyst for the graft reaction. The solution was continuously continuously added to the reactor, and the graft reaction was carried out for 3 hours while the pressure of the reactor was maintained at 1 MPa. After the completion of the reaction, the pressure was returned to normal pressure, the temperature of the reactor was raised to 7 ° C, and 6 parts by weight of BHT as a stabilizer was added. This solution was poured into a large amount of methanol, and the product of maleic anhydride grafted L-LDPE was separated from the solvent, and it was known that the product analysis result was 1.4% by weight of Malay-132-200925171 anhydride, gel. It is % by weight. The obtained lanthanum maleate grafted L-LDPE was thinned by the same method as in Example 79, and then heated and pressed with the plaque wood sheet under the conditions of pressure 〇1 MPa, temperature 15 (TC, 30 seconds). Further, a stainless steel sheet having a thickness of 1 mm was heated and pressure-bonded under the conditions of a pressure of 0.1 MPa, a temperature of 180 ° C, and a temperature of 60 seconds to obtain a multilayer laminate.
製成與此層合物同一構成的剝離試驗片,以拉伸速度 3 0 0mm/分鐘的條件進行T型剝離試驗的結果,金屬層與 接著層之間的剝離強度爲47N/15mm之優異値’木材與接 著層之間的剝離強度超過木材自體的破裂強度,此外’確 認此層合物以-4〇°C彎折並未見到剝離’低溫特性亦優異 ,此外,本層合物經由200次的熱循環試驗後亦未見到剝 離,爲接著強度高的層合物。 實施例83 將實施例81所得到的丙烯酸接枝L-LDPE的薄膜’ 與厚度0.3mm的橡樹薄片以壓力0.15MPa、溫度160°C、 30秒的條件進行加熱壓黏,而且,與厚度1mm的不鏽鋼 薄片以壓力〇· IMPa、溫度1 70°C、7〇秒的條件進行加熱 壓黏,得到多層層合物。 製成與此層合物同一構成的剝離試驗片,以拉伸速度 300mm/分鐘的條件進行T型剝離試驗的結果,金屬層與 接著層之間的剝離強度爲45N/1 5mm之優異値’木材與接 著層之間的剝離強度超過木材自體的破裂強度,此外,確 -133- 200925171 認此層合物以-40°C彎折並未見到剝離,低溫特性亦優異 ,此外,本層合物經由200次的熱循環試驗後亦未見到剝 離,爲接著強度高的層合物。 實施例84 <不飽和羧酸接枝聚烯烴的製造>A peeling test piece having the same structure as that of the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 47 N/15 mm. 'The peel strength between the wood and the adhesive layer exceeds the crack strength of the wood itself. In addition, it is confirmed that the laminate is bent at -4 ° C and no peeling is observed. The low temperature property is also excellent. In addition, the laminate is excellent. No peeling was observed after 200 cycles of the heat cycle test, and the laminate was high in strength. Example 83 The film of the acrylic acid grafted L-LDPE obtained in Example 81 and the oak sheet having a thickness of 0.3 mm were heat-pressed under the conditions of a pressure of 0.15 MPa, a temperature of 160 ° C, and a temperature of 30 seconds, and a thickness of 1 mm. The stainless steel sheet was heat-pressed under the conditions of pressure 〇 IMPa, temperature of 1 70 ° C, and 7 〇 second to obtain a multilayer laminate. A peeling test piece having the same structure as that of the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 45 N/1 5 mm. The peel strength between the wood and the adhesive layer exceeds the fracture strength of the wood itself. In addition, it is confirmed that the laminate is not peeled off at -40 ° C, and the low temperature characteristics are excellent. The laminate did not show peeling after 200 cycles of heat cycle test, and was a laminate having high strength. Example 84 <Production of Unsaturated Carboxylic Acid-Grafted Polyolefin>
將5000重量份的1,1,2-三氯乙烷與25 00重量份的 26%硫酸水溶液放進附有下口的10升燒瓶中激烈地攪拌 ,靜置後取出下層的有機層。接著、將被取出的有機層與 5 kg蒸餾水放進附有下口的10升燒瓶中激烈地攪拌,靜 置後取出下層的有機層之操作重複3次,去除1-丁醇及 1,2-環氧基丁烷。更藉由於取出的有機層中添加150重量 份的分子篩4A,用攪拌器攪拌而脫水,得到經純化的 1,1,2-三氯乙烷(以下,記爲純化TCE)。 於4升的玻璃製反應容器中裝入3000重量份的純化 TCE與200重量份的EVA、及5重量份的馬來酸酐,將 反應器昇溫至80°C ’然後藉由以80°C保持4小時均勻地 溶解EVA,此外在此期間,於反應器中以5升/分鐘的流 速導入氮氣,排除混入反應器的空氣’作爲接枝反應的觸 媒之使1.55重量份的BPO溶解於純化TCE 100重量份’ 將此溶液一倂添加至反應器後’在反應器的壓力保持在 1 MPa狀態下,進行3小時接枝反應。反應終了後、使壓 力回復至常壓,將反應器的溫度提高至70 爲止’添加作 爲安定劑之〇.〇6重量份的BHT。將此溶液注入至大量的 -134- 200925171 甲醇中’將生成物的馬來酸酐接枝EVA從溶劑分離出。 已知生成物係分析結果爲具有1.6重量%的不飽和羧 酸(馬來酸酐),凝膠爲0.012重量%。 <不飽和羧酸接枝聚烯烴薄膜的製造>5000 parts by weight of 1,1,2-trichloroethane and 260 parts by weight of a 26% aqueous sulfuric acid solution were placed in a 10-liter flask with a lower opening and vigorously stirred, and after standing, the lower organic layer was taken out. Next, the taken-out organic layer and 5 kg of distilled water were placed in a 10-liter flask with a lower mouth and vigorously stirred. After standing, the operation of taking out the lower organic layer was repeated three times to remove 1-butanol and 1,2. - Epoxybutane. Further, 150 parts by weight of molecular sieve 4A was added to the taken-out organic layer, and the mixture was stirred and dehydrated to obtain purified 1,1,2-trichloroethane (hereinafter referred to as purified TCE). A 4 liter glass reaction vessel was charged with 3000 parts by weight of purified TCE and 200 parts by weight of EVA, and 5 parts by weight of maleic anhydride, and the reactor was heated to 80 ° C ' and then maintained at 80 ° C. EVA was uniformly dissolved in 4 hours, and during this period, nitrogen was introduced into the reactor at a flow rate of 5 liters/min to exclude air mixed into the reactor. As a catalyst for the grafting reaction, 1.55 parts by weight of BPO was dissolved in the purification. TCE 100 parts by weight 'After adding this solution to the reactor', the grafting reaction was carried out for 3 hours while the pressure of the reactor was maintained at 1 MPa. After the completion of the reaction, the pressure was returned to normal pressure, and the temperature of the reactor was raised to 70. 5% by weight of BHT was added as a stabilizer. This solution was poured into a large amount of -134-200925171 methanol. The maleic anhydride grafted EVA of the product was separated from the solvent. The resulting product analysis was found to have 1.6% by weight of an unsaturated carboxylic acid (maleic anhydride) and a gel of 0.012% by weight. <Production of unsaturated carboxylic acid grafted polyolefin film>
使用復動式壓縮成形機WFA-50,將上述所得到的不 飽和羧酸接枝EVA,以加熱溫度1 50°C、壓力l〇MPa、加 熱時間1 0分鐘、冷卻溫度3 0 °C、壓力1 0 MP a、冷卻時間 5分鐘的條件進f了加壓成形,得到尺寸lOOmmxlOOmm、 厚度1 ΟΟμιη的薄膜,所得到的薄膜的外觀、性狀爲優良 ,看不到魚眼等之缺點。 <多層層合物的製造> 使所得到的尺寸lOOmmxlOOmm、厚度ΙΟΟμπι的薄膜 與以和紙補強裏面之厚度〇.3mm的黑檀薄片,以壓力 〇 O.IMPa、溫度180°C ' 1分鐘的條件進行加熱壓黏,得到 具有熱熔著性的黑檀薄片。將所得到的黑檀薄片重疊於未 進行表面處理尺寸lOOmmxlOOmm、厚度1mm的銘板,壓 力O.IMPa '溫度180°C、1分鐘的條件進行加熱壓黏,得 到多層層合物。所得到的層合物的各層係堅固地接著,雖 然加熱至40~80°C但未見到剝離,製成與此層合物同一構 成的剝離試驗片,以拉伸速度300mm/分鐘的條件進行T 型剝離試驗的結果,金屬層與接著層之間的剝離強度爲 45N/1 5mm之優異値,木材與接著層之間的剝離強度超過 -135- 200925171 木材自體的破裂強度,此外,確認此層合物以-40°C彎折 並未見到剝離,低溫特性亦優異,此外,本層合物經由 2 00次的熱循環試驗後亦未見到剝離,爲接著強度高的層 合物。 實施例8 5 使實施例 84所得到的尺寸 100mm X 100mm、厚度 0 ΙΟΟμιη的薄膜與以和紙補強裏面之厚度0.3mm的木瓜薄 片’以壓力O.IMPa、溫度180°C、1分鐘的條件進行加熱 壓黏’得到具有熱溶著性之木瓜薄片。將所得到的木瓜薄 片重疊於未進行表面處理之尺寸 lOOmmxlOOmm、厚度 1mm的鋁板,壓力O.lMPa、溫度180°C、1分鐘的條件進 行加熱壓黏,得到多層層合物。所得到的層合物的各層係 堅固地接著,雖然加熱至40〜80°C但未見到剝離,製成與 此層合物同一構成的剝離試驗片,以拉伸速度300mm/分 〇 鐘的條件進行τ型剝離試驗的結果,金屬層與接著層之間 的剝離強度爲50N/1 5mm之優異値,木材與接著層之間的 剝離強度超過木材自體的破裂強度,此外,確認此層合物 以-40°C彎折並未見到剝離,低溫特性亦優異,此外,本 層合物經由200次的熱循環試驗後亦未見到剝離,爲接著 強度高的層合物。 實施例8 6 於4升的玻璃製反應容器中裝入3 000重量份的純化 -136- 200925171 ΟUsing the double-action compression molding machine WFA-50, the unsaturated carboxylic acid obtained above was grafted with EVA at a heating temperature of 150 ° C, a pressure of 10 MPa, a heating time of 10 minutes, a cooling temperature of 30 ° C, The pressure of 10 0 MP a and the cooling time of 5 minutes were subjected to press molding to obtain a film having a size of 100 mm x 100 mm and a thickness of 1 μm, and the obtained film was excellent in appearance and properties, and the defects such as fish eyes were not observed. <Production of Multilayer Laminate> The obtained film having a size of 100 mm x 100 mm and a thickness of ΙΟΟμπι and a ebony sheet having a thickness of 〇.3 mm reinforced with paper and paper were subjected to a pressure of O.IMPa and a temperature of 180 ° C for 1 minute. The conditions were heat-pressed to obtain a blister sheet having heat fusion properties. The obtained ebony flakes were superposed on a nameplate having a surface treatment size of 100 mm x 100 mm and a thickness of 1 mm, and pressed at a pressure of O.IMPa 'temperature of 180 ° C for 1 minute to obtain a multilayer laminate. The layers of the obtained laminate were firmly adhered, and although peeling was not carried out at 40 to 80 ° C, peeling test pieces having the same constitution as the laminate were prepared at a tensile speed of 300 mm/min. As a result of the T-peel test, the peel strength between the metal layer and the adhesive layer was excellent at 45 N/15 mm, and the peel strength between the wood and the adhesive layer exceeded the fracture strength of the wood from -135 to 200925171, and It was confirmed that the laminate was not peeled off at -40 ° C, and the low-temperature characteristics were excellent. Further, the laminate did not show peeling after the thermal cycle test of 200 times, and was a layer having a high strength. Compound. Example 8 5 A film having a size of 100 mm X 100 mm and a thickness of 0 ΙΟΟμη obtained in Example 84 and a papaya sheet having a thickness of 0.3 mm in the same manner as the paper were subjected to a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute. Heat-pressed to obtain papaya flakes with heat solubility. The obtained papaya sheet was superposed on an aluminum plate having a size of 100 mm x 100 mm and a thickness of 1 mm which was not subjected to surface treatment, and was pressure-bonded under the conditions of a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute to obtain a multilayer laminate. The layers of the obtained laminate were firmly adhered to each other, and although peeling was not observed at 40 to 80 ° C, a peeling test piece having the same constitution as that of the laminate was prepared at a stretching speed of 300 mm/min. As a result of the τ-type peeling test, the peel strength between the metal layer and the adhesive layer was excellent at 50 N/15 mm, and the peel strength between the wood and the adhesive layer exceeded the crack strength of the wood itself. The laminate was not peeled off at -40 ° C, and was excellent in low-temperature characteristics. Further, the laminate did not show peeling after 200 cycles of heat cycle test, and was a laminate having high strength. Example 8 6 3 000 parts by weight of a 4 liter glass reaction vessel was charged -136-200925171 Ο
TCE與200重量份的L-LDPE、及6重量份的丙烯酸,將 反應器昇溫至80°C,然後藉由以80°C保持4小時均勻地 溶解L-LDPE,此外在此期間,於反應器中以5升/分鐘的 流速導入氮氣,排除混入反應器的空氣,作爲接枝反應的 觸媒之使1.4重量份的BPO溶解於純化TCE 100重量份 。將此溶液一倂添加至反應器後,在反應器的壓力保持在 1 MPa狀態下,進行3小時接枝反應。反應終了後、使壓 力回復至常壓,將反應器的溫度提高至70 °C爲止,添加作 爲安定劑之0.06重量份的BHT。將此溶液注入至大量的 甲醇中,將生成物的丙烯酸接枝L-LDPE從溶劑分離出。 已知生成物係分析結果爲具有1.8重量%的丙烯酸,凝膠 爲0.0 1 2重量%。 將所得到的丙烯酸接枝L-LDPE藉由與實施例84同 樣的手法薄膜化後,以壓力0.1 MPa、溫度180°C、1分鐘 的條件與鳥眼楓薄片進行加熱壓黏,而且,重疊於未進行 表面處理尺寸lOOmmxlOOmm、厚度lmm的銘板,以壓力 0.1 MPa、溫度180 °C、40秒的條件進行加熱壓黏,得到多 層層合物。 製成與此層合物同一構成的剝離試驗片,以拉伸速度 3 00mm/分鐘的條件進行T型剝離試驗的結果,金屬層與 接著層之間的剝離強度爲50N/1 5 mm之優異値,木材與接 著層之間的剝離強度超過木材自體的破裂強度,此外,確 認此層合物以-40°C彎折並未見到剝離,低溫特性亦優異 ,此外,本層合物經由2 0 0次的熱循環試驗後亦未見到剝 -137- 200925171 離,爲接著強度高的層合物。 實施例8 7TCE and 200 parts by weight of L-LDPE, and 6 parts by weight of acrylic acid, the reactor was heated to 80 ° C, and then L-LDPE was uniformly dissolved by maintaining at 80 ° C for 4 hours, and in addition, during the reaction Nitrogen gas was introduced at a flow rate of 5 liters/min to exclude air mixed into the reactor, and 1.4 parts by weight of BPO was dissolved as 100 parts by weight of purified TCE as a catalyst for the graft reaction. After the solution was added to the reactor at a time, the grafting reaction was carried out for 3 hours while maintaining the pressure of the reactor at 1 MPa. After the completion of the reaction, the pressure was returned to normal pressure, and the temperature of the reactor was raised to 70 ° C, and 0.06 part by weight of BHT as a stabilizer was added. This solution was poured into a large amount of methanol, and the resultant acrylic grafted L-LDPE was separated from the solvent. The resulting product analysis was found to have 1.8% by weight of acrylic acid and a gel of 0.012% by weight. The obtained acrylic grafted L-LDPE was thinned by the same method as in Example 84, and then heated and pressure-bonded with a bird's eye maple leaf under the conditions of a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute. The nameplate having a surface treatment size of 100 mm×100 mm and a thickness of 1 mm was heat-press-bonded under the conditions of a pressure of 0.1 MPa, a temperature of 180 ° C, and a temperature of 40 seconds to obtain a multilayer laminate. A peeling test piece having the same structure as that of the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 50 N/15 mm.値, the peel strength between the wood and the adhesive layer exceeds the crack strength of the wood itself, and further, it is confirmed that the laminate is not peeled off at -40 ° C, and the low-temperature property is also excellent, and further, the laminate After the thermal cycle test of 200 times, no peeling-137-200925171 was observed, which was followed by a high strength laminate. Example 8 7
G 於4升的玻璃製反應容器中裝入3 00 0重量份的純化 TCE與200重量份的L-LDPE、及5重量份的馬來酸酐, 將反應器昇溫至8 0 °C,然後藉由以8 0 °C保持4小時均勻 地溶解L-LDPE,此外在此期間,於反應器中以5升/分鐘 的流速導入氮氣,排除混入反應器的空氣,作爲接枝反應 的觸媒之使1.8重量份的BPO溶解於純化TCE 100重量 份,將此溶液一倂添加至反應器後,在反應器的壓力保持 在1 MPa狀態下,進行3小時接枝反應。反應終了後、使 壓力回復至常壓,將反應器的溫度提高至7 0 °C爲止,添加 作爲安定劑之0.06重量份的BHT。將此溶液注入至大量 的甲醇中,將生成物的馬來酸酐接枝L-LDPE從溶劑分離 出,已知生成物係分析結果爲具有1.4重量%的馬來酸酐 ’凝膠爲0.014重量%。 將所得到的馬來酸酐接枝L-LDPE藉由與實施例84 同樣的手法薄膜化後,與斑木樹薄片以壓力〇.1 MPa、溫 度150 °C、30秒的條件進行加熱壓黏,而且,與厚度1mm 的不鏽鋼板以壓力0.1 MPa、溫度180°C、60秒的條件進 行加熱壓黏,得到多層層合物。 製成與此層合物同一構成的剝離試驗片,以拉伸速度 300mm/分鐘的條件進行T型剝離試驗的結果,金屬層與 接著層之間的剝離強度爲45N/ 1 5mm之優異値’木材與接 -138- 200925171 著層之間的剝離強度超過木材自體的破裂強度’此外,確 認此層合物以-40°C彎折並未見到剝離,低溫特性亦優異 ,此外,本層合物經由2 0 0次的熱循環試驗後亦未見到剝 離,爲接著強度高的層合物。 實施例8 8 將實施例86所得到的丙烯酸接枝L-LDPE的薄膜, φ 與厚度〇.3mm的橡樹薄片以壓力0.15MPa、溫度160°C、 3 0秒的條件進行加熱壓黏,而且,與厚度1 mm的不鏽鋼 薄片以壓力O.IMPa、溫度170°C、70秒的條件進行加熱 壓黏,得到多層層合物。 製成與此層合物同一構成的剝離試驗片,以拉伸速度 3 00mm/分鐘的條件進行T型剝離試驗的結果,金屬層與 接著層之間的剝離強度爲44N/15 mm之優異値’木材與接 著層之間的剝離強度超過木材自體的破裂強度,此外,確 ξ) 認此層合物以-40°C彎折並未見到剝離,低溫特性亦優異 ,此外,本層合物經由200次的熱循環試驗後亦未見到剝 離,爲接著強度高的層合物。 比較例4 3 使用NAKATANI機械工業製的1 1 5mm φ、L/D = 50的 2軸擠壓機,將區段Cl、C2、C3設定於150、180、 200°C,將區段C4〜CIO、A、D設定於220°C,以旋轉數 llOrpm,從C6〜C7間的排氣口去除未反應的不飽和羧酸 -139- 200925171 進行接枝反應,亦即,將以 EVA100重量份、馬來酸酐 3.6重量份、DBPIB 2重量份的比率用亨雪莉混練機經均 均地混合的預摻合物供給至二軸擠壓機,進行接枝反應得 到經接枝馬來酸酐之EVA。所得到的EVA含有0.6重量% 的馬來酸酐,含有0.10重量%的凝膠。G was charged with 300 parts by weight of purified TCE and 200 parts by weight of L-LDPE, and 5 parts by weight of maleic anhydride in a 4 liter glass reaction vessel, and the reactor was heated to 80 ° C, and then borrowed. The L-LDPE was uniformly dissolved by maintaining at 80 ° C for 4 hours, and during this time, nitrogen gas was introduced into the reactor at a flow rate of 5 liter / minute to remove the air mixed into the reactor as a catalyst for the graft reaction. 1.8 parts by weight of BPO was dissolved in 100 parts by weight of purified TCE, and this solution was added to the reactor once, and the graft reaction was carried out for 3 hours while maintaining the pressure of the reactor at 1 MPa. After the completion of the reaction, the pressure was returned to normal pressure, the temperature of the reactor was raised to 70 ° C, and 0.06 part by weight of BHT as a stabilizer was added. This solution was poured into a large amount of methanol, and the product of maleic anhydride grafted L-LDPE was separated from the solvent, and it was found that the product analysis result was that the maleic anhydride 'gel having 1.4% by weight was 0.014% by weight. . The obtained maleic anhydride-grafted L-LDPE was thinned by the same method as in Example 84, and then heated and pressure-bonded with the porphyra tree flakes under the conditions of pressure 11 MPa, temperature 150 ° C, and 30 seconds. Further, a stainless steel sheet having a thickness of 1 mm was heated and pressure-bonded under the conditions of a pressure of 0.1 MPa, a temperature of 180 ° C, and a temperature of 60 seconds to obtain a multilayer laminate. A peeling test piece having the same structure as that of the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 45 N/15 mm. Wood and joint -138- 200925171 The peel strength between the layers exceeds the crack strength of the wood itself. In addition, it is confirmed that the laminate is not peeled at -40 ° C, and the low-temperature characteristics are also excellent. The laminate did not show peeling after the thermal cycle test of 200 times, and was a laminate having high strength. Example 8 8 The film of the acrylic acid grafted L-LDPE obtained in Example 86, φ and the thickness of 橡3 mm of the oak sheet were heated and pressure-bonded under the conditions of a pressure of 0.15 MPa, a temperature of 160 ° C, and 30 seconds, and The stainless steel sheet having a thickness of 1 mm was heat-press-bonded under the conditions of a pressure of 0.1 MPa, a temperature of 170 ° C, and 70 seconds to obtain a multilayer laminate. A peeling test piece having the same constitution as that of the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 44 N/15 mm. 'The peel strength between the wood and the adhesive layer exceeds the crack strength of the wood itself. In addition, it is confirmed that the laminate is not peeled off at -40 ° C, and the low temperature characteristics are also excellent. The compound did not show peeling after 200 cycles of heat cycle test, and was a laminate having high strength. Comparative Example 4 3 Sections Cl, C2, and C3 were set at 150, 180, and 200 ° C using a 1 1 5 mm φ, L/D = 50 2-axis extruder manufactured by NAKATANI Machinery Co., Ltd., and the section C4 was CIO, A, and D are set at 220 ° C, and the unreacted unsaturated carboxylic acid -139 - 200925171 is removed from the exhaust port between C6 and C7 at a number of revolutions of 10 rpm to carry out a graft reaction, that is, 100 parts by weight of EVA. The ratio of 3.6 parts by weight of maleic anhydride and 2 parts by weight of DBPIB is supplied to the two-axis extruder by a Hensley blender through a uniformly mixed pre-blend, and grafting reaction is carried out to obtain a grafted maleic anhydride. EVA. The obtained EVA contained 0.6% by weight of maleic anhydride and contained 0.10% by weight of a gel.
藉由使用復動式壓縮成形機WFA-50,將所得到的馬 來酸酐接枝EVA,以加熱溫度160°C、壓力lOMPa、加熱 時間1〇分鐘、冷卻溫度30°C、壓力lOMPa、冷卻時間5 分鐘的條件進行加壓成形,得到厚度1 1 〇μιη的薄膜。 將所得到的經接枝馬來酸酐之EVA藉由與實施例79 同樣的手法薄膜化後,與黑檀薄片以壓力0.1 MPa、溫度 1 50 °C、30秒的條件進行加熱壓黏,而且,重疊於厚度 1mm的鋁板,以壓力0.1 MPa、溫度180°C、1分鐘的條件 進行加熱壓黏,得到多層層合物。 製成與此層合物同一構成的剝離試驗片,以拉伸速度 3 00mm/分鐘的條件進行T型剝離試驗的結果,金屬層與 接著層之間的剝離強度爲50N/15mm之優異値’木材與接 著層之間的剝離強度超過木材自體的破裂強度’惟’使此 層合物以-4〇°C彎折的結果,見到一部分剝離’此外’本 層合物經由50次的熱循環試驗,鋁板一部分剝離’與實 施例比較下接著性明顯地較差。 比較例44 藉由與比較例4 3同樣的手法得到經接枝馬來酸酐之 -140- 200925171 L-LDPE,亦即,將以L-LDPE100重量份、馬來酸酐4.0The obtained maleic anhydride was grafted with EVA by using a double-action compression molding machine WFA-50 at a heating temperature of 160 ° C, a pressure of 10 MPa, a heating time of 1 minute, a cooling temperature of 30 ° C, a pressure of 10 MPa, and cooling. Press forming was carried out under the conditions of a time of 5 minutes to obtain a film having a thickness of 1 1 〇μηη. The obtained EVA of the grafted maleic anhydride was thinned by the same method as in Example 79, and then heat-pressed with the ebony flakes under the conditions of a pressure of 0.1 MPa, a temperature of 1,50 ° C, and 30 seconds, and The aluminum plate having a thickness of 1 mm was superposed on the aluminum plate having a thickness of 1 mm, and heated and pressure-bonded under the conditions of a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute to obtain a multilayer laminate. A peeling test piece having the same structure as that of the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was excellent at 50 N/15 mm. The peel strength between the wood and the adhesive layer exceeds the fracture strength of the wood itself. 'When the laminate is bent at -4 ° C, a part of the peeling 'in addition' of the laminate is seen through 50 times. The thermal cycle test, a part of the peeling of the aluminum plate was significantly inferior to the example. Comparative Example 44 -140-200925171 L-LDPE grafted with maleic anhydride was obtained by the same procedure as in Comparative Example 43, that is, 100 parts by weight of L-LDPE, maleic anhydride 4.0.
重量份、DBPIB2.2重量份的比率用亨雪莉混練機經均均 地混合的預摻合物供給至二軸擠壓機,將區段C1、C2、 C3設定於150、180、200°C ’將區段C4〜CIO、A、D設定 於220°C,以旋轉數llOrpm,一邊從C6〜C7間的排氣口 去除未反應的馬來酸酐一邊進行接枝反應,所得到的經接 枝馬來酸酐之L-LDPE含有0.4重量%的馬來酸酐,含有 0.1 3重量%的凝膠。 藉由使用復動式壓縮成形機WFA-50,將所得到的馬 來酸酐接枝L-LDPE以加熱溫度170°C、壓力lOMPa、加 熱時間10分鐘、冷卻溫度3(TC、壓力lOMPa、冷卻時間 5分鐘的條件進行加壓成形,得到厚度1 〇〇μηι的薄膜。 將所得到的經接枝馬來酸酐之L-LDPE,藉由與比較 例43同樣的手法薄膜化後,與鳥眼楓薄片以壓力0.1 MPa 、溫度15(TC、30秒的條件進行加熱壓黏,而且,重疊於 厚度1mm的鋁板,壓力O.IMPa、溫度180°C、1分鐘的條 件進行加熱壓黏,得到多層層合物。 製成與此層合物同一構成的剝離試驗片,以拉伸速度 3 00mm/分鐘的條件進行T型剝離試驗的結果,金屬層與 接著層之間的剝離強度爲43N/15mm之優異値,木材與接 著層之間的剝離強度超過木材自體的破裂強度,惟,使此 層合物以-4(TC彎折的結果,見到一部分剝離,本層合物 經由1 00次的熱循環試驗,鋁板一部分剝離,與實施例比 較下接著性明顯地較差。 -141 - 200925171 實施例8 9 <不飽和羧酸接枝聚烯烴的製造> 將5000重量份的1,1,2 -三氯乙烷與2500重量份的 26%硫酸水溶液放進附有下口的10升燒瓶中激烈地攪拌 ,靜置後取出下層的有機層。接著、將被取出的有機層與 5 kg蒸餾水放進附有下口的10升燒瓶中激烈地攪拌,靜 0 置後取出下層的有機層之操作重複3次,去除1-丁醇及 1,2-環氧基丁烷(藉由氣相層析裝置經確認)。更藉由於 取出的有機層中添加150重量份的分子篩4A、用攪拌器 攪拌而脫水,得到經純化的1 ,1,2-三氯乙烷(以下,記爲 純化T C E )。 於4升的玻璃製反應容器中裝入2480重量份的純化 TCE與200重量份的EVA、及4.1重量份的馬來酸酐,將 反應器昇溫至80°C,然後藉由以80°C保持4小時均勻地 Q 溶解EVA,此外在此期間,於反應器中以5升/分鐘的流 速導入氮氣,排除混入反應器的空氣,作爲接枝反應的觸 媒之使1.5重量份的BPO溶解於純化TCE 100重量份中 。將此溶液連續地持續添加至反應器,在反應器的壓力保 持在1 MPa狀態下,進行3小時接枝反應。反應終了後、 使反應器的壓力回復常壓後,將反應器的溫度降低至7CTC ,添加作爲安定劑之〇.〇6重量份的BHT後’將此溶液送 進加熱至160°C之鼓式乾燥機中,將生成物的改性EVA從 溶劑分離出。 -142- 200925171 已知生成物係分析結果爲具有5重量%的不飽和狻 酸(馬來酸酐),凝膠爲〇重量%’ Υϊ爲2及色相優良。 <不飽和羧酸接枝聚烯烴薄膜的製造> 使用復動式壓縮成形機WFA-50’將上述所得到的不 飽和羧酸接枝EVA,以加熱溫度150°C、壓力l〇MPa、加 熱時間10分鐘、冷卻溫度30°C、壓力lOMPa、冷卻時間 0 5分鐘的條件進行加壓成形,得到尺寸 i〇〇mmxl〇〇mm、 厚度13 Ομπι的薄膜(薄膜1),所得到的薄膜的外觀、性 狀爲優良,看不到魚眼等之缺點。 <銅箔的層合> 將所得到的尺寸1 OOmmx 1 00mm、厚度130μιη的薄膜 (薄膜 1)、及未進行表面處理尺寸 lOOmmxlOOmm、厚 度40μιη的銅箔(箔1),以壓力O.IMpa、溫度180。(:、 〇 #胃1分鐘的條件層合,得到聚烯烴與銅箔的層合物(以 下’稱爲銅箔層合聚烯烴薄膜)。 無塵室内將依所得到的銅箔層合聚烯烴薄膜、電路圖 使用聚酶亞胺膠帶固定於圓形石英玻璃製基板上 ’接著1 ’將經固定銅箔層合聚烯烴薄膜的上述的石英玻璃 製基板裝置於旋轉塗佈機,使光阻液61111流延於銅箔層合 聚稀煙薄膜上’使旋轉塗佈機以旋轉數3 OOrpm旋轉10秒 ’然後’使旋轉數花費5秒提高至15〇〇rpm爲止,使其以 此旋轉數旋轉20秒,得到光阻液一樣經塗佈的銅箔層合 -143- 200925171 聚烯烴薄膜。 將此銅箔層合聚烯烴薄膜固定於圓形石英玻璃製基板 的狀態下,以波長3 65nm的UV光進行15秒曝光,然後 ,在使上述的玻璃製基板旋轉的狀態下流延顯影液,進行 顯影,接下來水洗,一邊吹氮氣一邊使其乾燥。The ratio of parts by weight and DBPIB of 2.2 parts by weight is supplied to the two-axis extruder by the Hensley blender through the uniformly mixed pre-blend, and the sections C1, C2, C3 are set at 150, 180, 200°. C' set the sections C4 to CIO, A, and D at 220 ° C, and carry out a graft reaction by removing unreacted maleic anhydride from the exhaust port between C6 and C7 by a number of revolutions of 10 rpm. The L-LDPE grafted with maleic anhydride contained 0.4% by weight of maleic anhydride and contained 0.13% by weight of a gel. The obtained maleic anhydride was grafted with L-LDPE by a double-acting compression molding machine WFA-50 at a heating temperature of 170 ° C, a pressure of 10 MPa, a heating time of 10 minutes, a cooling temperature of 3 (TC, a pressure of 10 MPa, and cooling). The film was formed by press molding under the conditions of a time of 5 minutes to obtain a film having a thickness of 1 μm. The obtained grafted maleic anhydride L-LDPE was thinned by the same method as in Comparative Example 43 and then with the bird's eye. The maple flakes were heated and pressure-bonded under the conditions of a pressure of 0.1 MPa and a temperature of 15 (TC, 30 seconds), and were superposed on an aluminum plate having a thickness of 1 mm, and subjected to heating and pressure bonding under the conditions of a pressure of 0.1 MPa and a temperature of 180 ° C for 1 minute. A multilayer test piece was prepared. The peeling test piece having the same constitution as the laminate was subjected to a T-peel test at a tensile speed of 300 mm/min, and the peel strength between the metal layer and the adhesive layer was 43 N/ The excellent 値 of 15mm, the peeling strength between the wood and the adhesive layer exceeds the breaking strength of the wood itself, but the laminate is made to a part of the peeling of the laminate by -4 (TC bending, the laminate is passed through 1 00 thermal cycle test, part of the aluminum strip The adhesion was significantly inferior to the examples. -141 - 200925171 Example 8 9 <Production of Unsaturated Carboxylic Acid-Grafted Polyolefin> 5000 parts by weight of 1,1,2-trichloroethane and 2500 A part by weight of a 26% aqueous sulfuric acid solution was placed in a 10-liter flask with a lower mouth and vigorously stirred, and after standing, the lower organic layer was taken out. Then, the removed organic layer and 5 kg of distilled water were placed in the lower mouth. The 10-liter flask was vigorously stirred, and the operation of taking out the lower organic layer was repeated three times to remove 1-butanol and 1,2-epoxybutane (confirmed by a gas chromatography apparatus). Further, 150 parts by weight of the molecular sieve 4A was added to the taken-out organic layer, and the mixture was dehydrated by stirring with a stirrer to obtain purified 1,1,2-trichloroethane (hereinafter, referred to as purified TCE). The glass reaction vessel was charged with 2480 parts by weight of purified TCE and 200 parts by weight of EVA, and 4.1 parts by weight of maleic anhydride, and the reactor was heated to 80 ° C, and then uniformly maintained at 80 ° C for 4 hours. Q dissolves EVA, and during this time, nitrogen is introduced into the reactor at a flow rate of 5 liters/min. The air mixed into the reactor was excluded, and 1.5 parts by weight of BPO was dissolved in 100 parts by weight of purified TCE as a catalyst for the graft reaction. This solution was continuously continuously added to the reactor, and the pressure at the reactor was maintained at 1 MPa. In the state, the grafting reaction was carried out for 3 hours. After the reaction was completed, the pressure of the reactor was returned to normal pressure, the temperature of the reactor was lowered to 7 CTC, and 6 parts by weight of BHT was added as a stabilizer. The solution was fed into a drum dryer heated to 160 ° C, and the modified EVA of the product was separated from the solvent. From -142 to 200925171, it was found that the result of the analysis of the product was 5% by weight of unsaturated citric acid (maleic anhydride), and the gel had a weight % of ’ of 2 and a good hue. <Production of Unsaturated Carboxylic Acid-Grafted Polyolefin Film> The above-obtained unsaturated carboxylic acid was grafted with EVA using a double-acting compression molding machine WFA-50' at a heating temperature of 150 ° C and a pressure of 10 MPa. The film was heated under the conditions of a heating time of 10 minutes, a cooling temperature of 30° C., a pressure of 10 MPa, and a cooling time of 0 5 minutes to obtain a film (film 1) having a size of i〇〇mm×l〇〇mm and a thickness of 13 μm. The appearance and properties of the film are excellent, and the disadvantages such as fish eyes are not observed. <Lamination of Copper Foil> A film (film 1) having a size of 1 OO mm x 100 mm and a thickness of 130 μm and a copper foil (foil 1) having a surface treatment size of 100 mm x 100 mm and a thickness of 40 μm were subjected to a pressure of O. IMpa, temperature 180. (:, 〇# stomach laminated for 1 minute, to obtain a laminate of polyolefin and copper foil (hereinafter referred to as "copper foil laminated polyolefin film"). The clean room will be laminated according to the obtained copper foil. The olefin film and the circuit diagram were fixed on a circular quartz glass substrate by using a polyimide tape. Then, the above-mentioned quartz glass substrate having the fixed copper foil laminated polyolefin film was placed on a spin coater to make a photoresist. The liquid 61111 is cast on the copper foil laminated poly-smoke film, 'rotating the spin coater at a rotation of 3 00 rpm for 10 seconds' and then increasing the number of rotations to 15 rpm for 5 seconds, thereby rotating the liquid The number of rotations was 20 seconds to obtain a photoresist-coated copper foil-laminated-143-200925171 polyolefin film. The copper foil-laminated polyolefin film was fixed to a circular quartz glass substrate at a wavelength of 3 The phosphor light of 65 nm is exposed for 15 seconds, and then the developer is cast in a state where the above-mentioned glass substrate is rotated, and development is carried out, followed by washing with water, and drying while blowing nitrogen gas.
將所得到的顯影完成的銅箱層合聚稀烴薄膜於室溫以 蝕刻液處理3 0分鐘,水洗、以丙酮進行光阻層的剝離, 得到經形成電路圖型之可撓配線薄膜。 確認本配線薄膜經由2 0 0次的熱循環試驗,銅箔未剝 離、耐寒性及耐熱衝撃性優異,此外,將所得到的本配線 薄膜在使不飽和羧酸接枝聚烯烴側成爲接著面下以1 00 °C 、壓力0.1 MPa進行加熱壓黏於聚碳酸酯薄膜上而得到層 合物。確認此層合物經由200次的熱循環試驗,配線薄膜 未從聚碳酸酯剝離,對於熱衝撃爲堅強的層合物,此外, 測量所得到的層合物的剝離強度的結果、與銅的接著強度 顯示出60N/mm之極高的値,而且,進行MIT試驗的結果 ,本層合物經由150次的彎折試驗,銅箔未剝離、及薄膜 亦末破裂,耐彎折性與柔軟性優異。 實施例90 藉由與實施例89同樣的手法製造經接枝馬來酸酐之 LDPE,經薄膜化後,藉由與實施例89同一條件進行層合 ,依藉由加熱壓黏的銅箔的層合 '光阻塗佈、曝光、蝕刻 、光阻剝離的順序,於LDPE上形成銅的電路圖型’得到 -144- 200925171 可撓配線薄膜。 確認本配線薄膜經由2 0 0次 離,耐寒性及耐熱衝撃性優異, 線薄膜的剝離強度的結果, 5 5N/mm之極高値。而且,進行 薄膜經由1 5 0次的彎折試驗,銅 裂,耐彎折性與柔軟性優異。 〇 實施例9 1 藉由與實施例89同樣的手 LDPE ’經薄膜化後,藉由與實苗 膜的雙面上層合銅箔,得到由 LDPE/銅箔所成的3層的層合物 合物的片面,藉由與實施例89 面上藉由旋轉塗佈機塗佈光阻液 〇 在曝光面經保護下,另一側的面 後’進行顯影、水洗,然後,進 經接枝馬來酸酐之LDPE的雙面 可撓配線薄膜。 確認出本配線薄膜經由2 0 0 剝離、耐寒性及耐熱衝撃性優異 配線薄膜的剝離強度的結果、 56N/mm之極高値,而且,進行 薄膜經由1 5 0次的彎折試驗,銅 :的熱循環試驗,銅箔未剝 此外,測量所得到的本配 與銅的接著強度顯示出 MIT試驗的結果,本配線 丨箔未剝離、及薄膜亦末破 法製造經接枝馬來酸酐之 i例8 9同一條件,於此薄 銅箔/經接枝馬來酸酐之 ,首先,保護所得到的層 同樣的手法於層合物的單 、包覆、經曝光,接著, 上塗佈光阻、經曝光。然 行蝕刻處理、水洗,得到 上經形成銅的電路圖型之 次的熱循環試驗,銅箔未 。此外,測量所得到的本 與銅的接著強度顯示出 MIT試驗的結果,本配線 箔未剝離、及薄膜亦末破 -145- 200925171 裂,耐彎折性與柔軟性優異。 實施例92The obtained copper box-laminated dense hydrocarbon film obtained by development was treated with an etching solution for 30 minutes at room temperature, washed with water, and the photoresist layer was peeled off with acetone to obtain a flexible wiring film having a circuit pattern. It was confirmed that the wiring film was subjected to a thermal cycle test of 200 times, and the copper foil was not peeled off, and the cold resistance and the heat-resistant punching property were excellent. Further, the obtained wiring film was bonded to the polyolefin side of the unsaturated carboxylic acid. The laminate was heated and pressure-bonded to a polycarbonate film at a pressure of 0.1 MPa at 100 ° C to obtain a laminate. It was confirmed that the laminate was subjected to a thermal cycle test of 200 times, the wiring film was not peeled off from the polycarbonate, a strong laminate was obtained for hot stamping, and the peel strength of the obtained laminate was measured, and copper was measured. Then, the strength showed an extremely high enthalpy of 60 N/mm, and as a result of the MIT test, the laminate was subjected to a bending test of 150 times, the copper foil was not peeled off, and the film was broken at the same time, and the bending resistance and flexibility were obtained. Excellent sex. Example 90 LDPE grafted with maleic anhydride was produced by the same procedure as in Example 89, and after lamination, lamination was carried out under the same conditions as in Example 89, and a layer of a copper foil which was pressure-bonded by heating was applied. In the order of photoresist coating, exposure, etching, and photoresist peeling, a circuit pattern of copper was formed on the LDPE to obtain a flexible wiring film of -144 to 200925171. It was confirmed that the wiring film was excellent in cold resistance and heat resistance, and the peeling strength of the wire film was extremely high at 55 N/mm. Further, the film was subjected to a bending test of 150 times, and the copper crack was excellent in bending resistance and flexibility. Example 9 1 After the film was formed by the same hand LDPE as in Example 89, a three-layer laminate of LDPE/copper foil was obtained by laminating a copper foil on both sides of the seed film. The one side of the composition was coated with a photoresist liquid by a spin coater on the surface of Example 89, and the surface of the other side was subjected to development, water washing, and then grafted. A double-sided flexible wiring film of maleic anhydride LDPE. It was confirmed that the wiring film was excellent in the peeling strength of the wiring film by the peeling, the cold resistance and the heat-resistant squeezing property, and the extremely high enthalpy of 56 N/mm, and the film was subjected to a bending test of 150 times, copper: In the thermal cycle test, the copper foil was not peeled off. The measured bond strength of the copper and the copper showed the results of the MIT test. The wire 丨 foil was not peeled off, and the film was finally broken to produce grafted maleic anhydride. Example 8 9 The same conditions, the thin copper foil / grafted maleic anhydride, first, the resulting layer is protected by the same method of lamination, coating, exposure, and then coated with photoresist After exposure. Then, etching treatment and water washing were carried out to obtain a thermal cycle test of the circuit pattern on which copper was formed, and the copper foil was not. Further, the measured adhesion strength between the copper and the copper showed the result of the MIT test, and the wiring foil was not peeled off, and the film was also broken at -145 to 200925171, and the bending resistance and flexibility were excellent. Example 92
除了將實施例91與將不飽和羧酸由馬來酸酐變更爲 丙烯酸以外,藉由與實施例91同樣的手法製造經接枝丙 烯酸之LDPE,經薄膜化後,藉由與實施例89同一條件, 於此薄膜的雙面上層合銅箔,得到由銅箔/經接枝馬來酸 酐之LDPE/銅箔所成的3層的層合物,首先,保護所得到 的層合物的片面,藉由與實施例89同樣的手法於層合物 的單面上藉由旋轉塗佈機塗佈光阻液,包覆、曝光,接著 、在曝光面經保護下,另一側的面上塗佈光阻、經曝光。 然後,進行顯影、水洗,然後,進行蝕刻處理、水洗,得 到經接枝馬來酸酐之LDPE的雙面上經形成銅的電路圖型 之可撓配線薄膜。 確認本配線薄膜經由200次的熱循環試驗,銅箔未剝 離、耐寒性及耐熱衝撃性優異。此外,測量所得到的本配 線薄膜的剝離強度的結果、與銅的接著強度顯示出 5 4N/mm之極高値,而且,進行MIT試驗的結果,本配線 薄膜經由1 50次的彎折試驗,銅箔未剝離、及薄膜亦末破 裂,耐彎折性與柔軟性優異。 實施例93 使用NAKATANI機械工業製的115mm0、L/D = 50的 2軸擠壓機,將區段Cl、C2、C3設定於150、180、 -146- 200925171 2 00°C,將區段C4〜CIO、A、D設定於220°C,以旋轉數 1 lOrpm,從C6〜C7間的排氣口去除未反應的不飽和羧酸 進行接枝反應,亦即,將以 EVA100重量份、馬來酸酐 4.1重量份、DBPIB 2重量份的比率用亨雪莉混練機經均 均地混合的預摻合物供給至二軸擠壓機,進行接枝反應得 到經接枝馬來酸酐之EVA。所得到的EVA含有0.5重量% 的馬來酸酐,含有〇 . 1 3重量%的凝膠。The grafted acrylic acid LDPE was produced by the same method as in Example 91 except that Example 91 and the unsaturated carboxylic acid were changed from maleic anhydride to acrylic acid, and the same conditions as in Example 89 were carried out after thinning. The copper foil was laminated on both sides of the film to obtain a three-layer laminate of copper foil/grafted maleic anhydride LDPE/copper foil. First, the one side of the obtained laminate was protected. The photoresist was coated on one side of the laminate by a spin coater in the same manner as in Example 89, coated, exposed, and then coated on the exposed side, and coated on the other side. Light resistance, exposed. Then, development and washing with water were carried out, followed by etching treatment and water washing to obtain a flexible wiring film of a circuit pattern in which copper was formed on both sides of LDPE grafted with maleic anhydride. It was confirmed that the wiring film was subjected to a thermal cycle test for 200 times, and the copper foil was not peeled off, and was excellent in cold resistance and heat resistance. Further, as a result of measuring the peel strength of the obtained wiring film, the adhesion strength to copper showed an extremely high enthalpy of 5 4 N/mm, and as a result of the MIT test, the wiring film was subjected to a bending test of 150 times. The copper foil is not peeled off, and the film is also broken at the end, and is excellent in bending resistance and flexibility. Example 93 Using a 115 mm 0, L/D = 50 2-axis extruder manufactured by NAKATANI Machinery Co., Ltd., the sections C1, C2, and C3 were set at 150, 180, -146 - 200925171 2 00 ° C, and the section C4 was used. ~CIO, A, D are set at 220 ° C, and the unreacted unsaturated carboxylic acid is removed from the exhaust port between C6 and C7 at a rotation number of 1 lO rpm for grafting reaction, that is, 100 parts by weight of EVA, horse The ratio of 4.1 parts by weight of the anhydride to 2 parts by weight of DBPIB was supplied to the two-axis extruder by a Henkelly kneader through a uniformly mixed preblend, and grafting reaction was carried out to obtain EVA grafted with maleic anhydride. The obtained EVA contained 0.5% by weight of maleic anhydride and contained 0.13 % by weight of a gel.
使用復動式壓縮成形機WFA-50,使所得到的馬來酸 酐接枝EVA,以加熱溫度150°C、壓力lOMPa、加熱時間 1〇分鐘、冷卻溫度30°C、壓力lOMPa、冷卻時間5分鐘 的條件進行加壓成形,得到厚度1 〇〇μιη的薄膜。 於所得到的薄膜上藉由與實施例89同樣的手法,藉 由加熱壓黏層合銅箔而得到由銅箔/馬來酸酐接枝聚烯烴 所成的2層的層合物後,藉由微影術形成電路,得到可撓 配線薄膜。 本配線薄膜經由1 5 0次的熱循環試驗,銅箔未剝離, 雖然經由200次的試驗則稍微見到銅箔的剝離,但顯示出 實用上無問題的水準的耐寒性及耐熱衝撃性。此外,測量 所得到的本配線薄膜的剝離強度的結果、與銅的接著強度 顯示出57N/mm之極高値,而且,進行ΜΙΤ試驗的結果, 本配線薄膜經由1 50次的彎折試驗,銅箔未剝離、及薄膜 亦末破裂,耐彎折性與柔軟性優異。 比較例4 5 -147- 200925171 使聚-(苯乙烯-丁二烯-苯乙烯)嵌段共聚物溶解於 二氯甲烷,調製聚合物濃度15重量%的溶液,將此溶液 塗佈於聚醯亞胺薄膜使其形成聚_(苯乙烯-丁二烯-苯乙 烯)嵌段共聚物爲40μιη的厚度膜,將溶劑於室溫放置1 天1夜蒸發去除後’以常壓4 0°C使其乾燥4小時,更於室 溫減壓1天1夜下乾燥,然後,一邊避免銅箔與氣泡的混 入一邊壓層’從此附有銅箔之聚醯亞胺薄膜的薄膜側艾利 0 庫得羅點(音譯)型電子線加速裝置(熱能•科學公司製 ),以加速電壓168kv、照射量lOMrad的條件照射電子 線’經交聯處理。以下,藉由與實施例89同樣的手法在 附有銅箔之聚醯亞胺薄膜上藉由微影術形成電路圖型,得 到配線薄膜,與實施例比較下銅箔與聚醯亞胺的層壓需要 大量的時間與步驟數,所得到的配線薄膜經由1 〇 〇次的熱 循環試驗’銅箔一部分剝離,與實施例所得到的配線薄膜 比較下耐寒性及耐熱衝撃性差此外,本配線薄膜進行T型 Q 剝離試驗的結果,於剝離試驗中銅與接著層之間界面剝離 ,其剝離時的強度爲5N/15mm之低的値,而且,進行 MIT試驗的結果,本配線薄膜經由15〇次的彎折試驗,雖 然未見到聚醯亞胺層的破裂,銅箔剝離、耐彎折性差。 比較例46 將對苯二胺(杜邦公司製)8.0莫耳及4,4,-二胺基苯 基醚(和歌山精化公司製)2.0莫耳溶解於N -甲基-2-吡 咯烷酮(BASF日本製)24kg中後,將系統冷卻至1〇它, -148-Using the double-action compression molding machine WFA-50, the obtained maleic anhydride was grafted with EVA at a heating temperature of 150 ° C, a pressure of 10 MPa, a heating time of 1 〇 minutes, a cooling temperature of 30 ° C, a pressure of 10 MPa, and a cooling time of 5 The film was formed by press molding under the conditions of a minute to obtain a film having a thickness of 1 μm. A two-layer laminate of a copper foil/maleic anhydride grafted polyolefin was obtained by heating a pressure-bonded copper foil by the same method as in Example 89 on the obtained film. A circuit is formed by lithography to obtain a flexible wiring film. This wiring film was subjected to a heat cycle test of 150 times, and the copper foil was not peeled off. Although the peeling of the copper foil was slightly observed after 200 tests, the cold resistance and the heat-resistant punching property which were practically problem-free were exhibited. Further, as a result of measuring the peel strength of the obtained wiring film, the adhesion strength with copper showed an extremely high enthalpy of 57 N/mm, and as a result of the enthalpy test, the wiring film was subjected to a bending test of 150 times, copper. The foil is not peeled off, and the film is also broken at the end, and is excellent in bending resistance and flexibility. Comparative Example 4 5 - 147 - 200925171 The poly-(styrene-butadiene-styrene) block copolymer was dissolved in dichloromethane to prepare a solution having a polymer concentration of 15% by weight, and the solution was applied to the polyfluorene. The imine film is formed into a film of poly-(styrene-butadiene-styrene) block copolymer having a thickness of 40 μm, and the solvent is allowed to stand at room temperature for one day and one night to evaporate and then removed at a normal pressure of 40 ° C. It was dried for 4 hours, and dried at room temperature under reduced pressure for 1 day and 1 night. Then, while avoiding the incorporation of the copper foil and the bubbles, the layer was pressed. 'The film side of the polyimide film with the copper foil attached thereto. A Cudrow-type electron-line accelerating device (manufactured by Thermal Energy Scientific Co., Ltd.) irradiates the electron beam 'cross-linking treatment under conditions of an acceleration voltage of 168 kV and an irradiation amount of 1 OMrad. Hereinafter, a wiring pattern was obtained by lithography on a copper foil-attached polyimide film by the same method as in Example 89, and a copper foil and a polyimide layer were compared with the examples. The pressure required a large amount of time and the number of steps, and the obtained wiring film was partially peeled off by the thermal cycle test of one turn, and the cold resistance and the heat-resistant punching property were inferior to those of the wiring film obtained in the example. As a result of the T-type Q peeling test, the interface between the copper and the adhesive layer was peeled off in the peeling test, and the strength at the time of peeling was a low enthalpy of 5 N/15 mm, and as a result of the MIT test, the wiring film was passed through 15 〇. In the secondary bending test, although the crack of the polyimide layer was not observed, the copper foil was peeled off and the bending resistance was poor. Comparative Example 46 8.0 mol of p-phenylenediamine (manufactured by DuPont) and 2.0 mol of 4,4,-diaminophenyl ether (manufactured by Wakayama Seika Co., Ltd.) were dissolved in N-methyl-2-pyrrolidone (BASF). Made in Japan) After 24kg, cool the system to 1〇, -148-
200925171 慢慢地加入3,3’,4,4,-聯苯四羧酸酐(宇部興產公司 9 ·9莫耳而使其反應,以25。(:得到顯示出2.6萬厘泊 醯亞胺的前驅溶液。 將所得到的前驅溶液以硬化後的厚度成爲2 5 μιη 式塗佈於厚度40μιη、尺寸爲5cmx5cm的銅范上,使 風式乾燥爐以1 2 0 °C乾燥1 〇分鐘,將所得到的經塗佈 亞胺前驅的前述基板,在真空度爲ltorr的狀態下, 内用24小時昇溫至3 5 0°C,然後,用18小時自然冷 所得到的在附有銅箔之聚醯亞胺薄膜上藉由微影術形 路圖型’得到配線薄膜,與實施例比較下銅箔與聚醯 的層壓需要大量的時間與步驟數,所得到的配線薄膜 2〇〇次的熱循環試驗,雖然未見到銅箔的剝離,但本 薄膜進行T型剝離試驗的結果,於剝離試驗中銅與接 之間界面剝離,其剝離時的強度爲9N/1 5mm,相對 施例所得到的配線薄膜而言較差,而且,進行MIT 的結果,本配線薄膜經由150次的彎折試驗,雖然未 聚醯亞胺層的破裂,銅箔剝離、接著層發生裂縫、耐 性差。 比較例4 7 將11.6g的環氧樹脂A、3.9g的環氧樹脂B、7g 氧樹脂硬化劑、〇.lg的苯基咪唑溶解於THF80ml調 硬化性樹脂溶液。將所得到的熱硬化性樹脂溶液以硬 的厚度成爲20μιη的方式下用刮刀塗佈於厚度40μιη 製) 之聚 的方 用熱 聚醯 將爐 卻。 成電 亞胺 經由 配線 著層 於實 試驗 見到 彎折 的環 製熱 化後 、尺 -149- 200925171 寸爲5Cmx5Cm的聚醯亞胺薄膜上,以5(TC加熱20分鐘乾 燥0200925171 Slowly added 3,3',4,4,-biphenyltetracarboxylic anhydride (Ube Hiroshi Co., Ltd. 9 · 9 moles and reacted it to 25. (: It was shown to show 26,000 centipoise quinone imine The precursor solution was applied to a copper mold having a thickness of 40 μm and a size of 5 cm×5 cm in a thickness of 25 μm, and the air drying oven was dried at 120 ° C for 1 〇 minutes. The obtained substrate coated with the imine precursor was heated to 350 ° C in a state where the degree of vacuum was ltorr, and then naturally cooled by 18 hours to obtain a copper foil. On the polyimide film, the wiring film was obtained by the lithography pattern, and the lamination of the copper foil and the polysilicon required a large amount of time and steps compared with the example, and the obtained wiring film 2〇〇 In the secondary heat cycle test, although the peeling of the copper foil was not observed, the film was subjected to the T-peel test, and the interface between the copper and the joint was peeled off in the peeling test, and the strength at the time of peeling was 9 N/1 5 mm, The wiring film obtained by the example is inferior, and the result of MIT is The wiring film was subjected to a bending test of 150 times, and although the polyimide film was not broken, the copper foil was peeled off, cracks occurred in the adhesive layer, and the resistance was poor. Comparative Example 4 7 11.6 g of epoxy resin A, 3.9 g of epoxy Resin B, 7 g of an oxygen resin curing agent, and phenyl. phenyl imidazole were dissolved in THF (80 ml) to adjust the curable resin solution. The obtained thermosetting resin solution was applied to a thickness of 40 μm by a doctor blade so as to have a hard thickness of 20 μm. The condensed side of the system is heated by a poly-pyrene. The electro-imine is laminated to the polyamine film of the 5Cmx5Cm after the bending of the loop through the wiring layer. On, 5 (TC heating for 20 minutes to dry 0
將所得到的形成熱硬化性樹脂層之聚醯亞胺薄膜與厚 度40μηι的銅箔,使用加熱至130°C的滾筒經接著,爲了 使接著劑完全硬化,然後,將所得到的層合物以1 〇〇°C 1 小時、120 °C 1時間、180 °C5小時間進行加熱使接著層硬 化,製造層合物,於所得到的層合物上藉由微影術形成電 路圖型,得到配線薄膜,與實施例比較下銅箔與聚醯亞胺 的層壓需要大量的時間與步驟數。此外,所得到的配線薄 膜經由200次的熱循環試驗,銅箔一部分剝離,此外,本 配線薄膜進行T型剝離試驗的結果,於剝離試驗中銅與接 著層之間界面剝離,其剝離時的強度爲1 0N/1 5mm之低的 値,相對於實施例所得到的配線薄膜而言較差,而且,進 行MIT試驗的結果,本配線薄膜經由1 50次的彎折試驗 ,雖然未見到聚醯亞胺層的破裂,銅箔剝離、接著層發生 裂縫、耐彎折性差。 實施例94 <不飽和羧酸接枝聚烯烴的製造> 將5000重量份的1,1,2-三氯乙烷與2500重量份的 26 %硫酸水溶液放進附有下口的10升燒瓶中激烈地攪拌 ,靜置後取出下層的有機層。接著、將被取出的有機層與 5 kg蒸餾水放進附有下口的10升燒瓶中激烈地攪拌’靜 置後取出下層的有機層之操作重複3次,去除1-丁醇及 -150- 200925171 1,2-環氧基丁烷(藉由氣相層析裝置經確認)。更藉由於 取出的有機層中添加150重量份的分子篩4A、用攪拌器 攪拌而脫水,得到經純化的1,1,2-三氯乙烷(以下,記爲 純化TCE)。 〇The obtained polyimide film forming a thermosetting resin layer and a copper foil having a thickness of 40 μm were heated by using a roll heated to 130° C., and then the obtained laminate was completely cured in order to completely cure the adhesive. The laminate was cured by heating at 1 〇〇 ° C for 1 hour, 120 ° C for 1 hour, and 180 ° C for 5 hours to form a laminate, and a circuit pattern was formed by lithography on the obtained laminate. The wiring film requires a large amount of time and number of steps for lamination of the copper foil and the polyimide under comparison with the examples. Further, the obtained wiring film was subjected to a heat cycle test for 200 times, and the copper foil was partially peeled off. Further, as a result of the T-type peeling test of the wiring film, the interface between the copper and the adhesive layer was peeled off during the peeling test, and the peeling was performed. The enthalpy having a low strength of 10 N/1 5 mm was inferior to the wiring film obtained in the examples, and as a result of the MIT test, the wiring film was subjected to a bending test of 150 times, although no aggregation was observed. The bismuth imide layer is broken, the copper foil is peeled off, the subsequent layer is cracked, and the bending resistance is poor. Example 94 <Production of Unsaturated Carboxylic Acid-Grafted Polyolefin> 5000 parts by weight of 1,1,2-trichloroethane and 2500 parts by weight of a 26% aqueous sulfuric acid solution were placed in the lower mouth with 10 liters. The flask was vigorously stirred, and after standing, the lower organic layer was taken out. Next, the taken-out organic layer and 5 kg of distilled water were placed in a 10-liter flask with a lower opening and vigorously stirred. The operation of removing the organic layer of the lower layer was repeated three times to remove 1-butanol and -150- 200925171 1,2-Epoxybutane (confirmed by gas chromatography apparatus). Further, 150 parts by weight of molecular sieve 4A was added to the taken-out organic layer, and the mixture was dehydrated by stirring with a stirrer to obtain purified 1,1,2-trichloroethane (hereinafter referred to as purified TCE). 〇
於4升的玻璃製反應容器中裝入2480重量份的純化 TCE與200重量份的L-LDPE、及2.0重量份的馬來酸酐 ,將反應器昇溫至80°C,然後藉由以80°C保持4小時均 勻地溶解L-LDPE。此外在此期間,於反應器中以5升/分 鐘的流速導入氮氣,排除混入反應器的空氣,作爲接枝反 應的觸媒之使1.5重量份的BPO溶解於純化TCE 100重 量份中。將此溶液連續地持續添加至反應器,在反應器的 壓力保持在1 MPa狀態下,進行3小時接枝反應。反應終 了後、使反應器的壓力回復常壓後,將反應器的溫度降低 至70 °C,添加作爲安定劑之〇.〇6重量份的BHT後,將此 溶液送進加熱至1 60 °C之鼓式乾燥機中,將生成物的改性 L-LDPE從溶劑分離出。 已知生成物係分析結果爲具有1.5重量%的不飽和羧 酸(馬來酸酐),凝膠爲〇重量%,丫1爲2及色相優良。 <由不飽和羧酸接枝聚烯烴所成的薄膜的製造>A 4 liter glass reaction vessel was charged with 2480 parts by weight of purified TCE and 200 parts by weight of L-LDPE, and 2.0 parts by weight of maleic anhydride, and the reactor was heated to 80 ° C, and then by 80 °. C was uniformly dissolved in L-LDPE for 4 hours. Further, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liter / minute to exclude air mixed into the reactor, and 1.5 parts by weight of BPO was dissolved as a catalyst for the graft reaction in 100 parts by weight of the purified TCE. This solution was continuously continuously added to the reactor, and a graft reaction was carried out for 3 hours while maintaining the pressure of the reactor at 1 MPa. After the reaction is completed, the pressure of the reactor is returned to normal pressure, the temperature of the reactor is lowered to 70 ° C, and 6 parts by weight of BHT as a stabilizer is added, and the solution is heated to 1 60 °. In the drum dryer of C, the modified L-LDPE of the product was separated from the solvent. It is known that the product analysis result is 1.5% by weight of unsaturated carboxylic acid (maleic anhydride), the gel is 〇% by weight, 丫1 is 2, and the hue is excellent. <Production of a film formed of an unsaturated carboxylic acid grafted polyolefin>
藉由使用復動式壓縮成形機WFA-50,使上述所得到 的不飽和羧酸接枝 L-LDPE,以加熱溫度 180°C、壓力 lOMPa、力□熱時間10分鐘、冷卻溫度30°C、壓力lOMPa 、冷卻時間5分鐘的條件進行加壓成形,得到尺寸1 00mm X 200925171 100mm、厚度ΙΟΟμιη的薄膜(薄膜1),所得到的薄膜的 外觀、性狀爲優良,看不到魚眼等之缺點。 <銅箱的層合>The above-mentioned unsaturated carboxylic acid was grafted with L-LDPE by using a double-action compression molding machine WFA-50 at a heating temperature of 180 ° C, a pressure of 10 MPa, a force and heat time of 10 minutes, and a cooling temperature of 30 ° C. Pressure molding was carried out under the conditions of a pressure of 10 MPa and a cooling time of 5 minutes to obtain a film (film 1) having a size of 100 mm X 200925171 100 mm and a thickness of ΙΟΟμηη. The obtained film was excellent in appearance and properties, and no fisheye or the like was observed. Disadvantages. <Lamination of copper boxes>
將所得到的尺寸lOOmmxlOOmm、厚度ΙΟΟμιη的薄膜 (薄膜 1)、及未進行表面處理尺寸 lOOmmxlOOmm、厚 度40μπι的銅箔(箔1),以壓力O.IMpa、溫度180°C、 時間1分鐘的條件層合而得到不飽和羧酸接枝L-LDPE與 銅箔的層合物(以下,稱爲銅箔層合聚烯烴薄膜)。 <薄膜天線的製造> 無塵室内,依銅箔層合聚烯烴薄膜、天線電路圖型的 順序,使用聚醯亞胺膠帶經固定於圓形石英玻璃製基板上 ,接著,將上述之經固定銅箔層合聚烯烴薄膜的石英玻璃 製基板裝置於旋轉塗佈機,將光阻液6ml流延於銅箔層合 聚烯烴薄膜上,使旋轉塗佈機以旋轉數3 OOrpm旋轉1 0秒 ,然後,使旋轉數花費5秒提高至1500 rpm爲止,使其以 此旋轉數旋轉2 0秒,得到光阻液一樣經塗佈的銅箔層合 聚烯烴薄膜。 在將此銅箔層合聚烯烴薄膜固定於圓形石英玻璃製基 板的狀態下,以波長36 5nm的UV光進行1 5秒曝光,然 後,在使上述的玻璃製基板旋轉的狀態下流延顯影液,進 行顯影,接下來,水洗、一邊吹氮氣一邊使其乾燥。 將所得到的顯影完成的銅箔層合聚烯烴薄膜於室溫以 -152- 200925171 蝕刻液處理3 0分鐘,水洗、以丙酮進行光阻層的剝離, 得到經形成導電電路圖型的薄膜天線。 <薄膜天線的試驗> 本薄膜天線經由200次的熱循環試驗、銅箔未剝離、 耐寒性及耐熱衝撃性優異,此外,將所得到的本薄膜天線 在使不飽和羧酸接枝聚烯烴側成爲接著面的方式以100°C 0 、壓力o.l MPa加熱壓黏於聚碳酸酯薄膜,得到層合物。 本薄膜天線即使經由200次的熱循環試驗,天線電路 亦未剝離,此外,與聚碳酸酯的剝離亦未見到,顯示出實 用上無問題的水準的耐寒性及耐熱衝撃性。而且,進行 MIT試驗的結果,本薄膜天線經由1 5 0次的彎折試驗,銅 箔未剝離、及薄膜亦末破裂,耐彎折性與柔軟性優異。本 薄膜天線於135kHz之平均利益的最大値爲-2DBic,顯示 出實用水準的特性。 〇 實施例95 除了將L-LDPE變更爲EVA以外,藉由與實施例94 同樣的手法得到經接枝馬來酸酐之EV A,已知生成物係 分析結果爲具有1.8重量%的不飽和羧酸(馬來酸酐), 凝膠爲〇重量%,YI爲1及色相優良。將此不飽和羧酸接 枝EVA藉由與實施例94同樣的條件進行加壓成型,得到 尺寸lOOmmxlOOmm、厚度Ι20μπι的薄膜,所得到的薄膜 的外觀、性狀爲優良,看不到魚眼等之缺點。 -153- 200925171 將所得到的薄膜、及未進行表面處理尺寸lOOmmx 100mm、厚度40μηι的銅箔,以壓力O.IMpa、溫度180°C 、時間1分鐘的條件層合,得到不飽和羧酸接枝EVA與 銅箔的層合物(以下,亦爲銅箔層合聚烯烴薄膜)。 <薄膜天線的製造> 於無塵室内,依銅箔層合聚烯烴薄膜、天線電路圖型 0 的順序使用聚醯亞胺膠帶經固定於圓形石英玻璃製基板上 ,接著,將上述之經固定銅箔層合聚烯烴薄膜的石英玻璃 製基板裝置於旋轉塗佈機,將光阻液6ml流延於銅箔層合 聚烯烴薄膜上,使旋轉塗佈機以旋轉數30〇rpm旋轉1〇秒 ,然後,使旋轉數花費5秒提高至15 OOrpm爲止,使其以 此旋轉數旋轉2 0秒,得到光阻液一樣經塗佈的銅箔層合 聚烯烴薄膜。 在將此銅箔層合聚烯烴薄膜固定於圓形石英玻璃製基 ❾ 板的狀態下,以波長365nm的UV光進行15秒曝光,然 後,在使上述的玻璃製基板旋轉的狀態下流延顯影液,進 行顯影,接下來,水洗、一邊吹氮氣一邊使其乾燥。 將所得到的顯影完成的銅箔層合聚烯烴薄膜於室溫以 餓刻液處理30分鐘,水洗、以丙酮進行光阻層的剝離, 得到經形成導電電路圖型的薄膜天線。 <薄膜天線的試驗> 本薄膜天線經由200次的熱循環試驗、銅箔未剝離、 -154- 200925171 耐寒性及耐熱衝撃性優異,此外,使所得到的本薄膜天線 在不飽和羧酸接枝聚烯烴側成爲接著面的方式下以120°C 、壓力0.1 MPa加熱壓黏於聚醯亞胺薄膜,得到層合物。The obtained film (film 1) having a size of 100 mm×100 mm and a thickness of ΙΟΟμη, and a copper foil (foil 1) having a surface-treated size of 100 mm×100 mm and a thickness of 40 μm were subjected to a pressure of 0.1 Mpa, a temperature of 180° C., and a time of 1 minute. A laminate of an unsaturated carboxylic acid grafted L-LDPE and a copper foil (hereinafter referred to as a copper foil-laminated polyolefin film) was obtained by lamination. <Production of Film Antenna> In a clean room, a copper foil-laminated polyolefin film and an antenna circuit pattern are fixed on a circular quartz glass substrate by using a polyimide tape, and then the above-mentioned A quartz glass substrate device with a fixed copper foil laminated polyolefin film was applied to a spin coater, and 6 ml of the photoresist liquid was cast on the copper foil laminated polyolefin film, and the spin coater was rotated at a rotation number of 300 rpm. Secondly, the number of rotations was increased to 1500 rpm in 5 seconds, and the number of rotations was rotated for 20 seconds to obtain a photoresist-coated copper foil-laminated polyolefin film. In the state in which the copper foil-laminated polyolefin film is fixed to a circular quartz glass substrate, it is exposed to UV light having a wavelength of 35 5 nm for 15 seconds, and then cast and developed in a state where the above-mentioned glass substrate is rotated. The solution was developed, and then washed with water and dried while blowing nitrogen gas. The obtained developed copper foil-laminated polyolefin film was treated with an -152-200925171 etching solution at room temperature for 30 minutes, washed with water, and the photoresist layer was peeled off with acetone to obtain a film antenna having a conductive circuit pattern. <Test of film antenna> The film antenna was excellent in cold cycle test, copper foil peeling, cold resistance and heat resistance, and the obtained film antenna was grafted with unsaturated carboxylic acid. The olefin side was bonded to a polycarbonate film at 100 ° C 0 and a pressure of OL MPa to obtain a laminate. In the film antenna, the antenna circuit was not peeled off even after 200 thermal cycle tests, and the peeling with the polycarbonate was not observed, and the cold resistance and the heat-resistant punchability which were practically problem-free were exhibited. Further, as a result of the MIT test, the film antenna was subjected to a bending test of 150 times, the copper foil was not peeled off, and the film was finally broken, and the bending resistance and the flexibility were excellent. The maximum benefit of the film antenna at 135 kHz is -2 DBic, which shows practical characteristics. Example 95 An EV A grafted with maleic anhydride was obtained by the same procedure as in Example 94 except that the L-LDPE was changed to EVA, and the product was analyzed to have an unsaturated carboxyl group of 1.8% by weight. Acid (maleic anhydride), the gel is % by weight, YI is 1 and the hue is excellent. The unsaturated carboxylic acid grafted EVA was pressure-molded under the same conditions as in Example 94 to obtain a film having a size of 100 mm x 100 mm and a thickness of Ι 20 μm, and the obtained film was excellent in appearance and properties, and no fisheye or the like was observed. Disadvantages. -153- 200925171 The obtained film and the copper foil having a surface-treated size of 100 mm x 100 mm and a thickness of 40 μm were laminated at a pressure of 0.1 Mpa, a temperature of 180 ° C, and a time of 1 minute to obtain an unsaturated carboxylic acid bond. A laminate of a branch EVA and a copper foil (hereinafter, also a copper foil laminated polyolefin film). <Production of Film Antenna> In a clean room, a copper foil-laminated polyolefin film and an antenna circuit pattern 0 are sequentially fixed on a circular quartz glass substrate using a polyimide tape, and then the above-mentioned A quartz glass substrate device with a fixed copper foil laminated polyolefin film was applied to a spin coater, and 6 ml of a photoresist liquid was cast on a copper foil laminated polyolefin film, and the spin coater was rotated at a number of revolutions of 30 rpm. After 1 second, the number of rotations was increased to 15 rpm for 5 seconds, and the number of rotations was rotated for 20 seconds to obtain a copper foil-laminated polyolefin film coated with a photoresist. In the state where the copper foil-laminated polyolefin film is fixed to a circular quartz glass base plate, exposure is performed for 15 seconds with UV light having a wavelength of 365 nm, and then the film is rotated and developed in a state where the glass substrate is rotated. The solution was developed, and then washed with water and dried while blowing nitrogen gas. The obtained developed copper foil-laminated polyolefin film was treated with a bathing solution at room temperature for 30 minutes, washed with water, and peeled off with a photoresist layer to obtain a film antenna having a conductive circuit pattern. <Test of film antenna> The film antenna was excellent in cold resistance and heat-resistant squeezing property through 200 heat cycle tests, copper foil not peeling, -154-200925171, and the obtained film antenna was made into unsaturated carboxylic acid. The grafted polyolefin side was pressure-bonded to a polyimide film at 120 ° C and a pressure of 0.1 MPa to obtain a laminate.
本薄膜天線即使進行200次的熱循環試驗天線電路亦 未剝離,此外,亦未見到與聚醯亞胺薄膜剝離,但顯示出 實用上無問題的水準的耐寒性及耐熱衝撃性。而且,進行 MIT試驗的結果,本薄膜天線經由150次的彎折試驗,銅 箔未剝離、及薄膜亦末破裂,耐彎折性與柔軟性優異。本 薄膜天線於135kHz的平均利益的最大値爲-1.8DBic,顯 示出實用水準的特性。 實施例96 除了將L-LDPE變更爲鹼化EVA-1、將馬來酸酐變更 爲丙烯酸以外,藉由與實施例94同樣的手法得到經接枝 丙烯酸之鹼化EVA,已知生成物係分析結果爲具有1重 〇 量%的不飽和羧酸(丙烯酸),凝膠爲0重量%,YI爲1 及色相優良,將此不飽和羧酸接枝鹼化EVA藉由與實施 例94同樣的條件進行加壓成型,得到尺寸l〇〇mmxl00rnm 、厚度130μηι的薄膜,所得到的薄膜的外觀、性狀爲優 良,看不到魚眼等之缺點。 將所得到的薄膜、及未進行表面處理尺寸lOOmmx 100mm、厚度40μιη的銅箔,以壓力o.lMpa、溫度180°C 、時間1分鐘的條件層合,得到不飽和羧酸接枝鹼化 EVA與銅箔的層合物(以下,亦爲銅箔層合聚烯烴薄膜 -155- 200925171 <薄膜天線的製造> 於無塵室内’依銅箔層合聚烯烴薄膜、天線電路圖型 的順序使用聚醯亞胺膠帶經固定於圓形石英玻璃製基板上 ,接著’將上述之經固定銅箔層合聚烯烴薄膜的石英玻璃 製基板裝置於旋轉塗佈機’使光阻液6m 1流延於銅箔層合 Q 聚烯烴薄膜上’使旋轉塗佈機以旋轉數300 rpm旋轉10秒 ,然後’使旋轉數花費5秒提高至I500rpm爲止,使其以 此旋轉數旋轉20秒’得到光阻液一樣經塗佈的銅箔層合 聚烯烴薄膜。 在將此銅箔層合聚烯烴薄膜固定於圓形石英玻璃製基 板的狀態下,以波長365 nm的UV光進行15秒曝光,然 後,在使上述的玻璃製基板旋轉的狀態下流延顯影液,進 行顯影,接下來,水洗、一邊吹氮氣一邊使其乾燥。 0 將所得到的顯影完成的銅箔層合聚烯烴薄膜於室溫以 蝕刻液處理30分鐘,水洗、以丙酮進行光阻層的剝離, 得到經形成導電電路圖型的薄膜天線。 <薄膜天線的試驗> 本薄膜天線經由200次的熱循環試驗、銅箔未剝離' 耐寒性及耐熱衝撃性優異,此外,使所得到的本薄膜天線 在不飽和羧酸接枝聚烯烴側成爲接著面的方式下以120 °c 、壓力0.1 MPa加熱壓黏於聚醯亞胺薄膜,得到層合物。 -156- 200925171 本薄膜天線即使進行200次的熱循環試驗天線電路亦 未剝離,此外,亦未見到與聚醯亞胺薄膜剝離,但顯示出 實用上無問題的水準的耐寒性及耐熱衝撃性。而且,進行 MIT試驗的結果,本薄膜天線經由150次的彎折試驗,銅 箔未剝離、及薄膜亦末破裂,耐彎折性與柔軟性優異。本 薄膜天線之於135kHz中的平均利益的最大値爲-1.9DBic ,顯示出實用水準的特性。 ❹ 製造例3 將1 7500重量份的1,1,2-三氯乙烷與2500重量份的 26%硫酸水溶液放進附有下口的10升燒瓶中激烈地攪拌In the film antenna, the antenna circuit was not peeled off even after performing the thermal cycle test for 200 times, and the peeling of the polyimide film was not observed, but the cold resistance and the heat-resistant punching property which were practically problem-free were exhibited. Further, as a result of the MIT test, the film antenna was subjected to a bending test of 150 times, the copper foil was not peeled off, and the film was finally broken, and the bending resistance and the flexibility were excellent. The maximum benefit of this film antenna at an average benefit of 135 kHz is -1.8 DBic, indicating a practical level of characteristics. Example 96 An alkalized EVA grafted with acrylic acid was obtained by the same method as in Example 94 except that L-LDPE was changed to alkalized EVA-1 and maleic anhydride was changed to acrylic acid. The result was an unsaturated carboxylic acid (acrylic acid) having 1% by weight, a gel of 0% by weight, a YI of 1 and a good hue. The unsaturated carboxylic acid grafted alkalinized EVA was the same as that of Example 94. Under pressure, a film having a size of 10 mm×100 rnm and a thickness of 130 μm was obtained, and the obtained film was excellent in appearance and properties, and the defects such as fish eyes were not observed. The obtained film and the copper foil having a surface treatment size of 100 mm×100 mm and a thickness of 40 μm were laminated under the conditions of a pressure of 0.1 Mpa, a temperature of 180° C., and a time of 1 minute to obtain an unsaturated carboxylic acid graft alkalized EVA. Laminate with copper foil (hereinafter, also referred to as copper foil laminated polyolefin film-155-200925171 <Manufacturing of film antenna> in a clean room> in the order of copper foil laminated polyolefin film and antenna circuit pattern The film was fixed on a circular quartz glass substrate by using a polyimide tape, and then the above-mentioned quartz glass substrate having a fixed copper foil laminated polyolefin film was placed on a spin coater to flow a photoresist liquid of 6 m 1 . Extending on the copper foil laminated Q polyolefin film, 'rotating the spin coater at 300 rpm for 10 seconds, then 'reducing the number of rotations to 5500 seconds to I500 rpm, and rotating it for 20 seconds with this rotation number' A copper foil-laminated polyolefin film coated with a photoresist is applied. The copper foil-laminated polyolefin film is fixed to a circular quartz glass substrate, and exposed to UV light having a wavelength of 365 nm for 15 seconds. Then, in making the above glass The developing solution was cast in a state where the substrate was rotated, and development was carried out, followed by washing with water and drying while blowing nitrogen gas. 0 The obtained copper foil-laminated polyolefin film which was developed was treated with an etching solution at room temperature for 30 minutes. After washing with water, the photoresist layer was peeled off with acetone to obtain a film antenna having a conductive circuit pattern. <Test of film antenna> The film antenna was subjected to 200 heat cycle tests, and copper foil was not peeled off. Cold resistance and heat resistance. It is excellent in the squeezing property, and the obtained film antenna is heat-pressed and bonded to the polyimide film at 120 ° C and a pressure of 0.1 MPa on the side of the unsaturated carboxylic acid grafted polyolefin side to form a laminate. -156- 200925171 This film antenna has not been peeled off even after 200 cycles of thermal cycling test. In addition, no peeling from the polyimide film has been observed, but it shows a practically problem-free level of cold resistance. Thermal shock resistance. Moreover, as a result of the MIT test, the film antenna was subjected to a bending test of 150 times, the copper foil was not peeled off, and the film was broken at the same time, and the bending resistance and flexibility were resistant. The maximum benefit of the average benefit of the film antenna at 135 kHz is -1.9 DBic, which shows practical characteristics. ❹ Manufacturing Example 3 1 7500 parts by weight of 1,1,2-trichloroethane and 2500 weight a 26% aqueous solution of sulfuric acid was placed in a 10-liter flask with a lower mouth and stirred vigorously.
,靜置後取出下層的有機層。接著、將被取出的有機層與 5 kg蒸餾水放進附有下口的1〇升燒瓶中激烈地攪拌,靜 置後取出下層的有機層之操作重複3次,去除1-丁醇及 1,2-環氧基丁烷。更藉由於取出的有機層中添加150重量 份的分子篩4A、用攪拌器攪拌而脫水,得到經純化的 1,1,2-三氯乙烷(以下,記爲純化TCE )。 於4升的玻璃製反應容器中裝入1 750重量份的純化 TCE與100重量份的EVA、及5重量份的馬來酸酐,將 反應器昇溫至8 0 °C,然後藉由以8 0 °C保持4小時均勻地 溶解EVA,此外在此期間,於反應器中以5升/分鐘的流 速導入氮氣,排除混入反應器的空氣,作爲接枝反應的觸 媒之使0.16重量份的BPO溶解於純化TCE 100重量份, 將此溶液連續地持續添加至反應器,在反應器的壓力保持 -157- 200925171 在1 MPa狀態下,進行3小時接枝反應。反應終了後、使 反應器的壓力回復常壓後,將反應器的溫度降低至70 °C, 添加作爲安定劑之0.1重量份的BHT後,將此溶液送進 加熱至160°C之鼓式乾燥機中,將經接枝馬來酸酐之EVA 從溶劑分離出,生成物中的凝膠量係分析結果爲〇重量%After standing, the lower organic layer was taken out. Next, the taken-out organic layer and 5 kg of distilled water were placed in a 1-liter flask equipped with a lower mouth and vigorously stirred. After standing, the operation of taking out the lower organic layer was repeated three times to remove 1-butanol and 1, 2-epoxybutane. Further, 150 parts by weight of molecular sieve 4A was added to the taken-out organic layer, and the mixture was dehydrated by stirring with a stirrer to obtain purified 1,1,2-trichloroethane (hereinafter referred to as purified TCE). A 4 liter glass reaction vessel was charged with 1 750 parts by weight of purified TCE and 100 parts by weight of EVA, and 5 parts by weight of maleic anhydride, and the reactor was heated to 80 ° C, and then by 80 °C was uniformly dissolved for 4 hours, and during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liters/min to exclude air mixed into the reactor, and 0.16 parts by weight of BPO was used as a catalyst for the graft reaction. The solution was dissolved in 100 parts by weight of purified TCE, and this solution was continuously continuously added to the reactor, and the grafting reaction was carried out for 3 hours while maintaining the pressure of the reactor at -157 to 200925171 at 1 MPa. After the reaction was completed, the pressure of the reactor was returned to normal pressure, the temperature of the reactor was lowered to 70 ° C, and 0.1 part by weight of BHT as a stabilizer was added, and the solution was fed to a drum heated to 160 ° C. In the dryer, the EVA grafted with maleic anhydride is separated from the solvent, and the amount of gel analysis in the product is 〇% by weight.
製造例4 於4升的玻璃製反應容器中裝入1 750重量份的純化 TCE與100重量份的鹼化EVA-1、及7重量份的馬來酸酐 ,將反應器昇溫至80°C,然後藉由以80°C保持4小時使 鹼化EVA-1均勻地溶解。此外在此期間,於反應器中以5 升/分鐘的流速導入氮氣,排除混入反應器的空氣,作爲 接枝反應的觸媒之使0.2重量份的BPO溶解於純化TCE 1〇〇重量份,將此溶液連續地持續添加至反應器,在反應 器的壓力保持在IMPa狀態下,進行3小時接枝反應。反 應終了後、使反應器的壓力回復常壓後,將反應器的溫度 降低至7 0 °C,添加作爲安定劑之〇 . 1重量份的B HT後, 將此溶液送進加熱至160 °C之鼓式乾燥機中,將經接枝馬 來酸酐之鹼化EVA-1從溶劑分離出,生成物中的凝膠量 係分析結果爲〇重量%。 製造例5 除了將鹼化EVA-1變更爲鹼化EVA_2以外,藉由與 -158- 200925171 製造例4同樣的手法得到經接枝馬來酸酐之鹼化eva-2 , 生成物中的凝膠量係分析結果爲〇重量。/。。 製造例6 除了將馬來酸酐變更爲丙烯酸以外,藉由與製造例3 同樣的手法得到經接枝丙烯酸之EVA,生成物中的凝膠 量係分析結果爲0重量%。 〇 實施例9 7 將製造例3所得到的經接枝馬來酸酐之EVA (以下 ,稱爲改性 EVA ) 30g、碳黑 9g,使用 laboplastomill, 以1 5 0 °C熔融混練1 〇分鐘後,經由冷卻得到分散有碳黑的 改性EVA,將所得到的樹脂藉由以1 80°C加壓而得到厚度 爲100微米的薄膜,使用所得到的薄膜,接著圖1如示的 60mmx 13mmx5mm 的銅板,此時,接著面積部分爲 © 10mmxl3mm,用2個長尾夾挾住接著部分,如表16所示 的條件進行接著。接著後,用TESTER測量銅板間的電阻 的結果,所有的試樣爲0Ω,顯示出優良的導電性’此外 ,用Autograph測量拉伸強度的結果,所有的試樣顯示出 5 00N以上的強度,顯示出優異的接著性。 -159- 200925171 〔表 16〕 溫度 時間 [°c] [分] 條件—1 200 60 條件—2 180 60 條件—3 160 60 條件—4 140 60 條件一 5 200 30 條件一 6 200 15Production Example 4 Into a 4 liter glass reaction vessel, 1 750 parts by weight of purified TCE and 100 parts by weight of alkalized EVA-1 and 7 parts by weight of maleic anhydride were charged, and the reactor was heated to 80 ° C. The alkalized EVA-1 was then uniformly dissolved by holding at 80 ° C for 4 hours. Further, during this period, nitrogen gas was introduced into the reactor at a flow rate of 5 liters/min to remove air mixed into the reactor, and as a catalyst for the graft reaction, 0.2 part by weight of BPO was dissolved in 1 part by weight of the purified TCE. This solution was continuously continuously added to the reactor, and a graft reaction was carried out for 3 hours while the pressure of the reactor was maintained at 1 MPa. After the reaction is completed, the pressure of the reactor is returned to normal pressure, the temperature of the reactor is lowered to 70 ° C, and the stabilizer is added as a stabilizer. After 1 part by weight of B HT, the solution is heated to 160 °. In the drum dryer of C, the alkalized EVA-1 grafted with maleic anhydride was separated from the solvent, and the amount of gel analysis in the product was 〇% by weight. Production Example 5 The alkalinized eva-2 of the grafted maleic anhydride was obtained by the same method as in Production Example 4 of -158-200925171, except that the alkalized EVA-1 was changed to the alkalized EVA-2. The quantitative analysis results are the weight of 〇. /. . Production Example 6 The EVA of the grafted acrylic acid was obtained by the same method as in Production Example 3 except that the maleic anhydride was changed to acrylic acid, and the result of the gelation analysis in the product was 0% by weight. 〇Example 9 7 30 g of the grafted maleic anhydride obtained in Production Example 3 (hereinafter referred to as modified EVA) and 9 g of carbon black were melt-kneaded at 150 ° C for 1 〇 minutes using a laboplastomill. The modified EVA in which carbon black was dispersed was obtained by cooling, and the obtained resin was pressed at 180 ° C to obtain a film having a thickness of 100 μm, and the obtained film was used, followed by 60 mm x 13 mm x 5 mm as shown in FIG. The copper plate, at this time, the area of the area was © 10 mm x 13 mm, and the next part was clamped with two long tail clips, followed by the conditions shown in Table 16. Then, the results of measuring the electrical resistance between the copper plates by TESTER, all the samples were 0 Ω, showing excellent electrical conductivity. In addition, the tensile strength was measured by Autograph, and all the samples showed strengths of 500 ng or more. Shows excellent adhesion. -159- 200925171 [Table 16] Temperature Time [°c] [Minute] Condition - 1 200 60 Condition - 2 180 60 Condition - 3 160 60 Condition - 4 140 60 Condition 1 5 200 30 Condition 1 6 200 15
實施例9 8 將製造例3所得到的改性e V A 3 0 g、銅微粒子1 8 g, 使用laboplastomill以150°C熔融混練10分鐘後,藉由冷 卻得到分散有銅微粒子之改性EVA,藉由將所得到的樹 脂以180 °C加壓而得到厚度爲1〇〇微米的薄膜,除了使用 藉由上述方法所得到的含有銅微粒子之薄膜,取代含有碳 黑之薄膜以外’與實施例97同樣作法進行試驗,將熱處 理條件列示於表16 ’接著後,用TESTER測量銅板間的 電阻的結果,所有的試樣爲0Ω,顯示出優良的導電性, 此外’用Autograph測量拉伸強度的結果,所有的試樣顯 示出500N以上的強度,顯示出優異的接著性。 實施例9 9 與實施例97同樣使用含有碳黑之薄膜進行接著試驗 ,惟,本實施例係使單側的銅版使用ITO板(含有10重 量%Sn02之Ιη203 )及ZAO板(含有2重量%Al2〇3之Example 9 8 The modified e VA 30 g obtained in Production Example 3 and 18 g of copper fine particles were melt-kneaded at 150 ° C for 10 minutes using a laboplastomill, and then the modified EVA in which copper fine particles were dispersed was obtained by cooling. A film having a thickness of 1 μm was obtained by pressurizing the obtained resin at 180 ° C, except that the film containing copper microparticles obtained by the above method was used instead of the film containing carbon black. 97. The test was carried out in the same manner, and the heat treatment conditions are shown in Table 16'. Then, the resistance between the copper plates was measured by TESTER. All the samples were 0 Ω, showing excellent electrical conductivity, and 'measuring tensile strength with Autograph. As a result, all the samples showed an intensity of 500 N or more, showing excellent adhesion. Example 9 9 A film containing carbon black was used for the subsequent test in the same manner as in Example 97. However, in this example, a one-sided copper plate was used for an ITO plate (Ten 203 containing 10% by weight of Sn02) and a ZAO plate (containing 2% by weight). Al2〇3
ZnO ),進行200°C、1小時間的熱處理條件,接著後,用 -160- 200925171 TESTER測量板間的電阻的結果,ITO板/銅板接著試樣爲 5Ω,ZAO板/銅板接著試樣爲1Ω,顯示出優良的導電性, 此外,用Autograph測量拉伸強度的結果,兩試樣皆即使 5 00N的試驗力亦未剝離,確認爲優良的接著性。 實施例100ZnO), heat treatment conditions were carried out at 200 ° C for 1 hour, and then, the resistance between the plates was measured with -160 - 200925171 TESTER, and the ITO plate/copper plate was then 5 Ω, and the ZAO plate/copper plate was then sampled. 1 Ω showed excellent electrical conductivity. Further, as a result of measuring the tensile strength by Autograph, both of the samples were not peeled off even when the test force of 500 N was observed, and it was confirmed to be excellent adhesion. Example 100
將製造例3所得到的改性EVA30g、銅微粒子18g, 使用laboplastomill以150°C熔融混練1〇分鐘後,藉由冷 卻得到分散有銅微粒子之改性EVA,藉由將所得到的樹 脂以180°C加壓而得到厚度爲1〇〇微米的薄膜,除了使用 藉由上述方法所得到的含有銅微粒子之薄膜,取代含有碳 黑之薄膜以外,與實施例97同樣作法進行試驗,將熱處 理條件列示於表1 6,接著後,用TESTER測量銅板間的 電阻的結果,所有的試樣爲0Ω,顯示出優良的導電性, 此外,用Autograph測量拉伸強度的結果,所有的試樣顯 示出5 00N以上的強度,顯示出優異的接著性。 實施例1 〇 1 與實施例98同樣使用含有Cu粉末之薄膜進行接著試 驗,惟,本實施例係使單側的銅版使用ITO板(含有1 〇 重量%Sn02之Ιη203 )及ZAO板(含有2重量%A12〇3之 ZnO),以200°C進行1時間的熱處理條件,接著後、用 TESTER測量板間的電阻的結果,ITO板/銅板接著試樣爲 0Ω,ZAO板/銅板接著試樣爲1Ω,顯示出優良的導電性, -161 - 200925171 此外,用Autograph測量拉伸強度的結果,兩試樣皆即使 是5 0 0N的試驗力亦未剝離,確認爲優良的接著性。 實施例102 將製造例4所得到的經接枝馬來酸酐之鹼化EVA-1 ( 以下,稱爲改性EVA-1 ) 、30g、銅微粒子15g,使用 laboplastomill以15(TC熔融混練10分鐘後,藉由冷卻得 0 到分散有銅微粒子之改性EVA- 1,藉由使所得到的樹脂以 1 80°c加壓而得到厚度爲1 1 〇微米的薄膜,使用所得到的 含有銅微粒子之薄膜,將厚度1mm、寬度15mm、長度 100mm的銅片以180°C施加1分鐘的〇.2MPa壓力進行接 著,接著後,用TESTER測量銅板間的電阻的結果,所有 的試樣皆爲 0Ω,顯示出優良的導電性,此外,用 Autograph所測量的T型剝離強度爲35N/15 mm,顯示出 優異的接著性。 〇 實施例103 將製造例5所得到的經接枝馬來酸酐之鹼化EVa-2 ( 以下,稱爲改性 EVA-2 ) 、30g、碳黑 20g,使用 laboplastomill以150°C熔融混練10分鐘後,藉由冷卻得 到分散有碳黑之改性EVA-2,藉由將所得到的樹脂以 1 80°C加壓而得到厚度爲1 20微米的薄膜,使用所得到的 含有碳黑之薄膜,使厚度1mm、寬度15mm、長度100rnm 的銅片以180°C施加1分鐘的0.2MPa壓力而接著,接著 -162- 200925171 後,用TESTER測量銅板間的電阻的結果,所有的試樣皆 爲0Ω,顯示出優良的導電性’此外,用Autograph所測 量的T型剝離強度爲3 0N/15 mm,顯示出優異的接著性。 實施例104 使製造例6所得到的經接枝丙烯酸之EVA (以下’ 稱爲改性EVA) 30g、銅微粒子16g,使用laboplastomill 0 以150°C熔融混練1〇分鐘後,藉由冷卻而得到分散有銅微 粒子之改性EVA,藉由將所得到的樹脂以1 8 0 °C加壓而得 到厚度爲105微米的薄膜,使用所得到的含有銅微粒子之 薄膜,使厚度 1mm、寬度 15mm、長度 100mm的銅片以 180°C施加1分鐘的〇_2MPa壓力而接著’接著後、用 TESTER測量銅板間的電阻的結果,所有的試樣皆爲〇Ω, 顯示出優良的導電性,此外’用Aut〇graph所測量的T型 剝離強度爲30N/15mm’顯示出優異的接著性。 〇 由實施例97~ 104,確認出本發明的導電性薄膜不僅 是金屬彼此,金屬與導電性酸化物的接著亦優異。 實施例1〇5 使用經混練碳黑之接著聚合物薄片(碳黑含量:30 重量%),進行直徑76.2mm、厚度5mm大小的圓形純A1 成對標靶本體與銅製的背板之接著(bonding)。30 g of the modified EVA and 18 g of the copper fine particles obtained in Production Example 3 were melt-kneaded at 150 ° C for 1 minute using a laboplastomill, and then the modified EVA in which the copper fine particles were dispersed was obtained by cooling, and the obtained resin was 180. The film was pressed at a temperature of ° C to obtain a film having a thickness of 1 μm, and the film was subjected to the same procedure as in Example 97 except that the film containing the copper fine particles obtained by the above method was used instead of the film containing the carbon black. The results are shown in Table 16. Then, the results of the electrical resistance between the copper plates were measured by TESTER. All the samples were 0 Ω, showing excellent electrical conductivity. In addition, the tensile strength was measured by Autograph, and all the samples were displayed. The strength of 500 N or more showed excellent adhesion. Example 1 〇1 A film containing a Cu powder was used for the subsequent test in the same manner as in Example 98. However, in this example, a one-sided copper plate was used for an ITO plate (T 203 containing 1% by weight of Sn02) and a ZAO plate (containing 2). ZnO of weight %A12〇3, heat treatment conditions at 200 ° C for 1 time, and then, after measuring the resistance between the plates with TESTER, the ITO plate/copper plate was followed by a sample of 0 Ω, ZAO plate/copper plate followed by sample It was 1 Ω and showed excellent electrical conductivity. -161 - 200925171 In addition, the tensile strength was measured by Autograph, and even if the test force of the two samples was not peeled off, it was confirmed to be excellent adhesion. Example 102 The alkalized EVA-1 (hereinafter referred to as modified EVA-1), 30 g of copper microparticles obtained by grafting maleic anhydride obtained in Production Example 4, and 15 g of copper fine particles were mixed by laboplastmill for 15 minutes. Thereafter, a film having a thickness of 11 μm was obtained by cooling the obtained resin to a modified EVA-1 having copper fine particles dispersed thereon by pressurizing the obtained resin at 1800 ° C, and using the obtained copper-containing film. The film of the microparticles was subjected to a pressure of 2 MPa at a temperature of 1 mm, a width of 15 mm, and a length of 100 mm, which was applied at 180 ° C for 1 minute, and then, the results of electrical resistance between the copper plates were measured by TESTER, and all the samples were 0 Ω showed excellent electrical conductivity, and in addition, the T-peel strength measured by Autograph was 35 N/15 mm, showing excellent adhesion. 〇 Example 103 The grafted maleic anhydride obtained in Production Example 5 was obtained. The alkalized EVA-2 (hereinafter referred to as modified EVA-2), 30 g, and carbon black 20 g were melt-kneaded at 150 ° C for 10 minutes using a laboplastomill, and then the modified EVA-2 in which carbon black was dispersed was obtained by cooling. Thickness obtained by pressurizing the obtained resin at 180 ° C A 20 micron film was obtained by using a film containing carbon black obtained, and a copper sheet having a thickness of 1 mm, a width of 15 mm, and a length of 100 nm was applied at 180 ° C for 1 minute at a pressure of 0.2 MPa, and then, after -162 to 200925171, As a result of TESTER measuring the electrical resistance between the copper plates, all the samples were 0 Ω, showing excellent electrical conductivity. In addition, the T-peel strength measured by Autograph was 30 N/15 mm, showing excellent adhesion. Example 104 30 g of grafted acrylic acid EVA (hereinafter referred to as "modified EVA") and 16 g of copper fine particles obtained in Production Example 6 were melt-kneaded at 150 ° C for 1 minute using a laboplastomill 0, and then dispersed by cooling. The modified EVA having copper microparticles was obtained by pressurizing the obtained resin at 180 ° C to obtain a film having a thickness of 105 μm, and using the obtained film containing copper microparticles to have a thickness of 1 mm, a width of 15 mm, and a length. The 100 mm copper piece was applied at 180 ° C for 1 minute at a pressure of 〇 2 MPa and then 'afterwards, the resistance between the copper plates was measured by TESTER. All the samples were 〇 Ω, showing excellent electrical conductivity, in addition' Use Aut〇 The T-peel strength measured by graph was 30 N/15 mm', which showed excellent adhesion. From Examples 97 to 104, it was confirmed that the conductive film of the present invention is not only a metal but also a metal and a conductive acid. Excellent Example 1〇5 Using a blended carbon black followed by polymer sheet (carbon black content: 30% by weight), a circular pure A1 paired target body having a diameter of 76.2 mm and a thickness of 5 mm and a copper backing plate were used. Bonding.
將直徑約70mm的含有碳黑之薄膜挾於純A1成對標 靶本體與銅製的背板之間’以虎頭鉗固定後’進行200 °C -163- 200925171 、1小時的熱處理而進行接著,接著後,裝置於濺鑛裝置 ,使用Ar作爲濺鍍氣體,於0.5Pa的壓力中進行濺鍍放 電特性(電流-電壓特性)測量、成膜率測量,測量經濺 鍍成膜之薄膜的電阻率。 比較下,對於使用一般銦焊接進行接著之純A1標靶 ,亦進行同樣的測量。 圖2表示放電特性的測量結果,表1 7中列示出成膜 率、薄膜電阻率的測量結果。 〔表 17〕 成膜率 [nm/min] 電阻率 μΩοιη] 膜厚:lOOnm 膜厚:300nm 導電性薄膜 58.1 3.59 3.18 銦焊接 57.7 3.56 3.26 由圖2及表17,得知使用本發明的導電性薄膜經接 著的濺鍍標靶,與使用一般銦焊接進行接著之標靶具有同 樣的特性,確認出其可作爲接著材料使用。 實施例106 使用經混練銅微粒子之接著聚合物薄片(銅微粒子含 量:60重量% ),進彳了直徑76.2mm、厚度5mm大小的純 A1濺鍍標靶與銅製的背板本體之接著(bonding)。 將直徑約70mm之含有銅微粒子的接著聚合物薄片, 挾於純A1濺鍍標靶與銅製的背板之間,用虎頭鉗固定後 -164- 200925171 ’進行200°C、1小時的熱處理而進行接著。接著後、裝 置於濺鍍裝置,使用Ar作爲濺鍍氣體,於〇.5Pa的壓力 進行濺鍍放電特性(電流-電壓特性)測量、成膜率測量 ,測量經濺鍍成膜之薄膜的電阻率。 比較下’對於使用一般銦焊接進行接著之純A1標靶 ,亦進行同樣的測量。 圖3表示放電特性的測量結果,表is列示出成膜率 、薄膜電阻率的測量結果。 〔表 18〕 成膜率 [nm/minl 電阳率 μΩοηι] 膜厚:lOOnm 膜厚:300nm 導電性薄膜 58.4 3.47 3.18 銦焊接 57.7 3.56 3.26A carbon black-containing film having a diameter of about 70 mm was placed between a pure A1 paired target body and a copper backing plate, and then heat-treated at 200 ° C -163 - 200925171 for 1 hour. Then, the device is used in a sputtering apparatus, and Ar is used as a sputtering gas, and sputtering discharge characteristics (current-voltage characteristics) are measured at a pressure of 0.5 Pa, and a film formation rate is measured, and a film formed by sputtering is measured. Resistivity. In comparison, the same measurement was performed for the subsequent pure A1 target using general indium soldering. Fig. 2 shows the measurement results of the discharge characteristics, and Table 17 shows the measurement results of the film formation rate and the sheet resistivity. [Table 17] Film formation rate [nm/min] Resistivity μΩοιη] Film thickness: 100 nm Film thickness: 300 nm Conductive film 58.1 3.59 3.18 Indium soldering 57.7 3.56 3.26 From Fig. 2 and Table 17, it is known that the conductivity of the present invention is used. The film has the same characteristics as the subsequent target by using a general indium soldering through the subsequent sputtering target, and it is confirmed that it can be used as a bonding material. Example 106 Using a post-polymer sheet of copper fine particles (copper particle content: 60% by weight), a pure A1 sputtering target having a diameter of 76.2 mm and a thickness of 5 mm was bonded to a copper backing body (bonding) ). A copper polymer microparticle-containing adhesive polymer sheet having a diameter of about 70 mm was placed between a pure A1 sputtering target and a copper backing plate, and fixed with a vise clamp - 164 - 200925171 '200 ° C, 1 hour heat treatment And proceed. Then, the device is placed on a sputtering apparatus, and Ar is used as a sputtering gas, and sputtering discharge characteristics (current-voltage characteristics) are measured at a pressure of Pa5 Pa, and a film formation rate is measured, and the resistance of the film formed by sputtering is measured. rate. The same measurement was also carried out for the subsequent pure A1 target using general indium soldering. Fig. 3 shows the measurement results of the discharge characteristics, and the table is a graph showing the measurement results of the film formation rate and the sheet resistivity. [Table 18] Film formation rate [nm/minl Electro-positive rate μΩοηι] Film thickness: lOOnm Film thickness: 300 nm Conductive film 58.4 3.47 3.18 Indium soldering 57.7 3.56 3.26
由圖3及表18,得知得知使用本發明的導電性薄膜 經接著的濺鍍標靶,與使用一般銦焊接進行接著之標靶具 有同樣的特性’確認出其可作爲接著材料使用。 製造例7 將1 7500重量份的ΐ,ι,2-三氯乙烷與2500重量份的 26%硫酸水溶液’放進附有下口的1〇升燒瓶中激烈地攪 拌,靜置後取出下層的有機層,接著,將被取出的有機層 與5kg蒸餾水放進附有下口的10升燒瓶中激烈地攪拌, 靜置後取出下層的有機層之操作重複3次,去除1-丁醇 -165- 200925171 及1,2-環氧基丁烷。更藉由於取出的有機層中添加150重 量份的分子篩4A、用攪拌器攪拌而脫水,得到經純化的 1,1,2-三氯乙烷(以下,記爲純化TCE)。From Fig. 3 and Table 13, it is found that the use of the conductive film of the present invention through the subsequent sputtering target has the same characteristics as that of the subsequent target using general indium soldering, and it has been confirmed that it can be used as a bonding material. Production Example 7 1 7500 parts by weight of yttrium, iota, 2-trichloroethane and 2500 parts by weight of a 26% aqueous sulfuric acid solution were placed in a 1-liter flask equipped with a lower mouth and vigorously stirred, and the lower layer was taken out after standing. The organic layer was then vigorously stirred by placing the removed organic layer with 5 kg of distilled water in a 10-liter flask with a lower opening, and the operation of removing the organic layer of the lower layer after standing for 3 times was repeated to remove 1-butanol- 165- 200925171 and 1,2-epoxybutane. Further, 150 parts by weight of the molecular sieve 4A was added to the taken-out organic layer, and the mixture was dehydrated by stirring with a stirrer to obtain purified 1,1,2-trichloroethane (hereinafter referred to as purified TCE).
於4升的玻璃製反應容器中裝入1750重量份的純化 TCE與 100重量份的鹼化 EVA-1 (東曹(股)製、11-641 0M )、及9.7重量份的馬來酸酐,將反應器昇溫至 80°C,然後藉由以80°C保持4小時均与地溶解EVA,此外 在此期間,於反應器中以5升/分鐘的流速導入氮氣,排 除混入反應器的空氣,作爲接枝反應的觸媒之使0.16重 量份的BPO溶解於純化TCE 100重量份,將此溶液連續 地持續添加至反應器,在反應器的壓力保持在1 MPa狀態 下,進行3小時接枝反應。反應終了後、使反應器的壓力 回復常壓後,將反應器的溫度降低至70 °C,添加作爲安定 劑之0.1重量份的BHT後,將此溶液送進加熱至160°C之 鼓式乾燥機中,將經接枝馬來酸酐之鹼化EVA從溶劑分 離出,生成物中的凝膠量係分析結果爲〇重量%。 製造例8 除了將改性的聚烯烴由鹼化EVA-1變更爲鹼化EVA-2(東曹(股)製、H-6051K)以外,藉由與製造例7同 樣的手法得到經接枝馬來酸酐之鹼化EVA,生成物中的 凝膠量係分析結果爲〇重量%。 製造例9 -166- 200925171 除了將改性的聚烯烴由鹼化EVA-1變更爲鹼化EVA-3 (東曹(股)製、H-6960 )以外,藉由與製造例7同樣 的手法得到經接枝馬來酸酐之鹼化EVA,生成物中的凝 膠量係分析結果爲〇重量%。 製造例10A 4 liter glass reaction vessel was charged with 1750 parts by weight of purified TCE and 100 parts by weight of alkalized EVA-1 (manufactured by Tosoh Co., Ltd., 11-641 0 M), and 9.7 parts by weight of maleic anhydride. The reactor was heated to 80 ° C, and then EVA was dissolved in both at 80 ° C for 4 hours, and during this time, nitrogen was introduced into the reactor at a flow rate of 5 liter / minute to remove the air mixed into the reactor. As a catalyst for the graft reaction, 0.16 parts by weight of BPO was dissolved in 100 parts by weight of the purified TCE, and this solution was continuously continuously added to the reactor, and the pressure of the reactor was maintained at 1 MPa for 3 hours. Branch reaction. After the reaction was completed, the pressure of the reactor was returned to normal pressure, the temperature of the reactor was lowered to 70 ° C, and 0.1 part by weight of BHT as a stabilizer was added, and the solution was fed to a drum heated to 160 ° C. In the dryer, the alkalized EVA grafted with maleic anhydride was separated from the solvent, and the amount of the gel in the product was analyzed by weight %. Production Example 8 Grafting was carried out by the same method as in Production Example 7, except that the modified polyolefin was changed from alkalized EVA-1 to alkalized EVA-2 (manufactured by Tosoh Corporation, H-6051K). In the alkalized EVA of maleic anhydride, the amount of gel analysis in the product was 〇% by weight. Production Example 9-166-200925171 The same method as in Production Example 7 except that the modified polyolefin was changed from alkalized EVA-1 to alkalized EVA-3 (manufactured by Tosoh Corporation, H-6960). The alkalized EVA obtained by grafting maleic anhydride was obtained, and the amount of gel analysis in the product was 〇% by weight. Manufacturing Example 10
除了將改性的聚烯烴由鹼化EVA-1變更爲EVA以外 ,藉由與製造例7同樣的手法得到經接枝馬來酸酐之 EVA,生成物中的凝膠量係分析結果爲〇重量%。 製造例1 1 除了將改性的聚烯烴由鹼化EVA-1變更爲L-LDPE以 外,藉由與製造例7同樣的手法得到經接枝馬來酸酐之 L-LDPE,生成物中的凝膠量係分析結果爲〇重量%。 0 製造例12 除了將改性的聚烯烴由鹼化EVA-1變更爲EVA,將 接枝的不飽和羧酸變更爲丙烯酸以外,藉由與製造例7同 樣的手法得到經接枝丙烯酸之EVA,生成物中的凝膠量 係分析結果爲〇重量%。 製造例13 除了將改性的聚烯烴由鹼化EVA-1變更爲L-LDPE , 接枝的不飽和殘酸變更爲丙稀酸以外,藉由與製造例7同 -167- 200925171 樣的手法得到經接枝的丙烯酸之l-ldpe,生成物中的凝 膠量係分析結果爲0重量%。 製造例14The EVA of the grafted maleic anhydride was obtained by the same method as in Production Example 7, except that the modified polyolefin was changed from alkalized EVA-1 to EVA, and the gel amount analysis result in the product was 〇 weight. %. Production Example 1 1 L-LDPE grafted with maleic anhydride was obtained by the same method as in Production Example 7, except that the modified polyolefin was changed from alkalized EVA-1 to L-LDPE. The results of the analysis of the amount of glue were 〇% by weight. 0 Production Example 12 EVA of grafted acrylic acid was obtained by the same method as in Production Example 7, except that the modified polyolefin was changed from alkalized EVA-1 to EVA, and the grafted unsaturated carboxylic acid was changed to acrylic acid. The amount of gelation in the product was analyzed by the weight %. Production Example 13 In the same manner as in Production Example 7, except that the modified polyolefin was changed from alkalized EVA-1 to L-LDPE, and the grafted unsaturated residual acid was changed to acrylic acid, the same procedure as in Production Example 7-167-200925171 was used. The l-ldpe of the grafted acrylic acid was obtained, and the amount of gel analysis in the product was 0% by weight. Manufacturing Example 14
除了將改性的聚烯烴由鹼化EVA-1變更爲EVA,接 枝的不飽和羧酸變更爲甲基丙烯酸以外,藉由與製造例7 同樣的手法甲基得到經接枝丙烯酸之EVA,生成物中的 凝膠量係分析結果爲0重量%。 製造例1 5 除了將改性的聚烯烴由鹼化EVA-1變更爲L-LDPE, 將接枝的不飽和羧酸變更爲甲基丙烯酸以外,藉由與製造 例7同樣的手法甲基得到經接枝的丙烯酸之L-LDPE,生 成物中的凝膠量係分析結果爲0重量%。 〇 製造例16 除了將改性的聚烯烴由鹼化EVA-1變更爲PP,接枝 的不飽和羧酸變更爲甲基丙烯酸以外,藉由與製造例7同 樣的手法得到經接枝甲基丙烯酸之PP,生成物中的凝膠 量係分析結果爲〇重量%。 實施例1 0 7 使製造例7所得到的經接枝馬來酸酐之鹼化EvA1.08g 溶解於1,1,2-三氯乙烷而得到20g的聚合物溶液,於此溶 -168- 200925171 液中添加銀粒子20g,於室溫以超音波洗淨器分散銀粒子 而得到銀粒子均勻地經分散之膏狀液,雖然於室溫使此分 散液放置1週,分散狀態無變化,未見到銀粒子的沈澱, 此外,使用此分散液藉由絲網版印刷印刷法印刷電路於聚 醯亞胺薄膜,於室溫使溶劑揮發後,以220 °C進行熱處理 。所得到的電路的電阻率爲ΙΟμΩοιη,顯示出優良的導電 性,此外,本電路經由使用膠帶的剝離試驗,完全未剝離 ,顯示出與基材的優良的接著性。 實施例108The EVA of the grafted acrylic acid was obtained by changing the modified polyolefin to the EVA from the alkalized EVA-1 to the EVA, and changing the grafted unsaturated carboxylic acid to methacrylic acid by the same methylation method as in Production Example 7. The amount of gel in the product was analyzed by 0% by weight. Production Example 1 5 The modified polyolefin was changed from the alkalized EVA-1 to L-LDPE, and the grafted unsaturated carboxylic acid was changed to methacrylic acid, and the same methyl group as in Production Example 7 was used. The amount of the gel in the product of the grafted acrylic acid L-LDPE was 0% by weight. 〇Production Example 16 A grafted methyl group was obtained by the same method as in Production Example 7, except that the modified polyolefin was changed from alkalized EVA-1 to PP, and the grafted unsaturated carboxylic acid was changed to methacrylic acid. The amount of gel in the PP of acrylic acid was analyzed by the amount of 〇% by weight. Example 1 0 7 The alkalized EvA 1.08 g of the grafted maleic anhydride obtained in Production Example 7 was dissolved in 1,1,2-trichloroethane to obtain 20 g of a polymer solution, and the solution was dissolved in -168- 200925171 20 g of silver particles were added to the solution, and silver particles were dispersed in an ultrasonic cleaner at room temperature to obtain a paste liquid in which silver particles were uniformly dispersed. Although the dispersion was allowed to stand at room temperature for one week, the dispersion state did not change. No precipitation of silver particles was observed. Further, this dispersion was used to print a circuit on a polyimide film by screen printing, and the solvent was volatilized at room temperature, followed by heat treatment at 220 °C. The obtained circuit had a resistivity of ΙΟμΩοηη, and showed excellent conductivity. Further, this circuit was completely peeled off by a peeling test using a tape, and showed excellent adhesion to the substrate. Example 108
將製造例8所得到的經接枝馬來酸酐之鹼化EVA1.08g 溶解於三氯乙烷而得到20g的聚合物溶液,於此溶 液中添加銅粒子26g,於室溫以超音波洗淨器分散銅粒子 而得到銅粒子均勻地經分散之膏狀液,雖然於室溫使此分 散液放置1週,分散狀態無變化,未見到銅粒子的沈澱。 此外,使用此分散液藉由絲網版印刷印刷法印刷電路於聚 醯亞胺薄膜,於室溫使溶劑揮發後,以220°C進行熱處理 。所得到的電路的電阻率爲1 1 μΩ(;ηι,顯示出優良的導電 性,此外,本電路經由使用膠帶的剝離試驗,完全未剝離 ,顯示出與基材的優良的接著性。 實施例109 將製造例9所得到的經接枝馬來酸酐之鹼化EVA1.08g 溶解於1,1,2 -三氯乙烷而得到20g的聚合物溶液,於此溶 -169- 200925171 液中添加鋁16g,於室溫以超音波洗淨器分散鋁粒子而得 到鋁粒子均勻地經分散的膏狀液,雖然於室溫使此分散液 放置1週,分散狀態無變化,未見到鋁粒子的沈澱,此外 ,使用此分散液藉由絲網版印刷印刷法印刷電路於聚醯亞 胺薄膜,於室溫使溶劑揮發後,以220°C進行熱處理。此 外,本電路經由使用膠帶的剝離試驗,完全未剝離,顯示 出與基材的優良的接著性。 〇 實施例1 1 〇1.08 g of alkalized EVA of grafted maleic anhydride obtained in Production Example 8 was dissolved in trichloroethane to obtain 20 g of a polymer solution, and 26 g of copper particles were added to the solution, and ultrasonic cleaning was performed at room temperature. The copper particles were dispersed to obtain a paste liquid in which copper particles were uniformly dispersed. Although the dispersion was allowed to stand at room temperature for one week, there was no change in the dispersion state, and no precipitation of copper particles was observed. Further, using this dispersion, a polyimine film was printed by a screen printing method, and the solvent was volatilized at room temperature, followed by heat treatment at 220 °C. The obtained circuit had a resistivity of 1 1 μΩ (; ηι, which showed excellent conductivity, and this circuit showed no peeling at all by a peeling test using a tape, and showed excellent adhesion to the substrate. 109. 1.08 g of the alkalized EVA of grafted maleic anhydride obtained in Production Example 9 was dissolved in 1,1,2-trichloroethane to obtain 20 g of a polymer solution, which was added to the solution -169-200925171 16 g of aluminum was dispersed in an ultrasonic cleaner at room temperature to obtain a paste liquid in which aluminum particles were uniformly dispersed. Although the dispersion was allowed to stand at room temperature for one week, there was no change in the dispersion state, and no aluminum particles were observed. Further, using this dispersion, a polyimine film was printed by a screen printing method, and the solvent was volatilized at room temperature, and then heat-treated at 220 ° C. Further, the circuit was peeled off by using a tape. The test, which was not peeled at all, showed excellent adhesion to the substrate. 〇 Example 1 1 〇
使製造例1 〇所得到的經接枝馬來酸酐之EVA0.1 g溶 解於1,1,2-三氯乙烷而得到2g的聚合物溶液,於此溶液 中添加金粒子lg,於室溫以超音波洗淨器分散銀粒子而 得到金粒子均勻地經分散的膏狀液,雖然於室溫使此分散 液放置1週,分散狀態無變化,未見到金粒子的沈澱,此 外,使用此分散液藉由絲網版印刷印刷法於聚苯硫醚薄片 上印刷電路,於室溫使溶劑揮發後,以23 0 °C進行熱處理 ,所得到的電路的電阻率爲6μΩ cm ’顯示出優良的導電性 ,此外,本電路經由使用膠帶的剝離試驗,完全未剝離, 顯示出與基材的優良的接著性。 實施例1 1 1 使製造例7所得到的經接枝馬來酸酐之鹼化EVA0 ·05 g 溶解於1,1,2 -三氯乙烷而得到lg的聚合物溶液’於此溶 液中添加銀奈米膏〇 · 5 g ’於室溫以超音波洗淨器分散銀粒 -170- 200925171 子而得到銀粒子均勻地經分散之膏狀的液,雖然於室溫使 此分散液放置1週,分散狀態無變化,未見到銀粒子的沈 澱,此外,使用此分散液藉由絲網版印刷印刷法印刷電路 於聚碳酸酯薄膜,於室溫使溶劑揮發後,以23 0 °C進行熱 處理,所得到的電路的電阻率爲5μΩ(^πι,顯示出優良的導 電性,此外,本電路經由使用膠帶的剝離試驗,完全未剝 離,顯示出與基材的優良的接著性。 ❹ 實施例1 1 2 使製造例11所得到的經接枝馬來酸酐之L-LDPElg 溶解於1,1,2-三氯乙烷而得到20g的聚合物溶液,於此溶 液中添加銀粒子1 6g,於室溫以超音波洗淨器分散銀粒子 而得到銀粒子均勻地經分散之膏狀的液,雖然於室溫使此 分散液放置1週,分散狀態無變化,未見到銀粒子的沈澱 ,此外,使用此分散液藉由絲網版印刷印刷法印刷電路於 Q 聚醯亞胺薄膜,於室溫使溶劑揮發後,以230°C進行熱處 理,所得到的電路的電阻率爲ΙΟμΩοπι,顯示出優良的導 電性,此外,本電路經由使用膠帶的剝離試驗,完全未剝 離,顯示出與基材的優良的接著性。 實施例1 1 3 將製造例12所得到的經接枝丙烯酸之EVA lg溶解於 1,1,2-三氯乙烷而得到20g的聚合物溶液,於此溶液中添 加銀粒子1 2g,於室溫以超音波洗淨器分散銀粒子而得到 -171 - 200925171 銀粒子均勻地經分散之膏狀的液,雖然於室溫使此分散液 放置1週,分散狀態無變化,未見到銀粒子的沈澱,此外 ,使用此分散液藉由絲網版印刷印刷法印刷電路於聚醯亞 胺薄膜,於室溫使溶劑揮發後,以210 °C進行熱處理,所 得到的電路的電阻率爲9 μΩοιη,顯示出優良的導電性,此 外,本電路經由使用膠帶的剝離試驗,完全未剝離,顯示 出與基材的優良的接著性。 〇 實施例1 1 40.1 g of the grafted maleic anhydride-derived EVA obtained in Production Example 1 was dissolved in 1,1,2-trichloroethane to obtain 2 g of a polymer solution, and gold particles lg were added to the solution. In the ultrasonic cleaning device, the silver particles were dispersed to obtain a paste liquid in which the gold particles were uniformly dispersed. Although the dispersion was allowed to stand at room temperature for one week, the dispersion state did not change, and no precipitation of gold particles was observed. Using this dispersion, a circuit was printed on a polyphenylene sulfide sheet by screen printing, and the solvent was volatilized at room temperature, and then heat-treated at 23 ° C, and the obtained circuit had a resistivity of 6 μΩ cm ' Excellent electrical conductivity was obtained, and this circuit showed no peeling at all through the peeling test using a tape, and showed excellent adhesion to the substrate. Example 1 1 1 The alkalized EVA0·05 g of the grafted maleic anhydride obtained in Production Example 7 was dissolved in 1,1,2-trichloroethane to obtain a polymer solution of lg' added to this solution. Silver Nylon paste · 5 g 'Disperse silver particles -170- 200925171 at room temperature in an ultrasonic cleaner to obtain a paste-like liquid in which silver particles are uniformly dispersed, although the dispersion is allowed to stand at room temperature. Week, the dispersion state did not change, no precipitation of silver particles was observed, and in addition, the dispersion was printed on the polycarbonate film by screen printing using the dispersion, and the solvent was volatilized at room temperature at 23 ° C. The heat treatment was performed, and the obtained circuit had a specific resistance of 5 μΩ (^πι, which showed excellent electrical conductivity, and the circuit was completely peeled off by a peeling test using a tape, and showed excellent adhesion to the substrate. Example 1 1 2 L-LDPElg of the grafted maleic anhydride obtained in Production Example 11 was dissolved in 1,1,2-trichloroethane to obtain 20 g of a polymer solution, and silver particles 1 were added to the solution. 6g, dispersing silver particles in an ultrasonic cleaner at room temperature to obtain silver particles A uniformly dispersed paste-like liquid, although the dispersion was allowed to stand at room temperature for one week, the dispersion state did not change, and no precipitation of silver particles was observed, and further, the dispersion was printed by screen printing using the dispersion. The circuit was subjected to a Q polyimine film, and the solvent was volatilized at room temperature, and then heat-treated at 230 ° C. The obtained circuit had a resistivity of ΙΟμΩοπι, which showed excellent conductivity, and the circuit was peeled off by using a tape. The test was not peeled at all, and showed excellent adhesion to the substrate. Example 1 1 3 The grafted acrylic acid EVA lg obtained in Production Example 12 was dissolved in 1,1,2-trichloroethane to obtain 20 g of the polymer solution, 12 g of silver particles were added to the solution, and the silver particles were dispersed in an ultrasonic cleaner at room temperature to obtain a paste-like liquid in which the silver particles were uniformly dispersed, although at room temperature. The dispersion was allowed to stand for 1 week, the dispersion state was unchanged, and no precipitation of silver particles was observed. Further, the dispersion was printed on the polyimide film by screen printing using the dispersion, and the solvent was volatilized at room temperature. After, to 210 C was heat-treated, and the obtained circuit had a specific resistance of 9 μΩ, which showed excellent conductivity. Further, this circuit showed no peeling at all by a peeling test using a tape, and showed excellent adhesion to the substrate. Example 1 1 4
使製造例13所得到的經接枝丙烯酸之L-LDPE1.2g 溶解於1,1,2-三氯乙烷而得到20g的聚合物溶液,於此溶 液中添加銅粒子llg,於室溫以超音波洗淨器分散銅粒子 而得到銅粒子均勻地分散之膏狀液,雖然於室溫使此分散 液放置1週,分散狀態無變化,未見到銅粒子的沈澱。此 外,使用此分散液藉由絲網版印刷印刷法印刷電路於聚醯 亞胺薄膜,於室溫使溶劑揮發後,以21 (TC進行熱處理, 所得到的電路的電阻率爲9μΩ(ηη,顯示出優良的導電性, 此外,本電路經由使用膠帶的剝離試驗,完全未剝離,顯 示出與基材的優良的接著性。 實施例1 1 5 使製造例14所得到的甲基經接枝丙烯酸之EVA0.8g 溶解於1,1,2-三氯乙烷而得到20g的聚合物溶液,於此溶 液中添加銅粒子14g,於室溫以超音波洗淨器分散銅粒子 -172- 200925171 而得到銅粒子均勻地分散之膏狀液,雖然於室溫使此分散 液放置1週,分散狀態無變化,未見到銅粒子的沈澱。此 外,使用此分散液藉由絲網版印刷印刷法印刷電路於聚醯 亞胺薄膜,於室溫使溶劑揮發後,以1 90°c進行熱處理, 所得到的電路的電阻率爲8μΩεϊη,顯示出優良的導電性, 此外,本電路經由使用膠帶的剝離試驗,完全未剝離,顯 示出與基材的優良的接著性。1.2 g of grafted acrylic acid L-LDPE obtained in Production Example 13 was dissolved in 1,1,2-trichloroethane to obtain 20 g of a polymer solution, and 14 g of copper particles were added to the solution at room temperature. The ultrasonic cleaner disperse the copper particles to obtain a paste liquid in which the copper particles were uniformly dispersed. Although the dispersion was allowed to stand at room temperature for one week, the dispersion state did not change, and no precipitation of copper particles was observed. Further, using this dispersion liquid, a polyimine film was printed by a screen printing method, and the solvent was volatilized at room temperature, and then heat-treated at 21 (TC), and the obtained circuit had a resistivity of 9 μΩ (ηη, This circuit showed excellent conductivity, and this circuit showed no adhesion at all through the peeling test using a tape, and showed excellent adhesion to the substrate. Example 1 1 5 The methyl group obtained in Production Example 14 was grafted. Acrylic EVA 0.8g is dissolved in 1,1,2-trichloroethane to obtain 20g of polymer solution, 14g of copper particles are added to the solution, and copper particles are dispersed by ultrasonic cleaning at room temperature -172- 200925171 While the paste liquid in which the copper particles were uniformly dispersed was obtained, the dispersion was allowed to stand at room temperature for one week, and the state of dispersion was not changed, and precipitation of copper particles was not observed. Further, the dispersion was printed by screen printing using the dispersion. The printed circuit is printed on a polyimide film, and the solvent is volatilized at room temperature, and then heat-treated at 1 90 ° C. The obtained circuit has a resistivity of 8 μΩ ε η, which exhibits excellent conductivity, and the circuit uses a tape. Peel test, No separation, displayed an excellent adhesive properties to the substrate.
實施例116Example 116
使製造例15所得到的甲基經接枝丙烯酸之L-LDPE1.4g 溶解於1,1,2 -三氯乙烷而得到20g的聚合物溶液,於此溶 液中添加鋁粒子15g’於室溫以超音波洗淨器分散鋁粒子 而得到鋁粒子均勻地經分散的膏狀液,雖然於室溫使此分 散液放置1週,分散狀態無變化’未見到鋁粒子的沈澱。 此外,使用此分散液藉由絲網版印刷印刷法印刷電路於 PPS薄片,於室溫使溶劑揮發後’以23 0°C進行熱處理, 所得到的電路的電阻率爲12μΩειη’顯示出優良的導電性 ,此外,本電路經由使用膠帶的剝離試驗’完全未利離’ 顯示出與基材的優良的接著性。 實施例1 1 7 使製造例16所得到的甲基經接枝丙烯酸之PP〇.15g 溶解於1,1,2 -三氯乙烷而得到2〇g的聚合物溶液’於此溶 液中添加鐵粒子於室溫以超音波洗淨器分散鐵粒子 -173- 200925171 而得到鐵粒子均勻地經分散的膏狀液,雖然於室溫使此分 散液放置1週,分散狀態無變化,未見到鐵粒子的沈澱。 此外,使用此分散液藉由絲網版印刷印刷法印刷電路於聚 醯亞胺薄膜,於室溫使溶劑揮發後,以230°C進行熱處理 ,所得到的電路的電阻率爲13pQCm,顯示出優良的導電 性’此外,本電路經由使用膠帶的剝離試驗,完全未剝離 ,顯示出與基材的優良的接著性。 〇 比較例4 8 將十二烷胺6g溶解於葱品醇75g後,添加銀粒子 l〇g而得到銀粒子分散液,於此液中添加0.7g的甲基六氫 苯二甲酸酐而得到銀膏,將此銀膏藉由絲網版印刷印刷法 印刷電路於聚苯硫醚薄片,於室溫使溶劑揮發後,以 2 3 0 °C進行熱處理,雖然所得到的電路的電阻率爲8μΩ(ίΐη ’顯示出優良的導電性,但本電路經由使用膠帶的剝離試 〇 驗,剝離頻度爲100/100及容易與基材剝離。 比較例4 9 將比較例48所得到的銀膏藉由絲網版印刷印刷法印 刷電路於聚醯亞胺薄膜上,於室溫使溶劑揮發後,以 23 0 °C進行熱處理,雖然所得到的電路的電阻率爲8μΩ(;Ιη ’顯示出優良的導電性,但本電路經由使用膠帶的剝離試 驗,剝離頻度爲8 0/100及與基材的接著性不足。 -174- 200925171 比較例50 將十二烷胺6g溶解於葱品醇75g後’ 1 〇g而得到銀粒子分散液,於此液中添加〇-7g 苯二甲酸酐、〇.5g的酚樹脂而得到銀膏。 將所得到的銀膏藉由絲網版印刷印刷法印 醯亞胺薄膜上,於室溫使溶劑揮發後,雖然以 熱處理,但皮膜硬化需要70分鐘,雖然所得 0 電阻率爲ΙΟμΩίηη,顯示出優良的導電性,但 使用膠帶的剝離試驗,剝離頻度爲10/100及 著性不足。 比較例5 1 使EVAl.Og溶解於1,1,2-三氯乙烷而得到 物溶液,於此溶液中添加銀粒子1 5 g,於室溫 淨器分散銀粒子而得到膏狀液,於室溫放置此 果,經過1小時鐵粒子沈澱,未顯示出實用的 此液再次用超音波洗淨器分散銀粒子,馬上藉 刷印刷印刷電路於聚醯亞胺薄膜,於室溫使溶 雖然以230°C進行熱處理,但銀粒子沈澱,雖 阻率爲6μΩοιη,顯示出優良的導電性,但本電 接著,經由使用膠帶的剝離試驗,剝離頻度爲 完全看不到接著性。 比較例5 2 添加銀粒子 的甲基六氫 刷電路於聚 2 3 0 °C進行 到的電路的 本電路經由 與基材的接 2〇g的聚合 以超音波洗 分散液的結 分散性。使 由絲網版印 劑揮發後, 然電路的電 路未與基材 100/100 及 -175- 200925171 使L-LDPE1.0g溶解於1,1,2-三氯乙烷而得到20g的The methyl group obtained in Production Example 15 was dissolved in 1,1,2-trichloroethane by dissolving 1.4 g of L-LDPE of grafted acrylic acid to obtain 20 g of a polymer solution, and 15 g of aluminum particles were added to the solution. The aluminum particles were dispersed in the ultrasonic cleaner to obtain a paste liquid in which the aluminum particles were uniformly dispersed. Although the dispersion was allowed to stand at room temperature for one week, there was no change in the dispersion state. No precipitation of aluminum particles was observed. Further, using this dispersion, a PPS sheet was printed by a screen printing method, and the solvent was volatilized at room temperature, and then heat-treated at 23 ° C, and the obtained circuit had a resistivity of 12 μΩ ειη, which showed excellent Conductivity, in addition, this circuit showed excellent adhesion to the substrate via a peeling test using a tape, 'completely undivided'. Example 1 1 7 The methyl group obtained in Production Example 16 was dissolved in PP, 1.5 g of grafted acrylic acid, and dissolved in 1,1,2-trichloroethane to obtain 2 μg of a polymer solution. The iron particles were dispersed in the ultrasonic cleaner at room temperature by an ultrasonic cleaner-173-200925171 to obtain a paste liquid in which iron particles were uniformly dispersed. Although the dispersion was allowed to stand at room temperature for one week, the dispersion state did not change, and no Precipitation to iron particles. Further, using this dispersion liquid, a polyimine film was printed by a screen printing method, and the solvent was volatilized at room temperature, and then heat-treated at 230 ° C. The obtained circuit had a resistivity of 13 pQ Cm, which showed Excellent Conductivity' In addition, this circuit showed no peeling at all through a peeling test using a tape, and showed excellent adhesion to a substrate. 〇Comparative Example 4 8 After dissolving 6 g of dodecylamine in 75 g of onion alcohol, silver particles were added to obtain a silver particle dispersion, and 0.7 g of methylhexahydrophthalic anhydride was added to the solution. Silver paste, the silver paste is printed on a polyphenylene sulfide sheet by screen printing, and the solvent is volatilized at room temperature, and then heat treated at 230 ° C, although the resistivity of the obtained circuit is 8 μΩ (ίΐη ' showed excellent conductivity, but this circuit was tested by peeling using a tape, the peeling frequency was 100/100, and it was easy to peel off from the substrate. Comparative Example 4 9 The silver paste obtained in Comparative Example 48 was borrowed. The printed circuit was printed on a polyimide film by a screen printing method, and the solvent was volatilized at room temperature, and then heat-treated at 23 ° C, although the obtained circuit had a resistivity of 8 μΩ (; Ι η showed excellent Conductivity, but this circuit was subjected to a peeling test using a tape, the peeling frequency was 80/100, and the adhesion to the substrate was insufficient. -174- 200925171 Comparative Example 50 6 g of dodecylamine was dissolved in 75 g of onion alcohol ' 1 〇g to obtain a silver particle dispersion in this solution Adding -7 g of phthalic anhydride and 55 g of phenol resin to obtain a silver paste. The obtained silver paste is printed on a imprinted imide film by screen printing, and the solvent is volatilized at room temperature, although Heat treatment, but the film hardening takes 70 minutes. Although the obtained 0 resistivity is ΙΟμΩ ίηη, which shows excellent electrical conductivity, the peeling test using a tape, the peeling frequency is 10/100 and the originality is insufficient. Comparative Example 5 1 EVAl.Og The solution was dissolved in 1,1,2-trichloroethane, and 15 g of silver particles were added to the solution, and the silver particles were dispersed at room temperature to obtain a paste liquid, and the fruit was allowed to stand at room temperature. 1 hour of iron particle precipitation, did not show a practical use of this liquid again with the ultrasonic cleaner to disperse the silver particles, immediately by printing a printed circuit on the polyimide film, at room temperature to dissolve at 230 ° C, However, the precipitation of silver particles showed a good electrical conductivity although the resistivity was 6 μΩ οιη, but the electric power was subsequently peeled off by using a tape, and the peeling frequency was such that no adhesion was observed at all. Comparative Example 5 2 Addition of methyl groups of silver particles Hexahydro brush The circuit of the circuit which is carried out at a concentration of 230 ° C is ultrasonically washed by the polymerization of 2 〇 g with the substrate to wash the dispersion of the dispersion. After the evaporation of the screen printing agent, the circuit is The circuit was not dissolved with the substrate 100/100 and -175- 200925171, and 1.0 g of L-LDPE was dissolved in 1,1,2-trichloroethane to obtain 20 g.
聚合物溶液,於此溶液中添加銅粒子15g,於室溫以超音 波洗淨器分散銅粒子而得到膏狀液,於室溫放置此分散液 的結果,經過1時間銅粒子沈澱,未顯示出實用的分散性 。將此液再次使用超音波洗淨器分散銀粒子,馬上藉由絲 網版印刷印刷印刷電路於聚醯亞胺薄膜,於室溫使溶劑揮 發後’雖然以220°C進行熱處理,銅粒子沈澱,雖然電路 的電阻率爲7μΩ cm,顯示出優良的導電性,但本電路未與 基材接著,經由使用膠帶的剝離試驗,剝離頻度爲 1 0 0/1 00及全完看不到接著性。 雖然參考特定的實施態樣詳細地說明本發明,但在未 脫離本發明的精神與範圍內,可施加各式各樣的變更或修 正’這點熟悉該技術者當業者應可了解。 本發明係基於2007年8月10日申請的日本特許出願 (特願2007-2104 64 ) 、2007年8月10日申請的日本特 S午出願(特願2007-210465) 、2007年8月17日申請的 曰本特許出願(特願2007-213100) 、2007年9月3日申 請的日本特許出願(特願2007-228055) 、2007年9月6 曰申請的日本特許出願(特願2007-231554) 、2007年 η月13日申請的日本特許出願(特願2007_294826 )、 2007年11月28日申請的日本特許出願(特願2007-3 07897 ) 、2007年11月30日申請的日本特許出願(特 願2007-3 1 0203 ) 、2008年7月11日申請的日本特許出 願(特願2008-181970) 、2008年7月11日申請的日本 -176- 200925171 特許出願(特願2008-181971) 、2008年7月11日申請 的日本特許出願(特願2008- 1 8 1 972 )之發明,其内容參 考此等申請案而援用。 〔產業上可利用性〕 依據本發明,可提供不僅是與塑膠材料,與異種材料 的接著性優異,具有廣泛的有用性之不飽和羧酸接枝聚烯In the polymer solution, 15 g of copper particles were added to the solution, and copper particles were dispersed in an ultrasonic cleaner at room temperature to obtain a paste liquid. The dispersion was allowed to stand at room temperature, and copper particles were precipitated after 1 time, and were not shown. Practical dispersion. The liquid was again dispersed in the ultrasonic cleaner using an ultrasonic cleaner, and the printed circuit was immediately printed on the polyimide film by screen printing. After the solvent was volatilized at room temperature, the copper particles were precipitated after heat treatment at 220 ° C. Although the resistivity of the circuit is 7 μΩ cm, it shows excellent conductivity, but this circuit is not bonded to the substrate, and the peeling frequency is 10 0/1 00 through the peeling test using the tape, and the adhesion is not observed. . While the present invention has been described in detail with reference to the specific embodiments thereof, various modifications and modifications can be applied without departing from the spirit and scope of the invention. This will be understood by those skilled in the art. The present invention is based on the Japanese franchise application (Japanese Patent Application No. 2007-2104 64) filed on August 10, 2007, and the Japanese Special S (Autumn Wish 2007-210465) filed on August 10, 2007, August 17, 2007 Japan's application for the privilege of the Japanese franchise (Special Wish 2007-213100), the Japanese franchise application filed on September 3, 2007 (Special Wish 2007-228055), and the Japanese franchise application for September 6, 2007 (Special Wish 2007- 231,554, Japan's franchise application (2007-294826), which was applied for on November 13th, 2007, Japan's privilege, which was filed on November 28, 2007 (Special Wishes 2007-3 07897), and the Japanese franchise applied for on November 30, 2007 I wished for a wish (2007-3 1 0203), a Japanese franchise application filed on July 11, 2008 (Special Wish 2008-181970), Japan-176-200925171, which was applied for on July 11, 2008. 181971) The invention of the Japanese franchise (Japanese Patent Application No. 2008-181 1 972) filed on July 11, 2008, the contents of which are hereby incorporated by reference. [Industrial Applicability] According to the present invention, it is possible to provide an unsaturated carboxylic acid grafted polyolefin which is excellent in adhesion not only to a plastic material but also to a dissimilar material and has wide usefulness.
烴。 【圖式簡單說明】 〔圖1〕表示使用導電性薄膜之接著測試的試樣構成 之圖。 〔圖2〕表示實施例1〇5中濺鍍放電時的電流與電壓 的關係之圖。 〔圖3〕表示於實施例106中濺鍍放電時的電流與電 壓的關係之圖。 -177-hydrocarbon. BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] is a view showing a configuration of a sample which is subsequently tested using a conductive film. Fig. 2 is a graph showing the relationship between current and voltage at the time of sputtering discharge in the first embodiment. Fig. 3 is a graph showing the relationship between current and voltage at the time of sputtering discharge in Example 106. -177-
Claims (1)
Applications Claiming Priority (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2007210464A JP5584952B2 (en) | 2007-08-10 | 2007-08-10 | Process for producing unsaturated carboxylic acid grafted polyolefin |
JP2007210465A JP5417692B2 (en) | 2007-08-10 | 2007-08-10 | Process for producing modified polyolefin |
JP2007213100A JP2009045799A (en) | 2007-08-17 | 2007-08-17 | Multilayer laminated body and its manufacturing method |
JP2007228055A JP5104132B2 (en) | 2007-09-03 | 2007-09-03 | Multilayer laminate |
JP2007231554A JP5158332B2 (en) | 2007-09-06 | 2007-09-06 | Flexible wiring film and manufacturing method thereof |
JP2007294826A JP2009120678A (en) | 2007-11-13 | 2007-11-13 | Inorganic fine particle dispersion |
JP2007307897A JP2009135605A (en) | 2007-11-28 | 2007-11-28 | Film antenna |
JP2007310203A JP5458488B2 (en) | 2007-11-30 | 2007-11-30 | Conductive film, sputtering target using the same, and method for producing sputtering target |
JP2008181972A JP2010017974A (en) | 2008-07-11 | 2008-07-11 | Multilayered laminate |
JP2008181970A JP5169561B2 (en) | 2008-07-11 | 2008-07-11 | Unsaturated carboxylic acid grafted polyolefin and process for producing the same |
JP2008181971A JP2010017973A (en) | 2008-07-11 | 2008-07-11 | Multilayered laminated body and its manufacturing method |
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TW200925171A true TW200925171A (en) | 2009-06-16 |
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Application Number | Title | Priority Date | Filing Date |
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TW97130477A TW200925171A (en) | 2007-08-10 | 2008-08-08 | Unsaturated carboxylic acid-grafted polyolefin and its manufacturing method |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103339290A (en) * | 2010-11-24 | 2013-10-02 | 普兰西公司 | Method for separating a target of a rotary target |
CN111333991A (en) * | 2020-04-09 | 2020-06-26 | 安徽松泰包装材料有限公司 | High-temperature-resistant composite packaging film and preparation method thereof |
CN115734989A (en) * | 2020-07-28 | 2023-03-03 | 三菱工程塑料株式会社 | Resin composition, molded article, and method for producing molded article with plated product |
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2008
- 2008-08-08 TW TW97130477A patent/TW200925171A/en unknown
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103339290A (en) * | 2010-11-24 | 2013-10-02 | 普兰西公司 | Method for separating a target of a rotary target |
CN103339290B (en) * | 2010-11-24 | 2015-09-02 | 普兰西公司 | For separating of the method for the target of rotary target |
CN111333991A (en) * | 2020-04-09 | 2020-06-26 | 安徽松泰包装材料有限公司 | High-temperature-resistant composite packaging film and preparation method thereof |
CN111333991B (en) * | 2020-04-09 | 2023-01-13 | 安徽松泰包装材料有限公司 | High-temperature-resistant composite packaging film and preparation method thereof |
CN115734989A (en) * | 2020-07-28 | 2023-03-03 | 三菱工程塑料株式会社 | Resin composition, molded article, and method for producing molded article with plated product |
CN115734989B (en) * | 2020-07-28 | 2024-04-16 | 三菱工程塑料株式会社 | Resin composition, molded article, and method for producing molded article with plated material |
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