TWI473855B - Resin composition, fluorine-based resin composite including the same and method for manufacturing the same - Google Patents
Resin composition, fluorine-based resin composite including the same and method for manufacturing the same Download PDFInfo
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Description
本發明是有關於一種接著氟系樹脂之樹脂組成物、包含此樹脂組成物的氟系樹脂複合材及其製造方法。The present invention relates to a resin composition of a fluorine-based resin, a fluorine-based resin composite containing the resin composition, and a method for producing the same.
為了讓戶外用布料具有良好的耐候性，大多是將耐候性良好的氟系樹脂塗佈於基材上。然而，氟系樹脂層僅以物理方式接著基材，使得氟系樹脂層與基材間的黏著力不佳。在一段時間後，氟系樹脂層將會逐漸剝離，而使基材失去原有的耐候性。In order to make the outdoor fabric have good weather resistance, a fluorine-based resin having good weather resistance is often applied to a substrate. However, the fluorine-based resin layer only physically closes the substrate, so that the adhesion between the fluorine-based resin layer and the substrate is not good. After a period of time, the fluorine-based resin layer will gradually peel off, and the substrate loses its original weather resistance.
另一方面，也可藉由接著劑將氟系樹脂層貼合於基材上。但氟系樹脂的主鏈上的氫原子少，故將氟系樹脂層藉由一般的接著劑貼合於基材上，仍難以達到足夠的接著強度。若接著劑本身的耐候性不足，在長時間使用的情況下，氟系樹脂層仍可能會剝離。On the other hand, the fluorine-based resin layer may be bonded to the substrate by an adhesive. However, since the fluorine-based resin has a small number of hydrogen atoms in the main chain, it is difficult to achieve sufficient adhesion strength by bonding the fluorine-based resin layer to the substrate by a general adhesive. If the weather resistance of the adhesive itself is insufficient, the fluorine-based resin layer may peel off even when used for a long period of time.
因此，相關領域亟需一種對於氟系樹脂具有高黏著性且具有良好耐候性的接著劑，以期能提高氟系樹脂複合材的使用壽命。Therefore, there is a need in the related art for an adhesive having high adhesion to a fluorine-based resin and having good weather resistance, in order to improve the service life of the fluorine-based resin composite.
本發明提供一種對於氟系樹脂具有高黏著性且具有良好耐候性的樹脂組成物，而可有效地黏著氟系樹脂於各種基材上。The present invention provides a resin composition which has high adhesion to a fluorine-based resin and has good weather resistance, and can effectively adhere a fluorine-based resin to various substrates.
本發明之一態樣係提供一種用於接著氟系樹脂之樹脂組成物，其包含環氧樹脂與胺基聚矽氧烷。胺基聚矽氧烷是由胺基烷氧基矽烷與芳香族烷氧基矽烷進行水解縮合反應而形成。樹脂組成物與環氧樹脂之環氧基之莫耳比值為0.06至0.77。One aspect of the present invention provides a resin composition for a fluorine-based resin comprising an epoxy resin and an amine polyoxyalkylene. The amine polyoxyalkylene is formed by a hydrolysis condensation reaction of an amino alkoxydecane with an aromatic alkoxydecane. The molar ratio of the epoxy group of the resin composition to the epoxy resin is from 0.06 to 0.77.
根據本發明之一實施方式，胺基烷氧基矽烷與芳香族烷氧基矽烷之莫耳比值為1/3至1/1。According to an embodiment of the present invention, the molar ratio of the amino alkoxydecane to the aromatic alkoxydecane is 1/3 to 1/1.
根據本發明之一實施方式，胺基聚矽氧烷與環氧樹脂之重量比為1：20至4.5：10。According to an embodiment of the invention, the weight ratio of the amine polysiloxane to the epoxy resin is from 1:20 to 4.5:10.
根據本發明之一實施方式，樹脂組成物之無機矽之含量為1.0至5.0 wt%。According to an embodiment of the present invention, the content of the inorganic cerium of the resin composition is from 1.0 to 5.0% by weight.
根據本發明之一實施方式，胺基烷氧基矽烷之化學式為H2 N-R3 -Si(R2 )a (OR1 )3-a ，其中R1 、R2 為H或C1-C4烷基，a為0或1，R3 為C1-C10之烷基或R5 -NH-R4 ，R4 、R5 為C1-C10之烷基。According to an embodiment of the present invention, the amino alkoxydecane has the formula H 2 NR 3 -Si(R 2 ) a (OR 1 ) 3-a , wherein R 1 and R 2 are H or a C1-C4 alkyl group. , a is 0 or 1, R 3 is a C1-C10 alkyl group or R 5 -NH-R 4 , and R 4 and R 5 are a C1-C10 alkyl group.
根據本發明之一實施方式，芳香族烷氧基矽烷之化學式為R8 -Si(R7 )b (OR6 )3-b ，其中R6 、R7 為H或C1-C4烷基，b為0或1，R8 係選自由取代或無取代之苯基、取代或無取代之聯苯基、取代或無取代之萘基及其組合所構成之群組。According to an embodiment of the present invention, the aromatic alkoxydecane has the formula R 8 -Si(R 7 ) b (OR 6 ) 3-b , wherein R 6 and R 7 are H or a C1-C4 alkyl group, b R 0 or 1, R 8 is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, and combinations thereof.
本發明之另一態樣係提供一種用於接著氟系樹脂之樹脂組成物之製造方法，包含下列步驟。混合胺基烷氧基矽烷與芳香族烷氧基矽烷，以形成胺基聚矽氧烷。混合環氧樹脂與胺基聚矽氧烷，以形成樹脂組成物，其中樹脂組成物與環氧樹脂之環氧基之莫耳比值為0.06至0.77。Another aspect of the present invention provides a method for producing a resin composition for a fluorine-based resin, comprising the following steps. The amine alkoxy decane is mixed with an aromatic alkoxy decane to form an amine polyoxy siloxane. The epoxy resin and the amine polysiloxane are mixed to form a resin composition in which the molar ratio of the epoxy group of the resin composition to the epoxy resin is from 0.06 to 0.77.
根據本發明之一實施方式，胺基烷氧基矽烷與芳香族 烷氧基矽烷之莫耳比值為1/3至1/1。According to one embodiment of the invention, the amino alkoxy decane and the aromatic The alkoxydecane has a molar ratio of 1/3 to 1/1.
根據本發明之一實施方式，胺基聚矽氧烷與環氧樹脂之重量比為1：20至4.5：10。According to an embodiment of the invention, the weight ratio of the amine polysiloxane to the epoxy resin is from 1:20 to 4.5:10.
根據本發明之一實施方式，胺基烷氧基矽烷之化學式為H2 N-R3 -Si(R2 )a (OR1 )3-a ，其中R1 、R2 為H或C1-C4烷基，a為0或1，R3 為C1-C10之烷基或R5 -NH-R4 ，R4 、R5 為C1-C10之烷基。According to an embodiment of the present invention, the amino alkoxydecane has the formula H 2 NR 3 -Si(R 2 ) a (OR 1 ) 3-a , wherein R 1 and R 2 are H or a C1-C4 alkyl group. , a is 0 or 1, R 3 is a C1-C10 alkyl group or R 5 -NH-R 4 , and R 4 and R 5 are a C1-C10 alkyl group.
根據本發明之一實施方式，芳香族烷氧基矽烷之化學式為R8 -Si(R7 )b (OR6 )3-b ，其中R6 、R7 為H或C1-C4烷基，b為0或1，R8 係選自由取代或無取代之苯基、取代或無取代之聯苯基、取代或無取代之萘基及其組合所構成之群組。According to an embodiment of the present invention, the aromatic alkoxydecane has the formula R 8 -Si(R 7 ) b (OR 6 ) 3-b , wherein R 6 and R 7 are H or a C1-C4 alkyl group, b R 0 or 1, R 8 is selected from the group consisting of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, and combinations thereof.
根據本發明之一實施方式，胺基烷氧基矽烷與該芳香族烷氧基矽烷是於酸性環境下進行混合。According to an embodiment of the invention, the amino alkoxydecane and the aromatic alkoxy decane are mixed in an acidic environment.
根據本發明之一實施方式，酸性環境之pH值為1至3。According to one embodiment of the invention, the pH of the acidic environment is from 1 to 3.
本發明之另一態樣係提供一種氟系樹脂複合材之製造方法，包含下列步驟。提供一基材。形成一接著劑層於基材上，其中接著劑層包含上述之樹脂組成物。於90至120℃之環境下接著具有羥基之氟系樹脂層於接著劑層上。Another aspect of the present invention provides a method for producing a fluorine-based resin composite comprising the following steps. A substrate is provided. An adhesive layer is formed on the substrate, wherein the adhesive layer comprises the above resin composition. A fluorine-based resin layer having a hydroxyl group is then applied to the adhesive layer in an environment of 90 to 120 °C.
本發明之另一態樣係提供一種氟系樹脂複合材，由上述製造方法製造而得。Another aspect of the present invention provides a fluorine-based resin composite obtained by the above production method.
根據本發明之一實施方式，基材包含聚酯、玻璃纖維或其組合。According to an embodiment of the invention, the substrate comprises polyester, glass fibers or a combination thereof.
以下將以圖式揭露本發明之複數個實施方式，為明確 說明起見，許多實務上的細節將在以下敘述中一併說明。然而，應瞭解到，這些實務上的細節不應用以限制本發明。也就是說，在本發明部分實施方式中，這些實務上的細節是非必要的。此外，為簡化圖式起見，一些習知慣用的結構與元件在圖式中將以簡單示意的方式繪示之。In the following, a plurality of embodiments of the present invention will be disclosed in the drawings. For the sake of explanation, many practical details will be explained in the following description. However, it should be understood that these practical details are not intended to limit the invention. That is, in some embodiments of the invention, these practical details are not necessary. In addition, some of the conventional structures and elements are shown in the drawings in a simplified schematic manner in order to simplify the drawings.
本發明之一態樣係提供一種用於接著氟系樹脂之樹脂組成物的製造方法，包含下列步驟。混合胺基烷氧基矽烷與芳香族烷氧基矽烷，以形成胺基聚矽氧烷。混合環氧樹脂與胺基聚矽氧烷，以形成樹脂組成物，其中樹脂組成物與環氧樹脂之環氧基之莫耳比值為0.06至0.77。換言之，所合成的樹脂組成物中仍含有未反應的環氧基。未反應的環氧基可與氟系樹脂的羥基進行反應而形成化學鍵結，提昇樹脂組成物與氟系樹脂之間的黏著力。並且，胺基聚矽氧烷可提供良好的耐熱性。綜上所述，本發明之樹脂組成物對於氟系樹脂具有高黏著性，也具備有良好的耐熱性，而可有效地幫助氟系樹脂黏著於各種基材上。而上述製造方法的各個步驟的具體實施方式詳述如下。One aspect of the present invention provides a method for producing a resin composition for a fluorine-based resin, which comprises the following steps. The amine alkoxy decane is mixed with an aromatic alkoxy decane to form an amine polyoxy siloxane. The epoxy resin and the amine polysiloxane are mixed to form a resin composition in which the molar ratio of the epoxy group of the resin composition to the epoxy resin is from 0.06 to 0.77. In other words, the synthesized resin composition still contains an unreacted epoxy group. The unreacted epoxy group reacts with the hydroxyl group of the fluorine-based resin to form a chemical bond, thereby enhancing the adhesion between the resin composition and the fluorine-based resin. Also, the amine polyoxyalkylene can provide good heat resistance. As described above, the resin composition of the present invention has high adhesion to a fluorine-based resin and also has good heat resistance, and can effectively help the fluorine-based resin adhere to various substrates. Specific embodiments of the respective steps of the above manufacturing method are detailed below.
首先，混合至少一胺基烷氧基矽烷與至少一芳香族烷氧基矽烷，使其進行水解縮合反應，而形成胺基聚矽氧烷。詳細而言，胺基烷氧基矽烷與芳香族烷氧基矽烷的烷氧基可先水解形成羥基，再脫水縮合形成矽氧鍵結。以巨觀來看，在胺基烷氧基矽烷與芳香族烷氧基矽烷進行水解縮合反應後，即形成一種包含有無機矽氧結構及有機官能基(即芳香族基團及胺基等)的胺基聚矽氧烷。First, at least one amino alkoxydecane and at least one aromatic alkoxy decane are mixed and subjected to a hydrolysis condensation reaction to form an amine polysiloxane. In detail, the alkoxy group of the amino alkoxydecane and the aromatic alkoxydecane may be hydrolyzed to form a hydroxyl group, and then dehydrated and condensed to form a oxime bond. In a macroscopic view, after the hydrolysis and condensation reaction of the amino alkoxy decane with the aromatic alkoxy decane, an inorganic oxime structure and an organic functional group (ie, an aromatic group, an amine group, etc.) are formed. Amine polyoxyalkylene.
胺基烷氧基矽烷之化學式為H2 N-R3 -Si(R2 )a (OR1 )3-a ， 其中R1 、R2 為H或C1-C4烷基，a為0或1，R3 為C1-C10之烷基或R5 -NH-R4 ，R4 、R5 為C1-C10之烷基。胺基烷氧基矽烷可包含一級胺基、二級胺基或其組合。舉例來說，胺基烷氧基矽烷可為N-[3-(三甲氧基矽基)丙基]乙二胺(N-[3-(trimethoxysilyl)propyl]ethylenediamine)或3-氨基丙基三乙氧基矽烷(3-aminopropyltriethoxysilane)。胺基烷氧基矽烷的胺基可與環氧樹脂的環氧基進行開環反應，形成化學鍵結。The amino alkoxydecane has the formula H 2 NR 3 -Si(R 2 ) a (OR 1 ) 3-a , wherein R 1 and R 2 are H or a C1-C4 alkyl group, and a is 0 or 1, R 3 is a C1-C10 alkyl group or R 5 -NH-R 4 , and R 4 and R 5 are a C1-C10 alkyl group. The amino alkoxydecane may comprise a primary amine group, a secondary amine group or a combination thereof. For example, the amino alkoxydecane can be N-[3-(trimethoxysilyl)propyl]ethylenediamine or 3-aminopropyltri 3-aminopropyltriethoxysilane. The amine group of the amino alkoxydecane may undergo a ring opening reaction with an epoxy group of the epoxy resin to form a chemical bond.
芳香族烷氧基矽烷之化學式為R8 -Si(R7 )b (OR6 )3-b ，其中R6 、R7 為H或C1-C4烷基，b為0或1，R8 係選自由取代或無取代之苯基、取代或無取代之聯苯基、取代或無取代之萘基及其組合所構成之群組。也就是說，芳香族烷氧基矽烷的R8 具有至少一苯基，使芳香族烷氧基矽烷具有良好的耐熱性。芳香族烷氧基矽烷例如為三乙氧基苯矽烷(phenyltriethoxysilane)或萘基三乙氧基矽烷(naphthyltriethoxysilane)。The aromatic alkoxydecane has the formula R 8 -Si(R 7 ) b (OR 6 ) 3-b , wherein R 6 and R 7 are H or a C1-C4 alkyl group, b is 0 or 1, and the R 8 system is A group of freely substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, and combinations thereof. That is, R 8 of the aromatic alkoxydecane has at least one phenyl group, and the aromatic alkoxydecane has good heat resistance. The aromatic alkoxy decane is, for example, phenyltriethoxysilane or naphthyltriethoxysilane.
在一實施方式中，胺基烷氧基矽烷與芳香族烷氧基矽烷之莫耳比值為1/3至1/1。若芳香族烷氧基矽烷佔整體的比例過高(即莫耳比值小於1/3)，將使胺基聚矽氧烷的分子鏈過長，導致後續胺基與環氧基的反應碰撞機率降低，反應時間增加。因此，胺基烷氧基矽烷與芳香族烷氧基矽烷的莫耳比值較佳大於1/3。In one embodiment, the molar ratio of the amino alkoxydecane to the aromatic alkoxydecane is from 1/3 to 1/1. If the ratio of aromatic alkoxy decane to the whole is too high (ie, the molar ratio is less than 1/3), the molecular chain of the amine polyoxyalkylene will be too long, resulting in the collision probability of subsequent amine groups and epoxy groups. Lower, the reaction time increases. Therefore, the molar ratio of the amino alkoxydecane to the aromatic alkoxydecane is preferably more than 1/3.
在一實施方式中，胺基烷氧基矽烷與芳香族烷氧基矽烷是於酸性環境下進行混合。酸性環境之pH值例如為1至3。反應溫度例如為30至50℃。在上述的製程條件下， 所形成的胺基聚矽氧烷包含無機矽氧結構，而能夠提供良好的耐熱性。In one embodiment, the amino alkoxydecane and the aromatic alkoxy decane are mixed in an acidic environment. The pH of the acidic environment is, for example, from 1 to 3. The reaction temperature is, for example, 30 to 50 °C. Under the above process conditions, The amine-based polyoxyalkylene formed contains an inorganic oxime structure and can provide good heat resistance.
於形成胺基矽氧烷之後，再混合環氧樹脂與胺基聚矽氧烷，以形成樹脂組成物。詳細而言，胺基聚矽氧烷結構外露的胺基能與環氧樹脂的環氧基進行開環反應，形成包含有機交聯結構、無機矽氧結構以及環氧基的樹脂組成物。環氧基可用以與氟系樹脂的羥基進行反應，形成化學鍵結，而能夠提昇樹脂組成物與氟系樹脂之間的黏著力。After the formation of the amine siloxane, the epoxy resin and the amine polyoxyalkylene are further mixed to form a resin composition. In detail, the exposed amine group of the amine polyoxyalkylene structure can undergo a ring-opening reaction with an epoxy group of the epoxy resin to form a resin composition containing an organic crosslinked structure, an inorganic oxime structure, and an epoxy group. The epoxy group can be reacted with a hydroxyl group of the fluorine-based resin to form a chemical bond, and the adhesion between the resin composition and the fluorine-based resin can be enhanced.
上述環氧樹脂例如為雙酚A型環氧樹脂、雙酚P型環氧樹脂、溴化雙酚型環氧樹脂、聯苯基型環氧樹脂、脂環狀環氧樹脂、縮水甘油酯型環氧樹脂、縮水甘油胺型環氧樹脂、其他適合的環氧樹脂或上述之組合，但不限於此。The epoxy resin is, for example, a bisphenol A type epoxy resin, a bisphenol P type epoxy resin, a brominated bisphenol type epoxy resin, a biphenyl type epoxy resin, a lipid cyclic epoxy resin, or a glycidyl ester type. Epoxy resin, glycidylamine type epoxy resin, other suitable epoxy resin or a combination thereof, but are not limited thereto.
重要的是，製得的樹脂組成物與環氧樹脂之環氧基之莫耳比值為0.06至0.77。亦即胺基烷氧基矽烷與環氧樹脂反應後，剩下6%至77%的環氧基數量(相對於原環氧樹脂的環氧基數量)。例如可利用環氧當量測定法，分別測試環氧樹脂與樹脂組成物的環氧當量。「環氧當量」是指含有一當量環氧基的環氧樹脂克數。而環氧樹脂與樹脂組成物的環氧當量的比值即為樹脂組成物與環氧樹脂的環氧基的莫耳比值。It is important that the molar ratio of the epoxy resin obtained to the epoxy resin of the epoxy resin is from 0.06 to 0.77. That is, after the amino alkoxydecane is reacted with the epoxy resin, the amount of epoxy groups (relative to the number of epoxy groups of the original epoxy resin) is left from 6% to 77%. For example, the epoxy equivalent of the epoxy resin and the resin composition can be separately tested by an epoxy equivalent method. "Epoxy equivalent" means the number of grams of epoxy resin containing one equivalent of an epoxy group. The ratio of the epoxy equivalent of the epoxy resin to the resin composition is the molar ratio of the epoxy resin composition to the epoxy group.
環氧當量測定法簡述如下。首先將鹽酸加入待測物，讓所有的環氧基開環，再利用氫氧化鈉甲醇溶液滴定未反應的鹽酸分子，即可計算出環氧當量。計算方式如下式(1)所示：
W為待測物重(單位：克)，N為標準氫氧化鈉甲醇溶液的濃度(單位：當量/公升)。Vb為空白試驗時氫氧化鈉的消耗量(毫升)，Vs為滴定待測物時氫氧化鈉的消耗量(毫升)。若待測物的環氧基數量越多，則滴定待測物時氫氧化鈉的消耗量越少(亦即未反應的鹽酸分子較少)。若待測物的環氧基數量越少，則滴定待測物時氫氧化鈉的消耗量越多(亦即未反應的鹽酸分子較多)。因此，環氧基數量多的待測物的環氧當量較低，環氧基數量少的待測物的環氧當量較高。W is the weight of the analyte (unit: gram), and N is the concentration of the standard sodium hydroxide methanol solution (unit: equivalent / liter). Vb is the consumption of sodium hydroxide (ml) in the blank test, and Vs is the consumption of sodium hydroxide (ml) when the analyte is titrated. If the amount of epoxy groups of the analyte is larger, the amount of sodium hydroxide consumed when the analyte is titrated is less (that is, less unreacted hydrochloric acid molecules). If the amount of epoxy groups of the analyte is smaller, the amount of sodium hydroxide consumed when the analyte is titrated is increased (that is, the amount of unreacted hydrochloric acid molecules is larger). Therefore, the epoxy equivalent of the analyte having a large amount of epoxy groups is low, and the epoxy equivalent of the analyte having a small amount of epoxy groups is high.
具體的環氧當量測定方法例示如下。首先，將8.5毫升鹽酸與50毫升吡啶配製成一鹽酸-吡啶溶液。將25毫升0.2N的鹽酸-吡啶溶液加至裝有0.5克的樹脂組成物的錐形瓶中，於40℃下恆溫40分鐘。然後，將錐形瓶於115℃油浴中迴流30分鐘，再冷卻至室溫，並加入25毫升甲醇至錐形瓶中。隨後，加入酚酞指示劑，並以氫氧化鈉滴定，而可得到滴定待測物時氫氧化鈉的消耗量(Vs)。另外，取用25毫升0.2N的鹽酸-吡啶溶液混合25毫升甲醇，以相同於上述的方式滴定，可得到空白試驗時氫氧化鈉的消耗量(Vb)。再經由式(1)，即可計算出待測物的環氧當量。The specific epoxy equivalent measurement method is exemplified as follows. First, 8.5 ml of hydrochloric acid and 50 ml of pyridine were combined to form a hydrochloric acid-pyridine solution. 25 ml of a 0.2 N hydrochloric acid-pyridine solution was added to an Erlenmeyer flask containing 0.5 g of the resin composition, and the temperature was kept at 40 ° C for 40 minutes. Then, the Erlenmeyer flask was refluxed in an oil bath at 115 ° C for 30 minutes, cooled to room temperature, and 25 ml of methanol was added to the Erlenmeyer flask. Subsequently, a phenolphthalein indicator is added and titrated with sodium hydroxide to obtain a consumption amount (Vs) of sodium hydroxide when the analyte is titrated. Further, 25 ml of a 0.2 N hydrochloric acid-pyridine solution was mixed with 25 ml of methanol, and titrated in the same manner as above to obtain a sodium hydroxide consumption (Vb) in the blank test. Then, by the formula (1), the epoxy equivalent of the analyte can be calculated.
在一實施方式中，胺基聚矽氧烷與環氧樹脂之重量比為1：20至4.5：10。若胺基聚矽氧烷與環氧樹脂的重量比大於4.5：10(亦即胺基聚矽氧烷佔總重的重量百分比大於31%)，則剩餘環氧基的數量太少，將嚴重影響樹脂組成物 與氟系樹脂間的黏著力。但若胺基聚矽氧烷與環氧樹脂的重量比小於1：20(亦即胺基聚矽氧烷佔總重的重量百分比小於0.48%)，則環氧樹脂的交聯比例低且無機矽氧結構太少，將影響樹脂組成物的剛性及耐熱性。因此，胺基聚矽氧烷與環氧樹脂之重量比較佳介於1：20至4.5：10。In one embodiment, the weight ratio of amine polysiloxane to epoxy resin is from 1:20 to 4.5:10. If the weight ratio of the amine polyoxyalkylene to the epoxy resin is greater than 4.5:10 (ie, the weight percentage of the amine polyoxyalkylene to the total weight is greater than 31%), the amount of remaining epoxy groups is too small and will be severe. Affecting resin composition Adhesion to fluorine resin. However, if the weight ratio of the amine polysiloxane to the epoxy resin is less than 1:20 (that is, the weight percentage of the amine polysiloxane is less than 0.48%), the crosslinking ratio of the epoxy resin is low and inorganic. Too little oxygen structure will affect the rigidity and heat resistance of the resin composition. Therefore, the weight of the amine polyoxyalkylene and the epoxy resin is preferably from 1:20 to 4.5:10.
本發明之另一態樣係提供一種用於接著氟系樹脂之樹脂組成物，包含環氧樹脂與胺基聚矽氧烷。在一實施方式中，此樹脂組成物內沒有溶劑。環氧樹脂與胺基聚矽氧烷的具體實施方式請參照上述的實施方式。由於樹脂組成物包含可與氟系樹脂的羥基進行反應的環氧基，故樹脂組成物與氟系樹脂之間能夠形成良好的黏著力。Another aspect of the present invention provides a resin composition for a fluorine-based resin comprising an epoxy resin and an amine polyoxyalkylene. In one embodiment, there is no solvent in the resin composition. For specific embodiments of the epoxy resin and the amine polyoxyalkylene, please refer to the above embodiments. Since the resin composition contains an epoxy group which can react with the hydroxyl group of the fluorine-based resin, a good adhesion can be formed between the resin composition and the fluorine-based resin.
在一實施方式中，樹脂組成物的無機矽含量為1.0至5.0 wt%。例如可將硬化後的樹脂組成物進行EDX元素分析，可得到無機矽含量。或者，可將硬化後的樹脂組成物利用熱重分析儀(thermogravimetric analysis)於空氣環境下，以10℃/分鐘的升溫速率升溫至700℃。而在700℃下的待測物的剩餘重量，即為無機矽含量。In one embodiment, the resin composition has an inorganic cerium content of 1.0 to 5.0 wt%. For example, the resin composition after hardening can be subjected to EDX elemental analysis to obtain an inorganic cerium content. Alternatively, the cured resin composition may be heated to 700 ° C at a temperature increase rate of 10 ° C / min using a thermogravimetric analysis in an air atmosphere. The residual weight of the analyte at 700 ° C is the inorganic cerium content.
請參照第1圖，本發明之又一態樣係提供一種氟系樹脂複合材10的製造方法，包含下列步驟。Referring to Fig. 1, another aspect of the present invention provides a method for producing a fluorine-based resin composite material 10, which comprises the following steps.
首先，提供一基材110。在一實施方式中，基材110包含聚酯、玻璃纖維或其組合。具體而言，基材110例如為聚酯布或玻璃纖維布，但不限於此。First, a substrate 110 is provided. In an embodiment, the substrate 110 comprises polyester, fiberglass, or a combination thereof. Specifically, the substrate 110 is, for example, a polyester cloth or a glass cloth, but is not limited thereto.
然後，形成一接著劑層120於基材110上，其中接著劑層120包含上述之樹脂組成物。例如可使用任何塗佈方式形成接著劑層120於基材110上。在一實施方式中，接 著劑層120的厚度為0.05至0.15毫米。當然，也可於形成接著劑層120之後進行一加熱步驟，使接著劑層120處於半濕半乾的未成膜狀態(亦即未完全乾燥狀態)。在一實施方式中，加熱溫度為85至100℃。Then, an adhesive layer 120 is formed on the substrate 110, wherein the adhesive layer 120 contains the above-described resin composition. The adhesive layer 120 can be formed on the substrate 110, for example, using any coating method. In an embodiment, the connection The thickness of the primer layer 120 is 0.05 to 0.15 mm. Of course, a heating step may be performed after the formation of the adhesive layer 120, so that the adhesive layer 120 is in a semi-wet and semi-dry unfilmed state (that is, in an incompletely dried state). In one embodiment, the heating temperature is from 85 to 100 °C.
於形成接著劑層120後，再於90至120℃之環境下接著具有羥基之氟系樹脂層130於接著劑層120上。詳細而言，可先形成一層具有羥基之氟系樹脂層130於接著劑層120上，再進行加熱溫度為90至120℃的乾燥製程。在一實施方式中，具有羥基之氟系樹脂層130的厚度為0.20至0.40毫米。After the formation of the adhesive layer 120, the fluorine-based resin layer 130 having a hydroxyl group is then deposited on the adhesive layer 120 in an environment of 90 to 120 °C. Specifically, a fluorine-based resin layer 130 having a hydroxyl group may be first formed on the adhesive layer 120, and then a drying process at a heating temperature of 90 to 120 ° C may be performed. In one embodiment, the fluorine-based resin layer 130 having a hydroxyl group has a thickness of 0.20 to 0.40 mm.
具有羥基之氟系樹脂層130的材料為一種氟系樹脂塗料，其可包含具有羥基之氟系樹脂以及溶劑。The material of the fluorine-based resin layer 130 having a hydroxyl group is a fluorine-based resin coating material, and may contain a fluorine-based resin having a hydroxyl group and a solvent.
具有羥基之氟系樹脂例如為含有羥基支鏈的聚乙烯及氟碳聚合物聚合而成的共聚物。氟碳聚合物例如為聚氟乙烯(polyvinyl fluoride,PVF)、聚偏二氟乙烯(polyvinylidene difluoride PVDF)、聚四氟乙烯(polytetrafluoroethylene,PTFE)、乙烯四氟乙烯系共聚物(ethylene tetrafluoroethylene,ETFE)，但不限於此。溶劑例如為乙酸丁酯(butyl acetate)、二甲苯(xylene)、煤焦油精(coal-tar naphtha)或其組合。The fluorine-based resin having a hydroxyl group is, for example, a copolymer obtained by polymerizing a hydroxyl group-containing polyethylene and a fluorocarbon polymer. The fluorocarbon polymer is, for example, polyvinyl fluoride (PVF), polyvinylidene difluoride (PVDF), polytetrafluoroethylene (PTFE), or ethylene tetrafluoroethylene (ETFE). , but not limited to this. The solvent is, for example, butyl acetate, xylene, coal-tar naphtha or a combination thereof.
氟系樹脂塗料例如為市售型號為ZEFFLE GK570、GK500、GK510、GK550、GK580的氟碳樹脂，但不限於此。此類具有羥基之氟碳樹脂的部分化學結構如化學式(1)所示。The fluorine-based resin coating material is, for example, a fluorocarbon resin commercially available as ZEFFLE GK570, GK500, GK510, GK550, or GK580, but is not limited thereto. The partial chemical structure of such a fluorocarbon resin having a hydroxyl group is as shown in the chemical formula (1).
化學式(1)中的Y可為任何適合的官能基。m、n、x值可分別為任何整數。Y in the formula (1) may be any suitable functional group. The m, n, and x values can be any integer, respectively.
在一實施方式中，氟系樹脂塗料的羥基值(hydroxyl value)為30至100 mgKOH/克樹脂。在一實施方式中，氟系樹脂塗料的酸價(acid value)為1至13 mgKOH/克樹脂。在一實施方式中，氟系樹脂塗料的固含量為45至70 wt%。在一實施方式中，氟系樹脂塗料的黏度為100至600 mPa-s。In one embodiment, the fluororesin coating has a hydroxyl value of 30 to 100 mgKOH/g resin. In one embodiment, the fluororesin coating has an acid value of 1 to 13 mgKOH/g resin. In one embodiment, the fluororesin coating has a solid content of 45 to 70% by weight. In one embodiment, the fluororesin coating has a viscosity of 100 to 600 mPa-s.
於形成具有羥基之氟系樹脂層130於接著劑層120上之後，可將基材110、接著劑層120、氟系樹脂層130的層疊結構進行熱壓製程，使接著效果更佳。在一實施方式中，熱壓製程的最高溫度為90至120℃。在一實施方式中，加壓壓力為15kg以上。After the fluorine-based resin layer 130 having a hydroxyl group is formed on the adhesive layer 120, the laminated structure of the substrate 110, the adhesive layer 120, and the fluorine-based resin layer 130 can be subjected to a hot pressing step to further improve the subsequent effect. In one embodiment, the maximum temperature of the hot press is from 90 to 120 °C. In one embodiment, the pressurizing pressure is 15 kg or more.
以下的實施例係用以詳述本發明之特定態樣，並使本發明所屬技術領域中具有通常知識者得以實施本發明。以下的實施例不應用以限制本發明。The following examples are intended to be illustrative of specific aspects of the invention, and are intended to be The following examples are not intended to limit the invention.
首先，塗佈氟系樹脂塗料(型號：ZEFFLE GK570，台 灣大金先端化學股份有限公司製造，酸價64 mgKOH/克樹脂，羥基值55至65 mgKOH/克樹脂)於聚酯布上，再以90℃乾燥5分鐘。所形成的氟系樹脂層的厚度為0.3毫米。接著，將聚酯布、氟系樹脂層疊結構於90℃、加壓壓力為15公斤的條件下熱壓180秒。再將製得的氟系樹脂複合材以測試規範ISO2411(夾具間距7.5公分、測試速度100±10毫米/分鐘)測試90°剝離強度。比較例1的氟系樹脂複合材的90°剝離強度為15.52 N。First, apply a fluorine resin coating (Model: ZEFFLE GK570, Taiwan Manufactured by Bay Daikin Advanced Chemical Co., Ltd., acid price 64 mgKOH/g resin, hydroxyl value 55 to 65 mgKOH/g resin) on polyester cloth, and dried at 90 ° C for 5 minutes. The thickness of the formed fluorine-based resin layer was 0.3 mm. Next, the polyester cloth and the fluorine-based resin laminated structure were heat-pressed at 90 ° C for 15 seconds under a pressure of 15 kg. Further, the obtained fluorine-based resin composite material was tested for 90° peel strength in accordance with the test specification ISO2411 (clamp spacing: 7.5 cm, test speed: 100 ± 10 mm/min). The 90-degree peel strength of the fluorine-based resin composite material of Comparative Example 1 was 15.52 N.
首先，塗佈雙酚A型環氧樹脂(型號：NPEL 128，南亞公司製造)於聚酯布上，再以90℃乾燥1分鐘。所形成的環氧樹脂層的厚度為0.1毫米。然後，塗佈氟系樹脂塗料(型號：ZEFFLE GK570，台灣大金先端化學股份有限公司製造，酸價64 mgKOH/克樹脂，羥基值55至65 mgKOH/克樹脂)於環氧樹脂層上，再以90℃乾燥5分鐘。所形成的氟系樹脂層的厚度為0.3毫米。接著，將聚酯布、環氧樹脂層、氟系樹脂層疊結構於90℃、壓力為15公斤的條件下熱壓180秒。再將製得的氟系樹脂複合材以測試規範ISO2411(夾具間距7.5公分、測試速度100±10毫米/分鐘)測試90°剝離強度。比較例2的氟系樹脂複合材的90°剝離強度為16.84 N。First, a bisphenol A type epoxy resin (model: NPEL 128, manufactured by Nanya Corporation) was coated on a polyester cloth, and dried at 90 ° C for 1 minute. The thickness of the epoxy layer formed was 0.1 mm. Then, a fluorine-based resin coating (model: ZEFFLE GK570, manufactured by Taiwan Daikin Advanced Chemical Co., Ltd., acid value 64 mgKOH/g resin, hydroxyl value 55 to 65 mgKOH/g resin) was applied to the epoxy resin layer, and then Dry at 90 ° C for 5 minutes. The thickness of the formed fluorine-based resin layer was 0.3 mm. Next, the polyester cloth, the epoxy resin layer, and the fluorine-based resin laminated structure were heat-pressed at 90 ° C under a pressure of 15 kg for 180 seconds. Further, the obtained fluorine-based resin composite material was tested for 90° peel strength in accordance with the test specification ISO2411 (clamp spacing: 7.5 cm, test speed: 100 ± 10 mm/min). The 90-degree peel strength of the fluorine-based resin composite material of Comparative Example 2 was 16.84 N.
比較例3是以比較例2所述的方法製備氟系樹脂複合材，差異僅在於比較例3所使用的是日本信越化學工業公司製造之型號KBM-303的接著劑。將製得的氟系樹脂複合材以測試規範ISO2411(夾具間距7.5公分、測試速度100±10毫米/分鐘)測試90°剝離強度。比較例3的氟系樹脂複合材的90°剝離強度為29.64 N。In Comparative Example 3, a fluorine-based resin composite material was produced by the method described in Comparative Example 2, except that the adhesive of the model KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd. of Japan was used in Comparative Example 3. The obtained fluorine-based resin composite material was tested for 90° peel strength in accordance with the test specification ISO2411 (clamp spacing: 7.5 cm, test speed: 100 ± 10 mm/min). The 90-degree peel strength of the fluorine-based resin composite material of Comparative Example 3 was 29.64 N.
實驗例1-3是以比較例2所述的方法製備氟系樹脂複合材，差異僅在於實驗例1-3所使用的接著劑是本發明的樹脂組成物。Experimental Example 1-3 A fluorine-based resin composite material was produced by the method described in Comparative Example 2, except that the adhesive used in Experimental Example 1-3 was the resin composition of the present invention.
樹脂組成物的製備流程如下。首先，混合莫耳比為1：1的N-[3-(三甲氧基矽基)丙基]乙二胺與三乙氧基苯矽烷，於40℃下攪拌24小時，製得胺基聚矽氧烷。然後，將不同比例(胺基聚矽氧烷分別佔總重的10wt%、20 wt%、30 wt%)的胺基聚矽氧烷分別加入雙酚A型環氧樹脂(型號：NPEL 128，南亞公司製造，與比較例2的環氧樹脂相同)中，於40℃下攪拌12小時，分別得到實驗例1-3的樹脂組成物。其組成、環氧當量與環氧基莫耳比值列於表一中。The preparation process of the resin composition is as follows. First, N-[3-(trimethoxyindolyl)propyl]ethylenediamine having a molar ratio of 1:1 was mixed with triethoxybenzophenan, and stirred at 40 ° C for 24 hours to obtain an amine group polymerization. Oxane. Then, different ratios (10 wt%, 20 wt%, 30 wt% of the total weight of the amine polysiloxane) to the bisphenol A epoxy resin (Model: NPEL 128, respectively) were added. The resin composition of Experimental Example 1-3 was obtained by stirring at 40 ° C for 12 hours in the same manner as in the epoxy resin of Comparative Example 2. The composition, epoxy equivalent and epoxy molar ratio are listed in Table 1.
a 即胺基聚矽氧烷佔總重(即環氧樹脂與胺基聚矽氧烷的重量和)的重量百分比 a is the weight percentage of the amine polyoxymethane to the total weight (ie the weight of the epoxy resin and the amine polyoxyalkylene)
b 根據上述環氧當量測定方法計算環氧當量 b Calculate the epoxy equivalent according to the above epoxy equivalent determination method
c 即樹脂組成物與環氧樹脂的環氧基的莫耳比值 c is the molar ratio of the epoxy composition of the resin composition to the epoxy resin
為了瞭解環氧樹脂與胺基聚矽氧烷的反應狀況，將比較例2、實驗例1、實驗例3的樹脂組成物進行紅外線光譜鑑定，其結果如第2(a)-2(c)圖所示。以環氧基的特徵峰(914cm-1 )而言，特徵峰強度的大小關係依序為比較例2、實驗例1、實驗例3，證明實驗例1、實驗例3的環氧樹脂的部分環氧基的確已被開環。此外，實驗例1、實驗例3的樹脂組成物皆具有胺基特徵峰(3416cm-1 )，如第2(b)-2(c)圖所示。In order to understand the reaction state of the epoxy resin and the amine polyoxyalkylene oxide, the resin compositions of Comparative Example 2, Experimental Example 1, and Experimental Example 3 were identified by infrared spectroscopy, and the results were as shown in 2(a)-2(c). The figure shows. In the characteristic peak of the epoxy group (914 cm -1 ), the magnitude relationship of the characteristic peak intensity was in the order of Comparative Example 2, Experimental Example 1, and Experimental Example 3, and the epoxy resin portion of Experimental Example 1 and Experimental Example 3 was proved. The epoxy group has indeed been opened. Further, the resin compositions of Experimental Example 1 and Experimental Example 3 all had an amine-based characteristic peak (3416 cm -1 ) as shown in Fig. 2(b) - 2(c).
另外，為了瞭解樹脂組成物與氟系樹脂的反應狀況，將實驗例1的樹脂組成物、實驗例1的樹脂組成物與氟系樹脂層接觸後的初步產物及氟系樹脂層進行紅外線光譜鑑定，其結果如第3(a)-3(c)圖所示。如第3(a)圖所示，實驗例1的樹脂組成物具有矽氧鍵結的特徵峰(769、691cm-1 )及環氧基的特徵峰(914cm-1 )。如第3(b)圖所示，當實驗例 1的樹脂組成物與氟系樹脂層接觸後，環氧基的特徵峰(914cm-1 )消失，證明環氧基已與羥基反應。In addition, in order to understand the reaction state of the resin composition and the fluorine-based resin, the preliminary analysis of the resin composition of Experimental Example 1, the resin composition of Experimental Example 1, and the fluorine-based resin layer, and the fluorine-based resin layer were subjected to infrared spectrum identification. The results are shown in Figures 3(a)-3(c). As shown in Fig. 3(a), the resin composition of Experimental Example 1 has a characteristic peak of oxime-bonding (769, 691 cm -1 ) and a characteristic peak of epoxy group (914 cm -1 ). As shown in Fig. 3(b), when the resin composition of Experimental Example 1 was brought into contact with the fluorine-based resin layer, the characteristic peak of the epoxy group (914 cm -1 ) disappeared, and it was confirmed that the epoxy group had reacted with the hydroxyl group.
並將製得的氟系樹脂複合材以測試規範ISO2411(夾具間距7.5公分、測試速度100±10毫米/分鐘)測試90°剝離強度。比較例1-3、實驗例1-3的剝離強度測試結果列於表二中。The obtained fluorine-based resin composite material was tested for 90° peel strength in accordance with the test specification ISO2411 (clamp spacing: 7.5 cm, test speed: 100 ± 10 mm/min). The peel strength test results of Comparative Examples 1-3 and Experimental Examples 1-3 are shown in Table 2.
在表二中顯示，實驗例1-3的剝離強度均高於比較例1-3。其中以實驗例1的剝離強度最高，為比較例1的剝離強度的2.4倍左右。由此可知，實驗例1-3的樹脂組成物的確能夠有效地與氟系樹脂層形成化學鍵結，提昇氟系樹脂層與聚酯布之間的接著強度。As shown in Table 2, the peel strengths of Experimental Examples 1-3 were higher than those of Comparative Examples 1-3. Among them, the peel strength of Experimental Example 1 was the highest, and it was about 2.4 times of the peel strength of Comparative Example 1. From this, it was found that the resin composition of Experimental Example 1-3 can effectively form a chemical bond with the fluorine-based resin layer, and the adhesion strength between the fluorine-based resin layer and the polyester cloth can be improved.
為了瞭解接著劑層的無機矽含量，將實驗例1、實驗例2、實驗例3的接著劑層進行EDX元素分析，如第4-6圖所示，其中，各圖橫軸為受激發訊號的能量(KeV)，縱軸為訊號接收到的次數(counts)。由上述EDX元素分析可知，接著劑層的矽元素含量為1.03至2.37%之間。In order to understand the inorganic cerium content of the adhesive layer, the adhesive layers of Experimental Example 1, Experimental Example 2, and Experimental Example 3 were subjected to EDX elemental analysis, as shown in Figures 4-6, wherein the horizontal axis of each graph is the excited signal. The energy (KeV), the vertical axis is the number of times the signal is received (counts). It can be seen from the above EDX element analysis that the content of the ruthenium element of the adhesive layer is between 1.03 and 2.37%.
另將實驗例1、實驗例2、實驗例3的接著劑層進行氮氣環境下的熱重損失測試(升溫速率10℃/分鐘)，如第7圖所示。在200至400℃的溫度範圍下，主要是接著劑層中的小分子裂解。在400至470℃的溫度範圍下，主要是環氧樹脂主鏈段的熱裂解。重要的是，隨著胺基聚矽氧烷的 含量增加，環氧樹脂主鏈段熱裂解(在400至470℃的溫度範圍下)的速率變慢。代表添加胺基聚矽氧烷的確有助於提昇接著劑層的熱安定性。Further, the adhesive layers of Experimental Example 1, Experimental Example 2, and Experimental Example 3 were subjected to a thermogravimetric loss test under a nitrogen atmosphere (heating rate 10 ° C / min) as shown in Fig. 7. At a temperature range of 200 to 400 ° C, mainly small molecule cleavage in the adhesive layer. At temperatures ranging from 400 to 470 ° C, mainly thermal cracking of the epoxy resin backbone segment. Importantly, with the amino polyoxyalkylene As the content increases, the rate of thermal cracking of the epoxy resin main chain section (at a temperature range of 400 to 470 ° C) becomes slow. The addition of an amine-based polyoxyalkylene does help to improve the thermal stability of the adhesive layer.
又將實驗例1、實驗例2、實驗例3的接著劑層進行空氣環境下的熱重損失測試(升溫速率10℃/分鐘)，如第8圖所示。在200至400℃的溫度範圍下，主要是接著劑層中的小分子裂解。在400至470℃的溫度範圍下，主要是環氧樹脂主鏈段的熱裂解。在500至650℃的溫度範圍下，主要是矽氧結構的熱氧化裂解。另外，於700℃下，接著劑層的剩餘重量百分比(亦即無機矽的含量)約為1至3%左右，與EDX元素分析的結果相似。Further, the adhesive layers of Experimental Example 1, Experimental Example 2, and Experimental Example 3 were subjected to a thermogravimetric loss test in an air atmosphere (heating rate 10 ° C / min) as shown in Fig. 8. At a temperature range of 200 to 400 ° C, mainly small molecule cleavage in the adhesive layer. At temperatures ranging from 400 to 470 ° C, mainly thermal cracking of the epoxy resin backbone segment. At a temperature range of 500 to 650 ° C, it is mainly a thermal oxidative cracking of a helium oxygen structure. Further, at 700 ° C, the remaining weight percentage of the adhesive layer (that is, the content of inorganic cerium) is about 1 to 3%, which is similar to the result of EDX elemental analysis.
比較例4是以比較例1所述的方法製備氟系樹脂複合材，差異僅在於比較例4的基材為玻璃纖維布。In Comparative Example 4, a fluorine-based resin composite material was produced by the method described in Comparative Example 1, except that the base material of Comparative Example 4 was a glass fiber cloth.
比較例5是以比較例2所述的方法製備氟系樹脂複合材，差異僅在於比較例5的基材為玻璃纖維布。In Comparative Example 5, a fluorine-based resin composite material was produced by the method described in Comparative Example 2, except that the base material of Comparative Example 5 was a glass fiber cloth.
比較例6是以比較例3所述的方法製備氟系樹脂複合 材，差異僅在於比較例6的基材為玻璃纖維布。Comparative Example 6 was a method for preparing a fluorine-based resin composite by the method described in Comparative Example 3. The only difference was that the substrate of Comparative Example 6 was a glass fiber cloth.
實驗例4-6是以實驗例1-3所述的方法製備氟系樹脂複合材，差異僅在於實驗例4-6的基材為玻璃纖維布。也就是說，實驗例4、5、6所使用的樹脂組成物分別與實驗例1、2、3相同。Experimental Example 4-6 A fluorine-based resin composite material was prepared by the method described in Experimental Example 1-3, except that the substrate of Experimental Example 4-6 was a glass fiber cloth. That is, the resin compositions used in Experimental Examples 4, 5, and 6 were the same as Experimental Examples 1, 2, and 3, respectively.
將比較例4-6、實驗例4-6的剝離強度測試結果如表三所示。The peel strength test results of Comparative Examples 4-6 and Experimental Examples 4-6 are shown in Table 3.
在表二中顯示，實驗例4-5的剝離強度均高於比較例1-3。其中以實驗例4的剝離強度最高，為比較例1的剝離強度的2倍左右。由此可知，實驗例1-3的樹脂組成物的確能夠有效地與氟系樹脂層形成化學鍵結，提昇氟系樹脂層與玻璃纖維布之間的接著強度。As shown in Table 2, the peel strengths of Experimental Examples 4 to 5 were higher than those of Comparative Examples 1-3. Among them, the peel strength of Experimental Example 4 was the highest, and it was about twice the peeling strength of Comparative Example 1. From this, it was found that the resin composition of Experimental Example 1-3 can effectively form a chemical bond with the fluorine-based resin layer, and the adhesion strength between the fluorine-based resin layer and the glass fiber cloth can be improved.
將實驗例1的氟系樹脂複合材進行紫外光照射測試(即一種耐候測試)。如第9圖所示，左圖(A)為未照射紫外光的氟系樹脂複合材的表面，右圖(B)則為照射紫外光7天的 氟系樹脂複合材的表面。比較圖(A)與圖(B)可知，經過7天紫外光照射之後，氟系樹脂複合材的表面並沒觀察到顯色或外觀的明顯變化，亦即經紫外光照射7天後根據本發明之實驗例1的氟系樹脂複合材表面沒有出現黃變或硬化現象。The fluorine-based resin composite material of Experimental Example 1 was subjected to an ultraviolet light irradiation test (i.e., a weather resistance test). As shown in Fig. 9, the left image (A) is the surface of the fluorine-based resin composite material that is not irradiated with ultraviolet light, and the right image (B) is the ultraviolet light for 7 days. The surface of the fluorine-based resin composite. Comparing the graphs (A) and (B), it was found that after 7 days of ultraviolet light irradiation, no significant change in color development or appearance was observed on the surface of the fluorine-based resin composite material, that is, after 7 days of irradiation with ultraviolet light, according to the present. The surface of the fluorine-based resin composite material of Experimental Example 1 of the invention did not exhibit yellowing or hardening.
另外，將照射紫外光7天的氟系樹脂複合材測試90°剝離強度，其結果為36.36 N。代表在照射紫外光7天的狀況下，實驗例1的氟系樹脂複合材仍能夠維持良好的黏著力。Further, the fluorine-based resin composite material irradiated with ultraviolet light for 7 days was tested for 90° peel strength, and as a result, it was 36.36 N. The fluorine-based resin composite of Experimental Example 1 was able to maintain good adhesion even under the condition of irradiating ultraviolet light for 7 days.
雖然本發明已以實施方式揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and the present invention can be modified and modified without departing from the spirit and scope of the present invention. The scope is subject to the definition of the scope of the patent application attached.
10‧‧‧氟系樹脂複合材10‧‧‧Fluorine resin composite
110‧‧‧基材110‧‧‧Substrate
120‧‧‧接著劑層120‧‧‧ adhesive layer
130‧‧‧氟系樹脂層130‧‧‧Fluorinated resin layer
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂，所附圖式之說明如下：第1圖係顯示依照本發明一實施方式之氟系樹脂複合材的示意圖。The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt;
第2圖係顯示比較例2(a)、實驗例1(b)、實驗例3(c)的樹脂組成物的紅外線光譜圖。Fig. 2 is an infrared spectrum chart showing the resin compositions of Comparative Example 2 (a), Experimental Example 1 (b), and Experimental Example 3 (c).
第3圖係顯示實驗例1的樹脂組成物(a)、樹脂組成物與氟系樹脂層接觸後的初步產物(b)及氟系樹脂層(c)的紅外線光譜圖。Fig. 3 is an infrared spectrum diagram showing the resin composition (a) of Experimental Example 1, the preliminary product (b) and the fluorine-based resin layer (c) after the resin composition was brought into contact with the fluorine-based resin layer.
第4、5及6圖係分別顯示實驗例1、實驗例2、實驗 例3的EDX元素分析圖。Figures 4, 5 and 6 show experimental example 1, experimental example 2, and experiment respectively. Example 3 EDX element analysis chart.
第7圖係顯示比較例2、實驗例1、實驗例2、實驗例3的熱重損失分析圖(氮氣環境)。Fig. 7 is a graph showing the thermogravimetric loss analysis (nitrogen atmosphere) of Comparative Example 2, Experimental Example 1, Experimental Example 2, and Experimental Example 3.
第8圖係顯示比較例2、實驗例1、實驗例2、實驗例3的熱重損失分析圖(空氣環境)。Fig. 8 is a graph showing the thermogravimetric loss analysis (air environment) of Comparative Example 2, Experimental Example 1, Experimental Example 2, and Experimental Example 3.
10‧‧‧氟系樹脂複合材10‧‧‧Fluorine resin composite
110‧‧‧基材110‧‧‧Substrate
120‧‧‧接著劑層120‧‧‧ adhesive layer
130‧‧‧氟系樹脂層130‧‧‧Fluorinated resin layer
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