200944569 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種膠黏劑組合物、對膠黏劑改性的方 法及其製品。具體地說，關於一種有機矽壓敏膠黏劑組合 5 物、對有機矽壓敏膠黏劑進行改性的方法及其製品。 【先前技術】 q 目前’有機矽壓敏膠黏劑主要通過使聚二有機基矽氧 烧和具有共聚單元R^SiO^C簡稱爲Μ單元）和另一種共 10 聚單元Sl〇4/2 (簡稱爲Q單元）的共聚矽氧烷樹脂反應或 混合製得。有機矽壓敏膠黏劑由於其可黏接有機矽等低表 面能材料的特性和良好的高低溫性能，被廣泛的用於製造 各種壓敏膠帶。 但是’上述有機矽壓敏膠黏劑在某些應用中會産生一 15 些問題’例如’在有機矽壓敏膠黏劑塗布厚度較薄的情況 下所製成的壓敏膠帶對有機矽材料的黏接強度較弱，滿足 ® 不了應用的要求。 因此’目前急需一種對有機矽材料黏接強度較好的有 機矽壓敏膠黏劑組合物和壓敏膠帶製品。 20 【發明内容】 根據本發明的一個目的，提供了一種有機矽壓敏膠黏劑 組合物，其包含： 有機梦壓敏膠黏劑；和 5 200944569 含有硼氧鍵的化合物。 根據本發明的另一目的，提供了一種對有機矽壓敏膠黏 劑進行改性的方法，其包括在待改性的有機矽壓敏膠黏劑 中混入含有硼氧鍵的化合物。 5 根據本發明的又一目的，提供了一種壓敏膠帶製品，其 包含本發明的有機矽壓敏膠黏劑組合物。 在壓敏膠黏劑塗布厚度較薄的情況下，根據本發明的 某二實施方案的有機梦壓敏膠黏劑組合物和壓敏膝帶製品 對有機矽材料仍然具有較好的黏接強度。 10 本發明的以上概要並非意欲描述本發明的每個公開的 實施方案或每個執行方法。詳細的描述更具體地是用於例 不說明性實施方案，而不應當將它認做是對本發明的任何 限制。 15 【實施方式】 除非特別指明，術語“有機矽壓敏膠黏劑’，是指一種組 〇 合物，除了不包含“含有硼氧鍵的化合物’，外，其可以包含 常規有機矽壓敏膠黏劑所需的任何必要和非必要組分。 除非特別指明，術語“MQ樹脂”是指具有共聚單元 20 R3Si〇1/2 (簡稱爲M單元）和另一種共聚單元Si〇4/2 (簡稱 爲Q單元）的共聚矽氧烷樹脂，其中每個尺各自獨立地代表 一個含有不多於6個碳原子的一價烴基。在某些實施方案 中，其還含有一個或多個以下能與矽氧烷鍵合的官能圏： 氫；能與矽氧烷鍵合的烯基，如那些選自乙烯基、烯丙基、 25 丙烯基或更高級烯基的基團。 6 200944569 藉某除明術語“聚二有機基妙氧烷，，是指-種含有 i每:=團或_ 一種以上的聚二有機切氧 二！：：可獨立地選自由燒基基團、鍵稀基基團、 土和方基基團組成的組中的基團。例如經基封端 的聚二甲基矽氧烷和聚二甲基二苯基矽氧烷。 5 ❹ 10 15 ❹ 20 除非特別指明，所有份數、百分比、比例等均以重量計。 除非特別指明，認爲所有的數位均由術語“約，，所修 飾’並且根據端點的數位㈣的復述包括在此範圍以内所 包含的所有數位（例如’0.05至3G重量％包括gg5〇〇8、 (Μ、0.15、0.2、〇.25、ο」、〇 35、〇 4、〇 425、i、2、$、 10、15、18、20、25 和 30 重量％)。 本發明的有機矽壓敏膠黏劑組合物包含：有機矽壓敏 膠黏劑和含有硼氧鍵的化合物。 任何常規的有機矽壓敏膠黏劑都適用於本發明。 基於有機矽壓敏膠黏劑的總固含量，根據本發明的— 些實施方案的適用的有機矽壓敏膠黏劑包括： (1)30〜70重量％的MQ樹脂，MQ樹脂是具有R3Si〇i/2 單元（Μ單元）和SiO4,2單元（Q單元）的共聚矽氧烷樹 脂，其中每個R各自獨立地代表含有不多於6個碳原子的 一價烴基； (2) 30〜70重量％的聚二有機基矽氧燒，聚二有機基 矽氧烷是一種含有羥基、烯基官能團或氫化物中一種以上 的聚二有機基矽氧烷，並且聚二有機基矽氧烷的每個有機 基可以獨立地是選自由烷基基團、鏈烯基基團、環烧基基 7 200944569 5 ❹ 10 15 Ο 20 團和芳基所組成的群組中的基團。可以列出的實例是羥基 封端的聚二甲基矽氧烷和聚二甲基二苯基矽氧烷；和 (3) .任選固化催化劑，例如，選自由自由基聚合催化 劑例如二芳基過氧化物交聯劑，含氨基官能基團的矽烷， 有機酸的金屬鹽例如二丁基二乙酸錫組成的組。根據某些 實施方案的用量可爲0-10重量％。 基於有機石夕愿敏膠黏劑的總固含量，根據一些實施方 案的另一種適用的有機矽壓敏膠黏劑包括： (1) 30〜70重量％的MQ樹脂。MQ樹脂是具有R3Si〇1/2 單元（Μ單元）和SiOw單元（Q單元）的共聚矽氧烷樹 脂，其中每個R各自獨立地代表一個含有不多於6個碳原 子的一價烴基’並且具有一個或多個能與矽氧烷鍵合的官 能團：氫；能與矽氧烷鍵合的烯基，如那些選自乙稀基、 烯丙基、丙烯基或更高級烯基的基團； (2) 30〜70重量％的聚二有機基矽氧烷，例如，含乙 烯基基團的聚二曱基矽氧烷和聚二曱基二苯基石夕氧院； (3 )任選的交聯劑或增鏈劑，例如含有石夕氫基團或稀 基基團的矽油，根據某些實施方案的用量可爲〇Λ重量％_2〇 重量％ ;和 (4) 作爲矽氫化催化劑的Pt或其他貴金屬，基於以 上組分（1) - (3)的總重量，根據某些實施方案的量可以 是至少0.1 ppm。 這些組合物例子可參見美國專利3,527,842、 3,983,298、4,774,297、歐洲專利 355,991 和 393,426。 8 200944569 MQ增黏樹脂和聚二有機基石夕氧烧的存在形式例如可 以爲MQ增黏掛脂和石夕氧烧聚合物的共混物或反應産物形 式。 除上述實例外，無溶劑等其他類型和固化方式的有機 5 矽壓敏膠黏劑也同樣適用。實例包括但不限於紫外固化的 有機矽壓敏膠黏劑組合物、各種改性的有機矽壓敏膠組合 物0 在一些實施方案中，有機矽壓敏膠黏劑也可包括各種 〇 添加劑，如顏料和填料。 10 大量的市售有機矽壓敏膠黏劑是適用的。這些矽氧烷 壓敏黏合劑的例子包括但不限於Dow Corning的280A、 282、7355、7356、7358 ' 7502、7657、Q2-7406、Q2-7566 和 Q2-7735 ; Momentive 的 PSA590、PSA600、PSA595、 PSA610、PSA518、PSA6574、PSA529、PSA750-D1 和 15 PSA800—C;以及 ShinEtsu 的 KRT0(H、KRT002、KRT003、 KRT009、KR101-10、KR120 和 KR3700 ° _ 本發明中適用的含硼氧鍵化合物沒有特別限制，並且 其實例包括但不限於硼酸、硼酸酯（硼酸三曱基酯、硼酸 三乙基酯、硼酸三丙基酯、硼酸三丁酯、硼酸三辛酯、硼 20 酸三戊酯、硼酸三正十二烷基酯、硼酸三己烯乙二醇酯、 硼酸三異丁基甲基酯、硼酸三十八烷基酯、硼酸三苯酯、 硼酸三甲苯基酯）等、硼酸酐和其衍生物。在某些實施方 案中，含硼氧鍵化合物用量爲上述有機矽壓敏膠黏劑組合 物總固含量重量的0.05-30%。 9 200944569 由本發明的有機矽壓敏膠黏劑組合物製得的有機矽壓 敏膠帶製品包括但不限於，以各種材料爲基材的單面、雙 面壓敏膠帶和膠膜。 5 10 15 ❹ 20 根據某些實施方案的有機矽壓敏膠黏劑對有機矽材料 具有很咼的黏接強度，並且由其生産的壓敏膠帶可廣泛用 於有機矽材料的黏接。例如，有機矽材料之間的黏接，以 及有機矽材料和其他材料間的黏接。 實施例 黏接力的測試方法：測試所用矽橡膠爲ShinEtsu ΚΕ — 971TU熱壓成型，厚度約爲2mm。將所製得寬度爲12 7 mm 的膠帶貼在成型好的矽橡膠上，然後將試樣在5〇%相對濕 度和22.2度的條件下平衡72小時’再以3〇〇rnm/min速度 180度方向剝離。在每一實施例中測試3個樣品。記錄剝離 所需的力的平均數。 實施例中採用的聚對苯二甲酸乙二醇酯（PET )薄膜包 括通過化學和物理方法處理過的PET薄膜。 實施例1 通過攪拌將硼酸三甲酯（3重量，份）和Degussa DCLBP-50-PSI ( 6重量份）均勻分散到含有1〇〇重量份的 ShinEtsu KRT-002聚二曱基矽氧烷壓敏膠黏劑的溶液中。 然後將産生的固體含量爲40%的壓敏膠黏劑組合物塗覆在 〇.〇25mm的PET薄膜上，然後馬上在7〇°C乾燥1分鐘。然 25 200944569 後使乾膠在165°C固化2分鐘。得到的乾膠的厚度爲0.040 mm。 實施例2 5 將硼酸三曱酯（5重量份）和CAT-PL-50T催化劑 (ShinEtsuX 0.83重量份）加入到含有100重量份的ShinEtsu KR3700聚二甲基矽氧烷壓敏膠黏劑的溶液中，並且在攪拌 下分散均勻。然後將産生的固體含量爲40%的壓敏膠黏劑 ❹ 組合物塗覆在0.025mm的PET薄膜上，然後馬上在70°C乾 10 燥1分鐘。然後使乾膠在130°C固化2分鐘》得到的乾膠的 厚度爲0.040 mm。 實施例3 將棚酸三丁酯（28重量份）和Luperox® A75 ( 3重量 15 份）加入到含有100重量份的Momentive PSA610聚二甲基 矽氧烷壓敏膠黏劑的溶液中，並且在攪拌下分散均勻。然 後將産生的固體含量爲40%的壓敏膠黏劑組合物塗覆在 〇 0.025mm的PET薄膜上，然後馬上在70°C乾燥1分鐘。然 後使乾膠在177t固化2分鐘。得到的乾膠的厚度爲0〇4〇 20 mm ° 實施例4 將硼酸（3重量份）和Degussa DCLBP-50-PSI ( 3重量 份）加入到含有100重量份的Dow Corning 280A聚二甲基 25 矽氧烷壓敏膠黏劑的溶液中，並且在攪拌下分散岣勻。然 π 200944569 後將産生的固體含量爲40%的壓敏膠黏劑組合物塗覆在 0.025mm的PET薄膜上，然後馬上在70°C乾燥1分鐘。然 後使乾膠在165°C固化2分鐘。得到的乾膠的厚度爲0.040 mm。 5 實施例5 10 15 ❹ 20 將硼酸三丁酯（12重量份）和DegussaDCLBP-50-PSI (2重量份）加入到含有100重量份的Dow Corning 7355 聚二甲基矽氧烷壓敏膠黏劑的溶液中，並且在攪拌下分散 均勻。然後將産生的固體含量爲40%的壓敏膠黏劑組合物 塗覆在0.025mm的PET薄膜上，然後馬上在70°C乾燥1 分鐘。然後使乾膠在165°C固化2分鐘。得到的乾膠的厚度 爲 0.040 mm。 實施例6 將硼酸酐（3重量份）和Degussa DCLBP-50-PSI (3 重量份）加入到含有100重量份的Dow Corning Q2-7735 聚二甲基矽氧烷壓敏膠黏劑的溶液中，並且在攪拌下分散 均勻。然後將産生的固體含量爲40%的壓敏膠黏劑組合物 塗覆在0.025mm的PET薄膜上，然後馬上在70°C乾燥1 分鐘。然後使乾膠在165°C固化2分鐘。得到的乾膠的厚度 爲 0.040 mm。 與相對應的實施例相比，對比例不含硼氧鍵化合物， 其餘相同。 12 200944569 硼氧鍵化合 物名稱 蝴氧鍵化合 物用量，重 量％ 壓敏膠 催化劑/交聯劑名 稱 催化劑/交 聯劑用量， 重量％ 黏接強度 (N/mm) 實施例1 硼酸三甲酯 3 KRT002 DCLBP-50-PSI 6 0.74 對比例1 0 KRT002 DCLBP-50-PSI 6 0.27 實施例2 硼酸三甲酯 5 KR3700 CAT-PL-50T 0.83 0.36 對比例2 0 KR3700 CAT-PL-50T 0.83 0.09 實施例3 硼酸三丁酯 28 PSA610 A75 3 0.60 對比例3 0 PSA610 A75 3 0.33 實施例4 硼酸 3 280A DCLBP-50-PSI 3 0.96 對比例4 0 280A DCLBP-50-PSI 3 0.36 實施例5 硼酸三丁酯 12 7355 DCLBP-50-PSI 2 0.81 對比例5 0 7355 DCLBP-50-PSI 2 0.38 實施例6 硼酸酐 3 Q2-7735 DCLBP-50-PSI 3 1.31 對比例6 0 Q2-7735 DCLBP-50-PSI 3 0.41 實施例7 除以20%而非30%的固含量製備矽氧烷聚脲聚合物， Q 並且使用75/25而非70/30的甲苯/2-丙醇的溶劑摻和物以 5 外，根據US6,730,397B中在標題爲“矽氧烷聚脲聚合物的 製備”的部分中所提供的程式製備聚二有機基矽氧烷聚脲 嵌段共聚物（矽氧烷聚脲）壓敏膠黏劑。通過將63重量份 的彈性體溶液、24.3重量份的MQ樹脂J、11.63重量份的 甲苯以及1.08重量份的2-丙醇摻和並且良好混合以保證均 10 勻性，從而將彈性體配製成爲矽氧烷聚脲壓敏膠黏劑。MQ 樹脂J是爲了降低曱矽烷醇含量而經處理的MQ樹脂，並 13 200944569 5 10 15 ❹ 20 且由Μ、Q和Τ0Η結構單元組成，具有1.2的M/Q比率、 0.8%的SiOH含量、2820的數均分子量（Μη)，4600的重均 分子量（Mw )以及在二曱苯中的63.4wt%的固含量。如以 下所概括的，向此矽氧烷聚脲壓敏膠黏劑中加入各種量的 硼酸三丁酯（TBB)。據報導，TBB的量是以每100份的矽 氧烷聚脲膠黏劑的重量份計。將産生的壓敏膠黏劑組合物 刀塗，並且在70°C乾燥10分鐘，以在PET上製備0.051 mm 的乾燥塗層。 實施例8 如對於美國專利公開第20070148475號中的實施例1 所述，製備聚二有機基矽氧烷聚乙二醯胺共聚物（矽氧烷 聚乙二醯胺）膠黏劑。向100重量份的矽氧烷聚乙二醯胺 膠黏劑中加入硼酸三丁酯（6重量份）。將在曱苯中的此材 料的30%固體溶液與50%的SR545 MQ樹脂（獲自GE) 摻和，以形成膠黏劑組合物。將膠黏劑組合物刀塗，並且 在70°C乾燥10分鐘，以在PET上製備0.051 mm的乾燥塗 層。 通過下列方法測試具有和不具有TBB的所産生的PSA 膠帶對於矽氧烷的黏接：通過用2 kg的軋輥以30.5 cm/分 鐘在矽橡膠上碾壓一次，所述矽橡膠是來自McMaster Carr (Part# 8632K922)的 60 A Durometer Plain 4.2 mm 厚的橙-紅矽橡膠。 在IMASS試驗機中，通過以30.5 cm/分鐘（12英寸/ 分鐘）的速度和90度的剝離角從矽橡膠剝離黏合劑來測量 25 200944569 ' 在22°C和50%的相對濕度條件下保持15分鐘以及保持24 小時以後的剝離黏接。以克/英寸記錄結果，並且將其轉化 爲牛頓/mm。報導了 3次測量的平均平均值。 剝離黏接(N/mm) 實施例 黏合劑 TBB重量份 15分鐘保持 24小時保持 比較例7 矽氧烷聚脲 0 0.03 0.04 7a 矽氧烷聚脲 1 0.02 0.04 7b 矽氧烷聚脲 3 0.04 0.04 7c 矽氧烷聚脲 6 0.02 0.03 7d 矽氧烷聚脲 10 0.06 0.04 比較例8 矽氧烷聚乙二酰胺 0 0.06 0.41 8 矽氧烷聚乙二酰胺 6 0.31 高度黏接* *膠黏劑沒有從矽橡膠剝離，而從基材剝離。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive composition, a method for modifying an adhesive, and a product thereof. Specifically, a method for modifying an organic ruthenium pressure sensitive adhesive, and a method for modifying the organic ruthenium pressure sensitive adhesive. [Prior Art] q At present, 'organic ruthenium pressure sensitive adhesive is mainly made by polydiorgano oxime and a copolymerized unit R^SiO^C is simply referred to as a fluorene unit) and another 10 total unit S1 〇 4/2 The copolymerized oxirane resin (abbreviated as Q unit) is obtained by reaction or mixing. Organic ruthenium pressure sensitive adhesives are widely used in the manufacture of various pressure sensitive adhesive tapes due to their properties of low surface energy materials such as organic enamel and good high and low temperature properties. However, 'the above organic pressure-sensitive adhesives may cause some problems in some applications', for example, pressure-sensitive adhesive tapes made of organic tantalum materials in the case of thin coatings of organic tantalum pressure-sensitive adhesives. The bond strength is weak and meets the requirements of the application. Therefore, there is an urgent need for an organic pressure-sensitive adhesive composition and a pressure-sensitive adhesive tape product which have good adhesion strength to an organic tantalum material. 20 SUMMARY OF THE INVENTION In accordance with one aspect of the present invention, an organic pressure sensitive adhesive composition comprising: an organic dream pressure sensitive adhesive; and 5 200944569 a compound containing a boron oxygen bond is provided. According to another object of the present invention, there is provided a method of modifying an organic ruthenium pressure-sensitive adhesive comprising mixing a compound containing a boron-oxygen bond in an organic ruthenium pressure-sensitive adhesive to be modified. According to still another object of the present invention, there is provided a pressure-sensitive adhesive tape article comprising the organic ruthenium pressure-sensitive adhesive composition of the present invention. The organic dream pressure-sensitive adhesive composition and the pressure-sensitive knee-belt product according to a second embodiment of the present invention still have good adhesive strength to the organic tantalum material in the case where the pressure-sensitive adhesive coating thickness is thin. . The above summary of the present invention is not intended to describe each disclosed embodiment or every method of the invention. The detailed description is intended to be illustrative, and not restrictive. 15 [Embodiment] Unless otherwise specified, the term "organophthalic pressure-sensitive adhesive" means a group composition which, in addition to not containing a "compound containing a boron-oxygen bond", may comprise a conventional organic hydrazine pressure sensitive agent. Any necessary and non-essential components required for the adhesive. Unless otherwise specified, the term "MQ resin" means a copolymerized siloxane resin having a copolymerization unit 20 R3Si 〇 1/2 (abbreviated as M unit) and another copolymerization unit Si 〇 4/2 (abbreviated as Q unit), wherein Each ruler independently represents a monovalent hydrocarbon group containing no more than 6 carbon atoms. In certain embodiments, it further contains one or more of the following functional groups capable of bonding to a decane: hydrogen; an alkenyl group capable of bonding to a siloxane, such as those selected from the group consisting of vinyl, allyl, 25 A group of a propenyl or higher alkenyl group. 6 200944569 By the term "polydiorgano-based oxymethane", it is meant that the species contains i per: = group or _ more than one polydiorganooxy 2::: independently selected from the group consisting of alkyl groups a group in the group consisting of a bond group, a soil, and a aryl group, such as a ketal-terminated polydimethyl siloxane and a polydimethyldiphenyl siloxane. 5 ❹ 10 15 ❹ 20 Unless otherwise stated, all parts, percentages, ratios, etc. are by weight. Unless otherwise specified, all digits are considered to be included in the scope by the term "about, modified" and according to the repeat of the digit (4) of the endpoint. All digits contained within (eg '0.05 to 3G wt% include gg5〇〇8, (Μ, 0.15, 0.2, 〇.25, ο", 〇35, 〇4, 〇425, i, 2, $, 10 , 15, 18, 20, 25, and 30% by weight. The organic pressure sensitive adhesive composition of the present invention comprises: an organic pressure sensitive adhesive and a compound containing a boron oxygen bond. Any conventional organic pressure sensitive adhesive. Adhesives are suitable for use in the present invention. Based on the total solids content of the organic rhenium pressure sensitive adhesive, in accordance with the present invention - Suitable organic pressure sensitive adhesives for embodiments include: (1) 30 to 70% by weight of MQ resin, MQ resin having R3Si〇i/2 unit (Μ unit) and SiO4, 2 unit (Q unit) a copolymerized siloxane oxide wherein each R independently represents a monovalent hydrocarbon group having not more than 6 carbon atoms; (2) 30 to 70% by weight of polydiorgano oxime, polydiorgano oxime An alkane is a polydiorganomethoxy alkane containing a hydroxyl group, an alkenyl functional group or a hydride, and each of the organic groups of the polydiorganomethoxy alkane may be independently selected from the group consisting of an alkyl group and an alkene. a group in the group consisting of a group of aryl groups and a group of aryl groups. Examples which may be listed are hydroxy-terminated polydimethyl siloxanes and polydimethylene. And a curing catalyst, for example, selected from a radical polymerization catalyst such as a diaryl peroxide crosslinking agent, an amino functional group-containing decane, a metal salt of an organic acid For example, a group consisting of tin dibutyl diacetate. The amount may be 0-1 according to certain embodiments. 0% by weight. Based on the total solid content of the organic stone evening sensitive adhesive, another suitable organic pressure sensitive adhesive according to some embodiments includes: (1) 30 to 70% by weight of MQ resin. MQ resin Is a copolymerized rhodium oxide resin having R3Si〇1/2 unit (Μ unit) and SiOw unit (Q unit), wherein each R independently represents a monovalent hydrocarbon group having not more than 6 carbon atoms and has One or more functional groups capable of bonding to a siloxane; hydrogen; an alkenyl group capable of bonding to a siloxane, such as those selected from the group consisting of ethylene, allyl, propenyl or higher alkenyl; (2) 30 to 70% by weight of a polydiorganomethoxy alkane, for example, a vinyl group-containing polydidecyloxyne and a polydidecyldiphenyl oxalate; (3) optional A crosslinking agent or a chain extender, such as an eucalyptus oil containing a Rhizon hydrogen group or a dilute group, may be used in an amount of from 〇% by weight to 2% by weight according to certain embodiments; and (4) as a catalyst for hydrogenation of hydrazine Pt or other precious metal, based on the total weight of the above components (1) - (3), the amount according to certain embodiments may be Less 0.1 ppm. Examples of such compositions can be found in U.S. Patent Nos. 3,527,842, 3,983,298, 4,774,297, European Patent Nos. 355,991 and 393,426. 8 200944569 The present form of MQ tackifying resin and polydiyl oxynoke can be, for example, a blend or a reaction product form of MQ viscosifying gums and agglomerated polymers. In addition to the above examples, other types and curing methods of organic 5 矽 pressure-sensitive adhesives without solvents are also suitable. Examples include, but are not limited to, UV-curable organic ruthenium pressure sensitive adhesive compositions, various modified organic ruthenium pressure sensitive adhesive compositions. In some embodiments, the organic ruthenium pressure sensitive adhesive may also include various ruthenium additives, Such as pigments and fillers. 10 A large number of commercially available organic barium pressure sensitive adhesives are suitable. Examples of such aerobicane pressure sensitive adhesives include, but are not limited to, Dow Corning's 280A, 282, 7355, 7356, 7358 '7502, 7657, Q2-7406, Q2-7566, and Q2-7735; Momentive's PSA590, PSA600, PSA595 , PSA610, PSA518, PSA6574, PSA529, PSA750-D1 and 15 PSA800-C; and KRT0 of ShinEtsu (H, KRT002, KRT003, KRT009, KR101-10, KR120 and KR3700 ° _ boron-containing oxygen-bonding compounds suitable for use in the present invention There is no particular limitation, and examples thereof include, but are not limited to, boric acid, boric acid ester (tridecyl borate, triethyl borate, tripropyl borate, tributyl borate, trioctyl borate, triammonium borate Ester, tri-n-dodecyl borate, trihexenyl borate, triisobutyl methyl borate, trioctadecyl borate, triphenyl borate, tricresyl borate, etc., boric anhydride And a derivative thereof. In certain embodiments, the boron-containing oxygen bonding compound is used in an amount of from 0.05 to 30% by weight based on the total solid content of the organic cerium pressure-sensitive adhesive composition. 9 200944569 The organic cerium pressure-sensitive adhesive of the present invention Organic bismuth pressure sensitive agent Tape products include, but are not limited to, single-sided, double-sided pressure-sensitive adhesive tapes and films based on various materials. 5 10 15 ❹ 20 The organic enamel pressure sensitive adhesive according to certain embodiments has a very high The adhesive strength of the crucible, and the pressure-sensitive adhesive tape produced therefrom can be widely used for the bonding of organic germanium materials, for example, bonding between organic germanium materials, and bonding between organic germanium materials and other materials. Test method for adhesion: The enamel rubber used for the test was ShinEtsu ΚΕ 971 TU thermoformed with a thickness of about 2 mm. The tape with a width of 12 7 mm was applied to the formed enamel rubber, and then the sample was placed at 5 〇% relative humidity and 22.2 degrees under equilibrium for 72 hours' and then stripped at a speed of 3〇〇rnm/min 180 degrees. Three samples were tested in each example. The average number of forces required for stripping was recorded. The polyethylene terephthalate (PET) film used in the examples included a PET film treated by chemical and physical methods. Example 1 Trimethyl borate (3 parts by weight) and Degussa DCLBP-50 were stirred by stirring. -PSI (6 parts by weight) Disperse evenly into a solution containing 1 part by weight of ShinEtsu KRT-002 polydidecyl decane ane pressure-sensitive adhesive. Then, a pressure-sensitive adhesive composition having a solid content of 40% was applied to the coating. 〇. 〇 25mm PET film, and then immediately dry at 7 ° C for 1 minute. Ran 25 200944569 After the dry glue was cured at 165 ° C for 2 minutes. The resulting dry glue has a thickness of 0.040 mm. Example 2 5 Triterpene borate (5 parts by weight) and CAT-PL-50T catalyst (ShinEtsuX 0.83 parts by weight) were added to a solution containing 100 parts by weight of ShinEtsu KR3700 polydimethyl decane pressure-sensitive adhesive. Medium and dispersed evenly under agitation. The resulting pressure-sensitive adhesive ❹ composition having a solid content of 40% was then coated on a 0.025 mm PET film, and immediately dried at 70 ° C for 1 minute. The dry glue was then cured at 130 ° C for 2 minutes to give a dry glue having a thickness of 0.040 mm. Example 3 Tributyl phthalate (28 parts by weight) and Luperox® A75 (3 parts by weight 15 parts) were added to a solution containing 100 parts by weight of Momentive PSA610 polydimethyl decane pressure sensitive adhesive, and Disperse evenly under stirring. Then, a pressure-sensitive adhesive composition having a solid content of 40% was applied onto a PET film of 〇 0.025 mm, and then immediately dried at 70 ° C for 1 minute. The dry glue was then cured at 177 t for 2 minutes. The thickness of the obtained dry glue was 0〇4〇20 mm ° Example 4 Boric acid (3 parts by weight) and Degussa DCLBP-50-PSI (3 parts by weight) were added to 100 parts by weight of Dow Corning 280A polydimethyl 25 A solution of a decane-pressure-sensitive adhesive, and disperse and stir while stirring. The pressure-sensitive adhesive composition having a solid content of 40% which was produced after π 200944569 was coated on a 0.025 mm PET film, and then immediately dried at 70 ° C for 1 minute. The dry glue was then cured at 165 ° C for 2 minutes. The resulting dry glue has a thickness of 0.040 mm. 5 Example 5 10 15 ❹ 20 Tributyl borate (12 parts by weight) and Degussa DCLBP-50-PSI (2 parts by weight) were added to 100 parts by weight of Dow Corning 7355 polydimethyl decane pressure sensitive adhesive. In the solution of the agent, and dispersed evenly under stirring. The resulting pressure-sensitive adhesive composition having a solid content of 40% was then coated on a 0.025 mm PET film and immediately dried at 70 ° C for 1 minute. The dry glue was then cured at 165 ° C for 2 minutes. The resulting dry glue has a thickness of 0.040 mm. Example 6 Boric anhydride (3 parts by weight) and Degussa DCLBP-50-PSI (3 parts by weight) were added to a solution containing 100 parts by weight of Dow Corning Q2-7735 polydimethyl decane pressure sensitive adhesive. And dispersed evenly under stirring. The resulting pressure-sensitive adhesive composition having a solid content of 40% was then coated on a 0.025 mm PET film and immediately dried at 70 ° C for 1 minute. The dry glue was then cured at 165 ° C for 2 minutes. The resulting dry glue has a thickness of 0.040 mm. The comparative examples contained no boron-oxygen bond compounds as compared to the corresponding examples, and the others were identical. 12 200944569 Boron-oxygen compound name: Oxygen bond compound amount, wt% Pressure-sensitive adhesive catalyst/crosslinker name catalyst/crosslinker amount, wt% Adhesive strength (N/mm) Example 1 Trimethyl borate 3 KRT002 DCLBP-50-PSI 6 0.74 Comparative Example 1 0 KRT002 DCLBP-50-PSI 6 0.27 Example 2 Trimethyl borate 5 KR3700 CAT-PL-50T 0.83 0.36 Comparative Example 2 0 KR3700 CAT-PL-50T 0.83 0.09 Example 3 Tributyl borate 28 PSA610 A75 3 0.60 Comparative Example 3 0 PSA610 A75 3 0.33 Example 4 Boric acid 3 280A DCLBP-50-PSI 3 0.96 Comparative Example 4 0 280A DCLBP-50-PSI 3 0.36 Example 5 Tributyl borate 12 7355 DCLBP-50-PSI 2 0.81 Comparative Example 5 0 7355 DCLBP-50-PSI 2 0.38 Example 6 Boric anhydride 3 Q2-7735 DCLBP-50-PSI 3 1.31 Comparative Example 6 0 Q2-7735 DCLBP-50-PSI 3 0.41 Example 7 The oxirane polyurea polymer was prepared by dividing the solid content by 20% instead of 30%, Q and using a solvent blend of 75/25 instead of 70/30 of toluene/2-propanol to 5, Preparation of a polymer according to the procedure provided in the section entitled "Preparation of a decane polyurea polymer" in US Pat. No. 6,730,397 B Silicon based organic siloxane polyurea block copolymer (silicone polyurea siloxane) pressure-sensitive adhesive. The elastomer was formulated by blending 63 parts by weight of an elastomer solution, 24.3 parts by weight of MQ resin J, 11.63 parts by weight of toluene, and 1.08 parts by weight of 2-propanol, and mixing well to ensure uniformity of 10 A phthalocyanine polyurea pressure sensitive adhesive. MQ resin J is a MQ resin treated to reduce the stanol content, and is composed of Μ, Q and Η0Η structural units, having an M/Q ratio of 1.2, a SiOH content of 0.8%, The number average molecular weight (??) of 2820, the weight average molecular weight (Mw) of 4600, and the solid content of 63.4% by weight in diphenylbenzene. As outlined below, various amounts of tributyl borate (TBB) were added to the decane polyurea pressure sensitive adhesive. The amount of TBB is reported to be in parts by weight per 100 parts of the siloxane polyurea adhesive. The resulting pressure-sensitive adhesive composition was knife-coated and dried at 70 ° C for 10 minutes to prepare a dry coating of 0.051 mm on PET. Example 8 A polydiorganooxaxane polyglyoxime copolymer (pyridoxane polyethyleneamine) adhesive was prepared as described in Example 1 of U.S. Patent Publication No. 20070148475. Tributyl borate (6 parts by weight) was added to 100 parts by weight of a decyloxypolyamine adhesive. A 30% solids solution of this material in toluene was blended with 50% SR545 MQ resin (available from GE) to form an adhesive composition. The adhesive composition was knife coated and dried at 70 ° C for 10 minutes to prepare a dry coating of 0.051 mm on PET. The adhesion of the resulting PSA tape with and without TBB was tested by the following method: by rolling on a silicone rubber at 30.5 cm/min with a 2 kg roll from McMaster Carr (Part# 8632K922) 60 A Durometer Plain 4.2 mm thick orange-red enamel rubber. In the IMASS testing machine, the adhesive was measured by peeling the adhesive from the silicone rubber at a speed of 30.5 cm/min (12 inches/minute) and a peel angle of 90 degrees. 2009 flat 2009' maintained at 22 ° C and 50% relative humidity. Peel adhesion after 15 minutes and after 24 hours. The results are recorded in grams per inch and converted to Newtons/mm. The average average of 3 measurements is reported. Peel adhesion (N/mm) Example adhesive TBB parts by weight for 15 minutes to maintain for 24 hours Comparative Example 7 Oxalane polyurea 0 0.03 0.04 7a Oxane polyurea 1 0.02 0.04 7b Oxide polyurea 3 0.04 0.04 7c oxoxane polyurea 6 0.02 0.03 7d decane polyurea 10 0.06 0.04 Comparative Example 8 矽 烷 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Peel off from the base rubber and peel off from the substrate.
上述實施例僅係為了方便說明而舉例而已，本發明所 主張之權利範圍自應以申請專利範圍所述為準，而非僅限 於上述實施例。 ❹ 10 【圖式簡單說明】 無 【主要元件符號說明】 無 15 15The above-described embodiments are merely examples for the convenience of the description, and the scope of the claims is intended to be limited by the scope of the claims. ❹ 10 [Simple diagram description] None [Main component symbol description] None 15 15