TW201305179A - Di-isoimide compounds, compositions, and preparation thereof - Google Patents

Abstract

The present invention deals with a novel aromatic di-isoimide compound that has utility as a catalyst and as a curing agent in epoxy compositions. The di-isoimide serves effectively as a thermally activated latent catalyst in epoxy curing, thereby increasing shelf life, and avoids premature cross-linking. Embodiments of useful compositions comprising the novel di-isomide, as well as a method of preparing the compound are provided herein. The preparation of novel laminated articles and printed wiring boards, including encapsulated printed wiring boards, are also disclosed. The inventive compound described herein can also be used as a flame retardant in thermoplastic and thermoset polymers.

Description

雙異醯亞胺化合物、組成物及其製備方法 Bis-isosine imine compound, composition and preparation method thereof 【相關專利申請案】 [related patent application]

本專利申請案係與以下案件相關：美國專利申請案第13/168,047號，名稱為「Curable composition comprising a di-isoimide,method of curing,and the cured composition so formed」；美國專利申請案第13/168,062號，名稱為「Laminate comprising curable epoxy film layer comprising a di-isoimide and process for preparing same」；美國專利申請案第13/168,069號，名稱為「Printed wiring board encapsulated by adhesive laminate comprising a di-isoimide,and process for preparing same」；以及美國專利申請案第13/168,081號，名稱為「Process for preparing substituted and unsubstituted diamino triazine aromatic di-isoimides」。 This patent application is related to the following: U.S. Patent Application Serial No. 13/168,047, entitled "Curable composition comprising a di-isoimide, method of curing, and the cured composition so formed"; U.S. Patent Application Serial No. 13/ No. 168,062, entitled "Laminate comprising curable epoxy film layer comprising a di-isoimide and process for preparing same"; U.S. Patent Application Serial No. 13/168,069, entitled "Printed wiring board encapsulated by adhesive laminate comprising a di-isoimide, And process for preparing the same; and U.S. Patent Application Serial No. 13/168,081, entitled "Process for preparing substituted and unsubstituted diamino triazine aromatic di-isoimides".

本發明係關於一種新穎之芳族雙異醯亞胺化合物及其組成物，其具有於環氧樹脂組成物中作為硬化劑及催化劑之用途。其亦可作為熱塑性及熱固性聚合物中的阻燃劑。 The present invention relates to a novel aromatic bisisoinlimine compound and a composition thereof having the use as a hardener and a catalyst in an epoxy resin composition. It can also be used as a flame retardant in thermoplastic and thermosetting polymers.

環氧樹脂組成物係廣泛用於許多應用上，包括電子產業及其他領域。在某些應用中，會將環氧樹脂組成物與橡膠調合在一起，以提供改良的可撓性、韌性及黏合 強度。其中一種此類應用為可撓性印刷線路板的可撓性覆蓋層。 Epoxy resin compositions are widely used in many applications, including the electronics industry and other fields. In some applications, the epoxy composition is blended with the rubber to provide improved flexibility, toughness, and adhesion. strength. One such application is a flexible cover layer for flexible printed wiring boards.

雖然環氧樹脂提供許多理想的特性，但已知其具有可燃性而不甚理想，通常需要添加阻燃劑至可硬化環氧樹脂調配物中才能符合耐火標準。此外，可硬化環氧樹脂組成物之儲放壽命理想上越長越好。達成長儲放壽命的一種作法是製備所謂的潛伏硬化催化劑或交聯劑(硬化劑)。潛伏催化劑或硬化劑於室溫可不具活性，但可在遠高於室溫的溫度被熱活化。由於實務上的考量，理想上未硬化組成物可在高達40或50℃的溫度保持安定。因此，若潛伏催化劑或硬化劑可在高於50℃之溫度但低於會破壞環氧樹脂或電子電路元件的溫度活化，在本領域中是非常理想的。可無需使用阻燃添加劑的催化劑或硬化劑在最終組成物的性質上特別有利。 While epoxy resins offer many desirable properties, they are known to be less flammable, and it is often desirable to add flame retardants to hardenable epoxy formulations to meet fire resistance standards. In addition, the shelf life of the hardenable epoxy resin composition is desirably as long as possible. One way to achieve a long shelf life is to prepare a so-called latent hardening catalyst or crosslinker (hardener). The latent catalyst or hardener may be inactive at room temperature, but may be thermally activated at temperatures well above room temperature. Due to practical considerations, the ideally unhardened composition can remain stable at temperatures up to 40 or 50 °C. Thus, it is highly desirable in the art if the latent catalyst or hardener can be activated at temperatures above 50 ° C but below temperatures that would damage the epoxy or electronic circuit components. Catalysts or hardeners which do not require the use of flame retardant additives are particularly advantageous in terms of the nature of the final composition.

本發明之組成物提供一種適用於可硬化環氧樹脂組成物之硬化催化劑及交聯劑、一種藉此製備之可硬化環氧樹脂組成物、一種由此製備之經硬化組成物、一種塗覆有該可硬化組成物之膜或板以及一種包含該經硬化組成物之經封裝之印刷線路板。 The composition of the present invention provides a hardening catalyst and a crosslinking agent suitable for a hardenable epoxy resin composition, a hardenable epoxy resin composition prepared thereby, a hardened composition prepared thereby, and a coating A film or sheet having the hardenable composition and a packaged printed wiring board comprising the hardened composition.

在一態樣中，本發明提供一種雙異醯亞胺化合物，如結構I所示 其中R₁為H、鹵素、烴基、烴氧基、烴硫基、醯胺基、磺醯胺基、環胺基、醯基、嗎啉基、哌啶基或NR’R”，其中R’及R”各自獨立為H、經取代或未經取代之烷基或經取代或未經取代之芳族。 In one aspect, the invention provides a bisisoindenine compound as shown in Structure I Wherein R ₁ is H, halogen, hydrocarbyl, alkoxy, hydrocarbylthio, decylamino, sulfonylamino, cyclic amine, decyl, morpholinyl, piperidinyl or NR'R", wherein R' And R" are each independently H, substituted or unsubstituted alkyl or substituted or unsubstituted aromatic.

在另一態樣中，本發明提供一種用於製備結構I所示之雙異醯亞胺化合物的第一製程，該製程包括在-10至160℃之溫度範圍於第一溶劑中將具有以下結構之焦蜜石酸二酐(PMDA) 與結構II所示之經取代或未經取代之二胺基三【口+井】進行混合 其中R₁為H、鹵素、烴基、烴氧基、烴硫基、醯胺基、磺醯胺基、環胺基、醯基、嗎啉基、哌啶基或NR’R”，其中R’及R”各自獨立為H、經取代或未經取代之烷基或經取代或未經取代之芳族。 In another aspect, the present invention provides a first process for preparing a bisisoindenine compound of structure I, which process comprises a temperature in the range of -10 to 160 ° C in a first solvent. Structure of pyrethic acid dianhydride (PMDA) Mixing with substituted or unsubstituted diamine-based three [mouth + well] as shown in structure II Wherein R ₁ is H, halogen, hydrocarbyl, alkoxy, hydrocarbylthio, decylamino, sulfonylamino, cyclic amine, decyl, morpholinyl, piperidinyl or NR'R", wherein R' And R" are each independently H, substituted or unsubstituted alkyl or substituted or unsubstituted aromatic.

在又一態樣中，本發明提供一種可硬化組成物，包括一溶劑或溶劑混合物，其包括一第一溶劑以及至少一其中混合有一環氧樹脂及一結構I所示之雙異醯亞胺化合物之第二溶劑 其中R₁為H、鹵素、烴基、烴氧基、烴硫基、醯胺基、磺醯胺基、環胺基、醯基、嗎啉基、哌啶基或NR’R”，其中R’及R”各自獨立為H、經取代或未經取代之烷基或經取代或未經取代之芳族。 In still another aspect, the present invention provides a hardenable composition comprising a solvent or a solvent mixture comprising a first solvent and at least one bisisoinimine mixed with an epoxy resin and a structure I Second solvent of the compound Wherein R ₁ is H, halogen, hydrocarbyl, alkoxy, hydrocarbylthio, decylamino, sulfonylamino, cyclic amine, decyl, morpholinyl, piperidinyl or NR'R", wherein R' And R" are each independently H, substituted or unsubstituted alkyl or substituted or unsubstituted aromatic.

在又一態樣中，本發明提供一種第二製程，包括將此處之可硬化組成物加熱至100至250℃之範圍的一溫度達一段30秒至5小時之範圍的時間，藉此形成對應的經硬化組成物。 In still another aspect, the present invention provides a second process comprising heating a hardenable composition herein to a temperature in the range of 100 to 250 ° C for a period of 30 seconds to 5 hours, thereby forming Corresponding hardened composition.

在另一態樣中，本發明係關於一種積層物品，包括一基材及沉積於其上之塗層，其中該基材為一聚合物板或膜，而該塗層包括一可硬化組成物，其包括其中混合有一環氧樹脂及一結構I所示之雙異醯亞胺化合物之第二溶劑。 In another aspect, the present invention is directed to a laminated article comprising a substrate and a coating deposited thereon, wherein the substrate is a polymeric sheet or film and the coating comprises a hardenable composition It comprises a second solvent in which an epoxy resin and a bisisoindenine compound represented by structure I are mixed.

在又一態樣中，本發明係關於一種印刷線路板，其依序包括一第一介電基材之第一層、位於該第一介電基材上之一或多個分離導電途徑之第二層、與該分離導電途徑黏合接觸之黏合性結合層之第三層以及一可撓性第二介電基材之第四層，該黏合性結合層包括一可硬化組成物，其包括一其中混合有一環氧樹脂及一結構I所示之雙異醯亞胺化合物之第二溶劑。 In still another aspect, the present invention is directed to a printed wiring board comprising a first layer of a first dielectric substrate, one or more separate conductive paths on the first dielectric substrate. a second layer, a third layer of an adhesive bonding layer in adhesive contact with the separate conductive path, and a fourth layer of a flexible second dielectric substrate, the adhesive bonding layer comprising a hardenable composition comprising A second solvent in which an epoxy resin and a bisisoindenine compound represented by the structure I are mixed.

在另一態樣中，本發明提供一種用於製備經封裝之印刷線路板的製程，該製程包括將表面上設置有塗層的積層物品之塗覆表面與設置在一介電基材之分離導電途徑之至少一部分黏合性接觸，藉此形成一多層物品；以及在100至250℃之範圍的一溫度施加壓力至由此形成的印刷線路板達一段30秒至5小時之範圍的時間，藉此形成一經封裝之印刷線路板；其中該印刷線路板依序包括一第一介電基材之第一層、位於該第一介電基材上之一或多個分離導電途徑之第二層、與該分離導電途徑黏合接觸之黏合性結合層之第三層以及一可撓性第 二介電基材之第四層，該黏合性結合層包括一可硬化組成物，其包括一其中混合有一環氧樹脂及一結構I所示之雙異醯亞胺化合物之第二溶劑。 In another aspect, the present invention provides a process for preparing a packaged printed wiring board, the process comprising separating a coated surface of a laminated article having a coating on a surface from a dielectric substrate. At least a portion of the electrically conductive pathway is adhesively contacted thereby forming a multilayer article; and applying a pressure to a temperature of the range of from 100 to 250 ° C to the thus formed printed wiring board for a period of from 30 seconds to 5 hours, Forming a packaged printed circuit board; wherein the printed circuit board sequentially includes a first layer of a first dielectric substrate, and a second one of the plurality of separate conductive paths on the first dielectric substrate a layer, a third layer of the adhesive bonding layer in contact with the separated conductive path, and a flexible portion A fourth layer of a dielectric substrate, the adhesive bonding layer comprising a hardenable composition comprising a second solvent in which an epoxy resin and a bisisoindenine compound of structure I are mixed.

術語「環氧樹脂」係指包含環氧化物基團之聚合性(通常為寡聚性)化合物。適用於本文製程之交聯劑為一種與環氧化物基團反應之多官能性分子。其經交聯反應產物為交聯劑與環氧樹脂分子內的環氧化物或其他基團反應時所形成的反應產物。術語「環氧樹脂」傳統上係指含有環氧化物基團之未經硬化之樹脂。透過此種表達方式，一旦環氧樹脂經硬化，其本質上就將不再是環氧樹脂。然而，當於經硬化材料之上下文中指涉到本文之環氧樹脂時，其應理解為係指該經硬化材料。術語「經硬化環氧樹脂」應理解為代表本文所定義之環氧樹脂與本文所定義之硬化劑的反應產物。 The term "epoxy resin" refers to a polymerizable (usually oligomeric) compound comprising an epoxide group. Crosslinkers suitable for use in the processes herein are polyfunctional molecules that react with epoxide groups. The crosslinked reaction product is a reaction product formed when the crosslinking agent reacts with an epoxide or other group in the epoxy resin molecule. The term "epoxy resin" conventionally refers to an uncured resin containing an epoxide group. Through this expression, once the epoxy resin is hardened, it will essentially no longer be an epoxy resin. However, when reference is made to an epoxy resin herein in the context of a hardened material, it is understood to mean the hardened material. The term "cured epoxy resin" is understood to mean the reaction product of an epoxy resin as defined herein with a hardener as defined herein.

術語「經硬化」係指經歷實質交聯的環氧樹脂組成物，用語「實質」代表環氧樹脂中75%至100%的可用硬化位置進行交聯。在「完全經硬化」環氧樹脂組成物中，較佳係超過90%的可用硬化位置被交聯。術語「未經硬化」係指環氧樹脂組成物經歷輕度交聯。術語「經硬化」及「未經硬化」應理解為功能性用語。未經硬化環氧樹脂組成物之特徵在於其可溶解於有機溶劑且在環境條件下有能力經歷塑性流。適用於實施本發明的經硬化環氧樹脂組成物之特徵在於其不溶於有機溶劑且在環境條件下沒有塑性流。本領域已熟知未經硬化環氧 樹脂組成物內的部分可用硬化位置可被交聯，且經硬化環氧樹脂組成物內的部分可用硬化位置尚未被交聯。然而，不論在哪一種情況中，各別組成物的區隔性特質都不會被顯著影響。 The term "hardened" refers to an epoxy resin composition that undergoes substantial cross-linking, and the term "substantial" means that 75% to 100% of the available hardening sites in the epoxy resin are crosslinked. In the "fully cured" epoxy resin composition, it is preferred that more than 90% of the available hardening sites are crosslinked. The term "unhardened" means that the epoxy resin composition undergoes mild crosslinking. The terms "hardened" and "unhardened" are to be understood as functional terms. The uncured epoxy resin composition is characterized in that it is soluble in an organic solvent and has the ability to undergo plastic flow under ambient conditions. A cured epoxy resin composition suitable for use in the practice of the invention is characterized in that it is insoluble in organic solvents and has no plastic flow under ambient conditions. Unhardened epoxy is well known in the art The portion within the resin composition may be crosslinked by a hardening position, and a portion of the hardened epoxy resin composition that has been used in the hardened position has not been crosslinked. However, in either case, the distinguishing characteristics of the individual compositions are not significantly affected.

本領域也區分出部分經硬化之環氧樹脂組成物，已知為「B階段」材料。B階段材料可含有至多10重量%的溶劑，且展現出介於實質經硬化與未經硬化狀態之間的性質。 Partially cured epoxy resin compositions are also known in the art and are known as "B-stage" materials. The B-stage material may contain up to 10% by weight of solvent and exhibit properties between substantially hardened and unhardened states.

為本發明之目的，術語「可硬化組成物」應指一種組成物，其包括生產「經硬化」組成物所需的所有元素，但尚未經歷「硬化製程」且因而尚未被硬化。可硬化組成物可輕易變形及處理，但經硬化組成物則不然。術語「可硬化」及「經硬化」在意義上分別類似於術語「可交聯」及「經交聯」。 For the purposes of the present invention, the term "hardenable composition" shall mean a composition which includes all of the elements required to produce a "hardened" composition, but which has not yet undergone a "hardening process" and thus has not yet been hardened. The hardenable composition can be easily deformed and treated, but the hardened composition is not. The terms "hardenable" and "hardened" are similar in meaning to the terms "crosslinkable" and "crosslinked".

雖然本發明並不受限於此，但咸信環氧樹脂與本文之雙異醯亞胺的反應很大程度屬於一種反應，其中雙異醯亞胺的胺基會打開環氧乙烷環(或常被稱為環氧基)，因而形成一氮碳鍵結以及一烷基羥基。因此，在上述情形中雙異醯亞胺係作為交聯劑。舉例而言，若同時也存在苯酚酚醛，乙烷環之開環反應主要將受到酚醛之苯酚羥基與乙烷環之反應的影響，藉此產生一氧碳鍵結以及一烷基羥基。若不存在更具活性的交聯劑(例如苯酚)，則雙異醯亞胺同時作為交聯劑與催化劑。 Although the invention is not limited thereto, the reaction of the salty epoxy resin with the bisisoindenine herein is largely a reaction in which the amine group of the bisisointhine opens the oxirane ring ( Or often referred to as an epoxy group, thereby forming a nitrogen-carbon bond and a mono-alkyl group. Therefore, in the above case, the bisisoindenine is used as a crosslinking agent. For example, if phenol novolac is also present, the ring opening reaction of the ethane ring is mainly affected by the reaction of the phenolic hydroxyl group of the phenolic aldehyde with the ethane ring, thereby producing an oxygen-oxygen bond and a monoalkylhydroxy group. If a more reactive crosslinker (such as phenol) is not present, the bisisoindenine acts as both a crosslinker and a catalyst.

術語「膜」及「板」係指平面狀的物品，其長及寬相對大於厚度。膜及板只在厚度上有差異。板在本領域中通常界定為厚度大於或等於250微米，而膜在本領域 中通常界定為厚度小於250微米。如本文所使用，術語「膜」涵蓋設置於一表面上的塗層。 The terms "film" and "plate" refer to a planar article having a length and width that are relatively greater than the thickness. Membranes and plates differ only in thickness. Plates are generally defined in the art as having a thickness greater than or equal to 250 microns, while membranes are in the art It is generally defined as having a thickness of less than 250 microns. As used herein, the term "film" encompasses a coating disposed on a surface.

術語「分離導電途徑」於本文中係指一種導電途徑，其係設置於膜或板形式的介電基材上，可於基材平面上由一點引導至另一點，或透過平面由一側引導至另一側。 The term "isolated conductive pathway" as used herein refers to a conductive pathway that is disposed on a dielectric substrate in the form of a film or sheet that can be guided from one point to another on the plane of the substrate or guided from one side through the plane. To the other side.

於本發明中有數個術語被重複使用，其僅於第一次提及時詳細描述。然而，為了避免繁瑣，術語的描述於其再次出現於後文時並不再次重複。應了解的是，為了本發明之目的，當一術語在文中重複時，該術語的描述及意義並未改變且與其第一次提及時相同。舉例而言，術語「結構I所示之雙異醯亞胺化合物」每次出現時都應理解為涵蓋其於文中第一次出現時針對結構I引述的所有可能實施例。另舉一例，術語「第二溶劑」應理解為係指該術語於文中第一次出現時「第二溶劑」所描述的同一組溶劑。 There are several terms that are reused in the present invention, which are described in detail only when first mentioned. However, in order to avoid cumbersomeness, the description of the term is not repeated again when it appears again in the following text. It will be appreciated that for the purposes of the present invention, when a term is repeated in the text, the description and meaning of the term does not change and is the same as when it is first mentioned. For example, the term "biisinimide compound as shown in structure I" should be understood to encompass every possible embodiment cited for structure I when it first appears in the text. As another example, the term "second solvent" is understood to mean the same group of solvents as the term "second solvent" when the term first appears.

為本發明之目的，術語「室溫」係用於表示環境實驗條件。如本領域之術語，「室溫」通常用於代表約23℃，涵蓋約20℃至約30℃之溫度。 For the purposes of the present invention, the term "room temperature" is used to denote environmental experimental conditions. As the term is used in the art, "room temperature" is generally used to mean about 23 ° C, and covers temperatures of from about 20 ° C to about 30 ° C.

術語「印刷線路板」(PWB)應指一種介電基材層，其上設置有複數分離導電途徑。基材為板或膜。在本發明一實施例中，介電基材為一聚醯亞胺膜。在又一實施例中，聚醯亞胺膜具有5至75微米之厚度。在一實施例中，分離導電途徑為銅。 The term "printed wiring board" (PWB) shall mean a dielectric substrate layer on which a plurality of discrete conductive paths are disposed. The substrate is a plate or film. In an embodiment of the invention, the dielectric substrate is a polyimide film. In yet another embodiment, the polyimide film has a thickness of from 5 to 75 microns. In one embodiment, the separated conductive pathway is copper.

適用於實施本發明的PWB可藉由本領域已知且廣泛採用的方式製備。概言之，適合的PWB可由一製程 製備，其包括利用一黏合層之組合(通常為環氧樹脂)將一銅箔積層至一介電膜或板以及施加熱及壓力。將光阻施用於銅表面以獲得高解析度電路線(寬度125微米)。光阻為一種光敏性有機材料，當光阻經顯影而表面被蝕刻且其經歷影像式曝光時會形成刻痕。於適合的PWB中，影像係以複數形式分離導電途徑位於介電膜或板表面。 PWBs suitable for use in the practice of the invention can be prepared by methods known in the art and widely employed. In summary, a suitable PWB can be prepared by a process that includes laminating a copper foil to a dielectric film or plate and applying heat and pressure using a combination of adhesive layers (typically epoxy). Applying photoresist to the copper surface to obtain high resolution circuit lines (width 125 microns). The photoresist is a photosensitive organic material that forms a score when the photoresist is developed and the surface is etched and it undergoes imagewise exposure. In a suitable PWB, the image is separated in a plurality of forms and the conductive path is on the surface of the dielectric film or plate.

光阻可以液態施用並進行乾燥，或以例如沉積於聚酯離形膜上的聚合物膜形式積層。於使用液態塗覆時，需特別注意以確保均勻厚度。於曝光(通常為紫外光輻射)時，光阻會經歷光聚合反應，藉此改變其於「顯影劑」化合物中的溶解度。負光阻通常由丙烯酸酯單體、聚合物黏結劑及光起始劑的混合物所組成。在經由圖案化光罩進行影像式UV曝光後，光阻的曝光區將聚合且變成不溶於顯影劑。未曝光區則保持可溶且被洗去，留下代表導電途徑的銅區域，其於後續移除未受保護之導電途徑的蝕刻步驟中會由經聚合光阻所保護。在蝕刻後，利用任一種方便的技術將經聚合光阻移除，包括溶解於適當的溶劑中或表面剝蝕。正光阻則以相反方式作用，其UV曝光區域會變成可溶於顯影溶劑中。正光阻和負光阻皆於商業上被廣泛使用。一種知名的正光阻為所謂的DNQ/酚醛光阻組成物。 The photoresist can be applied in a liquid state and dried, or laminated in the form of a polymer film deposited, for example, on a polyester release film. When using liquid coating, special care is required to ensure uniform thickness. Upon exposure (usually ultraviolet radiation), the photoresist undergoes photopolymerization, thereby altering its solubility in the "developer" compound. The negative photoresist is usually composed of a mixture of an acrylate monomer, a polymer binder, and a photoinitiator. After imagewise UV exposure via a patterned mask, the exposed areas of the photoresist will polymerize and become insoluble in the developer. The unexposed regions remain soluble and washed away, leaving a copper region representative of the conductive pathway that is protected by the polymeric photoresist during the subsequent etching step to remove the unprotected conductive pathway. After etching, the polymerized photoresist is removed using any convenient technique, including dissolution in a suitable solvent or surface ablation. The positive photoresist acts in the opposite manner and its UV exposed areas become soluble in the developing solvent. Both positive and negative photoresists are widely used commercially. A well-known positive photoresist is the so-called DNQ/phenolic photoresist composition.

任一種根據本領域之方法製備的PWB皆適用於本發明。 Any of the PWBs prepared according to methods in the art are suitable for use in the present invention.

在一態樣中，本發明提供一種結構I所示之雙異醯亞胺化合物 其中R₁為H、鹵素、烴基、烴氧基、烴硫基、醯胺基、磺醯胺基、環胺基、醯基、嗎啉基、哌啶基或NR’R”，其中R’及R”各自獨立為H、經取代或未經取代之烷基或經取代或未經取代之芳族。在一實施例中，R₁為NH₂。 In one aspect, the invention provides a bisisoindenine compound of structure I Wherein R ₁ is H, halogen, hydrocarbyl, alkoxy, hydrocarbylthio, decylamino, sulfonylamino, cyclic amine, decyl, morpholinyl, piperidinyl or NR'R", wherein R' And R" are each independently H, substituted or unsubstituted alkyl or substituted or unsubstituted aromatic. In an embodiment, R ₁ is NH ₂ .

在另一態樣中，本發明提供一種可用於製備結構I所示之組成物的第一製程，該第一製程包括在-10至+160℃之溫度範圍於第一溶劑中將PMDA與結構II所示之二胺基三【口+井】進行混合 In another aspect, the present invention provides a first process for preparing a composition of Structure I, the first process comprising PMDA and structure in a first solvent at a temperature ranging from -10 to +160 °C Diamine-based three [mouth + well] shown in II for mixing

其中R₁為H、鹵素、烴基、烴氧基、烴硫基、醯胺基、磺醯胺基、環胺基、醯基、嗎啉基、哌啶基或NR’R”， 其中R’及R”各自獨立為H、經取代或未經取代之烷基或經取代或未經取代之芳族。 Wherein R ₁ is H, halogen, hydrocarbyl, alkoxy, hydrocarbylthio, decylamino, sulfonylamino, cyclic amine, fluorenyl, morpholinyl, piperidinyl or NR'R", wherein R' And R" are each independently H, substituted or unsubstituted alkyl or substituted or unsubstituted aromatic.

在一實施例中，R₁為NH₂。 In an embodiment, R ₁ is NH ₂ .

適合的第一溶劑包括但不限於極性/非質子性溶劑，其特徵在於一偶極矩之範圍為1.5至3.5 D。儘管胺基【口+井】與PMDA間的反應發生於溶液中，反應物於溶劑中並不需要完全互溶。即使有限的溶解度也會讓反應得以進行，其中額外的反應物在反應中被消耗時會溶解。適合的第一溶劑包括但不限於丙酮、甲基乙基酮(MEK)、甲基異丁基酮、丙酸乙酯、3-乙氧基丙酸乙酯、環己酮及其混合物。也適用含有少量(例如少於30重量%)非極性溶劑(例如苯)的上述混合物。在一實施例中，該溶劑為環己酮。 Suitable first solvents include, but are not limited to, polar/aprotic solvents, characterized by a dipole moment ranging from 1.5 to 3.5 D. Although the reaction between the amine group [mouth + well] and PMDA occurs in the solution, the reactants do not need to be completely miscible in the solvent. Even limited solubility allows the reaction to proceed, with additional reactants that dissolve when consumed in the reaction. Suitable first solvents include, but are not limited to, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, ethyl propionate, ethyl 3-ethoxypropionate, cyclohexanone, and mixtures thereof. The above mixtures containing a small amount (for example, less than 30% by weight) of a nonpolar solvent such as benzene are also suitable. In one embodiment, the solvent is cyclohexanone.

若偶極矩低於1.5 D，已經很低的三聚氰胺溶解度會變得更低，以至於反應需要數週才能完成。若溶劑的偶極矩高於3.5 D，將雙異醯亞胺轉化為二醯亞胺的反應速率會過快而不方便，導致所欲之雙異醯亞胺過多損失。 If the dipole moment is less than 1.5 D, the already low melamine solubility will be lower, so that the reaction takes several weeks to complete. If the dipole moment of the solvent is higher than 3.5 D, the reaction rate of converting the bisisoindolimide to diimine will be too fast and inconvenient, resulting in excessive loss of the desired diisoindole.

根據本發明之第一製程，在一適當之第一溶劑的存在下，將PMDA與一前述之適當二胺基三【口+井】(經取代或未經取代)結合，並使其反應。反應溫度可為-10至+160℃之範圍。溫度增加則二醯亞胺的產率也增加，而雙異醯亞胺則被消耗。雖然本發明是關於雙異醯亞胺的製備及有利用途，存在部分二醯亞胺與雙異醯亞胺混合在一起並不必然會有特別的負面影響。在某些情況 中，使用較高的反應溫度而造成選擇性較低但反應速率較高可能是有利的。 According to the first process of the present invention, PMDA is combined with a suitable diamine tris[mouth + well] (substituted or unsubstituted) in the presence of a suitable first solvent and allowed to react. The reaction temperature may range from -10 to +160 °C. The increase in temperature increases the yield of bis-imine, while bisisoinimide is consumed. Although the present invention is directed to the preparation and advantageous use of bisisoindolimimine, the presence of a portion of the diimine and the bisisoindenine does not necessarily have a particular negative impact. In some cases It may be advantageous to use a higher reaction temperature resulting in lower selectivity but higher reaction rates.

一般而言，較高的反應溫度會對應到較快的反應。選擇性取決於溫度以及二酐、三【口+井】與溶劑的特定選擇。舉例而言，溶於環己酮之三聚氰胺及PMDA在25℃產生純異醯亞胺，在50℃產生幾乎純的異醯亞胺，在回流(~155℃)下產生約80%異醯亞胺。在相同溫度，PMDA與三聚氰胺在N,N-二甲基甲醯胺(DMF)中的反應比在環己酮中更快，但若反應未及時停止，則反應會持續進行而由雙異醯亞胺中間體形成醯亞胺。 In general, a higher reaction temperature will correspond to a faster reaction. Selectivity depends on temperature and the specific choice of dianhydride, three [mouth + well] and solvent. For example, melamine and PMDA dissolved in cyclohexanone produce pure isoindole at 25 ° C, producing almost pure isoindole at 50 ° C and about 80% isoindole at reflux (~ 155 ° C). amine. At the same temperature, the reaction of PMDA with melamine in N,N-dimethylformamide (DMF) is faster than in cyclohexanone, but if the reaction does not stop in time, the reaction will continue to proceed from the diisoindole The imine intermediate forms a quinone imine.

在一實施例中，反應溫度之範圍為室溫至100℃。在又一實施例中，反應溫度之範圍為室溫至50℃。 In one embodiment, the reaction temperature ranges from room temperature to 100 °C. In yet another embodiment, the reaction temperature ranges from room temperature to 50 °C.

為能提供結構I所示之所欲雙異醯亞胺，本發明之第一製程不需使用水清除劑(例如三氟乙酸)。本發明之第一製程較佳係省略任一種水清除劑，以避免後續需要在反應完成後移除水清除劑。 In order to provide the desired diisoindoleimine as shown in Structure I, the first process of the present invention does not require the use of a water scavenger (e.g., trifluoroacetic acid). The first process of the present invention preferably omits any water scavenger to avoid subsequent removal of the water scavenger after completion of the reaction.

為能使反應物完全轉化成雙異醯亞胺產物，在反應期間維持高度混合非常重要。舉例而言，三聚氰胺在適當溶劑中的溶解度非常有限。PMDA也僅是稍微可溶。為能於商業上可行的時段內達到高轉化率，有必要維持反應物彼此間及與溶劑間的良好互混。儘管本發明不受限於此，咸信反應物之溶液平衡會導致少量反應物溶解，且藉此溶解的反應物會反應以形成雙異醯亞胺沉澱，據此造成額外的反應物溶解。咸信此製程會持續直到反應物用盡，且轉化率可由溶劑分散液的紅外光(IR)光譜儀中反應物峰的消失而量化。 In order to completely convert the reactants into diisoindolimine products, it is important to maintain a high degree of mixing during the reaction. For example, the solubility of melamine in a suitable solvent is very limited. PMDA is also only slightly soluble. In order to achieve high conversion rates in a commercially viable time period, it is necessary to maintain good intermixing of the reactants with each other and with the solvent. Although the invention is not limited thereto, the solution equilibrium of the salty reactants will cause a small amount of reactant to dissolve, and thereby the dissolved reactant will react to form a bisisoindenine precipitate, thereby causing additional reactant dissolution. It is believed that this process will continue until the reactants are used up and the conversion can be quantified by the disappearance of the reactant peaks in the infrared light (IR) spectrometer of the solvent dispersion.

可利用機械攪拌(如磁性攪拌)達成適當的混合。當溶劑中反應物(及產物)分散液具有均勻外觀而不存在滯留固體區域時即為良好的混合狀態。較佳係進行攪拌以於整個反應期間都維持均勻外觀。 Appropriate mixing can be achieved using mechanical agitation, such as magnetic agitation. A good mixed state is obtained when the reactant (and product) dispersion in the solvent has a uniform appearance without the presence of a retained solid region. Stirring is preferably carried out to maintain a uniform appearance throughout the reaction.

經發現，於本發明實作時，如實例7及8所例示，在溶液中存在含有羧酸基團之橡膠的條件下進行第一製程會使反應達到比沒有使用橡膠的相同反應更高的轉化率。 It has been found that, in the practice of the present invention, as exemplified in Examples 7 and 8, performing the first process under conditions in which a rubber containing a carboxylic acid group is present in the solution causes the reaction to be higher than the same reaction without using rubber. Conversion rates.

在又一態樣中，本發明提供一種可硬化組成物，包括一其中混合有一環氧樹脂及一結構I所示之雙異醯亞胺化合物之第二溶劑。在一實施例中，該第二溶劑與該第一溶劑相同。 In still another aspect, the present invention provides a hardenable composition comprising a second solvent in which an epoxy resin and a bisisoindenine compound of structure I are mixed. In an embodiment, the second solvent is the same as the first solvent.

經觀察，於本發明實作時，在相對溫和的低沸點溶劑(例如環己酮及MEK)中，此處的雙異醯亞胺具有比類似的醯亞胺更高的溶解度。需要使用沸點較高的溶劑，例如二甲基乙醯胺(DMAC)或n-甲基吡咯啶酮(NMP)來溶解醯亞胺。本文之雙異醯亞胺的此特色對於配製具有實際商業應用性之環氧樹脂而言至為重要。在移除高沸點溶劑時卻不同時引發環氧樹脂硬化是非常困難的。對於黏合應用而言，特別是例如製造本文所述之經封裝PWB的高度關鍵應用上，由於黏合劑被密封於所結合的兩個表面之間，且溶劑無法在不造成最終產品中的泡泡及空隙的情形下逸出，因此將溶劑完全移除是非常重要的。泡泡及空隙會對介電常數的均一性造成不良影響。 It has been observed that in the practice of the present invention, the bisisoindenine herein has a higher solubility than similar quinones in relatively mild low boiling solvents such as cyclohexanone and MEK. It is necessary to use a solvent having a higher boiling point such as dimethylacetamide (DMAC) or n-methylpyrrolidone (NMP) to dissolve the quinone. This feature of the diisoindole imine herein is important for formulating epoxy resins with practical commercial applicability. It is very difficult to cause the epoxy resin to harden at the same time when the high boiling point solvent is removed. For bonding applications, particularly in highly critical applications such as the fabrication of packaged PWBs described herein, the adhesive is sealed between the two surfaces being bonded, and the solvent cannot be bubbled in the final product. In the case of voids, it escapes, so it is very important to completely remove the solvent. Bubbles and voids can adversely affect the uniformity of the dielectric constant.

適合用作為第二溶劑的溶劑包括但不限於丙酮、MEK、環己酮、戊酮、二氧雜環戊烷、四氫呋喃、二醇醚、丙二醇甲醚醋酸酯(PMA)、N-甲基吡咯啶酮、N,N-二甲基乙醯胺、DMF、二甲亞碸、N,N-二乙基乙醯胺、N,N-二乙基甲醯胺、N,N-二甲基甲氧基乙醯胺。較佳的溶劑為MEK、環己酮、PMA及DMF。亦適用溶劑的混合物。 Suitable solvents for use as the second solvent include, but are not limited to, acetone, MEK, cyclohexanone, pentanone, dioxolane, tetrahydrofuran, glycol ether, propylene glycol methyl ether acetate (PMA), N-methylpyrrole Iridone, N,N-dimethylacetamide, DMF, dimethyl hydrazine, N,N-diethyl acetamide, N,N-diethylformamide, N,N-dimethyl Methoxyacetamide. Preferred solvents are MEK, cyclohexanone, PMA and DMF. A mixture of solvents is also suitable.

參見結構I，在一實施例中，R₁為NH₂。 Referring to Structure I, in one embodiment, R ₁ is NH ₂ .

適用於本文之可硬化組成物的環氧樹脂為每聚合物鏈平均含有至少兩個環氧化物基團的環氧樹脂。適合的環氧樹脂包括但不限於多酚化合物之多官能性環氧樹脂環氧丙基醚、酚醛樹脂之多官能性環氧樹脂環氧丙基醚、脂環族環氧樹脂、脂族環氧樹脂、雜環狀環氧樹脂、環氧丙基酯環氧樹脂、環氧丙基胺環氧樹脂以及環氧丙基化鹵化苯酚環氧樹脂。較佳之環氧樹脂包括環氧樹脂酚醛、聯酚環氧樹脂、雙酚-A環氧樹脂以及萘環氧樹脂。較佳之環氧樹脂為具有1至5個重複單元的寡聚物。最佳係該環氧樹脂為雙酚-A或酚醛環氧樹脂，特別是雙酚A二環氧丙基醚。 Epoxy resins suitable for use in the hardenable compositions herein are those having an average of at least two epoxide groups per polymer chain. Suitable epoxy resins include, but are not limited to, polyfunctional epoxy resins of polyphenolic compounds, glycidyl ether, polyfunctional epoxy resins of phenolic resins, epoxy propyl ethers, cycloaliphatic epoxy resins, aliphatic rings. Oxygen resin, heterocyclic epoxy resin, epoxy propyl ester epoxy resin, epoxypropylamine epoxy resin, and epoxypropylated halogenated phenol epoxy resin. Preferred epoxy resins include epoxy resin phenolics, biphenol epoxy resins, bisphenol-A epoxy resins, and naphthalene epoxy resins. Preferred epoxy resins are oligomers having from 1 to 5 repeating units. Preferably, the epoxy resin is bisphenol-A or a phenolic epoxy resin, especially bisphenol A diglycidyl ether.

環氧樹脂可由本領域所述之任一種方式進行衍生。尤其它們可被鹵化，特別是以溴進行鹵化以達到阻燃性，或由氟進行鹵化。 The epoxy resin can be derivatized by any of the means described in the art. In particular, they can be halogenated, in particular halogenated with bromine to achieve flame retardancy, or halogenated by fluorine.

在本文之可硬化組成物一實施例中，R₁為NH₂；溶劑為MEK、環己酮、丙二醇甲醚醋酸酯、DMF或其混合物；以及該環氧樹脂為雙酚-A型。 In one embodiment of the hardenable composition herein, R ₁ is NH ₂ ; the solvent is MEK, cyclohexanone, propylene glycol methyl ether acetate, DMF or a mixture thereof; and the epoxy resin is bisphenol-A type.

結構I所示之雙異醯亞胺可於本文之可硬化組成物中同時作為硬化催化劑及/或作為硬化劑。異醯亞胺部分降低經硬化環氧樹脂之可燃性(相較於苯酚酚醛，其不具有可比較的阻燃效果)，因而降低阻燃劑的需求。在一實施例中，該可硬化組成物更包括一硬化劑。任一種本領域已知的硬化劑皆可用於本文所揭露的組成物及製程中。適合的硬化劑包括有機酸酐及苯酚。為能方便處理，較佳係使用單酐硬化劑。 The bisisoindenine of the structure I can be used both as a hardening catalyst and/or as a hardener in the hardenable composition herein. The isoindole imine reduces the flammability of the cured epoxy resin (which does not have comparable flame retardant effects compared to phenol novolac), thus reducing the need for flame retardants. In one embodiment, the hardenable composition further comprises a hardener. Any of the hardeners known in the art can be used in the compositions and processes disclosed herein. Suitable hardeners include organic acid anhydrides and phenols. In order to facilitate handling, it is preferred to use a monoanhydride hardener.

在另一實施例中，本文之可硬化組成物並不包括另外的硬化劑。經發現，在本發明此實施例的實作上，胺基的親核性質會因為三【口+井】環與異醯亞胺鍵聯的存在而大幅降低。更進一步發現，一旦環上的其中一個胺基經歷反應，則第二個胺基會變得較不具反應性。因此，於調配本實施例的可硬化組成物上，藉由將每莫耳的結構I的雙異醯亞胺視為由環氧樹脂之交聯觀點的兩當量，可達成令人滿意的結果。經發現，據此含有環氧樹脂當量20%過量之調配物可令人滿意。 In another embodiment, the hardenable composition herein does not include an additional hardener. It has been found that in the practice of this embodiment of the invention, the nucleophilic nature of the amine group is substantially reduced by the presence of the triple [mouth + well] ring and the isoindole imine linkage. It has further been found that once one of the amine groups on the ring undergoes a reaction, the second amine group becomes less reactive. Therefore, in formulating the hardenable composition of the present embodiment, satisfactory results can be obtained by considering the bisisointhine imine of structure I per mole as two equivalents from the viewpoint of crosslinking of the epoxy resin. . It has been found that a formulation containing an excess of 20% epoxy equivalent is satisfactory.

此處之可硬化組成物可包括本領域中常用於環氧樹脂內的各種添加劑之任一者或全部。此可包括阻燃劑、橡膠或其他增韌劑、無機粒子、塑化劑、表面活性劑及流變改質劑。 The hardenable composition herein may include any or all of the various additives commonly used in epoxy resins in the art. This may include flame retardants, rubber or other toughening agents, inorganic particles, plasticizers, surfactants, and rheology modifiers.

在一實施例中，此處之可硬化組成物包括低分子量液態環氧樹脂，其係作為用於結構I所示之雙異醯亞胺化合物的分散介質。低分子量環氧樹脂，例如EPON^TM Resin 828，特徵在於當量重量為185至192 g/eq。然而，此種低分子量環氧樹脂較不如本領域熟知的更具糊狀 且更黏的高分子量高效能環氧樹脂。高分子量環氧樹脂，例如EPON^TM Resin 1001F，之特徵在於當量重量為525至550 g/eq。雖然可將高分子量環氧樹脂形成的反應混合物加熱以降低黏性，為該目的進行加熱並不理想，特別是存在催化劑時，因為這樣有可能會造成過早硬化。在一極佳實施例中，高分子量環氧樹脂被溶解於此處之第二溶劑中，或只是分散於其中，之後將結構I的雙異醯亞胺化合物的溶液或分散液分散至其中以形成此處的可硬化組成物。 In one embodiment, the hardenable composition herein comprises a low molecular weight liquid epoxy resin as a dispersion medium for the bisisoindenine compound of structure I. Low molecular weight epoxy resins such as EPON ^TM Resin 828, wherein an equivalent weight of 185 to 192 g / eq. However, such low molecular weight epoxy resins are less viscous and more viscous high molecular weight high performance epoxy resins as are well known in the art. High molecular weight epoxy resins such as EPON ^TM Resin 1001F, wherein the equivalent weight is 525 to 550 g / eq. Although the reaction mixture formed of the high molecular weight epoxy resin can be heated to lower the viscosity, heating for this purpose is not desirable, especially in the presence of a catalyst, since it is possible to cause premature hardening. In a very preferred embodiment, the high molecular weight epoxy resin is dissolved in the second solvent herein, or is merely dispersed therein, after which a solution or dispersion of the bisisoindenine compound of structure I is dispersed therein. The hardenable composition is formed here.

適合的硬化劑為苯酚及芳族酸酐。環氧樹脂及硬化劑係基於其當量重量之數量進行混合。在苯酚硬化劑之情形中，針對每當量的環氧樹脂，經發現適合者較佳係使用0.3至0.9當量的苯酚。針對酸酐硬化劑，每一當量的環氧樹脂較佳係使用0.4至0.6當量的酸酐。 Suitable hardeners are phenol and aromatic anhydrides. The epoxy resin and the hardener are mixed based on the equivalent weight thereof. In the case of a phenol hardener, it is preferred to use 0.3 to 0.9 equivalents of phenol per equivalent of epoxy resin. For the anhydride hardener, it is preferred to use 0.4 to 0.6 equivalents of an acid anhydride per equivalent of the epoxy resin.

適合的苯酚硬化劑包括聯酚、雙酚A、雙酚F、四溴雙酚A、二羥二苯基碸、酚醛及利用前述苯酚與甲醛進行反應而得之其他苯酚寡聚物。適合的酸酐硬化劑為納迪克甲基酸酐(nadic methyl anhydride)、甲基四氫鄰苯二甲酸酐及芳族酸酐。 Suitable phenolic hardeners include biphenol, bisphenol A, bisphenol F, tetrabromobisphenol A, dihydroxydiphenyl hydrazine, phenolic aldehydes, and other phenol oligomers obtained by reacting the aforementioned phenol with formaldehyde. Suitable anhydride hardeners are nadic methyl anhydride, methyltetrahydrophthalic anhydride, and aromatic anhydrides.

芳族酸酐硬化劑包括但不限於芳族四羧酸二酐，例如焦蜜石酸二酐、聯苯四羧酸二酐、二苯基酮四羧酸二酐、氧雙鄰苯二甲酸二酐、4,4'-(六氟亞異丙基)雙鄰苯二甲酸二酐、萘四羧酸二酐、噻吩四羧酸二酐、3,4,9,10-苝四羧酸二酐、吡【口+井】四羧酸二酐及3,4,7,8-蒽醌四羧酸二酐。其他適合的酸酐硬化劑為寡聚物或聚合物，其係由順丁烯二酸酐和乙烯、異丁烯、乙烯基甲基 醚及苯乙烯進行共聚合反應而得。順丁烯二酸酐接枝之聚丁二烯亦可作為硬化劑。 Aromatic anhydride hardeners include, but are not limited to, aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, biphenyl tetracarboxylic dianhydride, diphenyl ketone tetracarboxylic dianhydride, oxydiphthalic acid II Anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, naphthalenetetracarboxylic dianhydride, thiophene tetracarboxylic dianhydride, 3,4,9,10-nonanedicarboxylic acid Anhydride, pyridinium + well tetracarboxylic dianhydride and 3,4,7,8-anthracene tetracarboxylic dianhydride. Other suitable anhydride hardeners are oligomers or polymers which are composed of maleic anhydride and ethylene, isobutylene, vinyl methyl The ether and styrene are obtained by copolymerization. Maleic anhydride grafted polybutadiene can also be used as a hardener.

適合的增韌劑為低分子量彈性體或熱塑性聚合物，且含有用於和環氧樹脂進行反應之官能基。實例為聚丁二烯、聚丙烯酸、苯氧基樹脂、聚苯醚、聚苯硫及聚苯碸、端羧基丁二烯腈彈性體(CTBN)、CTBN之環氧樹脂加成物、端胺基丁二烯腈彈性體(ATBN)、羧基官能化之彈性體、多元醇彈性體及端胺基多元醇彈性體。較佳係使用CTBN之環氧樹脂加成物、CTBN及羧基官能化之彈性體。 Suitable toughening agents are low molecular weight elastomers or thermoplastic polymers and contain functional groups for reaction with the epoxy resin. Examples are polybutadiene, polyacrylic acid, phenoxy resin, polyphenylene ether, polyphenylene sulfide and polyphenylene fluorene, terminal carboxylated butadiene nitrile elastomer (CTBN), epoxy resin adduct of CTBN, terminal amine A butadiene nitrile elastomer (ATBN), a carboxyl functionalized elastomer, a polyol elastomer, and a terminal amine based polyol elastomer. Preferably, an epoxy resin adduct of CTBN, CTBN and a carboxyl functionalized elastomer are used.

在一實施例中，可將雙異醯亞胺預分散於由其製備的溶劑中。在另一實施例中，可將雙異醯亞胺以粒子形式加入環氧樹脂溶液中，並利用機械攪動法將其分散於其中。 In one embodiment, the bisisoindenine may be predispersed in a solvent prepared therefrom. In another embodiment, the bisisoindenine may be added to the epoxy resin solution as a particle and dispersed therein by mechanical agitation.

在又一態樣中，本發明提供一種第二製程，其為用於由此處之可硬化組成物製備經硬化組成物之製程，此係藉由將該可硬化組成物加熱至100至250℃之範圍的溫度達一段30秒至5小時之範圍的時間而達成。針對黏合劑應用，需要在硬化前將溶劑完全移除，如後文實例所述。 In still another aspect, the present invention provides a second process for preparing a hardened composition from the hardenable composition herein by heating the hardenable composition to 100 to 250 The temperature in the range of °C is reached for a period of time ranging from 30 seconds to 5 hours. For adhesive applications, the solvent needs to be completely removed prior to hardening, as described in the examples below.

未經硬化組成物之黏度可被調整，可添加溶劑來降低黏度，或可將溶劑蒸發以提高黏度。可將未經硬化組成物倒入模具中，之後進行硬化，以形成任何所欲形狀的成型物品。本領域中已知的一種該製程為反應射出成型。具體而言，該組成物可用於形成膜或板或塗層。將溶液的黏度適當調整以符合特定製程之要求。膜、板或 塗層係使用本領域任一種已知製程來製備。適合的製程包括但不限於溶液澆鑄、噴塗、旋轉塗覆或塗裝。一較佳的製程為溶液澆鑄，其利用Meyer桿來引下沉積於基材上的澆鑄溶液。可對基材進行處理以改善其塗層之濕潤及離形特性。溶液澆鑄膜之厚度一般為10至75微米。於後文之具體實施例中，將進一步描述將此處的溶液/分散液進行溶液澆鑄至基材膜或板上以形成積層物品。 The viscosity of the unhardened composition can be adjusted, a solvent can be added to reduce the viscosity, or the solvent can be evaporated to increase the viscosity. The unhardened composition can be poured into a mold and then hardened to form a shaped article of any desired shape. One such process known in the art is reactive injection molding. In particular, the composition can be used to form a film or sheet or coating. Adjust the viscosity of the solution to meet specific process requirements. Membrane, plate or The coating is prepared using any of the processes known in the art. Suitable processes include, but are not limited to, solution casting, spraying, spin coating or painting. A preferred process is solution casting, which utilizes a Meyer rod to draw down a casting solution deposited on a substrate. The substrate can be treated to improve the wetting and release properties of the coating. The thickness of the solution cast film is generally from 10 to 75 microns. In the specific examples that follow, the solution/dispersion herein will be further described as being solution cast onto a substrate film or sheet to form a laminate.

在另一態樣中，本發明係關於一種積層物品，其包括一基材及一黏合沉積於其上之塗層，其中該基材為一聚合物板或膜，而該塗層包括一可硬化組成物，其包括一其中混合有一環氧樹脂及一結構I所示之雙異醯亞胺化合物之第二溶劑。在一實施例中，該基材為一聚醯亞胺膜。在又一實施例中，該第二介電基材為一全芳族聚醯亞胺膜或板。在又一實施例中，該聚醯亞胺膜之厚度為10至50微米。在一實施例中，R₁為NH₂。在一實施例中，該塗層之厚度為10至75微米。 In another aspect, the invention relates to a laminated article comprising a substrate and a coating adhered thereto, wherein the substrate is a polymer sheet or film, and the coating comprises a A hardened composition comprising a second solvent in which an epoxy resin and a bisisoindenine compound of structure I are mixed. In one embodiment, the substrate is a polyimide film. In yet another embodiment, the second dielectric substrate is a wholly aromatic polyimide film or sheet. In still another embodiment, the polyimide film has a thickness of 10 to 50 microns. In an embodiment, R ₁ is NH ₂ . In one embodiment, the coating has a thickness of from 10 to 75 microns.

在一實施例中，該基材於其兩側均被塗覆。在又一實施例中，兩側的該等塗層係化學上等同。 In an embodiment, the substrate is coated on both sides thereof. In yet another embodiment, the coatings on both sides are chemically equivalent.

在又一態樣中，本發明係關於一種印刷線路板，其依序包括一第一介電基材之第一層、位於該第一介電基材上之一或多個分離導電途徑之第二層、與該分離導電途徑黏合接觸之結合層之第三層且黏合性設置於一第四層上，該第四層包括一第二介電基材，該結合層包括一可硬化組成物，其包括一其中混合有一環氧樹脂及一結構I所示之雙異醯亞胺化合物之第二溶劑。 In still another aspect, the present invention is directed to a printed wiring board comprising a first layer of a first dielectric substrate, one or more separate conductive paths on the first dielectric substrate. a second layer, a third layer of the bonding layer in adhesive contact with the separate conductive path, and adhesively disposed on a fourth layer, the fourth layer comprising a second dielectric substrate, the bonding layer comprising a hardenable composition And a second solvent in which an epoxy resin and a bisisoindenine compound represented by structure I are mixed.

在此處之印刷線路板之一實施例中，該第一層為一聚醯亞胺膜，其厚度為10至50微米。 In one embodiment of the printed wiring board herein, the first layer is a polyimide film having a thickness of 10 to 50 microns.

在此處之印刷線路板之一實施例中，該等導電途徑為銅。 In one embodiment of the printed wiring board herein, the electrically conductive paths are copper.

在此處之印刷線路板之又一實施例中，該等銅導電途徑之特徵在於厚度為10至50微米，且線距為10至150微米。 In still another embodiment of the printed wiring board herein, the copper conductive paths are characterized by a thickness of 10 to 50 microns and a line pitch of 10 to 150 microns.

在此處之印刷線路板之一實施例中，於該黏合性結合層中，該第二溶劑為MEK、環己酮、PMA、DMF或其混合物。 In one embodiment of the printed wiring board herein, in the adhesive bonding layer, the second solvent is MEK, cyclohexanone, PMA, DMF or a mixture thereof.

在此處之印刷線路板之一實施例中，於該黏合性結合層中，在該結構I所示之雙異醯亞胺化合物內，R₁為NH₂。 In one embodiment of the printed wiring board herein, in the adhesive bonding layer, in the bisisoinlimine compound shown by the structure I, R ₁ is NH ₂ .

在此處之印刷線路板之一實施例中，該第二介電基材為一聚醯亞胺膜或板。在又一實施例中，該第二介電基材為一全芳族聚醯亞胺膜或板。在另一實施例中，該第二介電基材為一包括聚醯亞胺之膜或板，該聚醯亞胺為PMDA與4,4’-ODA之縮合產物。在另一實施例中，該第二介電基材為一全芳族聚醯亞胺膜，其厚度為10至50微米。 In one embodiment of the printed wiring board herein, the second dielectric substrate is a polyimide film or sheet. In yet another embodiment, the second dielectric substrate is a wholly aromatic polyimide film or sheet. In another embodiment, the second dielectric substrate is a film or sheet comprising polyimine which is a condensation product of PMDA and 4,4'-ODA. In another embodiment, the second dielectric substrate is a wholly aromatic polyimide film having a thickness of from 10 to 50 microns.

可將此處之積層物品之塗層側與設置於第一介電基材上的導電途徑進行接觸，而輕易製備此處的印刷線路板。此處之印刷線路板具有數個實施例，其壓密度彼此不同。在一實施例中，僅將至少一表面上設置有一或多個分離導電途徑的第一介電基材設置於一水平表面上即形成此處之印刷線路板，其中該等導電途徑係面朝 上；之後將此處之積層物品的一塗層側接觸至該等導電途徑，藉此製備所謂的「胚體」或未經硬化印刷線路板。 The printed wiring board herein can be easily prepared by contacting the coated side of the laminated article herein with a conductive path disposed on the first dielectric substrate. The printed wiring board here has several embodiments in which the pressure densities are different from each other. In one embodiment, only the first dielectric substrate having at least one surface on which one or more separate conductive paths are disposed is disposed on a horizontal surface to form a printed wiring board therein, wherein the conductive paths are oriented And then a coated side of the laminated article herein is brought into contact with the conductive paths, thereby preparing a so-called "embroid body" or an unhardened printed wiring board.

在又一實施例中，對該胚體印刷線路板施加壓力，以造成部分壓密。在又一實施例中，對該胚體印刷線路板施加壓力及溫度。溫度處理可足以只誘發少量的交聯或硬化。此代表所謂的「B階段」硬化，其為一種中度的壓密，可使該印刷線路板具有部分結構完整性，但同時保留可成形性及可處理性。B階段之後可進行完整硬化。抑或是可在單一加熱及加壓步驟中由胚體狀態進行完整硬化。 In yet another embodiment, pressure is applied to the blank printed circuit board to cause partial compaction. In yet another embodiment, pressure and temperature are applied to the blank printed circuit board. The temperature treatment may be sufficient to induce only a small amount of crosslinking or hardening. This represents the so-called "B-stage" hardening, which is a moderate compaction that allows the printed wiring board to have partial structural integrity while retaining formability and handleability. Complete hardening can be carried out after the B stage. Or it is possible to perform complete hardening from the state of the embryo body in a single heating and pressurizing step.

在此處之印刷線路板之一實施例中，該第一介電基材於兩側上都具有導電途徑，以在第一介電基材的兩側上都形成前述的多層架構。 In one embodiment of the printed wiring board herein, the first dielectric substrate has a conductive path on both sides to form the aforementioned multilayer structure on both sides of the first dielectric substrate.

在此處之印刷線路板之另一實施例中，在第二介電基材的兩側上都塗覆一組成物，該組成物包括一環氧樹脂溶液/分散液、一第二溶劑以及結構I所示的雙異醯亞胺化合物。 In another embodiment of the printed wiring board herein, a composition is coated on both sides of the second dielectric substrate, the composition comprising an epoxy resin solution/dispersion, a second solvent, and The bisisoindenine compound shown in Structure I.

在又一實施例中，該第一介電基材於兩側上都具有導電途徑，且該第二介電基材於兩側上都具有塗層，該塗層包括一環氧樹脂溶液/分散液、一第二溶劑以及結構I所示的雙異醯亞胺化合物。此實施例使此處的印刷線路板得以裝設有不限重複次數的多層物品之基本結構。 In still another embodiment, the first dielectric substrate has a conductive path on both sides, and the second dielectric substrate has a coating on both sides, the coating comprising an epoxy resin solution / a dispersion, a second solvent, and a bisisoinlimine compound as shown in Structure I. This embodiment enables the printed wiring board herein to be provided with an essential structure of a multi-layer article of an unlimited number of repetitions.

在又一實施例中，藉由所謂的「導孔」來連接介電基材的兩側，使至少一部分設置在該第一介電基材一側 的導電途徑係與至少一部分設置在該第一介電基材另一側的導電途徑電性接觸。 In still another embodiment, the two sides of the dielectric substrate are connected by a so-called "via" such that at least a portion is disposed on the side of the first dielectric substrate The conductive path is in electrical contact with at least a portion of the conductive path disposed on the other side of the first dielectric substrate.

在另一態樣中，本發明提供一種第三製程，其為用於製備經封裝之印刷線路板的製程，該製程包括將表面上設置有塗層的積層物品之塗覆表面與設置在一介電基材之分離導電途徑之至少一部分黏合性接觸，藉此形成一多層物品；其中該塗層包括一可硬化組成物，其包括一其中混合有一環氧樹脂及一結構I所示之雙異醯亞胺化合物之第二溶劑；以及在100至250℃之範圍的一溫度施加壓力至由此形成的印刷線路板達一段30秒至5小時之範圍的時間，藉此形成一經封裝之印刷線路板。 In another aspect, the present invention provides a third process for preparing a packaged printed wiring board, the process comprising: providing a coated surface of a laminated article having a coating on a surface thereof Forming at least a portion of the separate conductive pathways of the dielectric substrate, thereby forming a multilayer article; wherein the coating comprises a hardenable composition comprising an epoxy resin and a structure I a second solvent of the bisisoindenine compound; and applying a pressure to the thus formed printed wiring board at a temperature in the range of 100 to 250 ° C for a period of 30 seconds to 5 hours, thereby forming a packaged Printed circuit board.

在一實施例中，此處之第三製程更包括在施加壓力至該印刷線路板之前先萃取該第二溶劑。可於設定在110℃之空氣循環爐內加熱一段2至20分鐘的時間來輕易完成溶劑萃取。 In one embodiment, the third process herein further includes extracting the second solvent prior to applying pressure to the printed wiring board. Solvent extraction can be easily accomplished by heating in an air circulating oven set at 110 ° C for a period of 2 to 20 minutes.

在此處第三製程之一實施例中，R₁為NH₂。 In one embodiment of the third process herein, R ₁ is NH ₂ .

在此處第三製程之一實施例中，該第一及第二介電基材均為聚醯亞胺膜。 In one embodiment of the third process herein, the first and second dielectric substrates are all polyimide films.

在此處第三製程之又一實施例中，該等聚醯亞胺膜為全芳族聚醯亞胺。 In still another embodiment of the third process herein, the polyimine film is a wholly aromatic polyimine.

在此處第三製程之再一實施例中，該等聚醯亞胺膜為PMDA與ODA之縮合產物。 In still another embodiment of the third process herein, the polyimine film is a condensation product of PMDA and ODA.

於以下具體實施例中將進一步描述本發明，但本發明並不受限於此等實施例。 The invention will be further described in the following specific examples, but the invention is not limited thereto.

實例 Instance 確認反應完成點 Confirm the completion point of the reaction

在以下實例中，利用紅外光譜(IR)來確認反應終點。利用滿滴管取回小等分的反應介質，將其於真空爐內利用N₂吹洗在約60℃乾燥約60分鐘。依照傳統製備IR光譜分析用固體之方法，將所得粉體與KBr混練，之後對所得化合物施加壓力，藉此形成測試顆粒。監測1836 cm^-1及1769 cm^-1處的IR吸收峰，以追蹤雙異醯亞胺產物的濃度增加。相同地，監測1856 cm^-1及1805 cm^-1處代表PMDA的IR吸收峰及1788 cm^-1處代表三聚氰胺之IR吸收峰，以追蹤反應物之消耗。當PMDA及三聚氰胺峰變成無法偵測時，即將反應視為已完成。 In the following examples, infrared spectroscopy (IR) was used to confirm the end point of the reaction. Retrieved using a dropper full of small aliquots of the reaction medium, which was used for N ₂ purged vacuum oven at about 60 deg.] C and dried for about 60 minutes. The obtained powder was kneaded with KBr in accordance with a conventional method for preparing a solid for IR spectrum analysis, and then pressure was applied to the obtained compound, thereby forming test particles. IR absorption peaks at 1836 cm ^-1 and 1769 cm ^{-1 were} monitored to track the increase in the concentration of the diisoindole imine product. Similarly, IR absorption peaks representing PMDA at 1856 cm ^-1 and 1805 cm ^-1 and IR absorption peaks representing melamine at 1788 cm ^{-1 were} monitored to track the consumption of reactants. When the PMDA and melamine peaks become undetectable, the reaction is considered complete.

同時也監測1788 cm^-1及1732 cm^-1處代表醯亞胺的IR吸收峰，以追蹤本製程任何醯亞胺副產物的形成。 At the same time, IR absorption peaks representing quinone imine at 1788 cm ^-1 and 1732 cm ^-1 were also monitored to track the formation of any quinone imine by-products in the process.

經觀察發現，反應完成所需時間會隨著反應溫度及特定溶劑的選擇而有顯著不同。 It has been observed that the time required for the completion of the reaction will vary significantly depending on the reaction temperature and the choice of the particular solvent.

反應介質 Reaction medium

三聚氰胺及PMDA兩者都僅輕微可溶於本文所使用的溶劑，因此在反應期間有必要維持良好的混合以確保高度轉化。若沒有恆定的劇烈混合，則固體將會沉降且反應會變慢或停止。藉由觀察來確認混合所需之能量。當分散液之外觀均一，且沒有觀察到滯留固態時，可將混合視為具有足夠能量。雙異醯亞胺產物形成小板狀粒子，其大小範圍為數百奈米。這些小板狀粒子於混合下仍保持懸浮。在反應完成之時，反應混合物中不存在可偵測的PMDA或三聚氰胺數量，所有的懸浮粒子 都是雙異醯亞胺，或在某些實施例中是其中混合有部分醯亞胺的雙異醯亞胺。 Both melamine and PMDA are only slightly soluble in the solvents used herein, so it is necessary to maintain good mixing during the reaction to ensure high conversion. Without constant vigorous mixing, the solids will settle and the reaction will slow down or stop. The energy required for mixing is confirmed by observation. When the appearance of the dispersion is uniform and no retained solid state is observed, the mixing can be considered to have sufficient energy. The diisoindoleimine product forms small plate-like particles having a size in the range of hundreds of nanometers. These small plate-like particles remain suspended while being mixed. At the completion of the reaction, there is no detectable amount of PMDA or melamine in the reaction mixture, all suspended particles Both are diisoindoleimine or, in certain embodiments, a diisoindoleimine in which a portion of the quinone imine is mixed.

印刷線路板 Printed circuit board

根據商業上常用的蝕刻製程將一Pyralux® AC182000R包銅積層板(Dupont Company)蝕刻，以形成一系列平行銅導電條，35微米高、100微米寬且彼此間隔100微米。將此用於實例9至12，並於此處將其稱為「PWB測試板」。印刷線路板之製備方法的資訊可見於Chris A.Mack,Fundamental Principles of Optical Lithography：The Science of Microfabrication,John Wiley & Sons,(London：2007).Hardback ISBN：0470018933；Paperback ISBN：0470727306。 A Pyralux® AC182000R copper clad laminate (Dupont Company) was etched according to a commercially available etching process to form a series of parallel copper strips 35 microns high, 100 microns wide and spaced 100 microns apart. This was used for Examples 9 through 12 and is referred to herein as a "PWB Test Board." Information on the preparation of printed wiring boards can be found in Chris A. Mack, Fundamental Principles of Optical Lithography: The Science of Microfabrication, John Wiley & Sons, (London: 2007). Hardback ISBN: 0470018933; Paperback ISBN: 0470727306.

試劑 Reagent

除非另有提及，所有試劑均得自Sigma Aldrich Chemical Company。 All reagents were obtained from Sigma Aldrich Chemical Company unless otherwise mentioned.

實例1 Example 1

利用磁性攪拌器將6.31克的三聚氰胺、5.45克的PMDA以及25克的MEK於一圓底燒瓶中混合。於氮氣下將混合物回流兩天，直到完成轉化。在回流期間依需要添加MEK，以保持反應混合物的體積大致固定。將由此製備的產物混合物冷卻至室溫同時保持攪拌。以IR光譜確認，可知產物混合物僅含MEK及雙異醯亞胺。 沒有可偵測的醯亞胺。藉此製得的分散液係適合於立刻用來調配可硬化環氧樹脂組成物。 6.31 grams of melamine, 5.45 grams of PMDA, and 25 grams of MEK were mixed in a round bottom flask using a magnetic stirrer. The mixture was refluxed under nitrogen for two days until the conversion was completed. MEK is added as needed during reflux to keep the volume of the reaction mixture substantially constant. The product mixture thus prepared was cooled to room temperature while maintaining stirring. It was confirmed by IR spectroscopy that the product mixture contained only MEK and diisoindenine. There are no detectable imines. The dispersion thus obtained is suitable for immediate use in formulating a hardenable epoxy resin composition.

實例2 Example 2

將6.31克的三聚氰胺、5.45克的PMDA及35克的3-乙氧基丙酸乙酯於圓底燒瓶中混合。於氮氣下將混合物回流兩天，直到完成轉化。將混合物冷卻至室溫。將來自混合物的少量樣本用MEK沖洗。以IR光譜確認，可知產物混合物含有MEK、雙異醯亞胺以及少量的醯亞胺(由1734 cm^-1處的小IR峰可知)。藉此製得的分散液係適合於立刻用來調配可硬化環氧樹脂組成物。 6.31 grams of melamine, 5.45 grams of PMDA, and 35 grams of ethyl 3-ethoxypropionate were mixed in a round bottom flask. The mixture was refluxed under nitrogen for two days until the conversion was completed. The mixture was cooled to room temperature. A small sample from the mixture was rinsed with MEK. It was confirmed by IR spectroscopy that the product mixture contained MEK, bisisoindenine, and a small amount of quinone (known from a small IR peak at 1734 cm ^-1 ). The dispersion thus obtained is suitable for immediate use in formulating a hardenable epoxy resin composition.

實例3 Example 3

將69.69克的三聚氰胺(0.534莫耳)、60.26克的PMDA(0.267莫耳)以及360克的環己酮加入一反應容器，並於室溫攪拌6天，直到完成轉化。將來自反應混合物的樣本於真空爐中乾燥。最終固體產物的IR光譜顯示1856 & 1805 cm^-1處PMDA峰及1558 cm^-1處三聚氰胺峰的消失以及1836 & 1769 cm^-1處異醯亞胺峰的出現。 69.69 grams of melamine (0.534 moles), 60.26 grams of PMDA (0.267 moles), and 360 grams of cyclohexanone were added to a reaction vessel and stirred at room temperature for 6 days until conversion was complete. The sample from the reaction mixture was dried in a vacuum oven. The IR spectrum of the final solid product showed the disappearance of the PMDA peak at 1856 & 1805 cm ^-1 and the melamine peak at 1558 cm ^-1 and the appearance of the isoindole peak at 1836 & 1769 cm ^-1 .

實例4 Example 4

將6.31克的三聚氰胺、5.45克的PMDA及25克的MIBK(甲基異丁基酮)於圓底燒瓶中混合。將混合物於氮氣下回流90分鐘。將混合物冷卻至室溫。將樣本乾燥。乾燥樣本的IR光譜顯示異醯亞胺的形成(1836 & 1769 cm^-1處的峰)。反應完成至雙異醯亞胺，且未偵測到醯亞胺。 6.31 grams of melamine, 5.45 grams of PMDA, and 25 grams of MIBK (methyl isobutyl ketone) were mixed in a round bottom flask. The mixture was refluxed under nitrogen for 90 minutes. The mixture was cooled to room temperature. Dry the sample. The IR spectrum of the dried sample showed the formation of isoindole (peak at 1836 & 1769 cm ^-1 ). The reaction was completed to diisoindolimine and no imine was detected.

實例5 Example 5

在室溫將5.81克的三聚氰胺、5.00克的PMDA、10克的DMF及10克的乙酸乙酯於燒瓶中混合過夜。反應完成至雙異醯亞胺，且未偵測到醯亞胺。將少量樣本乾燥。乾燥樣本的IR光譜顯示異醯亞胺的形成(1836 & 1769 cm^-1處的峰)。 5.81 g of melamine, 5.00 g of PMDA, 10 g of DMF and 10 g of ethyl acetate were mixed in a flask at room temperature overnight. The reaction was completed to diisoindolimine and no imine was detected. A small amount of sample is dried. The IR spectrum of the dried sample showed the formation of isoindole (peak at 1836 & 1769 cm ^-1 ).

實例6 Example 6

在室溫將5.81克的三聚氰胺、5.00克的PMDA、10克的MIBK以及10克的甲苯於燒瓶中混合過夜。將少量樣本乾燥。乾燥樣本的IR光譜顯示異醯亞胺的形成(1836 & 1769 cm^-1處的峰)。反應完成至雙異醯亞胺，且未偵測到醯亞胺。 5.81 g of melamine, 5.00 g of PMDA, 10 g of MIBK, and 10 g of toluene were mixed in a flask at room temperature overnight. A small amount of sample is dried. The IR spectrum of the dried sample showed the formation of isoindole (peak at 1836 & 1769 cm ^-1 ). The reaction was completed to diisoindolimine and no imine was detected.

實例7 Example 7

將3克的Vamac® G(得自DuPont)及12克的MEK於圓底燒瓶混合，以形成一溶液。將3.30克的苯酚/甲醛樹脂(GP 5300，得自Georgia Pacific)以及15克的DMF加入該圓底燒瓶，並混合以形成一溶液。於溶液形成時，將3.48克的三聚氰胺及3.01克的PMDA加入溶液中。於氮氣下將溶液在100℃加熱30分鐘、在120℃加熱30分鐘並在140℃加熱60分鐘。將混合物冷卻至室溫。將來自混合物的少量樣本於MEK中徹底清洗 (以移除GP5300 及Vamac-G)。IR光譜顯示異醯亞胺的形成(1836 & 1769 cm^-1處的峰)。酸酐與三聚氰胺峰在異醯亞胺峰出現時消失，且1734 cm^-1處極小的峰表示其中也存在少量的醯亞胺。 Three grams of Vamac® G (available from DuPont) and 12 grams of MEK were mixed in a round bottom flask to form a solution. 3.30 grams of phenol/formaldehyde resin (GP 5300 from Georgia Pacific) and 15 grams of DMF were added to the round bottom flask and mixed to form a solution. At the time of solution formation, 3.48 g of melamine and 3.01 g of PMDA were added to the solution. The solution was heated at 100 ° C for 30 minutes, heated at 120 ° C for 30 minutes and heated at 140 ° C for 60 minutes. The mixture was cooled to room temperature. A small sample from the mixture was thoroughly washed in MEK (to remove GP5300 and Vamac-G). IR spectroscopy showed the formation of isoindoles (peaks at 1836 & 1769 cm ^-1 ). The anhydride and melamine peaks disappeared at the appearance of the isoindole peak, and a very small peak at 1734 cm ^-1 indicates that a small amount of quinone was also present therein.

實例8 Example 8

將2.90克的端羧基丁二烯丙烯腈橡膠(CTBN橡膠，1300X13得自CVC Thermoset Specialties)、3.78克的三聚氰胺、3.27克的PMDA及15克的乾MEK於圓底燒瓶中混合。於氮氣下將該溶液回流5小時。將該混合物冷卻至室溫。將來自該混合物的少量樣本於MEK中徹底清洗(移除CTBN)。此樣本的IR光譜顯示異醯亞胺的形成(1836 & 1769 cm^-1處的峰)。酸酐及三聚氰胺峰消失。存在少量的醯亞胺。 2.90 grams of carboxybutadiene acrylonitrile rubber (CTBN rubber, 1300X13 from CVC Thermoset Specialties), 3.78 grams of melamine, 3.27 grams of PMDA, and 15 grams of dry MEK were mixed in a round bottom flask. The solution was refluxed for 5 hours under nitrogen. The mixture was cooled to room temperature. A small sample from this mixture was thoroughly washed in MEK (CTBN was removed). The IR spectrum of this sample shows the formation of isoindoles (peaks at 1836 & 1769 cm ^-1 ). The anhydride and melamine peaks disappeared. A small amount of quinone is present.

比較例A Comparative Example A

在反應容器中，將25.22克的三聚氰胺(0.2莫耳)、21.81克的PMDA(0.1莫耳)以及125 ml的DMF回流5小時。將該混合物冷卻並以甲醇淬火。將固體產物過濾並乾燥。經過濾之固體產物的IR光譜顯示1856 & 1805 cm^-1處PMDA峰及1558 cm^-1處三聚氰胺峰的消失以及1788 & 1732 cm^-1處醯亞胺峰的出現。 In a reaction vessel, 25.22 grams of melamine (0.2 moles), 21.81 grams of PMDA (0.1 moles), and 125 ml of DMF were refluxed for 5 hours. The mixture was cooled and quenched with methanol. The solid product was filtered and dried. The IR spectrum of the filtered solid product showed the disappearance of the PMDA peak at 1856 & 1805 cm ^-1 and the melamine peak at 1558 cm ^-1 and the appearance of the quinone imine peak at 1788 & 1732 cm ^-1 .

比較例B Comparative Example B

在反應容器中，將50.45克的三聚氰胺(0.4莫耳)、43.62克的PMDA(0.2莫耳)以及400 ml的NMP(N-甲 基吡咯啶酮)回流30分鐘。將該混合物冷卻並以甲醇淬火。將固體產物過濾並乾燥。經過濾之固體產物的IR光譜顯示醯亞胺形成(1788 & 1732 cm^-1處的峰)。 In a reaction vessel, 50.45 grams of melamine (0.4 moles), 43.62 grams of PMDA (0.2 moles), and 400 ml of NMP (N-methylpyrrolidone) were refluxed for 30 minutes. The mixture was cooled and quenched with methanol. The solid product was filtered and dried. IR spectroscopy of the filtered solid product showed the quinone imine formation (peak at 1788 & 1732 cm ^-1 ).

實例9 Example 9

在燒瓶中，將分散於9.5克的環己酮中的3.50克雙異醯亞胺(如前述實例3所製備)與溶解於63克的MEK中的11.5克共聚物混合，該共聚物為丁二烯與經修飾而含有自由羧基的丙烯腈之共聚物(Nipol 1072J，得自Zeon Chemicals)。之後將11.20克的磷酸三聚氰胺/聚磷酸三聚氰胺/焦磷酸三聚氰胺阻燃劑(Phosmel 200 Fine，得自Nissan Chemical Industries)加入並混合於其中，以形成一第一溶液/分散液。將9.10克的一環氧樹脂-橡膠加成物(HyPox RK84L，得自CVC Thermoset Specialties)溶解於9.10克的MEK以形成一第二溶液。將第二溶液加入第一溶液/分散液，藉此形成一環氧樹脂溶液/分散液。利用7密耳量規(177.8微米)的刮刀，將藉此製備的環氧樹脂溶液/分散液塗覆至12微米厚的Kapton® 50FPC聚醯亞胺膜，之後將此澆鑄膜及基材置入60℃的真空爐一小時以移除溶劑，進而形成約25微米厚的塗層。 In a flask, 3.50 g of bisisoindenine (prepared as in Example 3) dispersed in 9.5 g of cyclohexanone was mixed with 11.5 g of a copolymer dissolved in 63 g of MEK, and the copolymer was butyl. A copolymer of a diene and an acrylonitrile modified to contain a free carboxyl group (Nipol 1072J, available from Zeon Chemicals). 11.20 grams of melamine phosphate/polyphosphate melamine/pyrophosphate melamine flame retardant (Phosmel 200 Fine, available from Nissan Chemical Industries) was then added and mixed to form a first solution/dispersion. 9.10 grams of an epoxy resin-rubber adduct (HyPox RK84L from CVC Thermoset Specialties) was dissolved in 9.10 grams of MEK to form a second solution. The second solution is added to the first solution/dispersion, thereby forming an epoxy resin solution/dispersion. The epoxy resin solution/dispersion prepared thereby was applied to a 12 micron thick Kapton® 50FPC polyimide film using a 7 mil gauge (177.8 micrometer) doctor blade, and then the cast film and substrate were placed. The furnace was placed in a vacuum oven at 60 ° C for one hour to remove the solvent, thereby forming a coating of about 25 microns thick.

之後將藉此製備的經塗覆Kapton®作為PWB測試板上的覆蓋層。參見圖1，藉此製備的該Kapton® 50FPC膜1係塗覆有該可硬化組成物2，將其接觸5該PWB測試板4的該等銅導電條3，其中該可硬化組成物2係直接接觸該等銅導電條3。之後將藉此形成的印刷線路 板6於一OEM Laboratory Vacuum Press在真空下進行壓密7，此係藉由將印刷線路板維持在175℃及2.25 MPa共80分鐘，藉此形成一可撓性印刷線路板8，其具有完全經封裝之銅導電途徑。 The coated Kapton® thus prepared was then used as a cover layer on the PWB test panel. Referring to Figure 1, the Kapton® 50FPC film 1 thus prepared is coated with the hardenable composition 2, which is in contact with the copper conductive strip 3 of the PWB test panel 4, wherein the hardenable composition 2 is Direct contact with the copper conductive strips 3. The printed circuit that will be formed thereafter The plate 6 is compacted 7 under vacuum in an OEM Laboratory Vacuum Press by maintaining the printed wiring board at 175 ° C and 2.25 MPa for 80 minutes, thereby forming a flexible printed wiring board 8 which is completely Encapsulated copper conductive pathway.

實例10 Example 10

在燒瓶中，將分散於9.5克環己酮中的3.50克雙異醯亞胺(如實例3所製備)以及溶解於55克MEK中的9.80克“Nipol 1072J”橡膠進行混合。將該混合物攪拌30分鐘。將1.40克的CTBN(端羧基丁二烯丙烯腈橡膠，CTBN 1300X13得自CVC Thermoset Specialties)以及11.20克的“Phosmel 200 Fine”阻燃劑(得自Nissan Chemical Industries)加入該混合物中。將9.10克的HyPox RK84L溶解於13.7克的MEK中，並將所形成之溶液加入該混合物。利用7密耳量規(177.8微米)的刮刀，將所製得的溶液/分散液塗覆至一12微米厚的Kapton® 50ENS聚醯亞胺膜，之後將經塗覆的Kapton®膜置入110℃的空氣循環爐中10分鐘以移除溶劑。此乾黏合膜厚度為27微米。 In a flask, 3.50 g of bisisoindenine (prepared as in Example 3) dispersed in 9.5 g of cyclohexanone and 9.80 g of "Nipol 1072J" rubber dissolved in 55 g of MEK were mixed. The mixture was stirred for 30 minutes. 1.40 g of CTBN (terminal carboxyl butadiene acrylonitrile rubber, CTBN 1300X13 from CVC Thermoset Specialties) and 11.20 g of "Phosmel 200 Fine" flame retardant (from Nissan Chemical Industries) were added to the mixture. 9.10 g of HyPox RK84L was dissolved in 13.7 g of MEK, and the resulting solution was added to the mixture. The resulting solution/dispersion was applied to a 12 micron thick Kapton® 50 ENS polyimine film using a 7 mil gauge (177.8 micron) doctor blade, after which the coated Kapton® film was placed The solvent was removed in an air circulating oven at 110 ° C for 10 minutes. This dry adhesive film has a thickness of 27 microns.

使用實例9中所述的材料及程序，將由此製得的經塗覆Kapton®膜用於製備一完全經封裝之可撓性印刷線路板。 The coated Kapton® film thus prepared was used to prepare a fully encapsulated flexible printed wiring board using the materials and procedures described in Example 9.

實例11 Example 11

在一燒瓶中將61.60克的“Nipol 1072J”橡膠溶解於350克的MEK中以形成一第一溶液。將分散於25克環 己酮中的9.10克雙異醯亞胺(由實例3製備)混合入第一溶液以形成一第二溶液/分散液，之後再混入42.25克的“Phosmel 200 Fine”阻燃劑(得自Nissan Chemical Industries)以形成一第三溶液/分散液。將34.45克的HyPox RK84L溶解於34.45克的MEK，並將所形成的第四溶液混入第三溶液/分散液中以形成一第五溶液/分散液。將2.6克的雙酚A二環氧丙基醚環氧樹脂(EPON^TM 828，得自Hexion Specialty Chemicals)混入第五溶液/分散液中以形成一環氧樹脂溶液/分散液。利用7密耳量規(177.8微米)的刮刀，將藉此製備的環氧樹脂溶液/分散液塗覆至一Kapton® 50FPC聚醯亞胺膜上。將經塗覆的Kapton®膜置入110℃的空氣循環爐中10分鐘以移除溶劑。乾塗層厚度約為25微米厚。 61.60 grams of "Nipol 1072J" rubber was dissolved in 350 grams of MEK in a flask to form a first solution. 9.10 g of bisisoindenine (prepared in Example 3) dispersed in 25 g of cyclohexanone was mixed into the first solution to form a second solution/dispersion, followed by 42.25 g of "Phosmel 200 Fine" A fuel (from Nissan Chemical Industries) was used to form a third solution/dispersion. 34.45 grams of HyPox RK84L was dissolved in 34.45 grams of MEK, and the resulting fourth solution was mixed into the third solution/dispersion to form a fifth solution/dispersion. 2.6 g of the diglycidyl ether of bisphenol A epoxy resin (EPON ^TM 828, available from Hexion Specialty Chemicals) mixed into the fifth solution / dispersion to form an epoxy resin solution / dispersion. The epoxy resin solution/dispersion prepared thereby was applied to a Kapton® 50FPC polyimide film using a 7 mil gauge (177.8 micron) doctor blade. The coated Kapton® film was placed in an air circulating oven at 110 ° C for 10 minutes to remove the solvent. The dry coating thickness is approximately 25 microns thick.

使用實例9中所述的材料及程序，將由此製得的經塗覆Kapton®膜用於製備一完全經封裝之可撓性印刷線路板。 The coated Kapton® film thus prepared was used to prepare a fully encapsulated flexible printed wiring board using the materials and procedures described in Example 9.

實例12 Example 12

將根據實例3之方法製備的三聚氰胺-PMDA雙異醯亞胺(26.9重量%之異醯亞胺含量)的55.8克之環己酮分散液，以及51.0克的橡膠(丁二烯與經修飾而含有自由羧基的丙烯腈之共聚物-Nipol 1072J，得自Zeon Chemicals)溶解於289克的MEK中以形成一溶液。例用機械攪拌器將36克的一環氧樹脂-橡膠加成物(HyPox RK84L，得自CVC Thermoset Specialties)以及48.0克的磷酸三聚氰胺/聚磷酸三聚氰胺/焦磷酸三聚 氰胺阻燃劑(Phosmel 200 Fine，得自Nissan Chemical Industries)混入該溶液。當所有成分都分散入溶液中時，將所形成的混合物均質化2.5分鐘(Silverson型號L5M之均質機)成分散液，其具有視覺上均一的外觀。之後將經均質化的混合物持續進行機械式攪拌直到開始進行塗覆，如後所述。 55.8 g of a cyclohexanone dispersion of melamine-PMDA bisisoindenine (26.9 wt% isodecyimine content) prepared according to the method of Example 3, and 51.0 g of rubber (butadiene and modified) A copolymer of free carboxyl acrylonitrile - Nipol 1072J from Zeon Chemicals) was dissolved in 289 grams of MEK to form a solution. Example 36 g of an epoxy resin-rubber adduct (HyPox RK84L from CVC Thermoset Specialties) and 48.0 g of melamine phosphate/polyphosphate melamine/pyrophosphate triglyceride A cyanamide flame retardant (Phosmel 200 Fine, available from Nissan Chemical Industries) was mixed into the solution. When all of the ingredients were dispersed into the solution, the resulting mixture was homogenized for 2.5 minutes (Silverson Model L5M homogenizer) into a dispersion having a visually uniform appearance. The homogenized mixture is then continuously mechanically agitated until coating begins, as will be described later.

利用7密耳量規(177.8微米)的刮刀，將藉此製備的分散液塗覆至Kapton® 50FPC聚醯亞胺膜上。將經塗覆的Kapton®膜置入110℃的空氣循環爐中10分鐘以移除溶劑。乾塗層厚度約為25微米厚。 The dispersion prepared thereby was applied to a Kapton® 50FPC polyimide film using a 7 mil gauge (177.8 micron) doctor blade. The coated Kapton® film was placed in an air circulating oven at 110 ° C for 10 minutes to remove the solvent. The dry coating thickness is approximately 25 microns thick.

將此經乾燥的塗覆膜積層至一PWB測試板。此印刷線路板6，如圖1所示，係進一步製備有一離形膜及一橡膠墊於每一側。將藉此製備的組合品***一快速積層壓機，並於185℃之溫度及9.8 MPa之壓力下壓製2分鐘，之後在160℃的空氣循環爐中硬化90分鐘。 This dried coating film was laminated to a PWB test panel. The printed wiring board 6, as shown in Fig. 1, is further provided with a release film and a rubber pad on each side. The composition thus prepared was inserted into a rapid laminator and pressed at a temperature of 185 ° C and a pressure of 9.8 MPa for 2 minutes, followed by hardening in an air circulating oven at 160 ° C for 90 minutes.

根據ISO 6133 IPC-TM-650 2.4.9，使用附著至Instron測試機之German輪進行量測，經確認塗覆膜對於PWB測試板之黏著力為2.16 N/mm(牛頓/毫米)。 The adhesion of the coated film to the PWB test panel was confirmed to be 2.16 N/mm (Newton/mm) according to ISO 6133 IPC-TM-650 2.4.9 using a German wheel attached to an Instron tester.

實例13 Example 13

使用實例12之材料與程序，不同處在於用量，如下表所示，並將程序作下述修改。 The materials and procedures of Example 12 were used, the difference being the amount, as shown in the following table, and the procedure was modified as follows.

將該三聚氰胺-PMDA異醯亞胺環己酮分散液、Nipol 1072J以及MEK結合以形成一第一溶液，將Phosmel 200 Fine加入第一溶液中以形成第一溶液/分散液。先將HyPox RK84L溶解於34.5克的MEK中，其中加入2.6克的Epon 828(得自Hexion)，藉此形成一第二溶液。之後將第二溶液加入第一溶液/分散液。之後進行實例12的後續程序及方法。經確認塗覆膜對於PWB測試板之黏著力為2.15 N/mm。 The melamine-PMDA isoindole cyclohexanone dispersion, Nipol 1072J and MEK were combined to form a first solution, and Phosmel 200 Fine was added to the first solution to form a first solution/dispersion. HyPox RK84L was first dissolved in 34.5 g of MEK to which 2.6 g of Epon 828 (from Hexion) was added, thereby forming a second solution. The second solution is then added to the first solution/dispersion. Subsequent procedures and methods of Example 12 are then performed. The adhesion of the coated film to the PWB test board was confirmed to be 2.15 N/mm.

1‧‧‧膜 1‧‧‧ film

2‧‧‧可硬化組成物 2‧‧‧hardenable composition

3‧‧‧銅導電條 3‧‧‧copper strip

4‧‧‧PWB測試板 4‧‧‧PWB test board

5‧‧‧接觸 5‧‧‧Contact

6‧‧‧印刷線路板 6‧‧‧Printed circuit board

7‧‧‧壓密 7‧‧‧Pressure

8‧‧‧可撓性印刷線路板 8‧‧‧Flexible printed circuit boards

圖1為本發明用於製造本文之印刷線路板的製程示意圖，如實例12所述。 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic illustration of the process for making a printed wiring board of the present invention, as described in Example 12.

1‧‧‧膜 1‧‧‧ film

2‧‧‧可硬化組成物 2‧‧‧hardenable composition

3‧‧‧銅導電條 3‧‧‧copper strip

4‧‧‧PWB測試板 4‧‧‧PWB test board

5‧‧‧接觸 5‧‧‧Contact

6‧‧‧印刷線路板 6‧‧‧Printed circuit board

7‧‧‧壓密 7‧‧‧Pressure

8‧‧‧可撓性印刷線路板 8‧‧‧Flexible printed circuit boards

Claims (18)

一種結構I所示之化合物 其中R₁為H、鹵素、烴基、烴氧基、烴硫基、醯胺基、磺醯胺基、環胺基、醯基、嗎啉基、哌啶基或NR’R”，其中R’及R”各自獨立為H、經取代或未經取代之烷基或經取代或未經取代之芳族。 a compound represented by structure I Wherein R ₁ is H, halogen, hydrocarbyl, alkoxy, hydrocarbylthio, decylamino, sulfonylamino, cyclic amine, decyl, morpholinyl, piperidinyl or NR'R", wherein R' And R" are each independently H, substituted or unsubstituted alkyl or substituted or unsubstituted aromatic. 如請求項1所述之化合物，其中R₁為NH₂。 The compound of claim 1, wherein R ₁ is NH ₂ . 一種製程，包括在一第一溶劑中結合焦蜜石酸二酐與一結構II所示之經取代或未經取代之二胺基三【口+井】 其中R₁為H、鹵素、烴基、烴氧基、烴硫基、醯胺基、磺醯胺基、環胺基、醯基、嗎啉基、哌啶基或NR’R”，其中R’及R”各自獨立為H、經取代或未經取代之烷基或經取代或未經取代之芳族，以形成一反應混合物，以及將該反應混合物維持在-10至+160℃之溫度範圍，藉此產生結構I所示之雙異醯亞胺化合物 A process comprising combining pyromellitic dianhydride with a substituted or unsubstituted diamine-based three-port + well as shown in structure II in a first solvent Wherein R ₁ is H, halogen, hydrocarbyl, alkoxy, hydrocarbylthio, decylamino, sulfonylamino, cyclic amine, decyl, morpholinyl, piperidinyl or NR'R", wherein R' And R" are each independently H, substituted or unsubstituted alkyl or substituted or unsubstituted aromatic to form a reaction mixture, and the reaction mixture is maintained at a temperature ranging from -10 to +160 °C Thereby producing a bisisointhine imine compound represented by structure I 如請求項3所述之製程，其中R₁為NH₂。 The process of claim 3, wherein R ₁ is NH ₂ . 如請求項3所述之製程，其中該第一溶劑之特徵在於一偶極矩之範圍為1.5至3.5德拜。 The process of claim 3, wherein the first solvent is characterized by a dipole moment ranging from 1.5 to 3.5 debye. 如請求項3所述之製程，其中該第一溶劑為環己酮。 The process of claim 3, wherein the first solvent is cyclohexanone. 一種可硬化組成物，包括一其中混合有一環氧樹脂及一結構I所示之化合物之第二溶劑 其中R₁為H、鹵素、烴基、烴氧基、烴硫基、醯胺基、磺醯胺基、環胺基、醯基、嗎啉基、哌啶基或NR’R”，其中R’及R”各自獨立為H、經取代或未經取代之烷基或經取代或未經取代之芳族。 A hardenable composition comprising a second solvent in which an epoxy resin and a compound of structure I are mixed Wherein R ₁ is H, halogen, hydrocarbyl, alkoxy, hydrocarbylthio, decylamino, sulfonylamino, cyclic amine, decyl, morpholinyl, piperidinyl or NR'R", wherein R' And R" are each independently H, substituted or unsubstituted alkyl or substituted or unsubstituted aromatic. 如請求項7所述之組成物，其中R₁為NH₂。 The composition of claim 7, wherein R ₁ is NH ₂ . 如請求項7所述之組成物，其中該第二溶劑為甲基乙基酮、環己酮、丙二醇甲醚醋酸酯、N,N-二甲基甲醯胺或其混合物。 The composition of claim 7, wherein the second solvent is methyl ethyl ketone, cyclohexanone, propylene glycol methyl ether acetate, N, N-dimethylformamide or a mixture thereof. 如請求項7所述之組成物，其中R₁為NH₂；該第二溶劑為甲基乙基酮、環己酮、丙二醇甲醚醋酸酯、N,N-二甲基甲醯胺或其混合物；以及該環氧樹脂為雙酚A二環氧丙基醚。 The composition of claim 7, wherein R ₁ is NH ₂ ; the second solvent is methyl ethyl ketone, cyclohexanone, propylene glycol methyl ether acetate, N, N-dimethylformamide or a mixture; and the epoxy resin is bisphenol A diglycidyl ether. 如請求項7所述之組成物，更包括一彈性體或熱塑性聚合物。 The composition of claim 7 further comprising an elastomer or a thermoplastic polymer. 如請求項10所述之組成物，更包括一彈性體或熱塑性聚合物。 The composition of claim 10, further comprising an elastomer or a thermoplastic polymer. 一種組成物，實質上係由一其中混合有一環氧樹脂及一結構I所示之化合物之第二溶劑所組成 其中R₁為H、鹵素、烴基、烴氧基、烴硫基、醯胺基、磺醯胺基、環胺基、醯基、嗎啉基、哌啶基或NR’R”，其中R’及R”各自獨立為H、經取代或未經取代之烷基或經取代或未經取代之芳族。 A composition consisting essentially of a second solvent in which an epoxy resin and a compound of structure I are mixed Wherein R ₁ is H, halogen, hydrocarbyl, alkoxy, hydrocarbylthio, decylamino, sulfonylamino, cyclic amine, decyl, morpholinyl, piperidinyl or NR'R", wherein R' And R" are each independently H, substituted or unsubstituted alkyl or substituted or unsubstituted aromatic. 如請求項13所述之組成物，其中R₁為NH₂；該第二溶劑為甲基乙基酮、環己酮、丙二醇甲醚醋酸酯、N,N-二甲基甲醯胺或其混合物；以及該環氧樹脂為雙酚A二環氧丙基醚。 The composition of claim 13, wherein R ₁ is NH ₂ ; the second solvent is methyl ethyl ketone, cyclohexanone, propylene glycol methyl ether acetate, N, N-dimethylformamide or a mixture; and the epoxy resin is bisphenol A diglycidyl ether. 一種組成物，實質上係由一其中混合有一環氧樹脂、一彈性體或熱塑性聚合物以及一結構I所示之化合物之第二溶劑所組成 其中R₁為H、鹵素、烴基、烴氧基、烴硫基、醯胺基、磺醯胺基、環胺基、醯基、嗎啉基、哌啶基或NR’R”，其中R’及R”各自獨立為H、經取代或未經取代之烷基或經取代或未經取代之芳族。 A composition consisting essentially of a second solvent in which an epoxy resin, an elastomer or a thermoplastic polymer, and a compound of structure I are mixed Wherein R ₁ is H, halogen, hydrocarbyl, alkoxy, hydrocarbylthio, decylamino, sulfonylamino, cyclic amine, decyl, morpholinyl, piperidinyl or NR'R", wherein R' And R" are each independently H, substituted or unsubstituted alkyl or substituted or unsubstituted aromatic. 如請求項15所述之組成物，其中R₁為NH₂；該第二溶劑為甲基乙基酮、環己酮、丙二醇甲醚醋酸酯、N,N-二甲基甲醯胺或其混合物；以及該環氧樹脂為雙酚A二環氧丙基醚。 The composition of claim 15 wherein R ₁ is NH ₂ ; the second solvent is methyl ethyl ketone, cyclohexanone, propylene glycol methyl ether acetate, N,N-dimethylformamide or a mixture; and the epoxy resin is bisphenol A diglycidyl ether. 一種製程，包括將請求項7所述之組成物加熱至100至250℃之範圍的一溫度達一段30秒至5小時之範圍的時間，藉此形成一經硬化組成物。 A process comprising heating the composition of claim 7 to a temperature in the range of from 100 to 250 ° C for a period of from 30 seconds to 5 hours, thereby forming a hardened composition. 一種製程，包括將請求項13所述之組成物加熱至100至250℃之範圍的一溫度達一段30秒至5小時之範圍的時間，藉此形成一經硬化組成物。 A process comprising heating the composition of claim 13 to a temperature in the range of from 100 to 250 ° C for a period of from 30 seconds to 5 hours, thereby forming a hardened composition.