1261603 九、發明說明： 【發明所屬之技術領域】 鹵素鋼箔 本發明係為-種無自素銅落印刷電路基板材料之組成製程 ^熱性、與基板尺寸安定性 '及z一軸膨脹係數、同時又具環保之^具 板材料，且具備可11過抗玻纖職(Anti—GAF)戦及無錯焊锡製 【先前技術】 -般FR-4之娜基板材料，其_:元素是㈣為主，但目其在燃燒時會 有大量黑煙放出及惡臭，並適放出有害物f，因此，在環保意識抬頭的現在曰， 無鹵素銅箔基板材料的需求也與日倶增； | 市面上最常見的無鹵素銅络基板材料，其主要係包括以鱗系樹脂或碟系 硬化劑搭配無機添加劑，氮系樹脂搭配無機添加劑或直接使用大量之無機添、 加劑為主或利用磷氮共乘效應之材料，其有中華民國專利公告第293831號及 322507號獲准公告，然因磷化物會釋出對水生動植物有害之成份，其極易對 生態產生破壞，實不具環保性，另外，高磷含量之材料，則又會有易吸水之 特性，而該特性卻又往往增加電路板製作上諸多困擾、且其機械、及電性上 的信賴性，亦比不上傳統FR—4 ; 因此，特別開發低碗之無鹵素銅箔基板材料，且電路板的製作，由於線鲁 距及孔距日:&南达度化，其對板材的要求也更加嚴謹，俾以確保電路板在更 嚴格的高溫、高濕、及高電壓環境下被操作使用時，仍有優良的機械、及電 性上的仏賴性；因此，所開發之無鹵素基板亦要有Anti—CAF(抗玻纖漏電）之 優點’且印刷電路板產品開發方向趨向環保要求，在焊錫之製程中也由原來 的錫乱製程’轉變為無錯之製程，也因此使印刷電路板在製程之加工溫度 由220 C升咼至250〜270°C，因此銅箔基板耐熱性之要求也顯重要； 因此’為滿足市場對無鹵素銅箔基板材料之要求，特別開發此材料組成 及製作技術； 1261603 本案發明人鑑於上述習知祕所衍生的各項缺點，乃亟思以改良創新， 並經多年苦錄騎叫究及職後，終於成功研發完成本案鋪基板材料 的配方。 【發明内容】 本發明之主要目的係提供—種無s素觸基板材料植減製程，其至 少包含含氮環之樹脂材料與磷系環氧樹脂材料，並添加適#的無機阻燃填充 劑來使基板材料能通過UL 94V-0之耐燃性測試者。 本發明之次要目的係提供—種錢素銅箱基板材料之組成及製程，其係 可使耐熱性、基板之尺寸安定性、z_姉脹係數皆較_般含㈣之銅箱基板 材料佳、同時又兼具環保、且又具備可通過抗玻纖漏電(組卜㈣測試及益籲 鉛焊錫製程者。 【實施方式】 為使貴審查貞方便簡捷瞭解本發明之其他特勘容紐點及其所達成 之功效能夠更為顯現，兹將本發明合關，詳細說明如下： 本發明係為一種無_素銅箔基板材料之組成及製程，其中該無函素銅箔 基板材料之組成包含： 一含氮環之樹脂(Benzoxazine):含氮量為5〜50%，分子量為500〜10000，鲁 其刀子結構清參閱圖-一所示。 一含磷環氧樹脂：使用之含磷環氧樹酯，其磷含量為丨〜汕％，環氧當量 (Epoxy Equivalent Weight，EEW)為2〇〇〜1〇〇〇，水解氣含量為小於5〇〇ppm。 硬化劑·使用之硬化劑可為氨類硬化劑(amine)、或酚類（油印〇1)硬 化劑；當以氨類硬化劑(amine)，其分子量為80〜1000，分子結構中至少含有1 個活性氫反應基，其使用量為2〜3〇份；而若以紛類（phen〇i)硬化劑2〇〜7〇份， 則以100份的環氧化合物為基準，作為聚合硬化反應之聚合劑^⑶^呢 agent)。 1261603 一催化劑·使用之催化劑係為雜環胺類如：2MI(2-methyl-imidazole)， 二甲基咪唑2E4MI(2-ethy卜4-methyl-imidazole)，二乙基四甲基咪唑 2PI(2-phenyl-imidazole)二苯基口米口坐，BDMA(Benyl dimethylamine)二甲 基苯基胺等。 一無機阻燃填充物，其包含： 含氮含攝材料(Ammonium Polyphosate或Melamine Pyrophosphate)，氮 含量為5〜50%，磷為1〜20%，粒徑為1〜l〇〇um。 含磷顆粒(Phosphorus particle)，磷含量為1〜20%，粒徑為1〜l〇〇um。 氫氧化鋁(A1(0H)3)、三氧化二鋁(A1203)、氫氧化鎂(Mg(0H)2)、氧化鎂 (MgO)等無機添加物，粒徑為1〜i〇〇um。 奈米級無機二氧化石夕，粒徑為1〜500nm。 一分散劑：使用分散劑為石夕烧偶合劑（Silane)，包括氨基石夕烧偶合劑 (amino-si lane)及環氧基石夕烧偶合劑（ep〇xy-si lane)。 一稀釋劑：可使用丙酮（Acetone)，曱乙酮(MEK)，環己酮(cyclohexanol)， 1曱氧基-2-丙醇（PM) ’ 1-甲氧基-2-丙醇曱S旨（PMA)。 其中： 所述之含氮環之樹脂，當曝露疊層物於火焰或高溫時，生成阻燃層以遲 緩燃燒’其使用含氮環樹脂材料之含氮量為5〜50%，分子量為500〜10000，使 用量為100份；其中氮含量若少於5%無阻燃效果，超過50%則影響材料之反應 性；且其分子量若小於7〇，則有流膠過大之現象，分子量若大於1〇〇〇()，則會 有樹脂與玻纖束間之濕潤(wetting)狀態會變差之現象。 所述之含磷環氧樹脂，係當曝露疊層物於火焰或高溫時，生成阻燃層以 遲緩燃燒，俾以形成清漆而浸透於織造玻璃布後，形成難燃疊層物，使之具 有良好焊接耐熱及抗泡性，其最佳磷含量範圍為丨〜?!)％，環氧當量（Ερ〇χγ1261603 IX. Description of the invention: [Technical field of the invention] Halogen steel foil The present invention is a composition process of a self-made copper-free printed circuit board material, heat resistance, substrate dimensional stability, and z-axis expansion coefficient, It is also environmentally friendly, with a material that can be used in anti-glass fiber (Anti-GAF) and error-free soldering [prior art] - FR-4 sina substrate material, _: element is (d) Lord, but when it burns, there will be a lot of black smoke and odor, and it will release harmful substances f. Therefore, in the current environmental awareness, the demand for halogen-free copper foil substrate materials is also increasing. The most common halogen-free copper matrix material, mainly consisting of scaly resin or dish-based hardener with inorganic additives, nitrogen-based resin with inorganic additives or directly using a large amount of inorganic additives, additives or phosphorus and nitrogen. The material of the synergistic effect, which has been approved by the Republic of China Patent Bulletin Nos. 293831 and 322507, is because the phosphide will release harmful components to aquatic plants and animals, which are highly vulnerable to ecological damage and are not environmentally friendly. Sex, in addition, the material with high phosphorus content will have the characteristics of easy water absorption, but this characteristic often increases the troubles in the manufacture of the circuit board, and its mechanical and electrical reliability is not comparable to the traditional. FR—4; Therefore, the low-thickness halogen-free copper foil substrate material has been specially developed, and the production of the circuit board is more stringent due to the line-to-rug distance and the pitch distance: & To ensure that the board is operated in more stringent high temperature, high humidity, and high voltage environments, it still has excellent mechanical and electrical dependencies; therefore, the halogen-free substrate developed must also have Anti - The advantages of CAF (anti-glass leakage) and the development direction of printed circuit board products tend to be environmentally friendly. In the process of soldering, the original tin process is also changed to an error-free process, thus making the printed circuit board in the process. The processing temperature is raised from 220 C to 250 to 270 ° C, so the requirements for the heat resistance of the copper foil substrate are also important; therefore, in order to meet the market requirements for halogen-free copper foil substrate materials, the material composition and fabrication technology have been specially developed. ; 1 261603 In view of the shortcomings derived from the above-mentioned secrets, the inventor of the present case succeeded in researching and developing the formulation of the substrate material of this case after improving and innovating, and after years of hard work and riding. SUMMARY OF THE INVENTION The main object of the present invention is to provide a s-free contact substrate material physico-reduction process comprising at least a nitrogen-containing ring-containing resin material and a phosphorus-based epoxy resin material, and adding an appropriate inorganic flame retardant filler. To enable the substrate material to pass the UL 94V-0 flame resistance tester. The secondary object of the present invention is to provide a composition and a process for the material of a copper alloy copper box substrate, which can improve the heat resistance, the dimensional stability of the substrate, and the z_flat expansion coefficient of the copper box substrate material. Good, at the same time, both environmentally friendly, and have the ability to pass the anti-glass fiber leakage (group (4) test and Yijin lead solder process. [Embodiment] In order to make your review easy and simple to understand other special features of the invention The point and the effect achieved thereby can be more apparent. The present invention will be described in detail as follows: The present invention is a composition and a process of a non-copper copper foil substrate material, wherein the elemental copper foil substrate material is The composition comprises: a nitrogen-containing ring resin (Benzoxazine): the nitrogen content is 5 to 50%, the molecular weight is 500 to 10000, and the structure of the knives is as shown in the figure -1. A phosphorus-containing epoxy resin: Phosphorus epoxy resin having a phosphorus content of 丨~汕%, an Epoxy Equivalent Weight (EEW) of 2〇〇~1〇〇〇, and a hydrolysis gas content of less than 5〇〇ppm. The hardener may be an ammonia hardener or an phenol (oil) Neem 1) hardener; when an amine hardener (amine), its molecular weight is 80~1000, the molecular structure contains at least one active hydrogen reactive group, and its use amount is 2~3〇; The phen〇i hardener is 2 to 7 parts by weight, and is used as a polymerization agent for the polymerization hardening reaction based on 100 parts of the epoxy compound. 1261603 A catalyst used as a heterocyclic amine such as 2MI (2-methyl-imidazole), dimethylimidazole 2E4MI (2-ethyb 4-methyl-imidazole), diethyltetramethylimidazole 2PI ( 2-phenyl-imidazole) Diphenyl porphyrin, BDMA (Benyl dimethylamine) dimethylphenylamine, and the like. An inorganic flame retardant filler comprising: a nitrogen-containing material (Ammonium Polyphosate or Melamine Pyrophosphate) having a nitrogen content of 5 to 50%, a phosphorus content of 1 to 20%, and a particle diameter of 1 to 10 μm. The phosphorus-containing particles (Phosphorus particles) have a phosphorus content of 1 to 20% and a particle diameter of 1 to 10 μm. An inorganic additive such as aluminum hydroxide (A1(0H)3), aluminum oxide (A1203), magnesium hydroxide (Mg(0H)2), or magnesium oxide (MgO), having a particle diameter of 1 to i〇〇um. The nano-scale inorganic dioxide has a particle size of 1 to 500 nm. A dispersant: a dispersant is used as a Silane, including an amino-si lane and an ep〇xy-si lane. A diluent: acetone (Acetone), acetophenone (MEK), cyclohexanol, 1 methoxy-2-propanol (PM) ' 1-methoxy-2-propanol oxime S can be used. Purpose (PMA). Wherein: the nitrogen ring-containing resin, when the exposed laminate is exposed to flame or high temperature, generates a flame-retardant layer to slowly burn 'the nitrogen content of the nitrogen-containing ring resin material is 5 to 50%, and the molecular weight is 500. ~10000, the use amount is 100 parts; wherein if the nitrogen content is less than 5%, there is no flame retardant effect, and if more than 50%, the reactivity of the material is affected; and if the molecular weight is less than 7〇, the flow gel is too large, and the molecular weight is When it is larger than 1 〇〇〇 (), the wetting state between the resin and the glass fiber bundle may be deteriorated. The phosphorus-containing epoxy resin is formed by forming a flame-retardant layer to slowly burn when exposed to a flame or a high temperature, and forming a varnish to be immersed in the woven glass cloth to form a flame-retardant laminate. Has good solder heat resistance and anti-foaming property, its optimum phosphorus content range is 丨~?!)%, epoxy equivalent (Ερ〇χγ
Equivalent Weight，EEW)為200〜1000，使用量為20〜70份；其中環氧當量若 高於1000會有樹脂與玻纖束間之濕潤(wetting)狀態會變差，若低於2〇〇會有 1261603 ml膠過大之現象，又該含填環氧樹脂之水解氣含量若大於5〇〇ppm，則會影響 硬化反應之進行；且當使用量低於20份，則阻燃效果不明顯，高於70份，則 基板之吸水性變大。 與環氧化合物進行聚合硬化反應的硬化劑可為氨類硬化劑(amine)，其分 子篁為80〜1000，分子結構中至少含有1個活性氫反應基，其使用量為2〜30份， 且在室溫下不會進行反應，其進行反應溫度須在170°C以上，因此可長時間儲 放。 胺類硬化劑與環氧化合物的反應使用量為每100份環氧化合物添加2〜30 伤’若低於2· 0份，則聚合反應的硬化程度不足，若高於3〇份，則會出現硬化 劑析出之現象；若以酚類硬化劑，則其分子量為1〇〇〜1〇〇〇g/m〇1•，其分子結馨 構至少含有一個活性氫反應基；酚類硬化劑與環氧化合物的反應使用量為每 100份環氧化合物添加20〜70份，若低於20份，則聚合反應的硬化程度不足， 若高於70份，則會出現流膠過大之現象。 所述之催化劑係為雜環胺，如2MI(2-methyl-imidazole)，二甲基咪唾， 2E4MI(2-ethyl-4-methyl-imidazole)，二乙基四甲基咪唑， 沈 1(2-phenyMmidazole)二苯基咪唑，BDMA(Benyldimethylamine)二甲基 笨基胺4 ’雜環胺之特性為降低反應溫度，若未使用雜環胺，則硬化反應在⑽ °C左右才開始，若使用雜環胺則硬化反應在丨別它左右就發生，使用量為 0.01〜1.0份，其中使用量若太高，則使反應性太快，影響儲存時間，而若用 量太小，則無效果。 所述之無機阻燃填充物，其中含氮含碟材料為含氮含鱗之顆粒，氮含量 為5〜50%，磷為1〜20%，粒徑為1〜l〇〇um，添加量為〇〜3〇份，其目的在加強基板 材料之阻燃性，使用I若超過30份，則基板之耐熱性會明顯變差。 所述之含填顆粒，攝含量為1〜20%，粒徑為1〜i〇〇um，添加量為〇〜3〇份， 目的在加強基板材料之阻燃性，使用量若超過3〇份，則基板之耐熱性會明顯變 1261603 所述之氫氧化铭(Al(〇H)3)，三氧化二紹(A1203)，氫氧化_g(〇H)2)， 氧化鎂（_等_添加物之選擇以不影響原㈣ 善的目標為主.使用量為㈣,若使用量太高，則使生膠“=所= 響其與玻璃布之濕潤(wetting);若用量太小，則無效果。 所述之奈米級無機二氧化矽，以不影響原材料之特性，並且能達到所要 改善的目標為主，使用量為〇〜30份，若使用量太高，則使生膠水太黏稍，影 響其與玻璃布之濕潤（wetting)，用量太小，則無效果。 另為使該無機添加物在環氧樹脂中分散均勻，本發明添加分散劑，其使 用之分散劑射賴合劑，包括氨射魏合·ami.silane)或環氧基石夕 烷偶合劑(ep〇xy-silane)，用以改善無機物及織造玻璃布間之結合穩定性，春 而達到分散均勻之目的，且此類偶合劑無重金屬存在，不會對人體造成不良 衫響，使用®為〇· 1〜5· 〇份，若使用量太高，則加快反應，影響儲存時間，用 量太小，則無效果。 所述之稀釋劑其選用之原則為在含浸至玻璃布上時，並在60〜19(rc下乾 燥之後不殘存於材料中，如可使用丙_ (Acef〇ne)，甲乙_ (mek)，環己 酮(cyclohexanol)，1-甲氧基-2-丙醇（pm)，1-甲氧基—2一丙醇甲酯（PMA)。 本發明的實施例可利用滚筒塗佈機將漿料塗佈於玻璃纖維布上，硬化乾 燥後即為一高分子基板。 $ 玻璃轉移溫度、耐熱性、熱應力測試與2軸膨脹係數的測試規範為電子電 路互聯與封裝學會（The Institute for Interconnecting and Packaging Electronic Circuits ’ IPC)之IPC-TM-650號檢測方法，其中玻璃移轉溫度 的測試規範為IPC-TM-650· 2· 4· 25C及24C號檢測方法，Z軸膨脹係數的測試規 範為IPC-TM-650· 2· 4. 41號檢測方法；耐熱性的測試規範為 IPC-TM-650. 2· 4· 24· 1號檢測方法；熱衝擊試驗為將試片放入2大氣壓、i2i°c 之高溫高濕的環境下1小時，再放入288它的錫爐中2〇秒後拉起，重複此浸入 拉起之動作5次；介電常數及介電損失是依據Ιρ(>ΤΜ—65〇_ 2· 5· 5. 3號檢測方 1261603 法；基板之吸濕性是依據IPC-ΤΜ-650. 2· 6_ 2· 1號檢測方法；抗玻纖漏電特性 測試是以日本工業標準（Japan Industrial Standard，JIS)之 JIS-Z3284 的 規範，測試方法為基板在溫度85°C，相對溼度為85%的環境下，通入1〇〇v之 直流電，檢測在孔對孔（孔距〇·7μι，孔徑〇.3mm)及線對線（線長ιοομρη，線 距ΙΟΟμηι)測試項目的電阻值小於1〇8 〇hm之時間（如下表所示）。Equivalent Weight (EEW) is 200~1000, and the amount used is 20~70 parts; if the epoxy equivalent is higher than 1000, the wetting state between the resin and the glass fiber bundle will be worse, if less than 2〇〇 There will be a phenomenon that the 1261603 ml gel is too large, and if the content of the hydrolysis gas containing the epoxy resin is more than 5 〇〇ppm, the hardening reaction will be affected; and when the amount is less than 20 parts, the flame retarding effect is not obvious. When it is higher than 70 parts, the water absorption of the substrate becomes large. The curing agent for the polymerization hardening reaction with the epoxy compound may be an ammonia hardener having a molecular weight of 80 to 1000 and having at least one active hydrogen reactive group in the molecular structure, and the amount thereof is 2 to 30 parts. Moreover, the reaction does not proceed at room temperature, and the reaction temperature must be 170 ° C or higher, so that it can be stored for a long time. The reaction amount of the amine hardener and the epoxy compound is 2 to 30% per 100 parts of the epoxy compound. If it is less than 2.0 parts, the degree of hardening of the polymerization reaction is insufficient, and if it is higher than 3 parts, The phenomenon of precipitation of hardener occurs; if it is a phenolic hardener, its molecular weight is 1〇〇~1〇〇〇g/m〇1•, its molecular structure contains at least one active hydrogen reactive group; phenolic hardener The reaction amount with the epoxy compound is 20 to 70 parts per 100 parts of the epoxy compound. If it is less than 20 parts, the degree of hardening of the polymerization reaction is insufficient. If it is more than 70 parts, the flow gel is excessively large. The catalyst is a heterocyclic amine such as 2MI (2-methyl-imidazole), dimethylmeridene, 2E4MI (2-ethyl-4-methyl-imidazole), diethyltetramethylimidazole, Shen 1 ( 2-phenyMmidazole) Diphenylimidazole, BDMA (Benyldimethylamine) dimethylphenylamine 4 'Heterocyclic amine is characterized by lowering the reaction temperature. If a heterocyclic amine is not used, the hardening reaction starts at about (10) °C. When a heterocyclic amine is used, the hardening reaction occurs by discriminating about it, and the amount used is 0.01 to 1.0 part. If the amount used is too high, the reactivity is too fast, which affects the storage time, and if the amount is too small, the effect is ineffective. . The inorganic flame retardant filler, wherein the nitrogen-containing disc material is a nitrogen-containing scale-containing particle, the nitrogen content is 5 to 50%, the phosphorus is 1 to 20%, and the particle diameter is 1 to l〇〇um, and the amount is added. The reason is to enhance the flame retardancy of the substrate material, and if the use I exceeds 30 parts, the heat resistance of the substrate is remarkably deteriorated. The filler-containing particles have a filming content of 1 to 20%, a particle diameter of 1 to i〇〇um, and an addition amount of 〇3 to 3 parts, in order to enhance the flame retardancy of the substrate material, and the amount of use exceeds 3〇. For the part, the heat resistance of the substrate will be significantly changed to 1261603, such as the hydroxide (Al (〇H) 3), the second oxide (A1203), the hydroxide _g (〇H) 2), magnesium oxide (_, etc. The choice of _ additives is based on the target of not affecting the original (four) good. The usage is (4). If the amount is too high, the raw rubber “================================================================= The nano-grade inorganic cerium oxide is mainly used without affecting the characteristics of the raw materials, and can achieve the target to be improved, and the amount of use is 〇~30 parts, and if the amount used is too high, it is made The glue is too sticky, which affects the wetting of the glass cloth. If the amount is too small, it has no effect. In addition, in order to uniformly disperse the inorganic additive in the epoxy resin, the dispersant is added in the present invention, and the dispersant used therein is used.射 合 mixture, including Ami- ami.silane or ep〇xy-silane, to improve inorganics and weaving The combination stability between the glass cloths achieves the purpose of uniform dispersion in spring, and the coupling agent has no heavy metal, and does not cause bad shirting to the human body. The use of ® is 〇·1~5· 〇, if the amount used is too If it is high, it will speed up the reaction and affect the storage time. If the dosage is too small, it will have no effect. The thinner is selected on the principle of impregnation on glass cloth and does not remain in the material after drying at 60~19 (r). For example, use propylene (Acef〇ne), methyl _ (mek), cyclohexanol, 1-methoxy-2-propanol (pm), 1-methoxy-2-propanol Methyl ester (PMA). The embodiment of the present invention can apply a slurry to a glass fiber cloth by a roll coater, and is a polymer substrate after hardening and drying. $ Glass transition temperature, heat resistance, thermal stress test and The test specification for the 2-axis expansion coefficient is the IPC-TM-650 test method of The Institute for Interconnecting and Packaging Electronic Circuits 'IPC, in which the test specification for glass transfer temperature is IPC-TM-650. · 2· 4· 25C and 24C test methods, Z-axis expansion The test specification for the coefficient is IPC-TM-650·2· 4. 41 test method; the test specification for heat resistance is IPC-TM-650. 2·4· 24·1 test method; thermal shock test is test piece Put it into a high-humidity environment of 2 atm, i2i °c for 1 hour, then put it into 288 of its tin furnace for 2 sec seconds, then pull it up, repeat the immersion pull operation 5 times; dielectric constant and dielectric The loss is based on Ιρ(>ΤΜ—65〇_ 2· 5· 5. 3 tester 1 126603 method; the hygroscopicity of the substrate is based on IPC-ΤΜ-650. 2· 6_ 2· 1 test method; The fiber leakage characteristic test is based on the Japanese Industrial Standard (JIS) JIS-Z3284. The test method is to apply a DC voltage of 1〇〇v to the substrate at a temperature of 85 ° C and a relative humidity of 85%. Detect the time when the resistance value of the hole-to-hole (hole distance 7·7μι, aperture 〇.3mm) and line-to-line (line length ιοομρη, line spacing ΙΟΟμηι) is less than 1〇8 〇hm (as shown in the following table) .
Anti CAF測試數據 時間(小時） 無鹵素材料電阻(ohm) _含溴FR-4電阻)〇hm) _ 0 5.94E+10 _438E+09_ 100 1 5.51E+10 4.49E+09 200 5.12E+10 _6.13E+09__ 300 4.92E+10 _5.19E+09__ 400 4.53E+10 _4.78E+09__ 500 3.77E+10 4.12E+09 600 3.22E+10 3.11E+09 700 2.99E+10 1.01E+09 800 2.81E+10 8.11E+08 ^_9〇〇 2.57E+10 4.21E+08 .^^000 2.25E+10 9 11E+07 1.99E+10 6 01E+07 ^_1200 1.81E+10 _9.51E+06_ &錯呈之测試條件是以5片含銅基板，尺寸大小為29〇*21〇腿，經IR Ref 1〇w 3 人(如下表所示）後，以Solder dip/288°C/20sec/5次之測試，觀察含銅基板 疋否有銅面制離或爆板之現象。Anti CAF test data time (hours) Halogen-free material resistance (ohm) _ bromine-containing FR-4 resistor) 〇 0) _ 0 5.94E+10 _438E+09_ 100 1 5.51E+10 4.49E+09 200 5.12E+10 _6.13E+09__ 300 4.92E+10 _5.19E+09__ 400 4.53E+10 _4.78E+09__ 500 3.77E+10 4.12E+09 600 3.22E+10 3.11E+09 700 2.99E+10 1.01E +09 800 2.81E+10 8.11E+08 ^_9〇〇2.57E+10 4.21E+08 .^^000 2.25E+10 9 11E+07 1.99E+10 6 01E+07 ^_1200 1.81E+10 _9 .51E+06_ & wrong test conditions are based on 5 copper-containing substrates, size 29 〇 * 21 〇 legs, IR Ref 1 〇 w 3 people (as shown in the table below), with Solder dip / 288 ° C / 20 sec / 5 times test, observe the copper-containing substrate, whether there is copper surface separation or explosion.
1261603 無錯製程之測試條件 /Γ * * * t -ji^ | * ί * - iiMXJ Λ——…一 Ηί + < I < Ύι i--- 一， TIIBRMOmACKKR mUm^' 一一、,,v〜一一八 »一? ，一一二 伽十冬―'· 1 ； $ 鉍 nm -r—r- A '上 rk _ 為>« XA 2仏 y * μβ” Π ^ ynu i fx， 籠 ϋ ύ ύ 0 ◎ 0 0 i) if <* ο '0 * mm m Ut )<0 祕 m m 纖_輸_麟_飾 鯽瞧讎 細娜耽 n、、 " m $ * ^ ίΜ >ΛΟ Υίϋ ά^-·λ ' 么 m 、 次妁— ί * U ΧίΛ 嫩汉 、 η a :ϋ ⑽ 、<m 1 咨和 i*C0 ii 50 1 π"·"·11· ... ! ' •- mm$mm x# X mm . rmm 麵細 : · 4¾ <y λ < ：* < y <·<·<·Ψ< <· > χ <·<.< *<-<. )¾ ‘，" v,^t cm 本發明係提供一種無函素銅箔基板材料之組成及製程，其製程如下： 請配合參閱圖二所示，其係將5〇份之含磷環氧樹脂與1〇〇份之含氮環樹脂 (Benzoxazine)，及35份之硬化劑及〇· 1份之催化劑，及3份之含磷填充物，及 3份之奈米級二氧化矽（1)，於室溫下透過攪拌器混合6〇分鐘（2)後，再加入無鲁 機填充物氫氧化鋁(A1(0H)3) 40份及分散劑1.5份及稀釋劑30份(3)。 將前述之製備於30〜45°C下攪拌120分鐘(4)後，再將所調之清漆於滾筒式 含浸機上將清漆含浸於7628之玻璃布（5)上。 將前述經含浸之玻璃布分別以7628*5之厚度(39 mi 1)於最外層兩面與各 一張loz之銅箔進行壓合(6)，再將壓合後之基板進行特性檢測（？）。 (如下表所示），由該測試數據與一般含溴F—4銅箔基板之測試數據可以發 現，本發明確可通過UL 94V-0之耐燃性測試，並使耐熱性、基板之尺寸安定 性、Z-軸膨脹係數皆較一般含鹵素之銅猪基板材料佳者，且又具備可通過抗 1261603 玻纖漏電(Anti-CAF)測試及無鉛焊錫製程。 無鹵素銅箔基板材料及一般含溴FR_4之材特性比較： ----- 特性檢測項目 方法條件/儀器 規範 無鹵素材料 含溴FR-4 玻璃轉移溫度 TgCC) DSC IPC-TM-650 150 135 z軸膨脹系數 Z-axis Expansion (25〜260〇C) % TMA IPC-TM-650 2.8 4.5 吸水性（°/〇) IPC-TM-650 0.01 0.028 T-260 (min) TMA IPC-TM-650 >60 12 T-288 (min) TMA IPC-TM-650 >60 1 阻燃性(UL-94V0) UL Standard Pass Pass 熱應力測試 PCT(2. Ohr) solder dip@ 288°C-lOOSec IPC-TM-650 Pass Fail 抗玻纖漏電(hrs) 1.85/RH 85V100 VDC 2. Pitch 0.7mm 9=0.3mm 3. Line-Line lOOum/lOOum JIS-Z3284 >1200hrs >1200hrs 〜900hrs 〜900hrs 無鉛製程 IR Reflow*3 Pass Fail 溴含量(ppm) 氯含量(I)pm) <900 <900 為使本發明更加顯現出其進步性與實用性，茲與習用作一比較分析如下： 習用缺失 1、 在燃燒時會有大量黑煙放出及惡臭，並適放出有害物質。 2、 對生態產生破壞。 3、 不具環保性。 本發明優點 1、 無重金屬存在，不會對人體造成不良影響。 2、 改善無機物及織造玻璃布間之結合穩定性。 12 !26l6〇3 3、具環保。 4 5 6 7 而才熱性佳。 基板之尺寸安定性佳。 Z-轴膨服係數佳。 可通過抗玻纖漏電(Ant卜CAF)測試及無錯 焊錫製程之基板材料。 综上所述，本發明確已達到所欲增進 之功效’且也非熟悉該項技藝者所 新穎性，顯已 【圖式簡單說明】 第一圖係為本發明含氮環之樹脂分子結構圖。 第二圖係為本發明之製程。 【主要元件符號說明】 1 ·. 50份含鱗糸環氧樹脂+ 1〇〇份之含氮環樹脂+ 35份之硬化劑+ 〇 1份之 催化劑+ 3份之含鱗無機阻燃填充物+ 3份之奈米級無機二氧化石夕 2··室溫下透過攪拌器混合60分鐘 春 3 ··加入無機填充物氫氧化銘40份+分散劑1· 5份+稀釋劑3〇份 4· _置於30〜45°C下攪拌120分鐘 5 ··將所調之清漆以滾筒塗佈機將清漆塗佈於7628之玻璃布上 6·.將經塗佈之玻璃布分別以7628*5之厚度（39 mil)於最外層兩面與各一 張loz之銅猪進行壓合 7 ··進行特性檢測 131261603 Test condition for error-free process /Γ * * * t -ji^ | * ί * - iiMXJ Λ——...一Ηί + < I < Ύι i--- One, TIIBRMOmACKKR mUm^' One, one, v~一一八»一?,一一二伽十冬-'·1 ; $ 铋nm -r-r- A '上 rk _ is >« XA 2仏y * μβ" Π ^ ynu i fx,笼ϋ ύ 0 ◎ 0 0 i) if <* ο '0 * mm m Ut )<0 Secret mm _ _ _ _ _ 鲫瞧雠 鲫瞧雠 耽 耽 n,, " m $ * ^ Μ >ΛΟ Υίϋ ά^-·λ ' 么m , 妁 妁 — ί * U ΧίΛ tenderness, η a :ϋ (10) , <m 1 咨询和 i*C0 ii 50 1 π"·"·11· . .. ! ' •- mm$mm x# X mm . rmm Surface details: · 43⁄4 <y λ < :* < y <·<·<·Ψ<<·> χ <· <.<*<-<.)3⁄4'," v,^t cm The present invention provides a composition and a process for a copper foil substrate material, the process of which is as follows: Please refer to Figure 2 It is shown that it is a 5-part phosphorus-containing epoxy resin and a 1-part nitrogen-containing cyclic resin (Benzoxazine), and 35 parts hardened. And 1 part of the catalyst, and 3 parts of the phosphorus-containing filler, and 3 parts of the nano-sized cerium oxide (1), mixed at room temperature for 6 minutes (2) through a stirrer, and then added 40 parts of aluminum hydroxide (A1(0H)3) and 1.5 parts of dispersing agent and 30 parts of diluent (3). The above preparation is stirred at 30~45 ° C for 120 minutes (4), and then The varnish was immersed on a glass cloth (5) of 7628 on a drum type impregnator. The impregnated glass cloth was respectively made to have a thickness of 7628*5 (39 mi 1) on both sides of the outermost layer. The copper foil of the loz is pressed (6), and then the pressed substrate is subjected to characteristic detection (?) (as shown in the following table), and the test data and the test data of the general bromine-containing F-4 copper foil substrate are used. It can be found that the present invention can pass the UL 94V-0 flame resistance test, and the heat resistance, the dimensional stability of the substrate, and the Z-axis expansion coefficient are better than those of the general halogen-containing copper pig substrate material, and Pass anti-1261603 glass fiber leakage (Anti-CAF) test and lead-free solder process. Comparison of characteristics of halogen-free copper foil substrate materials and materials containing bromine FR_4: ----- Characteristic test item Method conditions/Instrument specification Halogen-free material bromine-containing FR-4 Glass transfer temperature TgCC) DSC IPC-TM-650 150 135 Z-axis expansion coefficient Z-axis Expansion (25~260〇C) % TMA IPC-TM-650 2.8 4.5 Water absorption (°/〇) IPC-TM-650 0.01 0.028 T-260 (min) TMA IPC-TM-650 >60 12 T-288 (min) TMA IPC-TM-650 >60 1 Flame Retardancy (UL-94V0) UL Standard Pass Pass Thermal Stress Test PCT (2. Ohr) solder dip@ 288°C-lOOSec IPC -TM-650 Pass Fail Anti-glass leakage (hrs) 1.85/RH 85V100 VDC 2. Pitch 0.7mm 9=0.3mm 3. Line-Line lOOum/lOOum JIS-Z3284 >1200hrs >1200hrs ~900hrs ~900hrs Lead-free process IR Reflow*3 Pass Fail Bromine content (ppm) Chlorine content (I) pm) <900 < 900 In order to make the present invention more progressive and practical, a comparative analysis is used as follows: When burning, there will be a lot of black smoke and odor, and appropriate release of harmful substances. 2. Destruction of the ecology. 3. Not environmentally friendly. Advantages of the invention 1. No heavy metal exists, and will not cause adverse effects on the human body. 2. Improve the bonding stability between inorganic materials and woven glass cloth. 12 !26l6〇3 3. Environmentally friendly. 4 5 6 7 is only very hot. The substrate has good dimensional stability. The Z-axis expansion coefficient is good. The substrate material can be tested by anti-glass leakage (Ant CAF) and error-free soldering process. In summary, the present invention has indeed achieved the desired effect of the improvement 'and is not familiar with the novelty of the skilled person, and the first figure is the molecular structure of the resin containing the nitrogen ring of the present invention. Figure. The second figure is the process of the present invention. [Main component symbol description] 1 ·. 50 parts of scaly epoxy resin + 1 part of nitrogen-containing ring resin + 35 parts of hardener + 1 part of catalyst + 3 parts of scaly inorganic flame retardant filler + 3 parts of nano-grade inorganic sulphur dioxide eve 2 · Mixing at room temperature for 60 minutes in the spring 3 · Adding inorganic filler Hydroxide 40 parts + dispersing agent 1 · 5 parts + thinner 3 parts 4· _Stirring at 30~45°C for 120 minutes 5 ·· Apply the varnish to the 7628 glass cloth with a roller coater. 6. Apply the coated glass cloth to 7628 respectively. *5 thickness (39 mil) is pressed on the outermost two sides with each piece of loz copper pig.