TWI417188B - A copper foil substrate and an impregnating liquid for producing the copper foil substrate - Google Patents
A copper foil substrate and an impregnating liquid for producing the copper foil substrate Download PDFInfo
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- TWI417188B TWI417188B TW98139403A TW98139403A TWI417188B TW I417188 B TWI417188 B TW I417188B TW 98139403 A TW98139403 A TW 98139403A TW 98139403 A TW98139403 A TW 98139403A TW I417188 B TWI417188 B TW I417188B
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本發明係與電子電路有關，更詳而言之是指一種銅箔基板以及用來製作此銅箔基板所使用的含浸液。The present invention relates to electronic circuits, and more particularly to a copper foil substrate and an impregnation liquid for use in fabricating the copper foil substrate.
印刷電路板(printed circuit board,PCB)為具有預定線路佈局(pattern)的基板，其上可裝設有各式的電子元件，以達成預定的功能。印刷電路板的品質不但影響電子產品的可靠度，亦影響電子產品整體的性能。銅箔基板(copper clad laminate,CCL)則是製造印刷電路板之基礎材料，係利用絕緣紙、玻璃纖維布或其他纖維材料浸以環氧樹脂或酚醛樹脂膠黏劑，經乾燥、裁剪、疊合而成，然後單面或雙面覆上銅箔，在加熱加壓條件下成型而製成的。以玻璃纖維為基板之銅箔基板，由於具有良好的機械性質，已成為銅箔基板的主流。A printed circuit board (PCB) is a substrate having a predetermined line pattern on which various electronic components can be mounted to achieve a predetermined function. The quality of printed circuit boards not only affects the reliability of electronic products, but also affects the overall performance of electronic products. Copper clad laminate (CCL) is the basic material for manufacturing printed circuit boards. It is impregnated with epoxy resin or phenolic resin adhesive by insulating paper, glass fiber cloth or other fiber materials. It is dried, cut and stacked. It is made by combining and then forming a copper foil on one or both sides and molding under heat and pressure. The copper foil substrate with glass fiber as the substrate has become the mainstream of the copper foil substrate because of its good mechanical properties.
在習用技術中，有人在玻璃纖維銅箔基板加入一些填料以提高基板的機械性質，最常見的填料為二氧化矽。二氧化矽的四面體網狀結構型結晶會提高基板的硬度與降低基板的線性膨脹係數。高硬度的基板具有不易變形的優點，然而當需要鑽孔時，鑽孔製程的困難度是比較高的，而且鑽頭的損耗也因之提高。另外，鑽孔的過程產生過多的粉屑，也令不良率提高。另外，由於基板與其他材料的線性膨脹係數的差異，高線性膨脹係數會導致內應力的產生。在冷熱交替的製程下，容易造成基板微裂與線路斷路。以二氧化矽為填料的基板雖有較低的線膨脹係數，但若能使得基板的線膨脹係數更低，將更有助於上述基板微裂與線路斷路的改善。In the conventional technology, some fillers are added to the glass fiber copper foil substrate to improve the mechanical properties of the substrate, and the most common filler is cerium oxide. The tetrahedral network structure type crystal of cerium oxide increases the hardness of the substrate and lowers the linear expansion coefficient of the substrate. The high-hardness substrate has the advantage of being less deformable. However, when drilling is required, the difficulty of the drilling process is relatively high, and the loss of the drill bit is also increased. In addition, the process of drilling produces excessive dust, which also increases the defect rate. In addition, due to the difference in linear expansion coefficients of the substrate and other materials, a high linear expansion coefficient causes internal stress. Under the process of alternating hot and cold, it is easy to cause micro-cracking of the substrate and disconnection of the line. Although the substrate with ruthenium dioxide as a filler has a lower coefficient of linear expansion, if the linear expansion coefficient of the substrate is made lower, it will contribute to the improvement of microcracking and line breakage of the substrate.
本發明之主要目的在於提供一種用以製作銅箔基板之含浸液及其所製作出的銅箔基板，該銅箔基板為具有適當硬度與線膨脹係數的基板。SUMMARY OF THE INVENTION A primary object of the present invention is to provide an impregnation liquid for producing a copper foil substrate and a copper foil substrate produced by the same, which is a substrate having a suitable hardness and a coefficient of linear expansion.
緣以達成上述目的，本發明所提供之銅箔基板，包含有一玻璃纖維基板以及至少一銅箔結合於該玻璃纖維基板之至少一側面上；其中該玻璃纖維基板是由一玻璃纖維布含浸於一含浸液中，以製成半固膠片，爾後半固膠片結合銅箔經加壓加熱後製成該銅箔基板，其中該含浸液包含有樹脂以及5-80PHR之填料，其中該填料為有二氧化矽以及至少一種IIA或IIIA族金屬氧化物所共構成的非結晶性網狀結構複合材料，以此所製作出的銅箔基板具有適當的硬度與線膨脹係數。In order to achieve the above object, the copper foil substrate provided by the present invention comprises a glass fiber substrate and at least one copper foil bonded to at least one side of the glass fiber substrate; wherein the glass fiber substrate is impregnated with a glass fiber cloth. An impregnation liquid is prepared to form a semi-solid film, and the second semi-solid film is combined with a copper foil to be heated to obtain the copper foil substrate, wherein the impregnation liquid comprises a resin and a filler of 5-80 PHR, wherein the filler is A non-crystalline network structure composite composed of cerium oxide and at least one metal oxide of Group IIA or IIIA, and the copper foil substrate produced thereby has an appropriate hardness and coefficient of linear expansion.
第一圖顯示一般製作玻璃纖維銅箔基板的製程，其中包括有：將玻璃纖維布10送至一含浸槽12中，其中有含浸液。之後經一加熱器14加熱後，以刀具16裁切為預定尺寸，以形成若干半固膠片18備用。接著，將預定數量的半固膠片18以預定的纖維走向堆疊在一起，並在頂面與底面各設置一銅箔20，進行熱模壓製片22工作。熱模壓後的板片，經適當的修剪24後，即可得到中央為玻璃纖維基板而兩側均具有銅箔之銅箔基板26，整體的銅箔基板26結構由多數的半固膠片18及至少一銅箔20所構成，其中各該半固膠片18為玻璃纖維布10及含浸材(含浸液固化後)所構成。The first figure shows a process for making a glass fiber copper foil substrate in general, which includes: feeding the glass fiber cloth 10 to an impregnation tank 12 having an impregnation liquid therein. Thereafter, after heating by a heater 14, the cutter 16 is cut to a predetermined size to form a plurality of semi-solid films 18 for use. Next, a predetermined number of the semi-solid films 18 are stacked together in a predetermined fiber direction, and a copper foil 20 is provided on each of the top surface and the bottom surface to perform the work of the hot molded sheet 22. After the hot-molded sheet is properly trimmed 24, a copper foil substrate 26 having a center of a glass fiber substrate and copper foil on both sides is obtained, and the overall copper foil substrate 26 is composed of a plurality of semi-solid films 18 and At least one copper foil 20 is formed, wherein each of the semi-solid films 18 is composed of a glass fiber cloth 10 and an impregnated material (after the impregnation liquid is cured).
本發明之主要內容是針對銅箔基板及其含浸液的成分。本發明含浸液的主要成份為樹脂(本發明採用的是環氧樹脂)，另外添加有5-80PHR(Per Hundred Resin)的填料(亦即樹脂與填料的重量百分比為=100:5-80)。該填料的主要成份包括有二氧化矽(SiO2 )、三氧化二鋁(Al2 O3 )、三氧化二硼(B2 O3 )、氧化鈣(CaO)、氧化鎂(MgO)、氧化鍶(SrO)與氧化鋇(BaO)，且此填料為上述成分所共構成的非結晶性網狀結構複合材。；其中二氧化矽佔該填料的比例為50wt%~80wt%，而該各金屬氧化物總共佔該填料的比例為20wt%~50wt%。The main content of the present invention is directed to the composition of the copper foil substrate and its impregnation liquid. The main component of the impregnation liquid of the present invention is a resin (the epoxy resin used in the present invention), and a filler of 5-80 PHR (Per Hundred Resin) is additionally added (that is, the weight percentage of the resin and the filler is =100:5-80) . The main components of the filler include cerium oxide (SiO 2 ), aluminum oxide (Al 2 O 3 ), boron trioxide (B 2 O 3 ), calcium oxide (CaO), magnesium oxide (MgO), oxidation. SrO and BaO, and the filler is a non-crystalline network structure composite composed of the above components. The proportion of the cerium oxide to the filler is 50% by weight to 80% by weight, and the ratio of the respective metal oxides to the filler is 20% by weight to 50% by weight.
本發明填料之主要成分為二氧化矽，其功能，如前所述，藉由二氧化矽的四面體網狀結構型結晶可提高基板的硬度與降低線性膨脹係數。本發明之填料的其餘成分大致為金屬氧化物，而前述之金屬氧化物的金屬可選自週期表IIA族元素或是IIIA族元素。藉由金屬氧化物滲入二氧化矽的網狀結構中，使金屬原子佔據原來網狀結構中矽原子的位置，造成四面體網狀結構被破壞，而形成非結晶形的金屬氧化物與二氧化矽的複合材料。由於此複合材料為非結晶型，與結晶型二氧化矽比較，本發明之非結晶型複合材料具有較低的硬度；即使與非結晶型二氧化矽比較，本發明亦具有較低的硬度。The main component of the filler of the present invention is cerium oxide, and its function, as described above, can increase the hardness of the substrate and lower the linear expansion coefficient by the tetrahedral network structure crystallization of cerium oxide. The remainder of the filler of the present invention is substantially a metal oxide, and the metal of the foregoing metal oxide may be selected from Group IIA elements or Group IIIA elements of the Periodic Table. By infiltrating the metal oxide into the network structure of the ceria, the metal atoms occupy the position of the deuterium atoms in the original network structure, causing the tetrahedral network structure to be destroyed, and forming the amorphous metal oxide and the dioxide.矽 composite material. Since the composite material is amorphous, the amorphous composite of the present invention has a lower hardness than the crystalline cerium oxide; the present invention has a lower hardness even when compared with the amorphous cerium oxide.
根據發明人的實驗結果得知，如前述的金屬氧化物選自如IIIA族元素三氧化二鋁(Al2 O3 )、三氧化二硼(B2 O3 )或IIA族元素氧化鈣(CaO)、氧化鎂(MgO)、氧化鍶(SrO)及氧化鋇(BaO)之其中一種或是以上任兩種(或兩種以上)金屬氧化物的組合，其可降低硬度，使得鑽頭的損耗率降低；且，經實驗得知，在上述金屬氧化物中，若加入IIIA族元素三氧化二鋁(Al2 O3 )、三氧化二硼(B2 O3 )或IIA族元素氧化鈣(CaO)、氧化鎂(MgO)之其中一種或是以上任兩種(或兩種以上)金屬氧化物的組合時，更具有降低線膨脹係數的功效。According to the experimental results of the inventors, the metal oxide as described above is selected from, for example, a Group IIIA element of aluminum oxide (Al 2 O 3 ), boron trioxide (B 2 O 3 ) or a Group IIA element calcium oxide (CaO). , one of magnesium oxide (MgO), strontium oxide (SrO) and barium oxide (BaO) or a combination of two or more (or more) metal oxides, which can lower the hardness and reduce the loss rate of the drill bit And, experimentally, in the above metal oxide, if a group IIIA element of aluminum oxide (Al 2 O 3 ), boron trioxide (B 2 O 3 ) or IIA element calcium oxide (CaO) is added. When one of magnesium oxide (MgO) or a combination of two or more (or two or more) metal oxides has a function of lowering the coefficient of linear expansion.
因此，在銅箔基板的應用上，以上述IIIA族元素三氧化二鋁(Al2 O3 )、三氧化二硼(B2 O3 )或IIA族元素氧化鈣(CaO)、氧化鎂(MgO)的金屬氧化物的成分為最佳，在考慮其他性質，如化學耐久性或具有較低的介電常數等條件下，本發明填料的較佳重量配比關係為：二氧化矽(SiO2 )50-62%，三氧化二鋁(Al2 O3 )11-19%，三氧化二硼(B2 O3 )4-13%，氧化鈣(CaO)6-27%，氧化鎂(MgO)<6%，氧化鍶(SrO)<1.5%及氧化鋇(BaO)＜0.1%。Therefore, in the application of the copper foil substrate, the above-mentioned group IIIA element aluminum oxide (Al 2 O 3 ), boron trioxide (B 2 O 3 ) or IIA element calcium oxide (CaO), magnesium oxide (MgO) The composition of the metal oxide is optimal, and the preferred weight ratio of the filler of the present invention is: cerium oxide (SiO 2 ) under consideration of other properties such as chemical durability or a low dielectric constant. ) 50-62%, Al 2 O 3 (Al 2 O 3 ) 11-19%, boron trioxide (B 2 O 3 ) 4-13%, calcium oxide (CaO) 6-27%, magnesium oxide (MgO) <6%, strontium oxide (SrO) <1.5% and barium oxide (BaO) <0.1%.
茲以上述配比關係為基礎下，本發明採用填料，其與習用填料為二氧化矽的銅箔基板在線膨脹係數與鑽孔方面的比較如下：Based on the above ratio relationship, the present invention uses a filler, and the in-line expansion coefficient and the drilling aspect of the copper foil substrate with the conventional filler of cerium oxide are as follows:
【範例一】[Example 1]
編號A：習用不加填料時的樹脂成分如下：No. A: The resin composition when the filler is not used is as follows:
含浸時使用的玻纖布為7628,含浸後於170度C固化3分鐘時，疊構5層後，在半固膠片的雙面覆以1/2oz/ft2 的銅箔並加熱至170度C固化一小時，得一銅箔基板厚度為0.95mm。The glass fiber cloth used for impregnation is 7628, and after curing at 170 ° C for 3 minutes after impregnation, after stacking 5 layers, the 1/2 oz/ft 2 copper foil is coated on both sides of the semi-solid film and heated to 170 degrees. C was cured for one hour to obtain a copper foil substrate having a thickness of 0.95 mm.
以上述銅箔基板進行下列測試，具結果如下：The following tests were carried out on the above copper foil substrate, and the results were as follows:
編號B：若在上述樹脂成分中加入二氧化矽填料，其配比如下：No. B: If a cerium oxide filler is added to the above resin component, the ratio is as follows:
經同樣疊構和銅箔熱壓後，測試其特性結果如下：After the same stack and hot pressing of copper foil, the test results are as follows:
比較二者數據，可清楚了解，加入2um二氧化矽後,Tg增加且線膨脹係數降低。Comparing the data, it is clear that after adding 2 um of cerium oxide, the Tg increases and the coefficient of linear expansion decreases.
編號C：在維持與編號B相同的含浸液(樹脂加填料)比例下，若上述填料改為如下成分之金屬氧化物複合材料(D50=2um)：No. C: When the ratio of the impregnation liquid (resin plus filler) is the same as that of No. B, if the above filler is changed to the metal oxide composite material of the following composition (D50 = 2 um):
經同樣疊構和銅箔熱壓後，測試其特性結果如下：After the same stack and hot pressing of copper foil, the test results are as follows:
由上可得結論：以本例中之金屬氧化物複合材為填料時，可得相較於以二氧化矽為填料時更低的膨脹係數。From the above, it can be concluded that when the metal oxide composite material in this example is used as a filler, a lower expansion coefficient can be obtained than when the cerium oxide is used as a filler.
【範例二】[Example 2]
編號D：如上填料之成分比例更改如下：No. D: The composition ratio of the above filler is changed as follows:
經同樣疊構和銅箔熱壓後，測試其特性結果如下：After the same stack and hot pressing of copper foil, the test results are as follows:
編號E：在維持與編號D相同的含浸液(樹脂加填料)比例下，若上述填料改為如下成分之金屬氧化物複合材料(D50=2um)No. E: When the ratio of the impregnation liquid (resin plus filler) is the same as that of the number D, if the above filler is changed to the metal oxide composite material of the following composition (D50=2um)
經同樣疊構和銅箔熱壓後，測試其特性結果如下：After the same stack and hot pressing of copper foil, the test results are as follows:
比較上例，填料比例愈高,Tg愈高，膨脹係數愈低，而且在使用金屬氧化物複合材為填料時其效果更為明顯。Comparing the above examples, the higher the filler ratio, the higher the Tg, the lower the expansion coefficient, and the effect is more obvious when the metal oxide composite is used as the filler.
【範例三】[Example 3]
上述二例中所製作的銅箔基板編號A、B、C、D及E,同時進行鑽孔測試，如下表：The copper foil substrate numbers A, B, C, D and E produced in the above two cases were simultaneously drilled, as shown in the following table:
在二氧化矽成份，金屬氧化物複合材成分，含浸及銅箔熱壓的製程同上二例，鑽孔條件如下：In the bismuth dioxide component, metal oxide composite component, impregnation and copper foil hot pressing process as in the above two cases, the drilling conditions are as follows:
所獲得銅箔基板編號A、B、C、D及E之鑽孔製程能力和鑽頭損耗比較表分別以第二圖、第三圖、第四圖、第五圖及第六圖表示，其中鑽孔製程能力定義為：以鑽孔後平均位置為原點,X軸和Y軸以正負2mm為上下限規格，計算鑽孔製程能力；鑽頭損耗情形則由鑽頭影像觀察鑽頭損耗之嚴重程度。The drilling process capability and the bit loss comparison table of the obtained copper foil substrate numbers A, B, C, D and E are respectively represented by the second, third, fourth, fifth and sixth figures, wherein the drilling The hole process capability is defined as: the average position after drilling is taken as the origin, the X-axis and the Y-axis are measured by the positive and negative 2mm as the upper and lower limits, and the drilling process capability is calculated; the bit loss is observed by the bit image.
由第二圖、第三圖、第四圖、第五圖及第六圖所各別表示之銅箔基板編號A、B、C、D及E的鑽孔製程能力和鑽頭損耗比較表可清楚看出，不管樹脂配方如何，鑽孔數愈高時，由鑽頭影像可看出鑽頭的損耗增加，因而鑽頭搖擺大，精準度變差，造成鑽孔的製程能力變差,Cpk值變小。The comparison of the drilling process capability and the bit loss comparison table of the copper foil substrate numbers A, B, C, D and E respectively indicated by the second, third, fourth, fifth and sixth figures is clear It can be seen that regardless of the resin formulation, the higher the number of drilled holes, the more the loss of the drill bit can be seen from the image of the drill bit, so that the drill bit is swung large and the precision is deteriorated, resulting in poor drilling process capability and a small Cpk value.
若加入單一的二氧化矽填料，由於二氧化矽的硬度高，造成鑽孔的困難度增加，上述鑽頭的損耗更加明顯，且在高鑽孔數時，其精準度亦迅速惡化。二氧化矽的添加量愈多，此種現象更加嚴重。If a single cerium oxide filler is added, the hardness of the bismuth dioxide is increased, and the difficulty of drilling is increased. The loss of the above-mentioned drill bit is more obvious, and the accuracy is rapidly deteriorated at a high number of holes. The more the amount of cerium oxide added, the more serious this phenomenon is.
若加入本發明中的金屬氧化物複合材，由於其本身屬非結晶型的網狀結構，硬度低，相較於單一的二氧化矽，在高鑽孔數時，鑽頭損耗和未加填料時相差無幾，故仍能保持很好的鑽孔精準度和較好的鑽孔製程能力。當填料比例愈高時，和單一的二氧化矽相較，本發明中的金屬氧化物複合材更能顯現其低鑽頭損耗和更好的鑽孔製程能力之特性。If the metal oxide composite material of the present invention is added, since it is a non-crystalline network structure, the hardness is low, compared with a single cerium oxide, when the number of holes is high, the bit is worn and unfilled. It is still very similar, so it can still maintain good drilling accuracy and better drilling process capability. The higher the filler ratio, the more the metal oxide composite of the present invention exhibits its lower bit loss and better drilling process capability than a single ceria.
以上所述僅為本發明較佳可行實施例而已，舉凡應用本發明說明書及申請專利範圍所為之等效結構變化，理應包含在本發明之專利範圍內。The above is only a preferred embodiment of the present invention, and equivalent structural changes to the scope of the present invention and the scope of the claims are intended to be included in the scope of the present invention.
10‧‧‧玻璃纖維布10‧‧‧glass cloth
12‧‧‧含浸槽12‧‧‧Immersion tank
14‧‧‧加熱器14‧‧‧heater
16‧‧‧刀具16‧‧‧Tools
18‧‧‧半固膠片18‧‧‧ semi-solid film
20‧‧‧銅箔20‧‧‧ copper foil
22‧‧‧熱模壓製片22‧‧‧Thermal compression tablets
24‧‧‧修剪24‧‧‧ trim
26‧‧‧銅箔基板26‧‧‧ copper foil substrate
第一圖為製作銅箔基板的製程示意圖。The first figure is a schematic diagram of the process for making a copper foil substrate.
第二圖為銅箔基板編號A之鑽孔製程能力和鑽頭損耗比較表。The second figure is a comparison table of the drilling process capability and the bit loss of the copper foil substrate No. A.
第三圖為銅箔基板編號B之鑽孔製程能力和鑽頭損耗比較表。The third figure is a comparison table of the drilling process capability and the bit loss of the copper foil substrate No. B.
第四圖為銅箔基板編號C之鑽孔製程能力和鑽頭損耗比較表。The fourth figure is a comparison table of the drilling process capability and the bit loss of the copper foil substrate No. C.
第五圖為銅箔基板編號D之鑽孔製程能力和鑽頭損耗比較表。The fifth figure is a comparison table of the drilling process capability and the bit loss of the copper foil substrate No. D.
第六圖為銅箔基板編號E之鑽孔製程能力和鑽頭損耗比較表。The sixth figure is a comparison table of the drilling process capability and the bit loss of the copper foil substrate No. E.
10．．．玻璃纖維布10. . . Glass fiber cloth
12．．．含浸槽12. . . Immersion tank
14．．．加熱器14. . . Heater
16．．．刀具16. . . Tool
18．．．半固膠片18. . . Semi-solid film
20．．．銅箔20. . . Copper foil
22．．．熱模壓製片twenty two. . . Hot molded tablet
24．．．修剪twenty four. . . prune
26．．．銅箔基板26. . . Copper foil substrate
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW98139403A TWI417188B (en) | 2009-11-19 | 2009-11-19 | A copper foil substrate and an impregnating liquid for producing the copper foil substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW98139403A TWI417188B (en) | 2009-11-19 | 2009-11-19 | A copper foil substrate and an impregnating liquid for producing the copper foil substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201117955A TW201117955A (en) | 2011-06-01 |
| TWI417188B true TWI417188B (en) | 2013-12-01 |
Family
ID=44935434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW98139403A TWI417188B (en) | 2009-11-19 | 2009-11-19 | A copper foil substrate and an impregnating liquid for producing the copper foil substrate |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI417188B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105807576A (en) * | 2015-01-16 | 2016-07-27 | 佳能株式会社 | Exposure apparatus, and method for manufacturing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343402A (en) * | 2008-08-27 | 2009-01-14 | 南亚塑胶工业股份有限公司 | Resin composition with high-heat, high-glass transition temperature for printed circuit board, prepreg and coating substance |
-
2009
- 2009-11-19 TW TW98139403A patent/TWI417188B/en active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101343402A (en) * | 2008-08-27 | 2009-01-14 | 南亚塑胶工业股份有限公司 | Resin composition with high-heat, high-glass transition temperature for printed circuit board, prepreg and coating substance |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105807576A (en) * | 2015-01-16 | 2016-07-27 | 佳能株式会社 | Exposure apparatus, and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201117955A (en) | 2011-06-01 |
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