TW201527367A - Prepreg and method for manufacturing the same - Google Patents
Prepreg and method for manufacturing the same Download PDFInfo
- Publication number
- TW201527367A TW201527367A TW103127030A TW103127030A TW201527367A TW 201527367 A TW201527367 A TW 201527367A TW 103127030 A TW103127030 A TW 103127030A TW 103127030 A TW103127030 A TW 103127030A TW 201527367 A TW201527367 A TW 201527367A
- Authority
- TW
- Taiwan
- Prior art keywords
- formula
- reinforcing material
- glue
- film
- magnetic field
- Prior art date
Links
Abstract
Description
本發明係關於預浸片，更特別關於預浸片之組成與其形成方法。 The present invention relates to prepreg sheets, and more particularly to the composition of prepreg sheets and methods of forming the same.
複合材料應用在精密製品(如高密度多層電路板產品)中，若其厚度方向之熱膨脹率受製程溫度的影響小，則可提高其應用性。舉例而言，多層電路板中之增層片材，即預浸片(prepreg)，通常是由玻纖布含浸樹脂製作而成，由於在片材平面方向上有玻纖布的支撐，尺寸安定性高，熱膨脹率低，而在厚度方向上因為缺少玻纖布的支撐，其尺寸安定性需要提升。 Composite materials are used in precision products (such as high-density multilayer circuit board products). If the thermal expansion rate in the thickness direction is less affected by the process temperature, the applicability can be improved. For example, a pre-glued sheet in a multi-layer circuit board, that is, a prepreg, is usually made of a fiberglass cloth impregnated resin, and has a dimensional stability due to the support of the fiberglass cloth in the plane direction of the sheet. The high degree of thermal expansion is low, and the dimensional stability is required to be improved in the thickness direction due to the lack of support of the fiberglass cloth.
一般市售之電路板增層片材在厚度方向的熱膨脹率平均高於15ppm/℃，尚不足以滿足高階電子產品的高密度電路板製程需求。因此降低增層片材厚度方向的熱膨脹率十分重要。 The commercially available circuit board build-up sheets have an average thermal expansion rate in the thickness direction of more than 15 ppm/° C., which is insufficient to meet the high-density circuit board process requirements of high-end electronic products. Therefore, it is important to reduce the rate of thermal expansion in the thickness direction of the buildup sheet.
本發明一實施例提供之預浸片，包括：補強材；以及聚合物，其中聚合物係由有機棒狀分子之單體、寡聚物、或上述之組合聚合而成，有機棒狀分子具有光聚合基，有機棒狀分子之長軸方向磁化率大於其他方向之磁化率，且長軸方向 磁化率除以其他方向之磁化率所得的數值大於0.01且小於1。 A prepreg according to an embodiment of the present invention includes: a reinforcing material; and a polymer, wherein the polymer is polymerized from a monomer, an oligomer, or a combination thereof, of the organic rod-shaped molecule, and the organic rod-shaped molecule has Photopolymerizable group, the magnetic susceptibility of the long-axis direction of the organic rod-shaped molecules is larger than the magnetic susceptibility of the other directions, and the long-axis direction The value obtained by dividing the magnetic susceptibility by the magnetic susceptibility in other directions is greater than 0.01 and less than 1.
本發明一實施例提供之預浸片的形成方法，包括：取膠水與補強材組合形成膜狀物，且膠水包括光起始劑、溶劑、與有機棒狀分子之單體、寡聚物、或上述之組合，其中有機棒狀分子具有光聚合基，有機棒狀分子長軸方向磁化率大於其他方向之磁化率，且長軸方向磁化率除以其他方向之磁化率所得的數值大於0.01且小於1，以垂直於膜狀物之表面的方向施加磁場至膜狀物，以排列有機棒狀分子使有機棒狀分子的長軸平行於磁場且垂直於膜狀物表面；以及以紫外線照射膜狀物，使磁場排列後之有機棒狀分子聚合成聚合物，且聚合物與補強材複合形成預浸片。 A method for forming a prepreg according to an embodiment of the present invention comprises: taking a glue and a reinforcing material to form a film, and the glue comprises a photoinitiator, a solvent, a monomer and an oligomer with an organic rod-shaped molecule, Or a combination of the above, wherein the organic rod-shaped molecule has a photopolymerizable group, the magnetic susceptibility of the long-axis direction of the organic rod-shaped molecule is larger than the magnetic susceptibility of the other direction, and the magnetic susceptibility of the long-axis direction divided by the magnetic susceptibility of the other direction is greater than 0.01 and Less than 1, applying a magnetic field to the film in a direction perpendicular to the surface of the film to align the organic rod-shaped molecules such that the long axis of the organic rod-shaped molecules is parallel to the magnetic field and perpendicular to the surface of the film; and irradiating the film with ultraviolet rays The organic rod-shaped molecules after the magnetic field is aligned are polymerized into a polymer, and the polymer and the reinforcing material are combined to form a prepreg.
10‧‧‧膜狀物 10‧‧‧membrane
11‧‧‧輸送帶 11‧‧‧Conveyor belt
13‧‧‧磁場 13‧‧‧ magnetic field
15‧‧‧紫外線燈 15‧‧‧UV light
100‧‧‧預浸片 100‧‧‧Prepreg
第1圖係本發明一實施例中，連續式形成預浸片的示意圖。 Fig. 1 is a schematic view showing the continuous formation of a prepreg according to an embodiment of the present invention.
本發明一實施例提供預浸片的形成方法如下。首先配製膠水，其包含100重量份之有機棒狀分子的單體、寡聚物、或上述之組合，0.1至5重量份之光起始劑，0至60重量份之溶劑。有機棒狀分子具有光聚合基(比如碳碳雙鍵)，有機棒狀分子長軸方向磁化率大於其他方向之磁化率，且長軸方向磁化率除以其他方向之磁化率所得的數值大於0.01且小於1。在本發明一實施例中，有機棒狀分子長軸方向磁化率除以其他方向之磁化率所得的數值大於0.1且小於1。在本發明一實施例中，有機棒狀分子之結構如式1至式10或上述之組合： R1-O-Ph-A0-Ph-O-R2 (式1) An embodiment of the present invention provides a method of forming a prepreg as follows. First, a glue comprising 100 parts by weight of a monomer of an organic rod-like molecule, an oligomer, or a combination thereof, 0.1 to 5 parts by weight of a photoinitiator, and 0 to 60 parts by weight of a solvent are prepared. The organic rod-shaped molecule has a photopolymerizable group (such as a carbon-carbon double bond), the magnetic susceptibility of the long-axis direction of the organic rod-shaped molecule is larger than that of the other direction, and the value of the magnetic susceptibility of the long-axis direction divided by the magnetic direction of the other direction is greater than 0.01. And less than 1. In one embodiment of the present invention, the value of the magnetic susceptibility in the long-axis direction of the organic rod-shaped molecule divided by the magnetic susceptibility in the other direction is greater than 0.1 and less than 1. In an embodiment of the invention, the structure of the organic rod-shaped molecule is as shown in Formula 1 to Formula 10 or a combination thereof: R 1 -O-Ph-A 0 -Ph-OR 2 (Formula 1)
R1-O-Ph-A1-Ph-A2-Ph-O-R2 (式2) R 1 -O-Ph-A 1 -Ph-A 2 -Ph-OR 2 (Formula 2)
R1-O-Ph-A1-Ph-A2-Ph-A3-Ph-O-R2 (式3) R 1 -O-Ph-A 1 -Ph-A 2 -Ph-A 3 -Ph-OR 2 (Formula 3)
R1-O-Ph-A1-Ph-A2-Ph-A3-Ph-A4-Ph-O-R2 (式4) R 1 -O-Ph-A 1 -Ph-A 2 -Ph-A 3 -Ph-A 4 -Ph-OR 2 (Formula 4)
R1-O-Ph-A1-Ph-A2-Ph-A3-Ph-A4-Ph-A5-Ph-O-R2 (式5) R 1 -O-Ph-A 1 -Ph-A 2 -Ph-A 3 -Ph-A 4 -Ph-A 5 -Ph-OR 2 (Formula 5)
R1-O-Ph-A1-Ph-A2-Ph-A3-Ph-A4-Ph-A5-Ph-A6-Ph-O-R2 (式6) R 1 -O-Ph-A 1 -Ph-A 2 -Ph-A 3 -Ph-A 4 -Ph-A 5 -Ph-A 6 -Ph-OR 2 (Formula 6)
R1-O-Ph-A1-Ph-A2-Ph-A3-Ph-A4-Ph-A5-Ph-A6-Ph-A7-Ph-O-R2 (式7) R 1 -O-Ph-A 1 -Ph-A 2 -Ph-A 3 -Ph-A 4 -Ph-A 5 -Ph-A 6 -Ph-A 7 -Ph-OR 2 (Formula 7)
R1-O-Ph-A1-Ph-A2-Ph-A3-Ph-A4-Ph-A5-Ph-A6-Ph-A7-Ph-A8-Ph-O-R2 (式8) R 1 -O-Ph-A 1 -Ph-A 2 -Ph-A 3 -Ph-A 4 -Ph-A 5 -Ph-A 6 -Ph-A 7 -Ph-A 8 -Ph-OR 2 ( Equation 8)
R1-O-Ph-A1-Ph-A2-Ph-A3-Ph-A4-Ph-A5-Ph-A6-Ph-A7-Ph-A8-Ph-A9-Ph-O-R2 (式9) R 1 -O-Ph-A 1 -Ph-A 2 -Ph-A 3 -Ph-A 4 -Ph-A 5 -Ph - A 6 -Ph-A 7 -Ph-A 8 -Ph-A 9 - Ph-OR 2 (Equation 9)
R1-O-Ph-A1-Ph-A2-Ph-A3-Ph-A4-Ph-A5-Ph-A6-Ph-A7-Ph-A8-Ph-A9-Ph-A10-Ph-O-R2 (式10) R 1 -O-Ph-A 1 -Ph-A 2 -Ph-A 3 -Ph-A 4 -Ph-A 5 -Ph-A 6 -Ph-A 7 -Ph-A 8 -Ph-A 9 - Ph-A 10 -Ph-OR 2 (Formula 10)
在式1至式10中，Ph係取代有NO2、OH、OCH3、CH3、CF3、F、Cl、或Br之苯環或未取代之苯環，A0係-C≡C-；A1、A2、A3、A4、A5、A6、A7、A8、A9、與A10係各自為-CH2-、-O-、-(C=O)-、-(CH=CH)-、-C≡C-、-O-(C=O)-、-(NH)-(C=O)-、或單鍵；R1與R2係各自獨立，係-R3-O-(C=O)-C=CH2，且R3係C2-C12之烷撐基。 In Formulae 1 to 10, Ph is substituted with a benzene ring or an unsubstituted benzene ring of NO 2 , OH, OCH 3 , CH 3 , CF 3 , F, Cl, or Br, and A 0 is -C≡C- ; A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , A 7 , A 8 , A 9 , and A 10 are each -CH 2 -, -O-, -(C=O)- , -(CH=CH)-, -C≡C-, -O-(C=O)-, -(NH)-(C=O)-, or a single bond; R 1 and R 2 are each independent, Is -R 3 -O-(C=O)-C=CH 2 , and R 3 is a C 2 -C 12 alkylene group.
光起始劑在接觸紫外線後將裂解形成自由基，使有機棒狀分子中的光聚合基聚合。若光起始劑之用量過少，則無法有效起始上述聚合反應。若光起始劑之用量過多，將導致聚合物特性變差而且製程的環境光必須更嚴謹控制。在本發明 一實施例中，溶劑可為甲苯(CAS no.：108-88-3)、甲乙酮(CAS no.：78-93-9)、二甲基甲醯胺(CAS no.：68-12-2)、或γ-丁內酯(CAS no.：96-48-0)。上述溶劑可調整膠水黏度。若溶劑用量過多或過少，則膠水過稀或過黏而不易與補強材組合形成膜狀物。在本發明其他實施例中，上述膠水可進一步包含0.5至100重量份之環氧樹脂(EPON 828、NPCN-704)和0.5至100重量份之環氧樹脂硬化劑(Dicy：CAS no.：461-58-5,DDS：CAS no.：80-08-0,Novolac)。 The photoinitiator will cleave to form a radical upon contact with ultraviolet rays to polymerize the photopolymerizable group in the organic rod-like molecule. If the amount of the photoinitiator used is too small, the above polymerization reaction cannot be effectively started. If the amount of photoinitiator is too large, the polymer properties will be deteriorated and the ambient light of the process must be more strictly controlled. In the present invention In one embodiment, the solvent may be toluene (CAS no.: 108-88-3), methyl ethyl ketone (CAS no.: 78-93-9), dimethylformamide (CAS no.: 68-12-2) ), or γ-butyrolactone (CAS no.: 96-48-0). The above solvent can adjust the viscosity of the glue. If the amount of the solvent is too large or too small, the glue is too thin or too sticky to be easily combined with the reinforcing material to form a film. In other embodiments of the present invention, the above glue may further comprise 0.5 to 100 parts by weight of epoxy resin (EPON 828, NPCN-704) and 0.5 to 100 parts by weight of epoxy resin hardener (Dicy: CAS no.: 461 -58-5, DDS: CAS no.: 80-08-0, Novolac).
接著取膠水與補強材組合形成膜狀物。以100重量份之有機棒狀分子的單體、寡聚物、或上述之組合作基準，補強材之用量介於10至200重量份之間。若補強材之用量過高，則導致後續加工製程困難，良率下降，且膠片與銅箔之接著強度下降。若補強材之用量過低，則無法有效提升膜狀物之機械強度。在本發明一實施例中，補強材可為玻璃、陶瓷、碳材、樹脂、或上述之組合。在本發明一實施例中，補強材之形狀為纖維、粉體、片狀物、編織物、或上述之組合。在本發明一實施例中，取膠水與補強材組合形成膜狀物之步驟可為將補強材分散於膠水中，再塗佈於載體上。在本發明另一實施例中，補強材為編織物如玻纖布，且取膠水與補強材組合形成膜狀物之步驟可為將補強材(例如纖維或編織物)含浸於膠水中。在本發明又一實施例中，取膠水與補強材組合形成膜狀物之步驟可為將膠水塗佈於補強材上。 Then, the glue is combined with the reinforcing material to form a film. The reinforcing material is used in an amount of from 10 to 200 parts by weight based on 100 parts by weight of the monomer of the organic rod-shaped molecule, the oligomer, or the above-mentioned group standard. If the amount of the reinforcing material is too high, the subsequent processing process is difficult, the yield is lowered, and the bonding strength between the film and the copper foil is lowered. If the amount of the reinforcing material is too low, the mechanical strength of the film cannot be effectively improved. In an embodiment of the invention, the reinforcing material may be glass, ceramic, carbon material, resin, or a combination thereof. In an embodiment of the invention, the shape of the reinforcing material is a fiber, a powder, a sheet, a braid, or a combination thereof. In an embodiment of the invention, the step of combining the glue and the reinforcing material to form a film may be performed by dispersing the reinforcing material in the glue and then coating the carrier. In another embodiment of the present invention, the reinforcing material is a woven fabric such as a fiberglass cloth, and the step of combining the glue and the reinforcing material to form a film may be a step of impregnating the reinforcing material (for example, fiber or woven fabric) in the glue. In still another embodiment of the present invention, the step of taking the glue and the reinforcing material to form a film may be to apply the glue to the reinforcing material.
接著以垂直於膜狀物之表面的方向施加磁場至膜狀物，以排列有機棒狀分子使有機棒狀分子的長軸平行於磁場 且垂直於膜狀物表面。在本發明一實施例中，磁場可為靜磁場或可變脈衝磁場，且磁場強度介於0.1T至10T之間。若磁場強度過低，則無法有效排列有機棒狀分子。若磁場強度過高，則需過大體積之磁場設備，且生產時需額外安全措施導致量產成本大增。在本發明一實施例中，施加磁場至膜狀物的時間介於1秒至600秒之間(或5秒至100秒之間)。若施加磁場的時間過短，則無法有效排列有機棒狀分子。若施加磁場時間過久，則導致生產時間變長。 The magnetic field is then applied to the film in a direction perpendicular to the surface of the film to align the organic rod-shaped molecules such that the long axis of the organic rod-shaped molecules is parallel to the magnetic field. And perpendicular to the surface of the membrane. In an embodiment of the invention, the magnetic field may be a static magnetic field or a variable pulse magnetic field, and the magnetic field strength is between 0.1 T and 10 T. If the magnetic field strength is too low, the organic rod-shaped molecules cannot be efficiently aligned. If the magnetic field strength is too high, a large volume of magnetic field equipment is required, and additional safety measures are required during production, resulting in a large increase in mass production costs. In an embodiment of the invention, the time to apply a magnetic field to the membrane is between 1 second and 600 seconds (or between 5 seconds and 100 seconds). If the time for applying the magnetic field is too short, the organic rod-shaped molecules cannot be efficiently aligned. If the magnetic field is applied for too long, the production time becomes longer.
之後或同時以紫外線照射膜狀物，使磁場排列之有機棒狀分子聚合成聚合物，且聚合物與補強材複合形成預浸片。紫外線照射膜狀物的時間少於10秒，例如可為約大於0小於10秒，即可有效硬化膜狀物中的有機棒狀分子。 Thereafter, the film is irradiated with ultraviolet rays, and the organic rod-like molecules in which the magnetic field is aligned are polymerized into a polymer, and the polymer and the reinforcing material are combined to form a prepreg. The ultraviolet light illuminates the film for less than 10 seconds, for example, about 0 to less than 10 seconds, to effectively harden the organic rod-like molecules in the film.
可以理解的是，上述製程可為連續製程。如第1圖所示，可在輸送帶11上形成膠水與補強材組合而成的膜狀物10，再施加磁場13至膜狀物10上。上述磁場13施加的時間取決於輸送帶11傳動的速率。在輸送帶11末端為紫外線燈15，經磁場排列及紫外線硬化後，膜狀物10即形成預浸片100。在本發明一實施例中，紫外線燈15可與磁場13位於同一位置同步施加於膜狀物10上。與熱聚合的機制相較，上述光聚合機制的速率較快，除了可減少製程時間外，也比熱聚合機制更適用於連續性製程。 It can be understood that the above process can be a continuous process. As shown in Fig. 1, a film 10 in which a glue and a reinforcing material are combined can be formed on the conveyor belt 11, and a magnetic field 13 is applied to the film 10. The time during which the magnetic field 13 is applied depends on the rate at which the conveyor belt 11 is driven. At the end of the conveyor belt 11, the ultraviolet lamp 15 is placed, and after the magnetic field is arranged and the ultraviolet ray is hardened, the film 10 forms the prepreg 100. In an embodiment of the invention, the ultraviolet lamp 15 can be applied to the membrane 10 simultaneously with the magnetic field 13 at the same position. Compared with the mechanism of thermal polymerization, the above photopolymerization mechanism has a faster rate, and in addition to reducing the process time, it is also more suitable for the continuous process than the thermal polymerization mechanism.
在本發明另一實施例中，可在輸送帶上放置補強材，並直接將膠水塗佈於補強材上以形成膜狀物。後續施加磁場至膜狀物與紫外線硬化膜狀物之步驟與前述方法類似。 In another embodiment of the invention, a reinforcing material can be placed on the conveyor belt and the glue applied directly to the reinforcing material to form a film. The subsequent step of applying a magnetic field to the film and the ultraviolet hardened film is similar to the aforementioned method.
在本發明一實施例中，可由滾輪直接傳送補強材(不需要輸送帶)，使補強材含浸膠水形成膜狀物。後續施加磁場至膜狀物與紫外線硬化膜狀物之步驟與前述方法類似。 In an embodiment of the invention, the reinforcing material can be directly conveyed by the roller (the conveyor belt is not required), and the reinforcing material is impregnated with the glue to form a film. The subsequent step of applying a magnetic field to the film and the ultraviolet hardened film is similar to the aforementioned method.
上述預浸片可壓合至銅箔上以形成銅箔基板。由於本發明之預浸片在厚度方向的熱膨脹係數低於現有的預浸片，可有效降低爆板問題而提升製程良率。 The above prepreg sheet may be pressed onto a copper foil to form a copper foil substrate. Since the coefficient of thermal expansion of the prepreg of the present invention in the thickness direction is lower than that of the existing prepreg, the problem of the blasting plate can be effectively reduced to improve the process yield.
為了讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉數實施例配合所附圖示，作詳細說明如下： The above and other objects, features, and advantages of the present invention will become more apparent and understood.
取1g之4-(3-丙烯醯氧基丙氧基)苯甲酸-2-甲基-1,4-苯酯(4-(3-Acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester，CAS no.：174063-87-7)作為有機棒狀分子，並取0.03g之1-羥基環己基苯基甲酮(1-Hydroxy-cyclohexyl-phenyl-ketone，CAS no.：947-19-3)作為光起始劑，混合後置於玻璃基板上加熱至80℃，融化後蓋上另一片玻璃基板，且兩片基板之間以700μm厚之墊片隔開。將上述結構置於磁場2T的永久磁鐵裝置(維持80℃)中，且磁場方向垂直於基板表面，使混合物中的有機棒狀分子的長軸方向平行於磁場方向。在施加磁場10分鐘後以紫外線照射混合物，使混合物中磁場排列後的有機棒狀分子聚合，並固化混合物。將固化後之樣品切割成0.7cm*0.7cm(厚度約700μm)，以TMA測量樣品升溫時其厚度方向的尺寸變化。上述樣品於30-110℃溫度區 間中，厚度方向之CTE值如第1表所示。 1 g of 4-(3-Acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester , CAS no.: 174063-87-7) as an organic rod-like molecule, and take 0.03 g of 1-hydroxycyclohexyl-phenyl-ketone (CAS no.: 947-19- 3) As a photoinitiator, after mixing, it was placed on a glass substrate and heated to 80 ° C. After melting, another glass substrate was covered, and the two substrates were separated by a spacer of 700 μm thick. The above structure was placed in a permanent magnet device (maintained at 80 ° C) of a magnetic field of 2 T, and the direction of the magnetic field was perpendicular to the surface of the substrate such that the long axis direction of the organic rod-shaped molecules in the mixture was parallel to the direction of the magnetic field. After the magnetic field was applied for 10 minutes, the mixture was irradiated with ultraviolet rays to polymerize the organic rod-like molecules in which the magnetic field was aligned in the mixture, and the mixture was solidified. The cured sample was cut into 0.7 cm * 0.7 cm (thickness about 700 μm), and the dimensional change in the thickness direction of the sample when the sample was heated was measured by TMA. The above sample is in the temperature range of 30-110 °C In the middle, the CTE value in the thickness direction is as shown in Table 1.
與實施例1類似，差別在於永久磁鐵裝置的磁場強度由2T降低至1T。至於實施例2的其他參數如混合物的組成、加熱混合物的溫度、磁場方向、施加磁場的時間、紫外線照射、樣品切割後的尺寸均與實施例1相同。以TMA測量樣品升溫時其厚度方向的尺寸變化，上述樣品於30-110℃溫度區間中，厚度方向之CTE值如第1表所示。 Similar to Embodiment 1, the difference is that the magnetic field strength of the permanent magnet device is lowered from 2T to 1T. The other parameters of Example 2, such as the composition of the mixture, the temperature of the heated mixture, the direction of the magnetic field, the time of applying the magnetic field, the ultraviolet irradiation, and the size after the sample was cut, were the same as in Example 1. The dimensional change in the thickness direction of the sample when the sample was heated was measured by TMA, and the CTE value in the thickness direction of the sample in the temperature range of 30-110 ° C is shown in Table 1.
與實施例1類似，差別在於永久磁鐵裝置的磁場強度由2T降低至0.1T。至於實施例3的其他參數如混合物的組成、加熱混合物的溫度、磁場方向、施加磁場的時間、紫外線照射、樣品切割後的尺寸均與實施例1相同。以TMA測量樣品升溫時其厚度方向的尺寸變化，上述樣品於30-110℃溫度區間中，厚度方向之CTE值如第1表所示。 Similar to Embodiment 1, the difference is that the magnetic field strength of the permanent magnet device is lowered from 2T to 0.1T. The other parameters of Example 3, such as the composition of the mixture, the temperature of the heated mixture, the direction of the magnetic field, the time of applying the magnetic field, the ultraviolet irradiation, and the size after the sample was cut, were the same as in Example 1. The dimensional change in the thickness direction of the sample when the sample was heated was measured by TMA, and the CTE value in the thickness direction of the sample in the temperature range of 30-110 ° C is shown in Table 1.
與實施例1類似，差別在於未施加磁場。至於比較例1的其他參數如混合物的組成、加熱混合物的溫度、紫外線照射、樣品切割後的尺寸均與實施例1相同。以TMA測量樣品升溫時其厚度方向的尺寸變化，上述樣品於30-110℃溫度區間中，厚度方向之CTE值如第1表所示。 Similar to Example 1, the difference is that no magnetic field is applied. The other parameters of Comparative Example 1, such as the composition of the mixture, the temperature of the heated mixture, the ultraviolet irradiation, and the size after the sample was cut, were the same as in Example 1. The dimensional change in the thickness direction of the sample when the sample was heated was measured by TMA, and the CTE value in the thickness direction of the sample in the temperature range of 30-110 ° C is shown in Table 1.
在第1表中，CTE為正值時表示膨脹，CTE為負值時表示收縮。雖然實施例1的收縮程度高於比較例1的膨脹程度，但一般後續應用可容忍收縮(且難以接受膨脹)。舉例來說，含浸玻纖布中的混合物受熱後可收縮但不可膨脹，因玻纖布可減弱收縮程度。另一方面，若膠水中添加其他交聯劑，則交聯劑的膨脹性質可抵消上述混合物的收縮性質。 In the first table, when CTE is a positive value, it indicates expansion, and when CTE is a negative value, it indicates contraction. Although the degree of shrinkage of Example 1 is higher than that of Comparative Example 1, generally the subsequent application can tolerate shrinkage (and it is difficult to accept expansion). For example, a mixture of impregnated fiberglass cloth can shrink but not expand when heated, as the fiberglass cloth can reduce the degree of shrinkage. On the other hand, if other crosslinking agents are added to the glue, the swelling properties of the crosslinking agent can offset the shrinkage properties of the above mixture.
由第1表之比較可知，比較例1中未施加磁場形成之樣品於厚度方向之CTE值為正(膨脹)，而實施例1-3中施加磁場形成之樣品於厚度方向之CTE為負(收縮)，顯見本申請案之製程有助於形成厚度方向之CTE值為負的樣品。 As is clear from the comparison of the first table, the CTE value of the sample in which the magnetic field was not formed in Comparative Example 1 in the thickness direction was positive (expansion), and the sample formed by applying the magnetic field in Example 1-3 was negative in the CTE in the thickness direction ( Shrinkage), it is apparent that the process of the present application helps to form a sample having a negative CTE value in the thickness direction.
取1g之4-(3-丙烯醯氧基丙氧基)苯甲酸-2-甲基-1,4-苯酯(4-(3-Acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester，CAS no.：174063-87-7)作為有機棒狀分子，並取0.03g之1-羥基環己基苯基甲酮(1-Hydroxy-cyclohexyl-phenyl-ketone，CAS no.：947-19-3)作為光起始劑，混合後置於玻璃基板上加熱至80℃融化。之後將2cm×2cm之玻纖布(購自台灣玻璃工業股份有限公司之2116)置入融化後之混合物中，再蓋上另一片玻璃基板擠壓出空氣。將上述結構置於磁場2T的永久磁鐵裝置(維持80℃)中，且磁場方 向垂直於基板表面，使混合物中的有機棒狀分子的長軸方向平行於磁場方向。在施加磁場10分鐘後以紫外線照射混合物，使混合物中磁場排列後的有機棒狀分子聚合，並固化混合物。上述固化後之混合物與與玻纖布複合形成預浸片。將預浸片切割成0.7cm*0.7cm的樣品後(厚度約800μm，表面平坦且厚度均勻)，以TMA測量樣品升溫時其厚度方向的尺寸變化，上述樣品於50-288℃溫度區間中，厚度方向之Z軸膨脹率如第2表所示。 1 g of 4-(3-Acryloyloxypropyloxy)benzoic acid 2-methyl-1,4-phenylene ester , CAS no.: 174063-87-7) as an organic rod-like molecule, and take 0.03 g of 1-hydroxycyclohexyl-phenyl-ketone (CAS no.: 947-19- 3) As a photoinitiator, after mixing, it was placed on a glass substrate and heated to 80 ° C to melt. Then, a 2 cm × 2 cm fiberglass cloth (purchased from Taiwan Glass Industry Co., Ltd., 2116) was placed in the melted mixture, and another glass substrate was covered to extrude air. Place the above structure in a permanent magnet device (maintained at 80 ° C) with a magnetic field of 2 T, and the magnetic field The direction perpendicular to the surface of the substrate is such that the long axis direction of the organic rod-like molecules in the mixture is parallel to the direction of the magnetic field. After the magnetic field was applied for 10 minutes, the mixture was irradiated with ultraviolet rays to polymerize the organic rod-like molecules in which the magnetic field was aligned in the mixture, and the mixture was solidified. The cured mixture is combined with a fiberglass cloth to form a prepreg. After the prepreg is cut into a sample of 0.7 cm*0.7 cm (thickness is about 800 μm, the surface is flat and the thickness is uniform), the dimensional change of the thickness direction of the sample when the sample is heated is measured by TMA, and the sample is in the temperature range of 50-288 ° C, The Z-axis expansion ratio in the thickness direction is shown in Table 2.
與實施例4類似，差別在於未施加磁場。至於比較例2的其他參數如混合物的組成、加熱混合物的溫度、紫外線照射、樣品切割後的尺寸均與實施例4相同。以TMA測量樣品升溫時其厚度方向的尺寸變化，上述樣品於50-288℃溫度區間中，厚度方向之Z軸膨脹率如第2表所示。 Similar to Example 4, the difference is that no magnetic field is applied. The other parameters of Comparative Example 2, such as the composition of the mixture, the temperature of the heated mixture, the ultraviolet irradiation, and the size after the sample was cut, were the same as in Example 4. The dimensional change in the thickness direction of the sample when the sample was heated was measured by TMA, and the Z-axis expansion ratio in the thickness direction of the sample in the temperature range of 50-288 ° C is shown in Table 2.
由第2表之比較可知，比較例2中未施加磁場形成之樣品於厚度方向之Z軸膨脹率，比實施例4中施加磁場形成之樣品於厚度方向之Z軸膨脹率大，顯見本申請案之製程有助於形成厚度方向之Z軸膨脹率較小的樣品。 As can be seen from the comparison of the second table, the Z-axis expansion ratio of the sample in which the magnetic field is not formed in the comparative example 2 in the thickness direction is larger than the Z-axis expansion ratio in the thickness direction of the sample formed by the application of the magnetic field in the fourth embodiment. The process of the case helps to form a sample with a small Z-axis expansion ratio in the thickness direction.
與實施例1類似，差別在於使用可光聚合之非棒狀分子。至於比較例3的其他參數如加熱混合物的溫度、磁場方向、施加磁場的時間、紫外線照射、樣品切割後的尺寸均與實施例1相同。取1g之双酚A丙氧雜二丙烯酸甘油醇酯(Bisphenol A glycerolate(1 glycerol/phenol)diacrylate，CAS no.：4687-94-9)作為非棒狀分子，並取1-羥基環己基苯基甲酮(1-Hydroxy-cyclohexyl-phenyl-ketone，CAS no.：947-19-3)作為光起始劑。將固化後之樣品切割成0.7cm*0.7cm(厚度約700μm)，以TMA測量樣品升溫時其厚度方向的尺寸變化，上述樣品於30-110℃溫度區間中，厚度方向之CTE值如第3表所示。 Similar to Example 1, the difference is in the use of photopolymerizable non-rod molecules. The other parameters of Comparative Example 3, such as the temperature of the heating mixture, the direction of the magnetic field, the time of applying the magnetic field, the ultraviolet irradiation, and the size after the sample was cut, were the same as in Example 1. Take 1g of Bisphenol A glycerolate (1 glycerol/phenol) diacrylate, CAS no.: 4687-94-9 as a non-rod molecule, and take 1-hydroxycyclohexylbenzene 1-Hydroxy-cyclohexyl-phenyl-ketone (CAS no.: 947-19-3) is used as a photoinitiator. The cured sample was cut into 0.7 cm*0.7 cm (thickness: about 700 μm), and the dimensional change in the thickness direction of the sample was measured by TMA. The CTE value in the thickness direction of the sample in the temperature range of 30-110 ° C was as the third. The table shows.
由第3表之比較可知，比較例3中使用非棒狀分子形成之樣品於厚度方向之CTE值為正(膨脹)，而實施例1中使用棒狀分子形成之樣品於厚度方向之CTE值為負(收縮)，顯見本申請案之有機棒狀分子在相同強度磁場下有助於形成厚度方向之CTE值為負的樣品。 As is clear from the comparison of the third table, the CTE value in the thickness direction of the sample formed using the non-rod-like molecules in Comparative Example 3 was positive (expansion), and the CTE value in the thickness direction of the sample formed using the rod-shaped molecules in Example 1. Negative (shrinkage), it is apparent that the organic rod-shaped molecules of the present application contribute to the formation of a sample having a negative CTE value in the thickness direction under the same intensity magnetic field.
有機棒狀分子的磁化率可以藉由Gaussian Inc.提供的商用軟體Gaussian進行模擬估算。以實施例1~4所使用的4-(3-丙烯醯氧基丙氧基)苯甲酸-2-甲基-1,4-苯酯進行磁化率計算，可以得到第4表之長軸(Z)方向和垂直長軸(Z)方向磁化率估 算值。 The magnetic susceptibility of the organic rod-shaped molecules can be estimated by the commercial software Gaussian supplied by Gaussian Inc. Using the 4-(3-propenyloxypropoxy)benzoic acid-2-methyl-1,4-phenyl ester used in Examples 1 to 4 to calculate the magnetic susceptibility, the long axis of the fourth table can be obtained ( Z) direction and vertical long axis (Z) direction magnetic susceptibility estimation Calculated value.
由第4表可得知有機棒狀分子之長軸方向磁化率大於其他方向之磁化率，且長軸方向磁化率除以其他方向之磁化率所得的數值大於0.01且小於1。 From the fourth table, it is found that the magnetic susceptibility in the long axis direction of the organic rod-shaped molecules is larger than the magnetic susceptibility in the other direction, and the value obtained by dividing the magnetic susceptibility in the long-axis direction by the magnetic susceptibility in the other direction is larger than 0.01 and smaller than 1.
10‧‧‧膜狀物 10‧‧‧membrane
11‧‧‧輸送帶 11‧‧‧Conveyor belt
13‧‧‧磁場 13‧‧‧ magnetic field
15‧‧‧紫外線燈 15‧‧‧UV light
100‧‧‧預浸片 100‧‧‧Prepreg
Claims (11)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410507448.2A CN104761742B (en) | 2014-01-06 | 2014-09-28 | Prepreg and method for forming the same |
| US14/566,860 US20150191574A1 (en) | 2014-01-06 | 2014-12-11 | Prepreg and method for manufacturing the same |
| JP2014257638A JP5941130B2 (en) | 2014-01-06 | 2014-12-19 | Prepreg and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201461924077P | 2014-01-06 | 2014-01-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201527367A true TW201527367A (en) | 2015-07-16 |
| TWI500671B TWI500671B (en) | 2015-09-21 |
Family
ID=54198094
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW103127030A TWI500671B (en) | 2014-01-06 | 2014-08-07 | Prepreg and method for manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI500671B (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005085334A1 (en) * | 2004-03-09 | 2005-09-15 | Polymatech Co., Ltd. | Polymer composite formed article, printed wiring board using the formed article and method for producing them |
-
2014
- 2014-08-07 TW TW103127030A patent/TWI500671B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| TWI500671B (en) | 2015-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW432442B (en) | Method for precise molding and alignment of structures on a substrate using a stretchable mold | |
| JP3834594B2 (en) | Stabilized curable adhesive | |
| KR101824709B1 (en) | Process for producing laminate of light-transmitting rigid plates and device for laminating light-transmitting rigid plates | |
| US9808993B2 (en) | Method for solid freeform fabrication | |
| TWI395787B (en) | Resin composition and laminated resin film using the same | |
| JP2016520417A (en) | Method for curing thermoplastics with microwave energy | |
| TW200946633A (en) | Conductive adhesive precursor, method of using the same, and article | |
| JP2010001419A (en) | Uv nanoimprint molding and its manufacturing method | |
| CN103881594A (en) | Method and apparatus for bonding workpieces | |
| TWI500671B (en) | Prepreg and method for manufacturing the same | |
| US20140322499A1 (en) | Optical element and method for making same | |
| JP2019183118A (en) | Molded body, laminate, powder dispersion, and manufacturing method of powder dispersion | |
| CA2925392C (en) | Varnishes and prepregs and laminates made therefrom | |
| CN104761742B (en) | Prepreg and method for forming the same | |
| TW201945478A (en) | Method for forming a solder mask layer on a circuit board using double liquid type solder mask ink | |
| CN108724570A (en) | The method for making flexible board using solwution method | |
| JP6282239B2 (en) | Laminate showing reduced curl | |
| CN106170178B (en) | Method for peeling heat-resistant organic polymer layer and method for manufacturing flexible wiring board | |
| JP2019001859A (en) | Modification method of polymer film surface | |
| JPS63149116A (en) | Manufacture of cast-molded product | |
| JP2003246970A (en) | Apparatus and method for producing structure adhered by photoreactive adhesive | |
| KR101801044B1 (en) | Photosensitive resin composition | |
| WO2007111172A1 (en) | Continuous process for producing resin substrate and resin substrate | |
| JP3396974B2 (en) | Heat resistant composite film | |
| KR20190140502A (en) | Multilayer build sheet for 3D printers |