TWI432509B - 無鹵黏合膠片及其所用之樹脂 - Google Patents
無鹵黏合膠片及其所用之樹脂 Download PDFInfo
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- TWI432509B TWI432509B TW97150100A TW97150100A TWI432509B TW I432509 B TWI432509 B TW I432509B TW 97150100 A TW97150100 A TW 97150100A TW 97150100 A TW97150100 A TW 97150100A TW I432509 B TWI432509 B TW I432509B
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- halogen
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- 239000011342 resin composition Substances 0.000 title claims description 47
- 239000003822 epoxy resin Substances 0.000 claims description 62
- 229920000647 polyepoxide Polymers 0.000 claims description 62
- 229920005989 resin Polymers 0.000 claims description 51
- 239000011347 resin Substances 0.000 claims description 51
- 239000000758 substrate Substances 0.000 claims description 37
- 239000002313 adhesive film Substances 0.000 claims description 36
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims description 31
- 239000011574 phosphorus Substances 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 22
- 229920001634 Copolyester Polymers 0.000 claims description 18
- 239000000945 filler Substances 0.000 claims description 17
- 239000004848 polyfunctional curative Substances 0.000 claims description 17
- 239000004094 surface-active agent Substances 0.000 claims description 13
- 239000004744 fabric Substances 0.000 claims description 12
- 239000003365 glass fiber Substances 0.000 claims description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical group CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 claims 2
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical group CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 14
- 230000008569 process Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 229920001971 elastomer Polymers 0.000 description 8
- 238000005470 impregnation Methods 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 125000002243 cyclohexanonyl group Chemical group *C1(*)C(=O)C(*)(*)C(*)(*)C(*)(*)C1(*)* 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
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Description
本發明是有關於一種黏合膠片及其所用之樹脂，且特別是有關於一種無鹵黏合膠片及其所用之樹脂。
隨著科技的進步，並因應各式電子產品的設計、發展與應用，所需的電路板結構越趨複雜，因此常有多層電路板疊合之設計，如印表機列印頭、摺疊手機、手提電腦等。多層電路板常由不同特性的電路板疊合而成。
一般而言，電路板所使用的基板可區分為軟性基板(簡稱軟板)與硬性基板(簡稱硬板)。軟板多以聚亞醯胺(polyimide,PI)、聚對苯二甲酸乙二酯(Poly(ethylene Terephthalate),PET)、聚萘二甲酸乙二醇酯(poly(ethylene 2,6－naphthalate),PEN)或含摻橡膠樹脂等材料所製成，而硬板則多以環氧樹脂所製作而成。
由於各種軟硬板在材質上的差異，為使兩種不同特性的軟硬板有良好的接合效果，目前多為以黏合膠片作為界面，再進一步利用熱壓合方式使軟硬板相互貼合。然而，在熱壓合過程中，黏合膠片常會有溢膠現象，且隨著電子產品的尺寸越來越小，溢膠現象往往使得高密度之電路板的可靠性受到影響。根據電子電路互聯與封裝協會(The Institute for Interconnecting and Packing Electronic Circuits,IPC)之IPC－6013 3.3.1.3規範，軟硬板過度區之溢膠限制
需小於1.5公釐(millimeter,mm)，才能滿足加工及可靠性要求。
此外，由於環保意識的提昇與要求，以無鹵素的黏合膠片作為電路板間的接合界面，已漸漸成為世界各國環保規範之要求。
因此本發明之一態樣就是在提供一種不含鹵素之樹脂組成物，用於含浸製程中以製造無鹵黏合膠片，且此樹脂組成物於基板接合之熱壓合製程中，溢膠範圍小於1.5 mm。
根據本發明之上述態樣，提出一種無鹵樹脂組成物包含含磷無鹵環氧樹脂、經胺基甲酸脂改質之共聚酯、硬化劑、填充劑、界面活性劑與溶劑。其中含磷無鹵環氧樹脂為100重量份，共聚酯為5~15重量份，硬化劑為2.5~45重量份，填充劑為10~40重量份，界面活性劑為0.1~0.2重量份，而溶劑為30~60重量份。
本發明的另一態樣是在提供一種不含鹵素之黏合膠片，且此黏合膠片於基板接合之熱壓合製程中，溢膠範圍小於1.5 mm。
根據本發明之上述態樣，提出一種無鹵黏合膠片，包含玻璃纖維布，其上分佈有無鹵樹脂層。其中無鹵樹脂層包含無鹵樹脂組成物，而無鹵樹脂組成物包含含磷無鹵環氧樹脂、經胺基甲酸脂改質之共聚酯、硬化劑、填充劑、
界面活性劑與溶劑。其中含磷無鹵環氧樹脂為100重量份，共聚酯為5~15重量份，硬化劑為2.5~45重量份，填充劑為10~40重量份，界面活性劑為0.1~0.2重量份，而溶劑為30~60重量份。
本發明的又一態樣是在提供一種以無鹵黏合膠片接合多層基板之印刷電路板結構，且於基板接合之熱壓合製程中，無鹵黏合膠片之溢膠範圍小於1.5 mm。
根據本發明之上述態樣，提出一種印刷電路板，包含第一基板、第二基板與無鹵黏合膠片。其中無鹵黏合膠片位於第一基板與第二基板間，以接合第一基板與第二基板。無鹵黏合膠片包含玻璃纖維布，其上分佈有無鹵樹脂層。其中無鹵樹脂層包含無鹵樹脂組成物，而無鹵樹脂組成物包含含磷無鹵環氧樹脂、經胺基甲酸脂改質之共聚酯、硬化劑、填充劑、界面活性劑與溶劑。其中含磷無鹵環氧樹脂為100重量份，共聚酯為5~15重量份，硬化劑為2.5~45重量份，填充劑為10~40重量份，界面活性劑為0.1~0.2重量份，而溶劑為30~60重量份。
目前多以環氧樹脂為主材料之含浸樹脂製作黏合膠片，並以此黏合膠片作為軟硬板之接合界面。而為了減少溢膠現象，會於含浸樹脂中添加具橡膠成分或經橡膠改質之環氧樹脂。其中，具橡膠成分或經橡膠改質之環氧樹脂與未改質之主環氧樹脂的重量比值需大於0.3，才能夠改
變未經改質之主環氧樹脂的流動性而減少溢膠現象，但也因此造成以此含浸樹脂含浸製作出之黏合膠片的熱安定性變差且膨脹特性改變，造成軟硬板黏合之熱壓合過程容易產生軟硬板之變形。
此外，具橡膠成分或經橡膠改質之環氧樹脂與主環氧樹脂所用之溶劑特性間往往具有明顯的極性差異，因此調和不易。若只使用環氧樹脂所用之溶劑來調和的話，則具橡膠成分或經橡膠改質之環氧樹脂需要以大量溶劑稀釋後，才能與主環氧樹脂進行調和使用。
另外，目前也有以製作軟板的胺基甲酸酯高分子聚合物製作樹脂，所製作之樹脂黏度高可以塗覆於軟板。然而，由於胺基甲酸酯高分子聚合物之特性，無法直接調製為低黏度之樹脂膠液，使其利於以含浸方式製作黏合膠片，須混摻環氧樹脂才可製成含浸樹脂。由於胺基甲酸酯高分子聚合物與環氧樹脂溶劑之間極性的差異，若只使用環氧樹脂所用之溶劑來調和的話，胺基甲酸酯高分子聚合物也需經過大量溶劑稀釋才能與環氧樹脂調和。上述方式不僅製程繁複，成本也高。
有鑑於上述問題，在本發明的實施例中提出一種無鹵樹脂組成物，可使用含浸製程來製作黏合膠片。此無鹵樹脂組成物具有含磷無鹵環氧樹脂、經胺基甲酸脂(urethane)改質之共聚酯(co－polyester)、硬化劑、填充劑、界面活性劑與溶劑。
上述含磷無鹵環氧樹脂為無鹵樹脂組成物中之主要
樹脂成份，作為高分子聚合硬化反應之主要反應物。且由於環氧樹脂中不含鹵素，因此可符合各國目前環保規範之要求。而環氧樹脂中含磷可提高無鹵樹脂組成物之玻璃轉移溫度(glass transition temperature,Tg)與增加耐燃程度。含磷無鹵環氧樹脂例如可為長春公司之BEP 330A70(含磷Cresol Novolac Epoxy)，其樹脂成份重量比例為70%。
以胺基甲酸酯改質之共聚酯作為無鹵樹脂組成物中之流膠控制樹脂，其中被改質之共聚酯極性與環氧樹脂相近。而由於共聚酯之極性與環氧樹脂相近，因此經胺基甲酸酯改質之共聚酯不需經過大量溶劑之稀釋，即可與主成份之環氧樹脂調和。此外，加入胺基甲酸酯改質之共聚酯所製備之無鹵樹脂組成物的膨脹係數與接合之軟硬板之膨脹係數相近，因此以熱壓合處理軟硬板接合時，不會產生軟硬板之變形。在每100重量份之主要樹脂成份添加5~15重量份的胺基甲酸酯改質之共聚酯即可。以胺基甲酸酯改質之共聚酯例如可為東洋紡UR3500，分子量大於10000，而平均分子量為15000，樹脂成份重量比例40%。
與含磷無鹵環氧樹脂進行聚合硬化反應之硬化劑可為酚醛硬化劑、二氰二胺(Dicyandiamide)或兩者之組合物。其中，每100重量份之主要樹脂成份添加25~45重量份之酚醛硬化劑。或者是，每100重量份之主要樹脂成份添加2.5~4.0重量份之二氰二胺。
填充劑可為二氧化矽、氫氧化鋁、滑石粉、雲母或上
述任意組合之組合物。填充劑可降低含浸樹脂之膨脹係數，並增加無鹵樹脂組成物之耐熱與耐燃程度。每100重量份之主要樹脂成份添加10~40重量份之填充劑。
填充劑需搭配界面活性劑使用，於含浸製程時增加填充劑、玻璃纖維布與樹脂間之接合力。界面活性劑可為矽烷耦合劑。每100重量份之主要樹脂成份添加0.1~0.2重量份之填充劑。
上述樹脂組成物之所有成份需要分散於共同溶劑中進行調和。溶劑可為環己酮(Cyclohexanone)、丁酮(Methyl ethyl ketone,MEK)或兩者之組成物。每100重量份之主要樹脂成份需分散於30~60重量份之溶劑中。
上述樹脂組成物除單獨以含磷無鹵環氧樹脂作為主要樹脂成份外，也可包含四官能基環氧樹脂或者雙酚A酚醛環氧樹脂。其中含磷無鹵環氧樹脂混摻四官能基環氧樹脂可提高無鹵樹脂組成物之玻璃轉移溫度，以及使無鹵樹脂組成物具有抗紫外光之特性。每100重量份之含磷無鹵環氧樹脂可混摻5~10重量份之四官能基環氧樹脂。四官能基環氧樹脂例如可為長春公司之TNE 190A70，其樹脂成份重量比例為70%。而含磷無鹵環氧樹脂混掺雙酚A酚醛環氧樹脂也可提高無鹵樹脂組成物之玻璃轉移溫度，以及增加無鹵樹脂組成物之耐熱程度。每100重量份之含磷無鹵環氧樹脂可混掺5~10重量份之雙酚A酚醛環氧樹脂。雙酚A酚醛環氧樹脂例如可為長春公司之BNEA70，其樹脂成份重量比例為70%。
上述樹脂組成物也可含有微量之促進劑，作為聚合硬化反應之觸媒，縮短無鹵樹脂組成物之硬化時間。促進劑可為二－甲基咪唑(2－Methyl－Imidazole)。
根據本發明之一實施例，取100重量份之含磷無鹵環氧樹脂混掺5重量份之四官能基環氧樹脂與6.2重量份之雙酚A酚醛環氧樹脂，成為一主成份樹脂。上述含磷無鹵環氧樹脂為購自長春公司型號為BEP 330A70之樹脂(含磷Cresol Novolac Epoxy)，其樹脂成分重量比例為70%。四官能基環氧樹脂為購自長春公司型號TNE 190A70之樹脂，其樹脂成分重量比例為70%。而雙酚A酚醛環氧樹脂則為購自長春公司型號為BNEA70之樹脂，其樹脂成分重量比例為70%。
接著，取上述主成份樹脂100重量份，添加10重量份之胺基甲酸酯改質之共聚酯(購自東洋紡公司，型號UR3500，分子量大於10000，且平均分子量為15000，樹脂成份重量比例為40%)、38重量份之酚醛硬化劑、0.09重量份之二－甲基咪唑、25重量份之二氧化矽、微量之矽烷偶合劑與43重量份之環己酮，於室溫下使用攪拌器混合180分鐘。即成無鹵樹脂組成物，可用於含浸製程中製造無鹵黏合膠片。
無鹵黏合膠片包含玻璃纖維布，而玻璃纖維布上分佈有無鹵樹脂層，且無鹵樹脂層包含前述無鹵樹脂組成物。無鹵黏合膠片之製造方法為以滾筒含浸機將玻璃纖維布含浸於前述無鹵樹脂組成物中，再經過加熱製程，於溫度
150~200℃間將玻璃纖維布與樹脂乾燥成無鹵黏合膠片成品。其中，玻璃纖維布厚度為0.04~0.06公釐，重量為每平方公尺之玻璃纖維布重46~50公克。
無鹵黏合膠片根據電子電路互聯與封裝協會之IPC－TM－650檢測規範檢測各種特性，如流膠現象、耐熱性與電子絕緣特性。各特性之檢測數值如表一所示。
由表一檢測結果可知，無鹵黏合膠片根據IPC－TM－650 2.3.16.1檢測規範所得樹脂含量為63%。樹脂流膠量與溢膠範圍(Circular Flow)均表示膠片與軟硬板壓合後的流膠現象，值越低表示流膠或溢膠現象越少。根據IPC－TM－650 2.3.17檢測規範所測得之樹脂流膠量小於2%，溢膠範圍小於20密耳(mil，1 mil＝0.0254 mm)。
玻璃轉移溫度、熱裂解溫度、288度耐熱時間與浸錫
耐熱時間之檢測皆為表示無鹵黏合膠片之耐熱性，玻璃轉移溫度與熱裂解溫度越高，288度耐熱時間與浸錫耐熱時間越長代表膠片之耐熱性與耐燃性越好。根據IPC－TM－650 2.4.25C檢測規範以示差熱分析掃描儀(differential scanning calorimetry,DSC)檢測，無鹵黏合膠片之玻璃轉移溫度為155℃。而根據IPC－TM－650 2.4.24.6檢測規範以熱重分析儀(Thermal Gravimetric Analysis,TGA)檢測，無鹵黏合膠片之熱裂解溫度為350℃。又根據IPC－TM－650 2.4.24.1檢測規範以熱機械分析儀(Thermo－Mechanical Analysis,TMA)檢測，無鹵黏合膠片之288度耐熱時間大於60分鐘，同時，根據IPC－TM－650 2.4.13檢測規範測定，無鹵黏合膠片之浸錫耐熱時間大於10分鐘。
介電常數代表所製膠片的電子絕緣特性，數值越低代表電子絕緣特性越好。而介電損失因子則為表示物質在一定温度下吸收某一頻率之微波的能力，通常在通訊產品的規範裡，介電損失因子數值需越低越好。根據IPC－TM－650 2.5.5檢測規範，本發明之無鹵黏合膠片之介電常數為4.2，介電損失因子為0.018。
由上述表一之各檢測結果可知，本發明之無鹵黏合膠片具耐燃性與耐熱性。且在軟硬板間黏合時，溢膠範圍控制在小於20密耳，符合電子電路互聯與封裝協會需小於1.5公釐之規範。
此外，將無鹵黏合膠片與1盎司(oz)銅箔或氧化銅箔進行壓合，再依照IPC－TM－650 2.4.8檢測規範進行黏合
強度測試。無鹵黏合膠片與1盎司銅箔之黏合強度為8.0磅/英吋，而無鹵黏合膠片與1盎司氧化銅箔之黏合強度為3.5磅/英吋。
上述無鹵黏合膠片可用於電路板之軟硬板間的疊合。根據本發明之另一實施例，一種印刷電路板包含第一基板、第二基板與無鹵黏合膠片，其中無鹵黏合膠片位於第一基板與第二基板間，作為第一基板與第二基板接合之界面。
上述第一基板可為硬性基板或軟性基板，而上述第二基板也可為硬性基板或軟性基板。
雖然本發明已以實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
Claims (19)
- 一種無鹵樹脂組成物，至少包含：100重量份之含磷無鹵環氧樹脂；5~15重量份之共聚酯，經胺基甲酸脂改質；2.5~45重量份之硬化劑，用以與該含磷無鹵環氧樹脂進行聚合硬化反應；10~40重量份之填充劑，分散於該無鹵樹脂組成物中；0.1~0.2重量份之界面活性劑；以及30~60重量份之溶劑。
- 如申請專利範圍第1項所述之無鹵樹脂組成物，更包含一四官能基環氧樹脂。
- 如申請專利範圍第2項所述之無鹵樹脂組成物，其中每100重量份之該含磷無鹵環氧樹脂加入5重量份之該四官能基環氧樹脂。
- 如申請專利範圍第1項所述之無鹵樹脂組成物，更包含一雙酚A酚醛環氧樹脂。
- 如申請專利範圍第4項所述之無鹵樹脂組成物，其中每100重量份之該含磷無鹵環氧樹脂加入6.2重量份之該雙酚A酚醛環氧樹脂。
- 如申請專利範圍第1項所述之無鹵樹脂組成物，其中每100重量份之該含磷無鹵環氧樹脂加入10重量份之該共聚酯。
- 如申請專利範圍第1項所述之無鹵樹脂組成物，其中該硬化劑係選自由酚醛硬化劑、二氰二胺與上述任意組合物所組成之群組。
- 如申請專利範圍第7項所述之無鹵樹脂組成物，其中每100重量份之該含磷無鹵環氧樹脂加入38重量份之該酚醛硬化劑。
- 如申請專利範圍第7項所述之無鹵樹脂組成物，其中每100重量份之該含磷無鹵環氧樹脂加入3.5重量份之該二氰二胺。
- 如申請專利範圍第1項所述之無鹵樹脂組成物，其中該填充劑係選自由二氧化矽、氫氧化鋁、滑石粉、雲母與上述任意組合物所組成之群組。
- 如申請專利範圍第1項所述之無鹵樹脂組成物，其中該界面活性劑為矽烷偶合劑。
- 如申請專利範圍第1項所述之無鹵樹脂組成物，其中該溶劑係選自由環己酮、丁酮與上述任意組合物所組成之群組。
- 如申請專利範圍第12項所述之無鹵樹脂組成物，其中每100重量份之該含磷無鹵環氧樹脂加入43重量份之該溶劑。
- 如申請專利範圍第1項所述之無鹵樹脂組成物，更包含一促進劑。
- 如申請專利範圍第14項所述之無鹵樹脂組成物，其中該促進劑為二-甲基咪唑。
- 一種無鹵黏合膠片，至少包含：一玻璃纖維布；以及一無鹵樹脂層，分佈於該玻璃纖維布上，其中該無鹵樹脂層包含一無鹵樹脂組成物，該無鹵樹脂組成物包含：100重量份之含磷無鹵環氧樹脂；5~15重量份之共聚酯，經胺基甲酸脂改質；2.5~45重量份之硬化劑，用以與該含磷無鹵環氧樹脂進行聚合硬化反應；10~40重量份之填充劑，分散於該無鹵樹脂組成物中； 0.1~0.2重量份之界面活性劑；以及30~60重量份之溶劑。
- 一種印刷電路板，至少包含：一第一基板；一第二基板；以及一無鹵黏合膠片，位於該第一基板與該第二基板間，以接合該第一基板與該第二基板，其中該無鹵黏合膠片包含：一玻璃纖維布；以及一無鹵樹脂層，分佈於該玻璃纖維布上，且該無鹵樹脂層包含一無鹵樹脂組成物，該無鹵樹脂組成物包含：100重量份之含磷無鹵環氧樹脂；5~15重量份之共聚酯，經胺基甲酸脂改質；2.5~45重量份之硬化劑，用以與該含磷無鹵環氧樹脂進行聚合硬化反應；10~40重量份之填充劑，分散於該無鹵樹脂組成物中；0.1~0.2重量份之界面活性劑；以及30~60重量份之溶劑。
- 如申請專利範圍第17項所述之印刷電路板，其中該第一基板為一軟性基板或一硬性基板。
- 如申請專利範圍第17項所述之印刷電路板，其中該第二基板為一軟性基板或一硬性基板。
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW97150100A TWI432509B (zh) | 2008-12-22 | 2008-12-22 | 無鹵黏合膠片及其所用之樹脂 |
| US12/482,463 US8153709B2 (en) | 2008-12-22 | 2009-06-11 | Halogen-free prepreg and resin for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW97150100A TWI432509B (zh) | 2008-12-22 | 2008-12-22 | 無鹵黏合膠片及其所用之樹脂 |
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| TW201024368A TW201024368A (en) | 2010-07-01 |
| TWI432509B true TWI432509B (zh) | 2014-04-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| TW97150100A TWI432509B (zh) | 2008-12-22 | 2008-12-22 | 無鹵黏合膠片及其所用之樹脂 |
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| Country | Link |
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| US (1) | US8153709B2 (zh) |
| TW (1) | TWI432509B (zh) |
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| CN103468193B (zh) * | 2013-09-17 | 2016-05-18 | 广州聚合新材料科技股份有限公司 | 低卤低气味的环氧树脂灌封胶及其制备工艺 |
| CN108864924B (zh) * | 2018-07-04 | 2020-10-27 | 湖北恒驰电子科技有限公司 | 一种无卤树脂组合物及用其制备的挠性印制电路板用覆盖膜 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| AT400574B (de) * | 1993-10-21 | 1996-01-25 | Isovolta | Halogenfreie harzmischung, ein diese harzmischung enthaltendes, selbstverlöschendes prepreg sowie dessen verwendung |
| US5955184A (en) * | 1995-09-29 | 1999-09-21 | Toshiba Chemical Corporation | Halogen-free flame-retardant epoxy resin composition as well as prepreg and laminate containing the same |
| JP2001114996A (ja) * | 1999-10-15 | 2001-04-24 | Takeda Chem Ind Ltd | ハロゲンフリー難燃性ポリエステル樹脂組成物 |
| JP4238511B2 (ja) * | 2002-03-19 | 2009-03-18 | 東洋インキ製造株式会社 | 接着剤及びその利用 |
| JP2004107410A (ja) * | 2002-09-17 | 2004-04-08 | Toyo Ink Mfg Co Ltd | 接着剤及びその利用 |
| JP2008517136A (ja) * | 2004-11-26 | 2008-05-22 | エルジー・ケム・リミテッド | 非ハロゲン難燃性エポキシ樹脂組成物、ならびにそれを用いたプレプレッグおよび銅クラッドラミネート |
| JP2007051212A (ja) * | 2005-08-17 | 2007-03-01 | Shin Etsu Chem Co Ltd | 接着剤組成物ならびにそれを用いたカバーレイフィルムおよび接着シート |
| JP2007051211A (ja) | 2005-08-17 | 2007-03-01 | Shin Etsu Chem Co Ltd | 接着剤組成物ならびにそれを用いたカバーレイフィルムおよび接着シート |
| TW200732448A (en) * | 2006-02-23 | 2007-09-01 | Pont Taiwan Ltd Du | Non-halogen adhesive containing polyphosphate compounds |
| TWI324164B (en) * | 2006-06-21 | 2010-05-01 | Chang Chun Plastics Co Ltd | Novel phenolic resin, its preparation and its use |
| JP2008144141A (ja) * | 2006-11-15 | 2008-06-26 | Shin Etsu Chem Co Ltd | 接着シート |
-
2008
- 2008-12-22 TW TW97150100A patent/TWI432509B/zh active
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| Publication number | Publication date |
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| TW201024368A (en) | 2010-07-01 |
| US8153709B2 (en) | 2012-04-10 |
| US20100155123A1 (en) | 2010-06-24 |
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