TWI423741B - An epoxy resin composition and a film and a substrate made of the epoxy resin composition - Google Patents
An epoxy resin composition and a film and a substrate made of the epoxy resin composition Download PDFInfo
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- TWI423741B TWI423741B TW98104661A TW98104661A TWI423741B TW I423741 B TWI423741 B TW I423741B TW 98104661 A TW98104661 A TW 98104661A TW 98104661 A TW98104661 A TW 98104661A TW I423741 B TWI423741 B TW I423741B
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- epoxy resin
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- resin composition
- hardener
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- 239000003822 epoxy resin Substances 0.000 title claims description 87
- 229920000647 polyepoxide Polymers 0.000 title claims description 87
- 239000000203 mixture Substances 0.000 title claims description 55
- 239000000758 substrate Substances 0.000 title claims description 28
- 239000004848 polyfunctional curative Substances 0.000 claims description 76
- 229920005989 resin Polymers 0.000 claims description 33
- 239000011347 resin Substances 0.000 claims description 33
- 239000002131 composite material Substances 0.000 claims description 28
- 239000005011 phenolic resin Substances 0.000 claims description 28
- -1 poly(phenylmethyl phosphate) Polymers 0.000 claims description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 12
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical group C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 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 4
- 238000007598 dipping method Methods 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 24
- 238000010521 absorption reaction Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000009477 glass transition Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 150000005130 benzoxazines Chemical class 0.000 description 8
- 239000003292 glue Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VWFSMVKYHSOBOL-UHFFFAOYSA-N benzyl methyl hydrogen phosphate Chemical compound COP(O)(=O)OCC1=CC=CC=C1 VWFSMVKYHSOBOL-UHFFFAOYSA-N 0.000 description 1
- YTFJQDNGSQJFNA-UHFFFAOYSA-L benzyl phosphate Chemical compound [O-]P([O-])(=O)OCC1=CC=CC=C1 YTFJQDNGSQJFNA-UHFFFAOYSA-L 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本發明係有關於一種環氧樹脂組合物，尤指一種具有複合型環氧樹脂硬化劑之無鹵素的環氧樹脂組合物。The present invention relates to an epoxy resin composition, and more particularly to a halogen-free epoxy resin composition having a composite epoxy resin hardener.
目前印刷電路板所應用的範圍及領域相當廣泛，一般電子產品內的電子元件都插設在印刷電路板上，而現今的印刷電路板為了符合高功率及高熱量之元件的應用範圍，故在印刷電路板的散熱功效上進行開發及研究，以提高電路板的散熱效率及高功率。At present, the range and field of application of printed circuit boards are quite extensive. Electronic components in general electronic products are inserted on printed circuit boards, and today's printed circuit boards are designed to meet the application range of high-power and high-heat components. Development and research on the heat dissipation performance of printed circuit boards to improve the heat dissipation efficiency and high power of the circuit board.
而印刷電路板係由含浸膠片(PP)，或含銅箔膠片(Copper clad laminate，CCL)或銅箔等複數膠片利用熱壓合程序充份壓合；而該含浸膠片係將玻璃纖維布浸漬於一環氧樹脂膠液中，並進行乾燥等後續製程所形成一種薄型膠片。The printed circuit board is fully pressed by a film of impregnated film (PP) or copper clad laminate (CCL) or copper foil by a thermal compression process; and the impregnated film is impregnated with a glass fiber cloth. A thin film formed by a subsequent process such as drying in an epoxy resin glue.
但由於近年來環保意識的抬頭，許多消費性電子品已逐漸不使用含有鹵素的銅箔基板，而改用無鹵素銅箔基板。無鹵素銅箔基板多添加有含磷成分以補償阻燃的效果，傳統上，含磷材料的添加可以應用主樹脂或硬化劑樹脂成分結構上含磷的材料，或是以額外添加含磷化合物於樹脂配方內的方式，以增益阻燃的效果。However, due to the rise of environmental awareness in recent years, many consumer electronic products have gradually used halogen-free copper foil substrates instead of halogen-free copper foil substrates. The halogen-free copper foil substrate is additionally added with a phosphorus-containing component to compensate for the flame retardant effect. Traditionally, the phosphorus-containing material may be added with a material containing a main resin or a hardener resin component, or an additional phosphorus-containing compound. The way in the resin formulation is to gain a flame retardant effect.
習知用以製作無鹵素環氧樹脂基板之樹脂組成的基礎配方可以應用酚醛環氧樹脂為主成分，搭配苯酚環樹脂硬化劑，再添加含磷化合物，藉以達成所製成之樹脂膠片具備耐燃性，如中華民國第293831號及第583258號專利，利用具有苯并噁嗪環(Benzoxazine，BZ)之苯酚樹脂硬化劑調和其他酚醛樹脂硬化劑，以製作無鹵樹脂基板。然而其中的BZ酚醛樹脂硬化劑雖可降低吸水性且具有低的介電特性，但其所製成之基板具有韌性不佳，更有添加過量會導致耐熱性不足之問題。此外，對於業界採用之FR4基板的壓合製程亦有反應性過慢的問題，將導致該酚醛環氧樹脂所製基板的玻璃轉換溫度(Tg)僅能到達160度。The basic formulation of the resin composition for producing a halogen-free epoxy resin substrate can be applied with a phenolic epoxy resin as a main component, a phenol ring resin hardener, and a phosphorus-containing compound, thereby achieving a flame resistant resin film. For example, in the Republic of China No. 293831 and No. 583258, a phenol resin hardener having a benzoxazine (BZ) is used to blend other phenolic resin hardeners to produce a halogen-free resin substrate. However, the BZ phenolic resin hardener has a low water absorption property and a low dielectric property, but the substrate produced by the BZ phenolic resin hardener has poor toughness, and the excessive addition causes a problem of insufficient heat resistance. In addition, the FR4 substrate used in the industry is also too reactive, which causes the glass transition temperature (Tg) of the substrate made of the phenolic epoxy resin to reach only 160 degrees.
緣是，本發明人有感上述缺失之可改善，提出一種設計合理且有效改善上述缺失之本發明。The reason is that the inventors have felt that the above-mentioned deficiency can be improved, and proposes a present invention which is rational in design and effective in improving the above-mentioned deficiency.
本發明之主要目的，在於提供一種環氧樹脂組合物，利用聚伸苯甲基磷酸酯混摻苯酚樹脂硬化劑，以調製作為一種新型的環氧樹脂之硬化劑，以提升酚醛環氧樹脂的反應性，並提高所製成之基板的玻璃轉換溫度(Tg)，且不致影響基板之耐熱性及吸水性，而該基板亦具備有阻燃之特性。The main object of the present invention is to provide an epoxy resin composition by using a polyphenylene phosphate mixed with a phenol resin hardener to prepare a new type of epoxy resin hardener to enhance the novolac epoxy resin. The glass transition temperature (Tg) of the substrate to be formed is improved, and the heat resistance and water absorption of the substrate are not affected, and the substrate is also provided with a flame retardant property.
本發明提供一種環氧樹脂組合物，係包括：組份(A)：環氧樹脂；以及組份(B)：複合型環氧樹脂硬化劑，其中該複合型環氧樹脂硬化劑係由聚伸苯甲基磷酸脂樹脂硬化劑及苯酚樹脂硬化劑以一預定比例混合而成。The present invention provides an epoxy resin composition comprising: component (A): epoxy resin; and component (B): a composite epoxy resin hardener, wherein the composite epoxy resin hardener is polymerized The benzyl methyl phosphate resin hardener and the phenol resin hardener are mixed at a predetermined ratio.
本發明亦提供一種將該玻璃纖維布浸漬於上述的環氧樹脂組合物中，並經固化、乾燥等步驟後，而形成的膠片。The present invention also provides a film formed by immersing the glass fiber cloth in the above epoxy resin composition, curing, drying, and the like.
本發明更提供一種利用上述膠片經由壓合製程所製成之印刷電路板的基板。The present invention further provides a substrate for a printed circuit board produced by the above-described film via a press-bonding process.
本發明具有以下有益的效果：本發明係利用兩種硬化劑搭配組成一複合型環氧樹脂硬化劑，而使用該複合型環氧樹脂硬化劑於一主樹脂中以形成無鹵素環氧樹脂組合物之膠液，因此，當玻璃纖維布浸漬於該膠液，以提升硬化的反應速率，改善傳統醛類樹脂硬化劑所製作之基板的壓合溫度過高及時間過長之問題。The present invention has the following beneficial effects: the present invention utilizes two hardeners to form a composite epoxy resin hardener, and the composite epoxy resin hardener is used in a main resin to form a halogen-free epoxy resin combination. The glue of the object, therefore, when the glass fiber cloth is immersed in the glue to increase the reaction rate of hardening, the problem that the pressing temperature of the substrate made by the conventional aldehyde resin hardener is too high and the time is too long is improved.
為使能更進一步瞭解本發明之特徵及技術內容，請參閱以下有關本發明之詳細說明與附圖，然而所附圖式僅提供參考與說明用，並非用來對本發明加以限制者。For a better understanding of the features and technical aspects of the present invention, reference should be made to the accompanying drawings.
本發明係提供一種複合型環氧樹脂硬化劑，將該複合型環氧樹脂硬化劑添加於環氧樹脂中，使玻璃纖維布在經過含浸(dipping)步驟後得以增加硬化的反應速率，進而提升酚醛環氧樹脂的樹脂配方之反應性，並提高所製之基板的玻璃轉換溫度(Tg)，且不致影響基板之耐熱、吸水性、並具備阻燃之特性。此外，本發明更進一步改善醛類樹脂硬化劑製作基板壓合溫度過高及時間過長的問題；再者，本發明更添加適當比例的填充料，以製作出具有較佳耐燃及耐熱特性的膠片。The present invention provides a composite epoxy resin hardener, which is added to an epoxy resin to increase the reaction rate of the glass fiber cloth after the dipping step, thereby improving The reactivity of the resin formulation of the phenolic epoxy resin improves the glass transition temperature (Tg) of the substrate to be produced, and does not affect the heat resistance, water absorption, and flame retardancy of the substrate. In addition, the present invention further improves the problem that the substrate pressing temperature of the aldehyde resin hardener is too high and the time is too long; further, the present invention further adds a proper proportion of the filler to produce a flameproof and heat resistant property. film.
該複合型環氧樹脂硬化劑係主要由聚伸苯甲基磷酸脂樹脂硬化劑及苯酚樹脂硬化劑以一預定比例混合而成。其中，該聚伸苯甲基磷酸脂樹脂硬化劑係利用聚伸苯甲基磷酸酯(polyphenylene methylphosphonate)作為環氧樹脂之硬化劑應用，聚伸苯甲基磷酸酯可由化學式I所表示：The composite epoxy resin hardener is mainly composed of a poly(phenylene phosphate) resin hardener and a phenol resin hardener mixed in a predetermined ratio. Wherein, the poly(phenylene phosphate) resin hardener is applied by using polyphenylene methylphosphonate as a hardener for epoxy resin, and the polyphenylene phosphate can be represented by the chemical formula I:
而聚伸苯甲基磷酸脂樹脂可以提供較佳的阻燃及加速反應的特性，利用該聚伸苯甲基磷酸脂樹脂與苯酚樹脂硬化劑混摻調製作為一種應用於環氧樹脂的硬化劑，以提升環氧樹脂組成物之反應性，並提高所製成之基板的玻璃轉換溫度(Tg)，再者，所製成之基板的耐熱性、吸水性、以及阻燃特性均相當優良。The poly(phenylmethylphosphoric acid) resin can provide better flame retardant and accelerated reaction characteristics, and the polyphenylene phosphate resin and the phenol resin hardener are mixed and prepared as a hardener for epoxy resin. In order to improve the reactivity of the epoxy resin composition and increase the glass transition temperature (Tg) of the substrate to be produced, the substrate prepared is excellent in heat resistance, water absorption, and flame retardancy.
以下將針對上述之複合型環氧樹脂硬化劑進行多組實施例的搭配，以說明藉由複合型環氧樹脂硬化劑之組成比例調配而達成最佳的膠片特性。本發明主要提供一種環氧樹脂組合物，係包括：組份(A)：環氧樹脂；以及組份(B)：複合型環氧樹脂硬化劑，其中該複合型環氧樹脂硬化劑係由聚伸苯甲基磷酸脂樹脂硬化劑及苯酚樹脂硬化劑以一預定比例混合而成，請參考表1。In the following, a combination of a plurality of sets of examples will be described for the above-mentioned composite epoxy resin hardener to explain the optimum film characteristics by the composition ratio formulation of the composite epoxy resin hardener. The present invention mainly provides an epoxy resin composition comprising: component (A): epoxy resin; and component (B): a composite epoxy resin hardener, wherein the composite epoxy resin hardener is The polyphenylene phosphate resin hardener and the phenol resin hardener are mixed at a predetermined ratio. Please refer to Table 1.
表1顯示多種不同成分組成之環氧樹脂組合物，其中主樹脂(即組份(A)之環氧樹脂)係為100量份，且該環氧樹脂係為酚醛樹脂，例如：鄰甲酚-酚醛環氧樹脂、酚-酚醛環氧樹脂、雙酚A-酚醛環氧樹脂、或上述兩種或兩種以上之混和樹脂，但不以上述為限，該組份A之環氧樹脂更可以為非酚醛環氧樹脂；而表1之實施例1至實施例3主要係改變組份B之複合型環氧樹脂硬化劑中的聚伸苯甲基磷酸脂樹脂硬化劑及苯酚樹脂硬化劑的組成，並針對不同組成之環氧樹脂組合物膠液所製成的膠片進行各種特性分析。Table 1 shows an epoxy resin composition of a plurality of different compositions, wherein the main resin (i.e., the epoxy resin of the component (A)) is 100 parts by weight, and the epoxy resin is a phenol resin, for example, o-cresol - phenolic epoxy resin, phenol-phenolic epoxy resin, bisphenol A-phenolic epoxy resin, or a mixture of two or more of the above, but not limited to the above, the epoxy resin of the component A is more It may be a non-phenolic epoxy resin; and the first embodiment to the third embodiment of Table 1 mainly change the polyphenylene phosphate resin hardener and the phenol resin hardener in the composite epoxy resin hardener of the component B. The composition and analysis of various characteristics of the film made of epoxy resin composition of different compositions.
其中，吸水性又可稱做吸濕性，其主要在於判定該膠片的吸水特性，由於膠片會受環境之溫度及濕度影響而膨脹變形或吸附水氣。而在該等膠片含水量、含濕度過高的情況下，易使所壓製之印刷電路板產生爆板的問題或其他電路板的缺陷等等，故吸水性的特性是膠片的重要特點之一。傳統上，可針對該材料進行IR光譜分析或熱重量損失法分析，以確認該膠片的吸水性。Among them, water absorption can also be called hygroscopicity, which is mainly to determine the water absorption characteristics of the film, because the film will be affected by the temperature and humidity of the environment to expand and deform or adsorb moisture. In the case where the moisture content and humidity of the film are too high, the printed circuit board to be pressed may cause a problem of bursting or other circuit board defects, etc., so the water absorption property is one of the important characteristics of the film. . Traditionally, IR spectroscopy or thermogravimetric analysis can be performed on this material to confirm the water absorption of the film.
耐熱性：即漂錫結果，耐熱實驗係依據產業標準IPC-TM-650 Method 2.4.13.1，將散熱膠片浸泡於288℃錫爐至爆板所需時間(分)，其中可得知藉由本發明所提出的環氧樹脂組合物膠液進行玻璃纖維布浸漬作業之後製造的膠片具有較高的耐熱性，故爆板所需的時間較長且符合測試規範。Heat resistance: the result of floating tin, the heat resistance test is based on the industry standard IPC-TM-650 Method 2.4.13.1, the time required to soak the heat-dissipating film in the 288 ° C tin furnace to the blasting plate, which can be known by the present invention The film produced by the proposed epoxy resin composition glue after the glass fiber cloth impregnation operation has high heat resistance, so the time required for the explosion of the plate is long and conforms to the test specification.
耐燃性：即難燃性，依據UL 94法測定，係指塑膠材料耐燃性測試，其以塑膠材料標準試片經火焰燃燒後之自燃時間、自燃速度、掉落之顆粒狀態來訂定塑膠材料之耐燃等級。而依耐燃等級優劣，依次是HB、V-2、V-1、V-0、最高為5V等級。而UL 94測試方法係指塑膠材料以垂直方式在火燄上燃燒。以每十秒為一測試週期，其步驟如下：步驟一：將試片放進火焰中十秒再移開，測定移開之後該試片繼續燃燒時間(T1)；步驟二：俟試片火焰熄滅後，再放進火焰中十秒再移開，再測定移開之後該試片繼續燃燒時間(T2)；步驟三：重複數次實驗並取其平均值；步驟四：計算T1+T2之總合。而UL 94 V-0等級的要求係為在試片單一燃燒時間T1之平均及T2之平均皆不得超過10秒，且其T1與T2的總合不得超過50秒方符合UL 94 V-0要求。Flame resistance: that is, flame retardant, measured according to UL 94 method, refers to the flame resistance test of plastic materials. It is based on the self-ignition time, spontaneous combustion speed and falling particle state of the plastic material standard test piece after flame burning. The flame resistance rating. According to the quality of the fire resistance, the order is HB, V-2, V-1, V-0, and the highest is 5V. The UL 94 test method refers to the fact that the plastic material burns on the flame in a vertical manner. The test cycle is performed every ten seconds. The steps are as follows: Step 1: Put the test piece into the flame for ten seconds and then remove it, and measure the test piece to continue burning time (T1) after the removal; Step 2: Test piece flame After extinction, put it into the flame for ten seconds and then remove it, then measure the sample to continue burning time (T2) after removal; Step 3: Repeat several experiments and take the average value; Step 4: Calculate T1+T2 total. The requirement of UL 94 V-0 is that the average of the single burning time T1 and the average T2 of the test piece shall not exceed 10 seconds, and the total of T1 and T2 shall not exceed 50 seconds to meet the requirements of UL 94 V-0. .
在實施例1至實施例3的組成中，該複合型環氧樹脂硬化劑中之苯酚樹脂硬化劑係使用Benzoxazine(BZ)樹脂，其具有苯并噁嗪環之苯酚樹脂硬化劑，Benzoxazine(BZ)樹脂之特性係具有低介電損耗因數、高彈性率、高耐熱性、低吸水性、高玻璃化溫度、高難燃性等特性和沖孔加工性等，而可適當的控制該BZ樹脂的軟化點，以降低其主架構僵直而缺乏韌性之缺點；同時減少外形沖孔時之層間剝離，及提高與多層配線板內層電路接觸之樹脂層之黏接力，以改善內層脫落強度之效果。In the compositions of Examples 1 to 3, the phenol resin hardener in the composite epoxy resin hardener is a Benzoxazine (BZ) resin having a benzoxazine ring phenol resin hardener, Benzoxazine (BZ) The properties of the resin are low dielectric loss factor, high modulus of elasticity, high heat resistance, low water absorption, high glass transition temperature, high flame retardancy, and punching processability, etc., and the BZ resin can be appropriately controlled. Softening point, in order to reduce the rigidity of the main structure and lack of toughness; at the same time, reduce the peeling of the layer during punching, and improve the adhesion of the resin layer in contact with the inner layer circuit of the multilayer wiring board to improve the strength of the inner layer. effect.
因此，依表1所示之實驗結果顯示，實施例1、2、3之環氧樹脂組合物的硬化劑中增加有聚伸苯甲基磷酸脂樹脂硬化劑，對於所製成的基板之吸水性及耐熱性影響不大(相較於對照例1、2)，但因應配合一般FR4壓合製程(熱壓料溫195℃以上時間至少30分鐘)，由實施例1、2、3反應出該複合型環氧樹脂硬化劑有加速反應之效果，所製成之基板的玻璃轉換溫度(Tg)明顯由160℃提升至185℃以上，換言之，本發明可改善傳統醛類樹脂硬化劑製作基板壓合溫度過高及時間過長的問題。再一方面，本發明之複合型環氧樹脂硬化劑中之聚伸苯甲基磷酸脂樹脂與BZ樹脂之配比以1:10(如實施例1之比例)至3:10(如實施例3之比例)為佳，而藉由上述的混合組成，所製成之基板的玻璃轉換溫度(Tg)可提升至185℃以上，甚至大於200℃。Therefore, according to the experimental results shown in Table 1, the hardeners of the epoxy resin compositions of Examples 1, 2, and 3 are added with a poly(phenylmethyl phosphate) resin hardener, and the water absorption of the prepared substrate is increased. The properties and heat resistance have little effect (compared to the comparative examples 1 and 2), but they are reacted by the general FR4 pressure bonding process (the hot pressing temperature is 195 ° C or more for at least 30 minutes), and are reacted by the examples 1, 2, and 3 The composite epoxy resin hardener has the effect of accelerating the reaction, and the glass transition temperature (Tg) of the prepared substrate is obviously raised from 160 ° C to 185 ° C or higher. In other words, the invention can improve the substrate of the conventional aldehyde resin hardener. The problem of too high a press temperature and a long time. In another aspect, the ratio of the poly(phenylmethyl phosphate) resin to the BZ resin in the composite epoxy resin hardener of the present invention is 1:10 (as in the ratio of Example 1) to 3:10 (as in the embodiment). The ratio of 3 is preferable, and by the above-mentioned mixed composition, the glass transition temperature (Tg) of the resulting substrate can be raised to 185 ° C or more, or even more than 200 ° C.
另外，實施例4進一步說明複合型環氧樹脂硬化劑的變化實施態樣，該複合型環氧樹脂硬化劑中之苯酚樹脂硬化劑更可含酚醛樹脂硬化劑，如實施例4中所添加的雙酚A酚醛樹脂硬化劑，而利用實施例4之環氧樹脂組合物所製成之膠片的玻璃轉換溫度(Tg)亦可達180℃，因此同樣具有加速反應之效果。In addition, in the fourth embodiment, a modified embodiment of the composite epoxy resin hardener is further described. The phenol resin hardener in the composite epoxy resin hardener may further contain a phenolic resin hardener, as added in the embodiment 4. The bisphenol A phenolic resin hardener, and the film produced by using the epoxy resin composition of Example 4 can also have a glass transition temperature (Tg) of 180 ° C, and thus has an effect of accelerating the reaction.
再者，根據實施例1-4的組成及合理的數據分析，該組份(B)：複合型環氧樹脂硬化劑中之聚伸苯甲基磷酸脂樹脂硬化劑的用量係為該組份(A)的2至30份；而該組份(B)：複合型環氧樹脂硬化劑中之該苯酚樹脂硬化劑的用量係為該組份(A)的80至110份。Further, according to the composition of Example 1-4 and reasonable data analysis, the component (B): the amount of the poly(phenylmethyl phosphate) resin hardener in the composite epoxy resin hardener is the component. 2 to 30 parts of (A); and the component (B): the phenol resin hardener in the composite epoxy resin hardener is used in an amount of 80 to 110 parts by weight of the component (A).
該環氧樹脂組合物更包括有組份(C)：填充料，其中該填充料係包括氫氧化鋁或二氧化矽，且該組份(C)之填充料的用量係為該組份(A)的10至80份，以及組份(D)：溶劑，該組份(D)之溶劑的用量係為該組份(A)的10至30份。本發明之該環氧樹脂組合物更包括有添加物，例如表2中之促進劑，而在本最佳實施例中，該促進劑係為咪唑化合物，其用量係為該組份(A)的0.4至1份，例如2-甲基咪唑，其功用在於加速控制膠液的硬化時間；而組份(D)之溶劑則為10-30份之MEK、PM、環己酮等。表2則顯示該環氧樹脂組合物的最佳組成比例，其中，該組份(B)：複合型環氧樹脂硬化劑中之聚伸苯甲基磷酸酯樹脂的用量係為該組份(A)的18份；該組份(B)：複合型環氧樹脂硬化劑中之苯酚樹脂硬化劑的用量係為該組份(A)的98份，且該苯酚樹脂硬化劑係可為Bz樹脂硬化劑、酚醛樹脂硬化劑、或兩者之混合；該組份(C)之填充料的用量係為該組份(A)的30份，且該填充料係包括氫氧化鋁、二氧化矽、或兩者之混合；該組份(D)之溶劑的用量係為該組份(A)的20份，且該溶劑則包括甲基乙基酮(又稱丁酮；MEK)、丙二醇甲醚(PM)、環己酮、或任兩種或兩種以上之混合。The epoxy resin composition further comprises a component (C): a filler, wherein the filler comprises aluminum hydroxide or cerium oxide, and the filler of the component (C) is used in the component ( 10 to 80 parts of A), and component (D): solvent, the solvent of the component (D) is used in an amount of 10 to 30 parts of the component (A). The epoxy resin composition of the present invention further comprises an additive such as the accelerator in Table 2, and in the preferred embodiment, the accelerator is an imidazole compound in an amount of the component (A). 0.4 to 1 part, such as 2-methylimidazole, is used to accelerate the control of the hardening time of the glue; and the solvent of the component (D) is 10-30 parts of MEK, PM, cyclohexanone and the like. Table 2 shows the optimum composition ratio of the epoxy resin composition, wherein the component (B): the amount of the poly(phenylmethyl phosphate) resin in the composite epoxy resin hardener is the component ( 18 parts of A); the component (B): the phenol resin hardener in the composite epoxy resin hardener is used in an amount of 98 parts of the component (A), and the phenol resin hardener may be Bz a resin hardener, a phenolic resin hardener, or a mixture of the two; the filler of the component (C) is used in an amount of 30 parts of the component (A), and the filler comprises aluminum hydroxide, dioxide矽, or a mixture of the two; the solvent of the component (D) is used in an amount of 20 parts of the component (A), and the solvent includes methyl ethyl ketone (also known as methyl ethyl ketone; MEK), propylene glycol Methyl ether (PM), cyclohexanone, or a mixture of two or more of them.
本發明更進一步提出一種使用上述環氧樹脂組合物製造膠片的方法以及所製作成型之膠片。該方法係應用上述環氧樹脂組合物，其包括組份(A)：環氧樹脂；組份(B)：複合型環氧樹脂硬化劑，其中該複合型環氧樹脂硬化劑係由聚伸苯甲基磷酸脂樹脂硬化劑及苯酚樹脂硬化劑以一預定比例混合而成；該環氧樹脂組合物更進一步組份(C)：填充料，其中該填充料係包括氫氧化鋁、二氧化矽或兩者之混合；以及組份(D)：溶劑。將一玻璃纖維布浸漬(dipping)於該環氧樹脂組合物之膠液中，以製成較佳耐燃及耐熱特性的含浸膠片(PP)、或含銅箔膠片(Copper clad laminate，CCL)、或其他膠片，且上述膠片可應用製成印刷電路板用之基板，而該基板在通過壓合製程時可具有相當良好的反應性。The present invention further provides a method of producing a film using the above epoxy resin composition and a formed film. The method uses the above epoxy resin composition, which comprises component (A): epoxy resin; component (B): composite epoxy resin hardener, wherein the composite epoxy resin hardener is composed of polycondensation The benzyl phosphate resin hardener and the phenol resin hardener are mixed at a predetermined ratio; the epoxy resin composition is further component (C): a filler, wherein the filler comprises aluminum hydroxide, dioxide矽 or a mixture of the two; and component (D): solvent. Dipping a glass fiber cloth into the glue of the epoxy resin composition to form an impregnated film (PP) or a copper clad laminate (CCL) having better flame resistance and heat resistance. Or other film, and the above film can be applied to a substrate for a printed circuit board, and the substrate can have relatively good reactivity when passing through a press-bonding process.
綜上所述，本發明具有下列諸項優點：In summary, the present invention has the following advantages:
1、本發明主要係利用兩種硬化劑搭配組成一複合型的硬化劑，而使用該複合型環氧樹脂硬化劑於一主樹脂中以形成無鹵素的環氧樹脂組合物膠液，以提升使用該膠液所製成之膠片的耐燃性，也可以兼顧膠片的低吸水性及耐熱性；同時使用該複合型環氧樹脂硬化劑，可以增加所製成之基板的玻璃轉換溫度。1. The present invention mainly utilizes two kinds of hardeners to form a composite type hardener, and uses the composite epoxy resin hardener in a main resin to form a halogen-free epoxy resin composition glue to enhance The flame resistance of the film produced by using the glue can also achieve both low water absorption and heat resistance of the film, and the use of the composite epoxy resin hardener can increase the glass transition temperature of the substrate to be formed.
2、另一方面，本發明之環氧樹脂組合物中採用一種含磷成分之複合型環氧樹脂硬化劑，可以增加基板阻燃效果；且可進一步提高樹脂硬化的反應速率。2. On the other hand, in the epoxy resin composition of the present invention, a composite epoxy resin hardener containing a phosphorus component can be used to increase the flame retarding effect of the substrate; and the reaction rate of hardening of the resin can be further improved.
惟以上所述僅為本發明之較佳實施例，非意欲侷限本發明之專利保護範圍，故舉凡運用本發明說明書及圖式內容所為之等效變化，均同理皆包含於本發明之權利保護範圍內，合予陳明。The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Therefore, the equivalents of the present invention and the equivalents of the drawings are all included in the present invention. Within the scope of protection, it is given to Chen Ming.
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