TWI503351B - Ad type polyimide resin and method - Google Patents
Ad type polyimide resin and method Download PDFInfo
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- TWI503351B TWI503351B TW097101725A TW97101725A TWI503351B TW I503351 B TWI503351 B TW I503351B TW 097101725 A TW097101725 A TW 097101725A TW 97101725 A TW97101725 A TW 97101725A TW I503351 B TWI503351 B TW I503351B
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- Prior art keywords
- polyimine resin
- film
- type
- type polyimine
- resin
- Prior art date
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- 238000000034 method Methods 0.000 title description 8
- 229920001721 polyimide Polymers 0.000 title description 2
- 239000009719 polyimide resin Substances 0.000 title 1
- 229920005989 resin Polymers 0.000 claims description 40
- 239000011347 resin Substances 0.000 claims description 40
- 230000009477 glass transition Effects 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004227 thermal cracking Methods 0.000 claims 2
- 108010022233 Plasminogen Activator Inhibitor 1 Proteins 0.000 description 9
- 102100039418 Plasminogen activator inhibitor 1 Human genes 0.000 description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 8
- 102100024078 Plasma serine protease inhibitor Human genes 0.000 description 7
- 102000004179 Plasminogen Activator Inhibitor 2 Human genes 0.000 description 7
- 108090000614 Plasminogen Activator Inhibitor 2 Proteins 0.000 description 7
- 108010001953 Protein C Inhibitor Proteins 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 241000018242 Obba <basidiomycete fungus> Species 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002312 polyamide-imide Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- IHWDSEPNZDYMNF-UHFFFAOYSA-N 1H-indol-2-amine Chemical compound C1=CC=C2NC(N)=CC2=C1 IHWDSEPNZDYMNF-UHFFFAOYSA-N 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
本發明係有關於一種AR型聚醯亞胺樹脂及方法，尤指能製得一種聚醯胺醯亞胺樹脂的共聚合體。 The present invention relates to an AR type polyimine resin and a method, and more particularly to a copolymer of a polyamidoximine resin.
近年，工業上創造出許多消費性電子產品、電腦、通訊、工業用控制板及醫療器材設備基處零件對於積層板複合材料的需求，前有使用聚醚亞胺脂膜但是無法高溫耐熱，於是轉為針對聚醯亞胺樹脂所製得的薄膜取其耐熱性質的提高，其中又有許多變型聚樹醯亞胺樹脂膜與銅箔相互加工結合，因此對於耐熱性、機械性質與電氣性質要求甚高，甚有使用複合材料方式增加與銅箔之間的黏著力，但是往往造成加工的負荷與成本上的提高，因此，往往為了改善上述缺失其尋求一置換基作為改善實為目前非常艱難的工作。 In recent years, the industry has created a lot of consumer electronic products, computers, communications, industrial control panels and medical equipment and equipment based on the need for laminated composite materials, the former used polyether imide film but not high temperature heat, so The film obtained by the polyimine resin has improved heat resistance, and many of the modified polytree imine resin film and copper foil are processed and combined with each other, so heat resistance, mechanical properties and electrical properties are required. Very high, the use of composite materials to increase the adhesion between the copper foil, but often causes the processing load and cost increase, therefore, often in order to improve the above-mentioned lack of seeking a replacement base as an improvement is currently very difficult work.
本發明主要目的，係要提出一種AD型聚醯亞胺樹脂及方法的專利申請，因為本發明的產品係具有耐熱性高、物性優良及具加工性的接著劑，主要係利用(TPA,IPA,OBBA)、BTDA、MDI等單體以適當比例聚合成AD型聚醯亞胺樹脂(變型聚醯亞胺樹脂)，係於分子結構鏈中植入醯胺(-CONH-)基團，主要可以分為：1. MDI+BTDA+TPA→PAI-1。2. MDI+BTDA+IPA→PAI-2。3. MDI+BTDA+OBBA→PAI-3。上述三種型的樹脂係可以提高聚合體的熔融流動性、耐熱性、接著性及柔軟性，其耐熱性也比環氧樹脂高，當製備成AD型聚醯亞胺薄膜時，經由熱壓黏合形成具有兩層結構的銅箔積層電路板，使本發明所應用的產品具有簡單製程(一次塗佈加工)、優異物性及品質穩定的特性。 The main object of the present invention is to provide a patent application for an AD type polyimine resin and a method thereof, since the product of the present invention is an adhesive having high heat resistance, excellent physical properties, and workability, mainly utilizing (TPA, IPA). , OBBA, BTDA, MDI and other monomers are polymerized into AD type polyimine resin (modified polyimine resin) in an appropriate ratio, and the indoleamine (-CONH-) group is implanted in the molecular structure chain, mainly Can be divided into: 1. MDI + BTDA + TPA → PAI-1. 2. MDI + BTDA + IPA → PAI-2. 3. MDI + BTDA + OBBA → PAI-3. The above three types of resins can improve the melt flowability, heat resistance, adhesion and flexibility of the polymer, and the heat resistance is also higher than that of the epoxy resin. When the AD type polyimide film is prepared, it is bonded by thermocompression bonding. A copper foil laminated circuit board having a two-layer structure is formed, so that the product to which the present invention is applied has a simple process (primary coating process), excellent physical properties, and stable quality.
本發明係為一種AD型聚醯亞胺樹脂及方法，請參閱圖1所示係為AD型聚醯亞胺樹脂以下列化學結構式作為重覆單位：
R： R:
R’： R':
R”： R":
本發明製造AD型聚醯亞胺樹脂的製備方法： The preparation method of the invention for manufacturing AD type polyimine resin:
(1).本發明係利用二酸酐與二異氰酸鹽類製作成聚醯亞胺預聚合體如化學結構式-(I)式如圖2：
R： R:
R’： R':
(2).本發明將(I)式再與二酸單體共聚反應而獲得(Π)式，即獲得黏度值高之褐色透明之AD型聚醯亞胺樹脂(聚醯胺醯亞胺共聚合體)如圖3：
R’： R':
R”： R":
(1).聚醯亞胺預聚合物的合成：
將1~5莫耳的二酸酐(3.3’,4.4’-benzophenone tetracarboxylic dianhydride,BTDA)置入四口反應瓶中，加入N-甲基-2-吡咯啶(N-methyl-2-pyrrolidone,NMP)溶劑於50℃攪拌反應30分鐘，並使瓶內保持真空狀態，再加入2~6莫耳的二異氰酸酯(4.4’-diphenylmethane diisocyanate,MDI)，並維持固含量15%，在50℃反應4小時後，在合成過程中利用逆滴定法確定末端基NCO的含量，得到-NCO-封端的預聚醯亞胺預聚合體........(I’)式，其反應式如下：
(2).AD型聚醯亞胺樹脂：續將聚醯亞胺預聚合體……(I)式降至室溫，加1莫耳的二酸單體，同時加入二月桂酸二丁基錫(催化劑)(dibutyltin dilaurate,DBTDL)數滴，反應0.5小時後，逐漸升溫至80℃反應1hr，再升溫至120℃反應2小時，此時可以獲得相當黏度之褐色溶液的AD型聚醯亞胺樹脂……(Π’)式。其中，(Π’)式AD型聚醯亞胺樹脂的反應式：
R： R:
R’： R':
R”： R":
本發明係為一種AD型聚醯亞胺樹脂可以分為下列樹脂型式： The present invention is an AD type polyimine resin which can be classified into the following resin types:
1. PAI-1：MDI+BTDA+TPA 1. PAI-1: MDI+BTDA+TPA
2. PAI-2：MDI+BTDA+IPA 2. PAI-2: MDI+BTDA+IPA
3. PAI-3：MDI+BTDA+OBBA 3. PAI-3: MDI+BTDA+OBBA
其中，利用上述三種型樹脂製備成薄膜，其方法係將固體的聚醯胺醯亞胺使用NMP溶解，固含量維持在15%，再將溶解之樹脂倒至玻璃板上，以玻璃棒將樹脂均勻塗佈在玻璃板上，並控制厚度約25μm左右，然後再把玻璃板置入50℃的烘烤箱中抽真空烘12小時，而後多段升溫加熱，以使薄膜完全去除溶劑。 Among them, the above three types of resins are used to prepare a film by dissolving the solid polyamidoximine using NMP, the solid content is maintained at 15%, and then the dissolved resin is poured onto a glass plate, and the resin is poured with a glass rod. Evenly coated on a glass plate and controlled to a thickness of about 25 μm, and then placed in a 50 ° C oven for vacuum drying for 12 hours, and then heated in multiple stages to completely remove the solvent.
係將上述三種AD型聚醯亞胺樹脂所製備的薄膜(PAI-1,PAI-2,PAI-3)列舉比 較耐熱性質的測試結果如下： The film (PAI-1, PAI-2, PAI-3) prepared by the above three AD type polyimine resins is listed as a ratio The test results of the more heat resistant properties are as follows:
(1).TGA分析：當比較上述三種AD型聚醯亞胺薄膜(PAI-1,PAI-2,PAI-3)的TGA圖譜分析本發明的耐熱性得知：
(2).DMA分析：測量材料受正弦或其他週期性應力之形變，尋找該被測材料的玻璃轉移點(Tg)，當分析本發明三種AD型聚醯亞胺薄膜(PAI-1,PAI-2,PAI-3)所顯示的玻璃溫度轉移點(Tg)如下：
本發明係為一種AD型聚醯亞胺樹脂及方法，已符合專利要件，今爰依法提出專利申請。 The invention relates to an AD type polyimine resin and a method thereof, which have met the patent requirements, and the patent application is filed according to law.
圖1係為本發明之AD型聚醯亞胺樹脂的化學結構式。 Fig. 1 is a chemical structural formula of the AD type polyimine resin of the present invention.
圖2係為本發明之AD型聚醯亞胺樹脂製造方法(I)式的化學結構式。 Fig. 2 is a chemical structural formula of the method (I) of the method for producing an AD type polyimine resin of the present invention.
圖3係為本發明之AD型聚醯亞胺樹脂製造方法(Π)式的化學結構式。 Fig. 3 is a chemical structural formula of the method for producing an AD type polyimine resin of the present invention.
圖4係為本發明之AD型聚醯亞胺薄膜-PAI-1的TGA圖。 Figure 4 is a TGA diagram of the AD type polyimine film - PAI-1 of the present invention.
圖5係為本發明之AD型聚醯亞胺薄膜-PAI-2的TGA圖。 Figure 5 is a TGA diagram of the AD type polyimine film - PAI-2 of the present invention.
圖6係為本發明之AD型聚醯亞胺薄膜-PAI-3的TGA圖。 Fig. 6 is a TGA diagram of the AD type polyimine film-PAI-3 of the present invention.
圖7係為本發明之AD型聚醯亞胺薄膜-PAI-1的DMA圖。 Figure 7 is a DMA diagram of the AD type polyimine film - PAI-1 of the present invention.
圖8係為本發明之AD型聚醯亞胺薄膜-PAI-2的DMA圖。 Figure 8 is a DMA diagram of the AD type polyimine film - PAI-2 of the present invention.
圖9係為本發明之AD型聚醯亞胺薄膜-PAI-3的DMA圖。 Figure 9 is a DMA diagram of the AD type polyimine film - PAI-3 of the present invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW097101725A TWI503351B (en) | 2008-01-17 | 2008-01-17 | Ad type polyimide resin and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW097101725A TWI503351B (en) | 2008-01-17 | 2008-01-17 | Ad type polyimide resin and method |
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| Publication Number | Publication Date |
|---|---|
| TW200932790A TW200932790A (en) | 2009-08-01 |
| TWI503351B true TWI503351B (en) | 2015-10-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| TW097101725A TWI503351B (en) | 2008-01-17 | 2008-01-17 | Ad type polyimide resin and method |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200736299A (en) * | 2006-01-18 | 2007-10-01 | Arisawa Seisakusho Kk | Polyamideimide resin for flexible printed circuit boards; metal-clad laminate, coverlay, and flexible printed circuit board that use this resin; and resin composition |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200736299A (en) * | 2006-01-18 | 2007-10-01 | Arisawa Seisakusho Kk | Polyamideimide resin for flexible printed circuit boards; metal-clad laminate, coverlay, and flexible printed circuit board that use this resin; and resin composition |
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| Publication number | Publication date |
|---|---|
| TW200932790A (en) | 2009-08-01 |
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