JP5362752B2 - Polyamic acid composition, polyimide, polyimide film and method for producing them - Google Patents
Polyamic acid composition, polyimide, polyimide film and method for producing them Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims description 66
- 229920005575 poly(amic acid) Polymers 0.000 title claims description 65
- 239000000203 mixture Substances 0.000 title claims description 56
- 239000004642 Polyimide Substances 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 30
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 28
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 11
- 229920001400 block copolymer Polymers 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 108010025899 gelatin film Proteins 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 3
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- -1 aromatic tetracarboxylic acid Chemical class 0.000 description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 150000004984 aromatic diamines Chemical class 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000007363 ring formation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NBAUUNCGSMAPFM-UHFFFAOYSA-N 3-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=CC(C(O)=O)=C1C(O)=O NBAUUNCGSMAPFM-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- HGUCAHTVRDGMST-UHFFFAOYSA-N 3-[4-(3-amino-5-methylphenyl)phenyl]-5-methylaniline Chemical compound CC1=CC(N)=CC(C=2C=CC(=CC=2)C=2C=C(N)C=C(C)C=2)=C1 HGUCAHTVRDGMST-UHFFFAOYSA-N 0.000 description 1
- WECDUOXQLAIPQW-UHFFFAOYSA-N 4,4'-Methylene bis(2-methylaniline) Chemical compound C1=C(N)C(C)=CC(CC=2C=C(C)C(N)=CC=2)=C1 WECDUOXQLAIPQW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- LFBALUPVVFCEPA-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 LFBALUPVVFCEPA-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013005 condensation curing Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- IBBMAWULFFBRKK-UHFFFAOYSA-N picolinamide Chemical class NC(=O)C1=CC=CC=N1 IBBMAWULFFBRKK-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Moulding By Coating Moulds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
本発明は、特定のジアミン成分と、特定のテトラカルボン酸成分とを、特定の比率で用いたポリアミド酸組成物およびそれを硬化させて得られるポリイミドに関する。 The present invention relates to a polyamic acid composition using a specific diamine component and a specific tetracarboxylic acid component in a specific ratio, and a polyimide obtained by curing it.
芳香族テトラカルボン酸二無水物および芳香族ジアミンを縮重合し、硬化して得られるポリイミド組成物、その中でも特にポリイミドフィルムは、電気絶縁性や耐熱性などに優れているため、フレキシブルプリント基板（以下、ＦＰＣという）など電子基板材料の用途で多く利用されている。ＦＰＣは、ポリイミドフィルムと銅箔をエポキシ樹脂などの接着剤で張り合わせて銅張積層板（以下、ＣＣＬという）を作製し、その銅箔に回路を施すことで製造される。最近では電子機器の薄型化、小型化、微細化、実装化が進む中で、基板材料の高加工性、高精度化の要求が高まっており、ポリイミドフィルムの特性としても高弾性率、高寸法安定性、低熱膨張性、低吸水性などが求められている。そのようなポリイミドの特性向上の手段としては、ポリイミドモノマーの成分やその配列（ランダム、ブロックなど）を制御することがあり、現在までに種々の検討がなされている。 Polyimide composition obtained by condensation polymerization and curing of aromatic tetracarboxylic dianhydride and aromatic diamine, and in particular polyimide film is excellent in electrical insulation and heat resistance. In the following, it is widely used in applications of electronic substrate materials such as FPC). FPC is manufactured by bonding a polyimide film and a copper foil with an adhesive such as an epoxy resin to produce a copper-clad laminate (hereinafter referred to as CCL) and applying a circuit to the copper foil. Recently, as electronic devices are becoming thinner, smaller, finer, and more advanced, there is an increasing demand for high workability and high precision of substrate materials. There are demands for stability, low thermal expansion, low water absorption, and the like. As means for improving the characteristics of such polyimide, there are cases where the components of polyimide monomers and their arrangement (random, block, etc.) are controlled, and various studies have been made so far.
ＦＰＣはポリイミドフィルムと銅箔をエポキシ樹脂などの接着剤で張り合わせてＣＣＬを作製し、その銅箔にエッチング加工により電子回路を施すことで製造される。さらに最近では、電子回路のファインピッチ化の要求から、ＩＣチップ等をＦＰＣに金バンプ等を介して直接実装するチップオンフィルム（以下、ＣＯＦという）方式が多く用いられている。ＣＯＦ方式ではＩＣチップを実装する際、高温で直接ＣＣＬに圧着するなど、高温での加工工程がある。高温域でのポリイミドフィルムの熱膨張率が銅箔と異なると、ＣＣＬにしわやカールなどが発生する問題が生じる。また、ポリイミドフィルムのＴｇが低いと、実装時にポリイミドフィルムが軟化し、回路およびＩＣチップが沈み込む問題がある。そのため、ＩＣチップ実装を伴うＣＯＦ用途においては、ポリイミドフィルムの特性として、高温域においても熱膨張率が銅箔と同等であること、高いＴｇを有し高温圧着時に軟化しないことが求められる。しかし、既存のポリイミドフィルムであるピロメリット酸二無水物（以下、ピロメリット酸またはその無水物をＰＭＤＡと略称することがある）と４，４´−ジアミノジフェニルエーテル（以下、ＯＤＡと略称することがある）や、３，３´，４，４´−ビフェニルテトラカルボン酸二無水物（以下、当該カルボン酸またはその無水物をＢＰＤＡと略称することがある）とパラフェニレンジアミン（以下、ＰＤＡと略称することがある）との組合せからなる２成分系では、高温域における熱膨張率が銅箔よりも大きすぎたり小さすぎたりする問題がある。それらを組み合わせた３成分系や４成分系の多成分系では、モノマー比を調整することで熱膨張率をコントロールできるが、ＢＰＤＡ−ＯＤＡのような骨格が柔軟なブロックが存在するとポリイミドフィルムのＴｇが低下するという問題がある。 FPC is manufactured by bonding a polyimide film and a copper foil with an adhesive such as an epoxy resin to produce a CCL, and applying an electronic circuit to the copper foil by etching. In recent years, a chip-on-film (hereinafter referred to as COF) system in which an IC chip or the like is directly mounted on an FPC via a gold bump or the like is often used due to the demand for fine pitch electronic circuits. In the COF method, when an IC chip is mounted, there is a processing step at a high temperature, such as directly crimping to CCL at a high temperature. If the coefficient of thermal expansion of the polyimide film in the high temperature range is different from that of the copper foil, there arises a problem that wrinkles or curls occur in the CCL. Moreover, when Tg of a polyimide film is low, there exists a problem which a polyimide film softens at the time of mounting, and a circuit and an IC chip sink. For this reason, in COF applications involving IC chip mounting, the polyimide film is required to have a thermal expansion coefficient equivalent to that of a copper foil even in a high temperature region, and to have a high Tg and not be softened during high temperature pressure bonding. However, pyromellitic dianhydride (hereinafter, pyromellitic acid or its anhydride may be abbreviated as PMDA) and 4,4′-diaminodiphenyl ether (hereinafter, abbreviated as ODA), which are existing polyimide films. Or 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter, the carboxylic acid or its anhydride may be abbreviated as BPDA) and paraphenylenediamine (hereinafter abbreviated as PDA). In the two-component system consisting of a combination with the copper foil, there is a problem that the coefficient of thermal expansion in the high temperature range is too large or too small compared to the copper foil. In the case of ternary or quaternary multi-component systems that combine them, the coefficient of thermal expansion can be controlled by adjusting the monomer ratio, but if there is a flexible skeleton such as BPDA-ODA, the Tg of the polyimide film There is a problem that decreases.
例えば、特許文献１では、ＯＤＡ−ＢＰＤＡのブロック共重合部分や、ＯＤＡ−ＰＭＤＡのブロック共重合部分を含むポリアミド酸組成物からエナメル線製造用のワニスを得たことが記載される。
特許文献２では、モノマー成分の組合せとして、ＰＭＤＡ、ＯＤＡ、ＢＰＤＡおよびＰＤＡを混合して重合しポリアミド酸組成物を得て、ポリイミド膜を製造する方法が記載されている。
For example, Patent Document 1 describes that a varnish for producing an enameled wire was obtained from a polyamic acid composition containing a block copolymer part of ODA-BPDA or a block copolymer part of ODA-PMDA.
Patent Document 2 describes a method for producing a polyimide film by mixing and polymerizing PMDA, ODA, BPDA and PDA as a combination of monomer components to obtain a polyamic acid composition.
特許文献３には、ＯＤＡ−ＰＭＤＡのブロック共重合部分、ＯＤＡ−ジメチルベンジジンのブロック共重合部分を含むポリアミド酸共重合体溶液からポリイミド共重合体膜を得ることが記載されている。
特許文献４では、ＰＤＡ−ＢＰＤＡのポリアミド酸と、ＯＤＡ−ＰＭＤＡのポリアミド酸の混合物を得て、加熱して、ポリイミドを製造する旨が記載される。
Patent Document 3 describes that a polyimide copolymer film is obtained from a polyamic acid copolymer solution containing a block copolymer portion of ODA-PMDA and a block copolymer portion of ODA-dimethylbenzidine.
Patent Document 4 describes that a polyamic acid of PDA-BPDA and a polyamic acid of ODA-PMDA are obtained and heated to produce polyimide.
特許文献５には、ＰＤＡ−ＰＭＤＡのブロック共重合部分を有するポリアミド酸、ＯＤＡ―ＢＰＤＡのブロック共重合部分を有するポリアミド酸、さらにこれらにＰＭＤＡを重合させたポリアミド酸組成物の記載がある。
特許文献６には、ＰＤＡ−ＰＭＤＡのブロック共重合部分を有するポリアミド酸、ＯＤＡ−ＢＰＤＡのブロック共重合部分を有するポリアミド酸組成物に、さらにＰＭＤＡを重合させたポリアミド酸混合物からポリイミドフイルムを得たことが記載されている。
Patent Document 5 describes a polyamic acid having a block copolymerized portion of PDA-PMDA, a polyamic acid having a block copolymerized portion of ODA-BPDA, and a polyamic acid composition obtained by polymerizing PMDA thereon.
In Patent Document 6, a polyimide film was obtained from a polyamic acid mixture obtained by further polymerizing PMDA in a polyamic acid composition having a block copolymerization portion of PDA-PMDA and a polyamic acid composition having a block copolymerization portion of ODA-BPDA. It is described.
特許文献１、２、３、５では、ＰＤＡ−ＢＰＤＡのブロック共重合部分を有するポリアミド酸は記載されていない。一方、ＰＤＡ−ＰＭＤＡのブロック共重合部分を有するポリアミド酸を有する組成物では、得られるポリアミドのＴｇが低下して耐熱性に劣る恐れがある。
特許文献２では、ＰＤＡ、ＯＤＡ、ＢＰＤＡ、ＰＭＤＡを混合して、重合するので、耐熱性が低下し、分子量があまり高くならない問題がある。
特許文献４では、ＰＤＡ−ＢＰＤＡのポリアミド酸と、ＯＤＡ−ＰＭＤＡのポリアミド酸の混合物が記載され、共重合物の記載はない。また、モノマーの各成分は全てが等モルの場合の実施例のみが記載されていて、得られるポリイミドフィルムは表面に微細な凹状構造が形成されると記載され、耐熱性等の特性は不明である。ＰＤＡ−ＢＰＤＡのポリアミド酸とＯＤＡ−ＰＭＤＡのポリアミド酸は、室温では混ざるまで数日かかるので均一混合が難しく、混合できても、分子量が低下するという問題がある。
特許文献６では、ＰＤＡ−ＢＰＤＡのブロック共重合部分を有するポリアミド酸が得られているが、各成分の組成比と弾性率との関係において改善が望まれる。
Patent Documents 1, 2, 3, and 5 do not describe polyamic acid having a PDA-BPDA block copolymer moiety. On the other hand, in a composition having a polyamic acid having a PDA-PMDA block copolymer moiety, the Tg of the resulting polyamide may be reduced, resulting in poor heat resistance.
In Patent Document 2, since PDA, ODA, BPDA, and PMDA are mixed and polymerized, there is a problem that the heat resistance is lowered and the molecular weight is not so high.
In Patent Document 4, a mixture of polyamic acid of PDA-BPDA and polyamic acid of ODA-PMDA is described, and there is no description of a copolymer. In addition, only examples in which all the components of the monomer are equimolar are described, and the obtained polyimide film is described as having a fine concave structure formed on the surface, and characteristics such as heat resistance are unknown. is there. Since the polyamic acid of PDA-BPDA and the polyamic acid of ODA-PMDA take several days to mix at room temperature, uniform mixing is difficult, and even if they can be mixed, there is a problem that the molecular weight decreases.
In Patent Document 6, a polyamic acid having a PDA-BPDA block copolymer portion is obtained, but an improvement in the relationship between the composition ratio of each component and the elastic modulus is desired.
本発明は、従来技術の問題点を改善でき、優れた特性を有するポリイミドフィルムが得られるポリアミド酸組成物を提供することを目的とする。本発明のポリアミド酸組成物を用いて得られるポリイミドフィルムは、高温域においても銅箔と同等の熱膨張特性をもち、耐熱性が高い。 An object of this invention is to provide the polyamic-acid composition which can improve the problem of a prior art and can obtain the polyimide film which has the outstanding characteristic. The polyimide film obtained using the polyamic acid composition of the present invention has a thermal expansion characteristic equivalent to that of a copper foil even in a high temperature range, and has high heat resistance.
上記課題を解決する手段として、本発明は、ＯＤＡとＰＭＤＡとからなるブロック成分と、ＰＤＡとＢＰＤＡとからなるブロック成分が一定の比率で共重合されたポリアミド酸組成物およびそれを硬化させて得られるポリイミドを開発した。
すなわち、本発明は以下を提供する。
（１）パラフェニレンジアミン：５０ｍｏｌ％超〜９０ｍｏｌ％以下および
４，４´−ジアミノジフェニルエーテル：５０ｍｏｌ％未満〜１０ｍｏｌ％以上からなるジアミン成分ならびに
３，３´，４，４´−ビフェニルテトラカルボン酸二無水物：４５〜８７ｍｏｌ％および
ピロメリット酸二無水物：５５〜１３ｍｏｌ％からなるテトラカルボン酸成分からなるポリアミド酸組成物であって、
前記パラフェニレンジアミンと前記３，３´，４，４´−ビフェニルテトラカルボン酸二無水物の共重合体からなるブロック成分と
前記４，４´−ジアミノジフェニルエーテルと前記ピロメリット酸二無水物の共重合体からなるブロック成分を含むことを特徴とするポリアミド酸組成物。
（２）上記（１）に記載のポリアミド酸組成物が硬化されてなるポリイミド。
（３）上記（２）に記載のポリイミドがフィルムであるポリイミド。
（４）４００℃から５０℃への降温過程における熱膨張率が−１８〜−２５ｐｐｍ／℃、ガラス転移温度が３５０℃以上であり、引張弾性率が５．８ＧＰａ以下であることを特徴とする請求項３に記載のポリイミドフィルム。
（５）上記（１）に記載のポリアミド酸組成物の製造方法であって、
前記パラフェニレンジアミン１００ｍｏｌ％に対して前記３，３´，４，４´−ビフェニルテトラカルボン酸二無水物が９０〜１００ｍｏｌ％となる比率で、溶媒中で混合、反応させて、該パラフェニレンジアミンと該３，３´，４，４´−ビフェニルテトラカルボン酸二無水物のブロック共重合部分を得た後、
前記４，４´−ジアミノジフェニルエーテルを添加し、続いて前記ピロメリット酸二無水物を添加し、反応させて、該４，４´−ジアミノジフェニルエーテルと該ピロメリット酸二無水物のブロック共重合部分を得ることを特徴とするポリアミド酸組成物の製造方法。
（６）上記（５）で製造されたポリアミド酸組成物を硬化させて、ポリイミドを得るポリイミドの製造方法。
（７）上記（５）で製造されたポリアミド酸組成物を基板に塗布後、乾燥してゲルフィルムを製造後、前記ゲルフィルムを加熱してポリイミドフィルムを得ることを特徴とするポリイミドフィルムの製造方法。
As means for solving the above-mentioned problems, the present invention is obtained by curing a polyamic acid composition in which a block component composed of ODA and PMDA and a block component composed of PDA and BPDA are copolymerized at a certain ratio. Developed polyimide.
That is, the present invention provides the following.
(1) Paraphenylenediamine: more than 50 mol% to 90 mol% or less and 4,4′-diaminodiphenyl ether: a diamine component consisting of less than 50 mol% to 10 mol% or more, and 3,3 ′, 4,4′-biphenyltetracarboxylic acid A polyamic acid composition comprising a tetracarboxylic acid component consisting of an anhydride: 45-87 mol% and pyromellitic dianhydride: 55-13 mol%,
A block component composed of a copolymer of the paraphenylenediamine and the 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, a co-polymer of the 4,4′-diaminodiphenyl ether and the pyromellitic dianhydride. A polyamic acid composition comprising a block component made of a polymer.
(2) A polyimide obtained by curing the polyamic acid composition according to (1) above.
(3) The polyimide whose polyimide as described in said (2) is a film.
(4) The coefficient of thermal expansion in the temperature lowering process from 400 ° C. to 50 ° C. is −18 to −25 ppm / ° C., the glass transition temperature is 350 ° C. or more, and the tensile modulus is 5.8 GPa or less. The polyimide film according to claim 3.
(5) A method for producing the polyamic acid composition according to (1) above,
The 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is mixed in a solvent at a ratio of 90 to 100 mol% with respect to 100 mol% of the paraphenylenediamine, and the paraphenylenediamine is reacted. And a block copolymerized part of the 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
The 4,4'-diaminodiphenyl ether is added, and then the pyromellitic dianhydride is added and reacted to cause a block copolymer part of the 4,4'-diaminodiphenyl ether and the pyromellitic dianhydride. A process for producing a polyamic acid composition, characterized in that
(6) The manufacturing method of the polyimide which hardens the polyamic-acid composition manufactured by said (5), and obtains a polyimide.
(7) A polyimide film produced by applying the polyamic acid composition produced in (5) above to a substrate, drying to produce a gel film, and then heating the gel film to obtain a polyimide film. Method.
本発明のポリアミド酸組成物は、従来技術の問題点を改善でき、優れた特性を有するポリイミドフィルムが得られるポリアミド酸組成物である。本発明のポリアミド酸組成物を用いて得られるポリイミドフィルムは、高温域においても銅箔と同等の熱膨張特性をもち、耐熱性が高い。好ましくは、弾性率が適切範囲であるという優れた特性を持つ。 The polyamic acid composition of the present invention is a polyamic acid composition that can improve the problems of the prior art and obtain a polyimide film having excellent characteristics. The polyimide film obtained using the polyamic acid composition of the present invention has a thermal expansion characteristic equivalent to that of a copper foil even in a high temperature range, and has high heat resistance. Preferably, it has the outstanding characteristic that an elasticity modulus is an appropriate range.
上記課題を解決する手段として、ＯＤＡとＰＭＤＡとからなるブロック成分と、ＰＤＡとＢＰＤＡとからなるブロック成分が一定の比率で共重合されたポリアミド酸組成物およびそれを硬化させて得られるポリイミド組成物を開発した。
本発明は、パラフェニレンジアミン（ＰＤＡ）と３，３´，４，４´−ビフェニルテトラカルボン酸二無水物（ＢＰＤＡ）の共重合体からなるブロック成分と４，４´−ジアミノジフェニルエーテル（ＯＤＡ）とピロメリット酸二無水物（ＰＭＤＡ）の共重合体からなるブロック成分を含むポリアミド酸組成物である。成分比は、全芳香族ジアミン成分中ＰＤＡが５０ｍｏｌ％超〜９０ｍｏｌ％以上、ＯＤＡが５０ｍｏｌ％未満、１０ｍｏｌ％以上であり、かつ全芳香族テトラカルボン酸成分中ＰＭＤＡ１３〜５５ｍｏｌ％、ＢＰＤＡが４５〜８７ｍｏｌ％である。
有機溶媒中の本発明のポリアミド酸組成物は部分的にイミド化されている部分があっても本発明の組成物に含まれる。
As means for solving the above problems, a polyamic acid composition in which a block component composed of ODA and PMDA and a block component composed of PDA and BPDA are copolymerized at a certain ratio, and a polyimide composition obtained by curing the polyamic acid composition Developed.
The present invention relates to a block component comprising a copolymer of paraphenylenediamine (PDA) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) and 4,4′-diaminodiphenyl ether (ODA). And a polyamic acid composition containing a block component made of a copolymer of pyromellitic dianhydride (PMDA). The component ratio is such that PDA in the wholly aromatic diamine component is more than 50 mol% to 90 mol% or more, ODA is less than 50 mol%, 10 mol% or more, and PMDA is 13 to 55 mol% in the wholly aromatic tetracarboxylic acid component, and BPDA is 45 to 45 mol%. 87 mol%.
The polyamic acid composition of the present invention in an organic solvent is included in the composition of the present invention even if there is a partially imidized portion.
芳香族ジアミン成分において、ＰＤＡの割合が上記より少なく、ＯＤＡの割合が多くなりすぎると、得られるポリイミド組成物の弾性率が低下しすぎたり、熱膨張率が増大しすぎたりするので好ましくない。弾性率が、高すぎると製造工程や長時間の使用でポリイミドフィルムに破断や割れが生じやすくなり、特にＣＯＦ用途では使用上ある程度の柔軟性が求められる。また弾性率が、低すぎると製造工程や加工工程においてフィルムのハンドリングが悪くなる。
弾性率、熱膨張率がいずれも適切であるという理由で、好ましくは、ＰＤＡが５１〜９０ｍｏｌ％、ＯＤＡが１０〜４９ｍｏｌ％であり、より好ましくは、ＰＤＡが７０〜９０ｍｏｌ％、ＯＤＡが１０〜３０ｍｏｌ％である。
またＰＤＡの割合が上記より多く、ＯＤＡの割合が少なくすぎると、得られるポリイミドの吸水率が増大したり、熱膨張率が低下しすぎたり、弾性率が高くなりすぎて成形性を損なうので好ましくない。
In the aromatic diamine component, if the proportion of PDA is less than the above and the proportion of ODA is too large, the resulting polyimide composition will have an excessively low elastic modulus or an excessively high thermal expansion coefficient, which is not preferable. If the elastic modulus is too high, the polyimide film is likely to be broken or cracked in the production process or used for a long time, and a certain degree of flexibility is required for use particularly in COF applications. On the other hand, if the elastic modulus is too low, the handling of the film is deteriorated in the production process and the processing process.
The reason is that the elastic modulus and the coefficient of thermal expansion are both suitable, preferably, PDA is 51 to 90 mol%, ODA is 10 to 49 mol%, and more preferably, PDA is 70 to 90 mol% and ODA is 10 to 10 mol%. 30 mol%.
Further, if the proportion of PDA is larger than the above and the proportion of ODA is too small, the water absorption rate of the resulting polyimide increases, the thermal expansion coefficient decreases too much, or the elastic modulus becomes too high and the moldability is impaired. Absent.
芳香族テトラカルボン酸成分において、ＢＰＤＡの割合が上記の割合より少なく、ＰＭＤＡが多くなりすぎると、得られるポリイミドの弾性率が低下したり、吸水率が増大するので好ましくなく、またＢＰＤＡの割合が上記の割合より多く、ＰＭＤＡが少なくなりすぎると、得られるポリイミドの気体透過率が低下し、加熱硬化の際に、ポリアミド酸組成物の表面に気泡が発生したり、接着力が低下するので好ましくない。好ましくは、ＢＰＤＡが５０〜８７モル％、ＰＭＤＡが１３〜５０ｍｏｌ％未満である。 In the aromatic tetracarboxylic acid component, if the ratio of BPDA is less than the above ratio and the PMDA is excessive, the resulting polyimide has a low elastic modulus or an increased water absorption rate. More than the above ratio, if PMDA becomes too small, the gas permeability of the resulting polyimide is lowered, and it is preferable because bubbles are generated on the surface of the polyamic acid composition or the adhesive strength is reduced during heat curing. Absent. Preferably, BPDA is 50 to 87 mol% and PMDA is less than 13 to 50 mol%.
本発明のポリアミド酸組成物を硬化させて得られるポリイミドは、好ましくは、以下の特性を持つ。
４００℃から５０℃への降温過程における熱膨張率が−１８〜−２５ｐｐｍ／℃、ガラス転移温度が３５０℃以上であり、引張弾性率が５．８ＧＰａ以下である。
より好ましくは、４００℃から５０℃への降温過程における熱膨張率が−１８〜−２４ｐｐｍ／℃、ガラス転移温度が３５０℃〜４００℃であり、引張弾性率が５〜５．８ＧＰａである。
このポリイミドをフイルムに成形したポリイミドフイルムは、好ましくは、伸び率が５０％以上である。より好ましくは伸び率５０〜１００％である。
The polyimide obtained by curing the polyamic acid composition of the present invention preferably has the following characteristics.
The thermal expansion coefficient in the temperature lowering process from 400 ° C. to 50 ° C. is −18 to −25 ppm / ° C., the glass transition temperature is 350 ° C. or higher, and the tensile modulus is 5.8 GPa or lower.
More preferably, the thermal expansion coefficient in the temperature lowering process from 400 ° C. to 50 ° C. is −18 to −24 ppm / ° C., the glass transition temperature is 350 ° C. to 400 ° C., and the tensile elastic modulus is 5 to 5.8 GPa.
The polyimide film obtained by molding this polyimide into a film preferably has an elongation of 50% or more. More preferably, the elongation is 50 to 100%.
ポリアミド酸組成物を形成するＰＭＤＡおよびＢＰＤＡは、これら以外の芳香族テトラカルボン酸成分を本発明の目的を阻害しない範囲で含むことができ、それらの具体例としては、２，３’，３，４’−ビフェニルテトラカルボン酸、３，３’，４，４’−ベンゾフェノンテトラカルボン酸、２，３，６，７−ナフタレンジカルボン酸、２，２−ビス（３，４−ジカルボキシフェニル）エーテル、ピリジン−２，３，５，６−テトラカルボン酸およびこれらのアミド形成性誘導体が挙げられる。ポリアミド酸組成物の製造にあたっては、これらの芳香族テトラカルボン酸の酸無水物を少量添加してもかまわない。 PMDA and BPDA forming the polyamic acid composition may contain an aromatic tetracarboxylic acid component other than these as long as the object of the present invention is not impaired, and specific examples thereof include 2,3 ′, 3, 4'-biphenyltetracarboxylic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 2,3,6,7-naphthalenedicarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) ether Pyridine-2,3,5,6-tetracarboxylic acid and amide-forming derivatives thereof. In producing the polyamic acid composition, a small amount of these aromatic tetracarboxylic acid anhydrides may be added.
ポリアミド酸組成物を形成するパラフェニレンジアミンおよび４，４’−ジアミノジフェニルエーテルは、これら以外の芳香族ジアミン成分を本発明の目的を阻害しない範囲で含むことができ、それらの具体例としては、メタフェニレンジアミン、ベンチジン、パラキシリレンジアミン、３，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルスルホン、３，３’−ジメチル−４，４’−ジアミノジフェニルメタン、１，５−ジアミノナフタレン、３，３’−ジメトキシベンチジン、１，４−ビス（３メチル−５アミノフェニル）ベンゼンおよびこれらのアミド形成性誘導体が挙げられる。ポリアミド酸組成物の製造にあたっては、これらの芳香族ジアミン類を少量添加してもかまわない。 The paraphenylene diamine and 4,4′-diaminodiphenyl ether forming the polyamic acid composition can contain an aromatic diamine component other than these as long as they do not impair the object of the present invention. Phenylenediamine, benzidine, paraxylylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, Examples include 1,5-diaminonaphthalene, 3,3′-dimethoxybenzidine, 1,4-bis (3methyl-5aminophenyl) benzene, and amide-forming derivatives thereof. In producing the polyamic acid composition, a small amount of these aromatic diamines may be added.
本発明のポリアミド酸組成物の製造方法は、溶媒中で、ＰＤＡに対してＢＰＤＡが好ましくは、９０〜１００ｍｏｌ％となる比率で、混合、反応した後、ＯＤＡを添加し、続いてＰＭＤＡを全芳香族テトラカルボン酸類成分と全芳香族ジアミン成分とがほぼ等モルとなる量添加して、混合、反応することで得られる。
ポリアミック酸を構成する芳香族テトラカルボン酸成分と芳香族ジアミン成分とは、それぞれのモル数が大略等しくなる割合で重合される。ＰＤＡに対してＢＰＤＡが９０〜１００ｍｏｌ％となる比率で用いると、重合度を制御できるという利点があるからである。より好ましくは、ＰＤＡに対してＢＰＤＡが９５〜１００ｍｏｌ％となる比率で用いる。
重合反応は、有機溶媒中で撹拌および／または混合しながら、０〜８０℃の温度の範囲で、１０分〜３０時間進められるのが好ましく、上記の順序の範囲内であれば必要により重合反応を分割したり、温度を上下させたりしてもかまわない。重合反応中に真空脱泡することは、良質なポリアミド酸組成物の有機溶媒溶液を製造するのに有効な方法である。
In the method for producing the polyamic acid composition of the present invention, in a solvent, BPDA is mixed with PDA at a ratio of preferably 90 to 100 mol%, and after mixing and reacting, ODA is added, and then PMDA is completely added. The aromatic tetracarboxylic acid component and the wholly aromatic diamine component are added in an amount that is approximately equimolar, and are mixed and reacted.
The aromatic tetracarboxylic acid component and the aromatic diamine component constituting the polyamic acid are polymerized at a ratio in which the number of moles thereof is approximately equal. This is because when the BPDA is used in a ratio of 90 to 100 mol% with respect to the PDA, there is an advantage that the degree of polymerization can be controlled. More preferably, the BPDA is used in a ratio of 95 to 100 mol% with respect to the PDA.
The polymerization reaction is preferably allowed to proceed for 10 minutes to 30 hours in the temperature range of 0 to 80 ° C. with stirring and / or mixing in an organic solvent. If within the above order, the polymerization reaction is necessary. May be divided or the temperature may be raised or lowered. Vacuum degassing during the polymerization reaction is an effective method for producing an organic solvent solution of a good quality polyamic acid composition.
上記製造方法で使用する溶媒としては、Ｎ，Ｎ−ジメチルアセトアミド（以下、ＤＭＡｃと略称することがある）、ジメチルスルホキシド、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジエチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミドおよびジメチルスルホンなどが挙げられ、これらを単独あるいは混合して使用するのが好ましい。
上記製造方法で得られるポリアミド酸組成物は前記溶媒中に１０〜３０重量％の割合で調製するのが好ましい。
As the solvent used in the above production method, N, N-dimethylacetamide (hereinafter sometimes abbreviated as DMAc), dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-diethylacetamide, N, N- Examples thereof include dimethylformamide, N, N-diethylformamide and dimethylsulfone, and these are preferably used alone or in combination.
The polyamic acid composition obtained by the above production method is preferably prepared in a proportion of 10 to 30% by weight in the solvent.
上記製造方法で得られる共重合ポリアミド酸組成物を環化させて共重合ポリイミドにする際、脱水剤と触媒を用いて脱水する化学閉環法、熱的に脱水する熱閉環法のいずれで行っても良いが、化学閉環法で行った方が、ポリイミドフィルムの強度が向上する、生産性が向上するなどの点で好ましい。化学閉環法で使用する脱水剤としては、無水酢酸等の脂肪族酸無水物、フタル酸無水物等の芳香族酸無水物等が挙げられ、これらを単独あるいは混合して使用するのが好ましい。また触媒としては、ピリジン、ピコリン、キノリン等の複素環式第３級アミン類、トリエチルアミン等の脂肪族第３級アミン類、Ｎ，Ｎ−ジメチルアニリン等の芳香族第３級アミン類等が挙げられ、これらを単独あるいは混合して使用するのが好ましい。 When the copolymerized polyamic acid composition obtained by the above production method is cyclized into a copolymerized polyimide, either a chemical cyclization method in which dehydration is performed using a dehydrating agent and a catalyst, or a thermal cyclization method in which thermal dehydration is performed is performed. However, the chemical ring closure method is preferable from the viewpoint of improving the strength of the polyimide film and improving productivity. Examples of the dehydrating agent used in the chemical ring closure method include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as phthalic anhydride, and these are preferably used alone or in combination. Examples of the catalyst include heterocyclic tertiary amines such as pyridine, picoline and quinoline, aliphatic tertiary amines such as triethylamine, and aromatic tertiary amines such as N, N-dimethylaniline. These are preferably used alone or in combination.
上記ポリイミドフィルムの製造方法において、フィルムの延伸操作を行う場合は、まず一連の反応で得られたポリアミド酸組成物を環化触媒および脱水剤を用いて化学環化するか、加熱処理による熱環化により得られたポリイミドのゲルフィルムの端部を固定して二軸延伸を行い、縦方向（ＭＤ）に対する横方向（ＴＤ）の延伸率の比（ＴＤ／ＭＤ）が０．９５〜１．０５になるよう調整するのが好ましい。このような二軸延伸操作を行うと、得られるポリイミドフィルムの機械特性向上、さらには等方性が向上する。 In the above polyimide film production method, when the film is stretched, the polyamic acid composition obtained by a series of reactions is first chemically cyclized using a cyclization catalyst and a dehydrating agent, or is thermally circulated by heat treatment. The ends of the polyimide gel film obtained by crystallization are fixed and biaxial stretching is performed, and the ratio of the stretching ratio in the transverse direction (TD) to the longitudinal direction (MD) (TD / MD) is 0.95-1. It is preferable to adjust to 05. When such a biaxial stretching operation is performed, the mechanical properties of the resulting polyimide film are improved, and the isotropic property is improved.
ポリイミドフィルムの機械特性においては、引張弾性率が５．８ＧＰａ以下、伸び率が５０％以上に調整するのが好ましい。機械特性が上記範囲を外れると、製造工程や長時間の使用でポリイミドフィルムに破断や割れが生じやすくなる。またＣＯＦ用途ではポリイミドフィルムが硬くなりすぎて使用上取扱いにくくなる。 In the mechanical properties of the polyimide film, it is preferable to adjust the tensile modulus to 5.8 GPa or less and the elongation to 50% or more. If the mechanical properties are out of the above range, the polyimide film is likely to be broken or cracked during the manufacturing process or long-time use. In addition, in the COF application, the polyimide film becomes too hard and difficult to handle in use.
以下に、実施例および比較例を用いて本発明を具体例に説明する。本発明は以下の例に限定されない。
実施例、比較例の各特性は次の方法で評価した。
（１）熱膨張率（降温過程における熱膨張率）
機器：島津製作所製ＴＭＡ−５０
測定温度範囲：４００℃〜５０℃
昇温速度：−１０℃／ｍｉｎ
（２）引張弾性率および伸び率
ＪＩＳＫ７１１３に準じて、以下の装置を以下の条件で用いて、応力−歪曲線を得て、初期の立ち上がり部の勾配から引張弾性率を求めた。
機器：島津製作所製ＡＧＳ−Ｊ
引張速度：５１ｍｍ／ｍｉｎ
荷重範囲：４００ＭＰａ
（３）ガラス転移温度
機器：ＴＡインストルメント製ＤＭＡＱ８００
昇温速度：３℃／miｎ
温度範囲：５０〜４５０℃
周波数：１Ｈｚ
Hereinafter, the present invention will be described by way of specific examples using Examples and Comparative Examples. The present invention is not limited to the following examples.
Each characteristic of an Example and a comparative example was evaluated with the following method.
(1) Thermal expansion coefficient (thermal expansion coefficient in the temperature lowering process)
Equipment: TMA-50 manufactured by Shimadzu Corporation
Measurement temperature range: 400 ° C to 50 ° C
Temperature increase rate: −10 ° C./min
(2) Tensile modulus and elongation rate In accordance with JISK7113, the following apparatus was used under the following conditions to obtain a stress-strain curve, and the tensile modulus was determined from the gradient of the initial rising portion.
Equipment: AGS-J manufactured by Shimadzu Corporation
Tensile speed: 51 mm / min
Load range: 400 MPa
(3) Glass transition temperature equipment: DMAQ800 manufactured by TA Instruments
Temperature increase rate: 3 ° C / min
Temperature range: 50-450 ° C
Frequency: 1Hz
（実施例１）
５００ｍｌのセパラブルフラスコにＤＭＡｃ２５５．０ｇを入れ、ここにＰＤＡを１０．９５ｇ（０．１０モル）とＢＰＤＡを２８．１２ｇ（０．０９６モル）を添加し、常温常圧中で１時間反応させた。次にＯＤＡを２．２５ｇ（０．０１１モル）添加し、均一になるまで撹拌した後、ＰＭＤＡを３．６８ｇ（０．０１７モル）を添加し、１時間反応させポリアミド酸溶液を得た。なお、このポリアミド酸溶液から１５ｇを取り、アプリケーターを用いてガラス板に塗布し、１００℃で２０分間加熱乾燥したのち、ゲルフィルムをガラス板から剥離した。ゲルフィルム端部をピン止めし、ＭＤ方向およびＴＤ方向に表１に示す延伸比で二軸延伸した。その後２００℃で２０分間、３００℃で２０分間、続いて４００℃で２０分間加熱乾燥した後、ピン止めを外し、厚さ約３０μｍのポリイミドフィルムを得た。このフィルムの各特性の評価を行い、表１にその結果を示した。
Example 1
Into a 500 ml separable flask, 255.0 g of DMAc was added, and 10.95 g (0.10 mol) of PDA and 28.12 g (0.096 mol) of BPDA were added thereto and reacted at room temperature and normal pressure for 1 hour. It was. Next, 2.25 g (0.011 mol) of ODA was added and stirred until uniform, then 3.68 g (0.017 mol) of PMDA was added and reacted for 1 hour to obtain a polyamic acid solution. In addition, 15g was taken from this polyamic-acid solution, and it apply | coated to the glass plate using the applicator, and after heat-drying for 20 minutes at 100 degreeC, the gel film was peeled from the glass plate. The ends of the gel film were pinned and biaxially stretched in the MD direction and the TD direction at the stretch ratios shown in Table 1. Then, after heating and drying at 200 ° C. for 20 minutes, 300 ° C. for 20 minutes, and subsequently at 400 ° C. for 20 minutes, pinning was removed to obtain a polyimide film having a thickness of about 30 μm. Each characteristic of this film was evaluated, and the results are shown in Table 1.
（実施例２）
実施例１と同様の手順で、芳香族ジアミン成分および芳香族テトラカルボン酸成分を表１に示すモル比、添加順、延伸比でそれぞれポリアミド酸を重合、ポリイミドフィルムを作製、各特性評価を行い、表１にその結果を示した。なお、各成分モル比は、全芳香族ジアミン成分中および全芳香族テトラカルボン酸成分中のモル比とする。
(Example 2)
In the same procedure as in Example 1, the aromatic diamine component and the aromatic tetracarboxylic acid component were polymerized with polyamic acid in the molar ratio, the order of addition, and the stretch ratio shown in Table 1, respectively, and a polyimide film was prepared, and each characteristic was evaluated. Table 1 shows the results. In addition, let each component molar ratio be the molar ratio in a wholly aromatic diamine component and a wholly aromatic tetracarboxylic acid component.
（比較例１〜３）
実施例１と同様の手順で、芳香族ジアミン成分および芳香族テトラカルボン酸成分を表１に示すモル比、添加順、延伸比でそれぞれポリアミド酸組成物を重合、ポリイミドフィルムを作製、各特性評価を行い、表１にその結果を示した。なお、各成分モル比は、全芳香族ジアミン成分中および全芳香族テトラカルボン酸成分中のモル比とした。
(Comparative Examples 1-3)
In the same procedure as in Example 1, the aromatic diamine component and the aromatic tetracarboxylic acid component were polymerized with the polyamic acid composition in the molar ratio, the order of addition, and the stretch ratio shown in Table 1, respectively, and a polyimide film was prepared. Table 1 shows the results. In addition, each component molar ratio was made into the molar ratio in a wholly aromatic diamine component and a wholly aromatic tetracarboxylic acid component.
（比較例４）
ＤＭＡｃ２３９．１ｇを用い、ここにＰＤＡ１．８７０ｇ（０．０１７３モル）とＰＭＤＡ３．６５９ｇ（０．０１６８モル）を投入し、常温常圧中で１時間反応させた。次にここにＯＤＡ２５．３９８ｇ（０．１２６８モル）を投入し均一になるまで撹拌した後、ＢＰＤＡ８．４８１ｇ（０．０２８８モル）を添加し、１時間反応させた。続いてここにＰＭＤＡ２１．４９１ｇ（０．０９８５モル）を添加してさらに１時間反応させポリアミド酸溶液を得た。尚この重合で各原料の添加モル比は、表２に示す割合で行い、このポリアミド酸溶液から厚さ約２５μｍのポリイミドフィルムを得た。このフィルムの各特性の評価を行い、表２に示した。
(Comparative Example 4)
239.1 g of DMAc was used, and 1.870 g (0.0173 mol) of PDA and 3.659 g (0.0168 mol) of PMDA were added thereto and reacted at room temperature and normal pressure for 1 hour. Next, ODA25.398g (0.1268mol) was thrown here and it stirred until it became uniform, Then, BPDA8.481g (0.0288mol) was added, and it was made to react for 1 hour. Subsequently, 21.491 g (0.0985 mol) of PMDA was added thereto, and the mixture was further reacted for 1 hour to obtain a polyamic acid solution. In this polymerization, the addition molar ratio of each raw material was carried out at the ratio shown in Table 2, and a polyimide film having a thickness of about 25 μm was obtained from this polyamic acid solution. The properties of this film were evaluated and are shown in Table 2.
（比較例５）
実施例１と同様の原料で、ただし、ＰＤＡ３．２７ｇ（３０．２ｍｍｏｌ）とＮ，Ｎ−ジメチルアセトアミド２２３．５８ｇとを入れ、ＰＭＤＡ６．５４ｇ（３０．０ｍｍｏｌ）を数回に分けて投入し窒素雰囲気下、室温で１時間撹拌した。次に、これにＯＤＡ２４．２５ｇ（１２１．１ｍｍｏｌ）を入れ、３０分攪拌した後、ＢＰＤＡ、１．３４ｇ（４．５ｍｍｏｌ）を数回に分けて投入し、さらに３０分攪拌した後、ＰＭＤＡ、２４．５１ｇ（１１２．４ｍｍｏｌ）を数回に分けて投入した。１時間撹拌した後、ＰＭＤＡのＮ，Ｎ’−ジメチルアセトアミド溶液（６重量％）１２．６８ｇを３０分かけて滴下し、さらに１時間撹拌した。得られたポリアミド酸組成物から、延伸を行わず実施例１と同様の方法を用いて、ポリイミドフィルム（平均膜厚３０μｍ）を得た。
(Comparative Example 5)
The same raw materials as in Example 1, except that 3.27 g (30.2 mmol) of PDA and 223.58 g of N, N-dimethylacetamide were added, and 6.54 g (30.0 mmol) of PMDA was added in several portions. Stir for 1 hour at room temperature under atmosphere. Next, 24.25 g (121.1 mmol) of ODA was added to this and stirred for 30 minutes, and then BPDA and 1.34 g (4.5 mmol) were added in several portions, and after stirring for another 30 minutes, PMDA, 24.51 g (112.4 mmol) was added in several portions. After stirring for 1 hour, 12.68 g of an N, N′-dimethylacetamide solution (6 wt%) of PMDA was added dropwise over 30 minutes, and the mixture was further stirred for 1 hour. From the obtained polyamic acid composition, a polyimide film (average film thickness 30 μm) was obtained using the same method as in Example 1 without stretching.
（比較例６）
比較例７と同様に、ただし表２に示すモノマーモル比でポリアミド酸組成物を重合した。得られたポリアミド酸組成物から、比較例７と同様にポリイミドフイルム（平均膜厚３０μｍ）を得た。
(Comparative Example 6)
Similar to Comparative Example 7, except that the polyamic acid composition was polymerized at the monomer molar ratio shown in Table 2. From the obtained polyamic acid composition, a polyimide film (average film thickness 30 μm) was obtained in the same manner as in Comparative Example 7.
得られたポリイミドフィルムについて、ヤング率、線膨張係数、およびガラス転移温度を測定した結果を表２に示した。 The obtained polyimide film was measured for Young's modulus, linear expansion coefficient, and glass transition temperature. Table 2 shows the results.
本発明のポリイミドフィルムは、ＣＯＦ用途に対して適切な弾性と柔軟性、高温域においても銅箔と同等の熱膨張性などの優れた物性を有し、さらに低いＴｇをもつＢＰＤＡ−ＯＤＡブロック成分が少なく、３５０℃以上のＴｇを有するため、高温熱処理によるフィルムの軟化を軽減することができる。 The polyimide film of the present invention has a suitable BPDA-ODA block component having excellent physical properties such as elasticity and flexibility suitable for COF applications, thermal expansion equivalent to copper foil even in a high temperature range, and having a lower Tg. Therefore, the film has a Tg of 350 ° C. or higher, so that softening of the film due to high-temperature heat treatment can be reduced.
Claims (7)
４，４´−ジアミノジフェニルエーテル：５０ｍｏｌ％未満〜１０ｍｏｌ％以上からなるジアミン成分ならびに
３，３´，４，４´−ビフェニルテトラカルボン酸二無水物：４５〜８７ｍｏｌ％および
ピロメリット酸二無水物：５５〜１３ｍｏｌ％からなるテトラカルボン酸成分からなるポリアミド酸組成物であって、
前記パラフェニレンジアミンと前記３，３´，４，４´−ビフェニルテトラカルボン酸二無水物の共重合体からなるブロック成分と
前記４，４´−ジアミノジフェニルエーテルと前記ピロメリット酸二無水物の共重合体からなるブロック成分とを含むことを特徴とするポリアミド酸組成物。 Paraphenylenediamine: more than 50 mol% to 90 mol% or less and 4,4′-diaminodiphenyl ether: a diamine component consisting of less than 50 mol% to 10 mol% or more and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride: A polyamic acid composition comprising a tetracarboxylic acid component comprising 45 to 87 mol% and pyromellitic dianhydride: 55 to 13 mol%,
A block component composed of a copolymer of the paraphenylenediamine and the 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, a co-polymer of the 4,4′-diaminodiphenyl ether and the pyromellitic dianhydride. A polyamic acid composition comprising a block component made of a polymer.
ガラス転移温度が３５０℃以上であり、
引張弾性率が５．８ＧＰａ以下である請求項２または３に記載のポリイミド。 The coefficient of thermal expansion in the temperature lowering process from 400 ° C. to 50 ° C. is −18 to −25 ppm / ° C.
The glass transition temperature is 350 ° C. or higher,
The polyimide according to claim 2 or 3, wherein the tensile elastic modulus is 5.8 GPa or less.
前記パラフェニレンジアミン１００ｍｏｌ％に対して前記３，３´，４，４´−ビフェニルテトラカルボン酸二無水物が９０〜１００ｍｏｌ％となる比率で、溶媒中で混合、反応させて、該パラフェニレンジアミンと該３，３´，４，４´−ビフェニルテトラカルボン酸二無水物のブロック共重合部分を得た後、
前記４，４´−ジアミノジフェニルエーテルを添加し、続いて前記ピロメリット酸二無水物を添加し、反応させて、該４，４´−ジアミノジフェニルエーテルと該ピロメリット酸二無水物のブロック共重合部分を得ることを特徴とするポリアミド酸組成物の製造方法。 A method for producing the polyamic acid composition according to claim 1,
The 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride is mixed in a solvent at a ratio of 90 to 100 mol% with respect to 100 mol% of the paraphenylenediamine, and the paraphenylenediamine is reacted. And a block copolymerized part of the 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride,
The 4,4'-diaminodiphenyl ether is added, and then the pyromellitic dianhydride is added and reacted to cause a block copolymer part of the 4,4'-diaminodiphenyl ether and the pyromellitic dianhydride. A process for producing a polyamic acid composition, characterized in that
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