JP2022545961A - Polyimide film and its manufacturing method - Google Patents
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 108
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 47
- 150000004985 diamines Chemical class 0.000 claims abstract description 30
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 30
- 239000011574 phosphorus Substances 0.000 claims abstract description 30
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 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 claims abstract description 21
- 230000003746 surface roughness Effects 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 27
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 18
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 12
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 12
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 12
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 12
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- AWYVETCHVQGXMB-UHFFFAOYSA-N (3-hydroxyphenyl) diphenyl phosphate Chemical compound OC1=CC=CC(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)=C1 AWYVETCHVQGXMB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- -1 phosphorus compound Chemical class 0.000 abstract description 4
- 239000004642 Polyimide Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 230000008646 thermal stress Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N Resorcinol Natural products OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
本発明は、バブルの個数が減少した高弾性の表面粗さが調節された高厚度ポリイミドフィルムおよびこれを含むポリイミドフィルムの製造方法に関し、ピロメリット酸二無水物（ＰＭＤＡ）を含む二無水物酸成分と、ジアミノジフェニルエーテル（ＯＤＡ）およびパラフェニレンジアミン（ＰＰＤ）で構成されたジアミン成分とを含むポリアミック酸溶液をイミド化反応させて得られ、球状シリカ粒子およびリン系化合物を含むポリイミドフィルムを提供する。TECHNICAL FIELD The present invention relates to a highly elastic polyimide film with a reduced number of bubbles and a high-thickness polyimide film with controlled surface roughness, and a method for producing a polyimide film including the same, wherein dianhydride acid including pyromellitic dianhydride (PMDA) Provided is a polyimide film obtained by imidizing a polyamic acid solution containing a component and a diamine component composed of diaminodiphenyl ether (ODA) and paraphenylenediamine (PPD) and containing spherical silica particles and a phosphorus compound. .
Description
本発明は、ポリイミドフィルムに関し、さらに詳しくは、高弾性であって、表面粗さが制御されており、製造されたフィルムにバブルの個数を減少させた高厚度ポリイミドフィルムおよびその製造方法に関する。 TECHNICAL FIELD The present invention relates to a polyimide film, and more particularly, to a high thickness polyimide film having high elasticity, controlled surface roughness, and a reduced number of bubbles in the film produced, and a method for producing the same.
ポリイミド（ｐｏｌｙｉｍｉｄｅ、ＰＩ）は、剛直な芳香族主鎖と共に、化学的安定性が非常に優れたイミド環に基づいて、有機材料の中でも最高水準の耐熱性、耐薬品性、電気絶縁性、耐化学性、耐候性を有する高分子材料である。ポリイミドフィルムは、前述した特性が要求される多様な電子デバイスの素材として注目されている。
現在、大部分のポリイミドは、ポリアミック酸（ｐｏｌｙ（ａｍｉｃ ａｃｉｄ））形態で有機溶媒に溶解し、ポリイミドになると溶解しないため、ポリイミドの加工はポリアミック酸の溶液を用いており、その溶液を乾燥させることにより、所望のフィルムや成形物、コーティング膜を得た後に加熱し、イミド化させることによって製造されることが一般的である。
Polyimide (PI) has the highest level of heat resistance, chemical resistance, electric It is a polymer material with chemical properties and weather resistance. Polyimide films are attracting attention as materials for various electronic devices that require the above properties.
At present, most polyimides are dissolved in organic solvents in the form of poly(amic acid), and polyimides are not dissolved, so polyimide processing uses a solution of polyamic acid, and the solution is dried. Therefore, it is common to produce a desired film, molded article, or coating film by heating and imidization after obtaining the desired film, molded article, or coating film.
一方、最近、ポリイミドフィルムおよびその積層体をイミド化温度から室温に冷却する過程で発生する熱応力はよくカーリング、膜の剥離、割れなどの深刻な問題を生じている。特に、急速に進められている電子回路の高密度化とともに、多層配線基板の採用などにおいて熱応力による問題は深刻に受け止められている。すなわち、熱応力によって膜の剥離や割れには及ばなくても、多層基板における熱応力の残留はデバイスの信頼性を著しく低下させるからである。
このような熱応力の影響を減少させることができる方策としてはポリイミドの低膨張化が考慮されているが、低熱膨張係数を示すポリイミドは、一般的に剛直で直線的な主鎖構造を有しているため、水蒸気透過性が悪く、製膜条件によっては発泡を起こしやすいという問題点がある。すなわち、分子パッキングが密になるため、フィルムの水蒸気透過性が悪く、フィルムの製造工程においてよく内部にバブル（気泡、エアなど）が発生する。このようなバブルの発生は、製造されたポリイミドフィルムの表面粗さに悪影響を及ぼすだけでなく、ポリイミドフィルムの電気的、光学的、機械的特性を全体的に低下させることがある。
したがって、低膨張係数を示すポリイミドの耐熱性などの本来の特性を維持しながらも高弾性、低粗度の特性を有すると同時に、ポリイミドフィルムのバブルを減少させることができる方策が要求されている。
以上の背景技術に記載された事項は発明の背景に対する理解のためのものであって、この技術の属する分野における通常の知識を有する者にすでに知られた従来技術でない事項を含むことができる。
On the other hand, recently, the thermal stress generated in the process of cooling the polyimide film and its laminate from the imidization temperature to room temperature often causes serious problems such as curling, peeling and cracking of the film. In particular, along with the rapid increase in the density of electronic circuits, the problem of thermal stress is being taken seriously in the adoption of multi-layer wiring boards and the like. That is, even if the thermal stress does not lead to peeling or cracking of the film, the residual thermal stress in the multi-layer substrate significantly lowers the reliability of the device.
As a measure to reduce the influence of such thermal stress, it is considered to reduce the expansion of polyimide. Therefore, there is a problem that the water vapor permeability is poor and foaming is likely to occur depending on the film forming conditions. That is, since the molecular packing becomes dense, the water vapor permeability of the film is poor, and bubbles (bubbles, air, etc.) are often generated inside during the manufacturing process of the film. The occurrence of such bubbles not only adversely affects the surface roughness of the produced polyimide film, but also may degrade the electrical, optical and mechanical properties of the polyimide film as a whole.
Therefore, there is a demand for a method capable of reducing bubbles in polyimide films while maintaining the original properties of polyimide, such as heat resistance, which exhibits a low expansion coefficient, while maintaining high elasticity and low roughness properties. .
The above background information is provided for understanding the background of the invention and may include non-prior art material already known to those of ordinary skill in the art.
そこで、本発明は、表面粗さが制御された高弾性の高厚度ポリイミドフィルムを提供することを目的とする。
しかし、本発明が解決しようとする課題は以上に言及した課題に制限されず、言及されていないさらに他の課題は下記の記載から当業者に明確に理解されるであろう。
Accordingly, an object of the present invention is to provide a highly elastic, thick polyimide film with controlled surface roughness.
However, the problems to be solved by the present invention are not limited to the problems mentioned above, and still other problems not mentioned will be clearly understood by those skilled in the art from the following description.
上記の目的を達成するための、本発明の一側面は、ピロメリット酸二無水物（ｐｙｒｏｍｅｌｌｉｔｉｃ ｄｉａｈｙｄｒｉｄｅ、ＰＭＤＡ）を含む二無水物酸成分と、ジアミノジフェニルエーテル（４，４’－ｏｘｙｄｉａｎｉｌｉｎｅ、ＯＤＡ）およびパラフェニレンジアミン（ｐ－ｐｈｅｎｙｌｅｎｅ ｄｉａｍｉｎｅ、ＰＰＤ）で構成されたジアミン成分とを含むポリアミック酸溶液をイミド化反応させて得られ、
前記ジアミン成分の総含有量１００モル％を基準として、前記パラフェニレンジアミン（ＰＰＤ）の含有量が４０モル％以上５５モル％以下であり、前記ジアミノジフェニルエーテル（ＯＤＡ）の含有量が４５モル％以上６０モル％以下であり、
球状シリカ粒子およびリン（Ｐ）系化合物を含むポリイミドフィルムを提供する。
本発明の他の側面は、前記球状シリカ粒子の平均径が１μｍ以下である前記ポリイミドフィルムを提供する。
本発明のさらに他の側面は、前記リン系化合物が、前記二無水物酸成分および前記ジアミン成分の固形分対比０．１重量％超過３重量％未満含む前記ポリイミドフィルムを提供する。
本発明のさらに他の側面は、前記リン系化合物が、トリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）、トリキシレニルホスフェート（Ｔｒｉｘｙｌｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＸＰ）、トリクレシルホスフェート（Ｔｒｉｃｒｅｓｙｌ ｐｈｏｓｐｈａｔｅ、ＴＣＰ）、レゾルシノールジフェニルホスフェート（Ｒｅｓｏｒｃｉｎｏｌ ｄｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ）、およびアンモニウムポリホスフェート（ａｍｍｏｎｉｕｍ ｐｏｌｙｐｈｏｓｐｈａｔｅ）からなるグループより選択されたいずれか１つ以上である前記ポリイミドフィルムを提供する。
本発明のさらに他の側面は、弾性率が５ＧＰａ以上であり、表面粗さが０．００５μｍ以下であり、厚さが７０μｍ以上である前記ポリイミドフィルムを提供する。
本発明のさらに他の側面は、１ｍ2あたりのバブルの個数が５０個未満であるポリイミドフィルムを提供する。
本発明のさらに他の側面は、（ａ）ピロメリット酸二無水物（ＰＭＤＡ）を含む二無水物酸成分と、ジアミノジフェニルエーテル（ＯＤＡ）およびパラフェニレンジアミン（ＰＰＤ）で構成されたジアミン成分とを有機溶媒中にて重合してポリアミック酸を製造する第１ステップと、
（ｂ）前記第１ステップの前記ポリアミック酸に平均径が１μｍ以下の球状シリカ粒子を追加して混合する第２ステップと、
（ｃ）前記第２ステップの前記ポリアミック酸にイミド化触媒とリン（Ｐ）系化合物とを追加して混合する第３ステップと、
（ｃ）前記第３ステップの前記ポリアミック酸をイミド化する第４ステップとを含み、
前記ジアミン成分の総含有量１００モル％を基準として、前記パラフェニレンジアミン（ＰＰＤ）の含有量が４０モル％以上５５モル％以下であり、前記ジアミノジフェニルエーテル（ＯＤＡ）の含有量が４５モル％以上６０モル％以下であるポリイミドフィルムの製造方法を提供する。
本発明のさらに他の側面は、前記第２ステップが、ピロメリット酸二無水物（ＰＭＤＡ）溶液を添加して、最終粘度を１００，０００～１２０，０００ｃＰとする前記ポリイミドフィルムの製造方法を提供する。
本発明のさらに他の側面は、前記リン系化合物が、前記二無水物酸成分および前記ジアミン成分の固形分対比０．１重量％超過３重量％未満含むポリイミドフィルムの製造方法を提供する。
本発明のさらに他の側面は、前記リン系化合物が、トリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）、トリキシレニルホスフェート（Ｔｒｉｘｙｌｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＸＰ）、トリクレシルホスフェート（Ｔｒｉｃｒｅｓｙｌ ｐｈｏｓｐｈａｔｅ、ＴＣＰ）、レゾルシノールジフェニルホスフェート（Ｒｅｓｏｒｃｉｎｏｌ ｄｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ）、およびアンモニウムポリホスフェート（ａｍｍｏｎｉｕｍ ｐｏｌｙｐｈｏｓｐｈａｔｅ）からなるグループより選択されたいずれか１つ以上である前記ポリイミドフィルムの製造方法を提供する。
本発明のさらに他の側面は、前記ポリイミドフィルムの弾性率が５ＧＰａ以上であり、表面粗さが０．００５μｍ以下であり、厚さが７０μｍ以上である前記ポリイミドフィルムの製造方法を提供する。
本発明のさらに他の側面は、前記ポリイミドフィルムを含む保護フィルムを提供する。
本発明のさらに他の側面は、前記ポリイミドフィルムを含むキャリアフィルムを提供する。
In order to achieve the above objects, one aspect of the present invention is a dianhydride acid component comprising pyromellitic dianhydride (PMDA), diaminodiphenyl ether (4,4'-oxydianiline, ODA) and Obtained by imidizing a polyamic acid solution containing a diamine component composed of p-phenylene diamine (PPD),
Based on the total content of 100 mol% of the diamine component, the content of the paraphenylenediamine (PPD) is 40 mol% or more and 55 mol% or less, and the content of the diaminodiphenyl ether (ODA) is 45 mol% or more. 60 mol% or less,
Provided is a polyimide film containing spherical silica particles and a phosphorus (P)-based compound.
Another aspect of the present invention provides the polyimide film, wherein the spherical silica particles have an average diameter of 1 μm or less.
Still another aspect of the present invention provides the polyimide film, wherein the phosphorus-based compound comprises more than 0.1% by weight and less than 3% by weight based on the solid content of the dianhydride component and the diamine component.
In still another aspect of the present invention, the phosphorus-based compound is triphenyl phosphate (TPP), trixylenyl phosphate (TXP), tricresyl phosphate (TCP), resorcinol diphenyl The polyimide film is one or more selected from the group consisting of phosphate (resorcinol diphenyl phosphate) and ammonium polyphosphate.
Still another aspect of the present invention provides the polyimide film having an elastic modulus of 5 GPa or more, a surface roughness of 0.005 μm or less, and a thickness of 70 μm or more.
Yet another aspect of the invention provides a polyimide film having less than 50 bubbles per square meter.
Yet another aspect of the present invention provides (a) a dianhydride acid component comprising pyromellitic dianhydride (PMDA) and a diamine component composed of diaminodiphenyl ether (ODA) and paraphenylenediamine (PPD). a first step of polymerizing in an organic solvent to produce a polyamic acid;
(b) a second step of adding and mixing spherical silica particles having an average diameter of 1 μm or less to the polyamic acid of the first step;
(c) a third step of adding an imidization catalyst and a phosphorus (P)-based compound to the polyamic acid of the second step and mixing;
(c) a fourth step of imidizing the polyamic acid of the third step;
Based on the total content of 100 mol% of the diamine component, the content of the paraphenylenediamine (PPD) is 40 mol% or more and 55 mol% or less, and the content of the diaminodiphenyl ether (ODA) is 45 mol% or more. Provided is a method for producing a polyimide film having a content of 60 mol % or less.
Still another aspect of the present invention provides the method for producing the polyimide film, wherein the second step includes adding a pyromellitic dianhydride (PMDA) solution to make the final viscosity 100,000 to 120,000 cP. do.
Yet another aspect of the present invention provides a method for producing a polyimide film, wherein the phosphorus-based compound comprises more than 0.1% by weight and less than 3% by weight of the solid content of the dianhydride component and the diamine component.
In still another aspect of the present invention, the phosphorus-based compound is triphenyl phosphate (TPP), trixylenyl phosphate (TXP), tricresyl phosphate (TCP), resorcinol diphenyl Provided is a method for producing the polyimide film, which is at least one selected from the group consisting of phosphate (resorcinol diphenyl phosphate) and ammonium polyphosphate.
Still another aspect of the present invention provides a method for producing the polyimide film, wherein the polyimide film has an elastic modulus of 5 GPa or more, a surface roughness of 0.005 μm or less, and a thickness of 70 μm or more.
Yet another aspect of the present invention provides a protective film including the polyimide film.
Yet another aspect of the present invention provides a carrier film comprising the polyimide film.
本発明は、ジアミン成分の組成比、固形分含有量が調節され、球状シリカ粒子とリン系化合物とを含むポリイミドフィルムを提供することにより、５ＧＰａ以上の弾性率と０．００５μｍ以下の表面粗さを有する厚さが７０μｍ以上の高厚度ポリイミドフィルムを提供する。
また、製造されたポリイミドフィルムは、フィルムの厚さが７０μｍ以上と比較的厚いフィルムであるにもかかわらず、フィルムのバブルの個数が５０個／ｍ2未満と観察され、リン系化合物の含有量の変化によって観察されるバブルが存在しない優れた品質の高厚度フィルムを得ることができた。
このようなポリイミドフィルムは、高弾性の優れた機械的特性のみならず、表面粗さが低くバブル形成が抑制されて、特に表面品質が改善されるので、このような多様な特性のポリイミドフィルムが要求される分野に適用可能である。
The present invention provides a polyimide film containing spherical silica particles and a phosphorus-based compound, in which the composition ratio of the diamine component and the solid content are adjusted, and which has an elastic modulus of 5 GPa or more and a surface roughness of 0.005 μm or less. A thick polyimide film having a thickness of 70 μm or more is provided.
In addition, although the polyimide film produced was relatively thick with a film thickness of 70 μm or more, the number of bubbles in the film was observed to be less than 50/m 2 , and the phosphorus compound content was A high thickness film of excellent quality could be obtained without the presence of bubbles observed by the change in .
Such a polyimide film not only has excellent mechanical properties such as high elasticity, but also has low surface roughness and suppresses bubble formation, thereby improving surface quality. Applicable to required fields.
本明細書および特許請求の範囲に使われた用語や単語は、通常または辞書的な意味に限定して解釈されてはならず、発明者は自らの発明を最善の方法で説明するために用語の概念を適切に定義できるという原則に則って本発明の技術的思想に符合する意味と概念で解釈されなければならない。
したがって、本明細書に記載された実施例の構成は、本発明の最も好ましい一つの実施例に過ぎず、本発明の技術的思想をすべて代弁するものではないので、本出願時点においてこれらを代替できる多様な均等物と変形例が存在し得ることを理解しなければならない。
Terms and words used in the specification and claims should not be construed as being limited to their ordinary or dictionary meaning, and the inventors have used the terms to best describe their invention. should be construed with a meaning and concept consistent with the technical idea of the present invention on the principle that the concept of can be properly defined.
Therefore, the configurations of the embodiments described in this specification are merely one of the most preferred embodiments of the present invention, and do not represent all the technical ideas of the present invention. It must be understood that there may be various possible equivalents and variations.
本明細書において、単数の表現は文脈上明らかに異なって意味しない限り、複数の表現を含む。本明細書において、「含む」、「備える」または「有する」などの用語は、実施された特徴、数字、段階、構成要素またはこれらを組み合わせたものが存在することを指定しようとするものであって、１つまたはそれ以上の他の特徴や数字、段階、構成要素またはこれらを組み合わせたものの存在または付加の可能性を予め排除しないことが理解されなければならない。
本明細書において、「二無水物酸」は、その前駆体または誘導体を含むと意図されるが、これらは、技術的には二無水物酸でないかも知れないが、それにもかかわらず、ジアミンと反応してポリアミック酸を形成するはずであり、このポリアミック酸は再度ポリイミドに変換される。
本明細書において、量、濃度、または他の値またはパラメータが範囲、好ましい範囲または好ましい上限値および好ましい下限値の列挙として与えられる場合、範囲が別途に開示されるかに関係なく、任意の一対の任意の上側範囲の限界値または好ましい値、および任意の下側範囲の限界値または好ましい値で形成されたすべての範囲を具体的に開示すると理解されなければならない。
数値の範囲が本明細書において言及される場合、他に記述されなければ、その範囲はその終点およびその範囲内のすべての整数と分数を含むと意図される。本発明の範疇は、範囲を定義する時に言及される特定値に限定されないと意図される。
In this specification, singular terms include plural terms unless the context clearly dictates otherwise. As used herein, terms such as "include,""comprise," or "have" are intended to specify the presence of implemented features, numbers, steps, components, or combinations thereof. does not preclude the presence or addition of one or more other features, figures, steps, components or combinations thereof.
As used herein, "dianhydride acid" is intended to include precursors or derivatives thereof, which may technically not be dianhydride acids but nevertheless diamines and It should react to form polyamic acid, which is converted back to polyimide.
As used herein, when an amount, concentration, or other value or parameter is given as a range, a preferred range or a list of upper and preferred lower limits, any pair of It should be understood to specifically disclose all ranges formed from any upper range limit or preferred value and any lower range limit or preferred value of .
When a numerical range is referred to herein, unless otherwise stated, the range is intended to include the endpoints and all integers and fractions within the range. It is intended that the scope of the invention not be limited to the specific values recited in defining the range.
本発明の一実施形態によるポリイミドフィルムは、ピロメリット酸二無水物（ＰＭＤＡ）を含む二無水物酸成分と、ジアミノジフェニルエーテル（ＯＤＡ）およびパラフェニレンジアミン（ＰＰＤ）で構成されたジアミン成分とを含むポリアミック酸溶液をイミド化反応させて得られる。
前記ジアミン成分の総含有量１００モル％を基準として、前記パラフェニレンジアミン（ＰＰＤ）の含有量が４０モル％以上５５モル％以下であり、前記ジアミノジフェニルエーテル（ＯＤＡ）の含有量が４５モル％以上６０モル％以下であり、球状シリカ粒子およびリン（Ｐ）系化合物を含んでいる。パラフェニレンジアミン（ＰＰＤ）は、剛直なモノマーとしてパラフェニレンジアミン（ＰＰＤ）の含有量が増加するに伴って、合成されるポリイミドはさらに線状の構造を有するようになり、ポリイミドの弾性率などの機械的特性の向上に寄与する。
ジアミン成分の総量を基準として、パラフェニレンジアミン（ＰＰＤ）を４０モル％未満使用する場合（ジアミノジフェニルエーテル（ＯＤＡ）を６０モル％超過で使用する場合）、高厚度（フィルムの厚さが７０μｍ以上）ポリイミドフィルムの弾性率が低下することがある。
また、ジアミン成分の総量を基準として、パラフェニレンジアミンを５５モル％超過で使用する場合（ジアミノジフェニルエーテル（ＯＤＡ）を４５モル％未満で使用する場合）、特に１５重量％を超える固形分を含む場合には、２次結合によるゲル（ｇｅｌ）化が進行して高厚度ポリイミドフィルムを生産しにくいことがある。
A polyimide film according to one embodiment of the present invention includes a dianhydride acid component including pyromellitic dianhydride (PMDA) and a diamine component composed of diaminodiphenyl ether (ODA) and paraphenylenediamine (PPD). It is obtained by imidizing a polyamic acid solution.
Based on the total content of 100 mol% of the diamine component, the content of the paraphenylenediamine (PPD) is 40 mol% or more and 55 mol% or less, and the content of the diaminodiphenyl ether (ODA) is 45 mol% or more. It is 60 mol % or less and contains spherical silica particles and a phosphorus (P) compound. Paraphenylenediamine (PPD) is a rigid monomer, and as the content of paraphenylenediamine (PPD) increases, the polyimide synthesized has a more linear structure, and the elastic modulus of polyimide, etc. Contributes to the improvement of mechanical properties.
When using less than 40 mol% of paraphenylenediamine (PPD) (when using more than 60 mol% of diaminodiphenyl ether (ODA)) based on the total amount of diamine components, high thickness (film thickness of 70 μm or more) The modulus of elasticity of the polyimide film may decrease.
Also, based on the total amount of diamine components, when paraphenylenediamine is used in excess of 55 mol% (when diaminodiphenyl ether (ODA) is used in an amount of less than 45 mol%), especially when the solid content exceeds 15% by weight However, it may be difficult to produce a thick polyimide film due to gelation due to secondary bonding.
一方、パラフェニレンジアミン（ＰＰＤ）を含む高厚度ポリイミドフィルムは、厚さが増加するに伴って気泡の発生が頻繁になる。
このような気泡発生の増加は、パラフェニレンジアミン（ＰＰＤ）の含有量の増加に伴って、合成されたポリイミド鎖がさらに線状の形態を有するようになり、線状のポリイミド鎖は、ポリイミド鎖間の結合が強くなって溶媒および水の蒸発が困難になるためと考えられる。ポリイミドフィルムに生成された気泡は、ポリイミドフィルムの外観、機械的特性に大きく影響を及ぼす品質不良に相当し、製造されたポリイミドフィルムの他の特性に優れているとしても、多数の気泡が生成されたポリイミドフィルムは実際の製品に適用されにくい。
そこで、パラフェニレンジアミン（ＰＰＤ）が誘発したポリイミド鎖間の強力な結合に自由体積（ｆｒｅｅ ｖｏｌｕｍｅ）を付与してポリイミド鎖間の柔軟性を増加させることができる可塑剤特性を有するリン系化合物を添加した。このようなリン系化合物の添加によってポリイミドフィルムに形成される気泡の数が大きく減少することを確認した。
On the other hand, high-thickness polyimide films containing paraphenylenediamine (PPD) frequently generate air bubbles as the thickness increases.
This increase in bubble generation is accompanied by an increase in the content of paraphenylenediamine (PPD), and the polyimide chains synthesized have a more linear morphology, and the linear polyimide chains are This is probably because the bond between them becomes stronger and the solvent and water become difficult to evaporate. The bubbles generated in the polyimide film correspond to quality defects that greatly affect the appearance and mechanical properties of the polyimide film. Polyimide films are difficult to apply to actual products.
Therefore, a phosphorus-based compound having plasticizer properties that can increase the flexibility between polyimide chains by adding free volume to the strong bonds between polyimide chains induced by paraphenylenediamine (PPD). added. It was confirmed that the number of bubbles formed in the polyimide film was greatly reduced by adding the phosphorus-based compound.
本発明の他の実施形態によれば、ポリイミドフィルムに含まれる球状シリカ粒子の平均径が１μｍ以下で、シリカ粒子の平均径は、好ましくは８００ｎｍ以下であり、さらに好ましくは５００ｎｍ以下であってもよい。
球状シリカ粒子はポリイミドフィルムに含まれて、ポリイミドフィルムの表面に粗さが現れるようにして、ポリイミドフィルムが生産または使用中に互いに付着する現象を防止するアンチブロッキング（ａｎｉｔｉ ｂｌｏｃｋｉｎｇ）特性を付与する。シリカ粒子は、ポリイミドフィルムの添加剤として通常使用されるが、特に、球状シリカ粒子が無定形シリカ粒子に比べてアンチブロッキング特性に優れている。
球状シリカ粒子の平均径が１μｍを超える場合、表面粗さが大きくなってポリイミドフィルムと接する対象の表面にスクラッチを誘発させて製品不良が発生し、球状シリカ粒子の平均径が０．１μｍ未満の場合、フィルムのブロッキング現象を防止するアンチブロッキング特性が発現しない。
球状シリカ粒子は、ポリイミドフィルムの重量を基準として１，０００～３，０００ｐｐｍ含むことができるが、これに制限されるものではない。通常、球状シリカ粒子が３，０００ｐｐｍ超過で使用されると、粒子同士で凝集してフィルムに結合が現れ、１，０００ｐｐｍ未満で使用されると、フィルムの表面処理後にフィルム同士でくっつく現象によって巻取ステップの進行において困難が発生する。
According to another embodiment of the present invention, the average diameter of the spherical silica particles contained in the polyimide film is 1 μm or less, and the average diameter of the silica particles is preferably 800 nm or less, more preferably 500 nm or less. good.
The spherical silica particles are included in the polyimide film to make the surface of the polyimide film appear rough, thereby imparting anti-blocking properties to prevent the polyimide film from adhering to each other during production or use. Silica particles are commonly used as an additive for polyimide films. In particular, spherical silica particles are superior in anti-blocking properties to amorphous silica particles.
If the average diameter of the spherical silica particles exceeds 1 μm, the surface roughness increases and scratches are induced on the surface of the object that is in contact with the polyimide film, resulting in product defects. In this case, the anti-blocking property to prevent the blocking phenomenon of the film is not developed.
The spherical silica particles may be included in an amount of 1,000 to 3,000 ppm based on the weight of the polyimide film, but is not limited thereto. In general, when the spherical silica particles are used at more than 3,000 ppm, the particles agglomerate to form bonds in the film, and when the spherical silica particles are used at less than 1,000 ppm, the films stick together after surface treatment. Difficulties arise in the progress of the acquisition steps.
本発明の他の実施形態によれば、バブル形成の抑制に使用される可塑剤特性を有するリン系化合物は、ポリイミドの合成に使用された二無水物酸成分およびジアミン成分の固形分対比０．１重量％超過３重量％未満含むことができ、特に０．５～２．５重量％含むことが好ましく、２．０～２．５重量％含むことがさらに好ましい。リン系化合物を０．１重量％以下で含むと、バブル形成抑制の効果が十分に現れず、３重量％以上を含むと、ポリイミドフィルムの弾性率が減少する。
また、使用されるリン系化合物としては、トリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）およびアンモニウムポリホスフェート（ａｍｍｏｎｉｕｍ ｐｏｌｙｐｈｏｓｐｈａｔｅ）、トリキシレニルホスフェート（Ｔｒｉｘｙｌｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＸＰ）、トリクレシルホスフェート（Ｔｒｉｃｒｅｓｙｌ ｐｈｏｓｐｈａｔｅ、ＴＣＰ）、レゾルシノールジフェニルホスフェート（Ｒｅｓｏｒｃｉｎｏｌ ｄｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ）、およびアンモニウムポリホスフェート（ａｍｍｏｎｉｕｍ ｐｏｌｙｐｈｏｓｐｈａｔｅ）が挙げられる。
特に、トリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）およびアンモニウムポリホスフェート（ａｍｍｏｎｉｕｍ ｐｏｌｙｐｈｏｓｐｈａｔｅ）のいずれか１つ以上を使用することが好ましいが、これに制限されるものではなく、自由体積（ｆｒｅｅ ｖｏｌｕｍｅ）を付与してポリイミド鎖間の柔軟性を増加させることができる可塑剤特性を有するリン系化合物の中でバブル形成の抑制に寄与できるリン系化合物は、いかなる化合物でも使用可能である。
According to another embodiment of the present invention, the phosphorus-based compound with plasticizer properties used to inhibit bubble formation is 0.00% of the solids content of the dianhydride acid component and the diamine component used in the synthesis of the polyimide. More than 1% by weight and less than 3% by weight, particularly preferably 0.5 to 2.5% by weight, more preferably 2.0 to 2.5% by weight. If the phosphorus compound is contained in an amount of 0.1% by weight or less, the effect of suppressing bubble formation is not sufficiently exhibited, and if it is contained in an amount of 3% by weight or more, the elastic modulus of the polyimide film is reduced.
Phosphorus compounds used include triphenyl phosphate (TPP), ammonium polyphosphate, trixylenyl phosphate (TXP), tricresyl phosphate (TCP), ), Resorcinol diphenyl phosphate, and ammonium polyphosphate.
In particular, it is preferable to use one or more of triphenyl phosphate (TPP) and ammonium polyphosphate (ammonium polyphosphate). Among the phosphorus-based compounds having plasticizer properties that can be imparted to increase flexibility between polyimide chains, any phosphorus-based compound that can contribute to suppression of bubble formation can be used.
本発明の前記実施形態によるポリイミドフィルムは、弾性率が５ＧＰａ以上であり、表面粗さが０．００５μｍ以下であり、厚さが７０μｍ以上である高弾性、低粗度の特性を同時に有する高厚度ポリイミドフィルムである。
前記ポリイミドフィルムの弾性率は、パラフェニレンジアミン（ＰＰＤ）の含有量調節により５ＧＰａ以上の優れた弾性率を示し、このような優れた弾性率のポリイミドフィルムは多様な方面に適用可能であるが、特にキャリアフィルムや保護フィルムに適する。
また、前記ポリイミドフィルムは、低い表面粗さを示すが、これは、球状シリカ粒子の平均径と直接的な関連性があり、通常、球状シリカ粒子の平均径が大きくなるほど、表面粗さも大きくなる。平均径が１μｍを超える球状シリカ粒子を用いる場合、表面粗さが０．００５μｍを超えるようになり、上述のように、このような表面粗さの増加は、ポリイミドフィルムと接する対象の表面にスクラッチを誘発させて製品不良をもたらす。
これとともに、前記ポリイミドフィルムの７０μｍ以上の厚さを有する高厚度ポリイミドフィルムで、前記ポリイミドのフィルムの厚さは７５μｍ以上であることが好ましい。
前記ポリイミドフィルムは、１ｍ2あたりのバブルの個数が５０個未満で、バブルの個数は添加されるリン系化合物の含有量の増加に伴って減少する。リン系化合物の含有量を適宜調節することにより、バブルの個数を最小化（観察によってバブルの存在が確認されない）しながらも、製品の適用に適切な弾性率および表面粗さを維持することができる。
The polyimide film according to the embodiment of the present invention has an elastic modulus of 5 GPa or more, a surface roughness of 0.005 μm or less, and a thickness of 70 μm or more, which simultaneously exhibits high elasticity and low roughness. Polyimide film.
The elastic modulus of the polyimide film exhibits an excellent elastic modulus of 5 GPa or more by adjusting the content of paraphenylenediamine (PPD), and the polyimide film with such an excellent elastic modulus can be applied in various fields. Especially suitable for carrier films and protective films.
In addition, the polyimide film exhibits low surface roughness, which is directly related to the average diameter of the spherical silica particles, and generally, the larger the average diameter of the spherical silica particles, the greater the surface roughness. . When using spherical silica particles with an average diameter greater than 1 μm, the surface roughness becomes greater than 0.005 μm, and as described above, such an increase in surface roughness causes scratches on the surface of the object in contact with the polyimide film. and lead to product defects.
In addition, it is preferable that the polyimide film is a high-thickness polyimide film having a thickness of 70 μm or more, and the thickness of the polyimide film is 75 μm or more.
The number of bubbles per square meter of the polyimide film is less than 50, and the number of bubbles decreases as the content of the added phosphorus-based compound increases. By adjusting the content of the phosphorus-based compound appropriately, it is possible to minimize the number of bubbles (the presence of bubbles is not confirmed by observation) while maintaining the appropriate elastic modulus and surface roughness for product application. can.
本発明の他の実施形態は、（ａ）ピロメリット酸二無水物（ＰＭＤＡ）を含む二無水物酸成分と、ジアミノジフェニルエーテル（ＯＤＡ）およびパラフェニレンジアミン（ＰＰＤ）で構成されたジアミン成分とを有機溶媒中にて重合してポリアミック酸を製造する第１ステップと、
（ｂ）前記第１ステップの前記ポリアミック酸に平均径が１μｍ以下の球状シリカ粒子を追加して混合する第２ステップと、
（ｃ）前記第２ステップの前記ポリアミック酸にイミド化触媒とリン（Ｐ）系化合物とを追加して混合する第３ステップと、
（ｃ）前記第３ステップの前記ポリアミック酸をイミド化する第４ステップとを含み、
前記ジアミン成分の総含有量１００モル％を基準として、前記パラフェニレンジアミン（ＰＰＤ）の含有量が４０モル％以上５５モル％以下であり、前記ジアミノジフェニルエーテル（ＯＤＡ）の含有量が４５モル％以上６０モル％以下である、ポリイミドフィルムの製造方法に関する。
すなわち、本発明のポリイミドフィルムの製造方法において、球状シリカ粒子は、二無水物酸成分とジアミン成分とを含むポリアミック酸溶液の製造後、添加されて混合された後、順次にイミド化触媒とリン系化合物とが添加されて混合され、以後、イミド化反応してポリイミドフィルムが形成される。ポリアミック酸をイミド化する方法は、熱イミド化方法または化学的イミド化方法が適用可能であり、熱イミド化方法と化学的イミド化方法とを併行する方法も適用可能である。ここで、熱イミド化方法は、化学的触媒を排除し、熱風や赤外線乾燥機などの熱源でイミド化反応を誘導する方法であり、化学的イミド化方法は、脱水剤およびイミド化剤を用いる方法である。
前記第２ステップは、ピロメリット酸二無水物（ＰＭＤＡ）溶液を添加して、最終粘度を１００，０００～１２０，０００ｃＰとすれば良いが、これに制限されるものではない。
また、前記リン系化合物は、前記二無水物酸成分および前記ジアミン成分の固形分対比０．１重量％超過３重量％未満含むことができる。前記リン系化合物としては、トリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）、トリキシレニルホスフェート（Ｔｒｉｘｙｌｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＸＰ）、トリクレシルホスフェート（Ｔｒｉｃｒｅｓｙｌ ｐｈｏｓｐｈａｔｅ、ＴＣＰ）、レゾルシノールジフェニルホスフェート（Ｒｅｓｏｒｃｉｎｏｌ ｄｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ）、アンモニウムポリホスフェート（ａｍｍｏｎｉｕｍ ｐｏｌｙｐｈｏｓｐｈａｔｅ）などが挙げられる。特に、トリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）およびアンモニウムポリホスフェート（ａｍｍｏｎｉｕｍ ｐｏｌｙｐｈｏｓｐｈａｔｅ）のいずれか１つ以上を使用することが好ましいが、これに制限されるものではなく、自由体積（ｆｒｅｅ ｖｏｌｕｍｅ）を付与してポリイミド鎖間の柔軟性を増加させることができる可塑剤特性を有するリン系化合物の中でバブル形成の抑制に寄与できるリン系化合物は、いかなる化合物でも使用可能である。
Another embodiment of the present invention provides (a) a dianhydride acid component comprising pyromellitic dianhydride (PMDA) and a diamine component composed of diaminodiphenyl ether (ODA) and paraphenylenediamine (PPD). a first step of polymerizing in an organic solvent to produce a polyamic acid;
(b) a second step of adding and mixing spherical silica particles having an average diameter of 1 μm or less to the polyamic acid of the first step;
(c) a third step of adding an imidization catalyst and a phosphorus (P)-based compound to the polyamic acid of the second step and mixing;
(c) a fourth step of imidizing the polyamic acid of the third step;
Based on the total content of 100 mol% of the diamine component, the content of the paraphenylenediamine (PPD) is 40 mol% or more and 55 mol% or less, and the content of the diaminodiphenyl ether (ODA) is 45 mol% or more. The present invention relates to a method for producing a polyimide film having a polyimide film content of 60 mol % or less.
That is, in the method for producing a polyimide film of the present invention, the spherical silica particles are added and mixed after the production of the polyamic acid solution containing the dianhydride component and the diamine component, and then the imidization catalyst and the phosphorus are sequentially added. A polyimide film is formed by adding and mixing a system compound, followed by an imidization reaction. As a method for imidizing the polyamic acid, a thermal imidization method or a chemical imidization method can be applied, and a method combining the thermal imidization method and the chemical imidization method can also be applied. Here, the thermal imidization method is a method in which a chemical catalyst is eliminated and the imidization reaction is induced by a heat source such as hot air or an infrared dryer, and the chemical imidization method uses a dehydrating agent and an imidizing agent. The method.
In the second step, pyromellitic dianhydride (PMDA) solution is added to obtain a final viscosity of 100,000 to 120,000 cP, but is not limited thereto.
In addition, the phosphorus-based compound may include more than 0.1% by weight and less than 3% by weight based on the solid content of the dianhydride component and the diamine component. The phosphorus compounds include triphenyl phosphate (TPP), trixylenyl phosphate (TXP), tricresyl phosphate (TCP), resorcinol diphenyl phosphate, ammonium polyphosphate (ammonium polyphosphate) and the like. In particular, it is preferable to use one or more of triphenyl phosphate (TPP) and ammonium polyphosphate (ammonium polyphosphate). Among the phosphorus-based compounds having plasticizer properties that can be imparted to increase flexibility between polyimide chains, any phosphorus-based compound that can contribute to suppression of bubble formation can be used.
前記製造方法によって製造された前記ポリイミドフィルムは、弾性率が５ＧＰａ以上であり、表面粗さが０．００５μｍ以下であり、厚さが７０μｍ以上であった。
製造されたポリイミドフィルムは、保護フィルムやキャリアフィルムに適するが、これに制限されるものではなく、製造されたポリイミドフィルムの特性が適用できる多様な分野で使用可能である。
The polyimide film produced by the production method had an elastic modulus of 5 GPa or more, a surface roughness of 0.005 μm or less, and a thickness of 70 μm or more.
The produced polyimide film is suitable for a protective film or a carrier film, but is not limited thereto, and can be used in various fields to which the properties of the produced polyimide film can be applied.
以下、発明の具体的な製造例および実施例を通じて、発明の作用および効果をより詳述する。ただし、このような製造例および実施例は発明の例として提示されたものに過ぎず、これによって発明の権利範囲が限定されるものではない。 Hereinafter, the action and effects of the invention will be described in more detail through specific production examples and examples of the invention. However, such production examples and examples are merely presented as examples of the invention, and are not intended to limit the scope of rights of the invention.
製造例：ポリイミドフィルムの製造
本発明のポリイミドフィルムは、次のような当業界にて公知の通常の方法で製造できる。まず、有機溶媒に、上述した二無水物酸とジアミン成分とを反応させてポリアミック酸溶液を得る。この時、溶媒は、一般的に、アミド系溶媒として非プロトン性極性溶媒（Ａｐｒｏｔｉｃ ｓｏｌｖｅｎｔ）、例えば、Ｎ，Ｎ’－ジメチルホルムアミド、Ｎ，Ｎ’－ジメチルアセトアミド、Ｎ－メチル－ピロリドン、またはこれらの組み合わせを使用することができる。
前記二無水物酸とジアミン成分の投入形態は、粉末、塊、および溶液形態で投入することができ、反応初期には粉末形態で投入して反応を進行させた後、以後は重合粘度調節のために溶液形態で投入することが好ましい。
また、ポリイミドフィルムの多様な特性を改善するために充填剤を添加してもよい。使用可能な充填剤の例としては、酸化チタン、アルミナ、窒化ケイ素、窒化ホウ素、リン酸水素カルシウム、リン酸カルシウム、雲母などが挙げられるが、これらに制限されない。
得られたポリアミック酸溶液は、イミド化触媒および脱水剤と混合されて支持体に塗布される。
使用される触媒の例としては、３級アミン類（例えば、イソキノリン、β－ピコリン、ピリジンなど）があり、脱水剤の例としては無水酸があるが、これに制限されない。また、前記使用される支持体としては、ガラス板、アルミニウム箔、循環ステンレスベルト、またはステンレスドラムなどが挙げられるが、これらに制限されない。
前記支持体上に塗布されたフィルムは、乾燥空気および熱処理によって支持体上でゲル化される。
前記ゲル化されたフィルムは、支持体から分離されて熱処理して乾燥およびイミド化が完了する。
前記熱処理を終えたフィルムは、一定の張力下で熱処理されて、製膜過程で発生したフィルム内部の残留応力が除去できる。
Production Example: Production of Polyimide Film The polyimide film of the present invention can be produced by the following conventional methods known in the art. First, the dianhydride acid and the diamine component described above are reacted in an organic solvent to obtain a polyamic acid solution. At this time, the solvent is generally an aprotic polar solvent such as N,N'-dimethylformamide, N,N'-dimethylacetamide, N-methyl-pyrrolidone, or these as an amide-based solvent. can be used.
The dianhydride acid and diamine components may be added in the form of powder, lump, or solution. In the early stage of the reaction, the powder is added to allow the reaction to proceed, and then the polymerization viscosity is controlled. For this reason, it is preferable to introduce it in the form of a solution.
Also, fillers may be added to improve various properties of the polyimide film. Examples of fillers that can be used include, but are not limited to, titanium oxide, alumina, silicon nitride, boron nitride, calcium hydrogen phosphate, calcium phosphate, mica, and the like.
The resulting polyamic acid solution is mixed with an imidization catalyst and a dehydrating agent and applied to a support.
Examples of catalysts used include, but are not limited to, tertiary amines (eg, isoquinoline, β-picoline, pyridine, etc.), and examples of dehydrating agents include, but are not limited to, acid anhydride. Also, the support to be used includes, but is not limited to, a glass plate, an aluminum foil, a circulating stainless steel belt, or a stainless steel drum.
The film coated on the support is gelled on the support by dry air and heat treatment.
The gelled film is separated from the support and heat treated to complete drying and imidization.
The heat-treated film can be heat-treated under a certain tension to remove the residual stress inside the film generated during the film-forming process.
具体的には、撹拌機および窒素注入・排出管を備えた反応器に窒素を注入させながらＤＭＦを５００ｍｌ投入し、反応器の温度を３０℃に設定した後、ピロメリット酸二無水物（ＰＭＤＡ）、ジアミノジフェニルエーテル（ＯＤＡ）、パラフェニレンジアミン（ＰＰＤ）を調節された組成比で投入して完全に溶解させる。以後、窒素雰囲気下、４０℃に反応器の温度を上げて加熱しながら１２０分間撹拌を継続して、１次反応粘度が１，５００ｃＰのポリアミック酸を製造した。
このように製造したポリアミック酸に、平均径が５００ｎｍの球状シリカ粒子を、ポリイミドフィルムの重量を基準として１，５００ｐｐｍ添加後、ピロメリット酸二無水物（ＰＭＤＡ）溶液を添加して、最終粘度１００，０００～１２０，０００ｃＰとなるように撹拌させた。
このように製造した最終ポリアミック酸に、触媒および脱水剤と共に、リン系化合物としてトリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）の含有量を調節して添加させた後、アプリケータを用いて高厚度ポリイミドフィルムを製造した。
Specifically, 500 ml of DMF was added while injecting nitrogen into a reactor equipped with a stirrer and a nitrogen injection/exhaust pipe, and after setting the temperature of the reactor to 30 ° C., pyromellitic dianhydride (PMDA ), diaminodiphenyl ether (ODA), and paraphenylenediamine (PPD) are added in an adjusted composition ratio and completely dissolved. Thereafter, the temperature of the reactor was increased to 40° C. under a nitrogen atmosphere, and stirring was continued for 120 minutes to prepare a polyamic acid having a primary reaction viscosity of 1,500 cP.
After adding 1,500 ppm of spherical silica particles with an average diameter of 500 nm based on the weight of the polyimide film to the polyamic acid thus produced, pyromellitic dianhydride (PMDA) solution was added to obtain a final viscosity of 100. ,000 to 120,000 cP.
After adjusting the content of triphenyl phosphate (TPP) as a phosphorus-based compound along with a catalyst and a dehydrating agent to the final polyamic acid prepared as described above, a thick polyimide is formed using an applicator. A film was produced.
実施例および比較例
先に説明した製造例によって製造しかつ、二無水物酸成分としてはピロメリット酸二無水物（ＰＭＤＡ）のみが使用され、二無水物酸成分１００ｍｏｌ％を基準として、ジアミン成分１００ｍｏｌ％を反応させた。
ジアミン成分であるパラフェニレンジアミン（ＰＰＤ）およびジアミノジフェニルエーテル（ＯＤＡ）の組成比は、ジアミンの総含有量を１００ｍｏｌ％とした時、パラフェニレンジアミン（ＰＰＤ）が５５ｍｏｌ％であり、ジアミノジフェニルエーテル（ＯＤＡ）が４５ｍｏｌ％使用された。
下記表１に示すように、トリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）の含有量は、二無水物酸成分および前記ジアミン成分の固形分対比０．５～３重量％添加され、製造されたポリイミドフィルムの厚さはすべて７５μｍであった。
EXAMPLES AND COMPARATIVE EXAMPLES Manufactured according to the manufacturing examples described above, only pyromellitic dianhydride (PMDA) is used as the dianhydride component, and the diamine component is based on 100 mol % of the dianhydride component. 100 mol % was reacted.
The composition ratio of paraphenylenediamine (PPD) and diaminodiphenyl ether (ODA), which are diamine components, is 55 mol% of paraphenylenediamine (PPD) and diaminodiphenyl ether (ODA) when the total content of diamine is 100 mol%. was used at 45 mol %.
As shown in Table 1 below, the content of triphenyl phosphate (TPP) was 0.5 to 3% by weight based on the solid content of the dianhydride component and the diamine component. All films had a thickness of 75 μm.
すべての実施例および比較例で製造したポリイミドフィルムの表面粗さは、Ｋｏｓａｋａ Ｌａｂｏｒａｔｏｒｙ Ｌｔｄのフィルム粗さ分析器を用いて算術平均粗さ（Ｒａ）値を測定した。
測定された実施例および比較例のポリイミドフィルムの表面粗さはすべて０．００５μｍ以下であった。
また、すべての実施例および比較例で製造したポリイミドフィルムの弾性率は、インストロン装置（Ｓｔａｎｄａｒｄ Ｉｎｓｔｒｏｎ ｔｅｓｔｉｎｇ ａｐｐａｒａｔｕｓ）を用いてＡＳＴＭ Ｄ ８８２規定に合わせて３回をテストして平均値を取った。
平均バブルの個数は、先にポリイミドフィルムを映像装置が装着されたフィルム不良分析装置を用いて撮影し、撮影されたポリイミドフィルムの不良映像を肉眼で直接確認する手順を経て平均バブルの個数を求めた。
一定の幅と長さのフィルムを試料として採取してバブルの個数を測定し、以後、測定されたバブルの個数を１ｍ2あたりのバブルの個数で換算した。
The surface roughness of the polyimide films produced in all Examples and Comparative Examples was measured using a film roughness analyzer from Kosaka Laboratory Ltd. to measure the arithmetic mean roughness (Ra) value.
The measured surface roughness of the polyimide films of Examples and Comparative Examples was all 0.005 μm or less.
In addition, the elastic moduli of the polyimide films prepared in all Examples and Comparative Examples were tested three times according to ASTM D 882 using a Standard Instron testing apparatus, and the average value was taken.
The average number of bubbles is obtained by taking a picture of the polyimide film using a film defect analyzer equipped with an imager and directly checking the filmed defect image of the polyimide film with the naked eye. rice field.
A film having a constant width and length was taken as a sample and the number of bubbles was measured, and the measured number of bubbles was converted into the number of bubbles per 1 m 2 .
測定結果によれば、トリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）の含有量を０．５重量％から２．５重量％で添加させた実施例１～５の場合、高厚膜ポリイミドフィルムであるにもかかわらず、トリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）を全く使用しない比較例１（バブルの個数：１ｍ2あたり５０個）や、０．１重量％のトリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）を含んでいる比較例２（バブルの個数：１ｍ2あたり５０個）に比べてバブルの個数が大きく減少した。
特に、トリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）の含有量を０．５重量％から２．５重量％に増加させることにより、バブルの個数は１ｍ2あたり１８～２０個から０個に減少した。
また、トリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）の含有量を０．５重量％から２．５重量％（実施例１～５）で含む場合、比較例１および２（それぞれ、５．９１ＧＰａ、５．８９ＧＰａ）に比べて弾性率が一部減少する傾向を示したが、ポリイミドフィルムの弾性率は５．１５ＧＰａ～５．８２ＧＰａで５ＧＰａ以上の弾性率を示して、製造されたポリイミドフィルムの製品への適用には問題が全くないことを確認した。
トリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）の含有量を３重量％以上過剰に使用した場合（比較例３～５）、実施例５と同じく、バブルの個数は０個に維持されたが、弾性率が大きく減少して５ＧＰａ未満を示した。
トリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）の含有量の増加に伴う弾性率の減少は、トリフェニルリン酸（ｔｒｉｐｈｅｎｙｌ ｐｈｏｓｐｈａｔｅ、ＴＰＰ）の可塑剤特性に起因すると考えられる。
According to the measurement results, in the case of Examples 1 to 5 in which the content of triphenyl phosphate (TPP) was added from 0.5 wt% to 2.5 wt%, a thick polyimide film was obtained. Nevertheless, Comparative Example 1 (number of bubbles: 50 per m 2 ) in which no triphenyl phosphate (TPP) is used, and 0.1% by weight of triphenyl phosphate (TPP) ) (the number of bubbles: 50 per m 2 ), the number of bubbles was greatly reduced.
In particular, by increasing the content of triphenyl phosphate (TPP) from 0.5 wt% to 2.5 wt%, the number of bubbles decreased from 18-20 to 0 per m2 . .
In addition, when the content of triphenyl phosphate (TPP) is 0.5 wt% to 2.5 wt% (Examples 1 to 5), Comparative Examples 1 and 2 (5.91 GPa, respectively, 5.89 GPa), but the elastic modulus of the polyimide film is 5.15 GPa to 5.82 GPa, showing an elastic modulus of 5 GPa or more. It was confirmed that there is no problem in applying to
When the content of triphenyl phosphate (TPP) was excessively used by 3% by weight or more (Comparative Examples 3 to 5), the number of bubbles was maintained at 0 as in Example 5, but the elasticity was reduced. modulus decreased significantly to show less than 5 GPa.
The decrease in elastic modulus with increasing triphenyl phosphate (TPP) content is believed to be due to the plasticizer properties of triphenyl phosphate (TPP).
本発明であるポリイミドフィルムおよびポリイミドフィルムの製造方法の実施例は、本発明の属する技術分野における通常の知識を有する当業者が本発明を容易に実施できるようにする好ましい実施例に過ぎず、上述した実施例に限定されるものではないので、これによって本発明の権利範囲が限定されるものではない。したがって、本発明の真の技術的保護範囲は、添付した特許請求の範囲の技術的思想によって定められなければならない。また、本発明の技術的思想を逸脱しない範囲内で様々な置換、変形および変更が可能であることが当業者にとって明らかであり、当業者によって容易に変更可能な部分も本発明の権利範囲に含まれることは自明である。 The examples of the polyimide film and the method for producing the polyimide film according to the present invention are merely preferred examples that enable those skilled in the art having ordinary knowledge in the technical field to which the present invention belongs to easily carry out the present invention. It is not intended to limit the scope of the invention, as it is not intended to be limited to the examples given. Therefore, the true technical scope of protection of the present invention should be determined by the technical ideas of the attached claims. In addition, it is obvious to those skilled in the art that various substitutions, modifications and changes can be made without departing from the technical idea of the present invention. Included is self-evident.
本発明のポリイミドフィルムは、高弾性の優れた機械的特性だけでなく、表面粗さが低くバブル形成が抑制されて、特に表面品質が改善されるので、このような多様な特性のポリイミドフィルムが要求される分野に適用可能である。 The polyimide film of the present invention not only has excellent mechanical properties such as high elasticity, but also has low surface roughness and suppressed bubble formation, thereby improving surface quality. Applicable to required fields.
Claims (12)
前記ジアミン成分の総含有量１００モル％を基準として、前記パラフェニレンジアミン（ＰＰＤ）の含有量が４０モル％以上５５モル％以下であり、前記ジアミノジフェニルエーテル（ＯＤＡ）の含有量が４５モル％以上６０モル％以下であり、
球状シリカ粒子およびリン（Ｐ）系化合物を含む、ポリイミドフィルム。 A diamine composed of a dianhydride acid component containing pyromellitic dianhydride (PMDA), diaminodiphenyl ether (4,4'-oxydianiline, ODA) and paraphenylene diamine (PPD) Obtained by imidizing a polyamic acid solution containing a component,
Based on the total content of 100 mol% of the diamine component, the content of the paraphenylenediamine (PPD) is 40 mol% or more and 55 mol% or less, and the content of the diaminodiphenyl ether (ODA) is 45 mol% or more. 60 mol% or less,
A polyimide film containing spherical silica particles and a phosphorus (P) compound.
（ｂ）前記第１ステップの前記ポリアミック酸に平均径が１μｍ以下の球状シリカ粒子を追加して混合する第２ステップと、
（ｃ）前記第２ステップの前記ポリアミック酸にイミド化触媒とリン（Ｐ）系化合物とを追加して混合する第３ステップと、
（ｃ）前記第３ステップの前記ポリアミック酸をイミド化する第４ステップとを含み、
前記ジアミン成分の総含有量１００モル％を基準として、前記パラフェニレンジアミン（ＰＰＤ）の含有量が４０モル％以上５５モル％以下であり、前記ジアミノジフェニルエーテル（ＯＤＡ）の含有量が４５モル％以上６０モル％以下である、ポリイミドフィルムの製造方法。 (a) composed of a dianhydride acid component containing pyromellitic dianhydride (PMDA), diaminodiphenyl ether (4,4'-oxydianiline, ODA) and paraphenylene diamine (PPD); a first step of polymerizing the obtained diamine component in an organic solvent to produce a polyamic acid;
(b) a second step of adding and mixing spherical silica particles having an average diameter of 1 μm or less to the polyamic acid of the first step;
(c) a third step of adding an imidization catalyst and a phosphorus (P)-based compound to the polyamic acid of the second step and mixing;
(c) a fourth step of imidizing the polyamic acid of the third step;
Based on the total content of 100 mol% of the diamine component, the content of the paraphenylenediamine (PPD) is 40 mol% or more and 55 mol% or less, and the content of the diaminodiphenyl ether (ODA) is 45 mol% or more. 60 mol % or less, a method for producing a polyimide film.
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