JP2011080002A - Insulative polyimide film, coverlay film, and flexible printed wiring board - Google Patents
Insulative polyimide film, coverlay film, and flexible printed wiring board Download PDFInfo
- Publication number
- JP2011080002A JP2011080002A JP2009234856A JP2009234856A JP2011080002A JP 2011080002 A JP2011080002 A JP 2011080002A JP 2009234856 A JP2009234856 A JP 2009234856A JP 2009234856 A JP2009234856 A JP 2009234856A JP 2011080002 A JP2011080002 A JP 2011080002A
- Authority
- JP
- Japan
- Prior art keywords
- film
- polyimide film
- insulating polyimide
- black pigment
- filler
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 83
- 239000012787 coverlay film Substances 0.000 title claims abstract description 23
- 239000000049 pigment Substances 0.000 claims abstract description 55
- 239000000945 filler Substances 0.000 claims abstract description 43
- 239000010408 film Substances 0.000 claims abstract description 43
- 239000011164 primary particle Substances 0.000 claims abstract description 21
- 238000002834 transmittance Methods 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000006229 carbon black Substances 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- 239000010445 mica Substances 0.000 claims description 6
- 229910052618 mica group Inorganic materials 0.000 claims description 6
- 239000009719 polyimide resin Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 229910052582 BN Inorganic materials 0.000 claims description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 5
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 5
- 239000001506 calcium phosphate Substances 0.000 claims description 5
- 235000011010 calcium phosphates Nutrition 0.000 claims description 5
- 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 claims description 5
- 238000013461 design Methods 0.000 abstract description 7
- 239000006185 dispersion Substances 0.000 description 48
- 229920005575 poly(amic acid) Polymers 0.000 description 35
- 229920000642 polymer Polymers 0.000 description 30
- 238000000034 method Methods 0.000 description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 18
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- 238000009413 insulation Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 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 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 6
- -1 Ester anhydride Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 5
- SAVPSRHNNQVBLW-UHFFFAOYSA-N 3,5-diethylpyridine Chemical compound CCC1=CN=CC(CC)=C1 SAVPSRHNNQVBLW-UHFFFAOYSA-N 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 4
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 108010025899 gelatin film Proteins 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-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
- 239000002313 adhesive film Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
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- 239000000835 fiber 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
- 238000000059 patterning Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 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 group C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-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
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- FYYYKXFEKMGYLZ-UHFFFAOYSA-N 4-(1,3-dioxo-2-benzofuran-5-yl)-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1C1=CC=CC2=C1C(=O)OC2=O FYYYKXFEKMGYLZ-UHFFFAOYSA-N 0.000 description 1
- YPGXCJNQPKHBLH-UHFFFAOYSA-N 4-[2-[2-[2-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropan-2-yl]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=CC=C1OC1=CC=C(N)C=C1 YPGXCJNQPKHBLH-UHFFFAOYSA-N 0.000 description 1
- AJYDKROUZBIMLE-UHFFFAOYSA-N 4-[2-[2-[2-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=CC=C(OC=2C=CC(N)=CC=2)C=1C(C)(C)C1=CC=CC=C1OC1=CC=C(N)C=C1 AJYDKROUZBIMLE-UHFFFAOYSA-N 0.000 description 1
- KWOIWTRRPFHBSI-UHFFFAOYSA-N 4-[2-[3-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=CC(C(C)(C)C=2C=CC(N)=CC=2)=CC=1C(C)(C)C1=CC=C(N)C=C1 KWOIWTRRPFHBSI-UHFFFAOYSA-N 0.000 description 1
- HESXPOICBNWMPI-UHFFFAOYSA-N 4-[2-[4-[2-(4-aminophenyl)propan-2-yl]phenyl]propan-2-yl]aniline Chemical compound C=1C=C(C(C)(C)C=2C=CC(N)=CC=2)C=CC=1C(C)(C)C1=CC=C(N)C=C1 HESXPOICBNWMPI-UHFFFAOYSA-N 0.000 description 1
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- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 description 1
- HYDATEKARGDBKU-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]phenoxy]aniline Chemical group C1=CC(N)=CC=C1OC1=CC=C(C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 HYDATEKARGDBKU-UHFFFAOYSA-N 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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Abstract
Description
絶縁性ポリイミドフィルム、カバーレイフィルム、及びフレキシブルプリント配線板に関する。 The present invention relates to an insulating polyimide film, a coverlay film, and a flexible printed wiring board.
近年、電子機器の高性能化、高機能化、小型化が急速に進んでおり、これに伴って電子機器に用いられる電子部品に対しても小型化、軽量化の要請が高まっている。上記要請を受け、フレキシブルプリント配線板は、可撓性を有し、繰り返し屈曲に耐えるため、狭い空間に立体的高密度の実装が可能であり、電子機器への配線、ケーブル、あるいはコネクター機能を付与した複合部品としてのその用途が拡大している。特に最近では、カメラ、ビデオカメラ、ＣＤ−ＲＯＭドライブの光ピックアップ部等の電子・光学機器に使用されることが多くなり、それに伴ってフレキシブルプリント配線板に対する遮光性が重要となっている。この遮光性とは光学機器の嫌光部に用いられるフレキシブルプリント配線板に必要な特性で、外部から嫌光部に侵入しようとする光を配線板で遮り、かつ配線板によって遮られた光の反射光が再び嫌光部に侵入しないよう拡散させる必要がある。 2. Description of the Related Art In recent years, electronic devices have been rapidly improved in performance, function, and size, and accordingly, there is an increasing demand for downsizing and weight reduction of electronic components used in electronic devices. In response to the above request, the flexible printed wiring board is flexible and can withstand repeated bending, so it can be mounted three-dimensionally and densely in a narrow space, and functions as a wiring, cable, or connector for electronic devices. Its use as a given composite part is expanding. In recent years, in particular, they are frequently used in electronic and optical devices such as cameras, video cameras, and optical pickups of CD-ROM drives, and accordingly, light shielding properties for flexible printed wiring boards have become important. This light shielding property is a characteristic required for flexible printed wiring boards used in light-absorbing parts of optical equipment. Light that tries to enter the light-absorbing parts from the outside is blocked by the wiring board, and light blocked by the wiring board is blocked. It is necessary to diffuse the reflected light so that it does not enter the aphobic part again.
また、フレキシブルプリント配線板は、携帯電話やパソコンにも欠かすことのできない電子部品であり、その需要は年々増加している。携帯電話やパソコンにおいては、機能とともにデザイン性も重要となってきており、筐体を透明にする等の試みがなされている。このような意匠性の観点から、低光沢な、いわゆるマットな質感を有するフレキシブルプリント配線板も求められている。 In addition, the flexible printed wiring board is an electronic component that is indispensable for mobile phones and personal computers, and its demand is increasing year by year. In mobile phones and personal computers, design as well as function has become important, and attempts have been made to make the housing transparent. From the viewpoint of such design properties, a flexible printed wiring board having a low gloss, so-called matte texture is also demanded.
さらに、電子機器の小型軽量化に伴い、フレキシブルプリント配線板の厚みも薄くなってきており、それに伴いフレキシブルプリント配線板に用いられるカバーレイフィルムの厚みも薄くなってきている。 Furthermore, with the reduction in size and weight of electronic devices, the thickness of flexible printed wiring boards has been reduced, and accordingly, the thickness of coverlay films used for flexible printed wiring boards has also been reduced.
遮光性を付与させるために、従来はフレキシブルプリント配線板のカバーレイフィルム側の電気絶縁性フィルムに直接スクリーン印刷法等により黒色インクを印刷して対応していた。しかしながらこの方法では凹凸のあるフレキシブルプリント配線板にスクリーン印刷を行うため作業性が悪く、かつ回路加工工程中に印刷工程が増えることから、作業効率も悪くなってしまう。また、回路の外形加工時及び折り曲げ時に、黒色インクが折れたり剥れたりして遮光性が失われたり、黒色インクにより機器内部が汚染されてしまうという欠点があった。 In order to impart light-shielding properties, conventionally, black ink was printed directly on the electrically insulating film on the coverlay film side of the flexible printed wiring board by a screen printing method or the like. However, in this method, screen printing is performed on a flexible printed wiring board having unevenness, so that workability is poor, and the printing process is increased during the circuit processing process, so that work efficiency is also deteriorated. In addition, there is a drawback that the black ink breaks or peels off when the circuit is processed and bent, and the light shielding property is lost, or the inside of the device is contaminated by the black ink.
この課題を解決するために、カバーレイフィルムを黒色化する方法が提案されている（特許文献１）。しかしながら、厚みが薄い場合には十分な遮光性が得られないという問題があった。この問題を解決するため、黒色顔料を多量に添加すると、絶縁性が低下しカバーレイフィルムとしての機能を低下させてしまうことになる。また、熱硬化性接着剤へ黒色顔料を添加した場合は、下層の回路と黒色顔料とが接触し、絶縁不良を生じる恐れがあった。さらに遮光性が高いということは、黒色顔料が十分に分散しているということであり、この場合光沢度は高くなる。従って、遮光性とマットな質感とを両立させるのは困難であり、フィルムの厚みが薄い場合はさらに困難であった。 In order to solve this problem, a method of blackening the coverlay film has been proposed (Patent Document 1). However, when the thickness is small, there is a problem that sufficient light shielding properties cannot be obtained. In order to solve this problem, if a large amount of black pigment is added, the insulating property is lowered and the function as a coverlay film is lowered. In addition, when a black pigment is added to the thermosetting adhesive, the lower layer circuit and the black pigment come into contact with each other, which may cause an insulation failure. Further, the high light-shielding property means that the black pigment is sufficiently dispersed, and in this case, the glossiness is high. Therefore, it is difficult to achieve both the light shielding property and the matte texture, and it is further difficult when the film is thin.
本発明は、上記の課題に鑑みてなされたものであって、その目的は、遮光性、絶縁性に優れ、且つ優れた意匠性も有する絶縁性ポリイミドフィルム、及びそれを用いて得られるカバーレイフィルム、フレキシブルプリント配線板を提供することにある。 The present invention has been made in view of the above-described problems, and an object of the present invention is to provide an insulating polyimide film having excellent light shielding properties and insulating properties, and also having excellent design properties, and a coverlay obtained using the same. The object is to provide a film and a flexible printed wiring board.
本発明者等は、かかる課題を解決するために鋭意検討した結果、特定の黒色顔料と、フィラーとを含有する絶縁性ポリイミドフィルムを用いることにより、厚みが薄い場合にも優れた遮光性とマットな質感を両立し、また高い絶縁信頼性をも併せ持つカバーレイフィルムを得ることができることを見出し、本発明を完成するに至った。 As a result of intensive investigations to solve such problems, the present inventors have used an insulating polyimide film containing a specific black pigment and a filler, so that excellent light-shielding properties and mats can be obtained even when the thickness is thin. The present inventors have found that a cover lay film having both a good texture and high insulation reliability can be obtained, and the present invention has been completed.
即ち、本発明は、
１）一次粒径が２０ｎｍ以上５００ｎｍ以下の黒色顔料と、フィラーとを含有する絶縁性ポリイミドフィルムであって、該フィルムの１２．５μｍ厚みでの全光線透過率が５％以下、且つ光沢度が５％以下、且つ体積抵抗率が２×１０16Ω・ｃｍ以上であることを特徴とする絶縁性ポリイミドフィルム、
２）上記黒色顔料が、カーボンブラックであることを特徴とする１）に記載の絶縁性ポリイミドフィルム、
３）上記フィラーが、酸化チタン、雲母、窒化ホウ素、酸化アルミニウム、リン酸カルシウム及びシリカからなる群から選ばれる少なくとも1種のフィラーであることを特徴とする１）または２）に記載の絶縁性ポリイミドフィルム、
４）ポリイミド樹脂１００重量部に対して１〜１５重量部の黒色顔料を含有することを特徴とする１）〜３）のいずれか１つに記載の絶縁性ポリイミドフィルム、
５）ポリイミド樹脂１００重量部に対して１〜１５重量部のフィラーを含有することを特徴とする１）〜４）のいずれか１つに記載の絶縁性ポリイミドフィルム、
６）１）〜５）のいずれか１つに記載の絶縁性ポリイミドフィルムを用いてなるカバーレイフィルム、
７）１）〜５）のいずれか１つに記載の絶縁性ポリイミドフィルムを用いてなるフレキシブルプリント配線板、に関する。
That is, the present invention
1) An insulating polyimide film containing a black pigment having a primary particle size of 20 nm or more and 500 nm or less, and a filler, wherein the total light transmittance at 12.5 μm thickness of the film is 5% or less, and the glossiness is Insulating polyimide film characterized by having 5% or less and a volume resistivity of 2 × 10 16 Ω · cm or more,
2) The insulating polyimide film according to 1), wherein the black pigment is carbon black,
3) The insulating polyimide film according to 1) or 2), wherein the filler is at least one filler selected from the group consisting of titanium oxide, mica, boron nitride, aluminum oxide, calcium phosphate and silica. ,
4) The insulating polyimide film according to any one of 1) to 3), which contains 1 to 15 parts by weight of a black pigment with respect to 100 parts by weight of the polyimide resin,
5) Insulating polyimide film according to any one of 1) to 4), which contains 1 to 15 parts by weight of filler with respect to 100 parts by weight of polyimide resin.
6) A coverlay film using the insulating polyimide film according to any one of 1) to 5),
7) It is related with the flexible printed wiring board formed using the insulating polyimide film as described in any one of 1) -5).
本発明に係る絶縁性ポリイミドフィルム、ならびに該絶縁性ポリイミドフィルムを用いて得られるカバーレイフィルムは、優れた遮光性と絶縁信頼性を両立し、さらには低光沢度であり、意匠性にも優れる。 The insulating polyimide film according to the present invention and the coverlay film obtained by using the insulating polyimide film have both excellent light-shielding properties and insulation reliability, and also have low gloss and excellent design. .
本発明の実施の形態について、以下に説明する。 Embodiments of the present invention will be described below.
（黒色顔料）
本発明に係る黒色顔料は、一次粒径が２０ｎｍ以上５００ｎｍ以下であることを特徴とする。
(Black pigment)
The black pigment according to the present invention has a primary particle size of 20 nm or more and 500 nm or less.
黒色顔料は樹脂に分散させた場合、通常は凝集するため、一次粒径を保持することはないと言われている。従って分散性は、二次粒径で議論されるべきものである。特に化学反応を伴いながらフィルム化されるポリイミドにおいては、フィルム化した際には一次粒径を保持している可能性は極めて低いと考えられる。しかしながら本発明者らは、黒色顔料の一次粒径のみを考慮することにより分散性を議論できることを見出した。すなわち、一次粒径が２０ｎｍ以上５００ｎｍ以下の黒色顔料を用いれば良好に分散し、遮光性に優れることを見出した。ここで一次粒径は２２ｎｍ以上３００ｎｍ以下であることがより好ましく、２４ｎｍ以上２００ｎｍ以下であることがさらに好ましい。 When black pigment is dispersed in a resin, it usually agglomerates and is said not to retain the primary particle size. Dispersibility should therefore be discussed in terms of secondary particle size. In particular, in the case of a polyimide that is formed into a film with a chemical reaction, the possibility that the primary particle size is maintained when formed into a film is considered to be extremely low. However, the inventors have found that dispersibility can be discussed by considering only the primary particle size of the black pigment. That is, it was found that if a black pigment having a primary particle size of 20 nm or more and 500 nm or less is used, it is well dispersed and has excellent light shielding properties. Here, the primary particle size is more preferably 22 nm or more and 300 nm or less, and further preferably 24 nm or more and 200 nm or less.
一次粒径が２０ｎｍよりも小さい場合、及び５００ｎｍよりも大きい場合は、分散性が悪くなり、結果として遮光性も低下する。
一方で、一次粒径が２０ｎｍ以上の黒色顔料を用いるのみでは、遮光性は十分に得られるが、高光沢であり、マットな質感は得られない。従って、さらなる遮光性とマットな質感を得るために、本発明においてはフィラーを併用することが重要である。
本発明でいう一次粒径とは、黒色顔料をクロロホルムに投入し超音波を２０分間照射して分散させ、分散試料を支持膜に固定した後、透過型電子顕微鏡で写真撮影し、写真上の直径と写真の拡大倍率により計算して求める値のことを言う。
When the primary particle size is smaller than 20 nm and larger than 500 nm, the dispersibility is deteriorated, and as a result, the light shielding property is also lowered.
On the other hand, by using only a black pigment having a primary particle size of 20 nm or more, sufficient light shielding properties can be obtained, but it is highly glossy and a matte texture cannot be obtained. Therefore, in order to obtain further light-shielding properties and a matte texture, it is important to use a filler in the present invention.
The primary particle size as used in the present invention means that a black pigment is put into chloroform and dispersed by irradiating with ultrasonic waves for 20 minutes, and the dispersed sample is fixed to a support film, then photographed with a transmission electron microscope, This is the value calculated by calculating the diameter and magnification of the photo.
本発明に係る黒色顔料としては、ファーネスブラック、アセチレンブラック、サーマルブラック、チャンネルブラック等のカーボンブラック、グラファイト、酸化鉄黒、マンガン黒、チタンブラック等を挙げることができるが、その中でも、遮光性に優れるカーボンブラックを用いることが好ましい。本発明に好適なカーボンブラックとしては、三菱化学株式解社製の＃５２、＃４７、＃４５、＃４５Ｌ、＃４４、＃４０、＃３３、＃３２、＃３０、＃２５、＃２０、＃１０、＃５、＃９５、＃８５、＃２６０、ＣＦ９、ＭＡ７７、ＭＡ７、ＭＡ８、ＭＡ１１、ＭＡ１００、ＭＡ１００Ｒ、ＭＡ１００Ｓ、ＭＡ２３０、ＭＡ２２０、ＭＡ２００ＲＢ、ＭＡ１４、＃４０００Ｂ、＃４３５０Ｂ、エボニック インダストリーズ社製のＣｏｌｏｒ Ｂｌａｃｋ Ｓ１６０、Ｓｐｅｃｉａｌ Ｂｌａｃｋ５、Ｓｐｅｃｉａｌ Ｂｌａｃｋ４、Ｓｐｅｃｉａｌ Ｂｌａｃｋ４Ａ、Ｐｒｉｎｔｅｘ １５０Ｔ、Ｐｒｉｎｔｅｘ Ｕ、Ｐｒｉｎｔｅｘ Ｖ、Ｐｒｉｎｔｅｘ １４０Ｕ、Ｐｒｉｎｔｅｘ １４０Ｖ、Ｐｒｉｎｔｅｘ ５５、Ｓｐｅｃｉａｌ Ｂｌａｃｋ５５０、Ｐｒｉｎｔｅｘ ４５、Ｐｒｉｎｔｅｘ ４０、Ｐｒｉｎｔｅｘ Ｐ、Ｐｒｉｎｔｅｘ Ｌ６、Ｐｒｉｎｔｅｘ Ｌ、Ｐｒｉｎｔｅｘ ３００、Ｐｒｉｎｔｅｘ ３０、Ｐｒｉｎｔｅｘ ＥＳ２３、Ｐｒｉｎｔｅｘ ３、Ｐｒｉｎｔｅｘ ＥＳ２２、Ｓｐｅｃｉａｌ Ｂｌａｃｋ３５０、Ｐｒｉｎｔｅｘ ３５、Ｓｐｅｃｉａｌ Ｂｌａｃｋ２５０、Ｐｒｉｎｔｅｘ ２５、Ｐｒｉｎｔｅｘ ２００、Ｐｒｉｎｔｅｘ Ａ、Ｓｐｅｃｉａｌ Ｂｌａｃｋ１００、Ｓｐｅｃｉａｌ Ｂｌａｃｋ１０１、Ｐｒｉｎｔｅｘ Ｇ、を例示することができる。 Examples of the black pigment according to the present invention include carbon black such as furnace black, acetylene black, thermal black, and channel black, graphite, iron oxide black, manganese black, titanium black, and the like. It is preferable to use excellent carbon black. Carbon black suitable for the present invention includes # 52, # 47, # 45, # 45L, # 44, # 40, # 33, # 32, # 30, # 25, # 20, manufactured by Mitsubishi Chemical Corporation. # 10, # 5, # 95, # 85, # 260, CF9, MA77, MA7, MA8, MA11, MA100, MA100R, MA100S, MA230, MA220, MA200RB, MA14, # 4000B, # 4350B, manufactured by Evonik Industries Color Black S160, Special Black 5, Special Black 4, Special Black 4A, Printex 150T, Printex U, Printex V, Printex 140U, Printex 140V, Printex 55 k550, Printex 45, Printex 40, Printex P, Printex L6, Printex L, Printex 300, Printex 30, Printex ES23, Printex 3, Printex ES22, Special B Special Black 100, Special Black 101, and Printex G can be exemplified.
黒色顔料の添加量は特に制限は無いが、絶縁信頼性を確保するという観点、またフィルム化時のフィルムの機械的強度を確保するという観点から、ポリイミド樹脂１００重量部に対して１〜１５重量部であることが好ましく、１〜１３重量部であることがさらに好ましく、１〜１０重量部であることが特に好ましい。 Although there is no restriction | limiting in particular in the addition amount of a black pigment, 1-15 weight with respect to 100 weight part of polyimide resin from a viewpoint of ensuring insulation reliability and ensuring the mechanical strength of the film at the time of film formation. Parts, preferably 1 to 13 parts by weight, more preferably 1 to 10 parts by weight.
（フィラー）
本発明に係る絶縁性ポリイミドフィルムは、フィラーを含むことを特徴とする。本発明に係るフィラーは、絶縁性ポリイミドフィルムに添加することにより、マットな質感を得ることを主目的に使用される。また、黒色顔料のみでは十分な遮光性が得られない場合は、遮光性を付与する目的も有する。前記の目的を満たしさえすればフィラーとしては特に制限はなく、無機フィラー、有機フィラーに関わらず使用することが可能である。その中でも、マットな質感を得やすく、さらには遮光性も高く、黒色顔料と併せて添加しても凝集しにくく、少量添加でも十分な遮光性とマットな質感を得ることができるという観点から、酸化チタン、雲母、窒化ホウ素、酸化アルミニウム、リン酸カルシウム及びシリカからなる群から選ばれる少なくとも１種のフィラーであることが好ましく、酸化チタン、雲母、酸化アルミニウム、から選ばれる少なくとも１種のフィラーであることがさらに好ましい。尚、フィラーを添加することによりマットな質感が得られるのは、フィルム内部で入射光が拡散するためであると推定している。
(Filler)
The insulating polyimide film according to the present invention includes a filler. The filler according to the present invention is used mainly for obtaining a matte texture by adding to the insulating polyimide film. Moreover, when sufficient light-shielding property is not obtained only by a black pigment, it also has the objective of providing light-shielding property. The filler is not particularly limited as long as it satisfies the above purpose, and can be used regardless of inorganic fillers and organic fillers. Among them, it is easy to obtain a matte texture, and also has a high light-shielding property, and even if added together with a black pigment, it is difficult to agglomerate. It is preferably at least one filler selected from the group consisting of titanium oxide, mica, boron nitride, aluminum oxide, calcium phosphate, and silica, and is at least one filler selected from titanium oxide, mica, and aluminum oxide. Is more preferable. It is assumed that the matte texture can be obtained by adding the filler because the incident light diffuses inside the film.
酸化チタンとしては、ルチル型、アナタース型のいずれでもかまわない。また形状としても球状、針状、鱗片状などいずれを用いてもかまわない。 As the titanium oxide, either a rutile type or an anatase type may be used. Also, any shape such as a spherical shape, a needle shape, or a scale shape may be used.
雲母は、天然の雲母、合成雲母のいずれを使用することもできる。特に合成雲母はマットな質感を得やすいため好ましい。合成雲母としては、非膨潤性、膨潤性のいずれを用いてもよく、コープケミカル株式会社製のミクロマイカＭＫシリーズや、ソマシフＭＫ−１００、ＭＡＥ、ＭＴＥ、ＭＥＥ、ＭＰＥ、を例示することができる。 As the mica, either natural mica or synthetic mica can be used. Synthetic mica is particularly preferable because it is easy to obtain a matte texture. As the synthetic mica, any of non-swelling property and swelling property may be used, and examples thereof include Micromica MK series manufactured by Co-op Chemical Co., Ltd., Somasif MK-100, MAE, MTE, MEE, and MPE. .
窒化ホウ素としては、凝集状、球状、鱗片状、等のいずれの形状でもかまわない。窒化ホウ素を用いると、熱伝導性の向上も期待できる。 Boron nitride may be any shape such as agglomerated, spherical, and flaky. Use of boron nitride can be expected to improve thermal conductivity.
酸化アルミニウムは、球状、鱗片状、等のいずれの形状でもかまわない。また、本発明に係る絶縁性ポリイミドフィルムは、電子材料用途であることから、低ソーダタイプの酸化アルミニウムが好ましい。またα結晶粒径が０．０１〜４０μｍであることが好ましく、０．０２〜３０μｍであることがさらに好ましい。 Aluminum oxide may have any shape such as a spherical shape or a scale shape. Moreover, since the insulating polyimide film according to the present invention is used for electronic materials, low soda type aluminum oxide is preferable. Moreover, it is preferable that (alpha) crystal grain diameter is 0.01-40 micrometers, and it is more preferable that it is 0.02-30 micrometers.
リン酸カルシウムは、凝集状、球状、鱗片状、等のいずれの形状でもよい。 Calcium phosphate may have any shape such as agglomerated shape, spherical shape, and scale shape.
シリカは、溶融シリカ、フュームドシリカ、合成シリカ、等、いずれを用いてもよい。 As the silica, any of fused silica, fumed silica, synthetic silica, and the like may be used.
フィラーのサイズに特に制限は無いが、マットな質感が得られ易く、フィルム化時のフィルムの機械的強度を低下させないという観点から、粒状の場合、平均粒径は０．０１〜４０μｍであることが好ましく、０．０２〜３０μｍであることがさらに好ましい。針状の場合は、短軸径は、好ましくは０．０１〜１０μｍ、さらに好ましくは０．０５〜８μｍ、且つ長軸径は、好ましくは０．５〜５０μｍ、さらに好ましくは１〜４０μｍである。鱗片状の場合は、短軸の長さは、好ましくは０．０１〜１０μｍ、さらに好ましくは０．０５〜８μｍ、且つ長軸の長さは、好ましくは０．５〜５０μｍ、さらに好ましくは１〜４０μｍである。 There is no particular limitation on the size of the filler, but from the viewpoint of easily obtaining a matte texture and not reducing the mechanical strength of the film at the time of film formation, the average particle diameter is 0.01 to 40 μm. Is preferable, and it is further more preferable that it is 0.02-30 micrometers. In the case of needles, the short axis diameter is preferably 0.01 to 10 μm, more preferably 0.05 to 8 μm, and the long axis diameter is preferably 0.5 to 50 μm, more preferably 1 to 40 μm. . In the case of scaly, the length of the short axis is preferably 0.01 to 10 μm, more preferably 0.05 to 8 μm, and the length of the long axis is preferably 0.5 to 50 μm, more preferably 1 ˜40 μm.
フィラーの添加量は特に制限は無いが、フィルム化時の機械的強度を確保するという観点から、ポリイミド樹脂１００重量部に対して１〜１５重量部であることが好ましく、１〜１３重量部であることがさらに好ましく、１〜１０重量部であることが特に好ましい。 Although there is no restriction | limiting in particular in the addition amount of a filler, It is preferable that it is 1-15 weight part with respect to 100 weight part of polyimide resins from a viewpoint of ensuring the mechanical strength at the time of film formation, More preferably, it is 1 to 10 parts by weight.
（絶縁性ポリイミドフィルム）
本発明に係る絶縁性ポリイミドフィルムについて説明する。
(Insulating polyimide film)
The insulating polyimide film according to the present invention will be described.
ポリイミドフィルムは、その前駆体であるポリアミド酸重溶液から得られる。このポリアミド酸重合体溶液は、当業者が通常用いる方法で製造することができる。すなわち、１種または２種以上のテトラカルボン酸二無水物成分と１種または２種以上のジアミン成分を実質等モル使用し、有機極性溶媒中で重合してポリアミド酸重合体溶液が得られる。 A polyimide film is obtained from the polyamic-acid heavy solution which is the precursor. This polyamic acid polymer solution can be produced by a method commonly used by those skilled in the art. That is, one or more tetracarboxylic dianhydride components and one or more diamine components are used in substantially equimolar amounts and polymerized in an organic polar solvent to obtain a polyamic acid polymer solution.
ポリイミドフィルムの製造に用いられる代表的なテトラカルボン酸二無水物成分としては、ピロメリット酸二無水物、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’−ジフェニルスルホンテトラカルボン酸二無水物、１，４，５，８−ナフタレンテトラカルボン酸二無水物、２，３，６，７−ナフタレンテトラカルボン酸二無水物、４，４’−オキシジフタル酸無水物、３，３’，４，４’−ジメチルジフェニルシランテトラカルボン酸二無水物、３，３’，４，４’−テトラフェニルシランテトラカルボン酸二無水物、１，２，３，４−フランテトラカルボン酸二無水物、４，４’−ビス（３，４−ジカルボキシフェノキシ）ジフェニルプロパン二無水物、４，４’−ヘキサフルオロイソプロピリデンジフタル酸無水物、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物、ｐ−フェニレンビス（トリメリット酸モノエステル無水物）、ｐ−フェニレンジフタル酸無水物等の芳香族テトラカルボン酸二無水物等を挙げることができる。 Typical tetracarboxylic dianhydride components used in the production of polyimide films include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,4 ′ -Oxydiphthalic anhydride, 3,3 ', 4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3', 4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2, 3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 4,4′-hexafluoroisopropylide Diphthalic anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, p-phenylenebis (trimellitic acid mono Ester anhydride) and aromatic tetracarboxylic dianhydrides such as p-phenylenediphthalic anhydride.
一方、ジアミン成分としては、４，４’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、２，２−ビス（４−アミノフェノキシフェニル）プロパン、１，４−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（３−アミノフェノキシ）ベンゼン、ビス（４−（４−アミノフェノキシ）フェニル）スルフォン、ビス（４−（３−アミノフェノキシ）フェニル）スルフォン、４，４’−ビス（４−アミノフェノキシ）ビフェニル、２，２−ビス（４−アミノフェノキシフェニル）ヘキサフルオロプロパン、４、４’−ジアミノジフェニルスルフォン、３、３’−ジアミノジフェニルスルフォン、９、９−ビス（４−アミノフェニル）フルオレン、ビスアミノフェノキシケトン、４、４’−（１，４−フェニレンビス（１−メチルエチリデン））ビスアニリン、４、４’−（１，３−フェニレンビス（１−メチルエチリデン））ビスアニリン、メタフェニレンジアミン、パラフェニレンジアミン、４、４’−ジアミノベンズアニリド、３、３’−ジメチル−４、４’−ジアミノビフェニル、３、３’−ジメトキシ−４、４’−ジアミノビフェニル等の芳香族ジアミン、あるいはその他の脂肪族ジアミンを挙げることができる。 On the other hand, as the diamine component, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 2,2-bis (4-aminophenoxyphenyl) propane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) Phenyl) sulfone, 4,4′-bis (4-aminophenoxy) biphenyl, 2,2-bis (4-aminophenoxyphenyl) hexafluoropropane, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenyl Sulfone, 9,9-bis (4-aminophenyl) fluorene, bisaminophen Xyloketone, 4,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 ′-(1,3-phenylenebis (1-methylethylidene)) bisaniline, metaphenylenediamine, paraphenylene Aromatic diamines such as diamine, 4,4'-diaminobenzanilide, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, or other fats Group diamines can be mentioned.
本発明の絶縁性ポリイミドフィルムは、その前駆体であるポリアミド酸重合体の重量平均分子量は１０，０００〜１，０００，０００であることが望ましい。重量平均分子量が１０，０００未満ではできあがったフィルムが脆くなる場合がある。他方、重量平均分子量が１，０００，０００を越えるとポリイミド前駆体であるポリアミド酸ワニスの粘度が高くなりすぎ取扱いが難しくなるおそれがある。 As for the insulating polyimide film of this invention, it is desirable that the polyamic acid polymer which is the precursor has a weight average molecular weight of 10,000 to 1,000,000. If the weight average molecular weight is less than 10,000, the resulting film may become brittle. On the other hand, if the weight average molecular weight exceeds 1,000,000, the viscosity of the polyamic acid varnish, which is a polyimide precursor, becomes too high and handling may be difficult.
また、ポリアミド酸重合体に各種の有機、或いは無機の添加剤、或は各種の強化材を添加し、複合化されたポリイミドフィルムとすることも可能である。 It is also possible to form a composite polyimide film by adding various organic or inorganic additives or various reinforcing materials to the polyamic acid polymer.
ポリアミド酸重合体の生成反応に使用される有機極性溶媒としては、例えば、ジメチルスルホキシド、ジエチルスルホキシドなどのスルホキシド系溶媒；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミドなどのホルムアミド系溶媒；Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミドなどのアセトアミド系溶媒；Ｎ−メチル−２−ピロリドン、Ｎ−ビニル−２−ピロリドンなどのピロリドン系溶媒；フェノール、ｏ−、ｍ−、またはｐ−クレゾール、キシレノール、ハロゲン化フェノール、カテコールなどのフェノール系溶媒；あるいはヘキサメチルホスホルアミド、γ−ブチロラクトンなどを挙げることができる。これらは単独または混合物として用いるのが望ましい。更にはキシレン、トルエンのような芳香族炭化水素を前記溶媒に一部混合して使用してもよい。 Examples of the organic polar solvent used in the reaction for forming the polyamic acid polymer include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide; formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide; N , N-dimethylacetamide, N, N-diethylacetamide, and other acetamide solvents; N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, and other pyrrolidone solvents; phenol, o-, m-, or p- Phenol solvents such as cresol, xylenol, halogenated phenol and catechol; or hexamethylphosphoramide, γ-butyrolactone and the like can be mentioned. These are preferably used alone or as a mixture. Furthermore, aromatic hydrocarbons such as xylene and toluene may be partially mixed in the solvent.
また、このポリアミド酸重合体は前記の有機極性溶媒中に５〜４０重量％、好ましくは１０〜３０重量％溶解されているのが取扱いの面から望ましい。 Further, it is desirable from the viewpoint of handling that this polyamic acid polymer is dissolved in the organic polar solvent in an amount of 5 to 40% by weight, preferably 10 to 30% by weight.
このポリアミド酸重合体溶液から、ポリイミドフィルムを得るためには熱的に脱水する熱的方法、脱水剤を用いる化学的方法のいずれを用いてもよいが、化学的方法によると生成するポリイミドフィルムの伸び率や引張強度等の機械特性がすぐれたものになるので好ましい。 In order to obtain a polyimide film from this polyamic acid polymer solution, either a thermal method of thermally dehydrating or a chemical method using a dehydrating agent may be used. This is preferable because mechanical properties such as elongation and tensile strength are excellent.
以下に化学的方法による絶縁性ポリイミドフィルムの作製についての例を説明する。
上記ポリアミド酸重合体またはその溶液に化学量論以上の脱水剤と触媒量の第３級アミンを加えた溶液をドラム或はエンドレスベルト上に流延または塗布して膜状とし、その膜を２００℃以下の温度で約１０〜１００００秒乾燥し、自己支持性のポリアミド酸重合体の膜を得る。ついで、これを支持体より引き剥し端部を固定する。その後所定の温度で加熱することによりイミド化し、冷却後端部の固定を解放し絶縁性ポリイミドフィルムを得る。
The example about preparation of the insulating polyimide film by a chemical method is demonstrated below.
A solution obtained by adding a stoichiometric or higher amount of a dehydrating agent and a catalytic amount of a tertiary amine to the polyamic acid polymer or a solution thereof is cast or coated on a drum or an endless belt to form a film. Dry for about 10 to 10000 seconds at a temperature of ℃ or lower to obtain a self-supporting polyamic acid polymer film. Next, this is peeled off from the support and the end is fixed. Thereafter, it is imidized by heating at a predetermined temperature, and after cooling, fixing of the end portion is released to obtain an insulating polyimide film.
ここで言う脱水剤としては、例えば無水酢酸等の脂肪族酸無水物、無水安息香酸等の芳香族酸無水物などが挙げられる。また触媒としては、例えばトリエチルアミンなどの脂肪族第３級アミン類、ジメチルアニリン等の芳香族第３級アミン類、ピリジン、ピコリン、イソキノリン等の複素環式第３級アミン類などが挙げられる。 Examples of the dehydrating agent herein include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline.
また、絶縁性ポリイミドフィルムは、接着剤等の異種材料との密着性を向上させる目的で、熱硬化性樹脂、熱可塑性樹脂、有機モノマー、カップリング剤等の各種有機物をプライマーとして塗布する方法、金属水酸化物、有機アルカリ等で表面処理する方法、プラズマ処理、コロナ処理する方法、表面をグラフト化させる方法、等の各種表面処理を行うことができる。 Insulating polyimide film is a method of applying various organic substances such as a thermosetting resin, a thermoplastic resin, an organic monomer, and a coupling agent as a primer for the purpose of improving adhesion with different materials such as an adhesive, Various surface treatments such as a surface treatment with a metal hydroxide, an organic alkali, etc., a plasma treatment, a corona treatment, and a surface grafting method can be performed.
（厚み）
本発明においては、全光線透過率、光沢度、体積抵抗率を測定する際に１２．５μｍ厚みの絶縁性ポリイミドフィルムを用いる。ここで本発明でいう１２．５μｍ厚みとは、１００ｍｍ角サイズの絶縁性ポリイミドフィルムの任意の５点を厚み計（株式会社ミツトヨ製、レーザホロゲージ ＬＧＥ−１０１０）にて測定し、その５点の平均値が１２．５μｍであることをいう。
(Thickness)
In the present invention, an insulating polyimide film having a thickness of 12.5 μm is used when measuring total light transmittance, glossiness, and volume resistivity. Here, the 12.5 μm thickness referred to in the present invention means that any five points of a 100 mm square insulating polyimide film are measured with a thickness meter (Mitutoyo Co., Ltd., Laser Holo Gauge LGE-1010). Means an average value of 12.5 μm.
（全光線透過率）
本発明に係る絶縁性ポリイミドフィルムは、該フィルムの１２．５μｍ厚みでの全光線透過率が５％以下であることを特徴とする。本発明の全光線透過率は以下のようにして求めることができる。
(Total light transmittance)
The insulating polyimide film according to the present invention is characterized in that the total light transmittance of the film at a thickness of 12.5 μm is 5% or less. The total light transmittance of the present invention can be determined as follows.
評価用のサンプルとして、５０ｍｍ角、１２．５μｍ厚みの絶縁性ポリイミドフィルムを用い、日本電色工業株式会社製のヘーズメーター、ＮＤＨ ５０００を用いて、ＡＳＴＭ Ｄ １００３に従って全光線透過率（％）を測定することにより求めることができる。 As an evaluation sample, a 50 mm square, 12.5 μm thick insulating polyimide film was used, and a total light transmittance (%) was measured according to ASTM D 1003 using a Nippon Denshoku Industries Co., Ltd. haze meter, NDH 5000. It can be determined by measuring.
本発明において全光線透過率は遮光性を表す指標であり、全光線透過率が５％よりも大きい場合は、十分な遮光性を得ることができない。 In the present invention, the total light transmittance is an index representing the light shielding property. When the total light transmittance is larger than 5%, sufficient light shielding property cannot be obtained.
（光沢度）
本発明に係る絶縁性ポリイミドフィルムは、該フィルムの１２．５μｍ厚みでの光沢度が５％以下であることを特徴とする。本発明の光沢度は以下のようにして求めることができる。
(Glossiness)
The insulating polyimide film according to the present invention is characterized in that the glossiness of the film at a thickness of 12.5 μm is 5% or less. The glossiness of the present invention can be determined as follows.
評価用のサンプルとして、１００ｍｍ角、１２．５μｍ厚みの絶縁性ポリイミドフィルムを用い、ビック ガードナー社製の光沢度計、マイクロートリーグロスを用いて、入射角６０°での光沢度（％）測定することにより求めることができる。 Using a 100 mm square, 12.5 μm thick insulating polyimide film as a sample for evaluation, measuring glossiness (%) at an incident angle of 60 ° using a Bic Gardner gloss meter and Micro-Toe loss. Can be obtained.
本発明において光沢度はマットな質感を表す指標であり、光沢度が５％よりも大きい場合は、マットな質感を得ることができない。 In the present invention, the glossiness is an index representing a matte texture, and when the glossiness is greater than 5%, a matte texture cannot be obtained.
（体積抵抗率）
本発明に係る絶縁性ポリイミドフィルムは、体積抵抗率が２×１０16Ω・ｃｍ以上であることを特徴とする。
(Volume resistivity)
The insulating polyimide film according to the present invention has a volume resistivity of 2 × 10 16 Ω · cm or more.
評価用のサンプルとして、１００ｍｍ角、１２．５μｍ厚みの絶縁性ポリイミドフィルムを用い、株式会社アドバンテスト製デジタル超高抵抗／微小電流計 Ｒ８３４０と、レジスティビティチェンバ Ｒ１２７０２Ａとを組み合わせた装置を用い、１００Ｖ印加し１分経過後の抵抗値を測定することにより求めることができる。 As an evaluation sample, an insulating polyimide film having a 100 mm square and a thickness of 12.5 μm was used, and a 100 V voltage was applied using an apparatus combining a digital ultrahigh resistance / microammeter R8340 manufactured by Advantest Co., Ltd. and a resistance chamber R12702A. It can be obtained by measuring the resistance value after 1 minute has elapsed.
本発明において体積抵抗率は絶縁信頼性を表す指標であり、体積抵抗率が２×１０16Ω・ｃｍ未満である場合、十分な絶縁信頼性を確保することができない。 In the present invention, the volume resistivity is an index representing insulation reliability. When the volume resistivity is less than 2 × 10 16 Ω · cm, sufficient insulation reliability cannot be ensured.
（絶縁性ポリイミドフィルムの製造方法）
本発明に係る絶縁性ポリイミドフィルムの製造方法について説明する。本発明に係る絶縁性ポリイミドフィルムは、ポリアミド酸を重合する際にあらかじめ黒色顔料、フィラーを添加しておく方法、ポリアミド酸重合体と、黒色顔料分散液、フィラー分散液とを混合する方法、等の方法によりポリアミド酸重合体に黒色顔料、フィラーを分散させたポリアミド酸重合体溶液を得た後に、前記溶液を用いて熱的、あるいは化学的方法によりイミド化せしめることで得ることができる。一例として、ポリアミド酸重合体と、黒色顔料分散液、フィラー分散液とを混合する方法にてポリアミド酸重合体溶液を得た後に、化学的方法によりイミド化せしめて絶縁性ポリイミドフィルムを得る方法を説明する。
(Insulating polyimide film manufacturing method)
The manufacturing method of the insulating polyimide film according to the present invention will be described. The insulating polyimide film according to the present invention includes a method of adding a black pigment and a filler in advance when polymerizing polyamic acid, a method of mixing a polyamic acid polymer, a black pigment dispersion, a filler dispersion, and the like. After obtaining a polyamic acid polymer solution in which a black pigment and a filler are dispersed in the polyamic acid polymer by the above method, it can be obtained by imidizing by a thermal or chemical method using the solution. As an example, after obtaining a polyamic acid polymer solution by a method of mixing a polyamic acid polymer, a black pigment dispersion, and a filler dispersion, a method of imidizing by a chemical method to obtain an insulating polyimide film explain.
ポリアミド酸重合体溶液は、上述したように１種または２種以上のテトラカルボン酸二無水物成分と１種または２種以上のジアミン成分を実質等モル使用し、有機極性溶媒中で重合することによって得られる。黒色顔料分散液、フィラー分散液は、有機溶媒に縣濁させる方法、ポリアミド酸重合体の一部とともに有機溶媒に混合する方法、等の方法により得ることができる。特にポリアミド酸重合体の一部とともに有機溶媒に混合する方法は分散性の良い分散液を得ることができるため好ましい。分散方法としては、ボールミル、ビーズミル、三本ロール、ホモジナイザー、超音波、撹拌翼を用いた撹拌、等公知の分散技術を適用可能である。尚、黒色顔料とフィラーとは別々に分散液を作製してもよいし、１つの分散液としてもよい。 As described above, the polyamic acid polymer solution is polymerized in an organic polar solvent using substantially one mole of one or more tetracarboxylic dianhydride components and one or more diamine components. Obtained by. The black pigment dispersion and the filler dispersion can be obtained by a method such as a method of suspending in an organic solvent, a method of mixing in an organic solvent together with a part of the polyamic acid polymer, and the like. In particular, a method of mixing with a part of the polyamic acid polymer in an organic solvent is preferable because a dispersion having good dispersibility can be obtained. As a dispersion method, a known dispersion technique such as a ball mill, a bead mill, a three roll, a homogenizer, ultrasonic waves, stirring using a stirring blade, or the like can be applied. In addition, a black pigment and a filler may produce a dispersion liquid separately, and are good also as one dispersion liquid.
このようにして得たポリアミド酸重合体溶液、黒色顔料分散液、フィラー分散液、さらに脱水剤と第三級アミンとを混合、撹拌し、ドラム或はエンドレスベルト上に流延または塗布して膜状とし、その膜を２００℃以下の温度で約１０〜１００００秒乾燥し、自己支持性のポリアミド酸重合体の膜を得る。ついで、これを支持体より引き剥し端部を固定する。その後所定の温度で加熱することによりイミド化し、冷却後端部の固定を解放し絶縁性ポリイミドフィルムを得る。 The polyamic acid polymer solution, black pigment dispersion, filler dispersion, and dehydrating agent and tertiary amine thus obtained are mixed and stirred, and cast or coated on a drum or endless belt. The film is dried at a temperature of 200 ° C. or lower for about 10 to 10,000 seconds to obtain a self-supporting polyamic acid polymer film. Next, this is peeled off from the support and the end is fixed. Thereafter, it is imidized by heating at a predetermined temperature, and after cooling, fixing of the end portion is released to obtain an insulating polyimide film.
得られた絶縁性ポリイミドフィルムは、上述した方法により全光線透過率、光沢度、体積抵抗率を測定することができる。 The obtained insulating polyimide film can be measured for total light transmittance, glossiness, and volume resistivity by the method described above.
また、絶縁性ポリイミドの黒色については、評価用のサンプルとして１００ｍｍ角、１２．５μｍ厚みの絶縁性ポリイミドフィルムを用い、マクベス反射濃度計（Ｍａｃｂｅｔｈ ＲＤ９１４）を用いて測定した値を黒色度とすればよい。マクベス反射濃度計にて測定される黒色度は、０．７以上、好ましくは０．８以上あることが好ましい。黒色度が０．７より小さい場合は十分な黒色が得られていないため、嫌光部に使用することが困難になる。 Moreover, about the black of an insulating polyimide, if the value measured using the Macbeth reflection densitometer (Macbeth RD914) is 100 mm square and an insulating polyimide film with a thickness of 12.5 μm as a sample for evaluation, Good. The blackness measured with a Macbeth reflection densitometer is 0.7 or more, preferably 0.8 or more. When the blackness is less than 0.7, sufficient black color is not obtained, so that it is difficult to use it in the aphobic part.
また、絶縁信頼性を評価するため、表面抵抗率を測定してもよく、評価用のサンプルとして、１００ｍｍ角、１２．５μｍ厚みの絶縁性ポリイミドフィルムを用い、株式会社アドバンテスト製デジタル超高抵抗／微小電流計 Ｒ８３４０と、レジスティビティチェンバ Ｒ１２７０２Ａとを組み合わせた装置を用い、１００Ｖ印加し１分経過後の抵抗値を測定することにより求めることができる。 In addition, in order to evaluate the insulation reliability, the surface resistivity may be measured. As an evaluation sample, an insulating polyimide film having a 100 mm square and a thickness of 12.5 μm is used. Using a device combining a microammeter R8340 and a resiliency chamber R12702A, it can be obtained by applying a voltage of 100 V and measuring the resistance value after one minute has elapsed.
表面抵抗率は１×１０15Ω／□以上であることが好ましい。表面抵抗率が１×１０15Ω／□より小さい場合、十分な絶縁信頼性を確保することができない。 The surface resistivity is preferably 1 × 10 15 Ω / □ or more. When the surface resistivity is less than 1 × 10 15 Ω / □, sufficient insulation reliability cannot be ensured.
（カバーレイフィルム）
本発明に係る絶縁性ポリイミドフィルムは、プリント板の外側表面の導体パターンを全面的又は部分的にカバーするために使用される絶縁フィルムであるカバーレイフィルムに好適に用いることができる。 カバーレイフィルムは、該絶縁性ポリイミドフィルムの片面に接着剤を塗布・乾燥して形成するか、若しくは接着フィルムを貼り合せる事で形成し、必要に応じて接着剤面保護のためにセパレーターを貼り合わせることで得ることができる。
本発明の絶縁性ポリイミドフィルムは、そのもののみで十分な遮光性、及びマットな質感を有することから、接着剤に黒色顔料を添加する必要がなく、従って絶縁不良を生じる恐れもない。
また本発明の絶縁性ポリイミドフィルムは十分な絶縁性も確保していることから、外部との接触による絶縁不良を生じる恐れもなく、絶縁機能、保護機能に優れたカバーレイフィルムを得ることができる。
(Coverlay film)
The insulating polyimide film according to the present invention can be suitably used for a cover lay film which is an insulating film used for covering the conductor pattern on the outer surface of the printed board completely or partially. The cover lay film is formed by applying and drying an adhesive on one side of the insulating polyimide film, or by bonding an adhesive film, and if necessary, a separator is attached to protect the adhesive surface. It can be obtained by combining them.
Since the insulating polyimide film of the present invention itself has sufficient light-shielding properties and a matte texture, it is not necessary to add a black pigment to the adhesive, and therefore there is no risk of poor insulation.
In addition, since the insulating polyimide film of the present invention has sufficient insulating properties, it is possible to obtain a coverlay film excellent in insulating function and protective function without causing a failure of insulation due to contact with the outside. .
さらに、本発明の絶縁性ポリイミドフィルムは、１２．５μｍ厚みにおいても十分な遮光性、及びマットな質感を有することから、近年の技術トレンドである超薄膜カバーレイフィルムにも適用可能である。 Furthermore, since the insulating polyimide film of the present invention has a sufficient light-shielding property and a matte texture even at a thickness of 12.5 μm, it can be applied to an ultra-thin coverlay film which is a recent technical trend.
（フレキシブルプリント配線板）
上述のように、本発明に係る絶縁性ポリイミドフィルムからカバーレイフィルムを得、そのカバーレイフィルムを用いて得られるフレキシブルプリント配線板は、遮光性及び絶縁信頼性に優れるため、カメラ、ビデオカメラ、CD-ROMドライブの光ピックアップ部等の電子・光学機器に好適に用いられる。また、マットな質感を有するため、デザイン性、意匠性が要求される用途にも好適に用いられる。
(Flexible printed wiring board)
As described above, a cover lay film is obtained from the insulating polyimide film according to the present invention, and the flexible printed wiring board obtained using the cover lay film is excellent in light shielding properties and insulation reliability. It is suitably used for electronic and optical equipment such as an optical pickup section of a CD-ROM drive. Moreover, since it has a matte texture, it can be suitably used for applications that require design and design.
本発明に係るフレキシブルプリント配線板は、フレキシブル銅張積層板をパターニング加工したプリント配線板に、本発明に係る絶縁性ポリイミドフィルムから得たカバーレイフィルムを打ち抜き加工したものをプレス加工、ラミネート加工により貼り合せ、端子めっきを行い、必要に応じて補強板を貼り合せることで得ることができる。 The flexible printed wiring board according to the present invention is a printed wiring board obtained by patterning a flexible copper-clad laminate, punched with a coverlay film obtained from the insulating polyimide film according to the present invention, and subjected to pressing and laminating. Bonding and terminal plating can be performed, and a reinforcing plate can be bonded as necessary.
また、本発明に係る絶縁性ポリイミドフィルムは絶縁信頼性が高いため、カバーレイフィルムに限らず、フレキシブルプリント銅張積層板のベースフィルムとしても用いることが可能である。 Moreover, since the insulation polyimide film which concerns on this invention has high insulation reliability, it can be used not only as a coverlay film but as a base film of a flexible printed copper clad laminated board.
もちろん、本発明の用途はこれに限定されるものではなく、本発明の絶縁樹脂材料であれば、種々の用途に利用できることはいうまでもない。 Needless to say, the application of the present invention is not limited to this, and the insulating resin material of the present invention can be used for various applications.
以下、実施例および比較例に基づいて本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例および比較例における微細配線形成性は、次のようにして評価した。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to these. In addition, the fine wiring formability in an Example and a comparative example was evaluated as follows.
〔全光線透過率〕
５０ｍｍ角、１２．５μｍ厚みの絶縁性ポリイミドフィルムを用い、日本電色工業株式会社製のヘーズメーター、ＮＤＨ ５０００を用いて、ＡＳＴＭ Ｄ １００３に従って全光線透過率（％）を測定することにより求めた。
[Total light transmittance]
Using a 50 mm square, 12.5 μm thick insulating polyimide film, the total light transmittance (%) was measured according to ASTM D 1003 using a Nippon Denshoku Industries Co., Ltd. haze meter, NDH 5000. .
〔光沢度〕
１００ｍｍ角、１２．５μｍ厚みの絶縁性ポリイミドフィルムを用い、ビック ガードナー社製の光沢度計、マイクロートリーグロスを用いて、入射角６０°での光沢度（％）測定することにより求めた。
[Glossiness]
A 100 mm square, 12.5 μm thick insulating polyimide film was used, and the glossiness (%) at an incident angle of 60 ° was measured using a gloss meter made by Bic Gardner Co., Ltd. and a Microtole loss.
〔体積抵抗率〕
１００ｍｍ角、１２．５μｍ厚みの絶縁性ポリイミドフィルムを用い、株式会社アドバンテスト製デジタル超高抵抗／微小電流計 Ｒ８３４０と、レジスティビティチェンバ Ｒ１２７０２Ａとを組み合わせた装置を用い、１００Ｖ印加し１分経過後の抵抗値を測定することにより求めた。
[Volume resistivity]
Using a 100 mm square, 12.5 μm thick insulating polyimide film, a device combining a digital ultra-high resistance / microammeter R8340 manufactured by Advantest Co., Ltd. and a resiliency chamber R12702A, 100 V was applied and 1 minute later The resistance value was obtained by measuring.
〔フィルム化時のフィルムの機械的強度〕
フィルム化の際に、問題なくフィルム化できたものを○、フィルムが破断したものを×と判定した。
[Mechanical strength of film during film formation]
When the film was formed, it was determined that the film could be formed without any problem, and that the film was broken was determined as x.
〔遮光性〕
１２．５μｍ厚みの絶縁性ポリイミドフィルムを目視し、透けないもを○、透けるものを×と判定した。
[Light shielding]
An insulating polyimide film having a thickness of 12.5 μm was visually observed, and it was determined that “O” was not transparent and “X” was transparent.
〔マットな質感〕
１２．５μｍ厚みの絶縁性ポリイミドフィルムを目視し、マットな質感が得られているものを○、表面が光沢しており、マットな質感が得られていないものを×と判定した。
[Matte texture]
An insulating polyimide film having a thickness of 12.5 μm was visually observed, and a case where a mat-like texture was obtained was judged as ◯, and a case where the surface was glossy and a mat-like texture was not obtained was judged as x.
（合成例１；ポリアミド酸重合体の合成１）
１０℃に冷却したＮ，Ｎ−ジメチルホルムアミド（ＤＭＦ）６２０．４ｇにｐ−フェニレンジアミン（ｐ−ＰＤＡ）を １０．１ｇ、及び４，４’−ジアミノジフェニルエーテル（４，４’−ＯＤＡ）を５６．２ｇ添加して溶解させた後、ピロメリット酸二無水物（ＰＭＤＡ）を７９．２ｇ添加して６０分攪拌し溶解させた。さらにこの溶液に別途調製してあったＰＭＤＡのＤＭＦ溶液（ＰＭＤＡ２．４５ｇ／ＤＭＦ３１．６ｇ）を注意深く添加し、粘度が３０００ポイズ程度に達したところで添加を止めた。１時間撹拌を行って固形分濃度約１８.５重量％、２３℃での回転粘度が３２００ポイズのポリアミド酸重合体溶液（ａ）を得た。
(Synthesis Example 1; Synthesis 1 of polyamic acid polymer)
To 620.4 g of N, N-dimethylformamide (DMF) cooled to 10 ° C., 10.1 g of p-phenylenediamine (p-PDA) and 56 of 4,4′-diaminodiphenyl ether (4,4′-ODA) After 2 g was added and dissolved, 79.2 g of pyromellitic dianhydride (PMDA) was added and stirred for 60 minutes to dissolve. Furthermore, a DMF solution of PMDA (PMD 2.45 g / DMF 31.6 g) separately prepared was carefully added to this solution, and the addition was stopped when the viscosity reached about 3000 poise. Stirring was performed for 1 hour to obtain a polyamic acid polymer solution (a) having a solid content concentration of about 18.5% by weight and a rotational viscosity at 23 ° C. of 3200 poise.
（合成例２；ポリアミド酸重合体の合成２）
１０℃に冷却したＤＭＦ６２０．５ｇに４，４’−ＯＤＡを５９．９ｇ添加して溶解させた後、ＰＭＤＡを７９．１ｇ添加して６０分攪拌し溶解させた。さらにこの溶液に別途調製してあったＰＭＤＡのＤＭＦ溶液（ＰＭＤＡ２．４５ｇ／ＤＭＦ３１．５ｇ）を注意深く添加し、粘度が３０００ポイズ程度に達したところで添加を止めた。１時間撹拌を行って固形分濃度約１８.５重量％、２３℃での回転粘度が３３００ポイズのポリアミド酸重合体溶液（ｂ）を得た。
(Synthesis Example 2; Synthesis 2 of polyamic acid polymer)
After 59.9 g of 4,4′-ODA was added and dissolved in 620.5 g of DMF cooled to 10 ° C., 79.1 g of PMDA was added and stirred for 60 minutes to dissolve. Furthermore, a DMF solution of PMDA (PMD 2.45 g / DMF 31.5 g) separately prepared was carefully added to this solution, and the addition was stopped when the viscosity reached about 3000 poise. Stirring was performed for 1 hour to obtain a polyamic acid polymer solution (b) having a solid content concentration of about 18.5% by weight and a rotational viscosity at 23 ° C. of 3300 poise.
（黒色顔料分散液の調整例１）
ＤＭＦ５０ｇにカーボンブラック（三菱化学株式会社製＃２５、一次粒径４７μｍ）を５ｇ添加し、ホモジナイザーにて３０分間撹拌した。さらにポリアミド酸重合体溶液（ａ）を１００ｇ添加し、ホモジナイザーにて１０分間撹拌し、黒色顔料分散液（Ａ）を得た。
(Example 1 of preparation of black pigment dispersion)
5 g of carbon black (Mitsubishi Chemical Corporation # 25, primary particle size 47 μm) was added to 50 g of DMF, and the mixture was stirred for 30 minutes with a homogenizer. Further, 100 g of the polyamic acid polymer solution (a) was added and stirred for 10 minutes with a homogenizer to obtain a black pigment dispersion (A).
（黒色顔料分散液の調整例２）
カーボンブラック（三菱化学株式会社製ＭＡ１００Ｒ、一次粒径２４μｍ）を用いた以外は調整例１と同様にして黒色顔料分散液（Ｂ）を得た。
(Example 2 of preparation of black pigment dispersion)
A black pigment dispersion (B) was obtained in the same manner as in Preparation Example 1 except that carbon black (MA100R manufactured by Mitsubishi Chemical Corporation, primary particle size: 24 μm) was used.
（黒色顔料分散液の調整例３）
カーボンブラック（エボニック インダストリーズ社製Ｓｐｅｃｉａｌ Ｂｌａｃｋ４、一次粒径２５μｍ）を用いた以外は調整例１と同様にして黒色顔料分散液（Ｃ）を得た。
(Example 3 of preparation of black pigment dispersion)
A black pigment dispersion (C) was obtained in the same manner as in Preparation Example 1 except that carbon black (Special Black 4 manufactured by Evonik Industries, primary particle size 25 μm) was used.
（黒色顔料分散液の調整例４）
カーボンブラック（エボニック インダストリーズ社製Ｐｒｉｎｔｅｘ２５、一次粒径５６μｍ）を用いた以外は調整例１と同様にして黒色顔料分散液（Ｄ）を得た。
(Example 4 of preparation of black pigment dispersion)
A black pigment dispersion (D) was obtained in the same manner as in Preparation Example 1 except that carbon black (Printex25 manufactured by Evonik Industries, Inc., primary particle size 56 μm) was used.
（黒色顔料分散液の調整例５）
カーボンブラック（三菱化学株式会社製＃９００、一次粒径１６μｍ）を用いた以外は調整例１と同様にして黒色顔料分散液（Ｅ）を得た。
(Example 5 of preparation of black pigment dispersion)
A black pigment dispersion (E) was obtained in the same manner as in Preparation Example 1 except that carbon black (# 900 manufactured by Mitsubishi Chemical Corporation, primary particle size: 16 μm) was used.
（黒色顔料分散液の調整例６）
カーボンブラック（三菱化学株式会社製＃２６００、一次粒径１３μｍ）を用いた以外は調整例１と同様にして黒色顔料分散液（Ｆ）を得た。
(Example 6 of preparation of black pigment dispersion)
A black pigment dispersion (F) was obtained in the same manner as in Preparation Example 1 except that carbon black (# 2600 manufactured by Mitsubishi Chemical Corporation, primary particle size 13 μm) was used.
（黒色顔料分散液の調整例７）
ＤＭＦ５０ｇにカーボンブラック（三菱化学株式会社製＃２５、一次粒径４７μｍ）を２０ｇ添加し、ホモジナイザーにて３０分間撹拌した。さらにポリアミド酸重合体溶液（ａ）を１００ｇ添加し、ホモジナイザーにて１０分間撹拌し、黒色顔料分散液（Ｇ）を得た。
(Example 7 of preparation of black pigment dispersion)
20 g of carbon black (Mitsubishi Chemical Corporation # 25, primary particle size 47 μm) was added to 50 g of DMF, and the mixture was stirred with a homogenizer for 30 minutes. Further, 100 g of the polyamic acid polymer solution (a) was added and stirred for 10 minutes with a homogenizer to obtain a black pigment dispersion (G).
（フィラー分散液の調整例１）
ＤＭＦ５０ｇに酸化チタン（石原産業株式会社製ＣＲ−６０、粒径０．２１μｍ）を５ｇ添加し、ホモジナイザーにて３０分間撹拌した。さらにポリアミド酸重合体溶液（ａ）を１００ｇ添加し、ホモジナイザーにて１０分間撹拌し、フィラー分散液（Ｐ）を得た。
(Filler dispersion adjustment example 1)
5 g of titanium oxide (CR-60 manufactured by Ishihara Sangyo Co., Ltd., particle size 0.21 μm) was added to 50 g of DMF, and the mixture was stirred for 30 minutes with a homogenizer. Further, 100 g of the polyamic acid polymer solution (a) was added and stirred for 10 minutes with a homogenizer to obtain a filler dispersion (P).
（フィラー分散液の調整例２）
針状酸化チタン（石原産業株式会社製ＦＴＬ−１１０、繊維長１．６８μｍ、繊維径０．１３μｍ）を用いた以外は調整例１と同様にしてフィラー分散液（Ｑ）を得た。
(Filler dispersion adjustment example 2)
A filler dispersion liquid (Q) was obtained in the same manner as in Preparation Example 1 except that acicular titanium oxide (FTL-110, manufactured by Ishihara Sangyo Co., Ltd., fiber length 1.68 μm, fiber diameter 0.13 μm) was used.
（フィラー分散液の調整例３）
酸化アルミニウム（昭和電工株式会社製ＡＬ−４３−Ｌ、α結晶粒径０．８μｍ）を用いた以外は調整例１と同様にしてフィラー分散液（Ｒ）を得た。
(Filler dispersion adjustment example 3)
A filler dispersion (R) was obtained in the same manner as in Preparation Example 1 except that aluminum oxide (AL-43-L, Showa Denko KK, α crystal grain size 0.8 μm) was used.
（フィラー分散液の調整例４）
合成雲母（コープケミカル株式会社製ＭＫ−１００、粒径３〜５μｍ）を用いた以外は調整例１と同様にしてフィラー分散液（Ｓ）を得た。
(Filler dispersion adjustment example 4)
A filler dispersion (S) was obtained in the same manner as in Preparation Example 1 except that synthetic mica (MK-100 manufactured by Co-op Chemical Co., Ltd., particle size 3 to 5 μm) was used.
（フィラー分散液の調整例５）
リン酸カルシウム（味の素ファインテクノ株式会社製トップフローＫ、最大粒径１０μｍ）を用いた以外は調整例１と同様にしてフィラー分散液（Ｔ）を得た。
(Filler dispersion adjustment example 5)
A filler dispersion liquid (T) was obtained in the same manner as in Preparation Example 1 except that calcium phosphate (Top Flow K manufactured by Ajinomoto Fine Techno Co., Ltd., maximum particle size 10 μm) was used.
（フィラー分散液の調整例６）
シリカ（エボニック インダストリーズ社製アエロジルＲ９７２、粒径１６ｎｍ）を用いた以外は調整例１と同様にしてフィラー分散液（Ｕ）を得た。
(Filler dispersion adjustment example 6)
A filler dispersion (U) was obtained in the same manner as in Preparation Example 1 except that silica (Aerosil R972, particle size 16 nm, manufactured by Evonik Industries) was used.
（実施例１）
ポリアミド酸重合体溶液（ａ）４０ｇに黒色顔料分散液（Ａ）１５．５ｇ、フィラー分散液（Ｐ）１５．５ｇ、及び無水酢酸／３,５―ジエチルピリジン／ＤＭＦ（重量比１２．９０／２．９６／１３．１４）からなる硬化剤を２９ｇ添加して０℃以下の温度で攪拌・脱泡し、コンマコーターを用いてアルミ箔上に流延塗布した。この樹脂膜を１３８℃×６０秒で加熱した後アルミ箔から自己支持性のゲル膜を引き剥がして金属枠に固定し、２５５℃×７秒、３３０℃×７秒、３８０℃×６秒、５４０℃×１０秒で乾燥・イミド化させて厚み１２．５μｍの絶縁性ポリイミドフィルムを得た。得られたフィルムの特性を表1に示す。
Example 1
40 g of the polyamic acid polymer solution (a), 15.5 g of the black pigment dispersion (A), 15.5 g of the filler dispersion (P), and acetic anhydride / 3,5-diethylpyridine / DMF (weight ratio: 12.90 / 29 g of a curing agent consisting of 2.96 / 13.14) was added, stirred and degassed at a temperature of 0 ° C. or lower, and cast-coated on an aluminum foil using a comma coater. The resin film was heated at 138 ° C. for 60 seconds, and then the self-supporting gel film was peeled off from the aluminum foil and fixed to the metal frame. The temperature was 255 ° C. for 7 seconds, 330 ° C. for 7 seconds, 380 ° C. for 6 seconds, The film was dried and imidized at 540 ° C. for 10 seconds to obtain an insulating polyimide film having a thickness of 12.5 μm. The properties of the obtained film are shown in Table 1.
（実施例２〜１０）
表１に示すポリアミド酸重合体溶液、黒色顔料分散液、フィラー分散液を用いた以外は実施例１と同様にして厚み１２．５μｍの絶縁性ポリイミドフィルムを得た。得られたフィルムの特性を表1に示す。
(Examples 2 to 10)
An insulating polyimide film having a thickness of 12.5 μm was obtained in the same manner as in Example 1 except that the polyamic acid polymer solution, black pigment dispersion, and filler dispersion shown in Table 1 were used. The properties of the obtained film are shown in Table 1.
（実施例１１）
実施例１の絶縁性ポリイミドフィルムにエポキシ樹脂系熱硬化性接着フィルム（味の素ファインテクノ株式会社製、ＡＢＦ−ＳＨ−９Ｋ）を重ねて、真空ラミネーターにて１００℃、６０秒の条件にて仮圧着し、絶縁性ポリイミドフィルム／接着層からなるカバーレイフィルムを得た。このカバーレイフィルムは遮光性が高く、マットな質感を有していた。また、株式会社カネカ製ピクシオに１８μｍの電解銅箔を張り合わせたフレキスブル銅張積層板にパターニングを施し、配線幅／配線間隔＝２５μｍ／２５μｍの配線パターンを有する配線基板を得、該配線基板上に該カバーレイフィルムを真空プレス機にて１５０℃／２ＭＰａ／６０分の条件で積層し、フレキシブルプリント配線板を得た。得られたフレキシブルプリント配線板は遮光性が高く、マットな質感を有していた。また、８５℃、８５％ＲＨ、印加電圧１００Ｖ、測定電圧１００Ｖ、１０００時間の条件にてマイグレーション試験を行ったところ、絶縁抵抗値は低下することなく、高い絶縁性を有していた。
(Example 11)
An epoxy resin thermosetting adhesive film (ABF-SH-9K, Ajinomoto Fine Techno Co., Ltd., ABF-SH-9K) is layered on the insulating polyimide film of Example 1, and is temporarily crimped with a vacuum laminator at 100 ° C. for 60 seconds. Thus, a cover lay film composed of an insulating polyimide film / adhesive layer was obtained. This coverlay film had a high light shielding property and a matte texture. Also, patterning was applied to a flexible copper-clad laminate obtained by pasting Kaneka Pixio with 18 μm electrolytic copper foil to obtain a wiring board having a wiring pattern of wiring width / wiring interval = 25 μm / 25 μm, on the wiring board. The cover lay film was laminated with a vacuum press machine at 150 ° C./2 MPa / 60 minutes to obtain a flexible printed wiring board. The obtained flexible printed wiring board had a high light shielding property and had a matte texture. In addition, when a migration test was performed under the conditions of 85 ° C., 85% RH, applied voltage 100 V, measurement voltage 100 V, and 1000 hours, the insulation resistance value did not decrease and had high insulation properties.
（比較例１）
ポリアミド酸重合体溶液（ａ）５０ｇに黒色顔料分散液（Ａ）１５．５ｇ、及び無水酢酸／３,５―ジエチルピリジン／ＤＭＦ（重量比１２．９０／２．９６／１８．１４）からなる硬化剤を３４ｇ添加して０℃以下の温度で攪拌・脱泡し、コンマコーターを用いてアルミ箔上に流延塗布した。この樹脂膜を１３８℃×６０秒で加熱した後アルミ箔から自己支持性のゲル膜を引き剥がして金属枠に固定し、２５５℃×７秒、３３０℃×７秒、３８０℃×７秒、５４０℃×１０秒で乾燥・イミド化させて厚み１２．５μｍの絶縁性ポリイミドフィルムを得た。得られたフィルムの特性を表1に示す。
(Comparative Example 1)
It consists of 15.5 g of black pigment dispersion (A) and acetic anhydride / 3,5-diethylpyridine / DMF (weight ratio: 12.90 / 2.96 / 18.14) to 50 g of the polyamic acid polymer solution (a). 34 g of a curing agent was added, stirred and degassed at a temperature of 0 ° C. or lower, and cast on an aluminum foil using a comma coater. The resin film was heated at 138 ° C. for 60 seconds, and then the self-supporting gel film was peeled off from the aluminum foil and fixed to the metal frame. The temperature was 255 ° C. for 7 seconds, 330 ° C. for 7 seconds, 380 ° C. for 7 seconds, The film was dried and imidized at 540 ° C. for 10 seconds to obtain an insulating polyimide film having a thickness of 12.5 μm. The properties of the obtained film are shown in Table 1.
（比較例２）
ポリアミド酸重合体溶液（ａ）５０ｇに黒色顔料分散液（Ｇ）１７．０ｇ、及び無水酢酸／３,５―ジエチルピリジン／ＤＭＦ（重量比１２．９０／２．９６／１８．１４）からなる硬化剤を３４ｇ添加して０℃以下の温度で攪拌・脱泡し、コンマコーターを用いてアルミ箔上に流延塗布した。この樹脂膜を１３８℃×６０秒で加熱した後アルミ箔から自己支持性のゲル膜を引き剥がして金属枠に固定し、２５５℃×７秒、３５０℃×７秒、３８０℃×６秒、５４０℃×１０秒で乾燥・イミド化させて厚み１２．５μｍの絶縁性ポリイミドフィルムを得た。得られたフィルムの特性を表1に示す。
(Comparative Example 2)
It consists of 17.0 g of black pigment dispersion (G) and acetic anhydride / 3,5-diethylpyridine / DMF (weight ratio: 12.90 / 2.96 / 18.14) to 50 g of the polyamic acid polymer solution (a). 34 g of a curing agent was added, stirred and degassed at a temperature of 0 ° C. or lower, and cast on an aluminum foil using a comma coater. This resin film was heated at 138 ° C. × 60 seconds, and then the self-supporting gel film was peeled off from the aluminum foil and fixed to the metal frame, 255 ° C. × 7 seconds, 350 ° C. × 7 seconds, 380 ° C. × 6 seconds, The film was dried and imidized at 540 ° C. for 10 seconds to obtain an insulating polyimide film having a thickness of 12.5 μm. The properties of the obtained film are shown in Table 1.
（比較例３〜４）
表１に示すポリアミド酸重合体溶液、黒色顔料分散液を用いた以外は比較例１と同様にして厚み１２．５μｍの絶縁性ポリイミドフィルムを得た。得られたフィルムの特性を表1に示す。
(Comparative Examples 3-4)
An insulating polyimide film having a thickness of 12.5 μm was obtained in the same manner as in Comparative Example 1 except that the polyamic acid polymer solution and the black pigment dispersion shown in Table 1 were used. The properties of the obtained film are shown in Table 1.
（比較例５）
ポリアミド酸重合体溶液（ａ）４０ｇに黒色顔料分散液（Ｅ）１５．５ｇ、フィラー分散液（Ｐ）１５．５ｇ、及び無水酢酸／３,５―ジエチルピリジン／ＤＭＦ（重量比１２．９０／２．９６／１３．１４）からなる硬化剤を２９ｇ添加して０℃以下の温度で攪拌・脱泡し、コンマコーターを用いてアルミ箔上に流延塗布した。この樹脂膜を１３８℃×６０秒で加熱した後アルミ箔から自己支持性のゲル膜を引き剥がして金属枠に固定し、２５５℃×７秒、３３０℃×７秒、３８０℃×６秒、５４０℃×１０秒で乾燥・イミド化させて厚み１２．５μｍの絶縁性ポリイミドフィルムを得た。得られたフィルムの特性を表1に示す。
(Comparative Example 5)
40 g of the polyamic acid polymer solution (a), 15.5 g of the black pigment dispersion (E), 15.5 g of the filler dispersion (P), and acetic anhydride / 3,5-diethylpyridine / DMF (weight ratio: 12.90 / 29 g of a curing agent consisting of 2.96 / 13.14) was added, stirred and degassed at a temperature of 0 ° C. or lower, and cast-coated on an aluminum foil using a comma coater. The resin film was heated at 138 ° C. for 60 seconds, and then the self-supporting gel film was peeled off from the aluminum foil and fixed to the metal frame. The temperature was 255 ° C. for 7 seconds, 330 ° C. for 7 seconds, 380 ° C. for 6 seconds, The film was dried and imidized at 540 ° C. for 10 seconds to obtain an insulating polyimide film having a thickness of 12.5 μm. The properties of the obtained film are shown in Table 1.
比較例１に示すように、一次粒径が２０ｎｍ以上の黒色顔料を選択すると、黒色顔料のみでも十分な遮光性は得られているが、マットな質感が得られない。また、比較例２に示すように、黒色顔料の配合量を２０重量部に増やすと、マットな質感は改善するものの、体積抵抗率の低下、フィルム化時の機械強度の低下を招く。
比較例３、４に示すように、一次粒径が２０ｎｍ未満の黒色顔料を用いると、分散性が悪いため、結果的にマットな質感は得られているが、十分な遮光性が得られていない。さらにフィラーとして酸化チタンを配合すると（比較例５）、さらに分散性及び遮光性が低下する結果となった。
As shown in Comparative Example 1, when a black pigment having a primary particle size of 20 nm or more is selected, a sufficient light-shielding property can be obtained with only the black pigment, but a matte texture cannot be obtained. Further, as shown in Comparative Example 2, when the blending amount of the black pigment is increased to 20 parts by weight, the matte texture is improved, but the volume resistivity is lowered and the mechanical strength at the time of film formation is reduced.
As shown in Comparative Examples 3 and 4, when a black pigment having a primary particle size of less than 20 nm is used, dispersibility is poor, and as a result, a matte texture is obtained, but sufficient light shielding properties are obtained. Absent. Furthermore, when titanium oxide was blended as a filler (Comparative Example 5), the dispersibility and the light shielding property were further reduced.
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