JP2003191423A - Laminated film - Google Patents
Laminated filmInfo
- Publication number
- JP2003191423A JP2003191423A JP2001399703A JP2001399703A JP2003191423A JP 2003191423 A JP2003191423 A JP 2003191423A JP 2001399703 A JP2001399703 A JP 2001399703A JP 2001399703 A JP2001399703 A JP 2001399703A JP 2003191423 A JP2003191423 A JP 2003191423A
- Authority
- JP
- Japan
- Prior art keywords
- film
- laminated
- laminated film
- polyester
- photoresist
- 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
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 60
- 229920006267 polyester film Polymers 0.000 claims abstract description 52
- 229920000728 polyester Polymers 0.000 claims abstract description 26
- 239000000470 constituent Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 50
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 17
- 238000006068 polycondensation reaction Methods 0.000 claims description 14
- 239000011164 primary particle Substances 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 12
- 229910052787 antimony Inorganic materials 0.000 claims description 11
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000002834 transmittance Methods 0.000 claims description 9
- 229920005672 polyolefin resin Polymers 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920002050 silicone resin Polymers 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000001993 wax Substances 0.000 claims description 3
- 150000004657 carbamic acid derivatives Chemical class 0.000 claims description 2
- 150000001844 chromium Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 22
- 230000001681 protective effect Effects 0.000 abstract description 12
- 239000002440 industrial waste Substances 0.000 abstract description 4
- 230000003578 releasing effect Effects 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 2
- -1 polyethylene terephthalate Polymers 0.000 description 20
- 239000002585 base Substances 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- 229920001634 Copolyester Polymers 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 5
- 238000010030 laminating Methods 0.000 description 5
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000011362 coarse particle Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004745 nonwoven fabric Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001463 antimony compounds Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002291 germanium compounds Chemical class 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229920001179 medium density polyethylene Polymers 0.000 description 2
- 239000004701 medium-density polyethylene Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- CVBWTNHDKVVFMI-LBPRGKRZSA-N (2s)-1-[4-[2-[6-amino-8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]purin-9-yl]ethyl]piperidin-1-yl]-2-hydroxypropan-1-one Chemical compound C1CN(C(=O)[C@@H](O)C)CCC1CCN1C2=NC=NC(N)=C2N=C1SC(C(=C1)Br)=CC2=C1OCO2 CVBWTNHDKVVFMI-LBPRGKRZSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- 229920006310 Asahi-Kasei Polymers 0.000 description 1
- 101710108306 Bifunctional dihydroflavonol 4-reductase/flavanone 4-reductase Proteins 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 101710170824 Dihydroflavonol 4-reductase Proteins 0.000 description 1
- 101100219325 Phaseolus vulgaris BA13 gene Proteins 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007763 reverse roll coating Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Materials For Photolithography (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は積層フィルムに関
し、更に詳しくはその製造及び取扱いが簡便で、特にプ
リント配線板の製造に有用なドライフィルムフォトレジ
スト用の積層フィルムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated film, and more particularly to a laminated film for a dry film photoresist which is easy to manufacture and handle and is particularly useful for manufacturing a printed wiring board.
【０００２】[0002]
【従来の技術】電子産業分野での主要な部品の一つであ
るプリント配線板は、ドライフィルムフォトレジスト
（ＤＦＲ）を用いて、写真法によって基板上に回路を形
成する方法で製造されることが多い。このＤＦＲは、従
来、厚み１５〜７５μｍのフォトレジスト層（３）を、
厚み１０〜２５μｍの二軸延伸ポリエチレンテレフタレ
ートフィルムからなるベースフィルム（１）と厚み２０
〜４０μｍのポリエチレンフィルムからなる保護フィル
ム（２）でサンドイッチした三層構造からなり（図１参
照）、通常幅１ｍ以上、長さ１２０〜１５０ｍのものを
ロール状に巻いて取り引きされている。2. Description of the Related Art A printed wiring board, which is one of the major components in the electronics industry, is manufactured by a method of forming a circuit on a substrate by a photographic method using a dry film photoresist (DFR). There are many. Conventionally, this DFR has a photoresist layer (3) with a thickness of 15 to 75 μm,
Base film (1) comprising a biaxially stretched polyethylene terephthalate film having a thickness of 10 to 25 μm and a thickness of 20
It has a three-layer structure sandwiched by a protective film (2) made of a polyethylene film having a thickness of up to 40 μm (see FIG. 1), and usually has a width of 1 m or more and a length of 120 to 150 m and is rolled and traded.
【０００３】ＤＦＲは、プリント配線板の製造におい
て、保護フィルムを剥離しながらフォトレジスト層側を
ラミネーター装置により銅箔基板に熱圧着させる。その
後、ベースフィルム上に回路を印刷したガラス版を密着
させ、このガラス板側から光を照射することで露光し、
次いで該ベースフィルムを剥離して現像するのが一般的
である。In the manufacture of printed wiring boards, DFR thermocompression-bonds the photoresist layer side to a copper foil substrate by a laminator device while peeling off the protective film. After that, a glass plate on which a circuit is printed is brought into close contact with the base film and exposed by irradiating light from this glass plate side,
Then, the base film is generally peeled off and developed.
【０００４】この保護フィルムにはインフレーション延
伸方式により製膜された中密度ポリエチレンフィルムな
どのポリオレフィンフィルムが使用されており、フォト
レジスト層（光硬化性樹脂層）の保護と同時に、ＤＦＲ
をロール状に巻いたときベースフィルムの裏面とフォト
レジスト層とが粘着するのを防止する機能をも兼備す
る。また、露光には波長３６５ｎｍ付近の紫外線（ＵＶ
光）が用いられるので、ベースフィルムには高透明でＵ
Ｖ透過性に優れた二軸延伸ポリエステルフィルムが使用
されている。As the protective film, a polyolefin film such as a medium density polyethylene film formed by an inflation stretching method is used. At the same time as protecting the photoresist layer (photocurable resin layer), the DFR is used.
It also has a function of preventing the back surface of the base film and the photoresist layer from sticking to each other when the film is rolled. In addition, for exposure, ultraviolet rays (UV
(Light) is used, so it is highly transparent and U
A biaxially stretched polyester film having excellent V transparency is used.
【０００５】ＤＦＲは、プリント配線板の製造におい
て、銅箔基板の規格に対応して保護フィルムを備えたま
まスリットされる。このため、剥がされた保護フィルム
やベースフィルムは再使用することができず、使用後の
フィルムは産業廃棄物として捨てられる。In the production of printed wiring boards, DFRs are slit while having a protective film in conformity with the standard of copper foil substrates. Therefore, the protective film and the base film that have been peeled off cannot be reused, and the used film is discarded as industrial waste.
【０００６】従って、ＤＦＲの透明ベースフィルムとし
て用いられるポリエステルフィルムは極力薄膜化し、か
つ保護フィルムも薄膜化して、ロール状巻取りをコンパ
クトにするのが理想的であるが、近年ロールの広幅化が
進み、高品質のＤＦＲを１．６ｍ以上の広幅で安定生産
するにはベースフィルムの厚みは１０〜２５μｍを必要
とし、そして該ベースフィルムと保護フィルムの総厚み
では５０〜１００μｍ程度とする構成がとられている。Therefore, it is ideal that the polyester film used as the transparent base film of the DFR is made as thin as possible, and the protective film is also made thin to make the roll winding compact, but in recent years, the width of the roll has been widened. The thickness of the base film is required to be 10 to 25 μm in order to stably produce a high quality DFR in a wide width of 1.6 m or more, and the total thickness of the base film and the protective film is about 50 to 100 μm. It is taken.
【０００７】そこで、従来のフォトレジスト層の上の保
護フィルムを無くし、保護フィルムを剥離する工程を省
略し、かつ産業廃棄物の軽減に寄与するＤＦＲとして、
透明ベースフィルムの一方の表面にフォトレジスト層を
塗設し、かつベースフィルムの他方の表面にフォトレジ
スト層に対して離型性を有するオレフィン系樹脂の離型
層を積層した複合フィルムからなり、該複合フィルムを
ロール状に巻いてフォトレジスト層を離型層で保護する
ようにしたドライフィルムフォトレジスト用ポリエステ
ルフィルム、いわゆるカバーレスフィルムが特許第２８
８２９５３号により知られている。Therefore, as a DFR that eliminates the conventional protective film on the photoresist layer, omits the step of peeling the protective film, and contributes to the reduction of industrial waste,
A photoresist layer is coated on one surface of the transparent base film, and is composed of a composite film in which a release layer of an olefin resin having releasability for the photoresist layer is laminated on the other surface of the base film, A polyester film for a dry film photoresist in which the composite film is wound in a roll shape so that the photoresist layer is protected by a release layer, a so-called coverless film is disclosed in Japanese Patent No. 28.
Known from No. 82953.
【０００８】最近では、特開平９−９６９０７号公報に
より、感光性組成物層を含み前記感光性組成物層に積層
されたフィルムと前記感光性組成物層とが剥離可能で可
撓性を有する感光性フィルムにおいて、二軸延伸ポリエ
ステルフィルムとポリエチレンフィルムからなる積層フ
ィルムの何れかの面に前記感光性組成物層が塗布され、
この感光性組成物層が形成された積層フィルムを巻き取
って形成されてなることを特徴とする感光性フィルムが
提唱されている。Recently, according to JP-A-9-96907, a film including a photosensitive composition layer and laminated on the photosensitive composition layer and the photosensitive composition layer are peelable and flexible. In the photosensitive film, the photosensitive composition layer is applied to any surface of a laminated film composed of a biaxially stretched polyester film and a polyethylene film,
A photosensitive film characterized by being formed by winding up a laminated film having this photosensitive composition layer formed thereon has been proposed.
【０００９】しかし、特開平９−９６９０７号公報に記
載のものではベースフィルムとして使用するポリエステ
ルフィルムはＵＶ透過性を上げる為の特別な工夫が成さ
れておらず、近年の高解像度ＤＦＲに使用するには十分
ではない。However, in the one disclosed in Japanese Patent Laid-Open No. 9-96907, the polyester film used as the base film has not been specially devised to improve the UV transparency, and is used for the high resolution DFR in recent years. Is not enough for.
【００１０】また、ドライフィルムフォトレジスト用フ
ィルムを製造する際の取扱い性、あるいはドライフィル
ムフォトレジスト自体の取扱い性が良好なものとするた
めに、支持体層のポリエステルフィルムは、適度な滑り
性と巻取り性および引裂き強度を有していることが要求
される。従来、かかる両方の特性を満足させようとし
て、ポリエステルフィルム中に微細粒子を含有させ、フ
ィルム表面に微細な突起を形成させる方法が用いられて
おり、例えば、特開平７−３３３８５３号公報には、少
なくとも片側の最外層に、平均粒径０．０１〜３．０μ
ｍの粒子（球状または不定形シリカ粒子、球状架橋高分
子粒子等）を含有し、該最外層表面のＲａ（中心線平均
粗さ）が０．００５μｍ以上、Ｒｔ（最大高さ）が１．
５μｍ未満であり、かつフィルムヘーズが１．５％以下
であるフォトレジスト用二軸配向積層ポリエステルフィ
ルムが提案されている。Further, in order to make the handling of the dry film photoresist film easy or the handling of the dry film photoresist itself good, the polyester film of the support layer has a proper slipperiness and It is required to have windability and tear strength. Conventionally, in order to satisfy both of these characteristics, a method has been used in which fine particles are contained in a polyester film to form fine protrusions on the film surface. For example, JP-A-7-333853 discloses At least one outermost layer has an average particle size of 0.01 to 3.0 μm.
m particles (spherical or amorphous silica particles, spherical cross-linked polymer particles, etc.), Ra (center line average roughness) of the outermost layer surface is 0.005 μm or more, and Rt (maximum height) is 1.
A biaxially oriented laminated polyester film for photoresist having a thickness of less than 5 μm and a film haze of 1.5% or less has been proposed.
【００１１】しかしながら、このポリエステルフィルム
では、十分な取扱い性が得られる程度に微細粒子を添加
すると、配向時にボイドが発生することとあいまって透
明性が低下してしまい、波長３６５ｎｍ近辺の光透過性
が不十分になる場合があり、解像度が低下して細密な回
路パータンが得られ難いという問題がある。また、上記
のような積層ポリエステルフィルムでは、その製造コス
トが高くなるという問題もある。However, in this polyester film, if fine particles are added to such an extent that sufficient handleability can be obtained, the transparency is lowered due to the occurrence of voids at the time of orientation, and the light transmittance in the vicinity of a wavelength of 365 nm. May become insufficient, and there is a problem that the resolution is lowered and it is difficult to obtain a fine circuit pattern. Further, the above-mentioned laminated polyester film also has a problem that the manufacturing cost thereof becomes high.
【００１２】また、最近の家電リサイクル法の制定によ
り、電気製品及びそれを製造する為の製品のリサイクル
を促進する為、それらを構成する材料は、アンチモン、
錫、鉛が含まれないことが要求されている。従来、ポリ
エステルフィルムを構成するポリエステルポリマーを製
造する為の重縮合触媒としてアンチモン化合物が用いら
れているが、アンチモン化合物以外の重縮合触媒を用い
ることが望まれている。In order to promote the recycling of electric appliances and products for manufacturing the appliances due to the recent enactment of the Home Appliance Recycling Law, antimony,
It is required to contain no tin or lead. Conventionally, an antimony compound has been used as a polycondensation catalyst for producing a polyester polymer constituting a polyester film, but it is desired to use a polycondensation catalyst other than the antimony compound.
【００１３】[0013]
【発明が解決しようとする課題】本発明の目的は、かか
る従来技術の問題点を解消し、高解像度ＤＦＲに使用し
得る透明性、ＵＶ透過性と取扱い性（滑り性）を満足
し、フォトレジスト層の上に保護フィルムを設ける工程
を省略し、かつ産業廃棄物の軽減に寄与するドライフィ
ルムフォトレジスト（ＤＦＲ）、いわゆるカバーレスＤ
ＦＲに有用な積層フィルムを提供することにある。SUMMARY OF THE INVENTION The object of the present invention is to solve the problems of the prior art and to satisfy the transparency, UV transparency and handleability (sliding property) that can be used for high resolution DFR. A so-called coverless D, a dry film photoresist (DFR) that eliminates the step of providing a protective film on the resist layer and contributes to the reduction of industrial waste.
It is to provide a laminated film useful for FR.
【００１４】[0014]
【課題を解決するための手段】本発明の課題は、本発明
によれば、ポリエステルを主要構成成分とするポリエス
テルフィルムの一方の表面に離型層を設けた積層フィル
ムであって、該積層フィルムの波長３６５ｎｍの光線透
過率が８０％以上であることを特徴とする積層フィルム
により達成できる。The object of the present invention is, according to the present invention, a laminated film in which a release layer is provided on one surface of a polyester film containing polyester as a main constituent. Can be achieved with a laminated film having a light transmittance of 80% or more at a wavelength of 365 nm.
【００１５】[0015]
【発明の実施の形態】以下、本発明について詳細に説明
する。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
【００１６】＜ポリエステル＞本発明において基材フィ
ルム（透明ベースフィルム）を構成するポリエステル
は、ポリエチレンテレフタレートホモポリマーまたはエ
チレンテレフタレートを主たる繰り返し単位とする共重
合体（共重合ポリエステル）である。ポリエチレンテレ
フタレートホモポリマーは、特に機械的強度が高く、短
波長可視光線やそれに近い近紫外線の透過率が高い点
で、ＤＦＲ用フィルムに適している。<Polyester> In the present invention, the polyester constituting the base film (transparent base film) is a polyethylene terephthalate homopolymer or a copolymer having ethylene terephthalate as a main repeating unit (copolymerized polyester). Polyethylene terephthalate homopolymer is particularly suitable for a DFR film because of its high mechanical strength and high transmittance for short-wavelength visible light and near-ultraviolet light.
【００１７】本発明において、ポリエステルが共重合ポ
リエステルの場合の共重合成分は、ジカルボン酸成分で
もジオール成分でもよい。ジカルボン酸成分としては、
イソフタル酸、フタル酸等の如き芳香族ジカルボン酸、
アジピン酸、アゼライン酸、セバシン酸、デカンジカル
ボン酸等の如き脂肪族ジカルボン酸、シクロヘキサンジ
カルボン酸の如き脂環族ジカルボン酸等が例示でき、ま
たジオール成分としては、１，４−ブタンジオール、
１，６−ヘキサンジオール、ジエチレングリコール等の
如き脂肪族ジオール、１，４−シクロヘキサンジメタノ
ールの如き脂環族ジオール、ビスフェノールＡの如き芳
香族ジオールが例示できる。これらは単独または二種以
上を使用することができる。これらの中では、イソフタ
ル酸が透明性、引裂き強度が共に高く、特に好ましい。In the present invention, when the polyester is a copolyester, the copolymerization component may be a dicarboxylic acid component or a diol component. As the dicarboxylic acid component,
Aromatic dicarboxylic acids such as isophthalic acid, phthalic acid, etc.
Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid and the like, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid and the like can be exemplified, and as the diol component, 1,4-butanediol,
Examples thereof include aliphatic diols such as 1,6-hexanediol and diethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and aromatic diols such as bisphenol A. These may be used alone or in combination of two or more. Among these, isophthalic acid is particularly preferable because it has high transparency and tear strength.
【００１８】共重合ポリエステルにおける共重合成分の
割合は、その種類にもよるが結果として、ポリマー融点
が２４５〜２５８℃（ホモポリマーの融点）の範囲にな
る割合である。融点が２４５℃未満では耐熱性が劣るこ
とになる。また熱収縮率が大きく、フィルムの平面性が
低下する。The proportion of the copolymerization component in the copolyester depends on the kind thereof, but as a result, the melting point of the polymer is in the range of 245 to 258 ° C. (melting point of homopolymer). If the melting point is less than 245 ° C, the heat resistance will be poor. Further, the heat shrinkage is large, and the flatness of the film is lowered.
【００１９】ここで、ポリエステルの融点測定は、Ｄｕ
Ｐｏｎｔ Ｉｎｓｔｒｕｍｅｎｔｓ ９１０ ＤＳＣ
を用い、昇温速度２０℃／分で融解ピークを求める方法
による。尚サンプル量は約２０ｍｇとする。The melting point of polyester is measured by Du
Pont Instruments 910 DSC
And a melting peak at a temperature rising rate of 20 ° C./min. The sample amount is about 20 mg.
【００２０】ポリエステルの固有粘度（オルトクロロフ
ェノール、３５℃）は０．５２〜１．５０であることが
好ましく、更に好ましくは０．５７〜１．００、特に好
ましくは０．６０〜０．８０である。この固有粘度が
０．５２未満の場合には引裂き強度が不足することがあ
り好ましくない。他方、固有粘度が１．５０を超える場
合には、原料製造工程およびフィルム製膜工程における
生産性が損なわれる。The intrinsic viscosity (orthochlorophenol, 35 ° C.) of the polyester is preferably 0.52 to 1.50, more preferably 0.57 to 1.00, particularly preferably 0.60 to 0.80. Is. If the intrinsic viscosity is less than 0.52, the tear strength may be insufficient, which is not preferable. On the other hand, when the intrinsic viscosity exceeds 1.50, the productivity in the raw material manufacturing process and the film forming process is impaired.
【００２１】本発明におけるポリエステルはその製法に
より限定されることはないが、ポリエチレンテレフタレ
ートの場合は、テレフタル酸、エチレングリコール、共
重合ポリエステルの場合は更に共重合成分を加えてエス
テル化反応させ、次いで得られた反応生成物を目的とす
る重合度になるまで重縮合反応させてポリエチレンテレ
フタレートまたは共重合ポリエステルとする方法があ
る。The polyester in the present invention is not limited by its production method, but in the case of polyethylene terephthalate, terephthalic acid, ethylene glycol, and in the case of a copolyester, a copolymerization component is further added to carry out an esterification reaction, and then, There is a method in which the obtained reaction product is subjected to a polycondensation reaction until it has a desired degree of polymerization to obtain polyethylene terephthalate or a copolyester.
【００２２】あるいはポリエチレンテレフタレートの場
合は、テレフタル酸ジメチルエステル、エチレングリコ
ールを、共重合ポリエステルの場合は更に共重合成分を
加えてエステル交換反応させ、次いで得られた反応生成
物を目的とする重合度になるまで重縮合反応させてポリ
エチレンテレフタレートまたは共重合ポリエステルとす
る方法を好ましく挙げることができる。Alternatively, in the case of polyethylene terephthalate, terephthalic acid dimethyl ester and ethylene glycol are added, and in the case of a copolyester, a copolymerization component is further added to carry out a transesterification reaction, and then the obtained reaction product is subjected to a desired degree of polymerization. Preferred is a method in which a polycondensation reaction is carried out until it becomes to be polyethylene terephthalate or a copolyester.
【００２３】また、上記の方法（溶融重合）により得ら
れたポリエチレンテレフタレートまたは共重合ポリエス
テルは、必要に応じて固相状態での重合方法（固相重
合）により、更に重合度の高いポリマーとすることがで
きる。Further, the polyethylene terephthalate or copolyester obtained by the above method (melt polymerization) is, if necessary, made into a polymer having a higher degree of polymerization by a polymerization method in a solid state (solid phase polymerization). be able to.
【００２４】前記重縮合反応に使用する触媒としては、
チタン化合物（Ｔｉ化合物）、ゲルマニウム化合物（Ｇ
ｅ化合物）などが好ましく挙げられる。更に好ましくは
ゲルマニウム化合物である。The catalyst used in the polycondensation reaction is
Titanium compound (Ti compound), Germanium compound (G
e compound) and the like are preferable. More preferably, it is a germanium compound.
【００２５】本発明の積層フィルムに用いるポリエステ
ル中の重縮合金属触媒残渣は、１５０ｐｐｍ未満である
ことが好ましく、更に１２０ｐｐｍ未満、特に１００ｐ
ｐｍ未満であることが好ましい。また、アンチモン金属
の割合が全酸成分１ｍｏｌ当り１５ｍｍｏｌ％以下であ
ることが好ましく、更に１０ｍｍｏｌ％以下、特に５ｍ
ｍｏｌ％以下であることが好ましい。The polycondensation metal catalyst residue in the polyester used in the laminated film of the present invention is preferably less than 150 ppm, more preferably less than 120 ppm, especially 100 p.
It is preferably less than pm. Further, the proportion of antimony metal is preferably 15 mmol% or less, more preferably 10 mmol% or less, especially 5 m per 1 mol of all acid components.
It is preferably not more than mol%.
【００２６】ポリエステルの重縮合金属触媒残渣が１５
０ｐｐｍを超えると、波長３６５ｎｍ近辺の光線透過率
が８０％未満になり易く好ましくない。ポリエステルの
重縮合金属触媒残渣を１５０ｐｐｍ未満にするために
は、アンチモン系の触媒を避ける必要があり、家電リサ
イクル法の見地からも好ましい。Polycondensation metal catalyst residue of polyester is 15
If it exceeds 0 ppm, the light transmittance around a wavelength of 365 nm tends to be less than 80%, which is not preferable. In order to reduce the polycondensation metal catalyst residue of polyester to less than 150 ppm, it is necessary to avoid the antimony-based catalyst, which is preferable from the viewpoint of the Home Appliance Recycling Law.
【００２７】好ましい重縮合触媒の具体例としては、チ
タン化合物、例えばチタンテトラブトキシド、酢酸チタ
ンなどが好ましく挙げられる。また、ゲルマニウム化合
物としては、（イ）無定形酸化ゲルマニウム、（ロ）微
細な結晶性酸化ゲルマニウム、（ハ）酸化ゲルマニウム
をアルカリ金属またはアルカリ土類金属もしくはそれら
の化合物の存在下にグリコールに溶解した溶液、（ニ）
酸化ゲルマニウムを水に溶解した溶液などが好ましく挙
げられる。更に、１０ｍｍｏｌ％以下のアンチモン化合
物および／またはチタン化合物と組み合わせて使用する
と、解像性の改善と共に、製造コストを低減することも
できるので好ましい。Specific examples of preferable polycondensation catalysts include titanium compounds such as titanium tetrabutoxide and titanium acetate. As the germanium compound, (a) amorphous germanium oxide, (b) fine crystalline germanium oxide, (c) germanium oxide were dissolved in glycol in the presence of an alkali metal or an alkaline earth metal or their compounds. Solution, (d)
A solution in which germanium oxide is dissolved in water is preferable. Furthermore, it is preferable to use it in combination with an antimony compound and / or a titanium compound in an amount of 10 mmol% or less, because the resolution can be improved and the manufacturing cost can be reduced.
【００２８】尚、本発明におけるポリエステルには、必
要に応じて酸化防止剤、熱安定剤、粘度調整剤、可塑
剤、色相改良剤、滑剤、核剤などの添加剤を加えること
ができる。If desired, the polyester of the present invention may contain additives such as antioxidants, heat stabilizers, viscosity modifiers, plasticizers, hue improvers, lubricants and nucleating agents.
【００２９】＜多孔質シリカ粒子＞本発明において、ポ
リエステルフィルムを構成するポリエステルには、多孔
質シリカ粒子が配合されていることが好ましい。シリカ
粒子は、従来のような球状又は不定形シリカ粒子では、
ポリエステルフィルムを延伸し分子を配向させる時にボ
イドが発生することがあり、フォトレジスト用フィルム
として使用するには透明性が不十分となることがある。<Porous Silica Particles> In the present invention, it is preferable that the polyester constituting the polyester film is blended with porous silica particles. Silica particles are spherical or amorphous silica particles such as conventional,
Voids may occur when the polyester film is stretched and the molecules are oriented, and the transparency may be insufficient for use as a photoresist film.
【００３０】多孔質シリカ粒子を構成する一次粒子の平
均粒径は０．０１〜０．１μｍの範囲内にあることが好
ましい。一次粒子の平均粒径が０．０１μｍ未満ではス
ラリー段階で解砕により極微細粒子が生成し、これが粗
大な凝集体を生成することがあり好ましくない。また、
一次粒子の平均粒径が０．１μｍを超えると、粒子の多
孔質性が失われ、その結果、ポリエステルとの親和性が
失われ、ボイドが生成しやすくなり、透明性が失われる
ことがあり好ましくない。The average particle size of the primary particles constituting the porous silica particles is preferably within the range of 0.01 to 0.1 μm. When the average particle size of the primary particles is less than 0.01 μm, ultrafine particles are generated by crushing in the slurry stage, which may form coarse aggregates, which is not preferable. Also,
When the average particle size of the primary particles exceeds 0.1 μm, the porosity of the particles is lost, and as a result, the affinity with polyester is lost, voids are easily generated, and transparency may be lost. Not preferable.
【００３１】更に、本発明における多孔質シリカ粒子の
細孔容積は０．５〜２．０ｍｌ／ｇ、好ましくは０．６
〜１．８ｍｌ／ｇの範囲内にあることが好ましい。細孔
容積が０．５ｍｌ／ｇ未満では、粒子の多孔性が失わ
れ、ボイドが発生し易くなり、透明性が低下することが
あるので不適当である。一方、細孔容積が２．０ｍｌ／
ｇより大きいと解砕、凝集が起こりやすく、粒径の調整
を行うことが困難となることがある。Further, the pore volume of the porous silica particles in the present invention is 0.5 to 2.0 ml / g, preferably 0.6.
It is preferably in the range of to 1.8 ml / g. If the pore volume is less than 0.5 ml / g, the porosity of the particles may be lost, voids may easily occur, and the transparency may decrease, which is not suitable. On the other hand, the pore volume is 2.0 ml /
If it is larger than g, crushing and aggregation are likely to occur, and it may be difficult to adjust the particle size.
【００３２】本発明における多孔質シリカ粒子の凝集体
の平均粒径は０．１〜５μｍの範囲内であることが好ま
しく、特に０．３〜３μｍであることが好ましい。凝集
体の平均粒径が０．１μｍ未満ではフィルムの滑り性が
不十分となることがあり、一方平均粒径が５μｍを超え
るとフィルムの表面が粗くなり過ぎて、回路を印刷した
ガラス板との密着性が不十分となり、解像度低下などの
欠陥が生じるのことがあるので好ましくない。The average particle size of the aggregate of porous silica particles in the present invention is preferably in the range of 0.1 to 5 μm, and particularly preferably 0.3 to 3 μm. If the average particle size of the agglomerates is less than 0.1 μm, the slipperiness of the film may be insufficient, while if the average particle size exceeds 5 μm, the surface of the film becomes too rough and a glass plate on which a circuit is printed. Adhesion is insufficient, and defects such as a decrease in resolution may occur, which is not preferable.
【００３３】多孔質シリカ粒子の添加量は０．０１〜
０．１重量％であることが好ましく、特に０．０２〜
０．０６重量％であることが好ましい。この添加量が
０．０１重量％未満では、フィルムの滑り性が不十分と
なり、製膜時の切断やスクラッチが頻発し製膜が困難と
なることがある。一方０．１重量％を超えると、透明性
が低下することがあるので不適当である。The amount of porous silica particles added is 0.01 to
It is preferably 0.1% by weight, particularly 0.02
It is preferably 0.06% by weight. If this addition amount is less than 0.01% by weight, the slipperiness of the film becomes insufficient, and cutting and scratches during film formation frequently occur, which may make film formation difficult. On the other hand, if it exceeds 0.1% by weight, the transparency may decrease, which is not suitable.
【００３４】＜ポリエステルフィルム＞本発明の積層フ
ィルムのベースフィルムに用いるポリエステルフィルム
は、前記ポリエステルを主要構成成分とするフィルムで
あって、通常、二軸配向フィルムとして用いられる。ポ
リエステルフィルム中には、大きさ５０μｍ以上の粗大
凝集粒子個数が１ｍ2 当り１０個 以下であることが好
ましく、更に５個以下、特に３個以下であることが好ま
しい。５０μｍ以上の大きさの粗大凝集粒子の個数が１
ｍ2 当り１０個を超えると、フィルム表面に不均一な突
起が生じ、回路を印刷したガラス板との密着性が悪化
し、解像度低下などの欠陥が生じるので不適当である。
実質的には１００μｍ以上の粗大凝集粒子の個数は２個
／ｍ2 以下であることが好ましい。<Polyester Film> The polyester film used as the base film of the laminated film of the present invention is a film containing the above polyester as a main constituent, and is usually used as a biaxially oriented film. In the polyester film, the number of coarse agglomerated particles with a size of 50 μm or more is 10 per 1 m 2. The number is preferably the following, more preferably 5 or less, and particularly preferably 3 or less. The number of coarse aggregate particles with a size of 50 μm or more is 1
If the number exceeds 10 per m 2, uneven projections are formed on the film surface, the adhesion to the glass plate on which the circuit is printed is deteriorated, and defects such as deterioration in resolution occur, which is unsuitable.
Substantially, the number of coarse aggregated particles having a size of 100 μm or more is preferably 2 particles / m 2 or less.
【００３５】粗大凝集粒子の個数を１０個／ｍ2 以下に
する為には、製膜時のフィルターとして、線径１５μｍ
以下のステンレス鋼細線よりなる、平均目開き１０〜２
０μｍ、好ましくは１５〜２５μｍの不織布型フィルタ
ーで濾過することが好ましい。フィルターの目開きが３
０μｍを超えると溶融ポリマー中の粗大粒子を減少させ
る効果がなく、一方目開きが１０μｍ未満の場合は濾過
時の圧力及び圧力上昇が大となり、フィルターとして工
業上実用化することは困難である。また線径が１５μｍ
を超えると、平均目開き１０〜３０μｍでは粗大粒子は
捕集できない。In order to reduce the number of coarse agglomerated particles to 10 particles / m 2 or less, a wire diameter of 15 μm is used as a filter during film formation.
The average openings 10 to 2 made of the following stainless steel thin wires
It is preferable to filter with a non-woven fabric type filter of 0 μm, preferably 15 to 25 μm. The opening of the filter is 3
If it exceeds 0 μm, there is no effect of reducing coarse particles in the molten polymer. On the other hand, if the mesh size is less than 10 μm, the pressure and the pressure rise during filtration become large, and it is difficult to industrially apply it as a filter. Wire diameter is 15 μm
If it exceeds, coarse particles cannot be collected with an average opening of 10 to 30 μm.
【００３６】フィルターとして、他の網状構造物や焼結
金属等を用いたのでは、たとえその平均目開きが上記平
均目開きと同じか小さくても、多孔質シリカ粒子の粗大
凝集粒子を捕集することが難しい。これは不織布型フィ
ルターを構成するステンレス鋼細線が多孔質シリカの粗
大粒子を捕集するだけでなく、粗大凝集粒子を解砕、分
散させる効果を持つ為と考えられる。If another reticulated structure or sintered metal is used as the filter, even if the average mesh size is the same as or smaller than the above average mesh size, coarse aggregated particles of porous silica particles are collected. Difficult to do. It is considered that this is because the stainless steel fine wire constituting the non-woven fabric filter has an effect of not only collecting coarse particles of porous silica but also crushing and dispersing coarse aggregated particles.
【００３７】多孔質シリカ粒子は、通常、ポリエステル
を形成する為の反応時、例えばエステル交換法による場
合のエステル交換反応中ないし重縮合反応中の任意の時
期、また直接重合法による場合の任意の時期に、反応系
中に添加（好ましくは、グリコール中のスラリーとし
て）される。特に、重縮合反応の初期、例えば固有粘度
が約０．３に至るまでの間に多孔質シリカ粒子を反応系
中に添加するのが好ましい。The porous silica particles are usually used at any time during the reaction for forming a polyester, for example, during the transesterification reaction or the polycondensation reaction in the case of the transesterification method, or in the direct polymerization method. At times, it is added to the reaction system (preferably as a slurry in glycol). In particular, it is preferable to add the porous silica particles to the reaction system at the initial stage of the polycondensation reaction, for example, before the intrinsic viscosity reaches about 0.3.
【００３８】＜製膜方法＞本発明におけるポリエステル
フィルムは、基本的には、前記ポリエステルを溶融製膜
し、二軸延伸し、更に熱処理することによって製膜され
るが、これら各工程の方法、条件自体は各々に公知の方
法、条件のうちから採用することができる。更に詳細に
説明すれば、まず、ポリエステルを溶融し、スリット状
のダイからシート状に押出し、キャスティングドラムで
冷却固化して未延伸シートを形成し、この未延伸シート
を延伸温度７０〜１２０℃、延伸倍率３〜５倍で縦及び
横方向に各々延伸し、しかる後２００〜２５０℃で熱処
理する。<Film Forming Method> The polyester film of the present invention is basically formed by melt-forming the polyester, biaxially stretching it, and further heat-treating it. The conditions themselves can be adopted from among known methods and conditions. More specifically, first, polyester is melted, extruded into a sheet form from a slit die, and cooled and solidified by a casting drum to form an unstretched sheet, and the unstretched sheet is stretched at a temperature of 70 to 120 ° C. Stretching is performed in the machine direction and the transverse direction at a draw ratio of 3 to 5 times, and then heat treatment is performed at 200 to 250 ° C.
【００３９】＜離型層＞本発明においてポリエステルフ
ィルムの一方の表面に積層する離型層は、下記の特性を
有することが好ましい。
（１）フォトレジスト層（光硬化性樹脂層）に対して離
型性を有し、剥離力（１８０度、低速剥離）で１〜１０
０ｇ／インチの範囲にある。
（２）剥離時の静電気の発生が少なく、ゴミ、異物等を
付着しない。
（３）フォトレジスト層を塗布した後の乾燥処理に耐え
る耐熱性や耐溶剤性を有する。耐熱性としては、例えば
１２０℃で１分間乾燥処理するのに耐えることが好まし
い。
（４）紫外線（ＵＶ光）をベースフィルム並に透過する
透明性を有することが好ましい。
（５）気泡抜け性を有することが好ましく、例えば離型
層の表面が０．１〜１０μｍ程度の凹凸を有することが
好ましい。<Release Layer> In the present invention, the release layer laminated on one surface of the polyester film preferably has the following characteristics. (1) It has releasability with respect to the photoresist layer (photocurable resin layer), and has a peeling force (180 degrees, low-speed peeling) of 1 to 10
It is in the range of 0 g / inch. (2) Little static electricity is generated at the time of peeling, and no dust or foreign matter is attached. (3) It has heat resistance and solvent resistance to withstand the drying treatment after applying the photoresist layer. As the heat resistance, for example, it is preferable to endure a drying treatment at 120 ° C. for 1 minute. (4) It is preferable to have transparency that allows ultraviolet rays (UV light) to pass through like a base film. (5) It is preferable that the release layer has a bubble-releasing property, and for example, the surface of the release layer preferably has irregularities of about 0.1 to 10 μm.
【００４０】離型剤を形成する成分としては、シリコー
ン系樹脂、フッ素系樹脂、オレフィン系樹脂、ワックス
類、ポリビニルカルバメート類、クロム錯体等を好まし
く例示することができる。Preferred examples of the component forming the release agent include silicone resins, fluorine resins, olefin resins, waxes, polyvinyl carbamates and chromium complexes.
【００４１】かかる離型層を形成する成分には、本発明
の目的を妨げない範囲で公知の各種添加剤を配合するこ
とができる。この添加剤としては、例えば紫外線吸収
剤、帯電防止剤、顔料、消泡剤等を例示することができ
る。Various known additives may be added to the components forming the release layer within a range not hindering the object of the present invention. Examples of this additive include an ultraviolet absorber, an antistatic agent, a pigment, an antifoaming agent, and the like.
【００４２】離型層の積層は、特許第２８８２９５３号
と同様に押出ラミネート法で積層しても良いし、離型層
を形成する成分を含む塗液を、ポリエステルフィルムの
製膜時に塗布して形成させることができ、また、二軸配
向ポリエステルフィルムに塗布し、加熱乾燥させて塗膜
を形成させることにより行うこともできる。製膜時にお
いてはどの工程において実施しても良いが、ドラムキャ
スティングした直後、もしくはドラムへキャスティング
した後の縦延伸直後に行うことが好ましい。また、二軸
配向ポリエステルフィルムへの塗布においては、乾燥条
件としては７０℃〜１５０℃で５〜１２０秒間、特に８
０℃〜１２０℃で１０〜６０秒間が好ましい。何れも塗
布方法は、任意の公知の方法が使用でき、例えばバーコ
ート法、リバースロールコート法、ドクターブレード
法、グラビアロールコート法などを好ましく例示するこ
とができる。The release layer may be laminated by an extrusion laminating method as in the case of Japanese Patent No. 2882953, or a coating liquid containing a component forming the release layer may be applied at the time of forming the polyester film. It can also be formed, or can be applied by applying it to a biaxially oriented polyester film and heating and drying to form a coating film. Although it may be carried out at any step during film formation, it is preferably carried out immediately after drum casting or immediately after longitudinal stretching after casting on a drum. When applied to a biaxially oriented polyester film, the drying condition is 70 ° C. to 150 ° C. for 5 to 120 seconds, and especially 8
The temperature is preferably 0 ° C to 120 ° C for 10 to 60 seconds. In any case, any known method can be used as a coating method, and a bar coating method, a reverse roll coating method, a doctor blade method, a gravure roll coating method and the like can be preferably exemplified.
【００４３】かかる離型層の厚みは、０．０１μｍ以上
０．５μｍ以下であることが好ましく、特に０．０２μ
ｍ以上０．２μｍ以下であることが好ましい。厚みが
０．０１μｍ未満であると十分な剥離力を得ることがで
きず、また０．５μｍより厚いとフィルムヘーズが高く
なってしまう。The thickness of the release layer is preferably 0.01 μm or more and 0.5 μm or less, and more preferably 0.02 μm.
It is preferably m or more and 0.2 μm or less. If the thickness is less than 0.01 μm, a sufficient peeling force cannot be obtained, and if it is more than 0.5 μm, the film haze becomes high.
【００４４】＜積層フィルム＞このようにして得られた
本発明の積層フィルムは、波長３６５ｎｍの紫外線透過
率が８０％以上であることが必要である。紫外線透過率
が８０％未満であると、フォトレジスト層の露光、硬化
工程が円滑に完了しないことがある。<Laminated Film> The laminated film of the present invention thus obtained must have an ultraviolet transmittance of 80% or more at a wavelength of 365 nm. If the UV transmittance is less than 80%, the exposure and curing steps of the photoresist layer may not be completed smoothly.
【００４５】また、本発明の積層フィルムは、ヘーズが
５％以下、更に４％以下、特には１．０％以下であるこ
とが好ましい。ヘーズがこの範囲であると、積層フィル
ムをドライフィルムフォトレジスト用に用いた際に透明
性に優れており、解像度が良好なものとなる。このよう
なヘーズの積層フィルムは、例えば、ポリエステル中に
多孔質シリカ粒子を０．０１〜０．１重量％含有し、ポ
リエステル中の重縮合金属触媒残渣が１５０ｐｐｍ未満
であり、アンチモン金属量が全酸成分に対し１５ｍｍｏ
ｌ％以下のものを用い、かつ離型層の厚みを０．０１μ
ｍ以上０．５μｍ以下とすることにより得ることができ
る。The haze of the laminated film of the present invention is preferably 5% or less, more preferably 4% or less, and particularly preferably 1.0% or less. When the haze is in this range, the laminated film is excellent in transparency when used for a dry film photoresist and the resolution is good. Such a haze laminated film contains, for example, 0.01 to 0.1% by weight of porous silica particles in polyester, the polycondensation metal catalyst residue in the polyester is less than 150 ppm, and the total amount of antimony metal is 15mmo for acid component
1% or less, and the thickness of the release layer is 0.01 μ
It can be obtained by setting the thickness to m or more and 0.5 μm or less.
【００４６】本発明の積層フィルムの厚みは２μｍ以上
２００μｍ以下であること、更に８μｍ以上１００μｍ
以下であること、特に１０μｍ以上２５μｍ以下である
ことが好ましい。厚みが２００μｍを超えると解像度が
低下するので好ましくない。一方、厚みが２μｍ未満で
は強度が不足し、特に剥離作業時の破れが頻発すること
がある。The laminated film of the present invention has a thickness of 2 μm or more and 200 μm or less, and further 8 μm or more and 100 μm.
It is preferably not more than 10 μm, more preferably not less than 10 μm and not more than 25 μm. If the thickness exceeds 200 μm, the resolution decreases, which is not preferable. On the other hand, if the thickness is less than 2 μm, the strength is insufficient, and breakage may occur frequently during peeling work.
【００４７】また、本発明の積層フィルムは、少なくと
も片面（特に離型層を設けない側の表面）の中心線平均
粗さ（Ｒａ）が０．００５μｍ以上であることが好まし
く、特に０．０１５μｍ以上であることが好ましい。中
心線平均粗さ（Ｒａ）がこの範囲であると積層フィルム
の滑り性が良好なものとなる。The laminated film of the present invention preferably has a center line average roughness (Ra) of at least one surface (particularly the surface on which the release layer is not provided) of 0.005 μm or more, and particularly 0.015 μm. The above is preferable. When the center line average roughness (Ra) is within this range, the slipperiness of the laminated film becomes good.
【００４８】更に、本発明の積層フィルムは、特開平７
―３３３８５３号公報に記載されているように、２層以
上の積層フィルム（図２参照）として、その最外層を前
記多孔質シリカ粒子を含有せしめたポリエステルフィル
ムで構成してもよい。Further, the laminated film of the present invention is disclosed in Japanese Patent Laid-Open No.
As described in JP-A-333853, a laminated film having two or more layers (see FIG. 2) may be constituted by a polyester film having the outermost layer containing the porous silica particles.
【００４９】本発明の積層フィルムは、フォトレジスト
用の支持体層として使用することができ、これにフォト
レジスト層を定法により積層することによりドライフォ
トレジストカーバーレスフィルムとすることができる。The laminated film of the present invention can be used as a support layer for a photoresist, and a photoresist layer can be laminated thereon by a conventional method to give a dry photoresist carverless film.
【００５０】[0050]
【実施例】以下、実施例をあげて本発明を更に説明す
る。尚、本発明における種々の物性値および特性は、以
下の如く測定されたものであり、かつ定義される。EXAMPLES The present invention will be further described below with reference to examples. Incidentally, various physical properties and characteristics in the present invention are measured and defined as follows.
【００５１】（１）フォトレジスト層剥離性
ポリエステルフィルムの離型層が施されていないもう片
方の面にポリメチルメタクリレートをバインダーとし、
架橋剤としてトリメチロールプロパントリアクリレー
ト、光重合開始剤としてアントラキセノン、安定剤とし
てハイドロキノン、着色剤としてメチルバイオレットか
らなる感光性組成物（フォトレジスト）を暗室にて０．
０２ｍｍの厚みにて塗布した。これを離型面がフォトレ
ジスト面と接するように２枚のシートを重ね合わせ２ｋ
ｇのローラーの自重で一往複、加圧ラミネートし剥離性
評価のためのサンプルを作成した。ラミネート直後の評
価サンプルに関し、離型処理ポリエステルフィルムの離
型処理面とフォトレジスト面を３００ｍｍ／ｍｉｎの速
度で１８０°剥離し、剥離性を下記の基準で評価した。
○：軽剥離力であり、ポリエステルフィルムにフォトレ
ジストが残留しなかった（フォトレジスト層剥離性良
好）。
△：中剥離力であり、ポリエステルフィルムに若干のフ
ォトレジストが残留した（フォトレジスト層剥離性やや
良好）。
×：重剥離力であり、ポリエステルフィルムに殆どのフ
ォトレジストが残留した（フォトレジスト層剥離性不
良）。(1) Photoresist Layer Polymethylmethacrylate was used as a binder on the other surface of the releasable polyester film on which the release layer was not applied,
A photosensitive composition (photoresist) comprising trimethylolpropane triacrylate as a cross-linking agent, anthraxenone as a photopolymerization initiator, hydroquinone as a stabilizer, and methyl violet as a colorant was prepared in a dark room at a rate of 0.
It was applied in a thickness of 02 mm. 2 sheets are superposed on each other so that the release surface is in contact with the photoresist surface 2k
A sample for evaluation of releasability was prepared by repeatedly laminating under pressure of the roller of g and laminating under pressure. For the evaluation sample immediately after lamination, the release-treated surface of the release-treated polyester film and the photoresist surface were peeled by 180 ° at a speed of 300 mm / min, and the peelability was evaluated according to the following criteria. ◯: Light peeling force, and the photoresist did not remain on the polyester film (photoresist layer peeling property was good). Δ: Medium peeling force, and a small amount of photoresist remained on the polyester film (removability of photoresist layer was rather good). X: Heavy peeling force, and most of the photoresist remained on the polyester film (photoresist layer peeling failure).
【００５２】（２）粒子の粒径
一次粒子の平均粒径は、シリカ粉体を個々の粒子ができ
るだけ重ならないように散在せしめ、金スパッター装置
によりこの表面に金属蒸着膜を厚み２００〜３００オン
グストロームで形成せしめ、走査型電子顕微鏡にて１０
０００〜３００００倍で観察し、日本レギュレーター
（株）製ルーゼックス５００にて画像処理し、１００個
の粒子から平均粒径を求めた。一次粒子の凝集体である
粒子の平均粒径は、遠心沈降式粒度分布測定装置で測定
した等価球形分布における積算体積分率５０％の直径を
平均粒径とした。(2) Particle diameter The average particle diameter of the primary particles is such that silica particles are scattered so that the individual particles do not overlap as much as possible, and a metal deposition film is formed on this surface by a gold sputtering device to a thickness of 200 to 300 angstroms. With a scanning electron microscope.
It was observed at 000 to 30,000 times, image-processed with Luzex 500 manufactured by Nippon Regulator Co., Ltd., and the average particle diameter was obtained from 100 particles. The average particle size of the particles, which are aggregates of primary particles, was defined as the diameter with an integrated volume fraction of 50% in the equivalent spherical distribution measured by a centrifugal sedimentation type particle size distribution analyzer.
【００５３】（３）細孔容積 窒素吸脱着法で測定し、ＢＥＴ式で計算した。(3) Pore volume It was measured by the nitrogen adsorption / desorption method and calculated by the BET formula.
【００５４】（４）フィルム中の粗大粒子の大きさ、個
数
万能投影機を用い、透過照明にて２０倍に拡大し、５０
μｍ以上の最大長をもつ粒子数をカウントした。測定面
積は１ｍ2 とした。(4) Size of coarse particles in film, using a universal projector, magnified 20 times with transillumination,
The number of particles having a maximum length of μm or more was counted. The measurement area was 1 m 2 .
【００５５】（５）中心線平均粗さ（Ｒａ）
ＪＩＳＢ０６０１に準じ、（株）小坂研究所製の高精度
表面粗さ計ＳＥ―３ＦＡＴを使用して、針の半径２μ
ｍ、荷重３０ｍｇで拡大倍率２０万倍、カットオフ０．
０８ｍｍの条件下にチャートを描かせ、表面粗さ曲線か
らその中心線方向に測定長さＬの部分を抜き取り、この
抜き取り部分の中心線をＸ軸、縦倍率の方向をＹ軸とし
て、粗さ曲線をｙ＝ｆ（ｘ）で表わしたとき、次の式で
与えられた値をμｍ単位で表わした。(5) Centerline average roughness (Ra) According to JISB0601, a high precision surface roughness meter SE-3FAT manufactured by Kosaka Laboratory Ltd. was used to measure the needle radius of 2 μm.
m, load 30 mg, magnification 200,000 times, cutoff 0.
A chart is drawn under the condition of 08 mm, a portion of the measurement length L is extracted from the surface roughness curve in the direction of the center line, and the center line of the extracted portion is taken as the X axis, and the direction of longitudinal magnification is taken as the Y axis. When the curve is represented by y = f (x), the value given by the following equation is represented in μm.
【００５６】[0056]
【数１】 [Equation 1]
【００５７】この測定は、基準長を１．２５ｍｍとして
４個測定し、平均値で表した。In this measurement, four pieces were measured with a reference length of 1.25 mm and expressed as an average value.
【００５８】（６）ヘーズ
ＪＩＳ−Ｋ７１０５に準じ、日本精密光学（株）製の積
分球式ヘーズメーターによりフィルムヘーズを測定し
た。(6) Haze According to JIS-K7105, the film haze was measured with an integrating sphere type haze meter manufactured by Nippon Seimitsu Optical Co., Ltd.
【００５９】（７）紫外線透過率
（株）島津製作所の分光光度計ＭＰＣ−３１００を用い
て波長３６５ｎｍの紫外線透過率を測定した。(7) Ultraviolet transmittance The ultraviolet transmittance at a wavelength of 365 nm was measured using a spectrophotometer MPC-3100 manufactured by Shimadzu Corporation.
【００６０】（８）融点
Ｄｕ Ｐｏｎｔ Ｉｎｓｔｒｕｍｅｎｔｓ ９１０ Ｄ
ＳＣを用い、昇温速度２０℃／分で融解ピークを求める
方法によった。尚、サンプル量は約２０ｍｇとする。(8) Melting point Du Pont Instruments 910D
According to the method of using SC, the melting peak was obtained at a temperature rising rate of 20 ° C./min. The sample amount is about 20 mg.
【００６１】（９）アンチモンの定量分析
フィルムを溶融成形して５ｃｍφ、厚み３ｍｍのプレー
トを作成し、蛍光Ｘ線（理学電機製 ＲＩＸ３０００）
にて測定して定量分析する。使用するＸ線管球はＣｒ、
Ｒｈが好ましいが、アンチモンが定量可能ならばその限
りではない。定量分析は、あらかじめアンチモン量既知
のサンプルより検量線（横軸：アンチモン量、縦軸：ア
ンチモン分析時の検出量（単位ｃｐｓ））を作成し、未
知試料のアンチモンの検出量（単位ｃｐｓ）から判定す
る。(9) Quantitative analysis of antimony A film was melt-molded to form a plate having a diameter of 5 cm and a thickness of 3 mm, and fluorescent X-ray (RIX3000 manufactured by Rigaku Denki) was used.
Measure and analyze quantitatively. The X-ray tube used is Cr,
Rh is preferable, but it is not limited thereto if antimony can be quantified. For quantitative analysis, a calibration curve (horizontal axis: antimony amount, vertical axis: detection amount during antimony analysis (unit cps)) was created in advance from a sample with a known antimony amount, and the amount of antimony detected in an unknown sample (unit cps) was used. judge.
【００６２】（１０）フィルム厚み
外付マイクロメータで１００点測定し、平均値を求めて
フィルムの厚みとする。(10) Film thickness 100 points were measured with an external micrometer, and the average value was calculated to obtain the film thickness.
【００６３】（１１）フォトレジストフィルム特性
得られたフォトレジストフィルムを用い、プリント回路
を作成して、解像度及び回路欠点を評価した。即ち、ガ
ラス繊維含有エポキシ樹脂板上に設けた銅版に、フォト
レジストフィルムのフォトレジスト層を密着させ、更に
その上から回路を印刷したガラス板を密着させて、ガラ
ス板側から紫外線の露光を行った後、フォトレジストフ
ィルムを剥離し、洗浄、エッチングを行い、回路を作成
して、目視及び顕微鏡で解像度及び回路欠点を観察し、
下記の基準で評価した。(11) Photoresist film characteristics A printed circuit was prepared using the obtained photoresist film, and the resolution and circuit defects were evaluated. That is, to the copper plate provided on the glass fiber-containing epoxy resin plate, the photoresist layer of the photoresist film is brought into close contact, and the glass plate on which the circuit is printed is further brought into close contact therewith, and the ultraviolet exposure is performed from the glass plate side. After that, the photoresist film is peeled off, washed and etched to create a circuit, and the resolution and circuit defects are visually and microscopically observed.
The following criteria evaluated.
【００６４】（ａ）解像度
○：解像度が高く、鮮明な回路が得られた。
△：鮮明性がやや劣り、線が太くなる等の現象が認めら
れた。
×：鮮明性が劣り、実用に供し得る回路は得られなかっ
た。(A) Resolution ◯: High resolution and clear circuit were obtained. Δ: Some phenomena such as slightly poor clarity and thick lines were observed. X: The sharpness was poor, and a circuit that could be put to practical use could not be obtained.
【００６５】（ｂ）回路欠点 ○：回路の欠点は認められなかった。 △：所々に回路の欠点が認められた。 ×：回路の欠点が多発し、実用に供し得なかった。(B) Circuit defects ◯: No defect in the circuit was recognized. Δ: Circuit defects were recognized in some places. X: Defects of the circuit occurred frequently and could not be put to practical use.
【００６６】（１２）滑り性（取扱い性）
製膜時のスリットを含めた巻取り工程、上記フォトレジ
ストフィルムを作成する工程を通して、滑り性を以下の
３段階で評価した。
○：フィルムにしわの発生も無く、問題なかった。
△：フィルムに時々しわが入った。
×：常にフィルムの一部、又は前面にしわが入った。(12) Slidability (Handlability) The slidability was evaluated in the following three stages through the winding process including the slits during film formation and the process for producing the photoresist film. ◯: There was no wrinkle on the film and there was no problem. Δ: The film sometimes wrinkled. X: A part of the film or the front surface was always wrinkled.
【００６７】［実施例１］
（離型層としてシリコーン系樹脂を設けた例）ジメチル
テレフタレートとエチレングリコールを、エステル交換
触媒として酢酸マンガンを、重合触媒として酸化ゲルマ
ニウムを、安定剤として亜燐酸を、更に一次粒子の平均
粒径が０．０２μｍの粒子の凝集体である細孔容積１．
６ｍｌ／ｇ、平均粒径１．５μｍの多孔質シリカ粒子を
０．０１重量％添加させた後、エステル交換及び重縮合
反応を行い、固有粘度（オルソクロロフェノール、３５
℃）０．６５ｄｌ／ｇのポリエチレンテレフタレートを
得た。Example 1 (Example of Providing Silicone Resin as Release Layer) Dimethyl terephthalate and ethylene glycol, manganese acetate as transesterification catalyst, germanium oxide as polymerization catalyst, phosphorous acid as stabilizer, Further, the pore volume of the primary particles is an aggregate of particles having an average particle diameter of 0.02 μm.
After adding 0.01% by weight of 6 ml / g of porous silica particles having an average particle size of 1.5 μm, transesterification and polycondensation reaction were performed to obtain an intrinsic viscosity (orthochlorophenol, 35
C.) 0.65 dl / g polyethylene terephthalate was obtained.
【００６８】次に、得られたポリエチレンテレフタレー
トのペレットを１７０℃において３時間乾燥後、押出機
のホッパーに供給し、溶融温度２９０℃で溶融し、線径
１３μｍのステンレス細線よりなる平均目開き２４μｍ
の不織布型フィルターで濾過し、スリット状ダイから押
出し、表面仕上げ０．３ｓ程度、表面温度２０℃の回転
冷却ドラム上にキャスティングして、未延伸フィルムを
得た。このようにして得られた未延伸フィルムを７５℃
に予熱し、低速ローラーと高速ローラーの間で１５ｍｍ
上方より８００℃の表面温度の赤外線ヒーター１本にて
加熱して縦方向に３．７倍に延伸し、縦延伸フィルムを
得た。Next, the obtained pellets of polyethylene terephthalate were dried at 170 ° C. for 3 hours, then fed to a hopper of an extruder and melted at a melting temperature of 290 ° C. to have an average aperture of 24 μm made of a stainless fine wire having a wire diameter of 13 μm.
Of the non-woven fabric type filter, extruded from a slit die, and cast on a rotary cooling drum having a surface finish of about 0.3 s and a surface temperature of 20 ° C. to obtain an unstretched film. The unstretched film thus obtained is at 75 ° C.
Preheat to 15mm between low speed roller and high speed roller
The film was heated from above by one infrared heater having a surface temperature of 800 ° C. and stretched 3.7 times in the longitudinal direction to obtain a longitudinally stretched film.
【００６９】縦延伸終了後のフィルムの片面に離型層Ａ
塗設用の下記塗液を乾燥横延伸後０．１μｍになるよう
にグラビアコーターで塗布した。The release layer A is formed on one surface of the film after the longitudinal stretching.
The following coating liquid for coating was applied by a gravure coater so as to have a thickness of 0.1 μm after dry transverse stretching.
【００７０】
＜離型層Ａを形成する塗液＞（シリコーン系樹脂）
旭化成ワッカーシリコーン（株）製ＤＥＨＥＳＩＶＥ３
９００５ＶＰ（１００重量部）、同ＤＥＨＥＳＩＶＥ３
９００６ＶＰ（１００重量部）、日本ユニカー（株）製
Ａ−１８７（２重量部）を含む１０％濃度水溶液
次いでステンターに供給し、１１０℃で横方向に４．０
倍延伸し、更に２３５℃で５秒間熱処理し、フィルム厚
み２５μｍの二軸配向積層ポリエステルフィルムを得
た。<Coating Liquid Forming Release Layer A> (Silicone Resin) DEHESIVE3 manufactured by Asahi Kasei Wacker Silicone Co., Ltd.
9005VP (100 parts by weight), DEHESIVE3
9006VP (100 parts by weight), a 10% concentration aqueous solution containing A-187 (2 parts by weight) manufactured by Nippon Unicar Co., Ltd., and then supplied to a stenter, and then 4.0 at a temperature of 110 ° C.
The film was double-stretched and further heat-treated at 235 ° C. for 5 seconds to obtain a biaxially oriented laminated polyester film having a film thickness of 25 μm.
【００７１】このようにして得られた積層ポリエステル
フィルムを用い、離型層の積層されていない表面にフォ
トレジスト層を積層して、プリント回路を作成し、その
特性を評価した。その結果を表１に示す。Using the laminated polyester film thus obtained, a photoresist layer was laminated on the surface on which the release layer was not laminated to prepare a printed circuit, and its characteristics were evaluated. The results are shown in Table 1.
【００７２】［実施例２、３、比較例１、２］
（ポリエステル中の多孔質シリカ粒子の添加量を変えた
例）多孔質シリカ粒子の添加量を表１に示す通りにした
以外は実施例１と同様にしてフィルム厚み２５μｍの二
軸配向積層ポリエステルフィルムを得た。[Examples 2 and 3, Comparative Examples 1 and 2] (Examples in which the addition amount of the porous silica particles in the polyester was changed) Except that the addition amount of the porous silica particles was as shown in Table 1. A biaxially oriented laminated polyester film having a film thickness of 25 μm was obtained in the same manner as in Example 1.
【００７３】このようにして得られた積層ポリエステル
フィルムを用い、離型層の積層されていない表面にフォ
トレジスト層を積層して、プリント回路を作成し、その
特性を評価した。その結果を、表１に示す。Using the laminated polyester film thus obtained, a photoresist layer was laminated on the surface on which the release layer was not laminated, to prepare a printed circuit, and its characteristics were evaluated. The results are shown in Table 1.
【００７４】尚、実施例２で用いた多孔質シリカ粒子の
一次粒子の平均粒径、細孔容積、平均粒径、ポリエステ
ルフィルム中のＳｂ量、触媒残渣濃度を表２に示す。ま
た、実施例２で得られた積層ポリエステルフィルムを用
い、離型層の積層されていない表面にフォトレジスト層
を積層して、プリント回路を作成し、その特性を評価し
た。その結果を表３に示す。Table 2 shows the average particle size, pore volume, average particle size, Sb amount in the polyester film, and catalyst residue concentration of the primary particles of the porous silica particles used in Example 2. Further, using the laminated polyester film obtained in Example 2, a photoresist layer was laminated on the surface on which the release layer was not laminated to prepare a printed circuit, and its characteristics were evaluated. The results are shown in Table 3.
【００７５】［実施例４］
（離型層としてフッ素系樹脂層を設けた例）一次粒子の
平均粒径、多孔質シリカ粒子の細孔容積、多孔質シリカ
粒子の平均粒径、Ｓｂ量、触媒残渣を表２の通りにし
て、縦延伸終了後のフィルムの片面に離型層Ｂとして旭
硝子（株）製サーフロンＳ−１１２の１５％濃度水溶液
を乾燥横延伸後０．０５μｍになるようにロールコータ
ーで塗布した以外は実施例２と同様にして２軸配向積層
ポリエステルフィルムを得た。[Example 4] (Example in which fluorine resin layer was provided as release layer) Average particle diameter of primary particles, pore volume of porous silica particles, average particle diameter of porous silica particles, Sb amount, The catalyst residue is as shown in Table 2, and a 15% aqueous solution of Surflon S-112 manufactured by Asahi Glass Co., Ltd. having a concentration of 15% was used as a release layer B on one surface of the film after completion of the longitudinal stretching so that the thickness became 0.05 μm after the lateral stretching. A biaxially oriented laminated polyester film was obtained in the same manner as in Example 2 except that coating was performed using a roll coater.
【００７６】このようにして得られた積層ポリエステル
フィルムを用い、離型層の積層されていない表面にフォ
トレジスト層を積層して、プリント回路を作成し、その
特性を評価した。その結果を表３に示す。Using the laminated polyester film thus obtained, a photoresist layer was laminated on the surface on which the release layer was not laminated to prepare a printed circuit, and its characteristics were evaluated. The results are shown in Table 3.
【００７７】［実施例５］
（離型層としてオレフィン系樹脂層を塗設した例）一次
粒子の平均粒径、多孔質シリカ粒子の細孔容積、多孔質
シリカ粒子の平均粒径、Ｓｂ量、触媒残渣を表２の通り
にして実施例２と同様にして得られたポリエチレンテレ
フタレートのペレットを１７０℃において３時間乾燥
後、押出機のホッパーに供給し、溶融温度２９０℃で溶
融し、線径１３μｍのステンレス細線よりなる平均目開
き２４μｍの不織布型フィルターで濾過し、スリット状
ダイから押出し、表面仕上げ０．３ｓ程度、表面温度２
０℃の回転冷却ドラム上にキャスティングして、未延伸
フィルムを得た。このようにして得られた未延伸フィル
ムを７５℃に予熱し、低速ローラーと高速ローラーの間
で１５ｍｍ上方より８００℃の表面温度の赤外線ヒータ
ー１本にて加熱して縦方向に３．７倍に延伸し、縦延伸
フィルムを得た。次いでステンターに供給し、１１０℃
で横方向に４．０倍延伸し、更に２３５℃で５秒間熱処
理し、フィルム厚み２５μｍの二軸配向ポリエステルフ
ィルムを得た。[Example 5] (Example in which olefin resin layer was applied as release layer) Average particle size of primary particles, pore volume of porous silica particles, average particle size of porous silica particles, Sb amount Polyethylene terephthalate pellets obtained in the same manner as in Example 2 with the catalyst residue as shown in Table 2 were dried at 170 ° C. for 3 hours, then fed to the hopper of the extruder and melted at a melting temperature of 290 ° C. It is filtered with a non-woven fabric type filter made of stainless fine wire with a diameter of 13 μm and an average opening of 24 μm, and extruded from a slit die, surface finish is about 0.3 s, surface temperature 2
An unstretched film was obtained by casting on a rotary cooling drum at 0 ° C. The unstretched film thus obtained is preheated to 75 ° C. and heated by a single infrared heater having a surface temperature of 800 ° C. from above 15 mm between the low speed roller and the high speed roller to obtain 3.7 times in the longitudinal direction. To obtain a longitudinally stretched film. Then supply to the stenter, 110 ℃
At a temperature of 235 ° C. for 5 seconds to obtain a biaxially oriented polyester film having a film thickness of 25 μm.
【００７８】得られた離型層の積層されていない２軸延
伸ポリエステルフィルムを用い、特許第２８８２９５３
号の実施例２と同様に、離型層Ｃとしてポリエステルフ
ィルムの片面にポリエチレンイミンアルキル変性体（日
本触媒化学（株）製ＰＲ−１０）をメチルエチルケトン
／トルエンの混合溶剤に溶解した固形分濃度１％の離型
剤塗液を１０ｇ／ｍ3塗布し、乾燥した。離型層塗膜は
０．１μｍである。Using the obtained biaxially stretched polyester film on which the release layer is not laminated, the patent No. 2882953 is used.
In the same manner as in Example 2 of the publication, a polyethyleneimine alkyl modified product (PR-10 manufactured by Nippon Shokubai Kagaku Co., Ltd.) was dissolved in a mixed solvent of methylethylketone / toluene as a release layer C on one side to obtain a solid content concentration of 1 % Release agent coating liquid was applied at 10 g / m 3 and dried. The release layer coating film has a thickness of 0.1 μm.
【００７９】このようにして得られた積層ポリエステル
フィルムを用い、離型層の積層されていない表面にフォ
トレジスト層を積層して、プリント回路を作成し、その
特性を評価した。その結果を表３に示す。Using the laminated polyester film thus obtained, a photoresist layer was laminated on the surface on which the release layer was not laminated to prepare a printed circuit, and its characteristics were evaluated. The results are shown in Table 3.
【００８０】［実施例６］
（離型層としてポリビニルカルバメート類の層を設けた
例）一次粒子の平均粒径、多孔質シリカ粒子の細孔容
積、多孔質シリカ粒子の平均粒径、Ｓｂ量、触媒残渣を
表２の通りにして、縦延伸終了後のフィルムの片面に離
型層Ｄとして一方社油脂工業（株）製ピーロイル４０６
の５％水溶液を乾燥横延伸後０．０５μｍになるように
ロールコーターで塗布した以外は実施例２と同様にして
２軸配向積層ポリエステルフィルムを得た。[Example 6] (Example in which layer of polyvinyl carbamate was provided as release layer) Average particle diameter of primary particles, pore volume of porous silica particles, average particle diameter of porous silica particles, Sb amount As shown in Table 2, the catalyst residue is used as a release layer D on one surface of the film after the longitudinal stretching, and Peeloyl 406 manufactured by Yasusha Oil & Fat Co., Ltd.
A biaxially oriented laminated polyester film was obtained in the same manner as in Example 2, except that the 5% aqueous solution of 1 was dried and laterally stretched and then applied by a roll coater so that the thickness became 0.05 μm.
【００８１】このようにして得られた積層ポリエステル
フィルムを用い、離型層の積層されていない表面にフォ
トレジスト層を積層して、プリント回路を作成し、その
特性を評価した。その結果を表３に示す。Using the thus obtained laminated polyester film, a photoresist layer was laminated on the surface on which the release layer was not laminated, to prepare a printed circuit, and its characteristics were evaluated. The results are shown in Table 3.
【００８２】［実施例７］
（離型層としてワックス類の層を設けた例）一次粒子の
平均粒径、多孔質シリカ粒子の細孔容積、多孔質シリカ
粒子の平均粒径、Ｓｂ量、触媒残渣を表２の通りにし
て、縦延伸終了後のフィルムの片面に離型層Ｅとして中
京油脂（株）製ＥＶ−４（２１９重量部）、同ハイミク
ロンＧ−２７０（１３７重量部）を含む１０％濃度水溶
液を乾燥横延伸後０．０５μｍになるようにロールコー
ターで塗布した以外は実施例２と同様にして２軸配向積
層ポリエステルフィルムを得た。Example 7 (Example of Providing Wax Layer as Release Layer) Average particle diameter of primary particles, pore volume of porous silica particles, average particle diameter of porous silica particles, Sb amount, The catalyst residue is as shown in Table 2, and EV-4 (219 parts by weight) manufactured by Chukyo Yushi Co., Ltd. and Hi-micron G-270 (137 parts by weight) manufactured by Chukyo Yushi Co., Ltd. are used as a release layer E on one surface of the film after the longitudinal stretching. A biaxially oriented laminated polyester film was obtained in the same manner as in Example 2, except that a 10% aqueous solution containing a.
【００８３】このようにして得られた積層ポリエステル
フィルムを用い、離型層の積層されていない表面にフォ
トレジスト層を積層して、プリント回路を作成し、その
特性を評価した。その結果を表３に示す。Using the laminated polyester film thus obtained, a photoresist layer was laminated on the surface on which the release layer was not laminated to prepare a printed circuit, and its characteristics were evaluated. The results are shown in Table 3.
【００８４】［実施例８］
（離型層としてオレフィン系樹脂層を押出ラミネートで
設けた例）実施例５と同様にして得られた離型層の積層
されていない２軸配向ポリエステルフィルムの片面に特
許第２８８２９５３号の実施例１と同様に、離型層Ｆと
して押出ラミネート法で中密度ポリエチレンを厚み１５
μで積層した。[Example 8] (Example in which olefin resin layer was provided as extrusion layer by extrusion laminating) One side of biaxially oriented polyester film having no release layer laminated thereon obtained in the same manner as in Example 5 In the same manner as in Example 1 of Japanese Patent No. 2882953, as the release layer F, medium density polyethylene having a thickness of 15 is formed by an extrusion laminating method.
Layered with μ.
【００８５】このようにして得られた積層ポリエステル
フィルムを用い、離型層の積層されていない表面にフォ
トレジスト層を積層して、プリント回路を作成し、その
特性を評価した。その結果を、表３に示す。Using the laminated polyester film thus obtained, a photoresist layer was laminated on the surface on which the release layer was not laminated to prepare a printed circuit, and its characteristics were evaluated. The results are shown in Table 3.
【００８６】［実施例９〜１３、比較例３、５〜９］一
次粒子の平均粒径、多孔質シリカ粒子の細孔容積、多孔
質シリカ粒子の平均粒径、Ｓｂ量、触媒残渣、離型層を
表２の通りにする以外は実施例２と同様に２軸延伸ポリ
エステルフィルムを得た。[Examples 9 to 13, Comparative Examples 3 and 5 to 9] Average particle size of primary particles, pore volume of porous silica particles, average particle size of porous silica particles, Sb amount, catalyst residue, separation A biaxially stretched polyester film was obtained in the same manner as in Example 2 except that the mold layer was as shown in Table 2.
【００８７】このようにして得られた積層ポリエステル
フィルムを用い、離型層の積層されていない表面にフォ
トレジスト層を積層して、プリント回路を作成し、その
特性を評価した。その結果を、表３に示す。Using the laminated polyester film thus obtained, a photoresist layer was laminated on the surface on which the release layer was not laminated, to prepare a printed circuit, and its characteristics were evaluated. The results are shown in Table 3.
【００８８】［比較例４］実施例５と同様にして得られ
た離型層の積層されていない２軸配向ポリエステルフィ
ルムの片方の表面にフォトレジスト層を積層して、プリ
ント回路を作成し、その特性を評価した。その結果を表
３に示す。[Comparative Example 4] A photoresist layer was laminated on one surface of a biaxially oriented polyester film having no release layer laminated thereon obtained in the same manner as in Example 5 to prepare a printed circuit. Its characteristics were evaluated. The results are shown in Table 3.
【００８９】[0089]
【表１】 [Table 1]
【００９０】[0090]
【表２】 [Table 2]
【００９１】[0091]
【表３】 [Table 3]
【００９２】尚、表１、表２の離型層欄で、各略号は以
下の離型層が設けられていることを表わす。
Ａ：離型層Ａが積層されている。
Ｂ：離型層Ｂが積層されている。
Ｃ：離型層Ｃが積層されている。
Ｄ：離型層Ｄが積層されている。
Ｅ：離型層Ｅが積層されている。
Ｆ：離型層Ｆが積層されている。
無し：離型層が積層されていない。In each of the release layer columns of Tables 1 and 2, each abbreviation indicates that the following release layers are provided. A: Release layer A is laminated. B: Release layer B is laminated. C: Release layer C is laminated. D: Release layer D is laminated. E: Release layer E is laminated. F: Release layer F is laminated. None: No release layer is laminated.
【００９３】表１〜表３に示す結果から明らかなよう
に、本発明の積層フィルムは、フォトレジスト層剥離
性、紫外線透過性、フォトレジストフィルム特性に優れ
たものである。As is clear from the results shown in Tables 1 to 3, the laminated film of the present invention is excellent in the photoresist layer releasability, ultraviolet ray transparency and photoresist film characteristics.
【００９４】[0094]
【発明の効果】本発明によれば、その製造及び取扱いが
簡便で、特にプリント配線板の製造に用いるドライフィ
ルムフォトレジスト用に有用な積層フィルムを提供する
ことができる。According to the present invention, it is possible to provide a laminated film which is easy to manufacture and handle and is particularly useful for a dry film photoresist used for manufacturing a printed wiring board.
【図１】ドライフィルムフォトレジスト（ＤＦＲ）の一
例を示した説明図である。FIG. 1 is an explanatory diagram showing an example of a dry film photoresist (DFR).
【図２】ベースフィルムとして１層以上からなる積層ポ
リエステルフィルムを用いたドライフィルムフォトレジ
スト（ＤＦＲ）の説明図である。FIG. 2 is an explanatory view of a dry film photoresist (DFR) using a laminated polyester film composed of one or more layers as a base film.
（１）ベースフィルム
（２）保護フィルム
（３）フォトレジスト層
（４）ベースフィルムとしての１層以上からなる積層ポ
リエステルフィルム
（５）離型層(1) Base film (2) Protective film (3) Photoresist layer (4) Laminated polyester film consisting of one or more layers as a base film (5) Release layer
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｇ０３Ｆ 7/004 ５１２ Ｇ０３Ｆ 7/004 ５１２ 7/09 ５０１ 7/09 ５０１ 7/11 ５０３ 7/11 ５０３ Ｈ０５Ｋ 3/00 Ｈ０５Ｋ 3/00 Ｆ (72)発明者 竹内 光 神奈川県相模原市小山３丁目37番19号 帝 人デュポンフィルム株式会社相模原研究セ ンター内 Ｆターム(参考） 2H025 AB11 DA19 DA20 DA33 4F006 AA35 AB13 AB19 AB39 BA11 DA04 4F100 AA20A AB01A AB22A AJ11B AK02B AK03B AK17B AK41A AK42 AK52B AK62B AK66B AR00B BA02 BA03 BA04 BA07 BA10B BA10C BA10D BA11A BA13 DD07A DD07B DE01A DJ10A EH17 EH46 EJ38 GB43 JA20 JK16 JL05 JL08A JL14B JN01 JN08 JN17C JN17D YY00 YY00A YY00B 4J002 CF001 CF061 DJ016 FD016 GF00 ─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. 7 Identification Code FI Theme Coat (Reference) G03F 7/004 512 G03F 7/004 512 7/09 501 7/09 501 7/11 503 7/11 503 H05K 3/00 H05K 3/00 F (72) Inventor Mitsuru Takeuchi 337-19 Oyama, Sagamihara City, Kanagawa Prefecture Tegami DuPont Films Co., Ltd. Sagamihara Research Center F-term (reference) 2H025 AB11 DA19 DA20 DA33 4F006 AA35 AB13 AB19 AB39 BA11 DA04 4F100 AA20A AB01A AB22A AJ11B AK02B AK03B AK17B AK41A AK42 AK52B AK62B AK66B AR00B BA02 BA03 BA04 BA07 BA10B BA10C BA10D BA11A BA13 DD07A DD07B DE01A DJ10A EH17 EH46 EJ38 GB43 JA20 JK16 JL05 JL08A JL14B JN01 JN08 JN17C JN17D YY00 YY00A YY00B 4J002 CF001 CF061 DJ016 FD016 GF00
Claims (9)
エステルフィルムの一方の表面に離型層を設けた積層フ
ィルムであって、該積層フィルムの波長３６５ｎｍの光
線透過率が８０％以上であることを特徴とする積層フィ
ルム。1. A laminated film having a release layer on one surface of a polyester film containing polyester as a main constituent, wherein the laminated film has a light transmittance of 80% or more at a wavelength of 365 nm. And laminated film.
の積層フィルム。2. The laminated film according to claim 1, which has a haze of 5% or less.
０１〜０．１重量％含有し、該多孔質シリカ粒子が細孔
容積０．５〜２．０ｍｌ／ｇ、平均粒径０．０１〜０．
１μｍの一次粒子の凝集体であって、該凝集体の平均粒
径が０．１〜５μｍであり、該多孔質シリカ粒子のうち
５０μｍ以上の大きさの粗大凝集粒子の個数がフィルム
１ｍ2 当り１０個以下である請求項１または２に記載の
積層フィルム。3. The polyester comprises a porous silica particle of 0.1.
01 to 0.1% by weight, the porous silica particles have a pore volume of 0.5 to 2.0 ml / g, and an average particle diameter of 0.01 to 0.
An aggregate of 1 μm primary particles, wherein the average particle size of the aggregate is 0.1 to 5 μm, and the number of coarse aggregate particles having a size of 50 μm or more in the porous silica particles is 1 m 2 of the film. The laminated film according to claim 1 or 2, which has 10 or less.
ａ）が０．００５μｍ以上である請求項１乃至３の何れ
か１項に記載の積層フィルム。4. A center line average roughness (R) of at least one surface.
The laminated film according to any one of claims 1 to 3, wherein a) is 0.005 µm or more.
脂、オレフィン系樹脂、ワックス類、ポリビニルカルバ
メート類及びクロム錯体よりなる群から選ばれる少なく
とも１種を含む請求項１乃至４の何れか１項に記載の積
層フィルム。5. The release layer contains at least one selected from the group consisting of silicone resins, fluorine resins, olefin resins, waxes, polyvinyl carbamates and chromium complexes. The laminated film according to item.
至５の何れか１項に記載の積層フィルム。6. The laminated film according to claim 1, which has a thickness of 2 to 200 μm.
１５０ｐｐｍ未満であり、かつアンチモン金属量が全酸
成分に対し１５ｍｍｏｌ％以下である請求項１乃至６の
何れか１項に記載の積層フィルム。7. The laminated film according to claim 1, wherein the polycondensation metal catalyst residue in the polyester is less than 150 ppm, and the amount of antimony metal is 15 mmol% or less based on all acid components.
層フィルムの少なくとも片面にフォトレジスト層を積層
してドライフィルムフォトレジスト用に用いる積層フィ
ルム。8. A laminated film for use as a dry film photoresist, wherein a photoresist layer is laminated on at least one surface of the laminated film according to claim 1.
層フィルムの少なくとも片面にフォトレジスト層を積層
した感光性積層体。9. A photosensitive laminate, wherein a photoresist layer is laminated on at least one surface of the laminated film according to any one of claims 1 to 7.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001399703A JP3920094B2 (en) | 2001-12-28 | 2001-12-28 | Coverless dry film Laminated film for photoresist |
| KR1020037013334A KR100919965B1 (en) | 2001-12-28 | 2002-12-20 | Laminated film |
| EP02786171.5A EP1459886B1 (en) | 2001-12-28 | 2002-12-20 | Laminated film |
| PCT/JP2002/013366 WO2003057484A1 (en) | 2001-12-28 | 2002-12-20 | Laminated film |
| US10/474,429 US20040234889A1 (en) | 2001-12-28 | 2002-12-20 | Laminated film |
| AU2002354229A AU2002354229A1 (en) | 2001-12-28 | 2002-12-20 | Laminated film |
| CNA028090276A CN1531481A (en) | 2001-12-28 | 2002-12-20 | Lamianted film |
| TW091137184A TW200301191A (en) | 2001-12-28 | 2002-12-24 | Laminating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001399703A JP3920094B2 (en) | 2001-12-28 | 2001-12-28 | Coverless dry film Laminated film for photoresist |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003191423A true JP2003191423A (en) | 2003-07-08 |
| JP3920094B2 JP3920094B2 (en) | 2007-05-30 |
Family
ID=27604622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001399703A Expired - Fee Related JP3920094B2 (en) | 2001-12-28 | 2001-12-28 | Coverless dry film Laminated film for photoresist |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3920094B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005007782A (en) * | 2003-06-20 | 2005-01-13 | Mitsubishi Polyester Film Copp | Polyester film for photosensitive resin plate base |
| WO2006025092A1 (en) * | 2004-08-30 | 2006-03-09 | Hitachi Chemical Co., Ltd. | Photosensitive film |
| JP2010153298A (en) * | 2008-12-26 | 2010-07-08 | Toyobo Co Ltd | Laminated film for touch panel |
| JP2011005648A (en) * | 2009-06-23 | 2011-01-13 | Toyobo Co Ltd | Base film for lens sheet |
| JP2011173362A (en) * | 2010-02-25 | 2011-09-08 | Fujimori Kogyo Co Ltd | Mold releasing film excelling in transparency |
| JP2011251511A (en) * | 2010-06-04 | 2011-12-15 | Toyobo Co Ltd | Base film for lens sheet |
| WO2016157622A1 (en) * | 2015-03-30 | 2016-10-06 | 日立化成株式会社 | Dry film, cured product, semiconductor device, and method for forming resist pattern |
| WO2016157605A1 (en) * | 2015-03-30 | 2016-10-06 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, cured product, and method for forming resist pattern |
| WO2016159133A1 (en) * | 2015-03-30 | 2016-10-06 | 日立化成株式会社 | Dry film, cured product, semiconductor device, and method for forming resist pattern |
| WO2016159160A1 (en) * | 2015-03-30 | 2016-10-06 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, cured product, and method for forming resist pattern |
-
2001
- 2001-12-28 JP JP2001399703A patent/JP3920094B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005007782A (en) * | 2003-06-20 | 2005-01-13 | Mitsubishi Polyester Film Copp | Polyester film for photosensitive resin plate base |
| WO2006025092A1 (en) * | 2004-08-30 | 2006-03-09 | Hitachi Chemical Co., Ltd. | Photosensitive film |
| JP2010153298A (en) * | 2008-12-26 | 2010-07-08 | Toyobo Co Ltd | Laminated film for touch panel |
| JP2011005648A (en) * | 2009-06-23 | 2011-01-13 | Toyobo Co Ltd | Base film for lens sheet |
| JP2011173362A (en) * | 2010-02-25 | 2011-09-08 | Fujimori Kogyo Co Ltd | Mold releasing film excelling in transparency |
| JP2011251511A (en) * | 2010-06-04 | 2011-12-15 | Toyobo Co Ltd | Base film for lens sheet |
| WO2016157622A1 (en) * | 2015-03-30 | 2016-10-06 | 日立化成株式会社 | Dry film, cured product, semiconductor device, and method for forming resist pattern |
| WO2016157605A1 (en) * | 2015-03-30 | 2016-10-06 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, cured product, and method for forming resist pattern |
| WO2016159133A1 (en) * | 2015-03-30 | 2016-10-06 | 日立化成株式会社 | Dry film, cured product, semiconductor device, and method for forming resist pattern |
| WO2016159160A1 (en) * | 2015-03-30 | 2016-10-06 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, cured product, and method for forming resist pattern |
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