JPS646228B2 - - Google Patents
Info
- Publication number
- JPS646228B2 JPS646228B2 JP2575280A JP2575280A JPS646228B2 JP S646228 B2 JPS646228 B2 JP S646228B2 JP 2575280 A JP2575280 A JP 2575280A JP 2575280 A JP2575280 A JP 2575280A JP S646228 B2 JPS646228 B2 JP S646228B2
- Authority
- JP
- Japan
- Prior art keywords
- crosslinked
- alkylene terephthalate
- polyester
- laminated
- heat
- 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.)
- Expired
Links
- 229920000728 polyester Polymers 0.000 claims description 52
- -1 alkylene terephthalate Chemical compound 0.000 claims description 46
- 239000004744 fabric Substances 0.000 claims description 21
- 239000004745 nonwoven fabric Substances 0.000 claims description 18
- 239000012210 heat-resistant fiber Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 239000000835 fiber Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 238000007747 plating Methods 0.000 description 4
- 230000005855 radiation Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- 238000005452 bending Methods 0.000 description 2
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229920003020 cross-linked polyethylene Polymers 0.000 description 2
- 239000004703 cross-linked polyethylene Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-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
- 229920000642 polymer Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000004753 textile Substances 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
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- XFDUHJPVQKIXHO-UHFFFAOYSA-N 3-aminobenzoic acid Chemical compound NC1=CC=CC(C(O)=O)=C1 XFDUHJPVQKIXHO-UHFFFAOYSA-N 0.000 description 1
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- BLFRQYKZFKYQLO-UHFFFAOYSA-N 4-aminobutan-1-ol Chemical compound NCCCCO BLFRQYKZFKYQLO-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- VEIOBOXBGYWJIT-UHFFFAOYSA-N cyclohexane;methanol Chemical compound OC.OC.C1CCCCC1 VEIOBOXBGYWJIT-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
- Polyesters Or Polycarbonates (AREA)
- Manufacturing Of Printed Wiring (AREA)
Description
本発明は耐熱寸法安定性、耐ハンダ性の優れた
架橋ポリエステルシート（シートの語にはフイル
ムを含む、以下同じ）およびこれを用いたフレキ
シブルプリント配線板、フラツトケーブル又は集
積回路用キヤリアテープに関する。
従来、ポリエチレンフタートフイルムは機械的
性質、電気的性質、耐化学薬品性、耐熱性等が優
れていることにより、電気絶縁用フイルムとし
て、広く用いられている。しかしフレキシブルプ
リント配線板、フラツトケーブル、集積回路用キ
ヤリアテープ用に用いるには、通常の（即ち260
℃以上の）ハンダ付けを伴う工程に耐える耐熱性
がない為、その使用が限定されている。この点を
改良する為に、ポリエチレンテレフタレートを架
橋する方法が提案されている。しかし、耐ハンダ
性を有するだけの充分な架橋ポリエチレンテレフ
タレートフイルム又はシートを工業的に容易に製
造する技術は実現していないし、又、架橋したポ
リエチレンテレフタレートフイルム又はシートで
あつても260℃以上の通常のハンダ付けの条件下
では機械的強さや剛性が非常に小さくなり、フレ
キシブルプリント配線板やキヤリアテープとし
て、その上にコンデンサーや集積回路チツプを装
着することは難しい。一方、従来の不飽和ポリエ
ステルの様な硬化性樹脂／ガラスクロス積層板は
高温での機械的強さや剛性を比較的高く出来る
が、可撓性がないため、フレキシブルプリント配
線板やキヤリアテープとして使用出来ない。この
様な現状に鑑み、本発明者らは可撓性と高温での
機械的強さや剛性を併せ持つた材料を開発し、こ
れをフレキシブルプリント配線板や集積回路用キ
ヤリアテープに応用することを目的に研究を行
い、通常のハンダ工程に於いて、充分な耐熱寸法
安定性と機械的強さや剛性を保持した架橋ポリエ
ステルシートおよび、これを用いたフレキシブル
プリント配線板フラツトケーブル、集積回路用キ
ヤリアテープを提供出来る本発明に到達した。
即ち本発明は、
１ ゲル分率が10％以上である架橋アルキレンテ
レフタレート系ポリエステル中に耐熱性繊維編
織物又は不織布が存在する構造の架橋ポリエス
テルシート。
２ ゲル分率が10％以上である架橋アルキレンテ
レフタレート系ポリエステル中に耐熱性繊維編
織物又は不織布が存在する架橋ポリエステルシ
ートの少なくとも片面に金属層が積層された構
造のフレキシブルプリント配線基板。
３ ゲル分率が10％以上である架橋アルキレンテ
レフタレート系ポリエステル中に耐熱性繊維編
織物又は不織布が存在する架橋ポリエステルシ
ートの少なくとも片面に金属導電層が積層され
た構造のフラツトケーブル。
４ ゲル分率が10％以上である架橋アルキレンテ
レフタレート系ポリエステル中に耐熱性繊維編
織物又は不織布が存在する架橋ポリエステルシ
ートの少なくとも片面に金属導電層が積層され
た構造の集積回路用キヤリアテープ。
に関する。
本発明の架橋されたアルキレンテレフタレート
系ポリエステルとはアルキレンテレフタレート系
ポリエステルに架橋剤を配合した組成物、自己架
橋性アルキレンテレフタレート系ポリエステル又
は該自己架橋性アルキレンテレフタレート系ポリ
エステルに架橋剤を配合した組成物、を架橋して
得られるポリエステルであり、アルキレンテレフ
タレート系ポリエステル部分を50重量％以上含有
している。
アルキレンテレフタレート系ポリエステルは炭
素数２〜10のアルキレングリコール（又は／およ
びその誘導体）例えばエチレングリコール、トリ
メチレングリコール、テトラメチレングリコー
ル、ヘキサメチレングリコール、ネオペンチルグ
リコール等とテレフタル酸（又は／およびその誘
導体）から形成されるアルキレンテレフタレート
単位を70モル％（好ましくは90モル％）以上含む
ポリエステルである。他の共重合成分としては、
酸の形で示せば、イソフタル酸、フタル酸、ナフ
タレンジカルボン酸、ビフエニルジカルボン酸、
ジフエノキシエタンジカルボン酸、（５―ナトリ
ウムスルホ）イソフタル酸などの芳香族ジカルボ
ン酸、コハク酸、アジピン酸、セバチン酸、ドデ
カンジオン酸、ダイマー酸などの脂肪族ジカルボ
ン酸等があり、グリコールの形で示せば例えばジ
エチレングリコール、トリエチレングリコール、
シクロヘキサンジメタノールや分子量300〜10000
のポリエチレングリコール、ポリテトラメチレン
グリコールビスフエノール（又は／およびハロゲ
ン化ビスフエノール）のエチレンオキサイドやプ
ロピレンオキサイドの附加物などがあり、芳香族
ジオールの形で示せばハイドロキノン、レゾルシ
ン、２，２―ビス（４―ヒドロキシフエニル）プ
ロパン、４，4′―ヒドロキシフエニルスルホン、
４，4′―ヒドロキシフエニルメタンなどがある。
又、架橋前には実質的に線状であればよく、三官
能以上のエステル形成基を有する化合物例えばト
リメリツト酸、トリメジン酸、ピロメリツト酸、
グリセリン、ペンタエリスリトールなどが一部共
重合されていてもよい。架橋前のポリアルキレン
テレフタレートの固有粘度は30℃のフエノール／
sym―テトラクロルエタン＝60／40（重量比）溶
液として測定して0.1〜1.0dl／ｇ好ましくは0.3〜
0.8dl／ｇである。架橋はアルキレンテレフタレ
ート系ポリエステルと多官能のエポキシ化合物、
イソシアネート化合物、エチレン性二重結合を有
する化合物等を混合して適当な反応触媒の存在又
は不存在下に加熱あるいは／および活性線を照射
することによつて行うことが出来る。
自己架橋性アルキレンテレフタレート系ポリエ
ステルは上記アルキレンテレフタレート系ポリエ
ステルを製造するための酸成分およびグリコー
ル、ジオール成分を用い、さらに自己架橋性単位
を導入することにより得られる。自己架橋性単位
を導入するためにはエチレン性不飽和結合を有す
る単量体、あるいは光架橋可能な単位を有する単
量体を共重合すればよい。好ましくは光架橋可能
な単位を有する単量体を用いる。光架橋可能な単
位として、特に好ましくは
The present invention relates to a cross-linked polyester sheet (the term "sheet" includes a film; the same applies hereinafter) having excellent heat-resistant dimensional stability and solder resistance, and a carrier tape for flexible printed wiring boards, flat cables, or integrated circuits using the same. . Conventionally, polyethylene ftath films have been widely used as electrically insulating films due to their excellent mechanical properties, electrical properties, chemical resistance, heat resistance, and the like. However, for use in flexible printed wiring boards, flat cables, and carrier tapes for integrated circuits, conventional (i.e. 260
Its use is limited because it does not have the heat resistance to withstand processes that involve soldering (at temperatures above ℃). In order to improve this point, a method of crosslinking polyethylene terephthalate has been proposed. However, the technology to industrially easily produce crosslinked polyethylene terephthalate films or sheets with sufficient solder resistance has not yet been realized, and even crosslinked polyethylene terephthalate films or sheets can be used at temperatures above 260°C. Under soldering conditions, the mechanical strength and rigidity are extremely low, making it difficult to attach capacitors and integrated circuit chips to flexible printed wiring boards or carrier tape. On the other hand, conventional curable resin/glass cloth laminates such as unsaturated polyester can have relatively high mechanical strength and rigidity at high temperatures, but are not flexible, so they are used for flexible printed wiring boards and carrier tapes. Can not. In view of the current situation, the present inventors developed a material that has both flexibility and mechanical strength and rigidity at high temperatures, and aimed to apply this material to flexible printed wiring boards and carrier tapes for integrated circuits. We conducted research to create a crosslinked polyester sheet that maintains sufficient heat-resistant dimensional stability, mechanical strength, and rigidity during normal soldering processes, as well as flexible printed wiring board flat cables and carrier tapes for integrated circuits using the same. We have arrived at the present invention, which can provide the following. That is, the present invention provides: 1. A crosslinked polyester sheet having a structure in which a heat-resistant fiber knitted fabric or nonwoven fabric is present in a crosslinked alkylene terephthalate polyester having a gel fraction of 10% or more. 2. A flexible printed wiring board having a structure in which a metal layer is laminated on at least one side of a crosslinked polyester sheet in which a heat-resistant fiber knitted fabric or nonwoven fabric is present in a crosslinked alkylene terephthalate polyester having a gel fraction of 10% or more. 3. A flat cable having a structure in which a metal conductive layer is laminated on at least one side of a crosslinked polyester sheet in which a heat-resistant fiber knitted fabric or nonwoven fabric is present in a crosslinked alkylene terephthalate polyester having a gel fraction of 10% or more. 4. A carrier tape for integrated circuits having a structure in which a metal conductive layer is laminated on at least one side of a crosslinked polyester sheet in which a heat-resistant fiber knitted fabric or nonwoven fabric is present in a crosslinked alkylene terephthalate polyester having a gel fraction of 10% or more. Regarding. The crosslinked alkylene terephthalate polyester of the present invention is a composition in which an alkylene terephthalate polyester is blended with a crosslinking agent, a self-crosslinking alkylene terephthalate polyester, or a composition in which a crosslinking agent is blended in the self-crosslinking alkylene terephthalate polyester; It is a polyester obtained by crosslinking and contains 50% by weight or more of an alkylene terephthalate polyester moiety. Alkylene terephthalate polyester is an alkylene glycol (or/and its derivatives) having 2 to 10 carbon atoms, such as ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, etc. and terephthalic acid (or/and its derivatives). It is a polyester containing 70 mol% or more (preferably 90 mol%) or more of alkylene terephthalate units formed from. Other copolymer components include:
In acid form, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid,
These include aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid and (5-sodium sulfo)isophthalic acid, and aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, dodecanedioic acid, and dimer acid, and in the form of glycol. For example, diethylene glycol, triethylene glycol,
Cyclohexane dimethanol or molecular weight 300-10000
These include polyethylene glycol, polytetramethylene glycol bisphenol (or/and halogenated bisphenol), and adducts of ethylene oxide and propylene oxide, and in the form of aromatic diols, hydroquinone, resorcinol, 2,2-bis( 4-hydroxyphenyl)propane, 4,4'-hydroxyphenyl sulfone,
Examples include 4,4'-hydroxyphenylmethane.
Further, before crosslinking, it is sufficient that the compound is substantially linear and has a trifunctional or higher functional ester-forming group, such as trimellitic acid, trimezic acid, pyromellitic acid,
Glycerin, pentaerythritol, etc. may be partially copolymerized. The intrinsic viscosity of polyalkylene terephthalate before crosslinking is phenol/
sym-Tetrachloroethane = 60/40 (weight ratio) measured as a solution of 0.1 to 1.0 dl/g, preferably 0.3 to 1.0 dl/g
It is 0.8dl/g. Crosslinking is done using alkylene terephthalate polyester and polyfunctional epoxy compound.
This can be carried out by mixing an isocyanate compound, a compound having an ethylenic double bond, etc., heating the mixture and/or irradiating it with active radiation in the presence or absence of a suitable reaction catalyst. The self-crosslinking alkylene terephthalate polyester can be obtained by using the acid component, glycol, and diol component for producing the above-mentioned alkylene terephthalate polyester, and further introducing a self-crosslinking unit. In order to introduce a self-crosslinkable unit, a monomer having an ethylenically unsaturated bond or a monomer having a photocrosslinkable unit may be copolymerized. Preferably, monomers having photocrosslinkable units are used. As photocrosslinkable units, particularly preferred are
【式】（一般
式１）単位
（R1，R2は同一又は異なる置換基であつて、
炭素数１以上の脂肪族、芳香族、または脂環族の
１価の基。ｍ，ｎは同一又は異なる０〜３の数）
を全エステル基100ケに対し20ケ〜0.1ケ、好まし
くは10ケ以下含有する様に共重合する。
本発明に用いられる自己架橋性アルキレンテレ
フタレート系ポリエステル中に前記一般式１の構
造単位を導入する為に、次の様な単量体又は／お
よび、その全駆体が用いられる。即ち芳香核に置
換基を含むあるいは含まないベンゾフエノンテト
ラカルボン酸又は／およびその誘導体（好ましく
は酸無水物）(A)と分子中に１ケの第１級アミノ基
および少くとも１ケのエステル形成性官能基を有
する化合物(B)とから製造され、次の一般式で表
される。
ここでR1，R2はベンゼン核への置換基を表し
炭素数１以上、通常１〜10の脂肪族、芳香族また
は脂環族の１価の残基であつて同じでも異なつて
もよい。ｍ，ｎは置換基の数を表し各々０〜３の
数を示し、同じでも異なつてもよい。R3，R4は
炭素数１以上通常１〜20の脂肪族、脂肪族又は芳
香族の２価の残基であつて、その中にエーテル結
合、エステル結合、アミド結合、イミド結合等が
含まれていてもよく、R3とR4は同じでも異なつ
ていてもよい。Ｘ，Ｙは、水酸基（又は／および
そのエステル）又はカルボキシル基（又は／およ
びそのエステル、酸ハライド等）であり、ＸとＹ
は同じでも、異つていてもよい。
更に具体的に一般式（）を説明する為に原料
(B)で示せば炭素数２〜10のアルカノールアミン例
えばモノエタノールアミン、プロパノールアミ
ン、ブタノールアミン等、炭素数２〜10のアミノ
酸例えばグリシン、β―アラニン、γ―アミノ―
ｎ―酪酸、ｐ―アミノ安息香酸、ｍ―アミノ安息
香酸などを挙げることが出来る。本発明において
用いるアルキレンテレフタレート系ポリエステル
及び、一般式（）の構造を導入したアルキレン
テレフタレート系ポリエステルは、一般式（）
の単量体又は／およびその全駆体や、先に述べた
単量体を用い、従来、公知のエステル交換法やエ
ステル化法によつて、公知の装置を用いて容易に
製造することが出来る。
自己架橋性アルキレンテレフタレート系ポリエ
ステルの架橋はラジカル開始剤を混合して加熱す
る、あるいはそのまま光照射することにより架橋
される。上記自己架橋性アルキレンテレフタレー
ト系ポリエステル中に、さらに前記架橋剤を配合
した組成物を上記と同様に架橋することもでき
る。
本発明に用いられる架橋されたアルキレンテレ
フタレート系ポリエステルは、ゲル分率が10％以
上好ましくは20％以上、更に好ましくは30％以上
である。ゲル分率は次の様に測定するものとす
る。即ち、架橋されたアルキレンテレフタレート
系ポリエステル（架橋のための触媒や架橋剤を含
むものとする）１ｇを120℃のフエノール／sym
―テトラクロルエタン＝60／40（重量比）混合溶
媒250c.c.中で２時間加熱した後の不溶部をNo.２の
ガラスフイルターで過後、上記混合溶媒、クロ
ロホルムの順で洗浄し、乾燥した後、その重量か
らゲル（不溶分）の分率を求める。ゲル分率が10
％未満であると耐ハンダ性や耐化学薬品性（エツ
チング液、メツキ液、レジスト除去液など）が悪
く不都合である。
本発明において用いる耐熱繊維編織物又は不織
布において、耐熱繊維はガラス繊維、金属繊維、
炭素繊維、黒鉛繊維、芳香族ポリアミド繊維、ポ
リイミド繊維、ポリアミドイミド繊維、ポスエス
テルイミド繊維など任意のものを選ぶことができ
る。編織物又は不織布は耐熱性繊維（長繊維又は
短繊維）を編んだもの、織つたものまたは繊維を
からませた集合体であり、その重さや厚み、繊維
の種類、編織法、繊維密度（一定面積当りの本
数）など任意に選ぶことが出来る。通常厚さ20〜
200μ、密度20〜60本／25mmのものが好ましい。
又、編織物（又は不織布）は、積層に先立ちクロ
ーム処理、シラン処理その他の樹脂処理などを行
うことも好ましい。
金属の種類は通常、鉄、アルミニウム、亜鉛、
銅、などである。織物の場合、平織又は目抜平織
が好ましい。
本発明の架橋アルキレンテレフタレート系ポリ
エステル中に耐熱性繊維編織物又は不織布が存在
する構造の架橋ポリエステルシートは、通常次の
様にして製造出来る。即即ちアルキレンテレフタ
レート系ポリエステルの架橋性組成物又は／およ
び自己架橋性アルキレンテレフタレート系ポリエ
ステルを溶液状態あるいは熔融状態で耐熱性繊維
編織物又は不織布に含浸し（溶媒を蒸発させた
後）加熱又は／および活性線を照射し、架橋せし
める。好ましくは前記一般式（）の単位を共重
合せしめた自己（光）架橋性アルキレンテレフタ
レート系ポリエステル樹脂を耐熱性繊維編織物又
は不織布に溶融コーテイングした後活性線を照射
して架橋させる方法である。編織物又は不織布な
どの網目の中まで樹脂が入り込むが、通常、編織
物や不織布などの上層面および下層面に、架橋さ
れたアルキレンテレフタレート系ポリエステル層
が１〜200μ好ましくは３〜50μ積層される。この
ような架橋ポリエステルシートは従来の不飽和ポ
リエステル等の硬化性樹脂を用いたガラスクロス
積層物と異り、可撓性を有するという特徴があ
り、しかも、260℃以上の高温に於いても剛性を
有するのである。この様に本発明のシートは、従
来得るのが困難であつた可撓性と高温での剛性を
併せ持つた性質を有することは驚くべきことであ
り、これは本発明において用いる熱可塑性で高分
子量のアルキレンテレフタレート系ポリエステル
の架橋体と、耐熱性繊維編織物又は不織布との複
合による効果である。これらの性質は本発明のシ
ートに、更に金属層を積層して、フレキシブルプ
リント回路板、フラツトケーブル、集積回路用キ
ヤリアテープとして用いるとき、効果的に利用出
来る。本発明シートに金属層を更に積層するに
は、接着剤樹脂を界在させて、積層出来るが、接
着剤を用いることなく、架橋されたアルキレンテ
レフタレート系ポリエステルを金属箔に直接加熱
積層したり、架橋していない（あるいは部分的に
架橋している）アルキレンテレフタレート系ポリ
エステルの架橋性組成物又は／および自己架橋性
アルキレンテレフタレート系ポリエステルを直
接、積層後加熱又は／および活性線照射により架
橋させる方法が好ましい。あるいは、メツキレジ
ストを部分的に積層し、化学メツキおよび要すれ
ば更に電気メツキにより、金属層を積層すること
も出来る。金属層の上に更に本発明において用い
る架橋アルキレンテレフタレート系ポリエステル
層（耐熱繊維編織物又は不織布を含んでいても、
含んでいなくてもよい）を積層することも出来
る。本発明における架橋アルキレンテレフタレー
ト系ポリエステル層中には難燃剤、滑剤、メツキ
活性化剤などとしてハロゲン化合物、リン化合
物、酸化アンチモン、酸化チタン、酸化硅素、酸
化アルミニウム、炭酸カルシウムなどの有機ある
いは無機化合物が含まれていてもよい。
以下に実施例を挙げて、本発明を更に説明する
が、これらにより本発明が限定されるものではな
い。
実施例 Ａ
テレフタル酸41.7Kg、エチレングリコール31.2
Kg、三酸化アンチモン18.3ｇ、トリエチルアミン
76.2ｇ、リン酸トリメチル4.6ｇ、シリカ微粒子
（サイロイド＃150富士デビソン社製）25ｇから成
る混合物を240℃、3.5Kg／cm2下で加熱し105分間
反応させた後常圧にしＮ，N′―ビス（β―ヒド
ロキシエチル）ベンゾフエノンテトラカルボン酸
イミド2051ｇを加え240℃常圧で15分間反応を続
けた後150の重縮合用反応容器に移し、温度を
240℃から75分間で280℃に上昇させ、同時に圧力
を徐々に減じて最終的に0.1mmＨｇとした。更に
280℃、0.1mmＨｇで70分間反応を続けた。得られ
たポリマーは融点255℃還元比粘度（フエノー
ル／sym―テトラクロロエタン重量比６／４の混
合溶媒25mlにポリマー100mg溶解して30℃で測定）
0.674dl／ｇであつた。
得られたエチレンテレフタレート系共重合体
（前記一般式の単位をエステル結合100ケ当り１
ケ含有する）100重量部と臭素化芳香族化合物系
難燃剤（旭ガラス社製AFR−3001X）を15重量
部と難燃助剤（三酸化アンチモン）５重量部をＶ
形ブレンダーで混合し、押出機を用い温度290℃
で押出し、冷却してカツトしペレツト状にした。
このペレツトを粉砕器を用いて粉砕し、140℃で
１夜真空下で乾燥した。
銅箔（福田金属箔粉工業社製T5A）と、有沢
製作所のガラスクロス（有沢製作所製EPC070）
と上記ポリマーブレンド物を油圧プレスで、温度
290℃で加熱加圧して積層し、フレキシブルプリ
ント配線板を作成した。この配線板を180℃で上
記油圧プレスを使用して熱処理し、その後2KW
高圧水銀灯（東芝電材株式会社製、80W／cmの空
冷ランプ一灯）を使用し、ランプから10cm離して
0.6m／分の速度で配線板を移動させて光照射し
た。
比較のためにポリエチレンテレフタレート
（PET）から作られたもの、さらに市販のガラス
クロス補強トリアジンシートに対して、本発明品
と比べ、難燃性、耐熱性、耐折曲性を調べた。[Formula] (General formula 1) unit (R 1 and R 2 are the same or different substituents,
An aliphatic, aromatic, or alicyclic monovalent group having 1 or more carbon atoms. (m, n are the same or different numbers from 0 to 3) are copolymerized so that 20 to 0.1, preferably 10 or less, are contained per 100 total ester groups. In order to introduce the structural unit of the general formula 1 into the self-crosslinking alkylene terephthalate polyester used in the present invention, the following monomers and/or their precursors are used. That is, benzophenonetetracarboxylic acid or/and its derivative (preferably an acid anhydride) containing or not containing a substituent in the aromatic nucleus (A) and one primary amino group and at least one It is produced from a compound (B) having an ester-forming functional group and is represented by the following general formula. Here, R 1 and R 2 represent substituents on the benzene nucleus, and are aliphatic, aromatic, or alicyclic monovalent residues having 1 or more carbon atoms, usually 1 to 10, and may be the same or different. . m and n represent the number of substituents, each representing a number of 0 to 3, and may be the same or different. R 3 and R 4 are aliphatic, aliphatic or aromatic divalent residues having 1 or more carbon atoms, usually 1 to 20, and include ether bonds, ester bonds, amide bonds, imide bonds, etc. R 3 and R 4 may be the same or different. X and Y are a hydroxyl group (or/and an ester thereof) or a carboxyl group (or/and an ester thereof, an acid halide, etc.), and X and Y
may be the same or different. In order to explain the general formula () more specifically, the raw materials
(B) indicates alkanolamines having 2 to 10 carbon atoms, such as monoethanolamine, propanolamine, butanolamine, etc., and amino acids having 2 to 10 carbon atoms, such as glycine, β-alanine, γ-amino-
Examples include n-butyric acid, p-aminobenzoic acid, m-aminobenzoic acid, and the like. The alkylene terephthalate polyester used in the present invention and the alkylene terephthalate polyester into which the structure of the general formula () has been introduced are of the general formula ()
It can be easily produced using a conventionally known transesterification method or esterification method using a known apparatus using a monomer or/and its entire precursor or the monomers mentioned above. I can do it. The self-crosslinking alkylene terephthalate polyester is crosslinked by mixing a radical initiator and heating it, or by directly irradiating it with light. A composition in which the above-mentioned crosslinking agent is further blended into the above-mentioned self-crosslinkable alkylene terephthalate polyester can also be crosslinked in the same manner as above. The crosslinked alkylene terephthalate polyester used in the present invention has a gel fraction of 10% or more, preferably 20% or more, and more preferably 30% or more. The gel fraction shall be measured as follows. That is, 1 g of crosslinked alkylene terephthalate polyester (contains a catalyst and crosslinking agent for crosslinking) is mixed with phenol/sym at 120°C.
- Tetrachloroethane = 60/40 (weight ratio) After heating in a mixed solvent of 250 c.c. for 2 hours, pass the insoluble part through a No. 2 glass filter, wash with the above mixed solvent and chloroform in that order, and dry. Then, calculate the gel (insoluble content) fraction from the weight. Gel fraction is 10
If it is less than %, solder resistance and chemical resistance (etching solution, plating solution, resist removal solution, etc.) are poor and it is inconvenient. In the heat-resistant fiber knitted fabric or non-woven fabric used in the present invention, the heat-resistant fiber is glass fiber, metal fiber,
Any fiber such as carbon fiber, graphite fiber, aromatic polyamide fiber, polyimide fiber, polyamideimide fiber, or postesterimide fiber can be selected. Knitted fabrics or non-woven fabrics are knitted, woven, or aggregates of heat-resistant fibers (long or short fibers), and their weight, thickness, fiber type, weaving method, fiber density (constant (number of pieces per area) can be selected arbitrarily. Normal thickness 20~
200μ and a density of 20 to 60 pieces/25mm are preferred.
It is also preferable that the knitted fabric (or nonwoven fabric) is subjected to chromium treatment, silane treatment, or other resin treatment prior to lamination. The metal types are usually iron, aluminum, zinc,
Copper, etc. In the case of woven fabrics, plain weave or open plain weave is preferred. The crosslinked polyester sheet of the present invention having a structure in which a heat-resistant fiber knitted fabric or nonwoven fabric is present in the crosslinked alkylene terephthalate polyester can be generally produced in the following manner. That is, a crosslinkable composition of an alkylene terephthalate polyester and/or a self-crosslinkable alkylene terephthalate polyester is impregnated into a heat-resistant textile knitted fabric or nonwoven fabric in a solution or molten state (after the solvent is evaporated) and heated or/and Irradiate with actinic radiation to cause crosslinking. A preferred method is to melt-coat a heat-resistant fiber knitted fabric or non-woven fabric with a self-(photo)crosslinkable alkylene terephthalate polyester resin copolymerized with units of the general formula (), and then crosslink it by irradiating it with actinic radiation. The resin penetrates into the mesh of the knitted fabric or nonwoven fabric, but usually a crosslinked alkylene terephthalate polyester layer of 1 to 200μ, preferably 3 to 50μ, is laminated on the upper and lower surfaces of the knitted or nonwoven fabric. . Unlike conventional glass cloth laminates using hardening resins such as unsaturated polyester, such cross-linked polyester sheets are characterized by their flexibility, and they are also rigid even at high temperatures of 260°C or higher. It has. As described above, it is surprising that the sheet of the present invention has properties that combine flexibility and rigidity at high temperatures, which have been difficult to obtain in the past. This effect is due to the composite of the crosslinked alkylene terephthalate polyester and a heat-resistant textile knitted fabric or nonwoven fabric. These properties can be effectively utilized when the sheet of the present invention is further laminated with a metal layer and used as a carrier tape for flexible printed circuit boards, flat cables, and integrated circuits. In order to further laminate a metal layer on the sheet of the present invention, it is possible to laminate the sheet with an adhesive resin interposed therebetween. There is a method of directly crosslinking a crosslinkable composition of an uncrosslinked (or partially crosslinked) alkylene terephthalate polyester and/or a self-crosslinkable alkylene terephthalate polyester by heating and/or irradiation with actinic radiation after lamination. preferable. Alternatively, a plating resist may be partially laminated, and a metal layer may be laminated by chemical plating and, if necessary, electroplating. Further on the metal layer, a cross-linked alkylene terephthalate polyester layer used in the present invention (even if it includes a heat-resistant fiber knitted fabric or non-woven fabric,
) can also be laminated. The crosslinked alkylene terephthalate polyester layer of the present invention contains organic or inorganic compounds such as halogen compounds, phosphorus compounds, antimony oxide, titanium oxide, silicon oxide, aluminum oxide, and calcium carbonate as flame retardants, lubricants, and plating activators. May be included. The present invention will be further explained with reference to Examples below, but the present invention is not limited by these. Example A Terephthalic acid 41.7Kg, ethylene glycol 31.2
Kg, antimony trioxide 18.3g, triethylamine
A mixture consisting of 76.2 g of trimethyl phosphate, 4.6 g of trimethyl phosphate, and 25 g of silica fine particles (Thyroid #150 manufactured by Fuji Davison) was heated at 240°C under 3.5 Kg/cm 2 and reacted for 105 minutes, and then brought to normal pressure with N,N' - 2051g of bis(β-hydroxyethyl)benzophenonetetracarboxylic acid imide was added and the reaction was continued at 240°C and normal pressure for 15 minutes, then transferred to a 150° polycondensation reaction vessel and the temperature was lowered.
The temperature was increased from 240°C to 280°C over 75 minutes, and at the same time the pressure was gradually reduced to a final level of 0.1 mmHg. Furthermore
The reaction was continued for 70 minutes at 280°C and 0.1 mmHg. The resulting polymer has a melting point of 255°C and a reduced specific viscosity (measured at 30°C by dissolving 100 mg of polymer in 25 ml of a mixed solvent with a phenol/sym-tetrachloroethane weight ratio of 6/4).
It was 0.674 dl/g. The obtained ethylene terephthalate copolymer (one unit of the above general formula per 100 ester bonds)
100 parts by weight of brominated aromatic compound flame retardant (AFR-3001X manufactured by Asahi Glass Co., Ltd.) and 5 parts by weight of flame retardant aid (antimony trioxide).
Mix with a blender and use an extruder at a temperature of 290℃
It was extruded, cooled and cut into pellets.
The pellets were ground using a grinder and dried under vacuum at 140°C overnight. Copper foil (T5A manufactured by Fukuda Metal Foil & Powder Industries Co., Ltd.) and glass cloth from Arisawa Seisakusho (EPC070 manufactured by Arisawa Seisakusho)
and the above polymer blend in a hydraulic press at a temperature of
They were laminated by heating and pressurizing at 290°C to create a flexible printed wiring board. This wiring board was heat treated at 180℃ using the above hydraulic press, and then 2KW
Use a high-pressure mercury lamp (manufactured by Toshiba Electric Materials Corporation, one 80W/cm air-cooled lamp) and keep it 10cm away from the lamp.
The wiring board was moved at a speed of 0.6 m/min and irradiated with light. For comparison, the flame retardance, heat resistance, and bending resistance of a sheet made from polyethylene terephthalate (PET) and a commercially available glass cloth-reinforced triazine sheet were compared with the product of the present invention.
【表】
難燃性：１cm×10cmの短冊状のものを垂直に吊
し、下端にマツチを燃やして３秒接炎し
て、燃えるか否かを調べた、燃焼するも
の（×）、燃焼しないもの（〇）で示す。
耐熱性：280℃のシリコンオイル中に10秒間浸漬
し形態の変化を調べた。形態変化なし
（〇）、形態が変化たもの（×）で示す。
耐折曲性：180゜に折曲げて破れるか否か調べた。
破壊するもの（×）、破壊しないもの
（〇）で示す。
本共重合ポリエステルをこの条件で光照射する
と、ゲル分率は60〜70％になる。光照射しない場
合は勿論ゲル分率０である。
実施例 Ｂ
第１表実施例３のサンプルについて、銅箔引き
剥し強さをJIS−Ｃ−6481により測定したところ
1.6Kg／cmであり、280℃×20秒間加熱後および、
沸騰トリクレンに３分間処理した後の引き剥し強
さは、各々1.7Kg／cm、1.5Kg／cmであつた。
実施例 Ｃ
実施例Ａ第１表中の実施例−２及び、比較の為
に、ガラスクロスを含まない以外実施例−２と同
様に製造したシートの熱変形温度を以下の様に測
定した。各シートを幅１mm、試長25mmにスリツト
し、10ｇ／1.5mm2の荷重をかけ、空気中、昇温速
度４℃／分で昇温させ、シートが切断する温度を
測定したところ、ガラスクロスを含まないシート
は280℃で切断したが、本発明品は300℃でも切断
しなかつた。[Table] Flame retardancy: A strip of 1 cm x 10 cm was hung vertically, and a piece of pine was burned at the bottom end and the flame was applied for 3 seconds to see if it would burn. Indicate by not doing so (〇). Heat resistance: Immersed in silicone oil at 280°C for 10 seconds to examine changes in morphology. No change in form (〇) and change in form (×) indicate. Bending resistance: Tested to see if it would break when bent at 180°.
Indicate by items that will be destroyed (×) and items that will not be destroyed (○). When this copolyester is irradiated with light under these conditions, the gel fraction will be 60 to 70%. Of course, when no light is irradiated, the gel fraction is 0. Example B The copper foil peel strength of the sample of Example 3 in Table 1 was measured according to JIS-C-6481.
1.6Kg/cm, after heating at 280℃ for 20 seconds and
The peel strength after being treated with boiling trichlorene for 3 minutes was 1.7 Kg/cm and 1.5 Kg/cm, respectively. Example C Example A The heat distortion temperature of a sheet manufactured in the same manner as Example-2 in Table 1 and, for comparison, Example-2 except that no glass cloth was included, was measured as follows. Each sheet was slit to a width of 1 mm and a test length of 25 mm, a load of 10 g/1.5 mm 2 was applied, the temperature was raised in air at a heating rate of 4°C/min, and the temperature at which the sheet was cut was measured. The sheet containing no carbon fiber was cut at 280°C, but the product of the present invention was not cut even at 300°C.
Claims (1)
レフタレート系ポリエステル中に耐熱性繊維編織
物又は不織布が存在する構造の架橋ポリエステル
シート。 ２ 特許請求の範囲第１項において、該架橋ポリ
エステルシートの少なくとも片面に金属層が積層
された構造の積層架橋ポリエステルシート。 ３ 特許請求の範囲第１項において、ゲル分率が
10％以上である架橋アルキレンテレフタレート系
ポリエステルは下記の一般式（）の構造単位を
全エステル基100ケに対し20ケ以下含有するアル
キレンテレフタレート系ポリエステルを活性線照
射することによつて得たものである架橋ポリエス
テルシート。 （R1，R2は同一又は異なる置換基であつて、
炭素数１以上の脂肪族、芳香族または脂環族の１
価の基。ｍ，ｎは同一又は異なる０〜３の数） ４ ゲル分率が10％以上である架橋アルキレンテ
レフタレート系ポリエステル中に耐熱性繊維編織
物又は不織布が存在する架橋ポリエステルシート
の少なくとも片面に金属層が積層された構造のフ
レキシブルプリント配線基板。 ５ ゲル分率が10％以上である架橋アルキレンテ
レフタレート系ポリエステル中に耐熱性繊維編織
物又は不織布が存在する架橋ポリエステルシート
の少なくとも片面に金属導電層が積層された構造
のフラツトケーブル。 ６ ゲル分率が10％以上である架橋アルキレンテ
レフタレート系ポリエステル中に耐熱性繊維編織
物又は不織布が存在する架橋ポリエステルシート
の少なくとも片面に金属導電層が積層された構造
の集積回路用キヤリアテープ。[Scope of Claims] 1. A crosslinked polyester sheet having a structure in which a heat-resistant fiber knitted fabric or nonwoven fabric is present in a crosslinked alkylene terephthalate polyester having a gel fraction of 10% or more. 2. A laminated crosslinked polyester sheet according to claim 1, having a structure in which a metal layer is laminated on at least one side of the crosslinked polyester sheet. 3 In claim 1, the gel fraction is
Cross-linked alkylene terephthalate polyester having a content of 10% or more is obtained by irradiating an alkylene terephthalate polyester containing 20 or less structural units of the following general formula () per 100 total ester groups with actinic rays. A cross-linked polyester sheet. (R 1 and R 2 are the same or different substituents,
Aliphatic, aromatic or alicyclic 1 having 1 or more carbon atoms
The basis of valence. (m, n are the same or different numbers from 0 to 3) 4 A metal layer is provided on at least one side of a crosslinked polyester sheet in which a heat-resistant fiber knitted fabric or nonwoven fabric is present in a crosslinked alkylene terephthalate polyester having a gel fraction of 10% or more. A flexible printed wiring board with a laminated structure. 5. A flat cable having a structure in which a metal conductive layer is laminated on at least one side of a crosslinked polyester sheet in which a heat-resistant fiber knitted fabric or nonwoven fabric is present in a crosslinked alkylene terephthalate polyester having a gel fraction of 10% or more. 6. A carrier tape for integrated circuits having a structure in which a metal conductive layer is laminated on at least one side of a crosslinked polyester sheet in which a heat-resistant fiber knitted fabric or nonwoven fabric is present in a crosslinked alkylene terephthalate polyester having a gel fraction of 10% or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2575280A JPS56121765A (en) | 1980-02-29 | 1980-02-29 | Bridged polyester sheet and flexible printed wiring board* flat cable or carrier tape for integrated circuit using said sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2575280A JPS56121765A (en) | 1980-02-29 | 1980-02-29 | Bridged polyester sheet and flexible printed wiring board* flat cable or carrier tape for integrated circuit using said sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56121765A JPS56121765A (en) | 1981-09-24 |
| JPS646228B2 true JPS646228B2 (en) | 1989-02-02 |
Family
ID=12174558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2575280A Granted JPS56121765A (en) | 1980-02-29 | 1980-02-29 | Bridged polyester sheet and flexible printed wiring board* flat cable or carrier tape for integrated circuit using said sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56121765A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03108628U (en) * | 1990-02-22 | 1991-11-08 |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59158578A (en) * | 1983-02-26 | 1984-09-08 | 日本メクトロン株式会社 | Flexible circuit board sheet material |
| JPS60166454A (en) * | 1984-02-10 | 1985-08-29 | 東洋紡績株式会社 | Crosslinking polyalkylene terephthalate group resin sheet |
| JPS61293847A (en) * | 1985-06-21 | 1986-12-24 | 東洋紡績株式会社 | Fiber reinforced resin sheet |
| GB201310837D0 (en) * | 2013-06-18 | 2013-07-31 | Dupont Teijin Films Us Ltd | Polyester film -IV |
-
1980
- 1980-02-29 JP JP2575280A patent/JPS56121765A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03108628U (en) * | 1990-02-22 | 1991-11-08 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56121765A (en) | 1981-09-24 |
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