JPS6383139A - Production of laminated sheet - Google Patents
Production of laminated sheetInfo
- Publication number
- JPS6383139A JPS6383139A JP22757486A JP22757486A JPS6383139A JP S6383139 A JPS6383139 A JP S6383139A JP 22757486 A JP22757486 A JP 22757486A JP 22757486 A JP22757486 A JP 22757486A JP S6383139 A JPS6383139 A JP S6383139A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- acid
- unsaturated polyester
- thermosetting resin
- polyester resin
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 19
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004014 plasticizer Substances 0.000 claims abstract description 10
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 10
- 239000002966 varnish Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 229920003987 resole Polymers 0.000 claims abstract description 4
- 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 claims description 12
- 239000003063 flame retardant Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- -1 bromine compound Chemical class 0.000 abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 abstract description 6
- 229920001225 polyester resin Polymers 0.000 abstract description 6
- 239000004645 polyester resin Substances 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 abstract description 4
- 229920006305 unsaturated polyester Polymers 0.000 abstract description 4
- 239000001361 adipic acid Substances 0.000 abstract description 3
- 235000011037 adipic acid Nutrition 0.000 abstract description 3
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical compound BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 abstract description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 150000007519 polyprotic acids Polymers 0.000 abstract 1
- 230000000979 retarding effect Effects 0.000 abstract 1
- 238000004080 punching Methods 0.000 description 10
- 239000002383 tung oil Substances 0.000 description 8
- 230000007423 decrease Effects 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical class C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 description 1
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- LIAWCKFOFPPVGF-UHFFFAOYSA-N 2-ethyladamantane Chemical compound C1C(C2)CC3CC1C(CC)C2C3 LIAWCKFOFPPVGF-UHFFFAOYSA-N 0.000 description 1
- WEHZNZTWKUYVIY-UHFFFAOYSA-N 3-oxabicyclo[3.2.2]nona-1(7),5,8-triene-2,4-dione Chemical compound O=C1OC(=O)C2=CC=C1C=C2 WEHZNZTWKUYVIY-UHFFFAOYSA-N 0.000 description 1
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 244000131360 Morinda citrifolia Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 240000002834 Paulownia tomentosa Species 0.000 description 1
- 235000010678 Paulownia tomentosa Nutrition 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000013040 bath agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 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
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009975 flexible effect Effects 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229940100630 metacresol Drugs 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000017524 noni Nutrition 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000009824 pressure lamination Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Reinforced Plastic Materials (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は難燃性及び打抜加工性に優ｎる積層板の製造法
に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a laminate having excellent flame retardancy and punching workability.
（従来の技術）
最近の電子機器工業の著しい発展に伴ない、電子機器の
高密度化が進み、安全性の面から、印刷配？ｆｓ板用積
層板の難燃性の要求が一段と厳しくなり【おり、米国Ｕ
Ｌ規格等の法制、規格も整備さｎｌその規制は強化され
つつある。また、最近、電子機器に使用さｎる印刷配線
板は高密度化に伴い、自動実装技術も進歩し、より厳し
い寸法精度が要求さｎｌこの要求金満たすため低温打抜
加工が行わｎる様になっている。(Prior art) With the recent remarkable development of the electronic equipment industry, the density of electronic equipment has increased, and printing layouts have become increasingly important from the standpoint of safety. The requirements for flame retardancy for laminates for fs boards have become even more stringent.
Legislation and standards such as the L standard have also been developed, and regulations are being strengthened. In addition, as printed wiring boards used in electronic devices have recently become denser, automatic mounting technology has also advanced, and stricter dimensional accuracy is required.In order to meet this requirement, low-temperature punching is being performed. It has become.
従来、打抜加工性を向上させるためには、熱硬化性樹脂
にリン酸エステ／Ｌ−類、ポリエーテル類等の可塑剤を
添加したり、ｆた乾性油類、ポリブタジェン類等の可塑
剤と熱硬化性樹脂の反応により、樹脂の改質かたさｎて
いる。Conventionally, in order to improve punching workability, plasticizers such as phosphate esters/L-types and polyethers were added to thermosetting resins, and plasticizers such as drying oils and polybutadienes were added to thermosetting resins. The modified hardness of the resin is determined by the reaction between the thermosetting resin and the thermosetting resin.
一方、熱硬化性樹脂の難燃化の方法にリン酸エステ／Ｌ
−類等のリン系化合物、ブロム化フェノール類、ブロム
化エボキク化曾物、ブロム化ビフェニルエーテル卿等ブ
ロム系化会物、トリアジン化合物等のテラ素糸化合物及
びアンチモン等の無機化合物を単独まｙ、＝に併用して
難燃化する熱硬化性樹脂に添加することに工りなさｎて
いる。On the other hand, phosphoric acid ester/L is used as a method for making thermosetting resin flame retardant.
Phosphorous compounds such as -, brominated phenols, brominated epoxy compounds, brominated biphenyl ethers, terazine compounds such as triazine compounds, and inorganic compounds such as antimony may be used alone. , = is used in combination with thermosetting resins to make them flame retardant.
（発明が解決しようとする問題点）
打抜加工温度の低温化に伴い、更に５１塑剤の増量が必
要となる。こｎにより、熱硬化性樹脂の架橋密度の低下
が生じ、打抜加工性については打抜穴周囲の月日（パル
ジンの発生や、１１ｉｔ熱性、耐溶剤性の低下か著しい
。かつ難燃性を付与するためには更に多量の難燃剤の添
加か必要となり、打抜加工性、耐熱性、耐溶剤性の劣化
が著しくなる。また、使用する可塑剤と難燃剤との相溶
性の問題か生じ、不均一硬化反応等で特性がばらつく等
、可塑剤量と難燃剤量とのバランスをとること力１難し
い。(Problems to be Solved by the Invention) As the punching temperature decreases, it becomes necessary to further increase the amount of 51 plasticizer. As a result, the crosslinking density of the thermosetting resin decreases, and the punching processability is affected by the generation of palsine around the punched hole and a significant decrease in heat resistance and solvent resistance. In order to impart this, it is necessary to add a larger amount of flame retardant, resulting in significant deterioration of punching workability, heat resistance, and solvent resistance.Also, there may be a problem with the compatibility between the plasticizer and flame retardant used. It is difficult to maintain a balance between the amount of plasticizer and the amount of flame retardant, as properties may vary due to non-uniform curing reactions.
本発明は、難燃性及び打抜加工性か同時に優ｎる積層板
の製造法全提供するものである。The present invention provides a complete method for manufacturing a laminate that is simultaneously superior in flame retardancy and punchability.
（問題点を解決するための手段）
本発明は、１分子中に１個以上の二重結合を有する臭素
含有不飽和ポリエステに樹脂を難燃性可塑剤として配合
した熱硬化性樹脂ワニス七所定量含浸付着させた基材を
成形することを特轍とするものである。(Means for Solving the Problems) The present invention provides a thermosetting resin varnish in which a bromine-containing unsaturated polyester having one or more double bonds in one molecule is blended with a resin as a flame-retardant plasticizer. This method is characterized by molding a base material that has been impregnated with a fixed amount.
上記に示しに不飽和ポリエステル樹脂とじては、マレイ
ン酸、無水マレイン酸、ツマｂｇ、シトラコン酸、イタ
コン酸等の二重結合全有するα、β不飽和二塩基酸、グ
リコ−ＡＭとしてはエチレングリコール、ジエチレンク
リコール、トリエチレンクリコール、プロピレングリコ
ール、ジプロピレングリコール、フタンシオール、ベン
タンジオール、ヘキテンジオー／−等、Ａ累含有化会物
としては、テトラブロモ無水フタル酸、ジブロモネオペ
ンチルグリコール、トリブロモアリルアルコール、また
はテトラブロモビス２エノーＡジグリシジｈエーテｈ等
の臭素含有エポキシ化合物等、可！！！性金増す化せ物
としては、アジピン酸、アゼライン酸、セバシン酸や、
ダイマー酸等の高級脂肪酸等、また必要に応じ、フタル
酸、イソフタル酸、テレフタＡ−酸、無水フタル酸、ジ
メテルテレアタル酸、ヘキサハイドロフタル酸、ヘキサ
／＼イドロ無水７タル酸等の多塩ＭＭを用い、反応温度
８０℃〜２８０℃て会成されろ。Examples of the unsaturated polyester resins shown above include maleic acid, maleic anhydride, tuma bg, citraconic acid, itaconic acid, etc., α, β unsaturated dibasic acids having all double bonds; and glyco-AM, ethylene glycol. , diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, phthanesiol, bentanediol, hextenediol/-, etc. Examples of A-containing compounds include tetrabromophthalic anhydride, dibromoneopentyl glycol, tribromoallylic alcohol. , or bromine-containing epoxy compounds such as tetrabromobis-2-eno-A diglycidi-ether, etc., are acceptable! ! ! Chemicals that increase sexual value include adipic acid, azelaic acid, sebacic acid,
Higher fatty acids such as dimer acid, and, if necessary, polyesters such as phthalic acid, isophthalic acid, terephthalic anhydride, phthalic anhydride, dimetertereatarate, hexahydrophthalic acid, hexa/\hydroheptalic anhydride, etc. The reaction temperature is 80°C to 280°C using salt MM.
臭素含有不飽和ポリエステル樹脂の臭素含有率は５％へ
４０％が好ましく、臭素含有率が高いと可視性が低下す
ることもある。また、臭素含有不瓢和ポリエステル樹脂
の平均分子ｍは１０００へ１２０００が好ｆＬ＜、分子
量が大きいはどｏＴ＠性は積すか、平均分子！ ｔ ７
０００以上だと熱硬化性１４脂との相だ性か低下するこ
とがある。The bromine content of the bromine-containing unsaturated polyester resin is preferably 5% to 40%, and a high bromine content may reduce visibility. In addition, the average molecule m of the bromine-containing non-synthetic polyester resin is preferably fL<, 1000 to 12000, and if the molecular weight is large, the average molecule is multiplied! t 7
If it is more than 000, compatibility with thermosetting 14 resin may decrease.
本発明で用いる熱硬化ｔ！Ｅｍ脂としてはフェノール拉
１月旨、エポキシ樹１１旨、メラミン校（脂、ベンゾグ
アナミン樹脂等でるる。Thermal curing t! used in the present invention! Em resins include phenol resin, epoxy resin, melamine resin, benzoguanamine resin, etc.
特に′ＰＡ硬化性樹脂か乾性油変性フェノール系レゾー
ル樹脂であると低温打抜加工性か更に良好となる。乾性
油としてに、桐油、脱水ヒマク油、オイデシカ油等の乾
性油が使用さｎ１フエノール系のフェノール類としては
フェノール、メタクレゾール、バラクレゾール、オルソ
クレゾール、パライソプロピルフェノール、パラター７
ヤリープチルフエノール、パラインプロベニ３フエノー
ル０）ｙＦリ−ｆマー、ノニ／Ｌ−７エノール、ビスフ
ヱノーＡＡ等が使用される。また、二重結合を有するポ
リエステル樹脂なので乾性油変性フェノール系レゾール
樹脂との相溶性も低下せず、積層板とした時の特性も安
定している。In particular, if the material is a PA curable resin or a drying oil-modified phenolic resol resin, the low-temperature punching processability will be even better. Drying oils such as tung oil, dehydrated castor oil, and eudesica oil are used as drying oils.N1 phenolic phenols include phenol, metacresol, baracresol, orthocresol, paraisopropylphenol, and parater 7.
Yarybutylphenol, parainprobeni-3phenol 0)yF ly-fmer, noni/L-7 enol, bisphenol AA, etc. are used. Furthermore, since the polyester resin has double bonds, its compatibility with the drying oil-modified phenolic resol resin does not decrease, and the properties when made into a laminate are stable.
本発明の１分子中に１個以上の二重結合を有する臭素含
有不飽和ポリエステル便脂ｒｚ熱硬化性樹脂１００部（
重Ｍ部以下同じ）に対して３へ１２Ω部含有さｎるが、
好しくは５へ５０部が良い。１２０部以上だと成型した
積層取り層間接着性が低下し、打抜加工で剥離や月日を
生じやすくなる。この臭素含有不飽和ポリエステル樹脂
を含有した熱硬化性樹脂にトルエン、アルコール、メチ
ルエテルケトン、アセトン、ジメチルホルムアミド、ス
チレン等の浴剤を用いて、ワニスとし、紙、ガラスクロ
ス、ガラス不織布、曾成繊維布等熱硬化性樹脂槓層仮の
通常の基材に所定量含浸付層させ、成型して１層板とす
る。100 parts of the bromine-containing unsaturated polyester stool rz thermosetting resin having one or more double bonds in one molecule of the present invention (
The same applies to heavy M parts and below), but 3 to 12 Ω parts are included,
Preferably 50 to 50 parts is good. If it exceeds 120 parts, the adhesion between the molded laminated layers will decrease, and peeling or aging will easily occur during punching. A thermosetting resin containing this bromine-containing unsaturated polyester resin is mixed with a bath agent such as toluene, alcohol, methyl ether ketone, acetone, dimethyl formamide, or styrene to make a varnish, which can be used to coat paper, glass cloth, glass nonwoven fabric, etc. A thermosetting resin layer such as fiber cloth is impregnated with a predetermined amount on a temporary ordinary base material and molded to form a one-layer board.
成型は兵累含有不飽和ポリエステ／Ｌ−ｖ５脂を配合し
た熱硬化性ａ（脂ワニスを含浸した基材の−枚或は必要
枚数重ね会せ、必要な＠度（室温も含む）、必要な圧力
（無圧も含む）で行なわｎる。筐た、補助的に難燃剤と
して、トリフェニルホスフェイト、クレジルジフェニル
ホスフェイト、イソプロピル２エニルジフエニルホスフ
エイト等のリン酸エステＡＦＪや、テトラブロモビスフ
ェノールＡ、ブロム化エポキシ化付物、ブロム化ビフェ
ニルエーテル化合物等のＪ！＃、素化合物を用いても工
い。The molding is done by stacking one sheet or the necessary number of sheets of a base material impregnated with a resin-containing unsaturated polyester/L-v5 fat, at the required temperature (including room temperature), and at the required temperature (including room temperature). The process is carried out under appropriate pressure (including no pressure).As an auxiliary flame retardant, phosphoric acid esters such as triphenyl phosphate, cresyl diphenyl phosphate, isopropyl 2-enyl diphenyl phosphate, etc., and tetra J!# and elementary compounds such as bromobisphenol A, brominated epoxidized adducts, and brominated biphenyl ether compounds can also be used.
（作用）
本発明は１分子中に１個以上の二重結−８−を有する臭
素含有不飽和ポリエステル樹脂を難燃性可塑剤として熱
硬化性樹脂に務加し、溶剤で調整する。この時、臭素含
有化合物を有する不飽和ポリエステル樹脂であるため、
難燃性の効果があり、また、長鎖状のポリエステル樹脂
構造を有するため可撓性の効果がある。この臭素含有不
飽和ポリエステル樹脂を配合した熱硬化性樹脂含浸ワニ
ス全紙等の基材に所定量含有付着させこｒＬを乾燥して
プリプレグとし、必要枚数、加熱加圧成形することによ
り、難燃性及び打抜加工性に優ｎる積層板が製造できる
。(Function) In the present invention, a bromine-containing unsaturated polyester resin having one or more -8- double bonds in one molecule is added to a thermosetting resin as a flame-retardant plasticizer, and adjusted with a solvent. At this time, since it is an unsaturated polyester resin containing a bromine-containing compound,
It has a flame retardant effect, and has a long chain polyester resin structure, so it has a flexible effect. A predetermined amount of thermosetting resin-impregnated varnish containing this bromine-containing unsaturated polyester resin is applied to a base material such as whole paper, dried to form a prepreg, and the required number of sheets is molded under heat and pressure to make it flame retardant. And a laminate with excellent punching workability can be produced.
実施例１゜
無水マレインｒ１１！４９０ｇ、テトラブロモ無水フタ
／Ｌ−酸６９６ ｇ、アジピン酸７３０ ｇ、エチレン
グリコール７４４ｇを３４反応容器に入ｎ１触媒として
テトラブチルジルコネートを用い、２２０℃で１０時間
反応を続け、臭素貧有＄１８％の不飽和ポリエステル樹
脂を得た。二重結合は平均１分子３〜４個で、酸価は２
０でめった。Example 1 490 g of anhydrous maleic R11, 696 g of tetrabromo anhydride/L-acid, 730 g of adipic acid, and 744 g of ethylene glycol were placed in a 34 reaction vessel and reacted at 220°C for 10 hours using tetrabutyl zirconate as the n1 catalyst. This was followed to obtain an unsaturated polyester resin with a bromine content of 18%. The average number of double bonds per molecule is 3 to 4, and the acid value is 2.
I got 0.
フェノール９４ｇと８０％パラホルムアルデヒド５５ｇ
ｔ−配合し、アルカリ触媒下でレゾール化し、フェノー
ル樹脂會得た。このフェノール樹脂１００部（固型分、
重量部以下同じ）に上記に示したポリエステル樹脂３０
部、テトラブロモビスフェノールＡ５ｍ、）リフエール
ホスフェイト３０部を配合して含浸用フェノとし、あら
かじめ水溶性メラミン変性フェノ−／Ｌ−樹脂で処理（
樹脂付着量１９〜２３％）した、クラフト基材に上記含
浸用ワニスを樹脂付着量５８〜６０％になる様に含浸乾
燥させ、このプリプレグ６枚と接着剤付＠はくと組み合
せて、加熱加圧積層して、１．６ ｍ１ｔｌの片面鋼張
積層板を得た。94g of phenol and 55g of 80% paraformaldehyde
T-blending was carried out and resolization was carried out under an alkali catalyst to obtain a phenol resin association. 100 parts of this phenolic resin (solid content,
Polyester resin 30 shown above in parts by weight (same below)
30 parts of Lifair Phosphate (30 parts of Tetrabromobisphenol A, 5m of Tetrabromobisphenol A) was blended to prepare a phenol for impregnation, and the mixture was pretreated with a water-soluble melamine-modified phenol/L-resin (
A craft base material with a resin adhesion of 19 to 23%) was impregnated with the above impregnating varnish to a resin adhesion of 58 to 60% and dried. Six sheets of this prepreg were combined with an adhesive @foil and heated. Pressure lamination was carried out to obtain a single-sided steel-clad laminate of 1.6 ml.
銅張積層板の特性を別表に示す。The characteristics of copper-clad laminates are shown in the attached table.
実施例２゜
桐油とフェノールを酸性触媒下で反応させ、次に８０％
バラホルムアルデヒドとアルカリ触媒下でレゾール化し
た桐油変性１ｉ３３％の桐油変性フェノール樹脂１００
部に実施例１で曾成したポリエステル樹脂３０部、テト
ラブロモビスフエ／−ｘＡ５ｉ、）！Ｊフェニルホス２
エイト３０部を配付して含浸用フェノとした。Example 2゜ Tung oil and phenol are reacted under acidic catalyst, then 80%
Tung oil modified 1i33% tung oil modified phenolic resin 100 resolized under rose formaldehyde and alkaline catalyst
30 parts of the polyester resin prepared in Example 1, tetrabromobisphene/-xA5i, )! J phenylphos 2
Thirty parts of Eight were distributed and used as phenol for impregnation.
以下、実施例１と同様な方法で鋼張積層板を得た。銅張
積層板の特性を別表に示す。Thereafter, a steel clad laminate was obtained in the same manner as in Example 1. The characteristics of copper-clad laminates are shown in the attached table.
比較例１゜
実施例１で示したフェノール樹脂１００部にテトラブロ
モビスフェノールＡ１４部、トリフェニルホスフェイト
３０部を配付して含浸用フェノを得、以下実施例１と同
様な方法で鋼張積層板金得た。鋼張積層板の特性を別表
に示す。Comparative Example 1゜14 parts of tetrabromobisphenol A and 30 parts of triphenyl phosphate were distributed to 100 parts of the phenolic resin shown in Example 1 to obtain a phenol for impregnation, and then a steel-clad laminate sheet metal was prepared in the same manner as in Example 1. Obtained. The properties of steel clad laminates are shown in the attached table.
比較例２゜
実施例２で示した桐油変性フェノ−／Ｌ−樹脂１００部
にテトラブロモビスフェノールＡ１４部、トリフェニル
ホス７エイト３０部を配付して含浸用ワニスを得、以下
実施例１と同様な方法で鋼張積層板を得た。銅張積層板
の特性を別表に示す。Comparative Example 2゜ 14 parts of tetrabromobisphenol A and 30 parts of triphenyl phosphatate were added to 100 parts of the tung oil-modified pheno-/L-resin shown in Example 2 to obtain an impregnating varnish, and the same as in Example 1 was obtained. Steel clad laminates were obtained using this method. The characteristics of copper-clad laminates are shown in the attached table.
比較例五
桐油とフェノールを酸触媒下で反応させ、次に８０％パ
ラホルムアルデヒドとアルカリ触媒下でレゾール化した
桐油ｆ性ｆｉＡ ａ５％の桐油変性フェノール樹脂１０
０部にテトラブロモビスフェノールＡＩ４部、トリフェ
ニルホスフェイト３０部を配合して含浸用フェノとした
。以下実施例と同様な方法で銅張槓層取を得た。銅張積
層板の特注を別表に示す。Comparative Example Tung oil modified phenolic resin with 5% a tung oil f-fiA a 5% a tung oil modified phenolic resin 10 in which tung oil and phenol were reacted under an acid catalyst, and then resolized with 80% paraformaldehyde and an alkali catalyst.
0 parts, 4 parts of tetrabromobisphenol AI and 30 parts of triphenyl phosphate were blended to prepare a phenol for impregnation. Thereafter, a copper clad layer was obtained in the same manner as in the example. Special orders for copper-clad laminates are shown in the attached table.
（発明の効果）
本発明に於ては、１分子に１個以上の二重結合を有する
臭素含有不飽和ポリエステル樹脂を難燃性可塑剤として
熱硬化性樹脂に用いることにより、難燃性、打抜加工性
、耐熱法、耐溶剤性に優ｎる積膚板を製造することがで
きる。(Effects of the Invention) In the present invention, flame retardant, It is possible to produce a laminated board with excellent punching workability, heat resistance, and solvent resistance.
Claims (1)
飽和ポリエステル樹脂を難燃性可塑剤として配合した熱
硬化性樹脂ワニスを所定量含浸付着させた基材を成形す
ることを特徴とする積層板の製造法。 ２、熱硬化性樹脂が乾性油変性フェノール系レゾール樹
脂である特許請求範囲第１項記載の積層板の製造法。[Claims] 1. A base material impregnated with a predetermined amount of a thermosetting resin varnish containing a bromine-containing unsaturated polyester resin having one or more double bonds in each molecule as a flame-retardant plasticizer. A method for manufacturing a laminate, characterized by forming. 2. The method for manufacturing a laminate according to claim 1, wherein the thermosetting resin is a drying oil-modified phenolic resol resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61227574A JPH0764937B2 (en) | 1986-09-26 | 1986-09-26 | Laminated board manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61227574A JPH0764937B2 (en) | 1986-09-26 | 1986-09-26 | Laminated board manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6383139A true JPS6383139A (en) | 1988-04-13 |
| JPH0764937B2 JPH0764937B2 (en) | 1995-07-12 |
Family
ID=16863046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61227574A Expired - Lifetime JPH0764937B2 (en) | 1986-09-26 | 1986-09-26 | Laminated board manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0764937B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02228356A (en) * | 1989-03-01 | 1990-09-11 | Daihachi Chem Ind Co Ltd | Flame-retardant resin composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS577187A (en) * | 1980-06-16 | 1982-01-14 | Kanegafuchi Chemical Ind | Flame resistant electric laminated board |
-
1986
- 1986-09-26 JP JP61227574A patent/JPH0764937B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS577187A (en) * | 1980-06-16 | 1982-01-14 | Kanegafuchi Chemical Ind | Flame resistant electric laminated board |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02228356A (en) * | 1989-03-01 | 1990-09-11 | Daihachi Chem Ind Co Ltd | Flame-retardant resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0764937B2 (en) | 1995-07-12 |
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