JPS63142012A - Unsaturated polyester resin composition - Google Patents
Unsaturated polyester resin compositionInfo
- Publication number
- JPS63142012A JPS63142012A JP28768386A JP28768386A JPS63142012A JP S63142012 A JPS63142012 A JP S63142012A JP 28768386 A JP28768386 A JP 28768386A JP 28768386 A JP28768386 A JP 28768386A JP S63142012 A JPS63142012 A JP S63142012A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- unsaturated
- resin
- weight
- unsaturated polyester
- 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
- 239000000203 mixture Substances 0.000 title abstract description 12
- 229920006337 unsaturated polyester resin Polymers 0.000 title description 8
- 238000001035 drying Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- -1 allyl ether compound Chemical class 0.000 claims abstract description 17
- 229920006305 unsaturated polyester Polymers 0.000 claims abstract description 15
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 13
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 9
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 6
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 abstract description 32
- 239000011347 resin Substances 0.000 abstract description 32
- 238000000034 method Methods 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 abstract description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 abstract description 2
- 239000011976 maleic acid Substances 0.000 abstract description 2
- LZDXRPVSAKWYDH-UHFFFAOYSA-N 2-ethyl-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)COCC=C LZDXRPVSAKWYDH-UHFFFAOYSA-N 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 239000001993 wax Substances 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002087 whitening effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 238000007605 air drying Methods 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical group CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 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
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- QYXHDJJYVDLECA-UHFFFAOYSA-N 2,5-diphenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=C(C=2C=CC=CC=2)C(=O)C=C1C1=CC=CC=C1 QYXHDJJYVDLECA-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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical group CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical group CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical group CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OAFDCGIFZLLFBG-UHFFFAOYSA-N butan-2-yl 2-methylprop-2-enoate;2-methylprop-2-enoic acid Chemical group CC(=C)C(O)=O.CCC(C)OC(=O)C(C)=C OAFDCGIFZLLFBG-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical group CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical group CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 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
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229940094537 polyester-10 Drugs 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明の不飽和、ｔ？ ＩＪエステル樹脂組成物は、ガ
ラス繊維、カーボン繊維、？リイミド繊維などと組合せ
て複合材料、ＦＲＰとし波平板、・ぐスタブ、船舶、車
輌などに用いられる、また骨材と組合せたレジンコンク
リート、レノンモルタルとしてブロックマンホール、フ
ラワーｅツクス、洗面台、テーブル、カウンター類、さ
らに木材やケイカル板の表面仕上げ用塗料、化粧板、釦
、注型品などに有用である。[Detailed Description of the Invention] [Industrial Application Field] The unsaturated t? IJ ester resin composition can be used for glass fiber, carbon fiber, ? It is used in composite materials such as FRP, corrugated flat plates, gas stubs, ships, vehicles, etc. in combination with reimide fibers, etc. It is also used in resin concrete in combination with aggregate, block manholes, flower e-ts, wash basins, tables, etc. as Rennon mortar. It is useful for counters, as well as for surface finishing paints on wood and calcination boards, decorative boards, buttons, cast products, etc.
一般に、不飽和ポリエステル樹脂は、多価アルコールと
不飽和多塩基酸（無水物）とを必要に応じて飽和多塩基
Ｉｆｌ（無水物〕、動植物油、エポキシ樹脂、イソシア
ナート類、少量（５チ以下）のアリルエーテル化合物の
存在下に反応させて得られる不飽和ポリエステルを重合
性モノマーに溶解して製造されるが、その硬化時空気中
の酸素によって樹脂表面の硬化が阻害され、そのためい
つまでも表面が乾燥せず、ごみやほこりが付着したり、
また樹脂本来の性能が発揮されないため、耐水性、耐溶
剤性に劣るという欠点があった。In general, unsaturated polyester resins are made by combining polyhydric alcohol and unsaturated polybasic acid (anhydride) with saturated polybasic Ifl (anhydride), animal and vegetable oils, epoxy resins, isocyanates, and a small amount (5% It is produced by dissolving an unsaturated polyester obtained by reacting it in the presence of an allyl ether compound (below) in a polymerizable monomer, but during curing, the curing of the resin surface is inhibited by oxygen in the air, so the surface remains does not dry and dirt and dust adhere to it,
Furthermore, since the original performance of the resin is not exhibited, it has the disadvantage of being inferior in water resistance and solvent resistance.
これらの欠点を改良するため今日まで二つの方法が採ら
れてきた。その一つの方法は、樹脂中に・ぐラフインワ
ックス類を溶解添加しておき、硬化時に・ぞラフインワ
ックス類を樹脂表面に析出させて空気と樹脂との接触を
遮断して硬化させる方法である。しかし、この方法では
樹脂の組成、使用時の環境温度、貯蔵時の安定性（凝集
析出防止〕などの点から、・ぞラフインワックスの種類
、使用量などが制限される難点がある。例えば、直射日
光の当る所や加熱炉（Ａ０℃以上）などの室温以上の温
度で使用する場合は、硬化時に樹脂表面にワックスを均
一に浮かせることが困難であり、また低温貯蔵時のノＥ
ラフインワックスの分離を防止することも困難である。To date, two approaches have been taken to remedy these shortcomings. One method is to dissolve and add rough-in waxes to the resin, and when it hardens, the rough-in waxes precipitate on the resin surface to cut off contact between air and the resin. It is. However, this method has the disadvantage that the type and amount of rough-in wax used are limited due to the composition of the resin, the environmental temperature during use, stability during storage (prevention of agglomeration and precipitation), etc. For example: When used at temperatures above room temperature, such as in places exposed to direct sunlight or in heating furnaces (A0°C or higher), it is difficult to float the wax uniformly on the resin surface during curing, and the E
It is also difficult to prevent separation of rough-in wax.
他の方法は、アリルエーテル化合物や乾性油を含む空乾
性樹脂を単独で使用する方法と一般の不飽和ポリエステ
ルに添加して空乾性を向上させる方法である。しかし、
この方法では多量添加では経済性が悪るし少量添加では
部分的に硬化不良を起し表面乾燥性が不充分になる欠点
があり、使用量に制限がある。Other methods include using an air-drying resin containing an allyl ether compound or drying oil alone, and adding it to general unsaturated polyester to improve air-drying properties. but,
This method has the disadvantage that if a large amount is added, it is not economical, and if a small amount is added, curing failure occurs partially, resulting in insufficient surface drying properties, so there is a limit to the amount used.
以上述べた如く、従来の方法では樹脂表面の乾燥性を良
くするためには、その使用範囲が限定される欠点があっ
たが、本発明はこれらの欠点を排除して、使用条件の制
限を無くシ念広い温度範囲で良好な表面乾燥を示し、且
つ高温での使用も可能とし、成形サイクルの向上した不
飽和ポリエステル樹脂組成物を提供するものである。As mentioned above, conventional methods have the drawback of limiting the scope of use in order to improve the drying properties of the resin surface, but the present invention eliminates these drawbacks and limits the usage conditions. The object of the present invention is to provide an unsaturated polyester resin composition that exhibits good surface drying over a wide temperature range, can be used at high temperatures, and has an improved molding cycle.
本発明の不飽和ポリエステル樹脂組成物は、（５）第１
段反応として不飽和多塩酸又はその無水物（以下不飽和
多塩酸類という）を含む有機多塩基酸又はその無水物（
以下有機多塩基酸類というつと多価アルコールとを、ジ
シクロペンタジェン又はその誘導体（以下ジシクロペン
タジェン類という）５〜４０重量係重量計仕込ｉＫ対し
）の存在下に反応させた後、第２段反応として第１ｇ反
応で生成したジシクロペンタジェン変性不飽和ポリエス
テルの１００重量部にアリルエーテル化合物又は乾性油
の０．５〜５重量部を反応させて得られる不飽和ポリエ
ステル、
（Ｂ） 重合性単量体及び
（Ｃ） ワックス類０．０１〜０．５重量部（（Ａ）
＋ （Ｂ）の１００重量部に対し）
から成ることを特徴とし、これによって前記問題点を解
決しｆｃ。The unsaturated polyester resin composition of the present invention comprises (5) the first
As a step reaction, organic polybasic acids or their anhydrides (hereinafter referred to as unsaturated polyhydrochloric acids) containing unsaturated polyhydrochloric acids or their anhydrides (hereinafter referred to as unsaturated polyhydrochloric acids)
After reacting organic polybasic acids with a polyhydric alcohol in the presence of dicyclopentadiene or a derivative thereof (hereinafter referred to as dicyclopentadiene) (based on a weight ratio of 5 to 40 iK), An unsaturated polyester obtained by reacting 0.5 to 5 parts by weight of an allyl ether compound or drying oil with 100 parts by weight of the dicyclopentadiene-modified unsaturated polyester produced in the first g reaction as a two-stage reaction, (B) Polymerizable monomer and (C) waxes 0.01 to 0.5 parts by weight ((A)
+ (based on 100 parts by weight of (B))), thereby solving the above problems and fc.
本発明の不飽和ポリエステル樹脂組成物は、前記した如
く構成することによって、樹脂の表面乾燥性及び耐水性
が広い範囲で確保されるのであるが、その特徴の第一は
特定の方法で製造された本発明の不飽和、ｔ？ ＩＪエ
ステルの使用にある。By having the unsaturated polyester resin composition of the present invention as described above, the surface drying properties and water resistance of the resin can be ensured over a wide range, but the first characteristic is that it is produced by a specific method. The unsaturation of the present invention, t? The reason lies in the use of IJ ester.
本発明の不飽和ポリエステルは、第１段反応として５〜
４０重量係重量計な少量のジシクロペンタノエン類で変
性した不飽和ポリエステルを合成した後、第２段反応で
０．５〜５重量部の非常に少量の了りルエーテル化合物
又は乾性油を反応させて製造されるが、かかる特定の反
応方法によって始めて高温時（Ａ０℃以上）での表面乾
燥性と耐水性が発揮される。低温時（１５℃以下）では
、その乾燥性は充分に発揮されないが、それは少量のワ
ックス類を配合し、それらの相互作用で表面乾燥性を補
足させることによって、広い温度範囲で表面乾燥性と耐
水性が確保できるものとなった。The unsaturated polyester of the present invention has 5-
After synthesizing an unsaturated polyester modified with a small amount of dicyclopentanoene equivalent to 40% by weight, a very small amount of 0.5 to 5 parts by weight of an alcoholic ether compound or drying oil is added in the second stage reaction. Although it is manufactured by reacting, surface drying properties and water resistance at high temperatures (A0° C. or higher) are exhibited only by such a specific reaction method. At low temperatures (below 15°C), its drying properties are not fully demonstrated, but by incorporating a small amount of waxes and supplementing the surface drying properties through their interaction, it is possible to achieve surface drying properties over a wide temperature range. Water resistance can now be ensured.
以下、本発明の不飽和ポリエステル樹脂組成物について
詳述する。Hereinafter, the unsaturated polyester resin composition of the present invention will be explained in detail.
本発明方法で使用される有機多塩基酸類としては、一般
に不飽和アルキッドの製造に用いられているマレイン酸
、フマル酸、イタコン酸、シトラ酸等の不飽和多塩基酸
の他無水マレイン酸らの不飽和多塩基酸の無水物を必須
成分として含み、フタル酸、テレフタル酸、イソフタル
酸等の飽和酸を任意成分として含むものである。勿論、
有機多塩基酸は単独又は併用して使用される。The organic polybasic acids used in the method of the present invention include unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid, and citric acid, which are generally used in the production of unsaturated alkyds, as well as maleic anhydride. It contains an anhydride of an unsaturated polybasic acid as an essential component, and contains saturated acids such as phthalic acid, terephthalic acid, and isophthalic acid as an optional component. Of course,
Organic polybasic acids may be used alone or in combination.
また、多価アルコールとしては、エチレングリコール、
フロピレンゲリコール、ジエチレングリコール、トリエ
チレンダリコール、ジエチレングリコール、１，３−ブ
タンジオール、１，６−ヘキサンジオール、■、６−シ
クロヘキサンジオール、ネオインチルグリコール、グリ
セリン、トリメチロールプロノぐン、ペンタエリスリト
ール、ソルビトール、水添ビスフェノールＡ１ポリブタ
ジエングリコール、ビスフェノールＡのプロピレンオキ
サイド２付加体などが単独又は併用して使用される。In addition, polyhydric alcohols include ethylene glycol,
Flopylene gelicol, diethylene glycol, triethylene dalicol, diethylene glycol, 1,3-butanediol, 1,6-hexanediol, ■,6-cyclohexanediol, neointhyl glycol, glycerin, trimethylolpronogne, pentaerythritol , sorbitol, hydrogenated bisphenol A1 polybutadiene glycol, propylene oxide diadduct of bisphenol A, etc. are used alone or in combination.
さらに、ジシクロペンタジェン類としては、シンクロペ
ンタジェン、ヒドロキシ化・クシクロ被ンタジェン、メ
チルジシクロペンタジェンなどのシンクロインタジエン
類が第１段反応の反応成分として好適に使用される。Further, as the dicyclopentadiene, synchlopentadiene, hydroxylated/cyclopentadiene, methyldicyclopentadiene, and the like are preferably used as a reaction component in the first stage reaction.
第１段反応における反応成分の割合は、有機多塩基酸と
多価アルコールとを３０〜７０ ＫＯＨｍ９７９の酸価
の不飽和ポリエステルが生成するように調節するのが好
ましい。好適には多価アルコールは有機多塩基酸と等モ
ルで使用し、シンクロインタジエン類を全仕込量に対し
５〜４０重量係、好適には有機多塩基酸１モル当り０．
１〜０．４モル使用する方がよい。The ratio of the reaction components in the first stage reaction is preferably adjusted so that an unsaturated polyester having an acid value of 30 to 70 KOHm979 is produced. Preferably, the polyhydric alcohol is used in an equimolar amount with the organic polybasic acid, and the synchrointadiene is used in an amount of 5 to 40% by weight based on the total amount charged, preferably 0.00% by weight per mole of the organic polybasic acid.
It is better to use 1 to 0.4 mol.
本発明の第２段反応は、第１段反応で生成したノンクロ
ペンタジェン変性不飽和ポリエステルの１００重量部に
了りルエーテル化合物又は乾性油の０．５〜５重量部を
反応させることＫよって進められる。In the second stage reaction of the present invention, 100 parts by weight of the non-clopentadiene modified unsaturated polyester produced in the first stage reaction is reacted with 0.5 to 5 parts by weight of the ether compound or drying oil. You can proceed.
第２段反応において、必要ならば有機多塩基酸類が追加
される。その使用量は、第１段反応で生成した不飽和ポ
リエステル１００重量部に対し３〜２０、好適には５〜
１５重量部が用いられる。In the second stage reaction, organic polybasic acids are added if necessary. The amount used is 3 to 20, preferably 5 to 20 parts by weight, per 100 parts by weight of the unsaturated polyester produced in the first stage reaction.
15 parts by weight are used.
本発明で使用されるアリルエーテル化合物又は乾性油と
しては、トリメチロールプロ・ぐンのモノ又は・シアリ
ルエーテル、ペンタエリスリトールトリアリルエーテル
の他グリセリンのモノ又はシアリルエーテル、インタエ
リスリトールのモノ又は・シアリルエーテル、アリルグ
リコール、アリルグＩＪ シジルエーテル等のアリル化
合物、乾性油のエステル交換物、脂肪酸などが挙げられ
る。さらに、一般式 Ｒ
薯
ＣＦＩ２＝ ＣＨ−ＣＨ２−０＋ＣＨ２−０Ｈ−０＋７
１Ｈ〔但し、Ｒは水素ま友はアルキル基であり、・は１
〜１０の整数である〕で表わされるアリルアルコールの
アルキレンオキシド付加物も使用可能である。その代表
例としては、エチレンオキシドとプロピレンオキシドの
混合物をアリルアルコールに付加して得られるＲが水素
及びメチル基が混在している化合物が好適に使用される
。The allyl ether compounds or drying oils used in the present invention include mono- or sialyl ether of trimethylol pro-gun, pentaerythritol triallyl ether, mono- or sialyl ether of glycerin, and mono- or sialyl ether of interaerythritol. , allyl glycol, allyl compounds such as allylg IJ cidyl ether, transesterified products of drying oils, fatty acids, and the like. Furthermore, the general formula R 薯CFI2= CH-CH2-0+CH2-0H-0+7
1H [However, R is hydrogen and is an alkyl group, . is 1
It is also possible to use an alkylene oxide adduct of allyl alcohol represented by the following formula: an integer from 1 to 10. As a typical example, a compound obtained by adding a mixture of ethylene oxide and propylene oxide to allyl alcohol and in which R includes a mixture of hydrogen and methyl groups is preferably used.
さらに、第２段反応時または反応終了後に添加される重
合性単量体の中に重合禁止剤の存在が必要である。重合
禁止剤としては、ｐ−ｔ−ブチルカテコール、２，５−
ノーｔ−ブチルハイドロキノン、モノ−ｔ−ブチルハイ
ドロキノン、２，５−ノー１−アミルハイドロキノン等
のノ・イドクキノン類、ｐ−ベンゾキノン、ナフトキノ
ン、ｐ−キシロキノン、２，５−ジフェニル−ｐ−ベン
ゾキノン、２．５−ノアセトキシーｐ−ぺ／ゾキノ／等
のキノン類、シーｔ−ブチルパラクレゾール、ノーイド
ロキノンモノメチルエーテル等のフェノール類が挙げら
れる。これらの重合禁止剤は、不飽和ポリエステル１０
０１肴部に対し００２〜０．０５重量部の範囲で用いら
れる。Furthermore, it is necessary that a polymerization inhibitor be present in the polymerizable monomers added during the second stage reaction or after the completion of the reaction. As a polymerization inhibitor, pt-butylcatechol, 2,5-
No-idokuquinones such as no-t-butylhydroquinone, mono-t-butylhydroquinone, 2,5-no-1-amylhydroquinone, p-benzoquinone, naphthoquinone, p-xyquinone, 2,5-diphenyl-p-benzoquinone, 2 Examples include quinones such as .5-noacetoxyp-pe/zoquino/, phenols such as t-butyl para-cresol, and nohydroquinone monomethyl ether. These polymerization inhibitors are used for unsaturated polyester 10
It is used in a range of 0.02 to 0.05 parts by weight per 0.01 servings.
かくして得られた不飽和、ｊ？ ＩＪエステルは、通常
の重合性単量体、例えば、スチレン、ビニルトルエン、
クロロスチレン、アクリル酸メチル、アクリル酸エチル
、アクリル酸ｎ−ブチル、アクリル酸イノブチル、アク
リル酸３級ブチル、アクリル酸２−エチルヘキシル、メ
タクリル酸メチル、メタクリル酸エチル、メタクリル酸
ｎ−ブチル、メタクリル酸イソブチル、メタクリル酸３
級ブチル、メタクリル酸２−エチルヘキシル、メタクリ
ル酸ラウリル、メタクリル酸シクロヘキシル、メタクリ
ル酸ペンノル、メタクリル酸テトラヒドロフルフリル、
酢酸ビニル及びゾロピオン酸ビニル等に溶解し、不飽和
ポリエステル樹脂が得られる。The unsaturated thus obtained, j? IJ ester is made of common polymerizable monomers such as styrene, vinyltoluene,
Chlorostyrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, ibutyl acrylate, tertiary butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , methacrylic acid 3
Butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, pennol methacrylate, tetrahydrofurfuryl methacrylate,
It is dissolved in vinyl acetate, vinyl zoropionate, etc. to obtain an unsaturated polyester resin.
不飽和ポリエステルと重合性単量体との割合は、特に制
限はないが、重合性単量体の割合が５００重量部上にな
ると高温時における空乾性が劣る傾向があるので好まし
くない。There is no particular restriction on the ratio of the unsaturated polyester to the polymerizable monomer, but if the ratio of the polymerizable monomer exceeds 500 parts by weight, air drying properties at high temperatures tend to be poor, which is not preferred.
本発明で使用されるワックス類は不飽和テリエステル樹
脂１００重量部に対し０．０１〜０．５重量部の範囲で
配合されるが、・ぞラフイン系のワ、りスが最も好適て
使用される。The waxes used in the present invention are blended in an amount of 0.01 to 0.5 parts by weight based on 100 parts by weight of the unsaturated terester resin, but . Ru.
本発明の不飽和ポリエステル樹脂組成物は、必要に応じ
、充填剤、補強剤、離型剤、着色剤、硬化剤、促進剤、
安定剤等を併用して化粧板、塗料、注型品、ＦＲＰ、成
形材料などに広く使用することができる。The unsaturated polyester resin composition of the present invention may contain fillers, reinforcing agents, mold release agents, colorants, curing agents, accelerators,
It can be widely used in decorative laminates, paints, cast products, FRP, molding materials, etc. in combination with stabilizers and the like.
以下、更に本発明を具体的に説明するために実施例を記
載する。文中の部又は係は重量部及び重量部の意味であ
る。Examples will be described below to further specifically explain the present invention. In the text, ``part'' means ``part by weight'' and ``part by weight''.
実施例１
３ｇの４つロフラスコに、エチレングリコール２８２ｇ
、ジエチレングリコール２６０！ｉ、無水フタルｆｉ３
１１．！１７．無水マレイン（Ｒ４８０９，）シクロペ
ンタノエン３７０Ｉを投入し、窒素気流中１４０〜１６
０℃で、・ゾシクロベンタノエンを反応後、２１０℃ま
で上昇し、２１０℃を保ち、酸価３５〜４０ ＫＯＨＩ
ｌ’＋９／！ｉになったら１５０℃まで冷却し、上記エ
ステル１００部に対してトリメチロールプロ・ぐンソ了
りルエーテル４部を加え１８０℃まで２時間かけて上昇
し、１８０℃を保ちスチレン３０幅で５〜９ポイズ／２
５℃、酸価２５〜３０で終点とした。反応終了後ハイド
ロキノンを０．０１部添加したスチレンに溶解した不飽
和ポリエステルに融点５２℃の／やチフィ１０．ｌＥｋ
添加した樹脂をＡとした。Example 1 282 g of ethylene glycol in a 3 g four-bottle flask
, diethylene glycol 260! i, anhydrophthalic fi3
11. ! 17. Anhydrous maleic (R4809,) cyclopentanoene 370I was introduced, and 140 to 16
After reacting with zocyclobentanoene at 0°C, the temperature rises to 210°C, the temperature is maintained at 210°C, and the acid value is 35-40.
l'+9/! When the temperature reaches 1, cool to 150°C, add 4 parts of trimethylol pro-gunso ether to 100 parts of the above ester, raise to 180°C over 2 hours, maintain 180°C and heat with styrene 30 width. 9 poise/2
The end point was 5°C and an acid value of 25 to 30. After completion of the reaction, 0.01 part of hydroquinone was added to the unsaturated polyester dissolved in styrene and the melting point was 52°C. lEk
The added resin was designated as A.
実施例２
３１の４つロフラスコに、エチレングリコール２８２ｇ
、ジエチレングリコール２６０＆、無水フタル酸２０７
．７１無水マレイン酸５４！Ｊ９ 、ジシクロペンタジ
エン３７０ｇを入れ窒素気流中で１１０Ｃまで上昇し、
発熱によって１４０１１まで上昇し、１．１０〜１６０
℃でノ７クロペンタゾエンを反応後２１０’Ｃまで上昇
し、２１０℃で保ち、酸価５０〜５５ ＫＯＨｍ９／ｇ
になりたら１５０℃まで冷却し、上記エステル１００部
に対してトリメチロールグロノ９ノジアリルエーテルを
２．５部幅ｉ、１５０℃〜１８０℃を２時間で上昇し、
１８０℃で保ち、−スチレン３０チで６〜１０ポイズ／
２５℃酸価３０ ＫＯＨｍ９／ｆｌ以下で終点とした。Example 2 282 g of ethylene glycol was added to a 31 four-bottle flask.
, diethylene glycol 260 & phthalic anhydride 207
．． 71 Maleic anhydride 54! J9, 370g of dicyclopentadiene was added and the temperature rose to 110C in a nitrogen stream.
Increased to 14011 due to fever, 1.10 to 160
After reacting with clopentazoene at ℃, the temperature was raised to 210℃, kept at 210℃, and the acid value was 50 to 55 KOHm9/g.
, cool to 150°C, add 2.5 parts of trimethylolgulono-9o diallyl ether to 100 parts of the above ester, and heat from 150°C to 180°C over 2 hours.
Maintain at 180℃, -6 to 10 poise with 30 inches of styrene/
The end point was defined as an acid value of 30 KOHm9/fl or less at 25°C.
ノ・イドロン１０．０１部を添加したスチレンに溶解し
たプリエステル樹脂に、ｍｐ、５２℃のノやラフインｉ
０．１部加温溶解した樹脂をＢとした。To the preester resin dissolved in styrene to which 10.01 parts of No-Idron was added, Noya rough-in I was added at mp, 52°C.
The resin obtained by heating and dissolving 0.1 part was designated as B.
比較例１
３１の４つロフラスコにプロげレンゲリコール８１４
ｇ、無水フタル酸７４１ｆ１．無水マレイン酸４４１ｇ
を入れ、窒素気流中で１１０℃まで上昇し、発熱で１６
５℃まで上昇し、２１０℃まで３時間で上昇し、スチレ
ン３５チで６〜９７ｔ？イズ／２５℃、酸価３５〜４０
ＫＯＨｍ９／！ｌを終点とした。Comparative Example 1 Progelengericol 814 in 31 4 flasks
g, phthalic anhydride 741f1. Maleic anhydride 441g
was heated to 110°C in a nitrogen stream, and the temperature rose to 16°C due to heat generation.
It rose to 5℃, rose to 210℃ in 3 hours, and 6 to 97 tons with 35 inches of styrene. Iz/25℃, acid value 35-40
KOHm9/! The end point was 1.
反応終了後・・イドロキノンを０．０１部添加したスチ
レンに溶解したポリエステル樹脂にｍｐ、 ５２℃の・
ぞラフインを０１部加温溶解した樹脂をＣとした。After completion of the reaction...polyester resin dissolved in styrene to which 0.01 part of hydroquinone was added was heated to 52°C.
A resin obtained by heating and dissolving 1 part of Zorafuin was designated as C.
比較例２
３ｇの４つロフラスコにエチレングリコール３７２．６
ｇ、ジエチレングリコール４２４．５Ｆ。Comparative Example 2 Ethylene glycol 372.6 in a 3g four-bottle flask
g, diethylene glycol 424.5F.
無水マレイン酸９８１．り、トリメチロールゾＣＩ／に
ンノアリルエーテル４２８ｇを入れ、窒素気流中１５０
〜１９０℃で、酸価２５以下で反応を終了し、ハイドロ
キノン０，０２部を添加した。スチレン３０係（対エス
テル１００部した樹脂をＤとした。Maleic anhydride981. 428 g of monoallyl ether was added to trimethylolzo CI/, and the mixture was heated to 150 g in a nitrogen stream.
The reaction was completed at ~190°C with an acid value of 25 or less, and 0.02 parts of hydroquinone was added. A resin containing 30 parts of styrene (100 parts of ester) was designated as D.
比較例３
樹脂Ｃ１００部に樹脂ＤＩＯ部添加した樹脂をＥとし、
樹脂０１００部に樹脂Ｄ２０部添加した樹脂をＦとした
。Comparative Example 3 A resin in which part of resin DIO was added to 100 parts of resin C was designated as E.
A resin obtained by adding 20 parts of resin D to 100 parts of resin was designated as F.
実施例１，２及び比較例１ ｙ ２ ＋ ３で得られた
Ａ、Ｂ、Ｃ，Ｄ、Ｅ及びＦの樹脂それぞれ１００部に、
ナフテン酸コバルト０．５部、メチルエチルケトン・Ｐ
−オキサイド１部を添加した樹脂を用いて、”４５０の
チョツプドストランドマット３枚を室温で積層し種々の
温度で１夜放置後、水に２０時間浸漬し、表面状態を観
察した。To 100 parts each of the resins A, B, C, D, E and F obtained in Examples 1 and 2 and Comparative Example 1 y 2 + 3,
0.5 parts of cobalt naphthenate, methyl ethyl ketone/P
- Using a resin to which 1 part of oxide was added, three pieces of chopped strand mats of "450" were laminated at room temperature, left overnight at various temperatures, then immersed in water for 20 hours, and the surface condition was observed.
表面の硬化状態が良好なものは変化なく、硬化状態の悪
いものは加水分解されて白く変色していた（通常白化現
象というつ。それらの結果を第１表に示す。Those with a good hardened surface showed no change, while those with a poorly hardened surface were hydrolyzed and turned white (usually referred to as a whitening phenomenon).The results are shown in Table 1.
第１表
○ 変化なし
Δ やや白化
× 白 化
×× 強い白化
第１表から明らかな如く、本発明の樹脂組成物である樹
脂Ａ及びＢは広い温度範囲で良好な乾燥性を示した。こ
れに対し、比較例の樹１１旨Ｃは室温以上では乾燥不良
であり、樹脂りは低温時で乾燥不良であり、樹脂Ｅは室
温以上で乾燥不良であり、（！ｌｉ、ｌ脂Ｆは室温以上
で乾燥性がやや不良であった。Table 1 ○ No change Δ Slight whitening × Whitening XX Strong whitening As is clear from Table 1, Resins A and B, which are the resin compositions of the present invention, exhibited good drying properties over a wide temperature range. On the other hand, Comparative Example Tree 11C has poor drying at room temperature or above, resin resin has poor drying at low temperatures, resin E has poor drying at room temperature or above, and (!li, l resin F has poor drying at room temperature or above. Drying performance was somewhat poor at temperatures above room temperature.
本発明の不飽和、ｔ？ ＩＪエステル樹脂組成を吻は、
二段エステル化反応の第１段階で・ノシクロにンタノエ
ン類を第２段反応でアリルエーテル化合物又は乾性油を
反応させた不飽和４リエステルを用いることにより、広
範囲の温度範囲で表面乾燥性にすぐれ、しかも耐水性も
良く、複合材料、ＦＲＰ 、塗料、化粧板、注型品など
の原材料・に有、甲である。The unsaturation of the present invention, t? The IJ ester resin composition is
In the first step of the two-step esterification reaction, by using an unsaturated 4-rester obtained by reacting ntanoene with nocyclo and an allyl ether compound or drying oil in the second step, excellent surface drying properties can be achieved over a wide temperature range. Moreover, it has good water resistance and is useful as a raw material for composite materials, FRP, paints, decorative laminates, cast products, etc.
Claims (1)
含む有機多塩基酸又はその無水物と多価アルコールとを
、ジシクロペンタジエン又はその誘導体５〜４０重量％
（合計仕込量に対し）の存在下に反応させた後、第２段
反応として第１段反応で生成したジシクロペンタジエン
変性不飽和ポリエステルの１００重量部にアリルエーテ
ル化合物又は乾性油の０．５〜５重量部を反応させて得
られる不飽和ポリエステル、 （Ｂ）重合性単量体及び （Ｃ）ワックス類０．０１〜０．５重量部（（Ａ）＋（
Ｂ）の１００重量部に対し） から成ることを特徴とする不飽和ポリエステル樹脂組成
物。Scope of Claims: (A) In the first stage reaction, an organic polybasic acid containing an unsaturated polyhydrochloric acid or its anhydride, or its anhydride, and a polyhydric alcohol are reacted in an amount of 5 to 40% by weight of dicyclopentadiene or its derivative.
After reacting in the presence of (based on the total amount charged), as a second stage reaction, 0.5 parts of an allyl ether compound or drying oil is added to 100 parts by weight of the dicyclopentadiene-modified unsaturated polyester produced in the first stage reaction. Unsaturated polyester obtained by reacting ~5 parts by weight, (B) polymerizable monomer and (C) wax 0.01 to 0.5 parts by weight ((A) + (
B) based on 100 parts by weight of B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28768386A JPS63142012A (en) | 1986-12-04 | 1986-12-04 | Unsaturated polyester resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28768386A JPS63142012A (en) | 1986-12-04 | 1986-12-04 | Unsaturated polyester resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63142012A true JPS63142012A (en) | 1988-06-14 |
| JPH0466247B2 JPH0466247B2 (en) | 1992-10-22 |
Family
ID=17720372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28768386A Granted JPS63142012A (en) | 1986-12-04 | 1986-12-04 | Unsaturated polyester resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63142012A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002022752A1 (en) * | 2000-09-14 | 2002-03-21 | Peter Clifford Hodgson | Synthetic composition based on thermosetting resins |
| WO2017112680A1 (en) | 2015-12-21 | 2017-06-29 | Myriant Corporation | Dicyclopentadiene modified ester oligomers useful in coating applications |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6039283A (en) * | 1983-08-12 | 1985-03-01 | Goto Minoru | Counter |
-
1986
- 1986-12-04 JP JP28768386A patent/JPS63142012A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6039283A (en) * | 1983-08-12 | 1985-03-01 | Goto Minoru | Counter |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002022752A1 (en) * | 2000-09-14 | 2002-03-21 | Peter Clifford Hodgson | Synthetic composition based on thermosetting resins |
| WO2017112680A1 (en) | 2015-12-21 | 2017-06-29 | Myriant Corporation | Dicyclopentadiene modified ester oligomers useful in coating applications |
| EP3383959A4 (en) * | 2015-12-21 | 2019-01-16 | PTTGC Innovation America Corporation | Dicyclopentadiene modified ester oligomers useful in coating applications |
| AU2016377580B2 (en) * | 2015-12-21 | 2021-05-13 | Ptt Global Chemical Public Company Limited | Dicyclopentadiene modified ester oligomers useful in coating applications |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0466247B2 (en) | 1992-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2002527589A (en) | Unsaturated polyester resin | |
| JP2003503515A (en) | Vinyl ethers in unsaturated polyester resins, vinyl esters and vinyl ester urethanes for structural applications | |
| JPS63142012A (en) | Unsaturated polyester resin composition | |
| US3957906A (en) | Chemically resistant polyester resins compositions | |
| JPS6264859A (en) | Unsaturated polyester composition | |
| JPS6147722A (en) | Urethane (meth)acrylate prepolymer | |
| JPH03168244A (en) | Unsaturated polyester resin composition and putty coating compound | |
| JPS6330522A (en) | Production of unsaturated polyester resin of excellent air dryability | |
| JP3467884B2 (en) | Oligomer excellent in curability, method for producing the oligomer, curable resin composition using the oligomer, and cured product obtained by curing the composition | |
| JPH09302046A (en) | Unsaturated polyester resin composition, production of cured product, and molding material | |
| JPS5934725B2 (en) | Unsaturated polyester resin composition | |
| KR830001395B1 (en) | Unsaturated Polyester Resin Manufacturing Method | |
| JP2006056975A (en) | Unsaturated polyester resin for gelcoat of high water resistance and weatherability, method for producing the unsaturated polyester resin and use thereof | |
| JPS6239612A (en) | Thermosetting resin composition | |
| JP2002226525A (en) | Resin composition and method for thermosetting using the same | |
| JPH06157731A (en) | Polyester acrylate resin composition | |
| JPS62115059A (en) | Resin composition for molding material | |
| AT247609B (en) | Process for the production of moldings and coatings with a tack-free surface | |
| JPH08134339A (en) | Unsaturated polyester resin composition, production of cured product and molding material | |
| JPH06157732A (en) | Production of polyester acrylate | |
| JPH0128764B2 (en) | ||
| JPH05320275A (en) | Unsaturated polyester resin composition, production of cured article, and molding material | |
| JP4710365B2 (en) | Curable resin composition, civil engineering building material and civil engineering building | |
| JPS6351451A (en) | Unsaturated polyester resin composition | |
| JP2006096911A (en) | Unsaturated polyester resin having toughness, method for producing the same and utilization thereof |