MXPA99007085A - Composition of polialilensulf resin - Google Patents
Composition of polialilensulf resinInfo
- Publication number
- MXPA99007085A MXPA99007085A MXPA/A/1999/007085A MX9907085A MXPA99007085A MX PA99007085 A MXPA99007085 A MX PA99007085A MX 9907085 A MX9907085 A MX 9907085A MX PA99007085 A MXPA99007085 A MX PA99007085A
- Authority
- MX
- Mexico
- Prior art keywords
- resin
- acid
- resin composition
- epoxy
- composition according
- Prior art date
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 96
- 239000011347 resin Substances 0.000 title claims abstract description 96
- 239000000203 mixture Substances 0.000 title claims description 17
- 239000003822 epoxy resin Substances 0.000 claims abstract description 59
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 59
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 239000011342 resin composition Substances 0.000 claims abstract description 38
- 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 claims abstract description 21
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- UCKMPCXJQFINFW-UHFFFAOYSA-N sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 7
- UBJVUCKUDDKUJF-UHFFFAOYSA-N Diallyl sulfide Chemical compound C=CCSCC=C UBJVUCKUDDKUJF-UHFFFAOYSA-N 0.000 claims abstract 2
- 229940008075 allyl sulfide Drugs 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 78
- -1 allylene sulfide Chemical class 0.000 claims description 53
- 239000002253 acid Substances 0.000 claims description 49
- 229920001577 copolymer Polymers 0.000 claims description 39
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 38
- 125000003700 epoxy group Chemical group 0.000 claims description 33
- 150000008064 anhydrides Chemical class 0.000 claims description 15
- 239000004593 Epoxy Substances 0.000 claims description 14
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 claims description 14
- 150000001993 dienes Chemical class 0.000 claims description 10
- 239000004711 α-olefin Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- 125000005907 alkyl ester group Chemical group 0.000 claims description 6
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 claims description 5
- 150000007942 carboxylates Chemical class 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 230000002787 reinforcement Effects 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 abstract description 20
- 239000004033 plastic Substances 0.000 abstract description 3
- 229920003023 plastic Polymers 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 20
- 239000000047 product Substances 0.000 description 17
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 16
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 16
- 239000004734 Polyphenylene sulfide Substances 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 229920000069 poly(p-phenylene sulfide) Polymers 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 230000001808 coupling Effects 0.000 description 11
- 239000000835 fiber Substances 0.000 description 11
- 125000003396 thiol group Chemical group [H]S* 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000010168 coupling process Methods 0.000 description 10
- 238000005859 coupling reaction Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- VOZRXNHHFUQHIL-UHFFFAOYSA-N Glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 150000004756 silanes Chemical class 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-Dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 7
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N Maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 7
- 238000010306 acid treatment Methods 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive Effects 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N (E)-but-2-enedioate;hydron Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PGLTVOMIXTUURA-UHFFFAOYSA-N Iodoacetamide Chemical compound NC(=O)CI PGLTVOMIXTUURA-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 5
- 229920001400 block copolymer Polymers 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N 2-methyl-2-propenoic acid methyl ester Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 235000012970 cakes Nutrition 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 239000011152 fibreglass Substances 0.000 description 4
- 239000002657 fibrous material Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N fumaric acid Chemical compound OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000005968 oxazolinyl group Chemical group 0.000 description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 3
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N DMA Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- RINCXYDBBGOEEQ-UHFFFAOYSA-N Succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000004432 carbon atoms Chemical group C* 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical class C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- RBCYCMNKVQPXDR-UHFFFAOYSA-N phenoxysilane Chemical compound [SiH3]OC1=CC=CC=C1 RBCYCMNKVQPXDR-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 229940014800 succinic anhydride Drugs 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 150000003573 thiols Chemical group 0.000 description 3
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 2
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-Trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 2
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- PZZYQPZGQPZBDN-UHFFFAOYSA-N Aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N Antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L Barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N Behenic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N Bis(4-hydroxyphenyl)methane Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N Bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N Bisphenol S Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L Calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N Diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N Lauric acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N Montanic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N N#B Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N Oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N Palmitic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 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
- GRVFOGOEDUUMBP-UHFFFAOYSA-N Sodium sulfide Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N Stearic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N Sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052977 alkali metal sulfide Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N butyl 2-methylprop-2-enoate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000036425 denaturation Effects 0.000 description 2
- 238000004925 denaturation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 125000002971 oxazolyl group Chemical group 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000011528 polyamide (building material) Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 230000003252 repetitive Effects 0.000 description 2
- 102220259718 rs34120878 Human genes 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
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- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 238000005429 turbidity Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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Abstract
Polyallyl sulfide resin compositions are provided which have dramatically improved tackiness with respect to the cured epoxy resin, which maintains both the characteristics of the polyallylene sulphide resin such as thermal resistance and chemical resistance. Internally described polyallylene sulfide resin compositions are obtained comprising as essential components in the allylsulfide resin (A), epoxy resin of the bisphenol type (B) and an oxazoline group containing amorphous polymer (C). The as-adhered polyallylene resin compositions can be used as superior design plastics in broad application fields such as electronic devices and in other applications.
Description
COMPOSITION OF POLYALYLENSULPHIDE RESIN
BACKGROUND OF THE INVENTION Field of the Invention The present application relates to polyallylene sulphide resin compositions having dramatically improved tackiness with respect to a cured epoxy resin, which retains both the characteristic properties of polyallylene sulfide resins such as thermal resistance and chemical resistance; and is practically related to polyallylene sulphide resin compositions useful in a wide range of industrial fields, such as automobile ignition coil covers used to seal the ignition coils in the coil shell made of polyallylene sulfide resin with a epoxy resin composition; and a coil cover for the so-called ignition system without distributor (hereinafter abbreviated as "DLI"); and it is related, in addition to electrical and electronic components such as semiconductor devices of the type sealed with epoxy resin.
Previous Technique Recently, polyallylsulphide (here abbreviated later as "PAS") has attracted attention as an excellent engineering plastic that has superior thermal and chemical resistances. One of the fields of application of the PAS resin that uses these characteristics is the production of various electronic and electrical components to seal varied electronic or electrical components, in covers made of the PAS resin composition formed in advance by injection molding. That is, to develop a new technique to produce electronic and electrical components (especially ignition coils or DLI), in the semiconductor elements or coils are first mounted on a cover made of PAS resin, uncured epoxy resin is poured into the cover for sealing those elements or coils, and the epoxy resin is finally cured, by, for example, heat treatment to seal those semiconductor elements or coils. When PAS resin is used for such applications, it is necessary that the products of the PAS resin be provided with a long term adhesiveness superior to the epoxy resin at wide ranges of temperatures of use, in addition to the intrinsic characteristics such as the properties of long-term thermal and chemical resistance. Practically, it is required that the PAS resin products sealed by the epoxy resin do not detach from the epoxy rim, even when the PAS resin product sealed by the epoxy resin is repeatedly used in a temperature range of -40 ° C to 140 °. C. As a matter of interest, since the PAS resin is intrinsically superior in adhesiveness to the epoxy resin, and the adhesion is weak even if it is reinforced by glass fibers or the like, the PAS resin has been considered unsuitable for use for applications sealing with epoxy resins. To improve the adhesion of the PAS resin with the epoxy resin, Japanese Patent Application, First Publication No. Hei 9-3326, describes a technique for improving adhesion by the addition of α-olefin / carboxylic acid glycidyl ester copolymer a, ß-unsaturated and a wax-like amido carboxylic acid to the PAS resin to release stress or strain caused at the interface between the PAS resin and the epoxy resin at the time of heating and cooling. However, the PAS resin composition described in Japanese Patent Application, First Publication No. Hei 9-3326, does not exhibit satisfactory adhesiveness for the epoxy resin and the generation of cracks is observed in the heating and cooling cycles, which means that conventional PAS resins are not sufficiently satisfactory at the level of practical use.
BRIEF DESCRIPTION OF THE INVENTION Therefore, it is an object of the present invention to provide a PAS resin which has a dramatically improved adhesive strength with the epoxy resin during heating and cooling operations., which retains both its superior intrinsic thermal and chemical resistance, and which has improved fracture resistance in heating and cooling cycles by incorporating a resin to improve impact resistance. The inventors of the present invention have carried out a series of studies to solve the above problems, and have completed the present invention by discovering that the adhesiveness of the PAS resin can be drastically improved by incorporating an epoxy resin of the bisphenol type and a group of Oxazolin containing amorphous polymer, and that a fracture strength higher than the PAS resin can be provided by incorporating an epoxy resin of the bisphenol type, a copolymer containing an oxazoline group, and a resin that improves the impact resistance. That is, the present invention relates to a polyallylene sulphide resin composition, wherein the polyallylene sulphide composition contains essentially polyallylene sulfide resin (A), epoxy resins of the bisphenol type (B), and an amorphous polymer containing oxazoline group ( C). Although there is no particular limitation on the polyallylene sulfide resins (A), it is preferable that the polyallylene sulfide (A) has repeating structural units expressed by a general formula [-Ar-S-] (in the formula, -Ar- represents an aromatic group divalent including at least one six-membered carbon ring) as the major structural units, and it is more preferable that the polyallylene sulfide contains more than 70 mol% of such structural units shown in the general formula 1 from the point of view of thermal resistance and chemistry. Among the polyallylene sulfide compositions containing more than 70 milli of structural units expressed by the formula 1, the polyphenylene sulfide (here abbreviated later as "PPS") containing the repetitive structural units expressed by the general formula 2 - [- fS- ] is preferred, and a polymer containing more than 70 mol% of repetitive structural units expressed by general formula 2 from the viewpoint of high mechanical strength which is a characteristic property for a crystalline polymer and is also particularly preferred. from the point of view of strength and chemical resistance.
Examples of copolymer components having the structural unit in the polyallylesulphide resin (A) expressed by formula 1 include couplings such as meta coupling, ether coupling, sulfonic coupling, sulfidoketone coupling, bisphenyl coupling, coupling of substituted phenylsulfide, biphenyl coupling, substituted phenylsulfide coupling, trifunctional phenylsulfide and naphthyl coupling, which are illustrated below by means of chemical formulas 2 to 10. The content of the copolymer component is preferably less than 30 mol%, but, when it includes more than one trifunctional coupling, the content is preferably less than 5 mol%, more preferably less than 3 mol%.
(in the formula, R represents an alkyl group, a nitro group, a phenyl group, an alkoxy group)
It should be noted that the polyallylene sulfide resin (A) used in the present invention has superior reactivity with the components (B) or (C), and the resin (A) is capable of providing high adhesiveness with the epoxy resin. From the viewpoint of the above superior reactivity of the components (B) and (C) and the high adhesiveness of the cured epoxy resin, it is preferable that the polyallylene sulfide resin provide the following properties; ? HC1 is not greater than 10 μmol / g,? NaOH is within 5 to 30 5 μmol / g, and (? NaOH-? HCl) = 5 μmol / g. Here,? HC1,? NaOH, and (? NaOH -? HC1) are obtained by the following measurements. 10 g of polyallylene sulfide resin (A) are stirred after adding 10 ml of 1 mol / l of HCl, and the suspension '10 was filtered. The separated solid is repeatedly washed with water until no HCl is detected, and all the filtrate used for washing is collected and the HCl in the collected filtrate is titrated with NaOH, and the molar HCl Index is defined as? HC1. 15 Next, the polyallylene sulfide resin (A)
> After being washed with water, disperse again with distilled water and stir after adding 10 ml of 1 mol / l of NaOH. The solution is filtered after stirring, and the filtered solid is washed repeatedly with water until it is not
detects NaOH. All the filtrate used for washing is collected and the NaOH in the filtrate is titrated with HCl, and the molar ratio of NaOH is defined as? NaOH. The (? NaOH-? HCl) is a difference between? NaOH and? HC1.
It is preferred that the concentration of terminal thiol groups of the polyallylene sulfide resin (A) be within a range of 5 to 50 μmol / g to give the resin (A) a superior reactivity with the components (B) and (C) , good dispersion capacity, superior training capacity, and better fluency. That is, when the concentration is increased to more than 5 μmol / g, the dispersion capacity increases, and when the concentration decreases below 50 μmol / g, the fluidity
»? it becomes superior. The concentration of terminal thiol groups is obtained by the iodoacetamide method. The iodoacetamide method is carried out by the steps of acidifying the PAS resin with an acid such as acid
Hydrochloric acid to convert it to thiol groups and then to generate the iodine by reacting the iodoacetamide with all terminal thiol groups by heating; while the concentration of terminal thiol groups present in the PAS resin in the initial stage is
obtained by calculating the molar ratio of acids consumed for acidification and the molar Iodine Index is determined by ÜV spectrometry. In more detail, the practical procedures of measurement are the following.
mg are weighed to 1 g of sample of pulverized PAS resin, after processed the sample is introduced in a sealed test tube, 1 ml of acetone and 3 ml of pure water are added, and it is stirred after adding more Hydrogen chloride 5 diluted. After stirring, the filtrate obtained by the filtration is again titrated by the use of a NaOH solution to obtain the molar Index of the hydrogen chloride consumed for the terminal acidification. Later, after being separated by filtration, the dO polymer sample is washed with pure water for 30 minutes, 2.5 ml of an acetone solution consisting of 2.5 ml of acetone and 50 mmol of iodoacetamide are added, sealed with a stopper, it is heated at 100 ° C for 60 minutes, the water is cooled and the seal is opened, the liquid phase is separated, and it is measured
the absorbance at 450 nm (absorbance at 12) by means of the
| ultraviolet light absorption spectrometer. The concentration of all terminal thiol groups is calculated by using a calibration curve produced in advance for the thiol compounds model "C1-C6H4-SH" (en
It is preferable to select a sample amount such that the concentration of the thiol compound in the actone suspension falls within a range of 0.1 to 0.3 mmol). The molar index obtained by subtracting the molar index of hydrogen chloride consumed by acidification
Terminal of all terminal thiol groups is the concentration of the terminal thiol groups of the PAS resin. The average concentration of terminal thiol groups for the same sprayed sample is obtained by taking three measurements. Any molecular structures of the polyallylsulphide resin (A) can be used in the present invention provided that the molecules are substantially linear structures without having branches or bridging structures, or that the molecules have klO branches or bridging structures, the resin (A) having a linear molecular structure is preferable from the viewpoints of reactivity and compatibility. Although there is no particular limitation in the polymerization method of such polyallylene sulfide resin (A), they are
Preferred are certain polymerization methods, including a nucleophilic displacement method such as method © by a reaction of a halogen-substituted aromatic compound with an alkali sulfide. Some practical examples of the above F method include: 20 F-1: a method for polymerizing p-dichlorobenzene under the presence of sulfur and sodium carbonate; F-2: a method for reacting p-dichlorobenzene with sodium sulfide in a polar solvent;
F-3: a method for reacting p-dichlorobenzene with sodium acid sulfide and sodium hydroxide in a polar solvent; and F-4: a method for reacting p-5 dichlorobenzene with hydrogen sulfide and sodium hydroxide in a polar solvent. In addition, another method © consists of the self-condensation of the thiophenols such as p-chlorothiophenol under the copresence of alkaline catalysts
1) 10 such as potassium carbonate or sodium carbonate and a copper salt such as copper iodide. Examples of polar solvents used in method F include amide-type solvents such as N-methylpyrrolidone, dimethylacetamide; and sulfolane. 15 The other polymerization method is a reaction of? Electrophilic substitution constituting a method ® which is a condensation polymerization of aromatic compounds such as benzene with sulfur chloride under the presence of an acid catalyst catalyst.
Lewis for a Friedel-Crafts reaction. Among these polymerization methods, the preferred one is F-2, since this method makes it possible to produce a polyallylsulphide resin having a large molecular weight and also allows to obtain a high yield of the polymerization. Practically, the most preferable method is to react p-dichlorobenzene with sodium sulfide in amide-type solvent such as N-methylpyrrolidone or dimethylacetamide; and in sulfone-type solvents such as sulfolane. It is also preferable to add alkali metal salts of carboxylic acid and sulfonic acid, or alkali hydroxide to control the degree of polymerization. As described above, it is preferable that the polyallylene sulfide resin (A) has a substantially linear structure from the viewpoints of reactivity and compatibility. Although there is no particular limitation, examples of methods for producing the polyallylene sulphide resin having substantially linear structure include reacting alkali metal sulfide and organic alkali metal carboxylates such as aromatic dihalo compounds and lithium acetate in an amide type solvent such as N-methylpyrrolidone and dimethylacetamide; and a two-step polymerization method with addition of water to add a quantity of water and increase the polymerization temperature of the reaction system during the polymerization reaction of the aromatic compound dihalo with an alkali metal sulfide in an amide-type organic solvent.
Particularly, the polyallylene sulfide resin (A) having a substantially linear structure suitable for the present invention is preferably used after being subjected to an acid treatment and washing. Although there is no limitation for acids for the acid treatment if the acid does not decompose the polyallylsulphide resin (A), examples of the acids used for the acid treatment include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Among these, acetic acid and hydrochloric acid are preferably used. Acid treatment methods include immersing the polyallylsulphide resin (A) in an acid or acid solution. Agitation or heating may be added during the dive if necessary. The acid treatment is carried out sufficiently in acetic acid by immersing the PAS resin in the solution of acetic acid of pH 4 heated at temperatures in a range of 80 to 90 ° C for 30 minutes. The PAS resin after the acid treatment is washed with water or hot water several times to physically remove the acid or salt remaining. The water used for washing is preferably distilled water or deionized water. The polyallylsulphide resin (A) to be used for the acid treatment may be in the form of a powder or in the form of a suspension obtained immediately after the polymerization. The epoxy resin of the bisphenol type (B) is an essential component for drastically improving the adhesion of the PAS resin to the cured epoxy resin, and the epoxy resin of the bisphenol (B) type is also useful for drastically improving the dispersion of the component of resistance - to impact (D), when that component (D), which will be described in the later section, is also used. As an epoxy resin of the bisphenol (B) type, any type of epoxy resins of the bisphenol type can be used, without any limitation, including the epoxy resin of the bisphenol A type, epoxy resin of the bisphenol F type, epoxy resin of the type of bisphenol AF and epoxy resin of the bisphenol AD type; and in the present invention, that of the bisphenol A type is most preferable because it increases the adhesiveness to the cured epoxy resin to a greater extent. Examples of epoxy resins of the bisphenol A type include the bisphenol A glycidyl ether, and a compound in which the glycidyl ether is converted to a higher molecular weight by the use of bisphenol A. It is preferred that the bisphenol type resin ( B) has an epoxy equivalent within the range of 150 to 2100 g / eq. The range of 700 to 2100 g / eq is more preferable for the resin composition (B) to provide better formability and better compatibility. The amorphous polymer containing oxazolino groups
(C), used as one of the essential components in the present invention, is useful, as well as the component (B) described above, for drastically improving the cured epoxy resin and also useful for improving the dispersibility of the resin which improves the impact resistance
(D) in PAS resin. That is, in the present invention, the PAS resin exhibits an unusual superior adhesion capacity to the epoxy resin cured by the use of component (B) and component (C) together. An amorphous polymer containing oxazolyl group (C) is very effective for the fine dispersion of the resin that improves the resistance to
impact (D) of the PAS resin and to improve the thermal shock resistance of the product of the resin composition as a whole. Here, the oxazoline group containing the amorphous polymer (C) is the polymer that contains equal to or more than 80% in
The weight of the amorphous state is conditioned on the condition that it is cooled from the liquid state to a temperature higher than its vitreous transition temperature or its melting temperature, and that it measures in a temperature range not higher than 200 ° C. Practically, the examples of amorphous polymer that
contain oxazolyl groups (C) include a homopolymerization of polymerizable unsaturated monomer containing an oxazolinyl group and a copolymer of such a monomer and the other polymerizable unsaturated monomers. A preferable example of polymerizable unsaturated monomer containing oxazolinyl group is vinyl oxazoline. Examples of other polymerizable unsaturated monomers that are copolymerizable with the polymerizable unsaturated monomer containing an oxazolinyl group include aromatic vinyls such as styrene; vinyl cyanides or vinyl acetates such as acrylonitrile; unsaturated carboxylic acids or their derivatives such as (meth) acrylate,
(meth) acrylate, maleic acid anhydride; and diene components such as α-olefin, butadiene and isoprene. Among those examples, styrene and acrylonitrile are preferable from the point of view of compatibility. The copolymers of the polymerizable unsaturated monomer containing oxazolinyl group and the other polymerizable unsaturated monomers are preferably a binary or ternary copolymer selected from the above monomeric components, and practically a combination of vinyl oxazoline and styrene and / or acrylonitrile is preferable. In the present invention, the addition of the resin that improves the impact resistance (D) in addition to the components (A) to (C) drastically improves the strength of the products formed, the adhesiveness to the cured epoxy resin, and, as The property of fracture resistance by thermal shock cycles was described above. Although there is no limitation in the selection of the resin that improves the impact resistance (D), it is preferable to use polymers of the vinyl type (di) containing an acid or epoxy group and a rubbery polymer (d2) containing a group acid or epoxy to improve the property of resistance to fracture. , Although there is no particular limitation, preferred examples of polymers of the vinyl type (di) containing an acid or epoxy group include the a-polyolefin (dl-1) which contains an acid group, or epoxy or alkyl ester polymer of α, β-unsaturated carboxylic acid (dl-2) that
contains an acid or epoxy group. > Although there is no particular limitation, examples of α-polyolefin (dl-1) containing an acid or epoxy group include copolymers of α-olefin and α, β-unsaturated carboxylic acids or their anhydrides; copolymers of
a-olefin, and α, β-unsaturated carboxylic acids or their anhydrides, and β-unsaturated alkyl ester carboxylates; copolymers of α-olefins, α, β-unsaturated glycidyl ester carboxylates; and copolymers of α-olefins, α, β-unsaturated glycidyl ester carboxylates, and α, β-unsaturated alkyl ester carboxylates. Here, examples of α-olefin include ethylene, propylene, butene-1-pentene-1, hexene-1, heptene-1,3-methylbutene-1, 4-methylpentene-1, and combinations thereof, but the preferable example It is ethylene. Examples of α, β-unsaturated carboxylic acids or their anhydrides include acrylic acid, methacrylic acid, clitonic acid, maleic acid, fumaric acid, itaic acid, citrazoic acid, butandicarbonic acid and its anhydrides, and maleic anhydride and succinic anhydride they are the most preferred examples. Examples of α, β-unsaturated glycidyl ester carboxylates include glycidylacrylate, glycidylmethacrylate, glycidylethacrylate, and the preferred example is glycidyl methacrylate. Examples of α, β-unsaturated alkylester carboxylates include unsaturated carboxylic acids of 3 to 8 carbon atoms such as alkyl esters including acrylic acid, methacrylic acid and ethacrylic acid; and practical examples include methylacrylate, ethylacrylate, n-propylacrylate, isopropylacrylate, n-butyl acrylate, t-butyl acrylate, isobutylacrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate., isobutylmethacrylate and the preferred examples methylmethacrylate, ethylacrylate and n-butylacrylate. The α, β-unsaturated carboxylic acids or their anhydrides, although there is no particular limitation, a denaturation ratio of each monomer component for the α-olefin is not greater than 10% by weight, preferably in a range of 0.1 to 5% by weight for a unit tlO weight of copolymer, when the denatured portion is converted as the weight of the monomer into the copolymer. When ce, β-unsaturated alkyl ester carboxylate is further used, the preferable range changes from 5 to 35% by weight. The polymers of alkyl ester α, β-unsaturated carboxylate (dl-2) containing an acid or epoxy group have a structure in which the acid group or the epoxy group is introduced into the carboxylate polymer of alkyl ester a, β- unsaturated, and the practical example is a compound obtained by the copolymerization of α, β-unsaturated carboxylic acid or its anhydride, or α, β-unsaturated glycidyl ester carboxylate or its anhydride with α, β-unsaturated alkyl ester carboxylates.
Any examples of the α, β-unsaturated alkyl ester carboxylates described may be used.
. previously in the present invention, and practical examples are the carboxylic acid of 3 to 8 carbon atoms
including acrylates such as methylacrylate, ethylacrylate, n-propylacrylate, isopropylacrylate, n-butylacrylate, t-butylacrylate,? -butyryl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate fclO and isobutylmethacrylate; and can be used alone or in combination. Among those compounds, the most preferable examples include methyl methacrylate, ethylacrylate and n-butylacrylate. Examples of α, β-unsaturated carboxylic acids
or its anhydrides to be copolymerized with carboxylates of
"α, β-unsaturated alkylesters include acrylic acid, methacrylic acid, ethacrylic acid, critical acid, maleic acid, fumaric acid, itacoic acid, citrazoic acid, butenedicarboxylic acid and its anhydrides, and the examples
Preferable are maleic anhydride and succinic anhydride. Practical examples of α, β-unsaturated glycidyl ester carboxylates to copolymerize with α, β-unsaturated alkylester carboxylate include glycidylacrylate, glycidyl methacrylate and glycidylethacrylate; and the glycidyl methacrylate is preferably used. When the structural units in a copolymer
) are converted into a weight ratio of a monomer, the
The denaturing ratio of the α, β-unsaturated carboxylic acids and their anhydrides is within the range of 0.10 to 10% by weight, more preferably in a range of 0.05 to 5% by weight for a unit weight of the copolymer. The denaturation ratio of the α, β-unsaturated glycidyl ester carboxylates used for copolymerization with α, β-unsaturated alkyl ester carboxylates is preferably in the range of 0.1 to 15% by weight, more preferably in a range of 5 to 15% by weight. to 10% by weight per unit weight of the copolymer. 15 Here, a type polymer is described
"gum (d2) containing an acid or epoxy group." Although there is no particular limitation, the gum-like polymer (d2) containing an acid or epoxy group is preferably a hydrogenated copolymer containing an acid or epoxy group of
conjugated dienes and aromatic vinyl monomers. A practical example of a compound obtained by hydrogenated copolymer graft copolymerization of conjugated dienes and aromatic vinyl monomers with α, β-unsaturated carboxylic acids or their α, β-unsaturated glycidyl ester anhydrides or carboxylates. The hydrogenated copolymers of the conjugated dienes and the aromatic vinyl hydrocarbons are defined as a block copolymer or a random copolymer of conjugated dienes and aromatic vinyl hydrocarbons and at least 80% of the copolymer is reduced by hydrogenation. In the present invention, a block copolymer of conjugated dienes is preferably used
'10 and aromatic vinyl hydrocarbons. It should be noted that unsaturated bonds that are reduced by hydrogenation do not include double bonds of the aromatic nucleus. Examples of conjugated dienes include 1,3-butadiene, isoprene, 1,3-pentadiene, and among the dienes
conjugates, 1,3-butadiene and isoprene are preferable. > Examples of aromatic vinyl hydrocarbons include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, and vinylnaphthalene; and styrene is the most preferable. Practical examples of the hydrogenated copolymer of the conjugated dienes and aromatic vinyl hydrocarbons include the styrene / butadiene / styrene three-block hydrogenated copolymer and the styrene / isoprene / styrene three-block hydrogenated copolymer, and the three-hydrogenated copolymer Styrene / butadiene / styrene blocks is preferred from the point of view of an excellent fracture toughness property. Examples of carboxylic acids a, ß-unsaturated or their anhydrides used for graft copolymerization with the hydrogenated copolymers shown in detail include acrylic acid, methacrylic acid, ethacrylic acid, clitonic acid, maleic acid, fumaric acid, itacoic acid, citrazoic acid, llO butenedicarboxylic acid and their anhydrides, and preferable examples are maleic anhydride and succinic anhydride. Practical examples of α, β-unsaturated glycidylcarboxylates include glycidyl acrylate, glycidyl methacrylate 15 and glycidylethacrylate, and glycidyl methacrylate is particularly preferable. Although there is no particular limitation, the content of the acid group or epoxy group in the hydrogenated compounds (d2) is preferably in the range of 0.01 to 10% by weight, and more preferably in the range of 0.05 to 5% by weight , for α, β-unsaturated carboxylic acids or their anhydrides; and preferably from 0.1 to 15% by weight, and more preferably in the range from 0.5 to 10% by weight, when the content of the functional groups is calculated as the content of monomers in the raw material. Among the two compounds which include the vinyl type polymers (di) containing the acid or epoxy group and the gum-like polymers (d2) which contain an acid or epoxy group, the compounds containing an acid group are preferable for their excellent adhesiveness to the cured epoxy and its superior fracture resistance property, and these properties become remarkable and it is preferable to use the vinyl type polymers containing an acid group
(di), and the α-olefin containing the acid group (dl-1) is most preferable, and the copolymers of α-olefin, α, β-unsaturated carboxylic acids or their anhydrides, and α, β-alkyl ester carboxylate. - Unsaturated are the most preferable. Although the percentage content of the respective components described above in the composition of the present invention is not limited, the preferable percentage content of the polyallylene sulfide resin (A) is in a range of 30 to 90% by weight, that of the Epoxy resin of the bisphenol A type (B) is in a range of 1 to 10% by weight, and that of the polymer containing oxazoline group (C) is in the range of 1 to 20% by weight to produce remarkable effects. When the component that improves the impact resistance (D) is used to improve the property of resistance to fracture, the percentage content of the component (D) is preferably in the range of 0.5 to 20% by weight. In the present invention, it is further preferable to incorporate fibrous reinforcing materials (E) in addition to those described above (A) to (C) or from (A) to (D). The fibrous reinforcement materials are not particularly limited, if the object of the present invention is achieved. Practical examples of fibrous reinforcement materials include fiberglass, carbon fiber, zinc oxide fiber, asbestos fibers, silica fiber, refractory ceramic aluminum borate fiber, silica-alumina fiber, zirconia fiber, fiber of boron nitride, silicon nitride fiber, potassium titanate fiber, inorganic fibrous materials such as metallic fibrous materials of stainless steel, aluminum, titanium, copper and bronze; high melting organic fibrous materials such as aramid fiber, fibrous polyamide materials, fluororesin, and acrylic resins; a fiberglass is generally preferable. Although the content of the fibrous material is not limited, a range of 5 to 50% by weight in the resin composition is a preferable range. The fibrous reinforcement materials can be used to improve the property of fracture resistance against thermal shock and the resin PAS is reinforced to withstand the stress due to its own expansion and contraction so that the generation of fractures or cracks is suppressed plus. The compatibilities of the PAS resin (A) with the oxazoline group-containing polymer (C) and with the resin that improves the impact resistance (D) are further improved by incorporating silane compounds (F). Particularly, the silane compounds are effective in a fine dispersion of resin that improves the impact resistance (D) so that the impact strength of the resin composition can be drastically improved. Any silane coupling agents containing organic functional groups and silicon atoms in the molecular structure such as silane compounds (F) can be used. Preferable examples of silane compounds (F) include alkoxysilane or phenoxysilane containing an epoxy, alkoxysilane or phenoxysilane group containing an amino group and alkoxysilane or phenoxysilane containing an isocyanate group. These compounds can be used alone or in combinations of two or more. It is preferable that the epoxy alkoxysilane or epoxy phenoxysilane have more than one epoxy group and have two or three alkoxy or phenoxy groups; and examples of such silane compounds include α-glycosopropyltriphenoxy silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and? - | glycidoxypropyltriethoxysilane. It is preferable that the aminoalkoxysilane or aminophenoxysilane have more than one amino group and have two or three alkoxy or phenoxy groups in one molecule; and examples of such silane compounds include α-aminopropyltriethoxysilane, α-aminopropyltrimethoxysilane, α-aminopropyltriphenoxysilane, α-aminopropylmethyldiethoxysilane,
? -aminopropylmethyldimethoxysilane, N-ß- (aminoethyl) -? - amino-propyltriethoxysilane, N-ß- (aminoethyl) -? - aminopropyltrimethoxysilane, N-ß- (aminoethyl) -? - aminopropylmethyldiethoxysilane, N-ß- (aminoethyl) -? - aminopropylmethyldimethoxysilane, N-β-phenyl-β-aminopropyltriethoxysilane, and N-β-phenyl-β-aminopropyl-15-trimethoxysilane. It is preferable that the isocyanatoalkoxysilane or isocyanatophenoxysilane have more than one isocyanate group and have two or three alkoxy or phenoxy groups in one molecule; and examples of such silane compounds include
Isocyanatopropyltriethoxysilane, isocyanatopropyltriphenoxy silane, isocyanatopropyltrimethoxysilane and isocyanatopropylmethyldiethoxysilane.
It is preferable to add the silane compound (F) in the composition of the resin present in a range of 0.01 to 3.0% by weight. Adding more polyhydric alcohol (G) higher fatty acid ester is useful to improve the mold lubrication of the resin after mold formation and it is also useful to further improve the adhesiveness of the resin products with the cured epoxy resin . Here, the preferable polyhydric alcohol includes an alcohol having more than two hydroxy groups, and the preferable higher fatty acid includes saturated or unsaturated fatty acids of 8 to 45 carbon atoms. Practical examples of higher fatty acid esters of polyhydric alcohol include fatty acids such as acrylic acid, lauric acid, myristic acid, behenic acid, stearic acid, montanic acid, oleic acid and palmitic acid; and esters of polyhydric alcohol and its branched polyester oligomer such as ethylene glycol, glycerin, 2-methylpropan-1, 2,3-trile, and pentaerythritol. It is preferable to add the higher fatty acid ester of polyhydric alcohol (F) in the range of 0.01 to
3. 0% by weight for the total amount of the resin composition. From the viewpoint of improving the thermal decomposition resistance of the PAS resin due to the high formation temperature, preferable examples of the compound (G) include ethylene glycol, 2-methyl-1,2,3-triol, Montanic acid of pentaerythritol and its branched polyester oliqomer. The resin composition of the present invention can use inorganic fillers within a range not contrary to the object. Examples of inorganic fillers include silicon carbide, boron nitride, various metal powders, barium sulfate, calcium sulfate, kaolin clay, clay, pyrophyllite, bentonite, sericite, zeolite, mica, nefelincinite, talc, adapaljite, wallastonite , PMF, ferrJta, aluminum silicate, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, alumina, oxide
magnesium, magnesium hydroxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass spheres, quartz, silica and fused silica. It is possible to add the other polymers to the resin composition of the present if they are effective for
improve the resin products of the present invention. Examples of other polymers include homopolymers or copolymers of monomers such as ethylene, butylene, pentene, isoprene, chloroprene, styrene, α-methylstyrene, vinylacetate, vinylchloride, acrylate ester,
methacrylate, and (meth) acrylonitrile; homopolymers, random copolymers, block copolymers and graft polymers of polyester monomers such as polyurethane, polybutylene terephthalate; polyacetal, polycarbonate, polyamide, polysulfone, polyalsulphone, polyethersulphone, polyallylate, polyphenylene oxide, polyetherketone, polyether ether ketone, polyimide, polyamideimide, polyetherimide, silicone resin, phenoxy resin, fluororesin, liquid crystalline polymer, and polyallyl ether. It may be preferable to add to the composition of
The resin of the present invention is a plasticizer, a small amount of mold lubricant, a coloring agent, a lubricant, a heat resistance stabilizer, a stabilizer of the environmental resistance, a forming agent, an oxide inhibitor and a flame retardant. The resin composition herein can be prepared by conventionally known methods. An example of a known method comprises the steps of mixing the PAS resin (A), the epoxy resin of the bisphenol type (B), and the oxazoline group containing polymer (C) and further, if necessary, the resin that improves the impact resistance (D) and the other materials homogeneously by means of a mixer such as a drum or Henschel type mixer, melt and knead the mixture at temperatures ranging from 200 to 350 ° C per
of a uniaxial or biaxial extruder and kneading machine, and produce granules of the resin composition herein. The resin composition of the present invention has superior adhesiveness with the cured epoxy resin, which is a product of the curing reactor of an epoxy resin and a curing agent. Examples of epoxy resins include bisphenol A, bisphenol F, bisphenol S, bisphenol AF, bisphenol AD, 4,4-dihydroxybiphenyl, resorcinol, saligenin, trihydroxy-diphenyldimethylmethane, tetraphenylolmethane, and their halogen substitution products and substitution products with alkyl groups; glycidyl ethers synthesized by the reaction of compounds containing more than two hydroxy groups such as butanediol, ethylene glycol, erythritol, novolac, glycerin and polyoxyalkylene with epichlorohydrin; glycidyl ester such as glycidyl ester phthalate; glycidylamines synthesized by reacting primary or secondary amines such as aniline, diaminodiphenylmethane, metaxylylenediane, 1,3-bis-aminomethylcyclohexane with epichlorohydrin; glycidylepoxy resin of the above compounds, epoxidized soybean oil; and non-glycidylepoxy resins such as vinylcyclohexendioxide, diclopentadiendioxide. Those epoxy resins are used alone or in combinations of two or more.
These epoxy resins are used after being cured by the curing agent. As described at the beginning, when an epoxy resin is used to seal various elements, the epoxy resin is generally poured into a shell made of PAS resin after mixing with a curing agent, and the epoxy resin is then heat cured. or similar. Examples of curing agents include amines, amino resins, acid anhydrides, polyhydric alcohols, phenol resins, polysulfides and isocyanates. The PAS resin compositions of the present invention can be applied not only to semiconductor or electrical devices represented by the covers of automobile ignition coils applied to the DLI system, but also various applications which require a property of superior fracture resistance or resistance to thermal shock and applications such as spray paints, solution type adhesives and paints.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram showing a test piece of the type of insert used for the evaluation of Examples 1 to 10 and Comparative Examples 1 to 9, where A is a metal block (S55C), and B is the resin composition of the present prepared by the above Examples.
DETAILED DESCRIPTION OF THE INVENTION Hereinafter, practical examples of this application will be described. However, it should be noted that the present invention is not limited to those embodiments. The methods for measuring the terminal thiol concentration, logarithmic viscosity (?), Melt flow rate and total sodium content of PPS obtained in the reference examples are as follows. (1) Concentration of terminal thiol: l) l0 The same method was used as the method of the
"Iodoacetoamide" described above. (2) Logarithmic viscosity (?): A relative viscosity of the a-methylchloridaphthalene solution of PPS (the concentration of PPS is 0.4 15 g / lOOml) at 206 ° C (400 ° F) was measured by the following equation, ? = ln (relative viscosity) / PPS concentration (3) Melt flow velocity: Melt flow velocity was measured according to ASTM D1238, diameter and length of the melt
holes are 0.2095 ± 0.0050 centimeters (0.0825 ± 0.002 inches) and 0.8001 + 0.0025 centimeters (0.315 + 0.001 inches), respectively, and the temperature and charge conditions are 316 ° C and 5000g, respectively. (4) Total sodium content:
The total sodium content was measured by the atomic absorption method for the polymer after the decomposition of the sulfate. (5)? HC1,? NaOH 5 10 ml of HCl was added to 10 g of the polymer and filtered after stirring. The filtered solid was washed repeatedly with water until no HCl was detected (until white turbidity was detected by dripping AgN03). All the filtrate used for washing was collected and the (10 HCl in the collected solution was titrated with NaOH, and the
Molar index of the HCl consumed has been defined as? HC1. Subsequently, the polyallylesulphide resin (A) was redispersed in distilled water, and 10 mol of lmol / l of NaOH were added and the dispersed system was filtered after
shake. The filtered solid was repeatedly washed with water
> until no NaOH was detected (until it was detected red by dripping phenoftalein). All the filtrate used for washing was collected and the NaOH in the collected solution was titrated with HCl, and the molar ratio of the
NaOH consumed was defined as? NaOH.
Reference Example 1 (Preparation of PPS-1) 7,900 g of N-methylpyrrolidone, 3,260 g (25 mol, containing 40% crystalline water) of sodium sulfate, 4.0 g of sodium hydroxide and 3,400 g (25 g) mol) of sodium acetate trihydrate were introduced into an autoclave with a stirrer and the temperature was gradually raised to 205 ° C for two hours in a nitrogen atmosphere, while stirring, and 1,500 ml of liquid distillate including 1,360 were removed. g of water. After the reaction system was cooled to
150 ° C, 3,750 g (25.5 mol) of p-dichlorobenzene were added and
2,000 g of methylpyrrolidone and a reaction was conducted in two steps at 230 ° C for four hours and for an additional two hours at 260 ° C. ** Subsequently, the autoclave was cooled and the contents separated by filtration. The cake was then washed with hot water five times, and after drying under
reduced pressure, granular PPS was produced (
82%). > In addition, approximately 2,200 g of this granular PPS resin was placed in 20 1 of solution heated with acetic acid water of pH4 and 90 ° C. The dispersed system was filtered after stirring for 30 minutes, and the filtered solid was washed with deionized water at 90 ° C until the pH was increased to 7, and dried at 120 ° C for 24 hours. The PPS resin thus obtained showed the following characteristic values: the terminal thiol concentration is
of 40 μmol / g, the logarithmic viscosity (?) Is 0.32, and the flow velocity of the melt is 100 g / 10 min, the total sodium content is 250 ppm,? HC1 = 2.0 μmol / g , and? NaOH = 20.0 μ mol / g. This resin is known as PPS-1.
Reference Example 2 (Preparation of PPS-2) 1.993 g of N-methylpyrrolidone, 537 g (4.1 mol) of sodium sulfate, 2.7 of hydrate, 1.6 g (0.04 mol) of sodium hydroxide, and 144 g (1.0 mol) of sodium benzoate were introduced into an autoclave with a stirrer. The
The temperature was gradually raised to 200 ° C for two hours in a nitrogen atmosphere while stirring and 102 ml of water was distilled. After the reaction system was cooled to 105 ° C, 603 g (4.1 mol) of p-dichlorobenzene were added,
1.8 g (0.01 mol) of 1, 2, 4-trichlorobenzene, and 310 g of N-r methylpyrrolidone and the two step reaction was conducted at 230 ° C for two hours and at 260 ° C for three hours. The internal pressure of the autoclave observed was 9.5 Kg / cm2 when the polymerization reaction had been completed. Subsequently, the autoclave was cooled, and the contents separated by filtration. The cake obtained was washed with hot water three times, and dried after washing with acetone twice and 394 g of light brown gray granular PPS were produced (yield = 89%).
The PPS thus obtained showed the following characteristic values: the concentration of the terminal thiol group is 15 μmol / g, the logarithmic viscosity (?) Is 0.25, the flow velocity of the melt is 550 g / 10 min, the content of Total sodium is 80 ppm,? HC1 = 10.0 μmol / g, and? NaOH = 20.0 μmol / g. This resin is known as PPS-2.
Reference Example 3 (Preparation of PPS-3) 1233 g of methylpyrrolidone, 636 g (5.0 mole, 61.5% by analysis) of sodium sulfate, 2.7 of hydrate, 510 g (5.0 mole) of ethyl acetate dihydrate, and 90 g (5.0 mol) of water were introduced into an autoclave with a stirrer. 290 ml of liquid distillate including 257 g of water was generated by means of a reaction at 205 ° C for about one hour and twenty minutes in a nitrogen atmosphere while stirring. After the reaction system was cooled to 150 ° C, a solution of 750 g (5.1 mol) of p-dichlorobenzene in 400 g of N-methylpyrrolidone was added and the reaction was conducted at 265 ° C for three hours. The internal pressure of the autoclave when the reaction was complete was 9.0 Kg / min. Subsequently, the autoclave was cooled to 150 ° C and the contents separated by filtration. The obtained cake was washed with hot water three times, and then washed with acetone twice, the cake was immersed in HCl solution of pH 1 at room temperature for 30 minutes. 467 g "of PPS resin was produced after washing with deionized water and drying at 80 ° C under reduced pressure (yield = 86%). The PPS thus obtained showed the following characteristic values: the concentration of the terminal thiol group is 35 μmol / g, the logarithmic viscosity (?) is 0.25, the flow velocity of the melt is 550 g / 10 min, the total sodium content is 100 ppm,? HC1 = 1.0 μ mol / g, and? NaOH = 12.0 μ mol / g.This resin is known as PPS-3.
Examples 1-10 The PPS resins produced according to the respective Reference Examples and the respective combined compounds shown in Tables 1 and 2 were mixed homogeneously in the mixing ratios shown in the same Table and the mixture was melted and kneaded by means of of a biaxial extruder with a diameter of 35 mm at 350 ° C, and granules were obtained. The properties and compatibility of these sample granules were evaluated by the use of test pieces which were formed by means of an injection molding machine of the three ounce type under the conditions of cylinder temperature at 290 ° C, mold at 140 ° C, injection pressure of 1,000 Kgf / cm2, and an average injection speed. The results of the evaluations are shown in Tables 1 and 2. A cut fiber glass fiber was used as the fiberglass shown in Tables 1 and 2.
The following properties were evaluated. < Mechanical properties > (1) Izod Impact Resistance Impact Resistance for Grooved and Non-Slotted Test Pieces 0.3175 centimeters (1/8 inch) thick, 1.27 centimeters (1/2 inch) wide, and 6.35 centimeters (2.5 inches) in length were measured according to ASTM D-256. A measured value was obtained by measuring five test pieces. (2) Fracture resistance property Products formed of the insert type, each formed by covering a metal block (S55C) A with a layer of resin B of 1 mm thickness as shown in Figure 1, were subjected to a steam heating and cooling test cycle, in which a set cycle was "-40 ° C / one hour ~ 140 ° C / one hour", and the number of cycles at which cracks were generated was recorded or fractures in the external wall. The number of test pieces for the test was n = 5. The results of the test were evaluated by ranges I according to the following rule. 5 Cracks or fractures were generated in less than 10 cycles ... "E" range. Cracks or fractures were generated within a range of 10-less than 100 cycles ... "D" range. Cracks or fractures were generated within a k10 interval of more than 100 and less than 800 cycles ... "C" range. Cracks or fractures were generated within a range of more than 300 and less than 1,000 cycles ... range "B". Cracks or fractures were generated in more than 1,000 cycles ... "A" range. 15 < Compatibility > Compatibility was evaluated according to the following standard by visual inspections of the appearance of sheets having dimensions of 2mm thickness, 50mm width and
100 mm in length, using a film gate. Or ... the surface of a formed product is uniform and no detachment was observed; ? ... the surface is not uniform and a similar shine to the opal was observed;
X ... the surface of the formed product is not uniform and detachment was observed.
< Dispersed particle size of the component that improves the impact strength > Fractured surfaces of test pieces with grooves were observed after testing the Izod impact resistance after immersion in hot xylene by a scanning electron microscope (amplification:
110 2, 500 times).
< Adhesive resistance to cured epoxy resin > Test pieces with dimensions of 25 mm in width, 75 mm in length and 3 mm in thickness were formed by means of
the resin of the present and an epoxy resin was coated to a? thickness of 40 to 50 μm on the test piece in a surface area of 25 mm x 10 mm. After fixing by means of a clamp, the coated layer was cured by first treating by holding it initially at 85 ° C for three hours,
Subsequently, maintenance was followed at 150 ° C for three hours and finally annealed. The resistance to the tensile cut was then measured at a tensile speed of 5 mm / min, and the actual loads were recorded.
The epoxy resin used to measure the adhesive strength is as follows: Main component: Epicron 850 (produced by Dainippon Ink &Chemicals Co. Ltd. containing silica) (filling speed: 50% by weight). Curing agent: hexahydrophthalic acid anhydride. The ratio of the main component / curing agent = 100/30.
< Adhesive strength of the epoxy filler material > A product was formed into a box with a base 30 mm wide and 80 mm long and with a height of 15 mm and a wall thickness of 2 mm, and the same epoxy resin used to measure the adhesive strength and poured to the height of 10 mm, and cured under the same conditions. Tests of the gas-phase heating and cooling cycle were carried out by repeating the cycles of "-40 ° C / one hour ~ 140 ° C / one hour", and the number of cycles until the interface of the internal surface of the box-shaped product and cured epoxy resin was recorded. The evaluation was carried out by ranking the number of cycles as follows.
The detachment was caused by less than 10 cycles: range IV. The detachment was caused __in an interval equal to or greater than 10 or less than 100 cycles ... range "III". The detachment was caused in an interval equal to or greater than 100 or less than 300 cycles ... range "II", the detachment was caused equal to or more than 300 cycles ... range "I".
Table 1
Table 1 (continued) Table 2 Table 2 (continued)
Comparative Examples 1 to 9 The PPS produced according to the respective Reference Examples and the respective combined compounds shown in Tables 3 and 4 were combined homogeneously at the mixing ratios shown in the same table and the mixture was melted and kneaded by means of of an axial exosorbidity at 300 ° C and were obtained in grams. The same properties as those for examples 1 to 10 were achieved. The results are shown in tables 3 and 4.
Table 3
Table 3 (continued)
Table 4 Table 4 (continued)
In Tables 1 to 4, the numerical values
(represent the% by weight, and the G components representing the ester of the higher fatty acid ester of the polyhydric alcohol The abbreviations in these tables indicate the following compounds: Bl: epoxy resin of the bisphenol A type, epoxy equivalent of 2,000; B-2: epoxy resin of the bisphenol A type, epoxy equivalent of 190;
B-3: epoxy resin of the bisphenol S type, epoxy equivalent of 210 (trademark: Epicron EXA-1514, produced by Dainippon Ink and Chemicals Inc.); B-4: epoxidized product of 1,6-dihydroxynaphthalene, equivalent of epoxy 150 (trademark: Epicron XP 4032, produced by Dainippon Ink and Chemicals Inc.). In the above compounds an epoxy resin of the bisphenol A (B) type. C-1: oxazoline / styrene copolymer containing 5% by weight of vinyl oxazoline; C-2: oxazoline / styrene / acrylonitrile copolymer containing by weight of vinyloxazoline, styrene / acrylonitrile = 70/25. The above compounds are polymer containing an oxazoline (C). D-1: maleic acid anhydride (Maah), grafted ethylene (Et), and propylene copolymer (PP), Et / PP / Maah = 58/40/2. D-2: ternary ethylene / ethylacrylate copolymer (EA) / maleic acid anhydride, Et / EA / Maah = 66/32/2. D-3: ethylene / glycidylmethacrylate copolymer (GMA), Et / GMA = 88/12. D-4: ternary copolymer of ethylene / ethylacrylate / glycidyl methacrylate, Et / EA / GMA = 68/24/8.
D-5: hydrogenated styrene block copolymer grafted with maleic acid / butadiene / styrene anhydride, ethylene-butene / styrene / Maah = 68/30/2. D-6: hydrogenated block copolymer of styrene copolymerized with GMA / butadiene / styrene, ethylene-butane / styrene / GMA = 68/30/2. D-7: ethylacrylate / butylacrylate copolymer (BA) / maleic acid anhydride, EA / BA / Maah = 62/36/2. D-8: ethylacrylate / butyl acrylate copolymer (BA) / glycidyl methacrylate, EA / BA / GMA = 62/36/2 = 68/30/2. D-9: ethylene / ethylacrylate copolymer (EA), Et / EA = 85/15. The above compounds are resins that improve the impact resistance (D). F-1:? -glycidoxypropyltrimethoxysilane; F-2:? -aminopropyltriethoxysilane; F-3: isocyanatopropyltriethoxysilane: The above compounds are silane compounds (F). G-1: ethyleneglycoldimontanate; G-2: trimethylolpropantrimontanate; G-3: pentaerythritoltetra-stearate. The above compounds are higher fatty acid esters of polyhydric alcohol.
The other components: Amida type wax; and wax of the aminocarboxylate type which is a product of the reaction of spherical acid, sebacic acid and ethylenediamine (it is an endothermic peak by the measurement of DSC appear at 143 ° C, and the content of ethylenebistearylamide is 30%). According to the present invention, it becomes possible to drastically improve the adhesive strength of the PAS resin to the cured epoxy resin, and to drastically improve the fracture resistance property of the PAS resin when subjected to heating and cooling cycles by the Use of a resin that improves strength. Accordingly, the resin compositions of the present invention can be used as addition plastics in different fields of application such as electronic devices and others.
Claims (14)
1. A polyallylsulphide resin composition, characterized in that it comprises an allylsulfide resin (A), an epoxy resin of the biphenol (B) type, 11O and an amorphous polymer (C) containing an oxazoline group as essential components. 2. The polyallylene sulphide resin composition according to claim 1, characterized in that the epoxy resin of the bisphenol type is an epoxy resin of the
The type of bisphenol A. fc
3. The resin composition according to claim 1, characterized in that the resin composition further comprises a resin that improves the impact resistance (D) in addition to the components of (A) to (a) C).
4. The resin composition according to any of claims 1 to 3, characterized in that the composition further comprises a fibrous reinforcement material (E) in addition to the components (A) to (D).
5. The resin composition in accordance with Any one of claims 1 to 5, characterized in that the allylene sulfide resin (A) is a resin having characteristic values, so that? HC1 is greater than 10 μmol / g,? NaOH in a range of 5 to 80 μmol /. g, and (? NaOH-? HCL) > 5μmol / g.
6. The resin composition according to claim 5, characterized in that the allylene sulfide resin (A) has more than 70 mol% of a structural unit expressed by the following chemical formula (1).
7. The resin composition according to claim 3, characterized in that the resin that improves the impact resistance (D) is a resin component selected from any of the vinyl type (di) polymers containing an acid or epoxy group or gum-type polymers (d2) containing an acid or epoxy group. The resin composition according to claim 7, characterized in that the vinyl type polymers containing an acid or epoxy group are a-polyolefin (dl-1) containing an acid or epoxy group. 9. The resin composition according to claim 8, characterized in that the α-polyolefin (dl-1) containing acid or epoxy groups is a copolymer of α-olefin, α, β-unsaturated carboxylic acid or its anhydride and carboxylate of carboxylated alkyl ester. 10. The resin composition according to claim 7, characterized in that the polymer of the type 5 vinyl (di) contains acid group or epoxy is α, β-unsaturated alkyl ester carboxylate polymer (dl-1) containing acid or epoxy groups. 11. The resin composition according to claim 7, characterized in that the amorphous polymer that ') L0 contains the oxazoline group (C) is a hydrogenated copolymer product containing conjugated diene acid or epoxy groups and aromatic vinyl type monomers. 12. The resin composition according to claim 7, characterized in that the amorphous polymer containing 15 the oxazoline group (C) is a copolymer comprised as components? of vinyl oxazoline or monomers of the styrene type. The resin composition according to any of claims 1 to 12, characterized in that in the resin composition it also comprises a 20 composed of silane. The resin composition according to any of claims 1 to 12, characterized in that the resin composition further comprises a higher fatty acid ester of polyhydric alcohol.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP10-214682 | 1998-07-30 |
Publications (1)
Publication Number | Publication Date |
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MXPA99007085A true MXPA99007085A (en) | 2000-12-06 |
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