JPS63312354A - Polyphenylene sulfide resin composition - Google Patents
Polyphenylene sulfide resin compositionInfo
- Publication number
- JPS63312354A JPS63312354A JP14687087A JP14687087A JPS63312354A JP S63312354 A JPS63312354 A JP S63312354A JP 14687087 A JP14687087 A JP 14687087A JP 14687087 A JP14687087 A JP 14687087A JP S63312354 A JPS63312354 A JP S63312354A
- Authority
- JP
- Japan
- Prior art keywords
- group
- polyphenylene sulfide
- bis
- polyetherimide
- aminophenoxy
- 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
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 30
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 30
- 239000011342 resin composition Substances 0.000 title claims description 14
- 239000004697 Polyetherimide Substances 0.000 claims abstract description 30
- 229920001601 polyetherimide Polymers 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 239000000460 chlorine Substances 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims abstract description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- 125000004149 thio group Chemical group *S* 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- -1 carbonyl thio Chemical group 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 12
- 238000000465 moulding Methods 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 125000002723 alicyclic group Chemical group 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 19
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 5
- 239000004305 biphenyl Substances 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920005575 poly(amic acid) Polymers 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001721 transfer moulding Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- OLQWMCSSZKNOLQ-UHFFFAOYSA-N 3-(2,5-dioxooxolan-3-yl)oxolane-2,5-dione Chemical compound O=C1OC(=O)CC1C1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-UHFFFAOYSA-N 0.000 description 1
- ZDBWYUOUYNQZBM-UHFFFAOYSA-N 3-(aminomethyl)aniline Chemical compound NCC1=CC=CC(N)=C1 ZDBWYUOUYNQZBM-UHFFFAOYSA-N 0.000 description 1
- UCFMKTNJZCYBBJ-UHFFFAOYSA-N 3-[1-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)C1=CC=CC(C(O)=O)=C1C(O)=O UCFMKTNJZCYBBJ-UHFFFAOYSA-N 0.000 description 1
- HBBBNZLAIQRGHX-UHFFFAOYSA-N 3-[1-(3-aminophenoxy)-4-(3,5-dimethylphenyl)-2,6-dimethylcyclohexa-2,4-dien-1-yl]oxyaniline Chemical group CC1C=C(C=C(C1(OC2=CC=CC(=C2)N)OC3=CC=CC(=C3)N)C)C4=CC(=CC(=C4)C)C HBBBNZLAIQRGHX-UHFFFAOYSA-N 0.000 description 1
- BUCRPLWBLGEXGT-UHFFFAOYSA-N 3-[4-[2-[4-(3-aminophenoxy)-3,5-dimethylphenyl]propan-2-yl]-2,6-dimethylphenoxy]aniline Chemical compound CC1=CC(C(C)(C)C=2C=C(C)C(OC=3C=C(N)C=CC=3)=C(C)C=2)=CC(C)=C1OC1=CC=CC(N)=C1 BUCRPLWBLGEXGT-UHFFFAOYSA-N 0.000 description 1
- KZGXKAPDSOGTQO-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)-3,5-dimethylphenyl]phenoxy]aniline Chemical group CC1=CC(C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=CC(C)=C1OC1=CC=CC(N)=C1 KZGXKAPDSOGTQO-UHFFFAOYSA-N 0.000 description 1
- IWBGRHNGPPHLKI-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)-3-bromophenyl]-2-bromophenoxy]aniline Chemical group NC1=CC=CC(OC=2C(=CC(=CC=2)C=2C=C(Br)C(OC=3C=C(N)C=CC=3)=CC=2)Br)=C1 IWBGRHNGPPHLKI-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- UTDAGHZGKXPRQI-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=C(S(=O)(=O)C=2C=CC(OC=3C=CC(N)=CC=3)=CC=2)C=C1 UTDAGHZGKXPRQI-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000001273 butane Substances 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
- 238000001816 cooling Methods 0.000 description 1
- 238000006210 cyclodehydration reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- XNFVGEUMTFIVHQ-UHFFFAOYSA-N disodium;sulfide;hydrate Chemical compound O.[Na+].[Na+].[S-2] XNFVGEUMTFIVHQ-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- GBASTSRAHRGUAB-UHFFFAOYSA-N ethylenetetracarboxylic dianhydride Chemical compound O=C1OC(=O)C2=C1C(=O)OC2=O GBASTSRAHRGUAB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- UMSVUULWTOXCQY-UHFFFAOYSA-N phenanthrene-1,2,7,8-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C2C3=CC=C(C(=O)O)C(C(O)=O)=C3C=CC2=C1C(O)=O UMSVUULWTOXCQY-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は成形用樹脂組成物に関する。更に詳しくは、耐
熱性、耐薬品性、機械、的強度などにすくれ、かつ成形
加工性にすくれたポリフェニレンスルフィド系樹脂組成
物に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a molding resin composition. More specifically, the present invention relates to a polyphenylene sulfide resin composition that has excellent heat resistance, chemical resistance, mechanical strength, mechanical strength, etc., and excellent moldability.
従来からポリフェニレンスルフィドは耐＝ 性、耐薬品
性、耐水性、成形加工性、および電気特性等に優れてお
り、電気・電子機器、宇宙航空用機器、輸送機器などの
分野で使用されており、今後共耐熱性が要求される分野
に広く用いられることが期待されている。Polyphenylene sulfide has traditionally had excellent resistance, chemical resistance, water resistance, moldability, and electrical properties, and has been used in fields such as electrical and electronic equipment, aerospace equipment, and transportation equipment. It is expected that it will be widely used in fields where heat resistance is required in the future.
しかし、ポリフェニレンスルフィドは機械的強度、特に
引張強度、引張伸度および耐衝撃性に劣るという欠点が
ある。However, polyphenylene sulfide has the drawback of poor mechanical strength, particularly tensile strength, tensile elongation, and impact resistance.
本発明の目的は、ポリフェニレンスルフィドが有する優
れた特性に加え、機械的強度、特に引張強度、引張伸度
および耐衝撃性の改善されたポリフェニレンスルフィド
系樹脂組成物を得ることにある。An object of the present invention is to obtain a polyphenylene sulfide resin composition that has improved mechanical strength, particularly tensile strength, tensile elongation, and impact resistance, in addition to the excellent properties of polyphenylene sulfide.
本発明者らは前記問題点を解、決するために鋭意研究を
行った結果、ポリフェニレンスルフィドと特定量の新規
ポリエーテルイミドとよりなる樹脂組成物が特に前記目
的に有効であることを見出し本発明を完成した。The present inventors conducted intensive research to solve the above-mentioned problems, and as a result, they discovered that a resin composition comprising polyphenylene sulfide and a specific amount of a new polyetherimide is particularly effective for the above-mentioned purpose. completed.
即ち本発明は、ポリフェニレンスルフィド１００重量部
に対し、式（Ｉ）
（式中、Ｘは直結、炭素数１乃至１０の２価の炭化水素
基、六フッ素化されたイソプロピリデン基、カルボニル
基、チオ基、またはスルホン基から成る群より選ばれた
基を表し、Ｐ、〜Ｒ４は水素、低級アルキル基、低級ア
ルコキシ基、塩素または臭素を示し、互いに同じであっ
ても異なっていてもよい。That is, the present invention uses a compound of the formula (I) (wherein, X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group, It represents a group selected from the group consisting of a thio group or a sulfone group, and P and ~R4 represent hydrogen, a lower alkyl group, a lower alkoxy group, chlorine or bromine, and may be the same or different.
Ｙは炭素数２以上の脂肪族基、環式脂肪族基、単環式芳
香族基、縮合多環式芳・香族基、芳香族が直接又は架橋
員により相互に連結された非縮合多環式芳香族基から成
る群より選ばれた４価の基を表す）
で示される繰り返し単位を有するポリエーテルイミド樹
脂１重量部以上１００重量部未満よりなるポリフェニレ
ンスルフィド系樹脂組成物である。Y is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a fused polycyclic aromatic/aromatic group, or a non-fused polycyclic group in which aromatic groups are interconnected directly or through a bridge member. A polyphenylene sulfide resin composition comprising 1 part by weight or more and less than 100 parts by weight of a polyetherimide resin having a repeating unit represented by (representing a tetravalent group selected from the group consisting of cyclic aromatic groups).
本発明で用いられるポリフェニレンスルフィドおよび特
公昭４５−３３６８号に開示されており、且つ例えば
″ライドン” （ＲＹＴＯｌｌ） （米国フィリップス
、ペトローリアム社商標）などとして市販されている。Polyphenylene sulfide used in the present invention and disclosed in Japanese Patent Publication No. 45-3368, and for example
It is commercially available as "RYTOll" (trademark of Petroleum Corporation, Philips, USA).
それによるとポリフェニレンスルフィドはＮ−メチルピ
ロリドン７容媒中、１６０〜２５０’Ｃ１加圧条件下に
ρ−クロロヘンゼンと硫化ナトリウム・１水塩とを反応
させることにより製造される。According to it, polyphenylene sulfide is produced by reacting ρ-chlorohenzene and sodium sulfide monohydrate in 7 volumes of N-methylpyrrolidone under pressurized conditions of 160 to 250'C1.
ポリフェニレンスルフィドは全く交叉結合のないものか
ら、部分的交叉結合を有するものまで、各種重合度のも
のを後熱処理工程にかけることにより自由に製造するこ
とができる。。またこれらのものは市販されており、従
って目的のブレンド物に適性な溶融粘度特性を有するも
のを任意に製造し、または市場で選択することができる
。Polyphenylene sulfide can be freely produced with various degrees of polymerization, from those with no cross-linking to those with partial cross-linking, by subjecting it to a post-heat treatment step. . Further, these materials are commercially available, and therefore, one having melt viscosity characteristics suitable for the desired blend can be arbitrarily manufactured or selected from the market.
本発明でポリフェニレンスルフィドの耐熱性および機械
的強度を向上させることを目的として併用されるポリエ
ーテルイミドは次式（Ｔ）（式中、Ｘ、ＹおよびＲＩ”
Ｒａは前に同じ）の繰り返し単位よりなるポリエーテ
ルイミドであり、本発明者が先に機械的性質、熱的性質
、電気的性質、耐溶剤性などにすくれ、かつ耐熱性を有
するポリイミドとして見出した（特願昭５９−２６５２
２０．６０−２０５２８３．６０−２２４８１２．６１
−０７６４７５．６１−２７４２０６等）ものであり１
、ジアミン成分として式（Ｉ［［）（式中、Ｘｌおよび
Ｒ，−Ｒ，は前に同じ）で表されるエーテルジアミンを
使用し、これと一種以上のテトラカルボン酸二無水物と
を反応させてえられるポリアミド酸を脱水環化して得ら
れるポリエーテルイミドである。In the present invention, the polyetherimide used in combination for the purpose of improving the heat resistance and mechanical strength of polyphenylene sulfide has the following formula (T) (wherein X, Y and RI"
It is a polyetherimide consisting of repeating units (Ra is the same as above), and the present inventor first developed it as a polyimide that has good mechanical properties, thermal properties, electrical properties, solvent resistance, etc., and has heat resistance. I found it (patent application 1986-2652)
20.60-205283.60-224812.61
-076475.61-274206 etc.) 1
, using an ether diamine represented by the formula (I[[) (in the formula, Xl and R, -R, are the same as before) as a diamine component, and reacting this with one or more tetracarboxylic dianhydrides. It is a polyetherimide obtained by cyclodehydration of a polyamic acid obtained by
このポリエーテルイミドに使用されるジアミンとしては
、ビス（４−（３−アミノフェノキシ）フェニル〕メタ
ン、１，１−ビス（４−（３−アミノフェノキシ）フェ
ニル〕エタン、１，２−ビス〔４−（３−アミノフェノ
キシ）フェニル〕エタン、２，２−ビス（１−（３−ア
ミノフェノキシ）フェニル〕プロパン、２− （４−（
３−アミノフェノキシ）フェニル）−２−（４−（３−
アミノフェノキシ）−３−メチルフェニル〕プロパン、
２．２−ビス（４−（３−アミノフェノキシ）−３−メ
チルフェニル〕プロパン、２−Ｃ４，Ｃ３−アミノフェ
ノキシ）フェニル）−２−Ｃ４−（３−アミノフェノキ
シ）−３，５−ジメチルフェニル〕プロパン、２，２−
ビス（４−（３−アミノフェノキシ） −３，５−ジメ
チルフェニル〕プロパン、２．２−ビス〔４〜（３−ア
ミノフェノキン）フェニル〕ブタン、２，２−ビス（４
−（３−アミノフェノキシ）フェニル−Ｌｌ、１，３，
３．３−ヘキサフルオロプロパン、４，４゛−ビス（３
−アミノフェノキン）ビフェニル、４，４゛−ビス（３
−アミノフェノキシ）−３−メチルビフェニル、４，４
゛−ビス（３−アミノフェノキシ’） −３，３”−ジ
メチルビフェニル、４．４’−ビス（３−アミノフェノ
キシ） −３，５−ジメチルビフェニル、４．４−ビス
（３−アミノフェノキシ） −３，３’、５．５’
−テトラメチルビフェニル、４，４゛−ビス（３−ア
ミノフェノキシ） −３，３”−ジクロロビフェニル
、４，４゛−ヒス（３−アミノフェノキシ）−３，５−
ジクロロビフェニル、４ 、−１ ’−ビス（３−アミ
ノフェノキシ） −３，３’、５．５’ −テトラ
クロロビフェニル、４．４’−ビス（３−アミノフェノ
キシ） −３，３’−ジブロモビフェニル、４゜４゛−
ビス（３−アミノフェノキシ） −３，５−ジブロモビ
フェニル、４，４“−ビス（３−アミノフェノキシ）
−３，３’、５．５’ −テトラブロモビフェニル、
ビス（４−（３−アミノフェノキン）フェニルコケトン
、ビスＣ４−＜３−アミノフェノキシ）フェニル〕スル
フィド、ビス（４−（３−アミノフェノキシ） ）−３
，３”−ジメトキシジフェニルスルフィド、ビス（４−
（３−アミノフェノキシ）〕−〕３．５−ジメトキシジ
フェニルスルフィドビス（４−（３−アミノフェノキシ
）） −３，３’、５．５’−テトラメトキシジフェニ
ルスルフィド、ビス〔４−（３−アミノフェノキシ）〕
スルホン等があげられ、これらは単独あるいは２種以上
混合して用いられる。Diamines used in this polyetherimide include bis(4-(3-aminophenoxy)phenyl)methane, 1,1-bis(4-(3-aminophenoxy)phenyl)ethane, and 1,2-bis[ 4-(3-aminophenoxy)phenyl]ethane, 2,2-bis(1-(3-aminophenoxy)phenyl)propane, 2-(4-(
3-aminophenoxy)phenyl)-2-(4-(3-
aminophenoxy)-3-methylphenyl]propane,
2.2-bis(4-(3-aminophenoxy)-3-methylphenyl]propane, 2-C4,C3-aminophenoxy)phenyl)-2-C4-(3-aminophenoxy)-3,5-dimethyl phenyl]propane, 2,2-
Bis(4-(3-aminophenoxy)-3,5-dimethylphenyl)propane, 2,2-bis[4-(3-aminophenoquine)phenyl]butane, 2,2-bis(4
-(3-aminophenoxy)phenyl-Ll, 1,3,
3.3-hexafluoropropane, 4,4゛-bis(3
-aminophenoquine) biphenyl, 4,4゛-bis(3
-aminophenoxy)-3-methylbiphenyl, 4,4
゛-Bis(3-aminophenoxy') -3,3''-dimethylbiphenyl, 4,4'-bis(3-aminophenoxy) -3,5-dimethylbiphenyl, 4,4-bis(3-aminophenoxy) -3,3',5.5'
-tetramethylbiphenyl, 4,4'-bis(3-aminophenoxy) -3,3''-dichlorobiphenyl, 4,4'-his(3-aminophenoxy)-3,5-
Dichlorobiphenyl, 4,-1'-bis(3-aminophenoxy)-3,3',5,5'-tetrachlorobiphenyl, 4,4'-bis(3-aminophenoxy)-3,3'-dibromo Biphenyl, 4゜4゛-
Bis(3-aminophenoxy) -3,5-dibromobiphenyl, 4,4"-bis(3-aminophenoxy)
-3,3',5.5'-tetrabromobiphenyl,
Bis(4-(3-aminophenoquine)phenylkoketone, bisC4-<3-aminophenoxy)phenyl]sulfide, bis(4-(3-aminophenoxy))-3
,3”-dimethoxydiphenyl sulfide, bis(4-
(3-aminophenoxy)]-]3.5-dimethoxydiphenylsulfide bis(4-(3-aminophenoxy))-3,3',5.5'-tetramethoxydiphenylsulfide, bis[4-(3- aminophenoxy)]
Examples include sulfone, and these may be used alone or in a mixture of two or more.
また、ポリエーテルイミドの特性をそこなわない範囲で
、他のポリイミドを製造するのに使用される公知のジア
ミンを併用してもよい。併用して用いることのできるジ
アミンとしては、例えば、ｍ−フェニレンジアミン、ｐ
−フェニレンジアミン、０−フェニレンジアミン、ｍ−
アミノベンジルアミン、ｐ−アミノヘンシルアミン、３
．３’−ジアミノジフェニルエーテル、３．４゛−ジア
ミノジフェニルエーテル、４．４’−ジアミノジフェニ
ルエーテル、３，３゛−ジアミノジフェニルスルフィド
、３゜４”−ジアミノジフェニルスルフィド、４，４”
−ジアミノジフェニルスルフィド、３．３゛−ジアミノ
ジフェニルスルホン、３．４’−ジアミノジフェニルス
ルホン、４．４゛−ジアミノジフェニルスルホン、３．
３“−ジアミノヘンシフエノン、３．４”−ジアミノヘ
ンシフエノン、４．４’−ジアミノヘンシフエノン、
１．３−ビス（３−アミノフェノキシ）ヘンゼン、１．
３−ビス（４〜アミノフエノキシ）ヘンゼン、１．４−
ビス（３−アミノフェノキシ）ヘンゼン、１．４−ビス
（４−アミノフェノキシ）ヘンゼン、２．２−ビス（４
−（４−アミノフェノキシ）フェニル〕プロパン、４．
４”−ビス（４−アミノフェノキシ）ビフェニル、４，
４゛−ビス（４−アミノフェノキシ）ケトン、ビス（４
−（４−アミノフェノキシ）フェニル〕スルフィト、ビ
ス（４−（４−アミノフェノキシ）フェニル〕スルホン
等があげられる。Further, known diamines used for producing other polyimides may be used in combination within a range that does not impair the properties of polyetherimide. Examples of diamines that can be used in combination include m-phenylenediamine and p-phenylenediamine.
-phenylenediamine, 0-phenylenediamine, m-
Aminobenzylamine, p-aminohensylamine, 3
．． 3'-diaminodiphenyl ether, 3.4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3'-4''-diaminodiphenyl sulfide, 4,4''
-diaminodiphenylsulfide, 3.3'-diaminodiphenylsulfone, 3.4'-diaminodiphenylsulfone, 4.4'-diaminodiphenylsulfone, 3.
3"-diaminohensiphenone, 3.4"-diaminohensiphenone, 4.4'-diaminohensiphenone,
1.3-bis(3-aminophenoxy)henzen, 1.
3-bis(4-aminophenoxy)henzen, 1.4-
Bis(3-aminophenoxy)henzen, 1.4-bis(4-aminophenoxy)henzen, 2.2-bis(4
-(4-aminophenoxy)phenyl]propane, 4.
4”-bis(4-aminophenoxy)biphenyl, 4,
4-bis(4-aminophenoxy)ketone, bis(4
-(4-aminophenoxy)phenyl]sulfite, bis(4-(4-aminophenoxy)phenyl)sulfone, and the like.
本発明に用いられるポリエーテルイミドは、前記ジアミ
ンとテトラカルボン酸二無水物とを有機溶媒中で反応さ
せ、脱水閉環して得られる。The polyetherimide used in the present invention is obtained by reacting the diamine and tetracarboxylic dianhydride in an organic solvent, followed by dehydration and ring closure.
（式中、Ｙは前に同し） で表されるテトラカルボン酸二無水物である。(In the formula, Y is the same as before) It is a tetracarboxylic dianhydride represented by
即ち、使用されるテトラカルボン酸二無水物としては、
エチレンテトラカルボン酸二無水物、ブタンテトラカル
ボン酸二無水物、ンクロペンクンカルポン酸二無水物、
ピロメリット酸二無水物、３．３“、４，４“ −ヘン
シフエノンテトラカルボン酸二無水物、２，２″、３．
３’ −ヘンシフエノンテトラカルボン酸二無水物、
３．３’、４．４’ −ビフェニルテトラカルボン酸
二無水物、２．２’、３．３’ −ビフェニルテトラカ
ルボン酸二無水物、２，２−ビス（３，４−ジカルボキ
シフェニル）プロパンニ無水物、２，２−ビス（２，３
−ジカルボキシフェニル）プロパンニ無水物、ビス（３
，４−ジカルボキシフェニル）エーテルニ無水物、ビス
（３，４−、ジカルボキシフェニル）スルホンニ無水物
、１，１−ビス（２，３−ジカルボキシフェニル）エタ
ンニ無水物、ビス（２，３−ジカルボキシフェニル）メ
クンニ無水物、ビス（３，４−ジカルボキシフェニル）
メタンニ無水物、４．４’ −（ｐ−フェニレンジオキ
シ）シフタル酸二無水物、４．４’ −（ｍ−フェニレ
ンジオキシ）シフクル酸二無水物、２，３．６．７−ナ
フタレンテトラカルボン酸二無水物、Ｌ４，５．８−ナ
フタレンテトラカルボン酸二無水物、１，２，５．６−
ナフタレンテトラカルボン酸二無水物、１，２，３．４
−ヘンゼンテトラカルボン酸二無水物、３，４，９．１
０−ペリレンテトラカルボン酸二無水物、２，３，６．
７−アントラセンテトラカルボン酸二無水物、１，２，
７．８−フェナントレンテトラカルボン酸二無水物など
であり、これらテトラカルボン酸二無水物は単独あるい
は２種以上混合して用いられる。That is, the tetracarboxylic dianhydride used is:
Ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, nclopencuncarboxylic dianhydride,
Pyromellitic dianhydride, 3.3", 4,4"-hensiphenotetracarboxylic dianhydride, 2,2", 3.
3'-hensiphenotetracarboxylic dianhydride,
3.3', 4.4'-biphenyltetracarboxylic dianhydride, 2.2', 3.3'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Propannianhydride, 2,2-bis(2,3
-dicarboxyphenyl)propanihydride, bis(3
,4-dicarboxyphenyl)ether dianhydride, bis(3,4-,dicarboxyphenyl)sulfone dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(2,3- dicarboxyphenyl) mecunni anhydride, bis(3,4-dicarboxyphenyl)
Methani dianhydride, 4.4'-(p-phenylenedioxy)cyphthalic dianhydride, 4.4'-(m-phenylenedioxy)cyphthalic dianhydride, 2,3.6.7-naphthalenetetra Carboxylic dianhydride, L4,5.8-Naphthalenetetracarboxylic dianhydride, 1,2,5.6-
Naphthalenetetracarboxylic dianhydride, 1,2,3.4
-Hensentetracarboxylic dianhydride, 3,4,9.1
0-perylenetetracarboxylic dianhydride, 2,3,6.
7-anthracenetetracarboxylic dianhydride, 1,2,
7,8-phenanthrenetetracarboxylic dianhydride, etc., and these tetracarboxylic dianhydrides may be used alone or in a mixture of two or more.
本発明のポリフェニレンスルフィド系樹脂組成物は、前
記ポリフェニレンスルフィド１００重量部に対し、上記
ポリエーテルイミドＩ重量部以上１００重量部未満の範
囲で使用される。The polyphenylene sulfide resin composition of the present invention is used in an amount of at least 100 parts by weight of the polyetherimide I based on 100 parts by weight of the polyphenylene sulfide.
ポリフェニレンスルフィドの物性、特に耐熱性を向上さ
せるにはポリエーテルイミドは通常ポリスルホン１００
重量部に対し１重量部好ましくは５重量部以上で効果が
ある。しかし１００重量部以上使用すると、ポリフェニ
レンスルフィドが有する良好な成形性が失われるので１
００重量部未満の範囲で使用するのが好ましい。To improve the physical properties of polyphenylene sulfide, especially its heat resistance, polyetherimide is usually treated with polysulfone 100.
It is effective to use 1 part by weight, preferably 5 parts by weight or more. However, if more than 100 parts by weight is used, the good moldability of polyphenylene sulfide will be lost.
It is preferable to use less than 0.00 parts by weight.
また本発明で用いられるポリエーテルイミドは従来のポ
リイミド樹脂に比較して、耐熱性および物理的特性は略
同等であるが、流動特性が優れている為、ポリフェニレ
ンスルフィドに併用することにより上記の効果かえられ
るものである。In addition, the polyetherimide used in the present invention has almost the same heat resistance and physical properties as conventional polyimide resins, but has superior flow properties, so when used in combination with polyphenylene sulfide, the above effects can be achieved. It is something that can be changed.
本発明による組成物を混合調製するにあたっては、通常
公知の方法により製造できるが、例えば次に示す方法な
どは好ましい方法である。The composition according to the present invention can be mixed and prepared by commonly known methods, but the following methods are preferred, for example.
（１）ポリフェニレンスルフィト粉末とポリエーテルイ
ミド粉末とを乳鉢、ヘンシェルミキサー、ドラムブレン
ター、タンブラープレンダー、ボールミルリボンブレン
ダーなどを利用して予（ｆＮｍＨし粉状とする。(1) Polyphenylene sulfite powder and polyetherimide powder are ground into powder using a mortar, a Henschel mixer, a drum blender, a tumbler blender, a ball mill ribbon blender, or the like.
（２）ポリエーテルイミド粉末をあらかじめ有機溶媒に
溶解あるいは懸濁させ、この溶液あるいは懸濁液にポリ
フェニレンスルフィドを添加し、均一に分散または溶解
させた後、ン容媒を除去して粉状とする。(2) Polyetherimide powder is dissolved or suspended in an organic solvent in advance, polyphenylene sulfide is added to this solution or suspension, and after uniformly dispersing or dissolving, the medium is removed to form a powder. do.
（３＋ 本発明のポリエーテルイミドの前駆体であるポ
リアミド酸の有ａ溶媒溶液に、ポリフェニレンスルフィ
ドを？客筋または懸濁させた後、１００〜４００°Ｃに
加熱処理するか、または通常用いられるイミド化剤を用
いて化学イミド化した後、溶剤を除去して粉状とする。(3+ After suspending polyphenylene sulfide in an aqueous solvent solution of polyamic acid, which is a precursor of the polyetherimide of the present invention, heat treatment is performed at 100 to 400°C, or After chemical imidization using an imidization agent, the solvent is removed to form a powder.
このようにして得られた粉状の樹脂組成物は、そのまま
各種成形用途、すなわち射出成形、圧縮成形、トランス
ファー成形、押出成形などに用いられるが、熔融ブレン
ドしてから用いるのはさらに好ましい方法である。こと
に前記組成物を混合調製するに当たり、ベレット同志、
あるいは粉末とペレットを溶融するのも、簡易で有効な
方法である。The powdered resin composition thus obtained can be used as it is for various molding purposes, such as injection molding, compression molding, transfer molding, and extrusion molding, but it is more preferable to use it after melt-blending. be. In particular, in mixing and preparing the said composition, Comrade Berrett,
Alternatively, melting powder and pellets is a simple and effective method.
溶融ブレンドには通常のゴム、またはプラスチック類を
溶融ブレンドするのに用いられる装置、例えば熱ロール
、バンバリーミキサ−、プラヘンダー、押出機などを利
用することができる。溶融温度は配合系が溶融可能な温
度以上で、かつ配合系が熱分解し始める温度以下に設定
されるが、その温度は通常２８０〜４２０℃、好ましく
は３００〜４００°Ｃである。For the melt blending, devices commonly used for melt blending rubbers or plastics, such as hot rolls, Banbury mixers, pla-henders, extruders, etc., can be used. The melting temperature is set above the temperature at which the blended system can be melted and below the temperature at which the blended system begins to thermally decompose, and the temperature is usually 280 to 420°C, preferably 300 to 400°C.
本発明の樹脂組成物の成形方法としては、均一溶融ブレ
ンド体を形成し、かつ生産性の高い成形方法である押出
成形または押出成形が好適であるが、その他のトランス
ファー成形、圧縮成形、焼結成形、押出しフィルム成形
などを適用してもなんらさしつかえない。As a method for molding the resin composition of the present invention, extrusion molding or extrusion molding, which forms a homogeneous melt blend and has high productivity, is suitable, but other methods such as transfer molding, compression molding, and sintering are suitable. There is no problem in applying shapes, extrusion film molding, etc.
なお、本発明の樹脂組成物に対して固体潤滑剤、例えば
二硫化モリブデン、グラファイト、窒化ホウ素、−酸化
鉛、鉛粉などを一種以上添加することができる。また補
強剤、例えばガラス繊維、炭素繊維、芳香族ポリアミド
、炭化ケイ素繊維、チタン酸カリウム繊維、ガラスピー
ズを一種以上添加することもできる。In addition, one or more solid lubricants such as molybdenum disulfide, graphite, boron nitride, lead oxide, lead powder, etc. can be added to the resin composition of the present invention. It is also possible to add one or more types of reinforcing agents, such as glass fibers, carbon fibers, aromatic polyamides, silicon carbide fibers, potassium titanate fibers, and glass peas.
なお本発明の樹脂組成物に対して、本発明の目的をそこ
なわない範囲で、酸化防止剤、熱安定剤、紫外線吸収剤
、難燃性剤、難燃助剤、帯電防止剤、滑剤、着色剤など
の通常の添加剤を一種以上添加
添加することができる。In addition, to the resin composition of the present invention, antioxidants, heat stabilizers, ultraviolet absorbers, flame retardants, flame retardant aids, antistatic agents, lubricants, One or more conventional additives such as colorants can be added.
以下、本発明を合成例、実施例および比較例によりさら
に詳細に説明する。Hereinafter, the present invention will be explained in more detail with reference to Synthesis Examples, Examples, and Comparative Examples.
合成例１
かきまぜ機、還流冷却器および窒素導入管を備えた反応
容器に４．４゛−ビス（３−アミノフェノキシ）ジフェ
ニルスルフィド４．０ｋｇ（１０モル）と、Ｎ、Ｎ−ジ
メチルアセトアミド３４．８ｋｇを装入し、室温で窒素
雰囲気下にピロメリット酸二無水物２．１４Ｋｇ（９，
８モル）を溶液温度の上昇に注意しながら加え、室温で
約２０時間かきまぜた。Synthesis Example 1 In a reaction vessel equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube, 4.0 kg (10 mol) of 4.4-bis(3-aminophenoxy) diphenyl sulfide and 34.0 kg of N,N-dimethylacetamide were placed. 8 kg of pyromellitic dianhydride (2.14 kg of pyromellitic dianhydride (9,
8 mol) was added while being careful not to increase the solution temperature, and the mixture was stirred at room temperature for about 20 hours.
このポリアミド酸溶液に、室温で窒素雰囲気下に２．０
２Ｋｇ（２０モル）のトリエチルアミンおよび２゜５５
ｈ（２５モル）の無水酢酸を滴下し、室温で２０時間か
きまぜて、黄色スラリーを得た。このスラリーを濾別し
、淡黄色ポリエーテルイミドを得た。Add 2.0% to this polyamic acid solution at room temperature under a nitrogen atmosphere.
2 Kg (20 moles) of triethylamine and 2°55
h (25 mol) of acetic anhydride was added dropwise and stirred at room temperature for 20 hours to obtain a yellow slurry. This slurry was filtered to obtain pale yellow polyetherimide.
このポリエーテルイミド粉をメタノールでスラッジした
後濾別し、１８０°Ｃで８時間減圧乾燥して５゜６３Ｋ
ｇ（収率約９７．５％）のポリエーテルイミド扮を得た
。This polyetherimide powder was sludged with methanol, filtered, and dried under reduced pressure at 180°C for 8 hours to a temperature of 5°63K.
g (yield: about 97.5%) of polyetherimide was obtained.
このポリエーテルイミド粉末の対数粘度は０．８５ｄｌ
／ｇであった。ここに対数粘度はポリエーテルイミド粉
末０．５ｇをｐ−クロロフェノール、フェノール混合溶
媒（９０： １０重量比）に加熱溶解した後、３５℃に
冷却して測定した値である。（以下に示す値も同し方法
で測定した）。The logarithmic viscosity of this polyetherimide powder is 0.85 dl
/g. Here, the logarithmic viscosity is a value measured by heating and dissolving 0.5 g of polyetherimide powder in a mixed solvent of p-chlorophenol and phenol (90:10 weight ratio) and then cooling the solution to 35°C. (The values shown below were also measured using the same method).
実施例１〜４
合成例１で得られたポリエーテルイミド粉末と、ポリフ
ェニレンスルフィド粉末（フィリップス社製″ライドン
Ｐ−４”）を表−１のように各種の組成割合でトライブ
レンドした後、圧縮比３．０／１．０のスクリューを備
えた口径４０闘押出機（処理温度３２０〜３４０℃）で
溶融混練しながら押出して均一配合ペレットを得た。Examples 1 to 4 The polyetherimide powder obtained in Synthesis Example 1 and polyphenylene sulfide powder (“Rydon P-4” manufactured by Philips) were triblended at various composition ratios as shown in Table 1, and then compressed. The mixture was extruded using a 40-diameter extruder (processing temperature: 320 to 340°C) equipped with a screw ratio of 3.0/1.0 while melt-kneading to obtain uniformly blended pellets.
次に、この均一配合ペレット、を通常の射出成形機によ
り、成形温度３５０〜３９０℃、金型温度１５０℃で射
出成形し、成形物の物理的、熱的性質および耐薬品性を
測定した。結果を表−１に示す。Next, this uniformly mixed pellet was injection molded using a conventional injection molding machine at a molding temperature of 350 to 390°C and a mold temperature of 150°C, and the physical and thermal properties and chemical resistance of the molded product were measured. The results are shown in Table-1.
表−１中、引張強度および破断伸度はＡＳＴＭ Ｄ−６
３日、曲げ強度及び曲げ弾性率ばＡＳＴＭ Ｄ−７９０
、アイゾツト衝撃値はＡＳＴＭ Ｄ−２５６、ガラス転
移温度はＴ肛針人法、熱変形温度はＡＳＴＭ Ｄ−６４
８に拠る。In Table 1, tensile strength and elongation at break are ASTM D-6.
3 days, bending strength and bending modulus ASTM D-790
, Izod impact value is ASTM D-256, glass transition temperature is T-shaped, heat distortion temperature is ASTM D-64.
Based on 8.
比較例１〜２
本発明の範囲外のものを用い、実施例１〜４と同様の操
作で得た成形物の物理的、熱的性質を測定した。結果を
表−１に併せて示す。Comparative Examples 1-2 The physical and thermal properties of molded products obtained in the same manner as in Examples 1-4 were measured using materials outside the scope of the present invention. The results are also shown in Table-1.
合成例２〜５
合成例１と同様の反応容器で下記原料を用い、合成例１
と同様の方法により各ポリエーテルイミド粉末を得た。Synthesis Examples 2 to 5 Synthesis Example 1 was carried out using the following raw materials in the same reaction vessel as in Synthesis Example 1.
Each polyetherimide powder was obtained in the same manner as above.
合成例２
４．４゛−ビス（３−アミノフェノキシ）ビフェニル
３．６８Ｋｇ（１０モル）３．３″、４
．４″ −ヘンシフエノンテトラカルボン酸二無水物
３．１ｆｌ＋Ｋｇ（９，８５モル）より対数粘度
０．６２ｄｌ／ｇのポリエーテルイミド粉末をえた。Synthesis example 2 4.4゛-bis(3-aminophenoxy)biphenyl
3.68Kg (10mol) 3.3″, 4
．． 4″-hensiphenotetracarboxylic dianhydride
A polyetherimide powder having a logarithmic viscosity of 0.62 dl/g was obtained from 3.1 fl+Kg (9.85 mol).
合成例３
４．４′−ビス（３−アミノフェノキシ）ビフェニル表
−１
３，６８Ｋｇ（１０モル）
ピロメリット酸二無水物２．１２５Ｋｇ（９，７５モル
）より対数粘度０．７０ｄｌ／ｇのポリエーテルイミド
粉末をえた。Synthesis Example 3 4.4'-Bis(3-aminophenoxy)biphenyl Table 1 3,68 Kg (10 moles) From 2.125 Kg (9,75 moles) of pyromellitic dianhydride, a compound with a logarithmic viscosity of 0.70 dl/g Obtained polyetherimide powder.
合成例４
４．４′−ビス（３−アミノフェノキシ）ジフェニルス
ルフィド ３．６Ｋｇ（９，０モル）４
．４゛−ジアミノジフェニルエーテル２．２（１２Ｋｇ
（１，０モル）
ピロメリット酸二無水物 ２．１１Ｋｇ（９，７モル）
より対数粘度０．７８ｃｌｌ／ｇのポリエーテルイミド
粉末をえた。Synthesis Example 4 4.4'-bis(3-aminophenoxy)diphenyl sulfide 3.6Kg (9.0mol)4
．． 4′-diaminodiphenyl ether 2.2 (12Kg
(1.0 mol) Pyromellitic dianhydride 2.11Kg (9.7 mol)
A polyetherimide powder having a logarithmic viscosity of 0.78 cll/g was obtained.
合成例５
４．４゛ −ビス（３−アミノフェノキシ）ビフェニ
ル ３．５Ｋｇ（９，５モル
）４．４”−ジアミノジフェニルエーテル０．１０１Ｋ
ｇ（０，５モル）
ピロメリット酸二無水物 ２．１０Ｋｇ（９，６５モル
）より対数粘度０．７２ｄｌ／ｇのポリエーテルイミド
粉末をえた。Synthesis Example 5 4.4''-bis(3-aminophenoxy)biphenyl 3.5Kg (9.5mol) 4.4''-diaminodiphenyl ether 0.101K
A polyetherimide powder having a logarithmic viscosity of 0.72 dl/g was obtained from 2.10 kg (9.65 mol) of pyromellitic dianhydride.
実施例５〜１５
合成例２〜７で得られたポリエーテルイミド粉末とポリ
フェニレンスルフィド粉末（フィリップス社製″ライド
ンＰ−４”）を表−２〜表−５に示すように各種の組成
割合でトライブレンドした後、実施例１〜４と同様にペ
レット化し、引き続き成形し、その熱的性質及び機械強
度を測定し、表−２〜表−５に示す結果をえた。Examples 5 to 15 The polyetherimide powder and polyphenylene sulfide powder ("Rydon P-4" manufactured by Philips) obtained in Synthesis Examples 2 to 7 were mixed in various composition ratios as shown in Tables 2 to 5. After triblending, the pellets were formed into pellets in the same manner as in Examples 1 to 4, and subsequently molded. The thermal properties and mechanical strength of the pellets were measured, and the results shown in Tables 2 to 5 were obtained.
表−１〜表−５の結果に示すようにポリフェニレンスル
フィド１００重量部に対しポリエーテルイミド１〜１０
０重量部の範囲で使用することにより、ポリフェニレン
スルフィドが有する良好な成形性を維持しながら、耐熱
性及び機械的性質などの緒特性が改善されていることが
理解できる。As shown in the results of Tables 1 to 5, 1 to 10 parts of polyetherimide was added to 100 parts by weight of polyphenylene sulfide.
It can be seen that by using within the range of 0 parts by weight, properties such as heat resistance and mechanical properties are improved while maintaining the good moldability of polyphenylene sulfide.
本発明におけるポリフェニレンスルフィド系樹脂組成物
はポリフェニレンスルフィドが木来有する特性に加え、
耐薬品性、耐熱性および機械的強度等を著しく改良した
ものであり、宇宙航空用機器、電子・電気Ｒ器、自動車
、精密機器、一般機表−２
表−３
＊リ 最イ鞘１出圧力か俣出Ｉ−１根４υＫｇ／ｃｍ′
七ｒ凹る。The polyphenylene sulfide resin composition of the present invention has the characteristics that polyphenylene sulfide has,
It has significantly improved chemical resistance, heat resistance, mechanical strength, etc., and is suitable for aerospace equipment, electronic/electrical equipment, automobiles, precision equipment, and general machinery. Pressure output I-1 root 4υKg/cm'
Seven r concave.
表−４
表−５
２今
器等広い分野において有用であり、その産業上の効果は
大きい。Table 4 Table 5 2 It is useful in a wide range of fields, such as modern equipment, and its industrial effects are great.
Claims (2)
次式（ I ） ▲数式、化学式、表等があります▼（ I ） （式中、Ｘは直結、炭素数１乃至１０の２価の炭化水素
基、六フッ素化されたイソプロピリデン基、カルボニル
基、チオ基、またはスルホニル基から成る群より選ばれ
た基を表し、Ｒ＿１〜Ｒ＿４は水素、低級アルキル基、
低級アルコキシ基、塩素または臭素を示し、互いに同じ
であっても異なっていてもよい。 Ｙは炭素数２以上の脂肪族基、環式脂肪族基、単環式芳
香族基、縮合多環式芳香族基、芳香族が直接又は架橋員
により相互に連結された非縮合多環式芳香族基から成る
群より選ばれた４価の基を表す） で示される繰り返し単位を有するポリエーテルイミド１
重量部以上１００重量部未満よりなるポリフェニレンス
ルフィド系樹脂組成物。(1) For 100 parts by weight of polyphenylene sulfide,
The following formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, X is a direct bond, a divalent hydrocarbon group having 1 to 10 carbon atoms, a hexafluorinated isopropylidene group, a carbonyl group , a thio group, or a sulfonyl group, and R_1 to R_4 are hydrogen, a lower alkyl group,
It represents a lower alkoxy group, chlorine or bromine, and may be the same or different. Y is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a fused polycyclic aromatic group, or a non-fused polycyclic group in which aromatics are interconnected directly or through a bridge member. Polyetherimide 1 having a repeating unit represented by (representing a tetravalent group selected from the group consisting of aromatic groups)
A polyphenylene sulfide resin composition comprising at least 100 parts by weight.
学式、表等があります▼（II） の繰り返し単位よりなる特許請求の範囲第一項記載の樹
脂組成物。(2) The resin composition according to claim 1, wherein the polyphenylene sulfide is a repeating unit of the formula (II) (which has a mathematical formula, chemical formula, table, etc.).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14687087A JPH0678488B2 (en) | 1987-06-15 | 1987-06-15 | Polyphenylene sulfide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14687087A JPH0678488B2 (en) | 1987-06-15 | 1987-06-15 | Polyphenylene sulfide resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63312354A true JPS63312354A (en) | 1988-12-20 |
| JPH0678488B2 JPH0678488B2 (en) | 1994-10-05 |
Family
ID=15417429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14687087A Expired - Fee Related JPH0678488B2 (en) | 1987-06-15 | 1987-06-15 | Polyphenylene sulfide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0678488B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5380820A (en) * | 1987-05-20 | 1995-01-10 | Mitsui Toatsu Chemicals, Inc. | Polyimides, process for the preparation thereof and polyimide resin compositions |
-
1987
- 1987-06-15 JP JP14687087A patent/JPH0678488B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5380820A (en) * | 1987-05-20 | 1995-01-10 | Mitsui Toatsu Chemicals, Inc. | Polyimides, process for the preparation thereof and polyimide resin compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0678488B2 (en) | 1994-10-05 |
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