JPH0518352B2 - - Google Patents
Info
- Publication number
- JPH0518352B2 JPH0518352B2 JP29458485A JP29458485A JPH0518352B2 JP H0518352 B2 JPH0518352 B2 JP H0518352B2 JP 29458485 A JP29458485 A JP 29458485A JP 29458485 A JP29458485 A JP 29458485A JP H0518352 B2 JPH0518352 B2 JP H0518352B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- pps
- ethylene
- ethylene copolymer
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920001038 ethylene copolymer Polymers 0.000 claims description 14
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 10
- 229920000412 polyarylene Polymers 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011342 resin composition Substances 0.000 claims description 3
- 239000004734 Polyphenylene sulfide Substances 0.000 description 19
- 229920000069 polyphenylene sulfide Polymers 0.000 description 19
- 239000000203 mixture Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000000835 fiber Substances 0.000 description 9
- 239000003365 glass fiber Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- -1 and among these Chemical compound 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- 229920013632 Ryton Polymers 0.000 description 3
- 239000004736 Ryton® Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000009863 impact test Methods 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
- 229910052742 iron Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-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
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 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 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 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 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
＜産業上の利用分野＞
本発明は衝撃強度の改良されたポリアリーレン
サルフアイド樹脂組成物に関する。
＜従来技術＞
ポリフエニレンサルフアイドなどに代表される
ポリアリーレンサルフアイド樹脂は耐熱性、難燃
性、剛性、耐薬品性などのすぐれたエンジニアリ
ングプラスチツクスとして、近年とくに電気部品
や自動車部品などの用途において注目され需要を
伸ばしている。
しかし、該樹脂は、延性に乏しく、脆弱である
といつた欠点を有している。
該樹脂にガラス繊維や炭素繊維等の繊維状強化
材を配合することにより、強度、剛性、靭性、耐
熱性、寸法安定性等のエンジニアリングプラスチ
ツクスとして要求される性能が大巾に改善される
ことが知られている。しかしながら、該繊維状の
強化材の配合によつてもなお、ポリアセタール、
変性PPO、ポリサルホン、ポリエーテルサルホ
ンなど他のエンジニアリングプラスチツクスに比
べて脆弱であり、すぐれた性質を有するにもかか
わらず多くの用途への適用が制限されている。
＜発明が解決しようとする問題点＞
本発明はポリアリーレンサルフアイド樹脂の耐
熱性、剛性などの優れた特性を低下させないで脆
弱さが改良された組成物を提供することを目的と
するものである。
＜問題点を解決するための手段＞
本発明者は、上記の状況に鑑み、鋭意検討した
結果、ポリアリーレンサルフアイド樹脂に、エチ
レン、α，β−不飽和カルボン酸アルキルエステ
ルおよび無水マレイン酸からなるエチレン共重合
体を配合することにより、ポリアリーレンサルフ
アイド樹脂の上記の特性を維持し、優れた衝撃特
性を有する組成物を得ることを見出し本発明に達
した。
すなわち本発明は、(A)ポリアリーレンサルフア
イド70〜99重量％および(B)エチレン50〜90重量
％、α，β−不飽和カルボン酸アルキルエステル
５〜49重量％および無水マレイン酸0.5〜10重量
％からなるエチレン共重合体30〜１重量％からな
ることを特徴とするポリアリーレンサルフアイド
樹脂組成物に関するものである。
本発明で用いるポリアリーレンサルフアイド
は、一般式（―Ar−Ｓ）―oで表わされる重合体であ
る。ここで−Ar−は、たとえば
<Industrial Application Field> The present invention relates to a polyarylene sulfide resin composition with improved impact strength. <Prior art> Polyarylene sulfide resins, such as polyphenylene sulfide, have been used as engineering plastics with excellent heat resistance, flame retardance, rigidity, and chemical resistance, and have recently been used particularly for electrical parts and automobile parts. It is attracting attention for its uses and demand is increasing. However, this resin has drawbacks such as poor ductility and brittleness. By blending fibrous reinforcing materials such as glass fiber and carbon fiber with the resin, the properties required for engineering plastics, such as strength, rigidity, toughness, heat resistance, and dimensional stability, are greatly improved. It has been known. However, even with the addition of the fibrous reinforcing material, polyacetal,
It is more fragile than other engineering plastics such as modified PPO, polysulfone, and polyethersulfone, which limits its application to many applications despite its excellent properties. <Problems to be Solved by the Invention> The object of the present invention is to provide a composition with improved brittleness without reducing the excellent properties such as heat resistance and rigidity of polyarylene sulfide resin. be. <Means for Solving the Problems> In view of the above-mentioned circumstances, the inventors of the present invention have made extensive studies and found that polyarylene sulfide resin contains ethylene, α,β-unsaturated carboxylic acid alkyl ester, and maleic anhydride. The present inventors have discovered that by blending an ethylene copolymer, it is possible to maintain the above-mentioned properties of polyarylene sulfide resin and obtain a composition having excellent impact properties. That is, the present invention comprises (A) 70-99% by weight of polyarylene sulfide and (B) 50-90% by weight of ethylene, 5-49% by weight of α,β-unsaturated carboxylic acid alkyl ester, and 0.5-10% by weight of maleic anhydride. The present invention relates to a polyarylene sulfide resin composition characterized by comprising 30 to 1% by weight of an ethylene copolymer. The polyarylene sulfide used in the present invention is a polymer represented by the general formula (-Ar-S) -o . Here −Ar− is, for example,
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】
などの少なくとも１つの炭素６員環を含む２価の
芳香族残基であり、さらに各芳香環に、Ｆ，Cl，
Br，CH3などの置換基が導入されることもある。
特に曲型的なポリアリーレンサルフアイド（以
下PPSと略称する）は一般式A divalent aromatic residue containing at least one carbon 6-membered ring such as [Formula], and each aromatic ring further includes F, Cl,
Substituents such as Br and CH 3 may also be introduced. In particular, curved polyarylene sulfide (hereinafter abbreviated as PPS) has the general formula
【式】
で表わされるポリフエニレンサルフアイドであ
り、これは米国フイリツプスペトローリアム社よ
り、“ライトン”の商標で一般に市販されている。
その製造方法は米国特許第3354129号明細書およ
びそれに対応する特公昭45−3368号公報に開示さ
れており、Ｎ−メチルピロリドン溶媒中160〜250
℃、加圧条件下にパラジクロルベンゼン
It is a polyphenylene sulfide represented by the formula: ##STR2## and is generally commercially available from Phillips Petroleum Company of the United States under the trademark "Ryton."
The method for its production is disclosed in U.S. Pat.
°C, paradichlorobenzene under pressure conditions
【式】と硫化ソーダ（Na2S・
H2O）を反応させることにより製造することが
できる。また、特公昭52−12240号公報、特公昭
53−25588号公報および特公昭53−25589号公報に
開示されているように酢酸リチウムまたは塩化リ
チウムなどの触媒を併用するとさらに高重合度化
したPPSを製造することもできる。
本発明で使用されるエチレン共重合体は、その
単量体成分が、エチレン、α，β−不飽和カルボ
ン酸アルキルエステル、および無水マレイン酸か
ら成り、エチレンが50〜90重量％、好ましくは60
〜85重量％、α，β−不飽和カルボン酸アルキル
エステルが５〜49重量％、好ましくは７〜45重量
％、および無水マレイン酸が0.5〜10重量％、好
ましくは１〜８重量％である。
α，β−不飽和カルボン酸アルキルエステル
は、炭素数が３〜８個の不飽和カルボン酸、例え
ば、アクリル酸、メタクリル酸などのアルキルエ
ステルであつて、具体例としては、アクリル酸メ
チル、アクリル酸エチル、アクリル酸ｎ−プロピ
ル、アクリル酸イソプロピル、アクリル酸ｎ−ブ
チル、アクリル酸ｔ−ブチル、アクリル酸イソブ
チル、メタクリル酸メチル、メタクリル酸エチ
ル、メタクリル酸ｎ−プロピル、メタクリル酸イ
ソプロピル、メタクリル酸ｎ−ブチル、メタクリ
ル酸ｔ−ブチル、およびメタクリル酸イソブチル
などがあり、これらのうちでも特に、アクリル酸
エチル、アクリル酸ｎ−ブチル、メタクリル酸メ
チルが好ましい。
これらエチレン共重合体をPPSへ配合する量
は、PPSとエチレン共重合体の合計量に対して、
PPS70〜99重量％、エチレン共重合体30〜１重量
％が適当であり、PPSが99重量％を越え、該エチ
レン共重合体が１重量％未満の場合には、目的と
する脆弱さを改良する効果が不十分である。また
PPSが70重量％未満、エチレン共重合体が30重量
％を越えた場合には、PPSの特徴である耐熱性、
剛性の低下が著しく、好ましくない。
本発明の組成物の配合手段は特に限定されな
い。PPS、エチレン共重合体を各々別々に溶融混
合機に供給することが可能であり、またあらかじ
めこれら原料類を乳鉢、ヘンシエルミキサー、ボ
ールミル、リボンブレンダーなどを利用して予備
混合してから溶融混合機に供給することもでき
る。
なお、本発明組成物に対して、本発明の目的を
そこなわない範囲で、酸化防止剤および熱安定
剤、紫外線吸収剤、滑剤、離型剤、染料、顔料な
どの着色剤、難燃剤、難燃助剤、帯電防止剤、結
晶化促進剤などの通常の添加剤を１種以上添加す
ることができる。
また、少量の他の熱可塑性樹脂（例えばポリエ
チレン、ポリプロピレン、ポリアミド、ポリカー
ボネート、ポリサルホン、ポリエーテルサルホ
ン、変性ポリフエニレンオキサイドなど）、熱硬
化性樹脂（例えばフエノール樹脂、エポキシ樹脂
など）を１種以上添加することができる。
さらに、ガラス繊維、カーボン繊維、ボロン繊
維、炭化ケイ素繊維、アスベスト繊維、金属繊維
などの補強剤、クレー、マイカ、シリカ、グラフ
アイト、ガラスビーズ、アルミナ、炭酸カルシウ
ムなどの充填剤を配合することも可能である。
特に、ガラス繊維またはカーボン繊維はその充
填による剛性度の向上、耐熱性の向上効果が顕著
であり、より有用な組成物を提供するため、全組
成物に対して10〜60wt％の範囲で充填すること
が好ましい。該繊維は直径５〜15μで長さ３〜８
mmの単繊維を数百〜数千本集束したチヨツプドス
トランドやチヨツプドフアイバーもしくは長繊維
であるロービングを用い、最終組成物中に平均繊
維長が0.15〜0.5mmの範囲となるよう均一に分散
させることが好ましい。
以下、実施例により本発明を説明するが、これ
らは単なる例示であり、本発明はこれに限定され
ることはない。
実施例 １〜３
ポリフエニレンサルフアイド（フイリツプスペ
トローリアム社製、“ライトン”PPS Ｐ−４）と
エチレン67％、アクリル酸エチル30.5％および無
水マレイン酸2.5％から成るエチレン共重合体を
第１表に示した組成物で混合し、二軸押出機（池
貝鉄工製PCM−30）により、280℃の温度で溶融
混練した後、ストランドを水冷、切断してペレツ
トを得た。
得られたペレツトを射出成形（住友重機−ネス
タール47／28射出成形機、シリンダー温度310℃、
金型温度130℃）し、アイゾツト衝撃試験片、曲
げ試験片、熱変形温度測定用試験片を得た。
それぞれASTM Ｄ−256、Ｄ−790、Ｄ−648
に従つて測定した。（結果を第１表に示す。）いず
れもすぐれた値が得られている。
比較例 １〜２
実施例１〜３に用いたPPSとエチレン共重合体
を第１表に示した割合で混合し、実施例１〜３と
同様の加工を行い物性を測定した。（結果を第１
表に示す。）実施例に比較して、著しく劣つてい
る。It can be produced by reacting [Formula] with sodium sulfide (Na 2 S/H 2 O). Also, Special Publication No. 52-12240, Special Publication No.
As disclosed in Japanese Patent Publication No. 53-25588 and Japanese Patent Publication No. 53-25589, when a catalyst such as lithium acetate or lithium chloride is used in combination, PPS with a higher degree of polymerization can be produced. The monomer components of the ethylene copolymer used in the present invention are ethylene, α,β-unsaturated carboxylic acid alkyl ester, and maleic anhydride, and ethylene is 50 to 90% by weight, preferably 60% by weight.
~85% by weight, α,β-unsaturated carboxylic acid alkyl esters from 5 to 49%, preferably 7 to 45%, and maleic anhydride from 0.5 to 10%, preferably 1 to 8% by weight. . The α,β-unsaturated carboxylic acid alkyl ester is an alkyl ester of an unsaturated carboxylic acid having 3 to 8 carbon atoms, such as acrylic acid and methacrylic acid. Specific examples include methyl acrylate, acrylic acid, etc. Ethyl acid, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-methacrylate -butyl, t-butyl methacrylate, and isobutyl methacrylate, and among these, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are particularly preferred. The amount of these ethylene copolymers to be added to PPS is based on the total amount of PPS and ethylene copolymer.
70-99% by weight of PPS and 30-1% by weight of ethylene copolymer are suitable; if PPS exceeds 99% by weight and the ethylene copolymer is less than 1% by weight, the desired brittleness is improved. The effects of this are insufficient. Also
If PPS is less than 70% by weight and ethylene copolymer is more than 30% by weight, the heat resistance, which is a characteristic of PPS,
This is not preferable because the rigidity is significantly reduced. The means of blending the composition of the present invention is not particularly limited. It is possible to feed PPS and ethylene copolymer separately to the melt mixer, or these raw materials can be premixed in advance using a mortar, Henschel mixer, ball mill, ribbon blender, etc. and then melt mixed. It can also be supplied to machines. The composition of the present invention may contain antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, mold release agents, colorants such as dyes and pigments, flame retardants, One or more conventional additives such as flame retardant aids, antistatic agents, crystallization promoters, etc. can be added. In addition, a small amount of other thermoplastic resin (e.g., polyethylene, polypropylene, polyamide, polycarbonate, polysulfone, polyethersulfone, modified polyphenylene oxide, etc.) or thermosetting resin (e.g., phenol resin, epoxy resin, etc.) or more can be added. Furthermore, reinforcing agents such as glass fiber, carbon fiber, boron fiber, silicon carbide fiber, asbestos fiber, and metal fiber, and fillers such as clay, mica, silica, graphite, glass beads, alumina, and calcium carbonate can be added. It is possible. In particular, filling glass fiber or carbon fiber has a remarkable effect of improving rigidity and heat resistance, and in order to provide a more useful composition, fill it in the range of 10 to 60 wt% based on the total composition. It is preferable to do so. The fibers have a diameter of 5-15μ and a length of 3-8
By using chopped strands, chopped fibers, or long fiber rovings made by bundling hundreds to thousands of mm single fibers, the average fiber length is in the range of 0.15 to 0.5 mm in the final composition. It is preferable to disperse it evenly. The present invention will be described below with reference to Examples, but these are merely illustrative and the present invention is not limited thereto. Examples 1 to 3 An ethylene copolymer consisting of polyphenylene sulfide (“Ryton” PPS P-4, manufactured by Phillips Petroleum) and 67% ethylene, 30.5% ethyl acrylate and 2.5% maleic anhydride was prepared. The compositions shown in Table 1 were mixed and melted and kneaded using a twin screw extruder (PCM-30 manufactured by Ikegai Iron Works) at a temperature of 280°C. The strands were water-cooled and cut to obtain pellets. The obtained pellets were injection molded (Sumitomo Heavy Industries - Nestal 47/28 injection molding machine, cylinder temperature 310℃,
The mold temperature was 130°C) to obtain Izotsu impact test pieces, bending test pieces, and heat distortion temperature measurement test pieces. ASTM D-256, D-790, D-648 respectively
Measured according to. (The results are shown in Table 1.) Excellent values were obtained in all cases. Comparative Examples 1-2 The PPS and ethylene copolymer used in Examples 1-3 were mixed in the proportions shown in Table 1, processed in the same manner as in Examples 1-3, and measured for physical properties. (Results first
Shown in the table. ) Significantly inferior to Examples.
【表】
実施例 ４〜５
ポリフエニレンサルフアイド（フイリツプスペ
トローリアム社製“ライトン”PPS Ｐ−６）、エ
チレン75.5％、アクリル酸エチル22.5％および無
水マレイン酸2.0％からなるエチレン共重合体お
よびガラス繊維（旭フアイバーグラス社製CS03
−MA497、長さ３mmのチヨツプドストランド）
を第２表に示した組成で混合し、二軸押出機（池
貝鉄工製PCM−30）により、290℃の温度で溶融
混練した後、ストランドを水冷、切断してペレツ
トを得た。
得られたペレツトを射出成形（住友重機−ネス
タール47／28射出成形機、シリンダー温度320℃、
金型温度130℃）し、アイゾツト衝撃試験片、曲
げ試験片、熱変形温度測定用試験片を得た。それ
ぞれASTM Ｄ−256、Ｄ−790、Ｄ−648に従つ
て測定した。（結果を第２表に示す。）いずれも高
い値が得られている。
比較例 ３
実施例４〜５に用いたPPSとガラス繊維を第２
表に示した割合で混合し、実施例４〜５と同様の
加工を行い、物性を測定した。（結果を第２表に
示す。）実施例に比較して、著しく劣つている。[Table] Examples 4-5 Ethylene copolymer consisting of polyphenylene sulfide (“Ryton” PPS P-6 manufactured by Phillips Petroleum), 75.5% ethylene, 22.5% ethyl acrylate and 2.0% maleic anhydride and glass fiber (CS03 manufactured by Asahi Fiberglass Co., Ltd.)
−MA497, chopped strand with a length of 3 mm)
were mixed in the composition shown in Table 2, melted and kneaded at a temperature of 290°C using a twin screw extruder (PCM-30 manufactured by Ikegai Iron Works), and then the strands were cooled with water and cut to obtain pellets. The obtained pellets were injection molded (Sumitomo Heavy Industries - Nestal 47/28 injection molding machine, cylinder temperature 320℃,
The mold temperature was 130°C), and an Izot impact test piece, a bending test piece, and a test piece for measuring heat distortion temperature were obtained. Measurements were made according to ASTM D-256, D-790, and D-648, respectively. (The results are shown in Table 2.) High values were obtained in all cases. Comparative Example 3 The PPS and glass fiber used in Examples 4 and 5 were
They were mixed in the proportions shown in the table, processed in the same manner as in Examples 4 and 5, and measured for physical properties. (The results are shown in Table 2.) Compared to the Examples, it is significantly inferior.
【表】
＜発明の効果＞
本発明のポリフエニレンサルフアイド樹脂にエ
チレン、α，β−不飽和カルボン酸アルキルエス
テルおよび無水マレイン酸からなるエチレン共重
合体を配合した組成物は、ポリフエニレンサルフ
アイド樹脂の耐熱性、剛性を低下させないで、脆
弱さが顕著に改良されたものである。[Table] <Effects of the Invention> A composition in which the polyphenylene sulfide resin of the present invention is blended with an ethylene copolymer consisting of ethylene, an α,β-unsaturated carboxylic acid alkyl ester, and maleic anhydride is a polyphenylene sulfide resin. The fragility is significantly improved without reducing the heat resistance and rigidity of the fied resin.
Claims (1)
％および (B) エチレン50〜90重量％、α，β−不飽和カル
ボン酸アルキルエステル５〜49重量％および無
水マレイン酸0.5〜10重量％からなるエチレン
共重合体30〜１重量％ からなることを特徴とする樹脂組成物。[Scope of Claims] 1 (A) 70-99% by weight of polyarylene sulfide and (B) 50-90% by weight of ethylene, 5-49% by weight of α,β-unsaturated carboxylic acid alkyl ester and 0.5% by weight of maleic anhydride. A resin composition comprising 30 to 1% by weight of an ethylene copolymer comprising 10% by weight.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29458485A JPS62151460A (en) | 1985-12-26 | 1985-12-26 | Polyarylene sulfide resin composition |
| PCT/JP1987/000447 WO1989000181A1 (en) | 1985-12-26 | 1987-06-30 | Polyarylene sulfide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29458485A JPS62151460A (en) | 1985-12-26 | 1985-12-26 | Polyarylene sulfide resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62151460A JPS62151460A (en) | 1987-07-06 |
| JPH0518352B2 true JPH0518352B2 (en) | 1993-03-11 |
Family
ID=17809668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29458485A Granted JPS62151460A (en) | 1985-12-26 | 1985-12-26 | Polyarylene sulfide resin composition |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS62151460A (en) |
| WO (1) | WO1989000181A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0653848B2 (en) * | 1986-01-23 | 1994-07-20 | 東レ株式会社 | Polyphenylene sulfide composition |
| JPH0826221B2 (en) * | 1987-09-14 | 1996-03-13 | 呉羽化学工業株式会社 | Polyarylene thioether composition and molded article thereof |
| US5270375A (en) * | 1988-11-04 | 1993-12-14 | Mitsubishi Rayon Co., Ltd. | Polyarylene sulfide resin |
| US5219920A (en) * | 1988-11-04 | 1993-06-15 | Mitsubishi Rayon Co., Ltd. | Polyarylene sulfide resin composition |
| KR930008743B1 (en) * | 1989-07-05 | 1993-09-13 | 아사히가세이고오교 가부시끼가이샤 | Polyphenylene sulfide resin composition |
| US5087666A (en) * | 1990-07-10 | 1992-02-11 | Phillips Petroleum Company | Modified poly(arylene sulfide) composition with improved impact strength and reduced shrinkage |
| US6428321B1 (en) * | 1997-12-08 | 2002-08-06 | Btio Educational Products, Inc. | Infant simulator |
| JP4307908B2 (en) | 2003-06-05 | 2009-08-05 | ポリプラスチックス株式会社 | Polyarylene sulfide resin composition and coated molded article |
| JP5029476B2 (en) * | 2008-04-15 | 2012-09-19 | 東ソー株式会社 | Polyarylene sulfide composition |
| JP6048019B2 (en) * | 2012-09-12 | 2016-12-21 | 東レ株式会社 | Polyphenylene sulfide resin composition molded article and method for producing the same |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56136847A (en) * | 1980-03-31 | 1981-10-26 | Dainippon Ink & Chem Inc | Polyarylenesulfide composition |
| JPS58154757A (en) * | 1982-03-10 | 1983-09-14 | Toray Ind Inc | Polyarylene sulfide resin composition |
| US4544700A (en) * | 1984-04-16 | 1985-10-01 | Phillips Petroleum Company | Poly(arylene sulfide) composition containing an ethylene polymer |
-
1985
- 1985-12-26 JP JP29458485A patent/JPS62151460A/en active Granted
-
1987
- 1987-06-30 WO PCT/JP1987/000447 patent/WO1989000181A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO1989000181A1 (en) | 1989-01-12 |
| JPS62151460A (en) | 1987-07-06 |
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