JPH03244658A - High impact polyester resin composition - Google Patents
High impact polyester resin compositionInfo
- Publication number
- JPH03244658A JPH03244658A JP4214890A JP4214890A JPH03244658A JP H03244658 A JPH03244658 A JP H03244658A JP 4214890 A JP4214890 A JP 4214890A JP 4214890 A JP4214890 A JP 4214890A JP H03244658 A JPH03244658 A JP H03244658A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- polyester
- component
- copolymer
- graft copolymer
- 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.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims description 16
- 229920001225 polyester resin Polymers 0.000 title claims description 4
- 239000004645 polyester resin Substances 0.000 title claims description 4
- 229920000728 polyester Polymers 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 230000009477 glass transition Effects 0.000 claims abstract description 4
- 150000003440 styrenes Chemical class 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- -1 acrylic ester Chemical class 0.000 abstract description 19
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 abstract 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 9
- 239000002253 acid Substances 0.000 description 6
- 125000005250 alkyl acrylate group Chemical group 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 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
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-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
- YJGUVTBNQCVSQB-UHFFFAOYSA-N 2,2-diphenylpropanedioic acid Chemical compound C=1C=CC=CC=1C(C(O)=O)(C(=O)O)C1=CC=CC=C1 YJGUVTBNQCVSQB-UHFFFAOYSA-N 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101100208721 Mus musculus Usp5 gene Proteins 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
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- QEZIKGQWAWNWIR-UHFFFAOYSA-N antimony(3+) antimony(5+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Sb+3].[Sb+5] QEZIKGQWAWNWIR-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 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
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt 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
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 150000002848 norbornenes Chemical class 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、耐衝撃性および耐熱性、成形品外観の良好な
成形品を与える耐衝撃性ポリエステル樹脂組成物に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an impact-resistant polyester resin composition that provides a molded product with good impact resistance, heat resistance, and molded product appearance.
(従来の技術)
従来より、ポリエステルの靭性や剛性を向上させるため
に、ポリエステルに^SA樹脂やAES樹脂を配合した
組成物は、例えば特公平1−15533号公報および特
公平1−36857号公報より公知である。(Prior Art) Conventionally, in order to improve the toughness and rigidity of polyester, compositions in which SA resin or AES resin is blended with polyester have been disclosed, for example, in Japanese Patent Publication No. 1-15533 and Japanese Patent Publication No. 1-36857. It is more well known.
しかしながら、これらの&IItc物は、いわゆる単純
に2者がブレンドされたものであり、ノツチ付アイゾツ
ト衝撃強度の向上は期待できるが、落錘衝撃強度の改良
はほとんど行われていないのが現状である。However, these &IItc products are simply a blend of the two, and although improvements in notched isot impact strength can be expected, there is currently little improvement in falling weight impact strength. .
(発明が解決しようとする課!!り
本発明は、ポリエステルの落錘衝撃強度を改良すると共
に、引張伸度を改良し、すぐれた表面特性、耐熱性を有
し成形収縮率の少ない射出成形品を得ることを課題とす
るものである。(Issues to be solved by the invention!!) The present invention improves the falling weight impact strength of polyester, improves the tensile elongation, and provides injection molding with excellent surface properties, heat resistance, and low molding shrinkage. The challenge is to obtain goods.
(課題を解決するための手段)
本発明者らは、前記課題を解決するため鋭意検討した結
果、遂に本発明を完成するに到った。(Means for Solving the Problems) As a result of intensive studies to solve the above problems, the present inventors have finally completed the present invention.
すなわち本発明は、ポリエステル(a)、^SA#A脂
および/またはAES樹脂(b)、およびガラス転移温
度がO″Cより低いポリマーを幹とし、(メタ)アクリ
ル酸アルキル類と、スチレン類より選ばれた一種以上の
モノマーの重合体の少なくとも一部がグラフトされてい
るグラフト共重合体(c)を含有することを特徴とする
耐衝撃性ポリエステル樹脂組酸物である。That is, the present invention uses polyester (a), ^SA#A resin and/or AES resin (b), and a polymer with a glass transition temperature lower than O''C as a backbone, and alkyl (meth)acrylates and styrenes. This is an impact-resistant polyester resin combination acid product characterized by containing a graft copolymer (c) to which at least a part of a polymer of one or more selected monomers is grafted.
本発明における(a)成分であらるポリエステルは、そ
の融点が150〜300°Cのものであり、たとえば、
ポリエチレンテレフタレート、ポリプロピレンテレフタ
レート、ポリブチレンテレフタレート、ポリシクロヘキ
サンジメチレンテレフタレート、ポリオキシエトキシベ
ンゾエート、ポリエチレンナフタレート、上記ポリエス
テル構成成分と他の酸成分および/またはグリコール成
分、たとえばイソフタル酸、P−オキシ安息香酸、アジ
ピン酸、セバシン酸、ゲルタール酸、ジフェニルメタン
ジカルボン酸、ダイマー酸のような酸成分、ヘキサメチ
レングリコール、ジエチレングリコール、ネオペンチル
グリコール、ビスフェノールA1ネオペンチルグリコー
ルアルキレンオキシド付加体のような、グリコール成分
を共重合したポリエステル、芳香族ポリエステル・ポリ
エーテルブロック共重合体、芳香族ポリエステル・ポリ
ラクトンブロック共重合体、ポリアクリレート等の広義
のポリエステルが例示され、単独または、複数樹脂のブ
レンドもしくは、それらの共重合体であってもよく、特
に融点が200°C以上のものが耐熱性の点から好まし
い0通常ポリエステルは、フェノール/テトラクロロエ
タン混合溶媒(6/4重量比)中30°Cで測定して求
めた固有粘度が0.5以上であることが好ましく、更に
は、0.6以上であることが特に好ましい。The polyester that is component (a) in the present invention has a melting point of 150 to 300°C, for example,
Polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, polyoxyethoxybenzoate, polyethylene naphthalate, the above polyester components and other acid components and/or glycol components, such as isophthalic acid, P-oxybenzoic acid, Copolymerized acid components such as adipic acid, sebacic acid, geltaric acid, diphenylmethanedicarboxylic acid, and dimer acid, and glycol components such as hexamethylene glycol, diethylene glycol, neopentyl glycol, and bisphenol A1 neopentyl glycol alkylene oxide adduct. Examples include polyesters in a broad sense such as polyester, aromatic polyester/polyether block copolymers, aromatic polyester/polylactone block copolymers, and polyacrylates. In particular, polyesters with a melting point of 200°C or higher are preferable from the viewpoint of heat resistance.0 Normally, polyesters have a characteristic value determined by measurement at 30°C in a mixed solvent of phenol/tetrachloroethane (6/4 weight ratio) The viscosity is preferably 0.5 or more, and particularly preferably 0.6 or more.
次に本発明における(b)成分である45A樹脂とは、
アルキルアクリレートで変性されたスチレンとアクリロ
ニトリルの共重合体であり、アルキルアクリレートの共
重合体中の含有量は5〜50重置%である。またスチレ
ンとアクリロニトリルの比率は重量比で90 : 10
〜65 : 35が好ましく、さらに82:18〜13
:21が望ましい。Next, the 45A resin which is the component (b) in the present invention is:
It is a copolymer of styrene and acrylonitrile modified with alkyl acrylate, and the content of alkyl acrylate in the copolymer is 5 to 50% by weight. Also, the ratio of styrene and acrylonitrile is 90:10 by weight.
~65:35 is preferable, more preferably 82:18~13
:21 is desirable.
この範囲以外ではポリエステルとの相溶性が不充分とな
るばかりか、(c)成分であるグラフト共重合体との相
溶性も不充分となり、耐衝撃性、特に落錘衝撃強度の低
下が生しるので好ましくない。Outside this range, not only will the compatibility with the polyester be insufficient, but also the compatibility with the graft copolymer, which is component (c), will be insufficient, resulting in a decrease in impact resistance, especially falling weight impact strength. This is not desirable because
なお共重合体成分としてスチレン以外にα−メチルスチ
レン、ビニルトルエン等でもよい、またアクリロニトリ
ル以外にメタアクリロニトリル等が挙げられる。アクリ
レートのエステル基を構成するもとのアルコール基は1
〜6個、好ましくは1〜4個の炭素原子数を有するもの
である。In addition to styrene, α-methylstyrene, vinyltoluene, etc. may be used as the copolymer component, and in addition to acrylonitrile, methacrylonitrile and the like may be used. The original alcohol group that constitutes the ester group of acrylate is 1
~6 carbon atoms, preferably 1 to 4 carbon atoms.
次に(b)成分であるAES樹脂とは、エチレン−プロ
ブレン系ゴムで変性されたスチレンとアクリロニトリル
共重合体であり、エチレン−プロピレン系ゴムは共重合
体中で5〜50重量%である。また、スチレンとアクリ
ロニトリルの比率は重量比で90:10〜65 : 3
5が好ましく、さらに82:1B 〜73:27が望ま
しい、この範囲以外ではポリエステルとの相溶性が不充
分となるばかりか、(c) 成分であるグラフト共重合
体との相溶性も不充分となり、耐衝撃性、特に落錘衝撃
強度の低下が生じるので好ましくない。Next, the AES resin which is component (b) is a styrene and acrylonitrile copolymer modified with ethylene-propylene rubber, and the ethylene-propylene rubber accounts for 5 to 50% by weight in the copolymer. In addition, the ratio of styrene and acrylonitrile is 90:10 to 65:3 by weight.
5 is preferable, and 82:1B to 73:27 is more preferable. Outside this range, not only will the compatibility with the polyester be insufficient, but also the compatibility with the graft copolymer, which is component (c), will be insufficient. This is not preferable because it causes a decrease in impact resistance, especially falling weight impact strength.
なお共重合体成分としてスチレン以外にα−メチルスチ
レン、ビニルトルエン等でもよい、またアクリロニトリ
ル以外にメタアクリロニトリル等が挙げられる。In addition to styrene, α-methylstyrene, vinyltoluene, etc. may be used as the copolymer component, and in addition to acrylonitrile, methacrylonitrile and the like may be used.
エチレン・プロピレン系ゴムには、エチレンとプロピレ
ンの重量比が90 : 10〜20 : 80の共重合
体、またはそれに少量の非共役ジエンを共重合させたも
のが適当である。非共役ジエンとしては、アルウニルノ
ルボルネンなどのノルボルネン類、シクロペンタジェン
などの環状ジエン類、ヘキサジエンなどの脂肪族ジエン
類などいずれでもよい。As the ethylene/propylene rubber, a copolymer of ethylene and propylene having a weight ratio of 90:10 to 20:80, or a copolymer thereof with a small amount of non-conjugated diene is suitable. The non-conjugated diene may be any of norbornenes such as alunylnorbornene, cyclic dienes such as cyclopentadiene, and aliphatic dienes such as hexadiene.
次に本発明における(c) m分であるグラフト共重合
体は、ガラス転移温度がO″Cより低いポリマーを幹と
し、(メタ)アクリル酸アルキル[(アクリル酸アルキ
ル類および/またはメタクリル酸アルキル類を意味する
)と、スチレン類より選ばれた一種以上のモノマーの重
合体の少なくとも一部がグラフトされているグラフト共
重合体のことである。ガラス転移温度が0°Cより低い
ポリマー(以下ゴム成分という)としては、ブタジェン
を主体とすることが望ましいが、アクリル酸アルキル類
、例えばアクリル酸ブチル、アクリル酸エチルのような
モノマーから得られるポリマーまたはポリエチレンを主
体としたポリマーであってもよい、またグラフトされる
(メタ)アクリル酸アルキル類としては、メタクリル酸
メチル、メタクリル酸エチル、メタクリル酸ブチル、ア
クリル酸メチル、アクリル酸エチル、アクリル酸ブチル
などが挙げられ、アクリル酸アルキル類とメタクリル酸
アルキル類との共重合でもよい、その際、アクリル酸ア
ルキル類とメタクリル酸アルキル類との重量比はO:1
00〜20 : 80であることが望ましい。Next, the graft copolymer (c) in the present invention has a polymer having a glass transition temperature lower than O''C as a backbone, and has an alkyl (meth)acrylate [(alkyl acrylate and/or alkyl methacrylate)] It refers to a graft copolymer in which at least a part of a polymer of one or more monomers selected from styrenes is grafted. The rubber component (referred to as a rubber component) is preferably mainly composed of butadiene, but it may also be a polymer obtained from monomers such as alkyl acrylates, such as butyl acrylate and ethyl acrylate, or a polymer mainly composed of polyethylene. Examples of the alkyl (meth)acrylates to be grafted include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, etc. Copolymerization with alkyls may also be used, in which case the weight ratio of alkyl acrylates and alkyl methacrylates is O:1.
00-20: 80 is desirable.
なお前記以外の(c1戒分としてグラフトされるスチレ
ン類は、(al tc分やい)成分との相溶性に関連し
て(メタ)アクリル酸アルキル類とスチレン類との重量
比で100:O〜50 : 50、好ましくは100:
O〜70 : 30.さらにtoo:o〜90 : 1
0が望ましい。In addition, the styrenes to be grafted as a c1 component other than those mentioned above have a weight ratio of alkyl (meth)acrylates and styrenes of 100:O in relation to compatibility with the (altc) component. ~50:50, preferably 100:
O~70: 30. Furthermore, too:o~90:1
0 is desirable.
本発明における(c)成分は前記い)成分であるASA
樹脂やAES樹脂と同様の製造方法により台底されるも
のであり、多段乳化重合等の方法によれば、シェル・コ
アー型の共重合体構造となる。コアー層を形成するゴム
成分の(c)成分中の含有量は0〜50重量%であるこ
とが望ましく、平均粒径は、0゜1〜0.6 μm特に
0.1〜0.4 μmが好ましい。Component (c) in the present invention is ASA, which is the component (d) above.
It is produced by the same manufacturing method as resin or AES resin, and by a method such as multi-stage emulsion polymerization, it becomes a shell-core copolymer structure. The content of the rubber component forming the core layer in component (c) is preferably 0 to 50% by weight, and the average particle size is 0.1 to 0.6 μm, particularly 0.1 to 0.4 μm. is preferred.
本発明において各成分の配合量としては、種々の用途に
応して幅広く選択でき、(a)成分、(b)成分はそれ
ぞれ1〜95重量%、(c) 成分は0.5〜98重量
%であり、特に(c)成分は(a)成分に対して5〜3
0重量%が好ましい。In the present invention, the blending amount of each component can be selected from a wide range depending on the various uses, and the (a) component and (b) component are each 1 to 95% by weight, and the (c) component is 0.5 to 98% by weight. %, especially component (c) is 5 to 3% relative to component (a).
0% by weight is preferred.
本発明組成物を得る方法としては、常用の混合装置、例
えばローラーニーダ−及び単一または、多量スクリュー
押出機、特に2軸スクリユ一押出機及びニーダを用いて
、前記各成分(a)、伽)および(c)成分の3戒分を
一緒に溶融して均質化するか、または(a)成分の溶融
体中へ、(b)成分および(c)成分を混合することに
よって得ることができる。The composition of the present invention can be obtained by using conventional mixing equipment such as a roller kneader and a single or multi-screw extruder, especially a twin-screw extruder and a kneader. ) and (c) by melting and homogenizing them together, or by mixing components (b) and (c) into a melt of component (a). .
本発明組成物の製造温度は、(a)成分であるポリエス
テルの融点より約10°C高い方がよ<、300’C以
下で、好ましくは245〜280 °Cがよい、なお(
a)成分としてポリブチレンテレフタレートとポリエチ
レンテレフタレートを混合して用いる場合、ポリブチレ
ンテレフタレート含量が高い&ll威物放物い温度で、
ポリエチレンテレフタレート含量が高い&11威物は高
い温度で、製造するのが好ましい。The manufacturing temperature of the composition of the present invention is preferably about 10°C higher than the melting point of the polyester as component (a), and 300°C or less, preferably 245 to 280°C.
a) When using a mixture of polybutylene terephthalate and polyethylene terephthalate as components, the polybutylene terephthalate content is high and the temperature is extremely high.
Polyethylene terephthalate-rich products are preferably produced at elevated temperatures.
本発明組成物は、常用の添加剤、例えば滑剤及び離型剤
、核形成剤、安定剤、及び補強材、難燃剤及び、染料や
顔料を配合することができ、特に好ましい補強材として
ガラス繊維、ガラスピーズ、マイカ、シリケート、石英
、タルク、二酸化チタン、珪石炭などが挙げられる。The composition of the present invention may contain conventional additives, such as lubricants and mold release agents, nucleating agents, stabilizers, reinforcing agents, flame retardants, dyes and pigments, and particularly preferred reinforcing materials include glass fibers. , glass peas, mica, silicates, quartz, talc, titanium dioxide, silica, etc.
これら添加剤は、全組成物に対して5〜50重置%、特
に10〜40重量%を配合することができる。These additives can be blended in an amount of 5 to 50% by weight, particularly 10 to 40% by weight, based on the total composition.
また本発明組成物の難燃性を向上させるために、無燃剤
を全組成物に対して30重量%以下配合させればよく、
難燃剤としては、例えばポリハロゲンジフェニル、ポリ
ハロゲンジフェニルエーテル、ポリハロゲンフタル酸と
その誘導体、及びポリハロゲン化ポリカーボネート、ポ
リハロゲン化ポリスチレン等があり、そのうち臭素含有
化合物が特に有効である。さらに通常の相乗化剤、例え
ば、二酸化アンチモンを含有するのが好ましい。In addition, in order to improve the flame retardancy of the composition of the present invention, it is sufficient to incorporate a nonflammable agent in an amount of 30% by weight or less based on the total composition.
Examples of flame retardants include polyhalogen diphenyl, polyhalogen diphenyl ether, polyhalogen phthalic acid and its derivatives, polyhalogenated polycarbonate, and polyhalogenated polystyrene, among which bromine-containing compounds are particularly effective. It is also preferred to contain customary synergists, such as antimony dioxide.
(作 用)
本発明組成物は、(c)成分であるグラフト共重合体が
、(al t2分であるポリエステルとい)成分である
ASA樹脂および/またはAES樹脂との相溶性を改善
することにより、均一な分散状態となり、伸度、および
落錘衝撃強度が飛躍的に向上するものと思われる。(Function) The composition of the present invention improves the compatibility of the graft copolymer, which is the component (c), with the ASA resin and/or AES resin, which is the (alt2 minute polyester) component. It is thought that this results in a uniformly dispersed state, and that the elongation and falling weight impact strength are dramatically improved.
(実施例)
本発明の&1It2物を実施例に基づき具体的に説明す
るが、本発明はこれらに限定されるものではない。(Example) The &1It2 product of the present invention will be specifically explained based on Examples, but the present invention is not limited thereto.
本発明の(b) 1分であるASA樹脂は、三菱レイヨ
ン社製ダイヤラックA、S−300を用い、^ES樹脂
は、住友ノーガタンク社製ユニプライトuB−600を
用いた。また(c)成分であるグラフト共重合体は表1
に示す組成比のものを用いた。For the ASA resin (b) 1 minute of the present invention, Dialac A, S-300 manufactured by Mitsubishi Rayon Co., Ltd. was used, and for the ES resin, Uniplyte uB-600 manufactured by Sumitomo Noga Tank Co., Ltd. was used. In addition, the graft copolymer which is the component (c) is shown in Table 1.
The composition ratio shown in was used.
なお実施例及び比較例中のアイゾツト衝撃値は^STM
−0256に準じ、引張強度は^STM・D638に準
拠して測定した。また、落錘衝撃強度については、戒部
品を140℃で2時間熱処理を行ったものについて、D
upont式落錘衝撃試験に基づいて測定し、材料が破
壊を起こさない領域での最大吸収エネルギーで示した。In addition, the Izod impact value in the examples and comparative examples is ^STM
-0256, and the tensile strength was measured according to STM D638. In addition, regarding the falling weight impact strength, D
It was measured based on the upont type falling weight impact test, and was expressed as the maximum absorbed energy in the area where the material does not break.
表1
グラフト共重合体組成比
実施例1〜7 比較例1〜7
固有粘度が0.63dl/ Hのポリエチレンテレフタ
レート、固有粘度が1.02dl/ gのポリブチレン
テレフタレート、^SAまたはAES樹脂、および(c
)成分であるグラフト共重合体とを所定量ブレンダで混
合し、30■φ2軸押出機を使用してシリンダー温度2
65℃で、混線押出し、ペレットとした。Table 1 Graft copolymer composition ratio Examples 1 to 7 Comparative examples 1 to 7 Polyethylene terephthalate with an intrinsic viscosity of 0.63 dl/H, polybutylene terephthalate with an intrinsic viscosity of 1.02 dl/g, ^SA or AES resin, and (c
) component (graft copolymer) is mixed in a blender in a predetermined amount, and then heated to a cylinder temperature of 2 using a 30 mm φ twin-screw extruder.
The mixture was cross-extruded at 65°C to form pellets.
このペレットを100℃で真空乾燥を5時間行った後、
射出成形機で成形品とした。金型温度は75℃であった
。比較のために(c)成分を用いない場合についても同
様に評、価した。After vacuum drying this pellet at 100°C for 5 hours,
It was made into a molded product using an injection molding machine. The mold temperature was 75°C. For comparison, a case in which component (c) was not used was similarly evaluated.
その結果を表2.3に示す。The results are shown in Table 2.3.
表1中 P8 ポリブタジェン PBu^ ポリアクリル酸ブチル MM^ メタクリル酸メチル St スチレン 以下余白 表2 表3 (発明の効果) 以上かかる構成よりなる本発明&ll威物放物伸度。In table 1 P8 Polybutadiene PBu^ Polybutyl acrylate MM^ Methyl methacrylate St Styrene Margin below Table 2 Table 3 (Effect of the invention) The present invention and the parabolic elongation having the configuration described above.
耐衝撃強度などの機械的強度が優れ、ヒケ、ソリ等のな
い表面性の優れた成形品を得ることができる。特に、−
40℃における落錘衝撃強度が著しく改善され、熱に対
する寸法安定性が優れているため、高度の寸法安定性、
高衝撃と共に高い耐薬品性が要求される部材、例えば熱
応力を受ける材料、自動車部品、バンパー、事務機器の
ハウジング等の射出成形及び、
押出し底形に広く利用でき、
産
業界に寄与すること大である。It is possible to obtain a molded product that has excellent mechanical strength such as impact resistance, and has excellent surface properties without sink marks, warpage, etc. In particular, −
The falling weight impact strength at 40℃ has been significantly improved, and the dimensional stability against heat is excellent, resulting in a high degree of dimensional stability.
It can be widely used in injection molding and extrusion bottom shapes of parts that require high impact and high chemical resistance, such as materials subject to thermal stress, automobile parts, bumpers, and housings for office equipment, making it a great contribution to industry. It is.
Claims (1)
樹脂(b)、およびガラス転移温度が0℃より低いポリ
マーを幹とし、(メタ)アクリル酸アルキル類と、スチ
レン類より選ばれた一種以上のモノマーの重合体の少な
くとも一部がグラフトされているグラフト共重合体(c
)を含有することを特徴とする耐衝撃性ポリエステル樹
脂組成物。Polyester (a), ASA resin and/or AES
Resin (b) and a polymer having a glass transition temperature lower than 0° C. are used as the backbone, and at least a portion of a polymer of an alkyl (meth)acrylate and one or more monomers selected from styrenes is grafted. Graft copolymer (c
) An impact-resistant polyester resin composition comprising:
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4214890A JPH03244658A (en) | 1990-02-22 | 1990-02-22 | High impact polyester resin composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4214890A JPH03244658A (en) | 1990-02-22 | 1990-02-22 | High impact polyester resin composition |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH03244658A true JPH03244658A (en) | 1991-10-31 |
Family
ID=12627859
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4214890A Pending JPH03244658A (en) | 1990-02-22 | 1990-02-22 | High impact polyester resin composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH03244658A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0787769A3 (en) * | 1996-02-02 | 1998-12-30 | General Electric Company | Impact modified polycarbonate and/or polyester compositions with high weather resistance |
-
1990
- 1990-02-22 JP JP4214890A patent/JPH03244658A/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0787769A3 (en) * | 1996-02-02 | 1998-12-30 | General Electric Company | Impact modified polycarbonate and/or polyester compositions with high weather resistance |
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