JPS63146955A - Heat-resistant and impact-resistant resin composition - Google Patents
Heat-resistant and impact-resistant resin compositionInfo
- Publication number
- JPS63146955A JPS63146955A JP61295592A JP29559286A JPS63146955A JP S63146955 A JPS63146955 A JP S63146955A JP 61295592 A JP61295592 A JP 61295592A JP 29559286 A JP29559286 A JP 29559286A JP S63146955 A JPS63146955 A JP S63146955A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- monomer
- parts
- conjugated diene
- 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.)
- Granted
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 149
- 229920005989 resin Polymers 0.000 claims abstract description 77
- 239000011347 resin Substances 0.000 claims abstract description 77
- 239000000203 mixture Substances 0.000 claims abstract description 74
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 51
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 47
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 38
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 38
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 21
- -1 N-substituted maleimide Chemical class 0.000 claims abstract description 21
- 238000010559 graft polymerization reaction Methods 0.000 claims abstract description 17
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 17
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 229920001971 elastomer Polymers 0.000 claims description 32
- 239000005060 rubber Substances 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 17
- 229920000126 latex Polymers 0.000 claims description 6
- 239000004816 latex Substances 0.000 claims description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 abstract description 15
- 238000004898 kneading Methods 0.000 abstract description 7
- 238000013329 compounding Methods 0.000 abstract 2
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 39
- 238000000034 method Methods 0.000 description 23
- 238000002156 mixing Methods 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 11
- 230000007423 decrease Effects 0.000 description 11
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- 238000012662 bulk polymerization Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- 229920001893 acrylonitrile styrene Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000375 suspending agent Substances 0.000 description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010556 emulsion polymerization method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- QYOJZFBQEAZNEW-UHFFFAOYSA-N 1-(2-methylphenyl)pyrrole-2,5-dione Chemical compound CC1=CC=CC=C1N1C(=O)C=CC1=O QYOJZFBQEAZNEW-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 101100208721 Mus musculus Usp5 gene Proteins 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 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、耐熱性耐衝撃性樹脂組成物に関する。[Detailed description of the invention] "Industrial application field" The present invention relates to a heat-resistant impact-resistant resin composition.
さらに詳しくは、Ｎ−置換マレイミドを含む単量体を共
役ジエン系ゴムにグラフト共重合させたゴム強化樹脂に
、ＡＢＳ樹脂を配合混練して得られる優れた耐熱性と耐
衝撃性とをもった成形品が得られる樹脂組成物に関する
ものである。More specifically, ABS resin is blended and kneaded with a rubber reinforced resin in which a monomer containing N-substituted maleimide is graft copolymerized with a conjugated diene rubber, which has excellent heat resistance and impact resistance. The present invention relates to a resin composition from which a molded article can be obtained.
［従来の技術１
従来より、硬質樹脂にゴムを配合し、このゴムによって
強化した耐衝撃性樹脂を得ることは、よく知られている
。ＡＢＳ樹脂はこの種の代表的なものであるが、硬質樹
脂としてのアクリロニトリル・スチレン共重合体（ＡＳ
樹脂）の耐熱性が不足しているため、さらに高い熱変形
温度を有する硬質樹脂が要望されていた。[Prior Art 1] Conventionally, it has been well known to blend rubber into a hard resin to obtain an impact-resistant resin reinforced by the rubber. ABS resin is a typical example of this type, but acrylonitrile-styrene copolymer (AS
Due to the lack of heat resistance of resins), there has been a demand for hard resins with even higher heat distortion temperatures.
この高い熱変形温度を有するスチレン系樹脂として、例
えば、Ｎ−置換マレイミド単量体と芳香族ビニル単量体
との共重合体が知られておＩ）（Ｌ。As a styrenic resin having a high heat distortion temperature, for example, a copolymer of an N-substituted maleimide monomer and an aromatic vinyl monomer is known.
Ｅ、Ｃｏｌｅｍａｎ ｅｔ ａｌ、＋Ｊ、 Ｐｏｌｙｍ
ｅｒ Ｓｃｉ、、第３８巻、第２４１頁、１９５９年発
行）、さらに、Ｎ−アリル置換マレイミド、芳香族ビニ
ル単量体およびアクリロニトリルよりなる単量体混合物
を共役ジエン系ゴムにグラフトしたグラフト共重合体、
およびこのグラフト共重合体を配合した樹脂組成物が提
案されている（米国特許第３，６５２，７２６号）。E., Coleman et al., +J., Polym.
er Sci, Vol. 38, p. 241, published in 1959), and a graft copolymer in which a monomer mixture consisting of N-allyl substituted maleimide, an aromatic vinyl monomer, and acrylonitrile is grafted onto a conjugated diene rubber. Union,
A resin composition containing this graft copolymer has also been proposed (US Pat. No. 3,652,726).
しかし、Ｎ−置換マレイミド単量体およびビニル単量体
よりなる共重合体は、Ｎ−置換マレイミド単量体の含有
量が多くなると熱変形温度は高くなるが、脆くなる。脆
さを改良する方法として、ＡＢＳ樹脂との配合が提案さ
れているが（特開昭５７−９８５３６、特開昭５７−１
３１２１３）、まだ充分ではない。However, a copolymer composed of an N-substituted maleimide monomer and a vinyl monomer becomes brittle, although its heat distortion temperature increases as the content of the N-substituted maleimide monomer increases. As a method to improve brittleness, blending with ABS resin has been proposed (Japanese Patent Laid-Open No. 57-98536, Japanese Patent Laid-Open No. 57-1)
31213), which is still not enough.
このようなＮ−置換マレイミド単量体・スチレン系共重
合体とＡＢＳ樹脂とを配合した紹成物について、耐衝撃
性を向上させるためには、組成物中のＡＢＳ樹脂の量、
または配合するＡＢＳ樹脂中のグラフトゴムの配合量を
増やす必要がある。In order to improve the impact resistance of a composite containing such an N-substituted maleimide monomer/styrene copolymer and ABS resin, the amount of ABS resin in the composition,
Alternatively, it is necessary to increase the amount of graft rubber blended in the ABS resin.
他方、耐熱性や剛性等の機械的性質は、ＡＢＳ樹脂の量
またはＡＢＳ樹脂中のグラフトゴムの配合量の増加とと
もに、低下する。このため、耐熱性および耐衝撃性の双
方ともに優れたＮ−置換マレイミド・スチレン系共重合
体の樹脂組成物が望まれている。On the other hand, mechanical properties such as heat resistance and rigidity decrease as the amount of ABS resin or the amount of graft rubber blended in the ABS resin increases. Therefore, a resin composition of an N-substituted maleimide-styrene copolymer that is excellent in both heat resistance and impact resistance is desired.
［発明が解決しようとする問題点］
本発明者らは、Ｎ−置換マレイミド単量体およびビニル
単量体よりなる共重合体を用いた従来のゴム強化樹脂に
、存在していた上記諸欠点を解決することを目的としで
、鋭意研究を重ねた結果、本発明に到達したものである
。すなわち、ＮＮ置換マレイミド単量体含む単量体を共
役ジエン系ゴムにグラフト重合したものを、一定のゴム
粒子径のＡＢＳ樹脂と混合混練することにより、耐熱性
と耐衝撃性に優れ、中でも落錘衝撃強度が顕著に改良さ
れた成形品が得られる樹脂組成物を提供しようとするも
のである。[Problems to be Solved by the Invention] The present inventors have solved the above-mentioned drawbacks that existed in conventional rubber reinforced resins using copolymers consisting of N-substituted maleimide monomers and vinyl monomers. The present invention was developed as a result of intensive research aimed at solving the problem. That is, by graft-polymerizing a monomer containing a NN-substituted maleimide monomer onto a conjugated diene rubber and mixing and kneading it with an ABS resin of a certain rubber particle size, it has excellent heat resistance and impact resistance. The object of the present invention is to provide a resin composition from which a molded article with significantly improved weight impact strength can be obtained.
１問題点を解決するための手段」
本発明の要旨とするところは、共役ジエン系ゴム（ａ）
２５〜７０重量部に、芳香族ビニル単量体３０〜８０重
量％、Ｎ−置換マレイミド単量体１０〜５０重量％、シ
アン化ビニル単量体１０〜４０重量％、およびこれら単
量体と共重合可能な他のビニル単量体０〜３０重量％よ
りなる単量体混合物（ただし、単量体混合物は合計１０
０重量％とする。）３０〜７５重量部を、グラフト重合
してなるグラフト共重合体樹脂（Ａ）５〜８９重量部、
芳香族ビニル単量体３０〜８０重量％、Ｎ−置換マレイ
ミド単量体１０〜５０重量％、シアン化ビニル単量体１
０〜４０重量％、およびこれら単量体と共重合可能な他
のビニル単量体０〜３０重量％よりなる単量体混合物（
ただし、単量体混合物は合計１００重量％とする。）を
、重合してなる共重合体樹脂（Ｂ）１０〜９０重量部、
共役ジエン系ゴム（ｃ）２〜１７重量部に、芳香族ビニ
ル単量体５５〜８５重量％、およびシアン化ビニル単量
体１５〜４５重量％よりなる単量体混合物（ただし、単
量体混合物は合計１００重量％とする。）８３〜９８重
量部を、グラフト重合してなるグラフト共重合体樹脂（
Ｃ）１〜４５重量部、および、
芳香族ビニル単量体５５〜８５重量％、およびシアン化
ビニル単量体１５〜４５重量％よりなる単量体混合物（
ただし、単量体混合物は合計１００重量％とする。）を
、重合してなる共重合体樹脂（Ｄ）０〜５０重量部、
を含有（ただし、共重合体樹脂（Ａ）、（Ｂ）、（Ｃ）
および（Ｄ）の合計は１００重量部とする。）してなる
ことを特徴とする耐熱性耐衝撃性樹脂組成物に存する。1. Means for Solving Problem 1" The gist of the present invention is to solve the following problems:
25 to 70 parts by weight, 30 to 80% by weight of aromatic vinyl monomer, 10 to 50% by weight of N-substituted maleimide monomer, 10 to 40% by weight of vinyl cyanide monomer, and these monomers. A monomer mixture consisting of 0 to 30% by weight of other copolymerizable vinyl monomers (however, the monomer mixture has a total of 10% by weight)
0% by weight. ) 5 to 89 parts by weight of a graft copolymer resin (A) obtained by graft polymerizing 30 to 75 parts by weight,
Aromatic vinyl monomer 30-80% by weight, N-substituted maleimide monomer 10-50% by weight, cyanide vinyl monomer 1
A monomer mixture consisting of 0 to 40% by weight and 0 to 30% by weight of other vinyl monomers copolymerizable with these monomers (
However, the total amount of the monomer mixture is 100% by weight. ), 10 to 90 parts by weight of a copolymer resin (B) obtained by polymerizing
A monomer mixture consisting of 2 to 17 parts by weight of conjugated diene rubber (c), 55 to 85% by weight of aromatic vinyl monomer, and 15 to 45% by weight of vinyl cyanide monomer (however, the monomer The total weight of the mixture is 100% by weight.) 83 to 98 parts by weight of the graft copolymer resin (
C) 1 to 45 parts by weight, and a monomer mixture consisting of 55 to 85% by weight of aromatic vinyl monomer and 15 to 45% by weight of vinyl cyanide monomer (
However, the total amount of the monomer mixture is 100% by weight. ), 0 to 50 parts by weight of a copolymer resin (D) formed by polymerizing (provided that the copolymer resins (A), (B), (C)
The total of (D) and (D) shall be 100 parts by weight. ) A heat-resistant and impact-resistant resin composition.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明に係る樹脂組成物を構成するグラフト共重合体樹
脂（Ａ）とは、共役ジエン系ゴム（ａ）２５〜７０重量
部に、芳香族ビニル単量体３０〜８０重量％、Ｎ−置換
マレイミド単量体１０〜５０重量％、シアン化ビニル単
量体１０〜４０重量％、およびこれら単量体と共重合可
能な他のビニル単量体０〜３０重量％よりなる単量体混
合物（Ｉ）（ただし、単量体混合物は合計１００重量％
とする。The graft copolymer resin (A) constituting the resin composition according to the present invention is composed of 25 to 70 parts by weight of conjugated diene rubber (a), 30 to 80 parts by weight of aromatic vinyl monomer, and N-substituted A monomer mixture consisting of 10-50% by weight of maleimide monomer, 10-40% by weight of vinyl cyanide monomer, and 0-30% by weight of other vinyl monomer copolymerizable with these monomers I) (However, the total monomer mixture is 100% by weight)
shall be.
以下同じ。）３０〜７５重量部を、グラフト重合して得
られるものをいう。このグラフト共重合体用脂（Ａ）は
、Ｎ−置換マレイミド単量体成分を含むので、優れた耐
熱性をもつ耐衝撃性樹脂である。same as below. ) 30 to 75 parts by weight is obtained by graft polymerization. Since this graft copolymer resin (A) contains an N-substituted maleimide monomer component, it is an impact-resistant resin with excellent heat resistance.
上記グラフト共重合体樹脂（Ａ）の構成成分である共役
ジエン系ゴム（ａ）とは、ブタジェン、イソプレン、ク
ロロプレン等の共役ジエン単量体成分を５０重量％以上
含む、ガラス転移温度が０℃以下のゴム状重合体をいう
。共役ジエン系ゴム（ａ）の具体例としては、ブタジェ
ンラバー（ＢＲ）、スチレンブタジェンラバー（Ｓ Ｂ
Ｒ）、ニトリルブタジェンラバー（ＮＢＲ）、インプ
レンラバー（Ｉ Ｒ）等の公知の合成ゴムがあげられる
。The conjugated diene rubber (a), which is a component of the graft copolymer resin (A), contains 50% by weight or more of a conjugated diene monomer component such as butadiene, isoprene, chloroprene, etc., and has a glass transition temperature of 0°C. Refers to the following rubbery polymers. Specific examples of conjugated diene rubber (a) include butadiene rubber (BR), styrene butadiene rubber (S B
Known synthetic rubbers such as R), nitrile butadiene rubber (NBR), and in-prene rubber (IR) can be mentioned.
この共役ジエン系ゴム（ａ）は、水中分散型のゴムラテ
ックス状態で、ゴムの平均粒子径が０．１〜０．５μｍ
の範囲にあるものが好ましい。０．１μｍより小さい場
合には、得られるグラフト共重合体樹脂の耐衝撃性を向
上し得ないので好ましくない。０．５μ諭より大きい場
合には、乳化グラフト重合が困難となり、ゴムラテック
スの安定性が低下するので好ましくない。This conjugated diene rubber (a) is in the state of water-dispersed rubber latex and has an average particle diameter of 0.1 to 0.5 μm.
Preferably, it falls within this range. If it is smaller than 0.1 μm, it is not preferable because the impact resistance of the resulting graft copolymer resin cannot be improved. If it is larger than 0.5 μm, emulsion graft polymerization becomes difficult and the stability of the rubber latex decreases, which is not preferable.
本発明において水に分散した共役ツエン系ゴム等の平均
粒子径とは、米国コールタ−電子社（Ｃｏｕｌｔｅｒ
Ｅ Ｉｅｃｔｒｏｎｉｃｓ Ｌ ｔｄ、）製ナノサイザ
ー（Ｃｏｕｌｔｅｒｅ Ｎ ａｎｏ−８ｉｚｅｒＴＭ）
により、ラテックスを２３℃の水中に分散した系で測定
した、重量平均粒子径をいう。In the present invention, the average particle size of the conjugated tzene rubber etc. dispersed in water is defined as
Nano-8izerTM manufactured by E Electronics Ltd.
It refers to the weight average particle diameter measured in a system in which latex is dispersed in water at 23°C.
上記単量体混合物（１）の成分である芳香族ビニル単量
体の具体例としては、スチレン、ａ−メチルスチレン等
のａ−アルキルスチレン、ｐ−メチルスチレン等の核置
換アルキルスチレン、ビニルナフタリン等があげられる
。これらは、１種または２種以上の混合物であってもよ
い。Specific examples of the aromatic vinyl monomer that is a component of the monomer mixture (1) include styrene, a-alkylstyrene such as a-methylstyrene, nuclear-substituted alkylstyrene such as p-methylstyrene, and vinylnaphthalene. etc. can be mentioned. These may be used alone or in a mixture of two or more.
芳香族ビニル単量体の単量体混合物（１）中に占める比
率は、３０〜８０重量％とする。この比率が、８０重量
％を超えると、製造した樹脂の耐熱性が低下したり、他
の硬質樹脂と混合するとき混和性が不良となる。３０重
量％未満の場合には、グラフト重合した樹脂の特性が変
化し、混合する他の共重合体樹脂の種類が限定されるの
で好ましくない。The proportion of the aromatic vinyl monomer in the monomer mixture (1) is 30 to 80% by weight. If this ratio exceeds 80% by weight, the heat resistance of the produced resin will decrease or the miscibility will be poor when mixed with other hard resins. If it is less than 30% by weight, the properties of the graft-polymerized resin will change and the types of other copolymer resins to be mixed will be limited, which is not preferable.
Ｎ−置換マレイミド単量体としては、マレイミ）ｒ、Ｎ
−フェニルマレイミド、Ｎ（ｏ−メチルフェニル）マレ
イミド、Ｎ−（＋ｎ−メチルフェニル）マレイミ）’、
Ｎ−（ａ−メチルフェニル）マレイミドおよびＮ−シク
ロヘキシルマレイミドからなる群から選ばれた少なくと
も１種の単量体があげられる。As the N-substituted maleimide monomer, maleimide)r, N
-phenylmaleimide, N(o-methylphenyl)maleimide, N-(+n-methylphenyl)maleimide)',
At least one monomer selected from the group consisting of N-(a-methylphenyl)maleimide and N-cyclohexylmaleimide is mentioned.
このなかでも、Ｎ−フェニルマレイミドが特に好ましい
６
Ｎ−置換マレイミド単量体は、単量体混合物（１）中に
１０〜５０重量％の範囲で含有される。含有量が５０重
単量を超える場合には、共重合体ｖＩ脂が不均質となり
、所望のグラフト共重合体樹脂が得られない。１０重量
％未満の場合には、耐熱性が不充分であり、Ｎｆｔｆ換
マレゴマレイミド単量体合させる効果がない。Among these, the 6 N-substituted maleimide monomer, particularly preferably N-phenylmaleimide, is contained in the monomer mixture (1) in an amount of 10 to 50% by weight. When the content exceeds 50 weight monomers, the copolymer vI fat becomes heterogeneous and the desired graft copolymer resin cannot be obtained. If it is less than 10% by weight, the heat resistance will be insufficient and there will be no effect of integrating the Nftf-converted maleomaleimide monomer.
シアン化ビニル単量体の具体例としては、アクリロニト
リル、メタクリロニトリル等があげられる。これらは、
ＩＮｌまたは２種以上の混合物であってもよい。シアン
化ビニル単量体の単量体混合物（１）中に占める比率は
、１０〜４０重量％の範囲でなければならない。この範
囲を外れると、グラフト重合した樹脂と他の共重合体樹
脂との分散性が低下したり、組成物から得られる成形品
の機械的物性および耐薬品性力を低下するおそれがある
ので好ましくない。Specific examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and the like. these are,
It may be INl or a mixture of two or more. The proportion of vinyl cyanide monomer in the monomer mixture (1) must be in the range from 10 to 40% by weight. If it is outside this range, the dispersibility of the graft-polymerized resin with other copolymer resins may decrease, or the mechanical properties and chemical resistance of the molded product obtained from the composition may decrease, so this is not preferred. do not have.
これら単量体と共重合可能な他のビニル単量体としては
、例えばアクリル酸エステル類、メタアクリル酸エステ
ル類またはこれらの混合物があげられる。Other vinyl monomers that can be copolymerized with these monomers include, for example, acrylic esters, methacrylic esters, or mixtures thereof.
このこれら単量体と共重合可能なビニル単量体は、単量
体混合物（Ｎ中に３０ｆｉ量％以下の量を含有させる。The vinyl monomer copolymerizable with these monomers is contained in the monomer mixture (N in an amount of 30 fi% or less).
３０重量％を超えると、グラフト重合の反応条件の変更
が必要となるばかりでなく、グラフト重合した０（脂の
物性が変化するので好ましくない。If it exceeds 30% by weight, it is not preferable because it not only requires changing the reaction conditions for graft polymerization, but also changes the physical properties of the graft polymerized O(fat).
本発明におけるグラフト共重合体樹脂（Ａ）は、前記の
共役ジエン系ゴム（ａ）２５〜７０重量部に上記単量体
混合物Ｎ）を３０〜７５重量部の範囲で混合し、混合系
を重合に付してグラフト重合させることにより製造する
。共役ジエン系ゴム（ａ）と単量体混合物（１）との上
記の重量部の割合が、上記の範囲を外れると、単量体混
合物（１）の共重合体が共役ジエン系ゴム粒子の表面を
被覆できない場合とか、グラフト共重合体樹脂中に占め
る共役ジエン系ゴムの割合が少なくなるので好ましくな
い。The graft copolymer resin (A) in the present invention is prepared by mixing 30 to 75 parts by weight of the monomer mixture N) to 25 to 70 parts by weight of the conjugated diene rubber (a) to form a mixed system. It is produced by subjecting it to polymerization and graft polymerization. If the above weight parts ratio of the conjugated diene rubber (a) and the monomer mixture (1) is out of the above range, the copolymer of the monomer mixture (1) will This is not preferable because the surface cannot be coated or the proportion of the conjugated diene rubber in the graft copolymer resin decreases.
このグラフト重合させる場合には、乳化重合法、懸濁重
合法、溶液重合法、または塊状重合法等の方法を採るこ
とができる。乳化重合法による場合には、水を媒体とす
る通常の乳化重合法により行うことができる。この際、
乳化重合の重合率に合わせて、単量体混合物（１）、分
子量調節剤、乳化剤および重合開始剤等を、適宜分割し
、時間経過に従って、重合系に添加する方法を採るのが
好ましい。In the case of graft polymerization, methods such as emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization can be used. In the case of emulsion polymerization, a normal emulsion polymerization method using water as a medium can be used. On this occasion,
It is preferable to adopt a method in which the monomer mixture (1), molecular weight regulator, emulsifier, polymerization initiator, etc. are appropriately divided according to the polymerization rate of emulsion polymerization and added to the polymerization system over time.
乳化型合法以外でグラフト重合を遂行するに当っては、
最初に、共役ジエン系ゴム粒子表面を硬質の樹脂で被覆
し、ゴム粒子のみによる分散が可能となったとき、乳化
系から懸濁系、溶液系または塊状重合系に移行して、グ
ラフト重合を続ける方法を採るのがよい。When carrying out graft polymerization using methods other than emulsion method,
First, the surface of conjugated diene rubber particles is coated with a hard resin, and when it becomes possible to disperse only the rubber particles, the emulsion system is shifted to a suspension system, a solution system, or a bulk polymerization system, and graft polymerization is carried out. It is better to take the method of continuing.
グラフト重合を終了した重合系には、公知の適当な後処
理、例えば、塩析、分離、洗浄、乾燥、混合、ペレット
化等の工程を、適宜組み合わせて行うことにより、グラ
フト共重合体樹脂（Ａ）を得ることができる。The graft copolymer resin ( A) can be obtained.
本発明に係る樹脂組成物を構成する共重合体樹脂（Ｂ）
とは、芳香族ビニル単量体３０〜８０重量％、Ｎｆｔ換
マレイミド単量体１０〜５０重景重量シアン化ビニル単
量体１０〜４０重量％、およびこれら単量体と共重合可
能な他のビニル単量体０〜３０重量％よりなる単量体混
合物（ｎ）を重合しで得られるものである。共重合体樹
脂（Ｂ）は、Ｎ−置換マレイミド単量体成分を含むので
、優れた耐熱性をもつ熱可塑性の硬質樹脂である。Copolymer resin (B) constituting the resin composition according to the present invention
means 30 to 80% by weight of aromatic vinyl monomer, 10 to 50% by weight of Nft-converted maleimide monomer, and 10 to 40% by weight of vinyl cyanide monomer, and others that can be copolymerized with these monomers. It is obtained by polymerizing a monomer mixture (n) consisting of 0 to 30% by weight of vinyl monomers. Since the copolymer resin (B) contains an N-substituted maleimide monomer component, it is a thermoplastic hard resin with excellent heat resistance.
上記共重合体樹脂（Ｂ）の構成成分である、芳香族ビニ
ル単量体、Ｎ−置換マレイミド単量体、シアン化ビニル
単量体、およびこれら単量体と共重合可能な他のビニル
単量体とは、先きに単量体混合物（１）の成分として例
示した各々のビニル単量体と同義である。これら各々の
ビニル単量体が単１、体部合物（ＩＩ）に占める比率は
、前記単量体混合物Ｎ）で限定された範囲と同一の範囲
である。しかし、単量体混合物（Ｕ）の組成は、上記範
囲内にあればよく、単量体混合物（１）の組成と全く同
一とする必要はない。Aromatic vinyl monomers, N-substituted maleimide monomers, vinyl cyanide monomers, and other vinyl monomers copolymerizable with these monomers, which are constituent components of the above copolymer resin (B). The monomer has the same meaning as each vinyl monomer exemplified above as a component of the monomer mixture (1). The proportion of each of these vinyl monomers in monomer compound (II) is within the same range as defined for monomer mixture N). However, the composition of the monomer mixture (U) only needs to be within the above range, and does not need to be exactly the same as the composition of the monomer mixture (1).
共重合体樹脂（Ｂ）は、本発明の樹脂組成物から得られ
る成形品が、目的とする優れた耐熱性と耐衝撃性を具備
するように、適当な分子量と組成を、適宜選択して設定
するのがよい。The copolymer resin (B) has an appropriate molecular weight and composition selected so that the molded article obtained from the resin composition of the present invention has the desired excellent heat resistance and impact resistance. It is better to set
上記単量体混合物＜ＩＴ）の重合方法および重合条件は
、例えば公知のアクリロニトリル・スチレン共重合体（
Ａｓ樹脂）の製造技術に準じて、乳化重合法、懸濁重合
法、溶液重合法、塊状重合法等の方法を、回分または連
続方式から、適宜選択することができる。The polymerization method and polymerization conditions for the above monomer mixture <IT) may be, for example, a known acrylonitrile-styrene copolymer (
Depending on the manufacturing technology of As resin), a method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, etc. can be appropriately selected from batch or continuous methods.
また、この単量体混合物（ＩＴ）の重合は、グラフト共
重合体樹脂（Ａ）のグラフト重合と同時に同一の重合系
内で行うこともできるが、通常は、別途重合条件を設定
して行うのが好ましい。Although the polymerization of this monomer mixture (IT) can be carried out simultaneously with the graft polymerization of the graft copolymer resin (A) in the same polymerization system, it is usually carried out by setting polymerization conditions separately. is preferable.
本発明樹脂組成物を構成するグラフト共重合体樹脂（Ｃ
）とは、共役ジエン系ゴム（Ｃ）２〜１７重量部に、芳
香族ビニル単量体５５〜８５重量％、およびシアン化ビ
ニル単量体１５〜４５重量％よりなる単量体混合物（Ｉ
ｎ）８３〜９８重量部を、グラフト重合しで得られるも
のをいう。グラフト共重合体樹脂（Ｃ）は、アクリロニ
トリル・ブタジェン・スチレン共重合体（ＡＢＳ樹脂）
の一種であり、優れた耐衝撃性をもつ熱可塑性樹脂であ
る。Graft copolymer resin (C
) is a monomer mixture (I
n) refers to the product obtained by graft polymerization of 83 to 98 parts by weight. Graft copolymer resin (C) is acrylonitrile-butadiene-styrene copolymer (ABS resin)
It is a type of thermoplastic resin with excellent impact resistance.
このグラフト共重合体樹脂（Ｃ）を構成する共役ツエン
系ゴム（Ｃ）のグラフトゴムの平均１． 子径は、０．
５μ論を超え５μｌ以下の範囲内にあるのが好ましい。The average of the graft rubber of the conjugated tsene rubber (C) constituting this graft copolymer resin (C) is 1. The child diameter is 0.
It is preferable that the amount is in the range of more than 5μl and less than 5μl.
この範囲を外れると、グラフト共重合体樹脂（Ａ）と１
み合わせて得られる樹脂組成物の耐衝撃性、特に落錘衝
撃強度が向上し得ないので好ましくない。なお、特に効
果的に耐衝撃性を上昇させるためには、グラフト共重合
体樹脂（Ｃ）のグラフトゴムの平均粒子径を０．７〜４
μ印の範囲から選ぶのが、特に好ましい。Outside this range, the graft copolymer resin (A) and 1
This is not preferred because the impact resistance, particularly the falling weight impact strength, of the resulting resin composition cannot be improved. In addition, in order to particularly effectively increase the impact resistance, the average particle diameter of the graft rubber of the graft copolymer resin (C) should be set to 0.7 to 4.
It is particularly preferable to select from the range indicated by μ.
本発明において、共役ジエン系ゴム成分のグラフトゴム
の平均粒子径とは、米国コールタ−電子社（Ｃｏｕｌｔ
ｅｒ Ｅｌｅｃｔｒｏｎｉｃｓ Ｌｔｄ、）製［コール
タ−カウンター・モデルＴＡＩＩＪを用いて、ツメチル
ホルムアミドに少量のグラフト共重合体を溶解し、微量
のチオシアン酸カリウムを加えた溶液を、２３℃で測定
した重量平均粒子径をいう。In the present invention, the average particle diameter of the graft rubber of the conjugated diene rubber component is
er Electronics Ltd.) [Using a Coulter Counter Model TAIIJ, a solution in which a small amount of the graft copolymer was dissolved in trimethylformamide and a small amount of potassium thiocyanate was added was measured at 23°C. Refers to the diameter.
上記グラフト共重合体樹脂（Ｃ）の構成成分である共役
ジエン系ゴム（Ｃ）とは、ブタジェン、イソプレン、ク
ロロプレン等の共役ジエン単量体成分を５０重量％以−
ヒ含む、ガラス転移温度が０℃以下のゴム状重合体をい
う。共役ジエン系ゴム（ｃ）の具体例としては、ブタジ
ェンラバー（ＢＲ）、スチレン・ブタノエンラバー（Ｓ
ＢＲ）、ニトリル・ブタジェンラバー（ＮＢＲ）、イン
ブレンラバー（■Ｒ）等の合成ゴムがあげられる。The conjugated diene rubber (C), which is a constituent component of the graft copolymer resin (C), contains 50% by weight or more of a conjugated diene monomer component such as butadiene, isoprene, chloroprene, etc.
Refers to rubber-like polymers with a glass transition temperature of 0°C or lower. Specific examples of conjugated diene rubber (c) include butadiene rubber (BR), styrene-butanoene rubber (S
Examples include synthetic rubbers such as BR), nitrile-butadiene rubber (NBR), and inbrene rubber (■R).
上記単量体混合物（Ｔ［Ｉ）の成分である芳香族ビニル
単量体およびシアン化ビニル単量体とは、先きにグラフ
ト共重合体樹脂（Ａ）を製造する際に用いる成分として
例示した各々のビニル単量体と同義である。単量体混合
物（ＩＩ）は、芳香族ビニル単量体５５％８５重量％、
およびシアン化ビニル単量１６一
体１５〜４５重量％の範囲で構成される。The aromatic vinyl monomer and vinyl cyanide monomer, which are the components of the monomer mixture (T[I), are exemplified above as components used in producing the graft copolymer resin (A). It has the same meaning as each vinyl monomer. Monomer mixture (II) contains 55% and 85% by weight of aromatic vinyl monomers,
and vinyl cyanide monomer 16 in a range of 15 to 45% by weight.
この範囲を外れると、グラフト重合した樹脂の特性が変
化し、混合する他の共重合体樹脂との混和性が不良とな
り、目的とする樹脂組成物の耐熱性または耐衝撃性を低
下させるので好ましくない。If it is outside this range, the characteristics of the graft-polymerized resin will change, the miscibility with other copolymer resins to be mixed will become poor, and the heat resistance or impact resistance of the target resin composition will decrease, so this is not preferred. do not have.
上記共役ジエン系ゴム（ｃ）２”−１７重量部に、この
単量体混合物（ＩＩＩ）を８３〜９８重量部の範囲で、
添加し、グラフト重合を行う。Adding this monomer mixture (III) to 2''-17 parts by weight of the conjugated diene rubber (c) in a range of 83 to 98 parts by weight,
and graft polymerization.
この際に添加する単量体混合物（ＩＩＩ）の量が８３重
量部より少なく共役ジエン系ゴム（ｃ）の量が１７重量
部を超える場合には、グラフトゴム粒子径を前記範囲内
でグラフト重合することが困難となり、グラフト共重合
体の外観も劣化するので好ましくない。If the amount of the monomer mixture (III) added at this time is less than 83 parts by weight and the amount of the conjugated diene rubber (c) exceeds 17 parts by weight, the graft polymerization is carried out with the graft rubber particle diameter within the above range. This is not preferable because it becomes difficult to do so and the appearance of the graft copolymer also deteriorates.
単量体混合物（■）の量が９８重量部を超え共役ジエン
系ゴム（ｅ）の量が２重量部より少ない場合には、グラ
フ１重合していない樹脂のみが増え、グラフト共重合体
樹脂中の共役ツエン系ゴム成分の濃度が下がるので好ま
しくない。When the amount of the monomer mixture (■) exceeds 98 parts by weight and the amount of the conjugated diene rubber (e) is less than 2 parts by weight, only the unpolymerized resin increases in graph 1, and the graft copolymer resin This is not preferable because the concentration of the conjugated tsene rubber component therein decreases.
このグラフト重合は、公知の塊状重合法、溶液重合法、
懸濁重合法、および／または乳化重合法等の方法を、回
分または連続方式で、これらの方法および方式を、適宜
組み合わせて採用することができる。塊状−′＠濁重重
合法よる例をあげると、まず、共役ジエン系ゴムを単量
体混合物に完全に溶解した溶液系を一旦形成させてから
、剪断応力をかけながら重合を行う。ついで、グラフト
ゴム粒子が安定して形成された後、懸濁重合に移行し、
重合を完結させるとともに未反応単量体を回収する。This graft polymerization can be carried out using known bulk polymerization methods, solution polymerization methods,
Methods such as a suspension polymerization method and/or an emulsion polymerization method can be employed in a batch or continuous manner, or in appropriate combinations of these methods and methods. To give an example of the bulk-'@turbidity polymerization method, first, a solution system in which the conjugated diene rubber is completely dissolved in a monomer mixture is once formed, and then polymerization is carried out while applying shear stress. Then, after the graft rubber particles are stably formed, suspension polymerization is carried out,
Upon completion of polymerization, unreacted monomers are recovered.
このグラフト重合においては、アクリロニトリル−ゴム
成分−スチレン系共重合体の公知の重合開始剤および、
必要に応じて、分子量調節剤、安定剤、酸化防止剤、界
面活性剤、懸濁安定剤等の助剤を、適宜組み今わせて用
いることができる。In this graft polymerization, a known polymerization initiator for acrylonitrile-rubber component-styrene copolymer and
If necessary, auxiliary agents such as molecular weight regulators, stabilizers, antioxidants, surfactants, and suspension stabilizers may be used in combination as appropriate.
本発明組成物を構成する共重合体樹脂（Ｄ）は、芳香族
ビニル単量体５５〜８５重量％、およびシアン化ビニル
単量体１５〜４５重量％よりなる単量体混合物（■）を
、重合して製造される。この共重合体樹脂（Ｄ）は、本
発明に係る樹脂組成物に合わせて、適当な分子量と組成
をもつ公知のアクリロニトリル・スチレン共重合体（Ａ
ｓ樹脂）である。The copolymer resin (D) constituting the composition of the present invention is a monomer mixture (■) consisting of 55 to 85% by weight of aromatic vinyl monomer and 15 to 45% by weight of vinyl cyanide monomer. , produced by polymerization. This copolymer resin (D) is a known acrylonitrile-styrene copolymer (A
s resin).
上記単量体混合物（ＩＶ）の重合方法および重合条件は
、公知のＡｓ樹脂製造技術に準じて、乳化重合法、懸濁
重合法、溶液重合法、塊状重合法等の方法を、回分また
は連続方式から、適宜選択することができる。単量体混
合物ＮＶ）の成分である芳香族ビニル単量体およびシア
ン化ビニル単量体とは、前記に例示した各々のビニル単
量体と同義である。The polymerization method and polymerization conditions for the above monomer mixture (IV) are based on known As resin manufacturing techniques, and include batch or continuous methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization. The method can be selected as appropriate. The aromatic vinyl monomer and vinyl cyanide monomer that are the components of the monomer mixture NV) have the same meanings as the vinyl monomers exemplified above.
これら各々のビニル単量体が単量体混合物（ＩＶ）に占
める比率は、前記単量体混合物（ＩＩ）で限定された範
囲と同一の範囲である。しかし、単量体混合物（ＴＶ）
の組成は、−上記範囲内にあればよく、単量体混合物（
ＩＩ）の組成と全く同一ということを必ずしも意味する
ものではない。この範囲を外れると、重合条件の変更が
必要となるぽかりでなく、配合する他のグラフト共重合
体樹脂の種類および組成が限定されるので好ましくない
。The proportion of each of these vinyl monomers in the monomer mixture (IV) is within the same range as defined for the monomer mixture (II). However, the monomer mixture (TV)
The composition of - may be within the above range, and the composition of the monomer mixture (
This does not necessarily mean that the composition is exactly the same as II). Outside this range, the polymerization conditions may need to be changed and the type and composition of other graft copolymer resins to be blended will be limited, which is not preferable.
本発明に係る樹脂組成物は、以−ヒ説明したようなグラ
フト共重合体樹脂を（Ａ）５〜８９重量部、共重合体樹
脂（Ｂ）を１０〜９０重量部、グラフト共重合体樹脂（
Ｃ）を１〜４５重量部、および共重合体樹脂（Ｄ）を０
〜５０重量部（ただし、共重合体樹脂（Ａ）、（Ｂ）、
（Ｃ）および（Ｄ）の合計は１００重量部とする。）の
範囲で秤量し、混合する。混合物はさらに溶融混線工程
に付すのが好ましい。各々の共重合体樹脂の配合量が、
上の範囲を外れると、目的とする耐熱性および耐衝撃性
が得られず、また加工性の良好な熱可塑性樹脂組成物と
することができない。The resin composition according to the present invention contains 5 to 89 parts by weight of the graft copolymer resin (A), 10 to 90 parts by weight of the copolymer resin (B), and the graft copolymer resin as described below. (
1 to 45 parts by weight of C) and 0 parts of copolymer resin (D)
~50 parts by weight (however, copolymer resins (A), (B),
The total of (C) and (D) is 100 parts by weight. ) and mix. Preferably, the mixture is further subjected to a melt mixing step. The amount of each copolymer resin is
If it is outside the above range, the desired heat resistance and impact resistance will not be obtained, and a thermoplastic resin composition with good processability will not be obtained.
この配合の際、グラフト共重合体樹脂（Ａ）に由来する
共役ジエン系ゴム（ａ）成分とグラフト共重合体樹脂（
Ｃ）に由来する共役ツエン系ゴム（ｃ）成分との割合が
、重量比で、共役ジエン系ゴム（ａ）成分／共役ジエン
系ゴム（ｃ）成分＝９７／３ないし５０１５０の範囲内
となるように、選択組み合わせるのがよい。この共役ジ
エン系ゴム（ａ）成分と共役ジエン系ゴム（ｃ）成分と
の配合範囲を離れて、共役ジエン系ゴム（ｃ）成分の含
有量が過少すぎても、過剰すぎても耐衝撃性が低下する
傾向があるので、前記割合の範囲で選択組み合わせるの
がよい。During this blending, the conjugated diene rubber (a) component derived from the graft copolymer resin (A) and the graft copolymer resin (
The weight ratio of the conjugated diene rubber (c) component derived from C) is within the range of conjugated diene rubber (a) component/conjugated diene rubber (c) component = 97/3 to 50150. It is better to combine them selectively. Even if the content of the conjugated diene rubber (c) component is too low or too high, the impact resistance will be improved even if the content of the conjugated diene rubber (c) component is too low or too high outside the blending range of the conjugated diene rubber (a) component and the conjugated diene rubber (c) component. Since there is a tendency for the ratio to decrease, it is preferable to select and combine them within the above ratio range.
また、本発明に係る樹脂組成物中に含有される共役ジエ
ン系ゴム（ａ）成分および共役ジエン系ゴム（ｃ）成分
の合計が、この樹脂組成物全体に対して５〜４０重量％
の範囲内となるように配合するのが好ましい。共役ジエ
ン系ゴム（ａ）成分および共役ジエン系ゴム（ｃ）成分
の合計が、上記範囲を離れて過少すぎると、耐衝撃性が
低下する傾向があり、過剰すぎると樹脂紹成物の耐熱性
、剛性、溶融流動性などが低下し、成形品外観などに好
ましくない影響を与えるので、上記の範囲にするのがよ
い。Further, the total amount of the conjugated diene rubber (a) component and the conjugated diene rubber (c) component contained in the resin composition of the present invention is 5 to 40% by weight based on the entire resin composition.
It is preferable to mix it so that it falls within the range of . If the total of the conjugated diene rubber (a) component and the conjugated diene rubber (c) component is too small outside the above range, the impact resistance will tend to decrease, and if it is too large, the heat resistance of the resin introduction product will decrease. , the rigidity, melt flowability, etc. will be reduced, and this will have an unfavorable effect on the appearance of the molded product, so it is preferable to keep it within the above range.
グラフト共重合体樹脂（Ａ）、共重合体樹脂（Ｂ）、グ
ラフト共重合体樹脂（Ｃ）および共重合体樹脂（Ｄ）を
配合し、混合混練するには、公知の混合混線方法によれ
ばよい。The graft copolymer resin (A), the copolymer resin (B), the graft copolymer resin (C), and the copolymer resin (D) are mixed and kneaded using a known mixing method. Bye.
例えば、粉末、ビード、またはペレットとなったこれら
共重合体樹脂の１種または２種以−ヒの混合物を、−軸
押出機、二軸押出機等の押出機、または、バンバリーミ
キサ−１加圧ニーグー、二本ロール等の混練機等により
、樹脂組成物とすることができる。また、場合によって
は、重合を終えたこれらの共重合体樹脂の１種または２
種以」二のものを未乾燥状態のまま混合し、析出し、洗
浄し、乾燥して、混練する方法を採ることもできる。For example, a mixture of one or two of these copolymer resins in the form of powder, beads, or pellets is processed using an extruder such as a -screw extruder or a twin-screw extruder, or a Banbury mixer. A resin composition can be prepared using a kneader such as a pressure kneader or a two-roll kneader. In some cases, one or two of these copolymer resins after polymerization may be used.
It is also possible to adopt a method in which two or more species are mixed in an undried state, precipitated, washed, dried, and kneaded.
この混合混練の順序としては、同時に４種類の成分樹脂
を混合混練してもよく、また、まず最初に成分樹脂の１
種または２種以上を混合混練し、別途１種または２種以
−ヒを混練したものをあとから合わせ混練して、目的の
樹脂組成物としてもよ（１゜
また、樹脂組成物中に揮発分が残留していると、耐熱性
が低下することがあるので、押出機を用いて混合混線の
際には、真空ベント等に上り脱揮操作を行うのがよい。As for the order of this mixing and kneading, four types of component resins may be mixed and kneaded at the same time, or one of the component resins may be mixed and kneaded first.
The desired resin composition may also be obtained by mixing and kneading one or more kinds, and then kneading one or more kinds separately and kneading them together later. If any fraction remains, the heat resistance may deteriorate, so when mixing and mixing using an extruder, it is recommended to go up to a vacuum vent or the like and perform a devolatilization operation.
本発明に係る樹脂組成物は、そのまま成形加工等に用い
ることができる。また、他の熱可塑性樹脂、例えば、ポ
リスチレン、ＡＳ樹脂、ＡＢＳ樹脂、ポリメチルメタク
リレート、ポリ塩化ビニル、ポリカーボネート、ポリア
ミド、ポリブチレンテレフタレート、ポリフェニレンオ
キシド、アクリロニトリル・ＥＰＤＭゴム・スチレン共
重合体（ＡＢＳ樹脂）等と混合混練して、耐熱性耐衝撃
性樹脂として用いることもできる。The resin composition according to the present invention can be used as it is for molding and the like. In addition, other thermoplastic resins such as polystyrene, AS resin, ABS resin, polymethyl methacrylate, polyvinyl chloride, polycarbonate, polyamide, polybutylene terephthalate, polyphenylene oxide, acrylonitrile/EPDM rubber/styrene copolymer (ABS resin) It can also be used as a heat-resistant and impact-resistant resin by mixing and kneading with the like.
本発明に係る樹脂組成物には、樹脂の性質を阻害しない
種類および量の潤滑剤、離型剤、着色剤、帯電防止剤、
難燃化剤、紫外線吸収剤、耐光性安定剤、耐熱性安定剤
、充填剤等の各種樹脂添加剤を、適宜組み合わせて添加
することができる。The resin composition according to the present invention includes a lubricant, a mold release agent, a coloring agent, an antistatic agent, in a type and amount that does not inhibit the properties of the resin,
Various resin additives such as flame retardants, ultraviolet absorbers, light resistance stabilizers, heat resistance stabilizers, and fillers can be added in appropriate combinations.
本発明に係る樹脂組成物は、射出成形法、押出成形法、
圧縮成形法等の各種加工方法によって、自動車部分、電
気部品、工業部品等の成形品とし、優れた耐熱性および
耐衝撃性が要求される用途に使用することができる。The resin composition according to the present invention can be produced by injection molding method, extrusion molding method,
By various processing methods such as compression molding, it can be made into molded products such as automobile parts, electrical parts, industrial parts, etc., and used in applications requiring excellent heat resistance and impact resistance.
「発明の効果」
本発明は、以上説明したとおりであり、次のように特別
に顕著な効果を奏し、その産業上の利用価値は極めて大
である。"Effects of the Invention" The present invention has been described above, and has particularly remarkable effects as described below, and its industrial utility value is extremely large.
（１）本発明に係る樹脂組成物は、グラフト共重合体樹
脂（Ａ）および共重合体樹脂（Ｂ）の構成成分として、
これら画構成成分には適量のＮ−置換マレイミド単量体
を含有しているので、優れた耐熱性をもつ。(1) The resin composition according to the present invention includes, as constituent components of the graft copolymer resin (A) and the copolymer resin (B),
Since these image constituents contain an appropriate amount of N-substituted maleimide monomer, they have excellent heat resistance.
（２）本発明に係る樹脂組成物は、グラフト共重合体樹
脂（Ａ）における共役ジエン系ゴム（ａ）成分およびグ
ラフト共重合体樹脂（Ｃ）における共役ジエン系ゴム（
Ｃ）成分について、各々のゴム成分割合、各々のゴム成
分を合計した配合量、および各々のゴム粒子径をそれぞ
れ最適化して配合しているので、優れた耐衝撃性、特に
落錘衝撃強度が大きい熱可塑性樹脂として利用すること
ができる。(2) The resin composition according to the present invention comprises the conjugated diene rubber (a) component in the graft copolymer resin (A) and the conjugated diene rubber (a) component in the graft copolymer resin (C).
As for component C), the ratio of each rubber component, the total blending amount of each rubber component, and the particle size of each rubber are optimized and blended, so it has excellent impact resistance, especially falling weight impact strength. Can be utilized as a large thermoplastic.
（３）本発明に係る樹脂組成物は、グラフト共重合体樹
脂（Ｃ）および共重合体樹脂（Ｄ）を含有するので、Ａ
ＢＳ樹脂の一品種として良好な加工性と耐薬品性をもつ
。(3) Since the resin composition according to the present invention contains the graft copolymer resin (C) and the copolymer resin (D), A
As a type of BS resin, it has good processability and chemical resistance.
（４）本発明に係る樹脂組成物は、他の硬質の熱可塑性
樹脂と優れた相溶性を持つので、混線混合することによ
り、耐熱性耐衝撃性の優れた別種の樹脂組成物を製造す
ることができる。(4) Since the resin composition according to the present invention has excellent compatibility with other hard thermoplastic resins, a different type of resin composition with excellent heat resistance and impact resistance can be produced by cross-mixing. be able to.
［実施例−１
次に本発明につき、実施例をあげて説明するが、本発明
は、その要旨を超えない限り、以下の実施例に限定され
るものではない。以下の例において１部」とあるのは、
「重量部」を表わす。[Example-1] Next, the present invention will be described with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof. In the following examples, "Part 1" means:
Represents "parts by weight".
製造例
（１）グラフト共重合体樹脂（Ａ）の製造スチレン（以
下Ｓｔと略記する。）４５部、Ｎ−フェニルマレイミド
（以下Ｎ−ＰＭＩと略記する。）３０部、アクリロニト
リル（以下ＡＮと略記する。）２５部およびテルピノレ
ン（分子量調節剤）０．６部よりなる単量体混合物（１
）を調製した。Production Example (1) Production of graft copolymer resin (A) Styrene (hereinafter abbreviated as St) 45 parts, N-phenylmaleimide (hereinafter abbreviated as N-PMI) 30 parts, acrylonitrile (hereinafter abbreviated as AN) ) and 0.6 parts of terpinolene (molecular weight regulator) (1
) was prepared.
撹拌装置、還流冷却器、温度計、助剤添加装置を備えた
ガラス製フラスコに、スチレン・ブタジェン・ゴムラテ
ックス（Ｓｔ含有量１０重量％、ゴム固形分濃度３０重
量％、ゴム粒子径０．３０μ＋６）３３３部（水を含む
。）、および脱イオン水１５０部を仕込み、窒素気流下
、撹拌しながら、内温を８０℃に昇温した。Styrene-butadiene rubber latex (St content 10% by weight, rubber solids concentration 30% by weight, rubber particle size 0.30 μ + 6 ) 333 parts (including water) and 150 parts of deionized water were charged, and the internal temperature was raised to 80°C while stirring under a nitrogen stream.
ついで、このフラスコに過硫酸カリウム（以下ＫＰＳと
略記する。）水溶液２部（０，１部のＫＰＳを含む。）
を２４０分間にわたって、単量体混合物（１）全量を２
１０分間にわたって、連続的に添加を始め、同温度で重
合を開始した。重合を開始してから６０分後および１８
０分後に、ドデシルベンゼンスルホン酸ナトリウム０．
２部づつを重合系に添加した。重合を開始してから、３
６０分間同温度でグラフト重合反応を続けた。Next, 2 parts of potassium persulfate (hereinafter abbreviated as KPS) aqueous solution (containing 0.1 part of KPS) was added to this flask.
for 240 minutes, the total amount of monomer mixture (1) was
Addition was started continuously over 10 minutes and polymerization started at the same temperature. 60 minutes after starting polymerization and 18
After 0 minutes, sodium dodecylbenzenesulfonate 0.
Two parts were added to the polymerization system. After starting polymerization, 3
The graft polymerization reaction was continued at the same temperature for 60 minutes.
グラフト重合反応を終了後に得られたラテックスを、９
５°Ｃに加温した４％硫酸マグネシウム水溶液へ滴下し
て塩析し、脱水、乾燥して粉末状のマレイミド系グラフ
ト共重合体樹脂（Ａ）を得た。The latex obtained after completing the graft polymerization reaction was
It was added dropwise to a 4% aqueous magnesium sulfate solution heated to 5°C for salting out, dehydrated, and dried to obtain a powdered maleimide-based graft copolymer resin (A).
（２）共重合体樹脂（Ｂ）の製造
還流コンデンサー、撹拌機および単量体供給装置を備え
た重合槽に、ポリビニルアルコール系懸濁剤０．０３部
を溶解した脱イオン水１００部を仕込んだ。さらにこの
重合槽に５ｔ３０部、ＡＮ１５部、Ｎ−ＰＭ Ｉ ２０
部よりなる単量体混合物を、テルビルン（分子量調節剤
）０．４部とともに仕込み、窒素気流下で撹拌しながら
、槽内温度を６０°Ｃに保持し、重合開始剤としてα、
ａ゛−アゾビスイソブチロニトリル０．０６部を添加し
て、重合反応を開始した。(2) Production of copolymer resin (B) 100 parts of deionized water in which 0.03 part of a polyvinyl alcohol suspension agent was dissolved was charged into a polymerization tank equipped with a reflux condenser, a stirrer, and a monomer supply device. is. Furthermore, 30 parts of 5t, 15 parts of AN, and 20 parts of N-PM I were added to this polymerization tank.
0.4 parts of terbirun (molecular weight regulator) were added together with 0.4 parts of terbirun (molecular weight regulator), and the temperature inside the tank was maintained at 60°C while stirring under a nitrogen stream.
A polymerization reaction was started by adding 0.06 part of a-azobisisobutyronitrile.
つぎに、重合反応を開始したあと直ちに、前記単量体供
給装置から重合槽への添加を開始し、５ｔ１５部、ＡＮ
１０部、Ｎ−ＰＭＩ １０部に、α。Next, immediately after starting the polymerization reaction, the addition from the monomer supply device to the polymerization tank was started, and 15 parts of AN
10 parts, N-PMI 10 parts, α.
α゛−アゾビスイソブチロニトリル００４部およびテル
ビルン０．２部を添加した残部の単量体混合物を１２０
分を要して連続的に添加した。また、重合反応を開始し
てから１５分経過した際に重合槽にポリビニルアルコー
ル系＠濁剤を０．０３部添加し、更に重合反応を開始し
てから３０分後、６０分後、９０分後、１２０分後にそ
れぞれ０．０２２５部づつのポリビニルアルコール系懸
濁剤を重合槽に添加した。この間重合糸の温度は６０℃
に維持した。004 parts of α゛-azobisisobutyronitrile and 0.2 parts of tervirune were added, and the remaining monomer mixture was added to 120 parts of
It was added continuously over a period of time. In addition, 0.03 parts of polyvinyl alcohol-based @turbidity was added to the polymerization tank 15 minutes after starting the polymerization reaction, and then 30 minutes, 60 minutes, and 90 minutes after starting the polymerization reaction. After 120 minutes, 0.0225 parts of a polyvinyl alcohol suspending agent was added to the polymerization tank. During this time, the temperature of the polymerized thread was 60℃.
maintained.
重合反応を開始してから１８０分経過後、重合槽にアク
リル酸・２エチルへキシルアクリレート共重合体（懸濁
剤）０．０３部、と、硫酸す） ＋７ウム０．２６部を
加え、３０分を要して重合系の温度を７５℃に昇温し、
同温度で１２０分間重合反応を継続した。続いて、重合
系の温度を８０℃に昇温しで、窒素ガス気流下でストリ
ッピングを行ないながら、１２０分間重合反応を行ない
、生成した共重合体樹脂のスラリーを濾過し、脱水乾燥
して、粒状のマレイミド系共重合体樹脂８６．５重量部
を得た。After 180 minutes from starting the polymerization reaction, 0.03 part of acrylic acid/2-ethylhexyl acrylate copolymer (suspending agent) and 0.26 part of sulfuric acid) were added to the polymerization tank. It took 30 minutes to raise the temperature of the polymerization system to 75°C,
The polymerization reaction was continued at the same temperature for 120 minutes. Subsequently, the temperature of the polymerization system was raised to 80°C, and the polymerization reaction was carried out for 120 minutes while stripping under a nitrogen gas stream. The resulting copolymer resin slurry was filtered, dehydrated and dried. , 86.5 parts by weight of granular maleimide copolymer resin was obtained.
このようにしてえられたマレイミド系共重合体樹脂に、
ステアリル−β−（３，５−ジ−ｔ−ブチル−４−ヒド
ロキシフェニル）プロピオネート（酸化防止剤）とステ
アリン酸マグネシウム（滑剤）とを、共重合体樹脂１０
０部当りそれぞれ０．１部配合し、ベント付き押出機で
脱気しながら混練し、ペレット化して、共重合体樹脂（
Ｂ）を得た。The maleimide copolymer resin obtained in this way has
Stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (antioxidant) and magnesium stearate (lubricant) were mixed into copolymer resin 10
0 parts per 0 parts of each, knead with a vented extruder while degassing, pelletize, and make the copolymer resin (
B) was obtained.
（３） グラフト共重合体樹脂（Ｃ）の製造イカリ型撹
拌装置を備えたオートクレーブ中にブタジェンゴム（ジ
エンＮ Ｆ −３５、ｍ化ｔ（株）製）１５５部をＡＮ
２１１部と５ｔ６３４部の混合物中に溶解した。これに
ｔｅｒｔ−ブチルパーアセテート０．１３部、ジーｔｅ
ｒｔ−ブチルパーオキサイド０．５部および安定剤混合
物０．７部を添加して、重合を開始した。混合物を窒素
雰囲気下１００℃に加熱、毎分１００回転の撹拌下で重
合を進め、この間６０分間当り約１部の割合でテルビル
ンを、重合を開始してから３００分間の時間にわたって
加え、最後に５部を追加した。(3) Production of graft copolymer resin (C) 155 parts of butadiene rubber (Diene NF-35, manufactured by MT Co., Ltd.) was placed in an autoclave equipped with an Ikari type stirring device.
It was dissolved in a mixture of 211 parts and 634 parts of 5t. To this was added 0.13 parts of tert-butyl peracetate,
Polymerization was started by adding 0.5 part of rt-butyl peroxide and 0.7 part of stabilizer mixture. The mixture was heated to 100° C. under a nitrogen atmosphere and the polymerization proceeded with stirring at 100 revolutions per minute. During this time, Tervirune was added at a rate of about 1 part per 60 minutes over a period of 300 minutes from the start of the polymerization, and finally Added 5 parts.
単量体の転化率が約３０％に達した時、重合混合物（シ
ロップ）を脱イオン水１２００部中懸濁剤（アクリル酸
・２エチルへキシルアクリレート共重合体）３部の水溶
液を収容したオートクレーブ（３枚後退翼付撹袢器を備
えたもの）に移し換えた。When the monomer conversion reached approximately 30%, the polymerization mixture (syrup) was charged with an aqueous solution of 3 parts of a suspending agent (acrylic acid/2-ethylhexyl acrylate copolymer) in 1200 parts of deionized water. The mixture was transferred to an autoclave (equipped with a stirrer with three swept blades).
窒素置換の後、この懸濁系を１３０°Ｃ１毎分５００回
転の条件下に１２０分間重合、さらに１５０℃にて６０
分間ストリッピングを行った。After nitrogen substitution, this suspension system was polymerized for 120 minutes at 130°C and 500 revolutions per minute, and further polymerized for 60 minutes at 150°C.
Stripping was performed for minutes.
得られた樹脂を水洗後乾燥して約９９０部のグラフト共
重合体樹脂（Ｃ）を得た。なお、このグラフト共重合体
樹脂中のゴム粒子径は約１．９μ【ｎであった。The obtained resin was washed with water and dried to obtain about 990 parts of graft copolymer resin (C). The diameter of the rubber particles in this graft copolymer resin was approximately 1.9 μm.
（４）共重合体樹脂（Ｄ＞
アクリロニトリル・スチレン共重合体（Ａｓｈ（脂、５
ＡＮｅ）−Ｃ１三菱モンサント化成（株）製）を用いた
。(4) Copolymer resin (D> Acrylonitrile-styrene copolymer (Ash, 5
ANe)-C1 (manufactured by Mitsubishi Monsanto Chemical Co., Ltd.) was used.
実施例トす４、比較例トす２
上記製造例に記載の方法で得られたグラフト共重合体樹
脂（Ａ）、共重合体樹脂（Ｂ）、グラフト共重合体樹脂
（Ｃ）および共重合体樹脂（Ｄ）を、第１表に記載した
配合割合（部）に従い、−軸押出機を用いてベントから
脱気しながら混練して、樹脂組成物のベレットを作成し
た。Example 4, Comparative Example 2 Graft copolymer resin (A), copolymer resin (B), graft copolymer resin (C) and copolymer obtained by the method described in the above production example The combined resin (D) was kneaded in accordance with the blending ratio (parts) shown in Table 1 using a -shaft extruder while degassing from the vent to create pellets of the resin composition.
この樹脂組成物のペレットを、熱可塑性樹脂射出成形磯
により、物性測定用の試験片を成形した。The pellets of this resin composition were molded into test pieces for measuring physical properties using a thermoplastic resin injection molding tool.
成形試験片について、第１表に記載した方法で、引張り
強さ、アイゾツト衝撃強さくノツチ付）、落鍾衝撃強さ
、ビカット軟化点およびメルト７０−レートをそれぞれ
測定した。結果を第１表に示す。The molded test pieces were measured for tensile strength, isot impact strength (notched), drop impact strength, Vicat softening point, and melt 70-rate using the methods listed in Table 1. The results are shown in Table 1.
第１表より、次のことが明らかになる。From Table 1, the following becomes clear.
（１）本発明に係る樹脂組成物は、グラフト共重合体樹
脂（Ａ）および共重合体樹脂（Ｂ）の構成成分として、
適量のＮ−置換マレイミド単量体を含有しているので優
れた耐熱性をもつ（実施例１〜グ
？参照）。(1) The resin composition according to the present invention includes, as constituent components of the graft copolymer resin (A) and the copolymer resin (B),
Since it contains an appropriate amount of N-substituted maleimide monomer, it has excellent heat resistance (see Example 1-G).
他方、Ｎ−置換マレイミド単量体成分を含よないグラフ
ト共重合体樹脂（Ｃ）は、耐熱性が低い（比較例１参照
）。On the other hand, the graft copolymer resin (C) that does not contain the N-substituted maleimide monomer component has low heat resistance (see Comparative Example 1).
（２）本発明に係る樹脂組成物は、グラフト共重合体樹
脂（Ａ）における共役ジエン系ゴム（ａ）成分およびグ
ラフト共重合体樹脂（Ｃ）における共役ジエン系ゴム（
Ｃ）成分について、各々のゴム成分割合、各々のゴム成
分を合計した配合量、および各々のゴム粒子径をそれぞ
れ最適化して配合しているので、優れた耐衝撃性、特に
大トな落錘衝撃グ
強度をもつ（実施例１〜２参照）。(2) The resin composition according to the present invention comprises the conjugated diene rubber (a) component in the graft copolymer resin (A) and the conjugated diene rubber (a) component in the graft copolymer resin (C).
As for component C), the ratio of each rubber component, the total blending amount of each rubber component, and the particle size of each rubber are optimized and blended, so it has excellent impact resistance, especially against large falling weights. It has high impact strength (see Examples 1 and 2).
また、本発明の範囲外で得られる樹脂組成物は、耐衝撃
性が劣る（比較例２参照）。Furthermore, resin compositions obtained outside the scope of the present invention have poor impact resistance (see Comparative Example 2).
Claims (5)
香族ビニル単量体３０〜８０重量％、Ｎ−置換マレイミ
ド単量体１０〜５０重量％、シアン化ビニル単量体１０
〜４０重量％、およびこれら単量体と共重合可能な他の
ビニル単量体０〜３０重量％よりなる単量体混合物（た
だし、単量体混合物は合計１００重量％とする。）３０
〜７５重量部を、グラフト重合してなるグラフト共重合
体樹脂（Ａ）５〜８９重量部、 芳香族ビニル単量体３０〜８０重量％、Ｎ−置換マレイ
ミド単量体１０〜５０重量％、シアン化ビニル単量体１
０〜４０重量％、およびこれら単量体と共重合可能な他
のビニル単量体０〜３０重量％よりなる単量体混合物（
ただし、単量体混合物は合計１００重量％とする。）を
、重合してなる共重合体樹脂（Ｂ）１０〜９０重量部、 共役ジエン系ゴム（ｃ）２〜１７重量部に、芳香族ビニ
ル単量体５５〜８５重量％、およびシアン化ビニル単量
体１５〜４５重量％よりなる単量体混合物（ただし、単
量体混合物は合計１００重量％とする。）８３〜９８重
量部を、グラフト重合しでなるグラフト共重合体樹脂（
Ｃ）１〜４５重量部、および、 芳香族ビニル単量体５５〜８５重量％、およびシアン化
ビニル単量体１５〜４５重量％よりなる単量体混合物（
ただし、単量体混合物は合計１００重量％とする。）を
、重合してなる共重合体樹脂（Ｄ）０〜５０重量部、 を含有（ただし、共重合体樹脂（Ａ）、（Ｂ）、（Ｃ）
および（Ｄ）の合計は１００重量部とする。）してなる
ことを特徴とする耐熱性耐衝撃性樹脂組成物。(1) Conjugated diene rubber (a) 25-70 parts by weight, 30-80% by weight of aromatic vinyl monomer, 10-50% by weight of N-substituted maleimide monomer, and 10% by weight of vinyl cyanide monomer.
~40% by weight, and 0 to 30% by weight of other vinyl monomers copolymerizable with these monomers (however, the total monomer mixture is 100% by weight) 30
~75 parts by weight, 5 to 89 parts by weight of graft copolymer resin (A) obtained by graft polymerization, 30 to 80 parts by weight of aromatic vinyl monomer, 10 to 50 parts by weight of N-substituted maleimide monomer, Vinyl cyanide monomer 1
A monomer mixture consisting of 0 to 40% by weight and 0 to 30% by weight of other vinyl monomers copolymerizable with these monomers (
However, the total amount of the monomer mixture is 100% by weight. ), 10 to 90 parts by weight of copolymer resin (B), 2 to 17 parts by weight of conjugated diene rubber (c), 55 to 85% by weight of aromatic vinyl monomer, and vinyl cyanide. A graft copolymer resin (
C) 1 to 45 parts by weight, and a monomer mixture consisting of 55 to 85% by weight of aromatic vinyl monomer and 15 to 45% by weight of vinyl cyanide monomer (
However, the total amount of the monomer mixture is 100% by weight. ), 0 to 50 parts by weight of a copolymer resin (D) formed by polymerizing (provided that the copolymer resins (A), (B), (C)
The total of (D) and (D) shall be 100 parts by weight. ) A heat-resistant and impact-resistant resin composition.
平均粒子径が０．１〜０．５μｍの範囲であることを特
徴とする、特許請求の範囲第（１）項記載の耐熱性耐衝
撃性樹脂組成物。(2) Heat resistance according to claim (1), wherein the conjugated diene rubber (a) has an average particle diameter in the latex state in the range of 0.1 to 0.5 μm. Impact resistant resin composition.
ン系ゴム（ｃ）のグラフトゴムの平均粒子径が０．５μ
ｍを超え５μｍ以下であることを特徴とする、特許請求
の範囲第（１）項または第（２）項のいずれか１項に記
載の耐熱性耐衝撃性樹脂組成物。(3) The average particle diameter of the graft rubber of the conjugated diene rubber (c) derived from the graft copolymer resin (C) is 0.5μ
The heat-resistant and impact-resistant resin composition according to claim 1 or 2, wherein the heat-resistant and impact-resistant resin composition has a particle diameter of more than m and less than or equal to 5 μm.
ン系ゴム（ａ）成分と、グラフト共重合体樹脂（Ｃ）に
由来する共役ジエン系ゴム（ｃ）成分との割合が、重量
比で 共役ジエン系ゴム（ａ）成分／共役ジエン系ゴム（ｃ）
成分＝９７／３ないし５０／５０ の範囲内で配合されてなることを特徴とする、特許請求
の範囲第（１）ないし（３）項のいずれか１項に記載の
耐熱性耐衝撃性樹脂組成物。(4) The ratio of the conjugated citric rubber (a) component derived from the graft copolymer resin (A) to the conjugated diene rubber (c) component derived from the graft copolymer resin (C) is Conjugated diene rubber (a) component/conjugated diene rubber (c)
The heat-resistant impact-resistant resin according to any one of claims (1) to (3), characterized in that the components are blended within the range of 97/3 to 50/50. Composition.
（ｃ）成分との合計が、樹脂組成物全体に対して５〜４
０重量％の範囲にされてなることを特徴とする、特許請
求の範囲第（１）ないし（４）項のいずれか１項に記載
の耐熱性耐衝撃性樹脂組成物。(5) The total of the conjugated diene rubber (a) component and the conjugated diene rubber (c) component is 5 to 4 with respect to the entire resin composition.
The heat-resistant, impact-resistant resin composition according to any one of claims (1) to (4), characterized in that the content is in the range of 0% by weight.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29559286A JPH0725981B2 (en) | 1986-12-11 | 1986-12-11 | Heat resistant and impact resistant resin composition |
| DE8787907831T DE3780952T2 (en) | 1986-12-11 | 1987-12-01 | HEAT RESISTANT AND IMPACT RESISTANT RESIN COMPOSITION. |
| US07/243,338 US4879343A (en) | 1986-12-11 | 1987-12-01 | Heat and impact resistant resin composition |
| EP87907831A EP0293490B1 (en) | 1986-12-11 | 1987-12-01 | Heat and impact resistant resin composition |
| KR1019880700970A KR960002985B1 (en) | 1986-12-11 | 1987-12-01 | Heat and impact resistant resin composition |
| PCT/JP1987/000931 WO1988004309A1 (en) | 1986-12-11 | 1987-12-01 | Heat and impact resistant resin composition |
| AU83210/87A AU596724B2 (en) | 1986-12-11 | 1987-12-01 | Heat and impact resistant resin composition |
| CA000554010A CA1304855C (en) | 1986-12-11 | 1987-12-10 | Heat and impact resistant resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29559286A JPH0725981B2 (en) | 1986-12-11 | 1986-12-11 | Heat resistant and impact resistant resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63146955A true JPS63146955A (en) | 1988-06-18 |
| JPH0725981B2 JPH0725981B2 (en) | 1995-03-22 |
Family
ID=17822622
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29559286A Expired - Lifetime JPH0725981B2 (en) | 1986-12-11 | 1986-12-11 | Heat resistant and impact resistant resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0725981B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000198905A (en) * | 1998-10-29 | 2000-07-18 | Ube Cycon Ltd | Thermoplastic resin composition |
| WO2020101275A1 (en) * | 2018-11-15 | 2020-05-22 | 주식회사 엘지화학 | Graft copolymer production method |
-
1986
- 1986-12-11 JP JP29559286A patent/JPH0725981B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000198905A (en) * | 1998-10-29 | 2000-07-18 | Ube Cycon Ltd | Thermoplastic resin composition |
| JP4618692B2 (en) * | 1998-10-29 | 2011-01-26 | ユーエムジー・エービーエス株式会社 | Rubber-containing graft polymer and thermoplastic resin composition |
| WO2020101275A1 (en) * | 2018-11-15 | 2020-05-22 | 주식회사 엘지화학 | Graft copolymer production method |
| KR20200056848A (en) * | 2018-11-15 | 2020-05-25 | 주식회사 엘지화학 | Method for prepraring graft copolymer |
| US11708443B2 (en) | 2018-11-15 | 2023-07-25 | Lg Chem, Ltd. | Method of preparing graft copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0725981B2 (en) | 1995-03-22 |
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