JPH02178346A - Thermoplastic resin composition - Google Patents
Thermoplastic resin compositionInfo
- Publication number
- JPH02178346A JPH02178346A JP33400688A JP33400688A JPH02178346A JP H02178346 A JPH02178346 A JP H02178346A JP 33400688 A JP33400688 A JP 33400688A JP 33400688 A JP33400688 A JP 33400688A JP H02178346 A JPH02178346 A JP H02178346A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- thermoplastic resin
- polyolefin
- modified polyolefin
- weight
- 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
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 20
- 239000011342 resin composition Substances 0.000 title claims description 5
- 229920000098 polyolefin Polymers 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 229920001971 elastomer Polymers 0.000 claims abstract description 13
- 239000005060 rubber Substances 0.000 claims abstract description 13
- 229920001155 polypropylene Polymers 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims abstract description 8
- 150000008360 acrylonitriles Chemical class 0.000 claims abstract description 3
- 239000004711 α-olefin Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 4
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- -1 acrylic ester Chemical class 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 10
- 238000000034 method Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical group C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SJLLJZNSZJHXQN-UHFFFAOYSA-N 1-dodecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCN1C(=O)C=CC1=O SJLLJZNSZJHXQN-UHFFFAOYSA-N 0.000 description 1
- CYAVCUNFWUJTHY-UHFFFAOYSA-N 1-ethyl-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(CC)C(=O)C=C1C1=CC=CC=C1 CYAVCUNFWUJTHY-UHFFFAOYSA-N 0.000 description 1
- HOLZCMFSCBLOLX-UHFFFAOYSA-N 1-octadecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCCCCCCCN1C(=O)C=CC1=O HOLZCMFSCBLOLX-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- BTOVVHWKPVSLBI-UHFFFAOYSA-N 2-methylprop-1-enylbenzene Chemical compound CC(C)=CC1=CC=CC=C1 BTOVVHWKPVSLBI-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- DYYFCJRYZVHEKQ-UHFFFAOYSA-N 3-butoxycarbonylbut-3-enoic acid Chemical compound CCCCOC(=O)C(=C)CC(O)=O DYYFCJRYZVHEKQ-UHFFFAOYSA-N 0.000 description 1
- NMXSDUSRXRNRLK-UHFFFAOYSA-N 3-methyl-4-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C)=C1C1=CC=CC=C1 NMXSDUSRXRNRLK-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 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
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 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
- 150000008064 anhydrides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 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
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野コ 本発明は熱可塑性樹脂組成物に関する。[Detailed description of the invention] [Industrial application fields] The present invention relates to thermoplastic resin compositions.
［従来の技術］
ＡＢＳ系樹脂の成形性（流動性）改良については、従来
よりゴムの粒子径とゴムに対する七ツマ−のグラフト率
の調整によって行なわれている。[Prior Art] The moldability (fluidity) of ABS resins has conventionally been improved by adjusting the particle size of the rubber and the grafting ratio of seven polymers to the rubber.
例えば、特開昭［１２−Ｉ６７３４． 特開昭５９−
１４７００号公報等に記載されている。For example, JP-A-Sho [12-I6734. Unexamined Japanese Patent Publication 1987-
It is described in Publication No. 14700 and the like.
［発明が解決しようとする課題］
しかしながら従来のものでは耐熱性を低下させずに成形
性（流動性）を改良することは難しかった。[Problems to be Solved by the Invention] However, with conventional products, it has been difficult to improve moldability (fluidity) without reducing heat resistance.
〔課題を解決するための手段］
本発明者らはＬ記問題点を鑑みて、鋭意検討した結果、
本発明に到達した。[Means for Solving the Problems] The present inventors have made extensive studies in view of the problems in Section L, and have found that:
We have arrived at the present invention.
すなわち本発明は、ゴム強化熱可塑性樹脂（Ａ）と不飽
和ジカルボン酸および／またはその誘導体で変性された
変性ポリオレフィン（Ｂ）からなる熱ｉｉＪ塑性樹脂組
成物である。That is, the present invention is a thermoplastic resin composition comprising a rubber-reinforced thermoplastic resin (A) and a modified polyolefin (B) modified with an unsaturated dicarboxylic acid and/or its derivative.
本発明に用いられるゴノ、強化熱可塑性樹脂（Ａ）とし
ては、ゴム（ａ）の存在下、芳香族ビニル化合物、シア
ン化ビニル化合物および不飽和モノカルボン酸アルキル
エステル化合物からなる群より選ばれた一挿具−にの化
合物（ｂ）を重合してなる重合体があげられる。The reinforced thermoplastic resin (A) used in the present invention is selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, and unsaturated monocarboxylic acid alkyl ester compounds in the presence of the rubber (a). Examples include polymers obtained by polymerizing compound (b).
ゴム強化熱可塑性樹脂（Ａ）を構成するゴム（ａ）とし
ては公知のゴムが使用でき、例としては、ポリブタジェ
ン、ブタジェン−スチレン共重合体、ブタジェン−（メ
タ）アクリロニトリル共重合体等の共役ツエン系ゴム、
エヂレンーブロビレン共重合体、エチレン−プロピレン
−非共役および共役ツエン共重合体等のエチレン−プロ
ピレン系ゴム、ポリブチル（メタ）アクリレート、ブチ
ル（メタ）アクリレート−スチレン共重合体等の（メタ
）アクリルエステル系ゴム、塩素化ポリエチレン、エチ
レン−酢酸ビニル共重合体等があげられる。As the rubber (a) constituting the rubber-reinforced thermoplastic resin (A), known rubbers can be used, such as conjugated tzenes such as polybutadiene, butadiene-styrene copolymer, butadiene-(meth)acrylonitrile copolymer, etc. rubber,
Ethylene-propylene rubbers such as ethylene-propylene copolymers, ethylene-propylene-nonconjugated and conjugated tsene copolymers, (meth)acrylates, butyl (meth)acrylate-styrene copolymers, etc. Examples include acrylic ester rubber, chlorinated polyethylene, and ethylene-vinyl acetate copolymer.
化合物（ｂ）のうち、芳香族ビニル化合物としては、公
知のものが使用でき、例えばスチレン、α−メチルスチ
レン、ジメチルスチレン、ビニルトルエン、ｔブチルス
チレン、クロルトルエン等を挙げることができる。Among compound (b), known aromatic vinyl compounds can be used, such as styrene, α-methylstyrene, dimethylstyrene, vinyltoluene, t-butylstyrene, chlorotoluene, and the like.
シアン化ビニル化合物としては、公知のものが使用でき
、例えばアクリロニトリル、メタクリロニトリル等を挙
げることができる。As the vinyl cyanide compound, known compounds can be used, such as acrylonitrile, methacrylonitrile, and the like.
不飽和モノカルボン酸アルキルエステル化合物としても
公知のものが使用でき、例としてはメチル（メタ）アク
リレート、エチル（メタ）アクリレート、ブチル（メタ
）アクリレート、ヒドロキシエチル（メタ）アクリレー
ト、ヒドロキシプロピル（メタ）アクリレート等が挙げ
られる。Known unsaturated monocarboxylic acid alkyl ester compounds can also be used; examples include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate. Examples include acrylate.
ゴム強化熱可塑性樹脂（Ａ）におけるゴム（ａ）と化合
物（ｂ）１は特に限定はないが、一般にはゴム（ａ）が
３〜７０重量％、化合物（ｂ）が３７〜３０重量％であ
ることが好ましい。The rubber (a) and compound (b) 1 in the rubber-reinforced thermoplastic resin (A) are not particularly limited, but generally the rubber (a) is 3 to 70% by weight and the compound (b) is 37 to 30% by weight. It is preferable that there be.
また、化合物（ｂ）の組成は上記の群から任意に選べ、
二種以上の化合物を使用する場合の組成比も限定ないが
、一般には、芳香族ビニル化合物４０〜８０重量％とシ
アン化ビニル化合物および／または不飽和カルボン酸ア
ルキルエステル化合物ＧＯ〜２０重量％からなる混合物
であることが好ましい。Further, the composition of compound (b) can be arbitrarily selected from the above group,
When using two or more kinds of compounds, the composition ratio is not limited, but generally it is composed of 40 to 80% by weight of an aromatic vinyl compound and 20 to 20% by weight of a vinyl cyanide compound and/or an unsaturated carboxylic acid alkyl ester compound GO. It is preferable that it is a mixture.
なお、ゴム強化熱可塑性樹脂の粒子径は、特に限定ない
が０．０５〜５μが好ましく、０．１〜０．５μが特に
好ましい。The particle diameter of the rubber-reinforced thermoplastic resin is not particularly limited, but is preferably 0.05 to 5 microns, particularly preferably 0.1 to 0.5 microns.
ゴム強化熱可塑性樹脂の具体例としてはＡＢＳ樹脂など
が挙げられる。A specific example of the rubber-reinforced thermoplastic resin includes ABS resin.
ゴム強化熱可塑性樹脂の製造法としては、公知の方法が
使用でき、例えば乳化重合法、懸濁重合法、塊状重合法
、溶液重合法、これらの組合せ等が挙げられる
本発明に用いられる変性ポリオレフィン（Ｂ）としては
、不飽和ノカルボン酸および／またその誘導体で変性さ
れたものが挙げられる。Known methods can be used to produce the rubber-reinforced thermoplastic resin, such as emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, and combinations thereof. Examples of (B) include those modified with unsaturated nocarboxylic acids and/or derivatives thereof.
変性に用いられる不飽和ジカルボン酸としてはマレイン
酸、イタコン酸、シトラコン酸、アクニット酸、または
、これらのノカルボン酸の無水物などが挙げられ、一種
または二種量１−を用いることができる。これらのうち
好ましいものは無水マレイン酸である。不飽和ジカルボ
ン酸の誘導体としては、マレイン酸ブチル、マレイン酸
ノブチル、イタコン酸ブチルなどの不飽和ノカルボン酸
モノマタはジエステル類、または、不飽和ジカルボン酸
のモノ、ノアミド類、Ｎ−フェニルマレイミド、Ｎ−２
−メチルフェニルマレイミド、Ｎ−２−エチルフェニル
マレイミドなどのＮ−フェニルマレイミド類、Ｎ−ラウ
リルマレイミド、Ｎ−ステアリルマレイミドなどの炭素
数２〜１８のアルキルマレイミド類が挙げられ、一種ま
たは二種以上を用いることができる。これらのうち好ま
しいものはＮ−フェニルマレイミドである。Examples of the unsaturated dicarboxylic acids used for modification include maleic acid, itaconic acid, citraconic acid, acunitic acid, and anhydrides of these nocarboxylic acids, and one or two types of these acids may be used. Among these, maleic anhydride is preferred. As derivatives of unsaturated dicarboxylic acids, unsaturated nocarboxylic acid monomers such as butyl maleate, butyl maleate, butyl itaconate, diesters, mono- and noamides of unsaturated dicarboxylic acids, N-phenylmaleimide, N- 2
- N-phenylmaleimides such as methylphenylmaleimide and N-2-ethylphenylmaleimide; alkylmaleimides having 2 to 18 carbon atoms such as N-laurylmaleimide and N-stearylmaleimide; Can be used. Among these, preferred is N-phenylmaleimide.
変性に用いる不飽和ジカルボン酸および／またはその誘
導体の量は、変性前のポリオレフィン重量にもとづいて
通常０．１〜３０重Ｍ％であり、好ましくは２〜２０重
量％である。０．１重量％未満ではゴム強化熱可塑性樹
脂中で均一な状態にすることが困難で、３０重１％を越
えると流動性が低下する。本発明に用いられる変性ポリ
オレフィン（Ｂ）は分子量に特に制限はないが、好まし
くは数平均分子量５００〜２００００、特に好ましくは
２０００〜＋５０００のものである。The amount of unsaturated dicarboxylic acid and/or its derivative used for modification is usually 0.1 to 30% by weight, preferably 2 to 20% by weight, based on the weight of the polyolefin before modification. If it is less than 0.1% by weight, it is difficult to maintain a uniform state in the rubber-reinforced thermoplastic resin, and if it exceeds 30% by weight, the fluidity will decrease. The molecular weight of the modified polyolefin (B) used in the present invention is not particularly limited, but preferably has a number average molecular weight of 500 to 20,000, particularly preferably 2,000 to +5,000.
ポリオレフィ／としては、高密度ポリエチレン、中密度
ポリエチレン、低密度ポリエチレン、プロピレン重合体
、ポリブテン、ポリ−４−メチルペンテン−１、エチレ
ンとα−オレフィンの共重合体、プロピレンとα−オレ
フィンの共重合体などノポリオレフィン類またはそのオ
リゴマー類；エチレン−プロピレンゴム、エチレン−プ
ロピレン−ツエン三元共重合体ゴム（ＥＰＤＭ）、
エチレン−酢酸ビニル共重合体、ブチルゴム、ブタジェ
ンゴム、低結晶性エチレン−プロピレン共重合体、プロ
ピレン−ブテン共重合体からなるポリオレフィン系熱可
塑性エラストマー類、またはそのオリゴマー類、ポリプ
ロピレンとエチレン−プロピレノゴムのブレンドを主体
とするポリオレフイア系熱可塑性エラストマー類などの
ポリオレフィン系エラストマー類、エチレン−ビニルエ
ステル共重合体、エチレン−アクリルエステル共重合体
およびそのオリゴマーなどを含み、これらの各種ポリオ
レフィンおよびオリゴマーのブレンド物も含まれる。こ
れらのうち好ましいのはプロピレン重合体、または、プ
ロビレ／とα−オレフィンの共重合体、または低密度ポ
リエチレンおよびそれらのオリゴマー類である。特に好
ましいのは、プロピレン重合体およびプロピレンとα−
オレフィンの共重合体およびそれらのオリゴマー類であ
る。Polyolefins include high density polyethylene, medium density polyethylene, low density polyethylene, propylene polymer, polybutene, poly-4-methylpentene-1, copolymer of ethylene and α-olefin, copolymer of propylene and α-olefin. Nopolyolefins or oligomers thereof; ethylene-propylene rubber, ethylene-propylene-tsene terpolymer rubber (EPDM),
Polyolefin thermoplastic elastomers consisting of ethylene-vinyl acetate copolymer, butyl rubber, butadiene rubber, low-crystalline ethylene-propylene copolymer, propylene-butene copolymer, or their oligomers, blends of polypropylene and ethylene-propylene rubber. Includes polyolefin elastomers such as polyolefin thermoplastic elastomers, ethylene-vinyl ester copolymers, ethylene-acrylic ester copolymers, and their oligomers, and also includes blends of these various polyolefins and oligomers. . Among these, preferred are propylene polymers, copolymers of propylene/alpha-olefin, or low-density polyethylene and oligomers thereof. Particularly preferred are propylene polymers and propylene and α-
These are copolymers of olefins and oligomers thereof.
変性に用いられるポリオレフィンの二重結合１は特に制
限はないが、末端および／または分子内に炭素数１００
０個当り０．５個以上をするものが好ましく、１．５個
より多く有するものが特に好ましい。さらには末端にの
み１．５個より多く有するものが好ましい。The double bond 1 of the polyolefin used for modification is not particularly limited, but it has 100 carbon atoms at the end and/or within the molecule.
It is preferable to have 0.5 or more per 0, and particularly preferable to have more than 1.5. Furthermore, it is preferable to have more than 1.5 molecules only at the ends.
変性ポリオレフィン（Ｂ）は上記の不飽和ジカルボン酸
および／またはその誘導体とポリオレフィ／とを有機過
酸化物の存在下で反応させることによって得られる。有
機過酸化物としては一般にラジカル重合において開始剤
として用いられているものが使用でき、特にその皿類は
制限されないが、−分間の半減期が！００°Ｃ以上のも
のが好ましい。The modified polyolefin (B) is obtained by reacting the above unsaturated dicarboxylic acid and/or its derivative with a polyolefin in the presence of an organic peroxide. As the organic peroxide, those generally used as initiators in radical polymerization can be used, and there are no particular restrictions on the types of dishes, but the half-life is - minutes! 00°C or higher is preferable.
具体的には、１，１−ビス−１−プチルバーオキン−３
゜３．５−トリメチルンクロヘキサンのようなケトンパ
ーオキノド、ジーｔ−プチルパーオキンド、ジクミルバ
ーオキンドのようなジアルキルパーオキシド、ベンゾイ
ルパーオキシドのようなジアシルパーオキシド、２．５
−ジメチルーソベンゾイルパーオキシヘキサンのような
パーオキシエステル、２，５−ジメチルヘキサン−２，
５−ハイドロパーオキシドのようなハイドロパーオキシ
ドなどが挙げられる。Specifically, 1,1-bis-1-butylverokine-3
゜3.5 Ketone peroquinide such as 5-trimethylchlorohexane, dialkyl peroxide such as di-t-butylperoquinde, dicumyl peroquinde, diacyl peroxide such as benzoyl peroxide, 2.5
- peroxy esters such as dimethyl-sobenzoyl peroxyhexane, 2,5-dimethylhexane-2,
Examples include hydroperoxides such as 5-hydroperoxide.
変性ポリオレフィン（Ｂ）の製造法としては溶液法、溶
融法いずれの公知の方法も用いることができる。溶液法
では、ポリオレフィンおよび前記不飽和ジカルボン酸お
よび／またはその誘導体を有機溶媒に溶解し、加熱する
ことにより得ることができる。使用する有機溶媒として
は、炭素数６−１２の炭化水素、または炭素数６−１２
のハロゲン化炭化水素などを用いることができる。また
、反応ｔｕ度は使用するポリオレフィンが溶解する温度
であり、一般には＋１０−１［ｉｏｏＣが好ましい。As a method for producing the modified polyolefin (B), any known method such as a solution method or a melt method can be used. In the solution method, it can be obtained by dissolving the polyolefin and the unsaturated dicarboxylic acid and/or its derivative in an organic solvent and heating the solution. The organic solvent used is a hydrocarbon having 6 to 12 carbon atoms, or a hydrocarbon having 6 to 12 carbon atoms.
halogenated hydrocarbons and the like can be used. Further, the reaction degree is the temperature at which the polyolefin used dissolves, and is generally preferably +10-1[iooC].
溶融法では、ポリオレフィンと前記不飽和ジカルボン酸
および／またはその誘導体を有機過酸化物と混合し、溶
融混合して反応させることによって得ることができる。In the melt method, it can be obtained by mixing a polyolefin and the unsaturated dicarboxylic acid and/or its derivative with an organic peroxide, melt-mixing, and reacting.
これは押し出し機、ブラベンダー ニーダ−及びバンバ
リーミキサ−などの各種混合機で行うことができる。ま
た、通常の反応槽でもポリオレフィンを溶融した後何機
過酸化物を加えて反応を行なうことができる。混練温度
は使用されるポリオレフィンの融点以上ないし３００″
Ｃ以下の温度範囲が好ましい。This can be done in various mixers such as extruders, Brabender kneaders and Banbury mixers. Further, even in a normal reaction tank, the reaction can be carried out by adding a number of peroxides after melting the polyolefin. The kneading temperature is above the melting point of the polyolefin used to 300"
A temperature range below C is preferred.
本発明の組成物において、ゴム強化熱可塑性樹脂（Ａ）
と変性ポリオレフィン（Ｂ）の組成は、通常、ゴム強化
熱可塑性樹脂（Ａ）１００重ｆｆ１ｆｆｌＥに対して変
性ポリオ、レフイン（Ｂ）は０．１〜３０重量部であり
、好ましくは０６５〜１０重量部である。 （Ｂ）が０
１重１部未膚では流動性などの改良効果が得られず、３
０重量部を越えると成形品に層剥離が起こりやすい。In the composition of the present invention, rubber reinforced thermoplastic resin (A)
The composition of the modified polyolefin (B) is usually 0.1 to 30 parts by weight, preferably 0.1 to 30 parts by weight, per 100 parts by weight of the rubber-reinforced thermoplastic resin (A). Department. (B) is 0
If 1 part is 1 part thick, no improvement effect such as fluidity can be obtained, and 3 parts
If the amount exceeds 0 parts by weight, layer peeling tends to occur in the molded product.
本発明の組成物の製造において各組成の混合は前記の各
種混合機を用いて実施される。この際、熱、酸素、およ
び光に対する各種安定剤、その他の添加剤を加えてもよ
く、この発明の組成物から射出成形、押し出し成形及び
圧縮成形など一般に用いられる各種成形法により成形品
に成形される。In producing the composition of the present invention, each composition is mixed using the various mixers described above. At this time, various stabilizers against heat, oxygen, and light and other additives may be added, and the composition of the present invention is molded into molded products by various commonly used molding methods such as injection molding, extrusion molding, and compression molding. be done.
［実施例コ
以下実施例により、本発明を具体的に説明するが、これ
に限定されるものではない。以下記載において部および
％はそれぞれ重量部および重量％を意味する。[Example] The present invention will be specifically explained with reference to the following example, but the present invention is not limited thereto. In the following description, parts and % mean parts by weight and % by weight, respectively.
製造例１
無水マレイン酸１０部とポリプロピレン（分子Ｑ４００
０、炭素数１０００個当りに５．２個末端二重結合金有
）９０部をキシレンに加熱溶解後、ジクミルパーオキン
ドの存在下に反応して無水マレイン酸含量９．５％（７
） ｊｊｊ（水マレイン酸変性ポリプロピレン（以下、
変性ポリオレフィン■）を得た。Production Example 1 10 parts of maleic anhydride and polypropylene (molecule Q400
After heating and dissolving 90 parts of (5.2 terminal double bond gold per 1000 carbon atoms) in xylene, the mixture was reacted in the presence of dicumyl peroquinide to obtain a maleic anhydride content of 9.5% (7
) jjj (water maleic acid modified polypropylene (hereinafter referred to as
A modified polyolefin (■) was obtained.
製造例２
Ｎ−フェニルマレイミド５部、ポリプロピレン（分子量
＋ ２０００． 炭素数１０００個当りに１．７個末
端二重結合金有）９５部を加熱溶融後、ノーｔ−ブチル
パーオキノドの存在下に反応してＮ−フェニルマレイミ
ド含量４．５％のＮ−フェニルマレイミド変性ポリプロ
ピレン（変性ポリオレフィン■）を得た。Production Example 2 After heating and melting 5 parts of N-phenylmaleimide and 95 parts of polypropylene (molecular weight + 2000, with 1.7 terminal double bond metals per 1000 carbon atoms), in the presence of t-butyl peroxide. In this reaction, N-phenylmaleimide-modified polypropylene (modified polyolefin ①) having an N-phenylmaleimide content of 4.5% was obtained.
実施例１〜４
ＡＢＳ樹脂と製造例１，２に示した変性ポリオレフィン
とを表−１に示した組成比でトライブレンドし、二軸押
し出し機を用いて混練して本発明の組成物を得た。組成
物をベレット化した後ベレットをシリンダー温度２３０
℃で射出成形して各種試験片を作成し、表−１に示した
評価を行なった。Examples 1 to 4 The ABS resin and the modified polyolefin shown in Production Examples 1 and 2 were triblended at the composition ratio shown in Table 1, and the mixture was kneaded using a twin-screw extruder to obtain the composition of the present invention. Ta. After the composition is pelletized, the pellet is heated to a cylinder temperature of 230
Various test pieces were prepared by injection molding at ℃ and evaluated as shown in Table 1.
比較例１
変性ポリオレフィンを添加しなかった以外は実施例１〜
４と同様の操作で評価を行なった。評価方法は以下の方
法によった。Comparative Example 1 Example 1~ except that no modified polyolefin was added
Evaluation was performed in the same manner as in 4. The evaluation method was as follows.
衝撃強度 （ＡＳＴＭ Ｄ２６Ｅ３． ノプチ付。Impact strength (ASTM D26E3. With knob.
３．２■■厚、２３℃）
熱変形温度（ＡＳＴＭ Ｄ６４８．４．６ｋｇ／ｃｍ
２）曲げ弾性率（ＡＳＴＭ Ｄ７９０）
ＭＩ （メルトフローインデックス。3.2■■Thickness, 23℃) Heat distortion temperature (ASTM D648.4.6kg/cm
2) Flexural modulus (ASTM D790) MI (melt flow index).
ＡＳＴＭ Ｄ１２３８．２００’Ｃ。ASTM D1238.200'C.
５ｋｇ／ａｍ２）
Ｓ型性 （エンボス加工した平板、８０ｘ８０ｘ２ｍ
ｍを射出成形してその様子を観察した。）
「発明の効果コ
本発明の熱可塑性樹脂組成物は耐熱性など他の特性を低
下させることなく成形性（流動性）を改良したものであ
る。また、離型性、滑性にも優れ各種成形材料に使用で
きる。5kg/am2) S type (embossed flat plate, 80x80x2m)
M was injection molded and its appearance was observed. ) "Effects of the Invention The thermoplastic resin composition of the present invention has improved moldability (fluidity) without deteriorating other properties such as heat resistance. It also has excellent mold releasability and slipperiness. Can be used for various molding materials.
Claims (1)
および／またはその誘導体で変性された変性ポリオレフ
ィン（Ｂ）からなる熱可塑性樹脂組成物。 ２、ゴム強化熱可塑性樹脂（Ａ）がゴムの存在下に芳香
族ビニル化合物、シアン化ビニル化合物、不飽和モノカ
ルボン酸アルキルエステル化合物からなる群より選ばれ
た一種以上の化合物を重合してなる重合体である請求項
１記載の組成物。 ３、変性ポリオレフィン（Ｂ）の数平均分子量が５００
〜２００００である請求項１または２記載の組成物。 ４、変性ポリオレフィン（Ｂ）がポリオレフィンに対し
て不飽和ジカルボン酸および／またはその誘導体単位０
．１〜３０重量％で変性されたものである請求項１〜３
の何れか記載の組成物。 ５、変性ポリオレフィン（Ｂ）のポリオレフィンがエチ
レンとα−オレフィンからなる群より選ばれるオレフィ
ンの重合体である請求項１〜４の何れか記載の組成物。 ６、変性ポリオレフィン（Ｂ）のポリオレフィンがプロ
ピレン重合体またはプロピレンとα−オレフィンの共重
合体である請求項１〜４の何れか記載の組成物。 ７、ゴム強化熱可塑性樹脂（Ａ）１００重量部と変性ポ
リオレフィン（Ｂ）０．１〜３０重量部からなる請求項
１〜８の何れか記載の組成物。[Scope of Claims] 1. A thermoplastic resin composition comprising a rubber-reinforced thermoplastic resin (A) and a modified polyolefin (B) modified with an unsaturated dicarboxylic acid and/or its derivative. 2. The rubber-reinforced thermoplastic resin (A) is obtained by polymerizing one or more compounds selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, and unsaturated monocarboxylic acid alkyl ester compounds in the presence of rubber. The composition according to claim 1, which is a polymer. 3. The number average molecular weight of the modified polyolefin (B) is 500
3. The composition according to claim 1 or 2, wherein the composition has a molecular weight of 20,000 to 20,000. 4. Modified polyolefin (B) has 0 unsaturated dicarboxylic acid and/or its derivative units in polyolefin
．． Claims 1 to 3 are modified by 1 to 30% by weight.
The composition according to any one of. 5. The composition according to any one of claims 1 to 4, wherein the polyolefin of the modified polyolefin (B) is a polymer of an olefin selected from the group consisting of ethylene and α-olefin. 6. The composition according to any one of claims 1 to 4, wherein the polyolefin of the modified polyolefin (B) is a propylene polymer or a copolymer of propylene and α-olefin. 7. The composition according to any one of claims 1 to 8, comprising 100 parts by weight of the rubber-reinforced thermoplastic resin (A) and 0.1 to 30 parts by weight of the modified polyolefin (B).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33400688A JPH02178346A (en) | 1988-12-28 | 1988-12-28 | Thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33400688A JPH02178346A (en) | 1988-12-28 | 1988-12-28 | Thermoplastic resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02178346A true JPH02178346A (en) | 1990-07-11 |
| JPH0577703B2 JPH0577703B2 (en) | 1993-10-27 |
Family
ID=18272442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33400688A Granted JPH02178346A (en) | 1988-12-28 | 1988-12-28 | Thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02178346A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0919595A1 (en) * | 1997-06-19 | 1999-06-02 | Mitsui Chemicals, Inc. | Molding resin composition |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60177071A (en) * | 1984-02-21 | 1985-09-11 | Sumitomo Naugatuck Co Ltd | Matte thermoplastic resin composition |
| JPS6119647A (en) * | 1984-07-05 | 1986-01-28 | Ube Ind Ltd | Modified polyethylene composition and multilayer laminate prepared by using it |
| JPS6164047A (en) * | 1984-09-05 | 1986-04-02 | Hitachi Ltd | Electron tube |
| JPS6272709A (en) * | 1985-09-26 | 1987-04-03 | Mitsui Petrochem Ind Ltd | Lubricant for synthetic resin and pigment dispersant |
| JPS62241913A (en) * | 1986-04-14 | 1987-10-22 | Mitsui Petrochem Ind Ltd | Substituted imide-modified, low-molecular weight polyolefin and its use |
-
1988
- 1988-12-28 JP JP33400688A patent/JPH02178346A/en active Granted
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60177071A (en) * | 1984-02-21 | 1985-09-11 | Sumitomo Naugatuck Co Ltd | Matte thermoplastic resin composition |
| JPS6119647A (en) * | 1984-07-05 | 1986-01-28 | Ube Ind Ltd | Modified polyethylene composition and multilayer laminate prepared by using it |
| JPS6164047A (en) * | 1984-09-05 | 1986-04-02 | Hitachi Ltd | Electron tube |
| JPS6272709A (en) * | 1985-09-26 | 1987-04-03 | Mitsui Petrochem Ind Ltd | Lubricant for synthetic resin and pigment dispersant |
| JPS62241913A (en) * | 1986-04-14 | 1987-10-22 | Mitsui Petrochem Ind Ltd | Substituted imide-modified, low-molecular weight polyolefin and its use |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0919595A1 (en) * | 1997-06-19 | 1999-06-02 | Mitsui Chemicals, Inc. | Molding resin composition |
| EP0919595A4 (en) * | 1997-06-19 | 2000-10-25 | Mitsui Chemicals Inc | Molding resin composition |
| US6221961B1 (en) | 1997-06-19 | 2001-04-24 | Mitsui Chemicals, Inc. | Molding resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0577703B2 (en) | 1993-10-27 |
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