JPH04164947A - Production of molded article excellent in impact strength - Google Patents
Production of molded article excellent in impact strengthInfo
- Publication number
- JPH04164947A JPH04164947A JP29307590A JP29307590A JPH04164947A JP H04164947 A JPH04164947 A JP H04164947A JP 29307590 A JP29307590 A JP 29307590A JP 29307590 A JP29307590 A JP 29307590A JP H04164947 A JPH04164947 A JP H04164947A
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- acid
- weight
- vinyl acetate
- graft polymer
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 238000000465 moulding Methods 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 13
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 12
- 229920001971 elastomer Polymers 0.000 claims abstract description 11
- 239000000806 elastomer Substances 0.000 claims abstract description 11
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 10
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 9
- 239000004952 Polyamide Substances 0.000 claims abstract description 8
- 229920002647 polyamide Polymers 0.000 claims abstract description 8
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 5
- 239000005977 Ethylene Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000000155 melt Substances 0.000 abstract description 3
- 238000007127 saponification reaction Methods 0.000 abstract description 3
- 230000009477 glass transition Effects 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane 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
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XSXIVVZCUAHUJO-AVQMFFATSA-N (11e,14e)-icosa-11,14-dienoic acid Chemical compound CCCCC\C=C\C\C=C\CCCCCCCCCC(O)=O XSXIVVZCUAHUJO-AVQMFFATSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- GUOSQNAUYHMCRU-UHFFFAOYSA-N 11-Aminoundecanoic acid Chemical compound NCCCCCCCCCCC(O)=O GUOSQNAUYHMCRU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JVPFOKXICYJJSC-UHFFFAOYSA-N 2-azaniumylnonanoate Chemical compound CCCCCCCC(N)C(O)=O JVPFOKXICYJJSC-UHFFFAOYSA-N 0.000 description 1
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- GDHIRZIUEIHCFO-UHFFFAOYSA-N CC(C(C=CCCCCCCCCCCC)=O)=O Chemical compound CC(C(C=CCCCCCCCCCCC)=O)=O GDHIRZIUEIHCFO-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- 235000021297 Eicosadienoic acid Nutrition 0.000 description 1
- JJOJFIHJIRWASH-UHFFFAOYSA-N Eicosanedioic acid Natural products OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 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 compound 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
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 240000008866 Ziziphus nummularia Species 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229960002684 aminocaproic acid Drugs 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CJYXCQLOZNIMFP-UHFFFAOYSA-N azocan-2-one Chemical compound O=C1CCCCCCN1 CJYXCQLOZNIMFP-UHFFFAOYSA-N 0.000 description 1
- YDLSUFFXJYEVHW-UHFFFAOYSA-N azonan-2-one Chemical compound O=C1CCCCCCCN1 YDLSUFFXJYEVHW-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000004653 carbonic acids Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000007602 hot air drying Methods 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
- 229920000554 ionomer Polymers 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 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
- 239000000178 monomer Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、エチレン−酢酸ビニル共重合体ケン化物にエ
チレン−プロピレン共重合体エラストマーを配合して溶
融成型することにより、優れた品質を有する成型物を製
造する方法に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention has excellent quality by blending an ethylene-propylene copolymer elastomer into a saponified ethylene-vinyl acetate copolymer and melt-molding the mixture. The present invention relates to a method of manufacturing a molded article.
［従来の技術］
エチレン−酢酸ビニル共重合体ケン化物は＃性、硬度、
耐摩耗性、帯電防止性などの点での他の成型用樹脂に比
し顕著に優れているが、耐衝撃性については充分ではな
いという難点がある。[Prior art] Saponified ethylene-vinyl acetate copolymer has # properties, hardness,
Although it is significantly superior to other molding resins in terms of abrasion resistance and antistatic properties, it has the disadvantage that impact resistance is not sufficient.
かかる対策としてスチレン−ブタジェン共重合体、アク
リロニトリル−ブタジェン共重合体等の合成ゴムやポリ
エステルエラストマー、熱可塑性ウレタン樹脂、エチレ
ン共重合体を配合することが知られている。As a countermeasure against this, it is known to blend synthetic rubbers such as styrene-butadiene copolymers and acrylonitrile-butadiene copolymers, polyester elastomers, thermoplastic urethane resins, and ethylene copolymers.
［発明が解決しようとする課題］
しカル合成ゴムの使用では成型時に熱分解がおこったり
、成型物の耐候性が不足し、ポリエステルエラストマー
の場合は成型物の耐薬品性が問題となったり耐衝撃性改
善効果も必ずしも充分でない。[Problems to be solved by the invention] When using Shical synthetic rubber, thermal decomposition occurs during molding and the weather resistance of the molded product is insufficient, and when polyester elastomer is used, chemical resistance of the molded product becomes a problem and resistance The effect of improving impact resistance is also not necessarily sufficient.
更に、熱可塑性ウレタンの場合は成型時の増粘が著しい
等の欠点があり、又、エチレン共重合体の場合はロング
ラン成型性が不足し、従来方法では充分なる耐衝撃性の
改善は不充分であるのが実情である。Furthermore, thermoplastic urethane has disadvantages such as significant viscosity increase during molding, and ethylene copolymer lacks long-run moldability, and conventional methods are insufficient to sufficiently improve impact resistance. The reality is that.
［課題を解決するための手段」
本発明者等はかかる課題を解決すへく鋭意研究を重ねた
結果、
（Ａ）エチレン−酢酸ビニル共重合体ケン化物に、（Ｂ
）エチレン−プロピレン共重合体エラストマー及び（Ｃ
）ポリオレフィン系樹脂にエチレン性不飽和カルボン酸
又はその誘導体をグラフト反応させ、更にポリアミドを
反応させてなるグラフト重合体を配合した組成物を溶融
成型する場合、目的が達成出来ることを見出し本発明を
完成した。[Means for Solving the Problems] As a result of intensive research aimed at solving the problems, the present inventors found that (A) saponified ethylene-vinyl acetate copolymer, (B
) ethylene-propylene copolymer elastomer and (C
) We have discovered that the object can be achieved by melt-molding a composition containing a graft polymer obtained by grafting a polyolefin resin with an ethylenically unsaturated carboxylic acid or a derivative thereof and further reacting it with a polyamide. completed.
本発明で対象とする（Ａ）エチレン−酢酸ビニル共重合
体ケン化物はエチレン含量２０〜６０モル％、好ましく
は２５〜５５モル％、酢酸ビニル成分のケン化度９５モ
ル％以上のものである。The saponified ethylene-vinyl acetate copolymer (A) targeted by the present invention has an ethylene content of 20 to 60 mol%, preferably 25 to 55 mol%, and a degree of saponification of the vinyl acetate component of 95 mol% or more. .
エチレン含量が２０モル％以下では耐水性が低下し、一
方６０モル％以上では剛性強度、耐摩耗性等の物性が低
下する。又、ケン化度が９５モル％以下では剛性、硬度
、耐水性が低下する。If the ethylene content is less than 20 mol%, water resistance will decrease, while if it is 60 mol% or more, physical properties such as rigidity strength and abrasion resistance will decrease. Furthermore, if the degree of saponification is less than 95 mol%, the rigidity, hardness, and water resistance will decrease.
又、該共重合体ケン化物は更に少量のプロピレン、イソ
ブチン、α−オクテン、α−ドデセノ、α−オクタデセ
ノ等のα−オレフィン、不飽和カルボン酸又はその塩、
部分アルキルエステル、完全アルキルエステル、ニトリ
ル、アミド、無水物や不飽和スルホン酸又はその塩等の
コモノマーを共重合成分として含有して差支えない。In addition, the saponified copolymer further contains a small amount of propylene, isobutyne, α-olefin such as α-octene, α-dodeceno, α-octadeceno, unsaturated carboxylic acid or a salt thereof,
Comonomers such as partial alkyl esters, complete alkyl esters, nitriles, amides, anhydrides, and unsaturated sulfonic acids or salts thereof may be contained as copolymerization components.
（Ｂ）エチレン−プロピレン共重合体エラストマーはエ
チレン組成が３０〜９０重量％の共重合体エラストマー
であり、密度は０．８５〜０．８７９７ｃｍ３程度、ガ
ラス転移温度が−５０〜−６０℃の範囲のものか多用さ
れる。(B) Ethylene-propylene copolymer elastomer is a copolymer elastomer with an ethylene composition of 30 to 90% by weight, a density of about 0.85 to 0.8797 cm3, and a glass transition temperature in the range of -50 to -60°C. Often used.
又、エチレン、プロピレン以外に第３成分としてジエン
系のモノマーを共重合させた三元共重合体の使用も可能
である。It is also possible to use a terpolymer copolymerized with a diene monomer as a third component in addition to ethylene and propylene.
本発明では（Ａ）と（Ｂ）との相溶性を改善するため（
Ｃ）の配合が必要である。In the present invention, in order to improve the compatibility between (A) and (B), (
C) is required.
（Ｃ）はポリオレフィン系樹脂にエチレン性不飽和カル
ホン酸又はその誘導体をグラフト反応させ、更に該カル
ボン酸又はその誘導体ポリアミドを反応させてなるグラ
フト重合体である。(C) is a graft polymer obtained by subjecting a polyolefin resin to a graft reaction with an ethylenically unsaturated carbonic acid or its derivative, and further reacting the carboxylic acid or its derivative polyamide.
該グラフト重合体はポリオレフィン系樹脂を適当な溶媒
に溶解又は懸濁させ、あるいは溶融状態で過酸化物やジ
アゾ系の開始剤でポリオレフィン系樹脂績を活性化して
、これにエチレン性不飽和カルボン酸又はその誘導体を
グラフト反応させて重合体を得、該重合体とポリアミド
を溶融状態で混合することによって製造される。The graft polymer is prepared by dissolving or suspending a polyolefin resin in a suitable solvent, or by activating the polyolefin resin in a molten state with a peroxide or diazo initiator, and then adding an ethylenically unsaturated carboxylic acid to the polyolefin resin. Alternatively, it is produced by grafting a derivative thereof to obtain a polymer, and then mixing the polymer and polyamide in a molten state.
かかる反応の際にはブラベンダー、パスブレンダー、単
軸スクリュー押出機、ウェーナー及びフライプラー型２
軸押出機等が使用される。Brabenders, path blenders, single screw extruders, Wehner and Frypler types 2 are used for such reactions.
A screw extruder or the like is used.
使用するポリオレフィン系樹脂の重合度は３５０〜４５
００、好ましくは５００〜１０００程度のものが選ばれ
る。メルトフロレート（２３０℃、荷重２Ｊ６０Ｐ、以
下同様）としては０．１〜５０ｉＪ／１０分程度か実用
的である。The degree of polymerization of the polyolefin resin used is 350 to 45.
00, preferably about 500 to 1000. The melt flow rate (230° C., load 2J60P, the same applies hereinafter) is about 0.1 to 50 iJ/10 minutes, which is practical.
ポリオレフィン系樹脂とエチレン性不飽和カルボン酸（
又はその誘導体）との反応比率は重量比換算で１００１
０．０５ 〜１００／ｌ Ｏ１好ましくは１００１０．
０５〜１００／３である。Polyolefin resin and ethylenically unsaturated carboxylic acid (
or its derivative) is 1001 in terms of weight ratio.
0.05 to 100/l O1 preferably 10010.
05 to 100/3.
１００・１０．０５以下ではＩ／＠溶性改善効果が不充
分となり１００／Ｉ ０以上では成型時の増粘が大きく
なり実用性に乏しい。If it is less than 100/10.05, the I/@ solubility improvement effect will be insufficient, and if it is more than 100/I0, the thickening during molding will be large and it will be impractical.
又、ポリアミドオリゴマーの重合度は８０〜１０００、
好ましくは１００〜５００程度が実用的であり、その反
応比率はカルボキンル基当たり０．０１〜１モル、好ま
しくは０．５〜０．９モルが望ましい。In addition, the degree of polymerization of the polyamide oligomer is 80 to 1000,
Preferably, about 100 to 500 is practical, and the reaction ratio is preferably 0.01 to 1 mol, preferably 0.5 to 0.9 mol, per carboquine group.
上記におけるポリオレフィン系樹脂としては直鎖状底密
度ポリエチレン・中密度・高密度ポリエチレン、アイオ
ノマー、エチレン−プロピレン共重合体、エチレン−ア
クリル酸エステル共重合体、エチレン−酢酸ビニル共重
合体などがあげられる。特に直鎖状低密度ポリエチレン
、低密度ポリエチレン、エチレン−プロピレン共重合体
、エチレン−酢酸ビニル共重合が実用的に重要である。Examples of the polyolefin resins mentioned above include linear bottom density polyethylene, medium density polyethylene, and high density polyethylene, ionomers, ethylene-propylene copolymers, ethylene-acrylic acid ester copolymers, ethylene-vinyl acetate copolymers, etc. . In particular, linear low density polyethylene, low density polyethylene, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer are practically important.
かかる幹ポリマーにグラフトさせるエチレン性不飽和カ
ルボン酸又はその誘導体とはアクリル酸、メタクリル酸
、クロトン酸、マレイン酸、フマル酸、イタコン酸など
の不飽和カルボン酸或はこれらの無水物、半エステル等
をいう。The ethylenically unsaturated carboxylic acids or derivatives thereof to be grafted onto the backbone polymer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, or their anhydrides and half esters. means.
又、ポリアミドはラクタムの重付加やアミノカルボン酸
の重縮合、ジアミンとジカルボン酸の重縮合等、周知の
方法で製造される。Polyamides can also be produced by well-known methods such as polyaddition of lactams, polycondensation of aminocarboxylic acids, and polycondensation of diamines and dicarboxylic acids.
上記ポリアミド原料としては具体的に、ε−カプロラク
タム、エナントラクタム、カプリルラクタム、ラウリル
ラクタム、α−ピロッドン、α−ピペυトンのようなラ
クタム類、６−アミノカプロン酸、７−アミノへブタン
酸、９−アミノノナン酸、１１−アミノウンデカン酸の
ようなω−アミノ酸類、アジピン酸、グルタル酸、ピメ
リン酸、スペリン酸、アゼライン酸、セバシン酸、ウン
デカンノオン酸、ドデカノオン酸、ヘキサデカジオン酸
、ヘキサデセンジオン酸、エイコサンジオン酸、エイコ
サジェンノオン酸、ジグリコール酸、２．２．４−１リ
メチルアジビン酸、キシリレンジカルボン酸、Ｉ、４−
シクロヘキサンジカルボン酸、テレフタル酸、イソフタ
ル酸のような二塩基酸類、ヘキサメチレンジアミン、テ
トラメチレンジアミン、ノナメチレンジアミン、ウンデ
カメチレンジアミン、ドデカメチレンジアミン、２，２
゜４（又は２，４．４）−）リメチルへキサメチレンジ
アミン、ビス−（４，４°−アミノシクロヘキシル）メ
タン、メタキシリレンジアミンのようなジアミン類など
が挙げられる。又、分子量の調節の目的でラウリルアミ
ン、オレイルアミン等のモノアミンも適宜使用し得る。Specifically, the above-mentioned polyamide raw materials include lactams such as ε-caprolactam, enantholactam, capryllactam, lauryllactam, α-pyrodone, α-pipeυton, 6-aminocaproic acid, 7-aminohebutanoic acid, 9 - Omega-amino acids such as aminononanoic acid, 11-aminoundecanoic acid, adipic acid, glutaric acid, pimelic acid, superic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, hexadecadioic acid, hexadecenedione Acid, eicosandioic acid, eicosadienoic acid, diglycolic acid, 2.2.4-1-limethyladibic acid, xylylenedicarboxylic acid, I, 4-
Dibasic acids such as cyclohexane dicarboxylic acid, terephthalic acid, isophthalic acid, hexamethylene diamine, tetramethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2
Diamines such as ゜4 (or 2,4.4)-)limethylhexamethylene diamine, bis-(4,4゜-aminocyclohexyl)methane, metaxylylene diamine, and the like can be mentioned. Furthermore, monoamines such as laurylamine and oleylamine may be used as appropriate for the purpose of controlling the molecular weight.
本発明の組成物において（Ａ）、（Ｂ）、（Ｃ）の配合
割合は（Ａ）か５０〜９９５重量％、好ましくは６０〜
９５重棗％、（Ｂ）か０．４〜５０重量％好ましくは４
，５〜３５重量％、（Ｃ）が０．１〜１５重量％好まし
くは０，５〜１０重量％てなければならない。In the composition of the present invention, the blending ratio of (A), (B), and (C) is 50 to 995% by weight, preferably 60 to 995% by weight of (A).
95% of jujube, (B) 0.4 to 50% by weight, preferably 4
, 5 to 35% by weight, and (C) 0.1 to 15% by weight, preferably 0.5 to 10% by weight.
（Ａ）が５０重量％以下、或は（Ｂ）が５０重量％以上
では剛性、硬度、耐摩耗性が低くなり、一方（Ａ）が９
９．５重量％以上、或は（Ｂ）が０．４重量％以下では
耐衝撃性の改善効果が不充分となる。又、（Ｃ）が０．
１重量％以下では（Ａ）と（Ｂ）との相溶性不良のため
耐衝撃性の改善効果が乏しく、１５重量％以上ではロン
グラン成型性が悪くなるので不利である。If (A) is less than 50% by weight or (B) is more than 50% by weight, the rigidity, hardness, and wear resistance will be low;
If the content of (B) is 9.5% by weight or more or 0.4% by weight or less, the effect of improving impact resistance will be insufficient. Also, (C) is 0.
If it is less than 1% by weight, the effect of improving impact resistance will be poor due to poor compatibility between (A) and (B), and if it is more than 15% by weight, long-run moldability will deteriorate, which is disadvantageous.
該組成物はそのまま成型に供され、或は−旦混合ペレッ
トを作製した後成型に供される。The composition is subjected to molding as it is, or mixed pellets are first prepared and then subjected to molding.
溶融成型法としては特に限定はなく、射出成型法、押出
成型法、圧縮成型法、回転成型法、ブロー成型法、流動
浸漬法などがいずれも採用される。The melt molding method is not particularly limited, and injection molding, extrusion molding, compression molding, rotational molding, blow molding, fluidized dipping, and the like may be employed.
成型時の溶融樹脂の温度は、樹脂が適度の流動性を保ち
、かつ熱分解を避けるために１７０〜２６０℃程度とす
るのが適当である。なお成型にあたっては上記樹脂混合
物に必要に応じて安定剤、可塑性、充填剤、着色剤、発
泡剤、膏剤などの公知の添加剤やガラス繊維、炭素繊維
なとの補強材を加えてもよい。The temperature of the molten resin during molding is preferably about 170 to 260°C in order to maintain appropriate fluidity of the resin and avoid thermal decomposition. In addition, during molding, known additives such as stabilizers, plasticizers, fillers, colorants, foaming agents, plasters, etc., and reinforcing materials such as glass fibers and carbon fibers may be added to the resin mixture as necessary. .
以上述べた方法によって得られた成型物は一般機械器具
部品、自動車・船舶・航空機部品、光学時計機器部品、
電気機器部品など種々の用途に使用しうる。The molded products obtained by the above method can be used for general machinery parts, automobile/ship/aircraft parts, optical watch equipment parts, etc.
It can be used for various purposes such as electrical equipment parts.
かかる用途以外に本発明の成型物はシート、フィルム、
ボトル等の包装材料としても有用である。In addition to such uses, the molded product of the present invention can be used as sheets, films,
It is also useful as a packaging material for bottles, etc.
該用途においてはエチレン−酢酸ビニル共重合体ケン化
物の酸素遮断性が特徴ある性質として発揮される。In this application, the saponified ethylene-vinyl acetate copolymer exhibits oxygen barrier properties as a characteristic property.
かかる用途においては本発明の成型物を単層として使用
するのみならず、ポリオレフィン、ポリエステル、ナイ
ロン等の各種の熱可塑性樹脂と積層されて用いられるこ
とが多い。又該成型品は必要に応じて一軸又は二軸延伸
処理を施して実用に供される。In such applications, the molded product of the present invention is often used not only as a single layer, but also in a laminated form with various thermoplastic resins such as polyolefin, polyester, and nylon. Further, the molded product is put into practical use after being subjected to uniaxial or biaxial stretching treatment, if necessary.
［作 用］
本発明では、（Ａ）エチレン−酢酸ビニル共重合体ケン
化物の耐衝撃性が（Ｂ）エチレン−プロピレン共重合体
エラストマー及び（Ｃ）特定のグラフト重合体の配合に
よって著しく向上する。[Function] In the present invention, the impact resistance of (A) the saponified ethylene-vinyl acetate copolymer is significantly improved by blending (B) the ethylene-propylene copolymer elastomer and (C) a specific graft polymer. .
［実施例］
次に実施例を挙げて本発明の成型物を更に具体的に説明
する。以下、「部」又は「％Ｊとあるのは特に断わりの
ない限り重量基準で表わしたものである。[Example] Next, the molded product of the present invention will be described in more detail with reference to Examples. Hereinafter, "parts" or "%J" are expressed on a weight basis unless otherwise specified.
試料の調製
実施例１−１０、対照例１〜２
（Ａ）、（Ｂ）、（Ｃ）の組成物をヘンノニルミキサー
にて粉末状でよく混合した後熱風乾燥蒸出で乾燥し、つ
いてこの粉末を射出！３５オンスの射出成型機に供給し
、ノズル温度２２０℃、前部温度２００℃、後部温度２
２０℃、金型温度、射出圧力１２００ｋｇ／ｃｍ’、サ
イクル３５秒の成型条件下に射出成型を行って、試験片
を作成した。Sample Preparation Example 1-10, Control Examples 1-2 The compositions (A), (B), and (C) were mixed well in powder form using a hennonyl mixer, and then dried using hot air drying evaporation. Inject this powder! Feeding a 35 oz injection molding machine, nozzle temperature 220°C, front temperature 200°C, back temperature 2
Injection molding was performed under molding conditions of 20° C., mold temperature, injection pressure 1200 kg/cm', and cycle 35 seconds to create a test piece.
かくして得られた試験片の物性を測定した。The physical properties of the test piece thus obtained were measured.
結果を第１表に示す。The results are shown in Table 1.
［効 果コ
本発明の（Ａ）、（Ｂ）、（Ｃ）よりなる組成物から製
造される成型物は、エチレン−酢酸ビニル共重合体ケン
化物のもつ成型加工性、成型物の外観等を何等損なうこ
となく、その耐衝撃性が大巾に向上する。[Effects] The molded product produced from the composition of (A), (B), and (C) of the present invention has good molding processability, appearance of the molded product, etc. of the saponified ethylene-vinyl acetate copolymer. Its impact resistance is greatly improved without any damage to it.
Claims (1)
（Ｂ）エチレン−プロピレン共重合体エラストマー及び
（Ｃ）ポリオレフィン系樹脂にエチレン性不飽和カルボ
ン酸又はその誘導体をグラフト反応させ、更にポリアミ
ドを反応させてなるグラフト重合体を配合した組成物を
溶融成型することを特徴とする耐衝撃性の優れた成型物
の製造法。 ２、（Ａ）エチレン−酢酸ビニル共重合体ケン化物が、
５０〜９９．５重量％、（Ｂ）エラストマーが０．４〜
５０重量％、（Ｃ）グラフト重合体が、０．１〜１５重
量％の割合からなる組成物を溶融成型する請求項１記載
の方法。[Claims] 1. (A) saponified ethylene-vinyl acetate copolymer,
Melt-molding a composition containing (B) an ethylene-propylene copolymer elastomer and (C) a polyolefin resin grafted with an ethylenically unsaturated carboxylic acid or a derivative thereof and further reacted with a polyamide. A method for producing molded products with excellent impact resistance. 2. (A) Saponified ethylene-vinyl acetate copolymer is
50-99.5% by weight, (B) elastomer is 0.4-99.5% by weight
2. The method of claim 1, wherein the composition comprises 50% by weight of the graft polymer (C) and 0.1 to 15% by weight of the graft polymer (C).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29307590A JP2940634B2 (en) | 1990-10-29 | 1990-10-29 | Manufacturing method of molded products with excellent impact resistance |
| US07/648,699 US5160475A (en) | 1990-02-01 | 1991-01-31 | Method of producing shaped articles having excellent impact resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29307590A JP2940634B2 (en) | 1990-10-29 | 1990-10-29 | Manufacturing method of molded products with excellent impact resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04164947A true JPH04164947A (en) | 1992-06-10 |
| JP2940634B2 JP2940634B2 (en) | 1999-08-25 |
Family
ID=17790127
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29307590A Expired - Fee Related JP2940634B2 (en) | 1990-02-01 | 1990-10-29 | Manufacturing method of molded products with excellent impact resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2940634B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6841618B2 (en) | 2002-02-22 | 2005-01-11 | Kuraray Co., Ltd. | Thermoplastic polymer composition having barrier properties |
-
1990
- 1990-10-29 JP JP29307590A patent/JP2940634B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6841618B2 (en) | 2002-02-22 | 2005-01-11 | Kuraray Co., Ltd. | Thermoplastic polymer composition having barrier properties |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2940634B2 (en) | 1999-08-25 |
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