JPH02133457A - Antistatic resin composition - Google Patents
Antistatic resin compositionInfo
- Publication number
- JPH02133457A JPH02133457A JP28577088A JP28577088A JPH02133457A JP H02133457 A JPH02133457 A JP H02133457A JP 28577088 A JP28577088 A JP 28577088A JP 28577088 A JP28577088 A JP 28577088A JP H02133457 A JPH02133457 A JP H02133457A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- pts
- copolymer
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 20
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 15
- 229920002614 Polyether block amide Polymers 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 11
- 229920003232 aliphatic polyester Polymers 0.000 claims abstract description 10
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 229920001971 elastomer Polymers 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 18
- -1 aliphatic diamine Chemical class 0.000 abstract description 13
- 150000004985 diamines Chemical class 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 8
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000005062 Polybutadiene Substances 0.000 abstract description 4
- 229920002857 polybutadiene Polymers 0.000 abstract description 4
- 229920001610 polycaprolactone Polymers 0.000 abstract description 4
- 239000004632 polycaprolactone Substances 0.000 abstract description 4
- 229920001515 polyalkylene glycol Polymers 0.000 abstract description 3
- 230000009477 glass transition Effects 0.000 abstract description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 229920006027 ternary co-polymer Polymers 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-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
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- ZRSKSQHEOZFGLJ-UHFFFAOYSA-N ammonium adipate Chemical compound [NH4+].[NH4+].[O-]C(=O)CCCCC([O-])=O ZRSKSQHEOZFGLJ-UHFFFAOYSA-N 0.000 description 1
- 235000019293 ammonium adipate Nutrition 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- AWSFEOSAIZJXLG-UHFFFAOYSA-N azepan-2-one;hydrate Chemical compound O.O=C1CCCCCN1 AWSFEOSAIZJXLG-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000011787 zinc oxide 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〕
本発明は耐衝撃性にすぐれ、かつ半永久的な制電性を有
する熱可塑性樹脂組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a thermoplastic resin composition having excellent impact resistance and semi-permanent antistatic properties.
耐１１ｉ７ｉ性にすぐれる高分子（オ料はＨｌｌ）Ｓ（
耐衝撃性ポリスチレン）、ＡＢＳ樹脂に代表さ机るよう
に、材ギ４のもつ優れた機械的特性により広１ｎな分野
で使用されているが、樹脂の渣］ＴＴ抵抗、ｌ、Ｔが高
いため、はこりの付着、静電気障害などによりその用途
が限定されていた。従って°し永久的な制電性をこれら
の樹脂に付与することによってそうした用途への展開が
可能となる。Polymer with excellent 11i7i resistance (O material is Hll) S (
Materials such as high impact polystyrene) and ABS resins are used in a wide range of fields due to their excellent mechanical properties, but the resin residue has high TT resistance, l, and T. Therefore, its use has been limited due to the adhesion of lumps and electrostatic damage. Therefore, by imparting permanent antistatic properties to these resins, it becomes possible to develop them into such applications.
半永久的な制電性を向上させるための方法としては各種
あるが、固有抵抗値の低いポリアルキレンオキサイドを
共重合体成分として含む樹脂組成物をブレンドすること
によって、樹脂の制電性を改良する方法が実用的であり
、広く用いられ“ζいる。There are various methods to improve semi-permanent antistatic properties, but the antistatic properties of resins are improved by blending a resin composition containing polyalkylene oxide, which has a low specific resistance value, as a copolymer component. The method is practical and widely used.
特開昭６２ｗｔ１７５９号公報においてシよ、ポリエー
テルアミドを制電性改良剤としてブレ〉・ドすることに
より、優れた制電性を有する熱可塑性樹脂ｕｌｌ動物得
られる技術が開示されている。JP-A-62-1759 discloses a technique for obtaining a thermoplastic resin having excellent antistatic properties by blending polyether amide as an antistatic property improver.
しかし、これらの制電性樹脂組成物は、制電性の向上を
はかるために、ポリエーテルアミド等をブレンドした結
果、耐衝！を強度等の機械的特性が著しく低下するとい
う欠点があり、実用上十分満足できるものではなかった
。However, these antistatic resin compositions have been blended with polyether amide, etc. in order to improve their antistatic properties, and as a result have become impact resistant! However, it has the disadvantage that mechanical properties such as strength are significantly reduced, and it is not fully satisfactory in practice.
本発明者らは、半永久的な制電性と耐１（１撃強度等の
機械的特性を併せ持った樹脂を且酸物を開発するため鋭
貨検耐した結果、ゴム質重合体に特定のビニル系中ｖ体
をグラフト重合してなるグラフト共重合体とポリエーテ
ルアミド共重合体に脂肪族ポリエステルを混合すること
により」二記目的が達成されることを見出し本発明を完
成した。The present inventors conducted extensive tests to develop a resin with mechanical properties such as semi-permanent antistatic properties and mechanical properties such as one-impact strength (1-impact strength), and as a result, they found that a rubber-like polymer with a specific The present invention has been completed by discovering that the second object can be achieved by mixing an aliphatic polyester with a polyetheramide copolymer and a graft copolymer obtained by graft polymerizing a V-form in a vinyl system.
すなわち、本発明は；
（Ａ）ゴム質重合体５〜６０ｗｔ％に１種または２種以
上のビニル単量体９５〜４０−Ｌ％を重合させたグラフ
ト共重合体
（Ｂ）ビニル重合体
（Ｃ）脂肪族ポリエステル
（Ｄ）ポリエーテルアミド共重合体からなり、（Ａ）（
Ｂ） 、 （Ｃ） 、 （Ｄ） 、の合計を１００重量
部としたとき、５００重量部≦Ａ） ≦９９重量部
０重量部≦（Ｂ）５９０重量部
０．５重量部≦（Ｃ） ５４９．５重量部０．５重量部
≦（Ｄ）５４９．５重量部 であろ制電性樹脂組成物で
ある。That is, the present invention includes: (A) a graft copolymer obtained by polymerizing 5 to 60 wt% of a rubbery polymer with 95 to 40 L% of one or more vinyl monomers; (B) a vinyl polymer ( C) aliphatic polyester (D) consisting of a polyetheramide copolymer, (A) (
When the total of B), (C), and (D) is 100 parts by weight, 500 parts by weight ≦ A) ≦ 99 parts by weight 0 parts by weight ≦ (B) 590 parts by weight 0.5 parts by weight ≦ (C) 549.5 parts by weight 0.5 parts by weight ≦ (D) 549.5 parts by weight is an antistatic resin composition.
以下、本発明を具体的に説明する。The present invention will be specifically explained below.
本発明において用いる（Ａ）グラフト共重合体のゴム質
重合体としては、ガラス転移温度が０°Ｃ以下のもので
あれば用いることができる。具体的には、ポリブタジェ
ン、スチレン−ブタジェン共重合ゴム、アクリロニトリ
ル−ブタジェン共重合ゴム等のジエン系ゴム、ポリイソ
プレン、ポリクロロプレン、ポリアクリル酸ブチル等の
アクリル系ゴム、エチレン−プロピレンゴム、エチレン
−プロピレン−ジエン三元共重合ゴム、スチレンーブタ
ジエンブロック共重合ゴム等のブロック共重合体および
それらの水素添加物等を使用することができる。As the rubbery polymer of the graft copolymer (A) used in the present invention, any polymer having a glass transition temperature of 0° C. or lower can be used. Specifically, diene rubbers such as polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, acrylic rubbers such as polyisoprene, polychloroprene, butyl polyacrylate, ethylene-propylene rubber, ethylene-propylene Block copolymers such as -diene ternary copolymer rubber and styrene-butadiene block copolymer rubber, hydrogenated products thereof, and the like can be used.
好ましくはポリブタジェン、スチレン−フタジエン共重
合ゴム、エチレン−プロピレン−ジエン三元共重合ゴム
が挙げられる。Preferred examples include polybutadiene, styrene-phtadiene copolymer rubber, and ethylene-propylene-diene ternary copolymer rubber.
ビニル単量体としては、スチレン、α−メチルスチレン
等の芳香族ビニル系単量体：アクリロニｌｗｔ，Ｉル、
メタクリレートリル等のシアン化ビニル系φ量体；メチ
ルメタクリレート等の（メタ）アクリル酸エステル単量
体；無水マレイン酸等のαβ−不飽和カルボン酸；Ｎ−
フェニルマレイミド等のマレイミド系単量体；グリシジ
ルメタクリレート等のグリシジル基含有単層体などが代
表的なものとして挙げられるが、基本的にはこれらゴム
質重合体と共重合可能なビニル’Ｆ−ｆｆｉ体であれば
用いることができる。Examples of vinyl monomers include aromatic vinyl monomers such as styrene and α-methylstyrene;
Vinyl cyanide-based φ-mers such as tolyl methacrylate; (meth)acrylic acid ester monomers such as methyl methacrylate; αβ-unsaturated carboxylic acids such as maleic anhydride; N-
Representative examples include maleimide monomers such as phenylmaleimide; glycidyl group-containing monolayers such as glycidyl methacrylate, but basically vinyl 'F-ffi that can be copolymerized with these rubbery polymers. Any body can be used.
好ましくはスチレン、α−メチルスチレン、アクリロニ
トリル、メチルメタクリレート等が用いられる。Styrene, α-methylstyrene, acrylonitrile, methyl methacrylate and the like are preferably used.
グラフト共重合体中のゴム質重合体の割合いは、５〜６
０ｗ ｔ％の範囲で用いられるが、白ｔ ｊｊｉ 撃性
と加工性の点で好ましくは１０〜５０ｗ ｔ％の範囲で
ある。The ratio of rubbery polymer in the graft copolymer is 5 to 6.
Although it is used in a range of 0 wt%, it is preferably in a range of 10 to 50 wt% in terms of white impact resistance and workability.
ビニル単量体としては、上記した単量体のうち１種又は
２種以上およびこれらと共重合可能な他のビニル単量体
の合計が９５〜４０ｗｔ％の範囲のもの、より好ましく
は９０〜５０ｗ ｔ％の範囲で用いられる。The vinyl monomer is one in which the total of one or more of the above-mentioned monomers and other vinyl monomers copolymerizable with these is in the range of 95 to 40 wt%, more preferably 90 to 40 wt%. It is used in a range of 50wt%.
これらビニル単量体は、ゴム質重合体の存在の下に公知
の方法、例えば■比重合法、塊状重合基、懸眉重合法等
の方法で重合することによりグラフト共重合体を得るこ
とができる。Graft copolymers can be obtained by polymerizing these vinyl monomers in the presence of a rubbery polymer using known methods such as specific polymerization method, bulk polymerization method, and hanging eyebrow polymerization method. .
この時に生成したグラフト共重合体のグラフト率“（１
）は（Ｉ−意に設定することができるが、好ましい範囲
としては５〜２００％の範囲である。Grafting ratio of the graft copolymer produced at this time “(1
) can be set arbitrarily, but is preferably in the range of 5 to 200%.
＊（１）・・
本発明における（Ｒ）ビニル重合体としては、グラフト
共重合体に用いるビニル単量体を１種または２種以上お
よびこれらと共重合可能なビニル単量体を重合して得ら
れるもの、好ましくはスチＬ・ン、α−メチルスチレン
、アクリロニトリル、メチルメタクリレート等が用いら
れる。*(1)... The (R) vinyl polymer in the present invention is a polymer made by polymerizing one or more vinyl monomers used in the graft copolymer and a vinyl monomer copolymerizable with these. Those obtained, preferably styrene, α-methylstyrene, acrylonitrile, methyl methacrylate, etc. are used.
ビニル重合体（Ｂ）は樹脂組成物１００重量部に対して
０〜９０重量部の範囲で配合される。好ましくは０〜１
５重量部の範囲である。The vinyl polymer (B) is blended in an amount of 0 to 90 parts by weight based on 100 parts by weight of the resin composition. Preferably 0-1
The range is 5 parts by weight.
本発明における（Ｃ）脂肪族ポリエステルとしては、ポ
リカプロラクトン、ポリエチレンアジペート、ポリブチ
レンアジペート等のアジピン酸とアルキレングリコール
とのポリエステル、ポリエチレンサクシネート等のコハ
ク酸とアルキレングリコールとのポリエステル、ポリブ
チレンセバケート等のセバシン酸とアルキレングリコー
ルとのポリエステル、ポリンクロヘキサンジメチレンサ
クシネート等のジカルボン酸とジクロロヘキサンジメチ
レングリコールとのポリエステルが代表的に用いられる
が、特にポリカプロラクトンが好ましい。(C) Aliphatic polyester in the present invention includes polyesters of adipic acid and alkylene glycol such as polycaprolactone, polyethylene adipate, and polybutylene adipate, polyesters of succinic acid and alkylene glycol such as polyethylene succinate, and polybutylene sebacate. Typical examples include polyesters of sebacic acid and alkylene glycol, such as, and polyesters of dicarboxylic acid and dichlorohexane dimethylene glycol, such as polychlorohexanedimethylene succinate, and polycaprolactone is particularly preferred.
脂肪族ボ、リエステルの添加量としては、樹脂組成物の
０５〜４９．５重量部の範囲で用いられるが、好ましく
は１．０〜１５重量部の範囲である。The amount of the aliphatic polyester added ranges from 05 to 49.5 parts by weight of the resin composition, preferably from 1.0 to 15 parts by weight.
脂肪族ポリエステルの分子量としては２，０００〜５０
０ 、０００の範囲のものが用いられる。樹脂の機械的
特性から特に好ましくは１０．０００〜１５０．０００
の範囲である。The molecular weight of aliphatic polyester is 2,000 to 50
A value in the range 0,000 is used. Particularly preferably from 10.000 to 150.000 in view of the mechanical properties of the resin.
is within the range of
本発明における（Ｄ）ポリエーテルアミド共重合体の構
成成分は、ポリアルキレングリコールジアミンとジカル
ボン酸、脂肪族ジアミン、ε−カプロラクタムを玉な成
分とする共重合体をいう。The component of the polyetheramide copolymer (D) in the present invention is a copolymer containing polyalkylene glycol diamine, dicarboxylic acid, aliphatic diamine, and ε-caprolactam as major components.
ポリアルキレングリコールジアミンとしては、代表的に
は分子量２００〜２００，０００のポリエヂレンオキシ
ド基をシアンエチル化した後水素添加することにより得
られる両末端ジアミン等を用いることができる。As the polyalkylene glycol diamine, it is typically possible to use a double-terminated diamine obtained by cyanethylating a polyethylene oxide group having a molecular weight of 200 to 200,000, followed by hydrogenation.
ポリエチレングリコールの分子量は、２００〜２０００
０の範囲が特に好ましく、帯電防止性能が高い。The molecular weight of polyethylene glycol is 200 to 2000
A range of 0 is particularly preferable, and the antistatic performance is high.
ポリエチレングリコールジアミンの添加量は、ポリエー
テルアミド共重合体に対して１０〜８０重量部が帯電防
止特性とグラフト共重合体との相溶性の点で好ましい。The amount of polyethylene glycol diamine added is preferably 10 to 80 parts by weight based on the polyetheramide copolymer from the viewpoint of antistatic properties and compatibility with the graft copolymer.
ジカルボン酸としては、アジピン酸、セバシン酸、アゼ
ライン酸、ベンゼンジカルボン酸等が、一種あるいは二
種以上混合して使用できる。As the dicarboxylic acid, adipic acid, sebacic acid, azelaic acid, benzenedicarboxylic acid, etc. can be used singly or in combination of two or more.
脂！ｌｊｊ族ジアミンとしては、ヘキサメチレンジアミ
ン等が代表的に使用できる。Fat! As the ljj group diamine, hexamethylene diamine and the like can be typically used.
以上のポリエチレングリコールジアミン、ジカルボン酸
、脂肪族ジアミン、ε−カプロラクタムの混合物を、窒
素雰囲気下で２２０〜２７０°Ｃに加熱重合することに
より４ミリ工−テルアミ１共重島体を得る。この重合２
こ際して、各種酸化防止剤、トデルヘンゼンスルホン酸
ソーダ等の界面活性剤、ＫＢｒ等の無機電解質等を安定
剤、改質剤として添加することができる。A mixture of the above polyethylene glycol diamine, dicarboxylic acid, aliphatic diamine, and ε-caprolactam is polymerized by heating at 220 to 270°C in a nitrogen atmosphere to obtain a 4-milliester-telamide 1 copolymer island. This polymerization 2
At this time, various antioxidants, surfactants such as sodium toderhenzenesulfonate, inorganic electrolytes such as KBr, etc. can be added as stabilizers and modifiers.
ポリエーテルアミド共重合体の添加量としては、樹脂組
成物の０．５〜４９．５重量部の範囲で用いられるが、
好ましくは５．０〜２５重ν部の範囲である。The amount of polyetheramide copolymer added is used in the range of 0.5 to 49.5 parts by weight of the resin composition,
The preferred range is 5.0 to 25 parts.
本発明における樹脂組成物の製造方法については、特に
限定はされず、通常の方法、例えば押出機混練によるメ
ルトブレンドなどにより製造することができる。The method for producing the resin composition in the present invention is not particularly limited, and the resin composition can be produced by a conventional method, such as melt blending using extruder kneading.
この際必要に応して、通常の帯電防止剤、酸化防止剤、
紫外線吸収剤、顔料、染料、滑剤、可塑剤等の添加剤を
添加することが可能である。At this time, if necessary, ordinary antistatic agents, antioxidants,
Additives such as ultraviolet absorbers, pigments, dyes, lubricants, plasticizers, etc. can be added.
本発明による樹脂組成物に対して、導電性充填剤を加え
ることにより、更に制電性を向上させた樹脂ＩＪＩ成吻
を容易に得ることができる。導電性材ギｗｔとしてシよ
り−ボンブラノク、金属粉末、金属酸化物（酸化亜鉛
酸化鉄等）金属塩（ＫＢｒ、Ｎａｉ￥；）が挙げらｎる
。By adding a conductive filler to the resin composition according to the present invention, a resin IJI growth with further improved antistatic properties can be easily obtained. From conductive materials such as bombranoch, metal powder, metal oxide (zinc oxide)
Examples include iron oxide, etc.) metal salts (KBr, Nai￥;).
また、本発明の樹脂組成物には、更に本発明の樹脂組成
物と相）容性のある他の熱可望性重合体をブレンドして
、成形用樹脂としての性能を改良することができる。Furthermore, the resin composition of the present invention can be further blended with other thermoplastic polymers that are compatible with the resin composition of the present invention to improve its performance as a molding resin. .
（実施例）
本発明をさらに具体的に説明するために、以下実砲例及
び比較例により説明するが、これらは本発明を制限する
ものでない。（以下「部」というのは「重量部」を意味
するものとする。）（１）グラフト共重合体の調製
ａｗｔ：ポリブタンエンラテソクス（重量平均粒子径３
０００人、ゲル含量８５％）２０部（固形分換算）に対
し、アクリロニトリル２２．４部、スチレン４．８部、
α−メチルスチレン５２．８部からなる単層体混合物を
乳化重合してグラフト共重合体ａ−］を得た。(Example) In order to explain the present invention more specifically, actual gun examples and comparative examples will be described below, but these are not intended to limit the present invention. (Hereinafter, "parts" shall mean "parts by weight.") (1) Preparation of graft copolymer awt: Polybutane latex (weight average particle diameter 3
000 people, gel content 85%) 20 parts (solid content equivalent), 22.4 parts acrylonitrile, 4.8 parts styrene,
A monolayer mixture consisting of 52.8 parts of α-methylstyrene was emulsion polymerized to obtain a graft copolymer a-].
ａ−２：ポリブタジェンラテックス（ａｗｔと同じ）４
５部（固形分換算）に対し、アクリロニトリル１１部、
スチレン４４部からなる単量体混合物を乳化重合してグ
ラフト共重合体ａ−２を得た。a-2: Polybutadiene latex (same as awt) 4
5 parts (solid content equivalent), 11 parts of acrylonitrile,
A monomer mixture consisting of 44 parts of styrene was emulsion polymerized to obtain graft copolymer a-2.
（２）ビニル重合体のｉｌｌ製
ｔ）ｗｔ：アクリロニトリル２０部、スチレン８０部を
共重合して重合体ｂｗｔを得た。(2) Vinyl polymer made by Ill t)wt: 20 parts of acrylonitrile and 80 parts of styrene were copolymerized to obtain a polymer bwt.
ｂ−２；メタクリル酸メチル７５部、スチレン２１部、
アクリロニトリル４部を共重合して重合体ｂ２を得た。b-2; 75 parts of methyl methacrylate, 21 parts of styrene,
Polymer b2 was obtained by copolymerizing 4 parts of acrylonitrile.
ｂ−３：アクリロニトリル２８部、スチレン６部、α−
メチルスチレン６６部を共重合して重合体ｂ３を得た。b-3: 28 parts of acrylonitrile, 6 parts of styrene, α-
Polymer b3 was obtained by copolymerizing 66 parts of methylstyrene.
（３）脂肪族ポリエステルの調製
ポリカプロラクトン（分子量７００００）を用いＣ１と
した。(3) Preparation of aliphatic polyester Polycaprolactone (molecular weight 70,000) was used as C1.
（４）ポリエーテルアミド共重合体の調製ｄｗｔ＝ポリ
エチレングリコールジアミン（エチレングリコール単位
２５のポリエチレングリコールジアミン）とアジピン酸
とを常法により塩反応を行い、ポリエチレングリコール
ジアンモニウムアジペートの４０ｗｔχ水ン容）夜を得
た。この水ン容ン夜１２゜５部（以下すべて固形分換算
とする）に、カプロラクタム水？８？＆２２．７部、ヘ
キサメチレンジアンモニウムアジペート水溶液６１．２
部、ＫＢｒｌ、８部を混合し、濃縮、重合を行いポリエ
ーテルアミドｄｗｔを調製した。(4) Preparation of polyetheramide copolymer dwt = polyethylene glycol diamine (polyethylene glycol diamine with 25 ethylene glycol units) and adipic acid are subjected to a salt reaction using a conventional method, and polyethylene glycol diammonium adipate (40 wt x water volume) Got the night. Add caprolactam water to 5 parts of this water (all amounts are converted to solid content). 8? &22.7 parts, hexamethylene diammonium adipate aqueous solution 61.2 parts
1 part and 8 parts of KBrl were mixed, concentrated, and polymerized to prepare polyetheramide dwt.
実施例１〜３及び比較例１〜３
グラフト共重合体、ビニル重合体、脂肪族ポリエステル
、ポリエーテルアミドを表１に示す組成比率でブレンド
し、設定温度２４０°Ｃの二軸押出機によりγ容融？昆
練しペレットとした。続いてシリンダー温度２４０°Ｃ
１金型温度４５°Ｃの射出成形機により試験片を成形し
て各種物性測定を行った。Examples 1 to 3 and Comparative Examples 1 to 3 Graft copolymers, vinyl polymers, aliphatic polyesters, and polyetheramides were blended in the composition ratios shown in Table 1, and γ Yutaka? It was kneaded into pellets. Then the cylinder temperature is 240°C.
A test piece was molded using an injection molding machine with a mold temperature of 45°C, and various physical properties were measured.
遇定方店 ■メルトフローレート（ＭＦＲ） ＪＩＳ Ｋ−７２１０に基づく。Fudingfang store ■Melt flow rate (MFR) Based on JIS K-7210.
■衝撃強度（１／４１Ｚ００）：ＡＳＴＭ Ｄ−２５６
に基づく。■Impact strength (1/41Z00): ASTM D-256
based on.
■引張り強さ：ＡＳＴＭ Ｄ−６３８に基づく。■Tensile strength: Based on ASTM D-638.
■ビカノト軟化点：ＡＳＴＭ Ｄｗｔ５２５に基づく。■Bikanoto Softening Point: Based on ASTM Dwt525.
■表面面イ１抵抗値（Ｒｓ）、体積固有抵抗値（１？ν
）の測定：大きさ４０ Ｘ ４０ｍｍ、厚さ３Ｉ＋ｌｌ
１１の射出成形平板をテストサンプルとし、超絶縁抵抗
計（東亜電波工業株式会社製１１ＯＤＥＬ Ｓ！ｌｗｔ
０Ｅ）によりｉｑ定した■成形片Ｉ、り離： ＩＺＯ［
＋衝撃強度測定後のサンプルの破断面を目視により観察
し、剥離状態を１：１１定した。■Surface resistance value (Rs), volume resistivity value (1?ν
) measurement: size 40 x 40mm, thickness 3I+ll
11 injection molded flat plate was used as a test sample, and a super insulation resistance meter (11ODEL S!lwt manufactured by Toa Denpa Kogyo Co., Ltd.) was used as a test sample.
■ Molded piece I, separation determined by 0E): IZO[
+The fractured surface of the sample after impact strength measurement was visually observed, and the peeling state was determined to be 1:11.
その結果を表１に示す。The results are shown in Table 1.
（発明の効果）
以上の実施例により、ポリエーテルアミドを単独で添加
した場合には耐ｊｉｉ情性が低く、成形片の！、ＩＩ
ｉｌｌがみられるが、脂肪族ポリエステルを併用するこ
とにより、制電性と耐衝撃性が共に高く、成形片’７．
１１離の極めて少ない半永久制電性樹脂組成物が得られ
る。(Effects of the Invention) According to the above examples, when polyether amide is added alone, the JII resistance is low, and the molded piece has poor stability. , II
Although the molded piece '7.
A semi-permanent antistatic resin composition with an extremely low separation of 11 is obtained.
Claims (1)
上のビニル単量体９５〜４０ｗｔ％を重合させたグラフ
ト共重合体 （Ｂ）ビニル重合体 （Ｃ）脂肪族ポリエステル （Ｄ）ポリエーテルアミド共重合体からなり、（Ａ）（
Ｂ）、（Ｃ）、（Ｄ）、の合計を１００重量部としたと
き、５０重量部≦（Ａ）≦９９重量部 ０重量部≦（Ｂ）≦９０重量部 ０．５重量部≦（Ｃ）≦４９．５重量部 ０．５重量部≦（Ｄ）≦４９．５重量部である制電性樹
脂組成物。[Scope of Claims] (A) Graft copolymer obtained by polymerizing 95 to 40 wt % of one or more vinyl monomers to 5 to 60 wt % of a rubbery polymer (B) Vinyl polymer (C) Consists of aliphatic polyester (D) polyetheramide copolymer, (A) (
When the total of B), (C), and (D) is 100 parts by weight, 50 parts by weight ≦ (A) ≦ 99 parts by weight 0 parts by weight ≦ (B) ≦ 90 parts by weight 0.5 parts by weight ≦ ( C)≦49.5 parts by weight 0.5 parts by weight≦(D)≦49.5 parts by weight.An antistatic resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28577088A JPH02133457A (en) | 1988-11-14 | 1988-11-14 | Antistatic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28577088A JPH02133457A (en) | 1988-11-14 | 1988-11-14 | Antistatic resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02133457A true JPH02133457A (en) | 1990-05-22 |
Family
ID=17695832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28577088A Pending JPH02133457A (en) | 1988-11-14 | 1988-11-14 | Antistatic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02133457A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008041356A1 (en) * | 2006-10-03 | 2008-04-10 | Techno Polymer Co., Ltd. | Thermoplastic resin composition and resin molded article |
-
1988
- 1988-11-14 JP JP28577088A patent/JPH02133457A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008041356A1 (en) * | 2006-10-03 | 2008-04-10 | Techno Polymer Co., Ltd. | Thermoplastic resin composition and resin molded article |
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