JPH0140057B2 - - Google Patents
Info
- Publication number
- JPH0140057B2 JPH0140057B2 JP5916980A JP5916980A JPH0140057B2 JP H0140057 B2 JPH0140057 B2 JP H0140057B2 JP 5916980 A JP5916980 A JP 5916980A JP 5916980 A JP5916980 A JP 5916980A JP H0140057 B2 JPH0140057 B2 JP H0140057B2
- Authority
- JP
- Japan
- Prior art keywords
- crosslinking
- polymer
- electron beam
- black
- conductive carbon
- 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.)
- Expired
Links
- 238000004132 cross linking Methods 0.000 claims description 33
- 229920000642 polymer Polymers 0.000 claims description 31
- 238000010894 electron beam technology Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- -1 methacryloyl group Chemical group 0.000 claims description 4
- 125000000349 (Z)-3-carboxyprop-2-enoyl group Chemical group O=C([*])/C([H])=C([H])\C(O[H])=O 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 2
- 239000006232 furnace black Substances 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 description 12
- 239000005060 rubber Substances 0.000 description 11
- 230000008961 swelling Effects 0.000 description 10
- 238000009864 tensile test Methods 0.000 description 6
- 229920002943 EPDM rubber Polymers 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 5
- 229920006027 ternary co-polymer Polymers 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- IXZDIALLLMRYOU-UHFFFAOYSA-N tert-butyl hypochlorite Chemical compound CC(C)(C)OCl IXZDIALLLMRYOU-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 235000019241 carbon black Nutrition 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000006235 reinforcing carbon black Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は電子線架橋用ポリマー組成物に関す
る。
近年、大型の電子線加速器の普及に伴ない、ゴ
ム、プラスチツク、塗料、接着剤等の電子線架橋
が盛んになりつつある。電子線架橋は従来の加熱
による架橋プロセスよりも(1)エネルギー効率が高
い、(2)架橋剤、架橋促進剤が不要である、(3)架橋
速度が極めて大きい、(4)連続架橋プロセスが可能
であるなど多くの利点を有している。反面、電子
線は被照射体に対する透過能力が小さく、特にカ
ーボンブラツク等の高密度の充填剤を添加したポ
リマー組成物では通常の照射条件のもとでは厚さ
が精々１mm程度の薄いシート状、管状あるいは線
状体にしか有効に適用されないという欠点を有し
ていた。
本発明者らはこの欠点を克服して、電子線架橋
の効率を上げ、更に厚物、電子線架橋をも可能に
するため種々研究を行なつた結果本発明を完成す
るに至つたものである。
すなわち本発明は炭素、炭素二重結合を有する
ポリマーの側鎖に付加反応により導入したアクリ
ロイル基、メタクリロイル基、マレイル基、アリ
ル基を有するポリマーに、該ポリマー100重量部
に対してアセチレンブラツクもしくはフアーネス
ブラツクから選ばれた導電性カーボンブラツク１
〜80重量部を配合してなり、架橋後の組成物の体
積固有抵抗が107Ω・cm以下であることを特徴と
する電子線架橋用ポリマー組成物に関するもので
ある。
本発明のポリマー組成物は、従来の組成物より
も通常の電子線照射条件で架橋密度が２〜３倍程
度高くなり、電子線透過能力も高いため従来満足
な架橋が行なえなかつた２〜３mmの厚さのものも
容易に架橋することが可能である。
以下に本発明の内容を詳述する。
電子線架橋型ポリマーは電子線の照射によつて
架橋反応が優先的に進行する型のポリマーで、本
発明で用いられる電子線架橋型ポリマーとしては
電子線照射によりすみやかに付加重合を起し得る
官能基であるアクリロイル基、メタクリロイル
基、マレイル基、またはアリル基を側鎖に導入し
た変性ポリマーである。
本発明のポリマー組成物には必要に応じて電子
線照射により速やかに共架橋する多官能モノマー
や電子線架橋促進剤を併用することができる。多
官能モノマーとしては、多価アルコールのアクリ
ル酸やメタアクリル酸等のα、β−不飽和カルボ
ン酸エステル、トリメリツト酸トリアリル等が、
また架橋促進剤としてはジスルフイド化合物、ト
リフエニルフオスフイン、２−オキサゾリン等が
通常使用される。
導電性カーボンブラツクとはゴムおよびプラス
チツク等のポリマーに充填した際に高い導電性を
付与しポリマーの体積固有抵抗率を107Ω・cm以
下にすることができるカーボンブラツクであつ
て、本発明においては導電性カーボンブラツクと
して、デンカブラツク（電気化学工業社製、商品
名）のようなアセチレンブラツク、および
Ketjen Black EC（オランダAKZO社製、商品
名）、Vulcan XC−72、Vulcan SC、Vulcan Ｃ
（いずれも米国CABOT社製、商品名）、旭HS−
500（旭カーボン社製、商品名）のような導電性フ
アーネスブラツクが用いられる。
導電性カーボンブラツクはポリマー成分100重
量部当り１〜80重量部配合する。これより配合量
の少ない場合にはポリマーの体積固有抵抗率を
107Ω・cm以下にすることが困難であり、一方80
重量部を越えた導電性カーボンブラツク配合ポリ
マーは混練作業性が悪く、物性の低下が著しくな
り実用的でない。
ポリマー組成物には導電性カーボンブラツクに
加えて通常の非導電性カーボンブラツクを配合す
ることが可能である。非導電性カーボンブラツク
の例としてはSAN（N110）、ISAF（N220）、HAF
（N330）、FF（N440）、FEF（N550）、GPF
（N660）、SFR（N770）、FT（N880）、MT
（N990）、などが代表的なものである。これらの
補強性の高いカーボンブラツクの添加によりポリ
マー組成物の物性が向上する。
本発明のポリマー組成物は、電子線照射のみに
よる架橋以外にゴムおよびプラスチツク製品の製
造ラインで行われている予備架橋プロセスに利用
することができる。加熱によりポリマーを架橋せ
しめる通常の架橋剤を含む未架橋ポリマー組成物
を電子線照射して部分的に予備架橋させたもの
は、グリーン強度が向上し、形くずれが防止でき
るので製造ラインの生産性向上、作業性の改良、
品質管理の向上に極めて有用である。本発明のポ
リマー組成物は架橋速度が大きく、厚物の電子線
架橋が可能であり予備架橋の応用範囲が広くな
る。
熱架橋のための架橋剤としては、硫黄、有機過
酸化物、金属酸化物、有機多価アミン、樹脂架橋
剤等通常の架橋剤であれば何れの架橋剤も使用す
ることができる。特に硫黄を配合したポリマー組
成物は、タイヤおよびベルト、ホース等の製造ラ
インにおける予備架橋プロセスに有用である。
本発明の電子線架橋用ポリマー組成物には補強
剤、充填剤、軟化剤、可塑剤、粘着付与剤、架橋
促進剤、架橋促進助剤、滑剤、老化防止剤、着色
剤、ワツクス類等通常使用される充填剤を任意に
加えることが可能である。
電子線架橋は通常線量が３〜50Mrad、加速電
圧が50〜10000KeVの照射条件で行われる。照射
は片面照射あるいは両面照射のいずれでもよい。
以下本発明を実施例によつて説明する。
本文および実施例において体積固有抵抗率は
ASTM D991−60に従つて測定した。膨潤度は
５×10×１（あるいは２）mmの大きさの架橋ポリ
マーを25℃のトルエン溶媒中で６時間膨潤後の重
量膨潤率で、次式により算出した。
重量膨潤率（％）＝膨潤ポリマー全重量／膨潤前ポリマ
ー重量×100
引張り試験はインストロン引張試験機、また動
的弾性率は粘弾性スペクトロメーターで測定し
た。なお実施例中の配合部数はすべて重量部で表
わす。
実施例 １
ｔ−ブチルハイポクロライトの存在下でエチレ
ン−プロピレン三元共重合ゴム（EP33、日本合
成ゴム社製、商品名）100ｇにメタクリル酸2.87
ｇを反応させて得られた変性EPDMゴム（反応
の詳細は特公昭53−6198号公報の記載に従つた）
に、導電性カーボンブラツクであるKet−jen
Black ECおよび従来の非導電性カーボンブラツ
クであるHAFを種々の割合で配合したゴム組成
物（配合を表１に示す）を厚さ２mmのシート状に
し、加速電圧500KeV、電流100ｍＡで10Mradの
線量を照射し電子線架橋を行つた。
各試料の体積固有抵抗率、膨潤度および80℃に
おける引張り試験結果を表１に示す。
導電性カーボンの配合により体積固有抵抗率が
107Ω・cm以下となり、膨潤度の低下、引張試験
の各測定結果の向上が認められ、２mmの厚物シー
トでも電子線架橋効率が向上していることが明ら
かである。
The present invention relates to polymer compositions for electron beam crosslinking. In recent years, with the spread of large-scale electron beam accelerators, electron beam crosslinking of rubber, plastics, paints, adhesives, etc. is becoming popular. Electron beam crosslinking has the following advantages over conventional heating crosslinking processes: (1) it is more energy efficient; (2) it does not require crosslinking agents or crosslinking accelerators; (3) it has an extremely high crosslinking rate; and (4) it is a continuous crosslinking process. It has many advantages such as: On the other hand, electron beams have a low ability to penetrate objects to be irradiated, and in particular polymer compositions containing high-density fillers such as carbon black, under normal irradiation conditions, emit light in the form of a thin sheet with a thickness of about 1 mm at most. It has the disadvantage that it can only be effectively applied to tubular or linear bodies. The present inventors have completed the present invention as a result of various studies to overcome this drawback, increase the efficiency of electron beam crosslinking, and enable electron beam crosslinking of thick materials. be. That is, the present invention applies acetylene black or black to a polymer having an acryloyl group, a methacryloyl group, a maleyl group, or an allyl group introduced into the side chain of a polymer having carbon or carbon double bonds by an addition reaction, based on 100 parts by weight of the polymer. Conductive carbon black 1 selected from Arnes Black
The present invention relates to a polymer composition for electron beam crosslinking, characterized in that the volume resistivity of the composition after crosslinking is 10 7 Ω·cm or less. The polymer composition of the present invention has a crosslinking density about 2 to 3 times higher than that of conventional compositions under normal electron beam irradiation conditions, and has a high electron beam transmission ability, so that it is difficult to achieve satisfactory crosslinking by 2 to 3 mm. can be easily crosslinked. The content of the present invention will be explained in detail below. An electron beam crosslinkable polymer is a type of polymer in which a crosslinking reaction proceeds preferentially by electron beam irradiation, and the electron beam crosslinkable polymer used in the present invention can quickly undergo addition polymerization by electron beam irradiation. It is a modified polymer in which a functional group such as an acryloyl group, a methacryloyl group, a maleyl group, or an allyl group is introduced into the side chain. The polymer composition of the present invention may contain a polyfunctional monomer and an electron beam crosslinking accelerator that rapidly co-crosslink by electron beam irradiation, if necessary. Examples of polyfunctional monomers include polyhydric alcohols such as acrylic acid and methacrylic acid, α, β-unsaturated carboxylic acid esters, triallyl trimellitate, etc.
Disulfide compounds, triphenylphosphine, 2-oxazoline, etc. are commonly used as crosslinking accelerators. Conductive carbon black is a carbon black that can impart high conductivity when filled into polymers such as rubber and plastics, and can reduce the specific volume resistivity of the polymer to 10 7 Ω・cm or less. As conductive carbon black, acetylene black such as Denka Black (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name), and
Ketjen Black EC (manufactured by AKZO in the Netherlands, product name), Vulcan XC-72, Vulcan SC, Vulcan C
(Both manufactured by CABOT, USA, product name), Asahi HS-
A conductive furnace black such as 500 (manufactured by Asahi Carbon Co., Ltd., trade name) is used. The conductive carbon black is blended in an amount of 1 to 80 parts by weight per 100 parts by weight of the polymer component. If the amount is less than this, the specific volume resistivity of the polymer is
It is difficult to reduce the resistance to 10 7 Ω・cm or less, while 80
Polymers containing conductive carbon black in excess of parts by weight have poor kneading workability and significant deterioration of physical properties, making them impractical. In addition to conductive carbon black, ordinary non-conductive carbon black can be blended into the polymer composition. Examples of non-conductive carbon blacks are SAN (N110), ISAF (N220), and HAF.
(N330), FF (N440), FEF (N550), GPF
(N660), SFR (N770), FT (N880), MT
(N990), etc. are typical examples. The addition of these highly reinforcing carbon blacks improves the physical properties of the polymer composition. In addition to crosslinking by electron beam irradiation alone, the polymer compositions of the present invention can be used in pre-crosslinking processes that are carried out in the production lines of rubber and plastic products. Uncrosslinked polymer compositions containing conventional crosslinking agents that crosslink polymers by heating are partially precrosslinked by electron beam irradiation, which improves green strength and prevents deformation, improving production line productivity. improvement, improved workability,
Extremely useful for improving quality control. The polymer composition of the present invention has a high crosslinking rate and can be crosslinked with electron beams to thick materials, thereby widening the range of applications for pre-crosslinking. As the crosslinking agent for thermal crosslinking, any common crosslinking agent such as sulfur, organic peroxides, metal oxides, organic polyvalent amines, resin crosslinking agents, etc. can be used. In particular, sulfur-loaded polymer compositions are useful in pre-crosslinking processes in production lines for tires, belts, hoses, and the like. The polymer composition for electron beam crosslinking of the present invention usually includes reinforcing agents, fillers, softeners, plasticizers, tackifiers, crosslinking accelerators, crosslinking accelerators, lubricants, anti-aging agents, colorants, waxes, etc. It is possible to optionally add the fillers used. Electron beam crosslinking is usually carried out under irradiation conditions with a dose of 3 to 50 Mrad and an accelerating voltage of 50 to 10,000 KeV. The irradiation may be done on one side or on both sides. The present invention will be explained below with reference to Examples. In the main text and examples, the specific volume resistivity is
Measured according to ASTM D991-60. The degree of swelling was calculated by the following formula using the weight swelling ratio after swelling a crosslinked polymer with a size of 5 x 10 x 1 (or 2) mm in a toluene solvent at 25°C for 6 hours. Weight swelling ratio (%) = total weight of swollen polymer/weight of polymer before swelling x 100 The tensile test was performed using an Instron tensile tester, and the dynamic elastic modulus was measured using a viscoelasticity spectrometer. It should be noted that all blended parts in the examples are expressed in parts by weight. Example 1 In the presence of t-butyl hypochlorite, 2.87 g of methacrylic acid was added to 100 g of ethylene-propylene ternary copolymer rubber (EP33, manufactured by Nippon Gosei Rubber Co., Ltd., trade name).
Modified EPDM rubber obtained by reacting g
Ket-jen, a conductive carbon black
A rubber composition containing Black EC and HAF, a conventional non-conductive carbon black, in various proportions (the composition is shown in Table 1) was formed into a 2 mm thick sheet, and a dose of 10 Mrad was applied at an accelerating voltage of 500 KeV and a current of 100 mA. was irradiated to perform electron beam crosslinking. Table 1 shows the specific volume resistivity, degree of swelling, and tensile test results at 80°C for each sample. The specific volume resistivity is increased by the combination of conductive carbon.
10 7 Ω·cm or less, a decrease in the degree of swelling and an improvement in each measurement result of the tensile test were observed, and it is clear that the electron beam crosslinking efficiency is improved even in a 2 mm thick sheet.
【表】
実施例 ２
種々の変性エチレン−プロピレン三元共重合ゴ
ム（変性率は実施例１と同じ）を用いて表２に示
すような配合につき厚さ２mmのシートを作成し、
実施例１と同じ条件の電子線照射を行つた。
体積固有抵抗率、膨潤度、80℃における引張試
験の測定結果を表２に示す。
導電性カーボンブラツクの配合による架橋効率
の向上が認められる。[Table] Example 2 Using various modified ethylene-propylene ternary copolymer rubbers (modification rate is the same as in Example 1), sheets with a thickness of 2 mm were prepared according to the formulation shown in Table 2,
Electron beam irradiation was performed under the same conditions as in Example 1. Table 2 shows the measurement results of volume resistivity, degree of swelling, and tensile test at 80°C. It is observed that the crosslinking efficiency is improved by adding conductive carbon black.
【表】
実施例 ３
ｔ−ブチルハイポクロライトの存在下でエチレ
ン−プロピレン三元共重合ゴム100ｇにアクリル
酸2.54ｇを反応させて得られた変性EPDMゴム
(A)、
ｔ−ブチルハイポクロライトの存在下でエチレ
ン−プロピレン三元共重合ゴム100ｇにマレイン
酸3.87ｇを反応させて得られた変性EPDMゴム
(B)、
ｔ−ブチルハイポクロライトの存在下でエチレ
ン−プロピレン三元共重合ゴム100ｇにアリルア
ルコール1.94ｇを反応させて得られた変性EPDM
ゴム(C)、
それぞれの変性EPDMゴム、導電性カーボン
ブラツクであるKetjen Black ECおよび従来の
非導電性カーボンブラツクであるHAFを種々の
割合で配合したゴム組成物（配合を表３に示す）
を厚さ２mmのシート状にし、加速電圧500KeV、
電流100ｍＡで10Mradの線量を照射し電子線架
橋を行つた。
各試料の体積固有抵抗率、膨潤度および80℃に
おける引張り試験結果を表３に示す。
導電性カーボンブラツクの配合により体積固有
抵抗率が107Ω・cm以下となり、膨潤度の低下、
引張試験の各測定結果の向上が認められ、各種官
能基をつけた変性ポリマーについても２mmの厚物
シートで電子線架橋効率が向上していることが明
らかである。[Table] Example 3 Modified EPDM rubber obtained by reacting 100 g of ethylene-propylene ternary copolymer rubber with 2.54 g of acrylic acid in the presence of t-butyl hypochlorite.
(A) Modified EPDM rubber obtained by reacting 100 g of ethylene-propylene ternary copolymer rubber with 3.87 g of maleic acid in the presence of t-butyl hypochlorite.
(B), Modified EPDM obtained by reacting 100 g of ethylene-propylene ternary copolymer rubber with 1.94 g of allyl alcohol in the presence of t-butyl hypochlorite.
Rubber compositions containing rubber (C), each modified EPDM rubber, Ketjen Black EC, a conductive carbon black, and HAF, a conventional non-conductive carbon black, in various proportions (the formulations are shown in Table 3).
was formed into a sheet with a thickness of 2 mm, and an acceleration voltage of 500 KeV was applied.
Electron beam crosslinking was performed by irradiating a dose of 10 Mrad at a current of 100 mA. Table 3 shows the specific volume resistivity, degree of swelling, and tensile test results at 80°C for each sample. The combination of conductive carbon black reduces the specific volume resistivity to 10 7 Ω・cm or less, reducing the degree of swelling and
Improvements were observed in each measurement result of the tensile test, and it is clear that the electron beam crosslinking efficiency of modified polymers with various functional groups was also improved with a 2 mm thick sheet.
Claims (1)
に付加反応により導入したアクリロイル基、メタ
クリロイル基、マレイル基、アリル基を有するポ
リマーに、該ポリマー100重量部に対してアセチ
レンブラツクもしくはフアーネスブラツクから選
ばれた導電性カーボンブラツク１〜80重量部を配
合してなり、架橋後の組成物の体積固有抵抗が
107Ω・cm以下であることを特徴とする電子線架
橋用ポリマー組成物。1. Acetylene black or furnace black is applied to a polymer having an acryloyl group, methacryloyl group, maleyl group, or allyl group introduced into the side chain of a polymer having carbon or carbon double bonds by an addition reaction, based on 100 parts by weight of the polymer. 1 to 80 parts by weight of a selected conductive carbon black is blended to increase the volume resistivity of the composition after crosslinking.
A polymer composition for electron beam crosslinking, characterized in that it has a resistance of 10 7 Ω·cm or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5916980A JPS56155238A (en) | 1980-05-02 | 1980-05-02 | Polymer composition for electron beam crosslinking |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5916980A JPS56155238A (en) | 1980-05-02 | 1980-05-02 | Polymer composition for electron beam crosslinking |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56155238A JPS56155238A (en) | 1981-12-01 |
| JPH0140057B2 true JPH0140057B2 (en) | 1989-08-24 |
Family
ID=13105603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5916980A Granted JPS56155238A (en) | 1980-05-02 | 1980-05-02 | Polymer composition for electron beam crosslinking |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56155238A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9125169B2 (en) | 2011-12-23 | 2015-09-01 | Rovi Guides, Inc. | Methods and systems for performing actions based on location-based rules |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5975939A (en) * | 1982-10-26 | 1984-04-28 | San Aroo Kagaku Kk | Production of vinyl chloride polymer composition |
| JP3972523B2 (en) * | 1999-07-07 | 2007-09-05 | 松下電器産業株式会社 | Carbon paste |
| JP2012149177A (en) * | 2011-01-19 | 2012-08-09 | Daicel Corp | Electron-beam-curable composition and cured product thereof |
-
1980
- 1980-05-02 JP JP5916980A patent/JPS56155238A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9125169B2 (en) | 2011-12-23 | 2015-09-01 | Rovi Guides, Inc. | Methods and systems for performing actions based on location-based rules |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56155238A (en) | 1981-12-01 |
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