JP2817241B2 - Method for producing elastic composition - Google Patents
Method for producing elastic compositionInfo
- Publication number
- JP2817241B2 JP2817241B2 JP21071789A JP21071789A JP2817241B2 JP 2817241 B2 JP2817241 B2 JP 2817241B2 JP 21071789 A JP21071789 A JP 21071789A JP 21071789 A JP21071789 A JP 21071789A JP 2817241 B2 JP2817241 B2 JP 2817241B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- elastic composition
- csm
- kneading
- 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 - Fee Related
Links
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は弾性体組成物の製法に関する。詳しくは、ク
ロロスルフオン化ポリエステル又は塩素化ポリエチレン
とポリプロピレンからなる弾性体組成物の製法に関す
る。本発明の弾性体組成物はゴム加工分野あるいは樹脂
加工分野において使用される。Description: TECHNICAL FIELD The present invention relates to a method for producing an elastic composition. More specifically, the present invention relates to a method for producing an elastic composition comprising chlorosulfonated polyester or chlorinated polyethylene and polypropylene. The elastic composition of the present invention is used in the field of rubber processing or resin processing.
（従来の技術） ゴムを原料とするゴム弾性体組成物の成形加工ではゴ
ムを架橋させるために加硫工程を必要とするが、動的熱
処理により部分架橋させたゴムである、ゲルを含有する
ゴムとポリオレフインを主原料とする弾性体組成物は加
硫工程を必要とせず短時間に成形加工でき、成形加工費
が低減出来る。このために、近年、ゲルを含有するゴム
とポリオレフインを主原料とする弾性体組成物の需要が
高まってきた。これに伴って、塩素を含有するクロロス
ルフオン化ポリエチレン又は塩素化ポリエチレンは耐油
性、耐オゾン性、耐候性、明色性が他のゴムより選れて
いることから、ゲルを含有するクロロスルフオン化ポリ
エチレン又は塩素化ポリエチレンとポリプロピレンを主
原料とする弾性体組成物も実用化の機運にある。(Prior Art) Molding of a rubber elastic composition using rubber as a raw material requires a vulcanization step in order to crosslink rubber, but contains gel, which is partially crosslinked rubber by dynamic heat treatment. The elastic composition mainly composed of rubber and polyolefin can be molded in a short time without requiring a vulcanizing step, and the molding cost can be reduced. For this reason, in recent years, the demand for an elastic composition mainly composed of rubber containing gel and polyolefin has been increasing. Along with this, chlorosulfonated polyethylene containing chlorine or chlorinated polyethylene is selected from other rubbers for oil resistance, ozone resistance, weather resistance, and lightness, and therefore chlorosulfonated polyethylene containing gel is used. Elastic compositions containing fluorinated polyethylene or chlorinated polyethylene and polypropylene as main raw materials are also in practical use.
しかしながら、ゲルを含有するクロロスルフオン化ポ
リエチレン又は塩素化ポリエチレンとポリプロピレンを
主原料とする弾性体組成物は、特開昭52−29845に開示
されている製法で得ると機械的性質である圧縮永久歪お
よび永久伸びの点で劣り、また特公昭64−4536に開示さ
れている製法では白色として得られるべき弾性体組成物
が茶褐色に変色する等の欠点がある。実用化のために
は、これらの欠点が解決された弾性体組成物の製法が強
く要望されている。However, a gel-containing chlorosulfonated polyethylene or an elastic composition containing chlorinated polyethylene and polypropylene as main raw materials has a mechanical property such as compression set obtained by the method disclosed in JP-A-52-29845. It is inferior in strain and permanent elongation, and the production method disclosed in Japanese Patent Publication No. 64-4536 has disadvantages such as that the elastic composition to be obtained as white turns brown. For practical use, there is a strong demand for a method for producing an elastic composition in which these disadvantages have been solved.
（発明が解決しようとする課題） 本発明は、上記問題点を解決するために鋭意研究の結
果、得られる弾性組成物の機械的性質である圧縮永久歪
および永久伸びの点が優れ、且つ、変色がない弾性体組
成物の製法を提供するものである。(Problems to be Solved by the Invention) As a result of intensive studies to solve the above problems, the present invention is excellent in the points of compression set and permanent elongation, which are mechanical properties of the obtained elastic composition, and An object of the present invention is to provide a method for producing an elastic composition without discoloration.
（課題を解決するための手段） 本発明はゲルを含有するクロロスルフオン化ポリエチ
レン又は塩素化ポリエチレンとポリプロピレンを主原料
とする弾性体組成物の製法にある。(Means for Solving the Problems) The present invention resides in a method for producing an elastic composition containing gel-containing chlorosulfonated polyethylene or chlorinated polyethylene and polypropylene as main raw materials.
即ち、本発明は、予めクロロスルフオン化ポリエチレ
ン又は塩素化ポリエチレンに脱塩酸捕捉剤と加硫剤及び
／又は加硫促進剤を混練し、次いで該混練物を使用ポリ
プロピレン量の５〜90％のポリプロピレンに添加して動
的熱処理を行なった後、残りのポリプロピレンに添加混
練することを特徴とする弾性組成物の製法にある。That is, in the present invention, a chlorsulfonated polyethylene or a chlorinated polyethylene is previously kneaded with a dehydrochlorination-capturing agent and a vulcanizing agent and / or a vulcanization accelerator, and then the kneaded material is used in an amount of 5 to 90% of the amount of polypropylene used. A method for producing an elastic composition, comprising adding dynamic kneading to polypropylene and then kneading the remaining polypropylene.
以下本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明の弾性組成物の製法に使用されるクロロスルフ
オン化ポリエチレン（以下CSMと云う）は、ポリエチレ
ン、エチレン−ブテン−１共重合体、エチレン−酢酸ビ
ニル共重合体、エチレン−プロピレン共重合体、エチレ
ン−アクリル酸エチル共重合体、エチレン−アクリル酸
メチル共重合体等に塩素およびクロロスルフオニル基を
導入しゴム状にしたものである。塩素およびクロロスル
フオニル基の導入方法には、該記ポリマーを四塩化炭素
等の不活性有機溶剤に溶解し、塩素ガスを吹込み塩素化
して次にクロロスルフオニルを添加反応させてクロロス
ルフオニル基を導入するか、あるいはクロロスルフオニ
ルによって塩素とクロロスルフオニル基を導入する等の
方法がある。CSMはゴム状であれば特に塩素量は限定さ
れないが15〜55重量％の塩素量のCSMがゴム状にある。
また本発明の製法に使用される塩素化ポリエチレン（以
下CPEと云う）は、該記ポリマーの粉末または粒子を水
に懸濁させるか、あるいは四塩化炭素等の不活性有機溶
剤に溶解して塩素ガスを吹込み塩素を導入しゴム状にし
たものである。CPEはCSMと同様にゴム状であれば特に塩
素量は限定されないが15〜55重量％の塩素量CPEがゴム
状にある。以上、CSMとCPEの製法を例記したが、本発明
に使用されるCSM又はCPEはこれらの製法に限定されるも
のではない。The chlorosulfonated polyethylene (hereinafter referred to as CSM) used in the method for producing the elastic composition of the present invention includes polyethylene, ethylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer , Ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, etc., into which a chlorine and chlorosulfonyl group are introduced to form a rubber. To introduce chlorine and chlorosulfonyl groups, the polymer is dissolved in an inert organic solvent such as carbon tetrachloride, and chlorinated by blowing in chlorine gas, and then chlorosulfonyl is added and reacted. There is a method of introducing a sulfonyl group or a method of introducing chlorine and a chlorosulfonyl group with chlorosulfonyl. The amount of chlorine is not particularly limited as long as the CSM is rubbery, but CSM having a chlorine amount of 15 to 55% by weight is in a rubbery state.
The chlorinated polyethylene (hereinafter referred to as CPE) used in the production method of the present invention is obtained by suspending the polymer powder or particles in water or dissolving it in an inert organic solvent such as carbon tetrachloride. It is made by blowing gas and introducing chlorine into rubber. As long as the CPE is rubbery like the CSM, the chlorine content is not particularly limited, but the chlorine content CPE of 15 to 55% by weight is rubbery. As mentioned above, the production methods of CSM and CPE are described, but the CSM or CPE used in the present invention is not limited to these production methods.
本発明の製造において、CSM又はCPEに混練される脱塩
酸捕捉剤としては、金属酸化物、金属鉛化合物、金属水
酸化物、脂肪酸金属石鹸類、例えば酸化マグネシウム、
酸化カルシウム、酸化亜鉛、一酸化鉛、四三酸化鉛、三
塩基性硫酸鉛、二塩基性亜燐酸鉛、水酸化カルシウム、
ステアリン酸ソーダ、ステアリン酸マグネシウム、ステ
アリン酸カルシウム等が挙げられる。そしてこれらは単
独又は混合して使用される。使用される量はCSM又はCPE
100重量部当り0.5〜30重量部である。In the production of the present invention, as the dehydrochlorination scavenger kneaded in CSM or CPE, metal oxides, metal lead compounds, metal hydroxides, fatty acid metal soaps, such as magnesium oxide,
Calcium oxide, zinc oxide, lead monoxide, lead tetroxide, tribasic lead sulfate, dibasic lead phosphite, calcium hydroxide,
Examples include sodium stearate, magnesium stearate, and calcium stearate. These are used alone or as a mixture. The amount used is CSM or CPE
0.5 to 30 parts by weight per 100 parts by weight.
本発明において使用される加硫剤及び／又は加硫促進
剤は、一般にCSM又はCPEの架橋に使用される加硫剤及び
／又は加硫促進剤であり、有機過酸化物、Ｚトリアジン
チオール系化合物、チオウレア系化合物、チウラム系化
合物、ポリアミン系化合物、多官能性メタクリレート系
化合物、多価アルコール・メタクリレート及びアクリレ
ート系化合物、その他の加硫剤及び／又は加硫促進剤
類、例えばｔ−ブチルハイドロパーオキサイド、2,5−
ジ−メチル−2,5−ジ−（ｔ−ブチルパーオキシ）ヘキ
サン、1,3,5−トリチオシアヌール酸、１−メトキシ−
3,5−ジメルカプトトリアジン、エチレンチオウレア、
ジブチルチオウレア、ジエチルチオウレア、ジペンタメ
チレン・チラウム・テトラサルフアイド、テトラメチル
・チウラム・ダイサルフアイド、ヘキサメチレン・ジア
ミン、ヘキサメチレンジアミン・カーバメイト、エチレ
ングリコール・ジメタアクリレート、メチロールプロパ
ン・トリメタアクリレート、ポリエチレングリコール・
ジアクリレート、トリメチロールプロパン・トリメタア
クリレート、ペンタエリスリトール、N,N'−ｍ−フエニ
レンビスマレイミド、トリアリル・イソシアヌレート等
が挙げられる。使用される量は、CSM又はCPEが動的熱処
理される必要量であって、CSM又はCPE100重量部当り0.0
1〜10重量部である。The vulcanizing agent and / or vulcanization accelerator used in the present invention is a vulcanizing agent and / or vulcanization accelerator generally used for crosslinking of CSM or CPE, and includes an organic peroxide, a Z triazine thiol type. Compounds, thiourea-based compounds, thiuram-based compounds, polyamine-based compounds, polyfunctional methacrylate-based compounds, polyhydric alcohol / methacrylate- and acrylate-based compounds, and other vulcanizing agents and / or vulcanization accelerators such as t-butylhydro Peroxide, 2,5-
Di-methyl-2,5-di- (t-butylperoxy) hexane, 1,3,5-trithiocyanuric acid, 1-methoxy-
3,5-dimercaptotriazine, ethylenethiourea,
Dibutylthiourea, diethylthiourea, dipentamethylene thiuram tetrasulfide, tetramethyl thiuram disulfide, hexamethylene diamine, hexamethylenediamine carbamate, ethylene glycol dimethacrylate, methylolpropane trimethacrylate, polyethylene glycol・
Examples include diacrylate, trimethylolpropane / trimethacrylate, pentaerythritol, N, N'-m-phenylenebismaleimide, triallyl isocyanurate and the like. The amount used is the amount required for the CSM or CPE to be dynamically heat treated, and is 0.0% per 100 parts by weight of the CSM or CPE.
1 to 10 parts by weight.
本発明の製法において、予め行うCSM又はCPEと、脱塩
酸捕捉剤、加硫剤及び／又は加硫促進剤との混練は、一
般にゴムあるいは樹脂の混練に使用される混練機、例え
ばロール混練機、バンバリーミキサー、双腕形ニーダ
ー、スクリュウ式混練機、ローター形連続混練基等を使
用して行なわれる。この混練の温度および時間は特に制
限されるものではないが、混練温度は低い方が好まし
い。100℃を越えた温度で混練した場合、得られる弾性
体組成物は機械的性質が劣るか、あるいは国褐色に変色
する場合があり、注意を要する。混練時間はCSM又はCPE
に脱塩酸捕捉剤と加硫剤及び／又は加硫促進剤が分散す
る時間であれば良く、例えばロール混練機を使用した場
合、５〜15分で分離する。そして、得られたCSM又はCPE
に脱塩酸捕捉剤と加硫剤及び／又は加硫促進剤を混練し
た混練物（以下ゴム混練物と云う）は、使用ポリプロピ
レン（以下PPと云う）量の５〜90％のポリプロピレン
に、好ましくは10〜80％のポリプロピレンに添加して動
的熱処理されるう。５％未満では得られる弾性体組成物
の機械的性質が劣り、90％を越えた量では、得られる弾
性体組成物の流動性が悪く成形が困難となる。In the production method of the present invention, the kneading of CSM or CPE previously performed with the dehydrochlorination scavenger, the vulcanizing agent and / or the vulcanization accelerator is carried out by a kneading machine generally used for kneading rubber or resin, for example, a roll kneading machine This is performed using a Banbury mixer, a double-arm kneader, a screw-type kneader, a rotor-type continuous kneader, or the like. The kneading temperature and time are not particularly limited, but the kneading temperature is preferably lower. When kneading at a temperature exceeding 100 ° C., the resulting elastic composition may have poor mechanical properties or may turn into a national brown color, so care must be taken. Mixing time is CSM or CPE
Any time may be employed as long as the dehydrochlorination scavenger and the vulcanizing agent and / or the vulcanization accelerator are dispersed. For example, when a roll kneader is used, separation takes 5 to 15 minutes. And the obtained CSM or CPE
A kneaded product obtained by kneading a dehydrochlorination scavenger with a vulcanizing agent and / or a vulcanization accelerator (hereinafter referred to as a rubber kneaded material) is preferably used in a polypropylene of 5 to 90% of the amount of polypropylene (hereinafter referred to as PP). Is added to 10-80% polypropylene and subjected to dynamic heat treatment. If the amount is less than 5%, the mechanical properties of the obtained elastic body composition are inferior. If the amount exceeds 90%, the resulting elastic body composition has poor flowability and molding becomes difficult.
本発明の製法に使用されるPPは、チーグラー・ナッタ
型の触媒を使用し、不活性溶剤中で、プロピレンを単独
重合、あるいはプロピレンとα−オレフィン、例えばエ
チレン、１−ブテン、１−ペンテン、４−メチル−１−
ペンテン等とプロピレンを共重合して得られる重合体で
あって、結晶性である。使用される量は、CSM又はCPE10
0重量部当り10〜50重量部であって、この範囲において
得られる組成物が弾性体である。PP used in the production method of the present invention, using a Ziegler-Natta type catalyst, in an inert solvent, propylene homopolymerization, or propylene and α-olefin, for example, ethylene, 1-butene, 1-pentene, 4-methyl-1-
A polymer obtained by copolymerizing pentene and propylene with propylene and is crystalline. The amount used is CSM or CPE10
10 to 50 parts by weight per 0 parts by weight, and the composition obtained in this range is an elastic body.
本発明のゴム混練物を使用するPPに添加して行う動的
熱処理は、一般にゴムあるいは樹脂の混練に使用される
混練機、例えば該記した混練機を使用して行なわれる。
ゴム混練物は使用されるPPが溶融状態となる温度から25
0℃の範囲内で添加され動的熱処理される。PPが溶融し
ていない状態で添加して動的熱処理を行なった場合は得
られる弾性体組成物の機械的性質が劣り好ましくない。
250℃を越えて動的熱処理した場合は得られる弾性体組
成物が変色する。例えばPP単独重合体の場合170〜200℃
の温度で混練することにより、得られる弾性組成物は機
械的性質が優れ、且つ変色がない。本発明の製法におい
ては、ここでの混練が特に重要であって、ゴム混練物を
PPに十分に分散させると同時に動的熱処理を行なう必要
がある。分散が劣ると得られる弾性体組成物の機械的性
質が劣り好ましくない。充分に分散させると同時に動的
熱処理を行なうに必要な時間は使用される脱塩酸捕捉
剤、加硫剤及び／又は加硫促進剤等の種類、量あるいは
混練機の種類等により異なり制限されるものではない
が、例えば、ロール混練機を使用し、ゴム混練物をCSM1
00重量部当りPP20重量部の50％に添加して動的熱処理す
る場合は180℃で２〜20分間の混練時間を必要とする。
そして得られた混練物（以下PP混練物と云う）は、次に
残りのPPに添加混練される。The dynamic heat treatment performed by adding to the PP using the rubber kneaded product of the present invention is generally performed using a kneading machine used for kneading rubber or resin, for example, the above-described kneading machine.
The rubber kneaded material should be heated from the temperature at which the PP used will be in a molten state.
It is added within the range of 0 ° C. and is subjected to dynamic heat treatment. When dynamic heat treatment is performed by adding PP in a state where it is not melted, the mechanical properties of the obtained elastic composition are inferior, which is not preferable.
When the dynamic heat treatment is performed at a temperature exceeding 250 ° C., the obtained elastic composition discolors. For example, in the case of PP homopolymer 170 to 200 ° C
The resulting elastic composition has excellent mechanical properties and has no discoloration. In the production method of the present invention, kneading here is particularly important, and
It is necessary to perform dynamic heat treatment simultaneously with sufficient dispersion in PP. If the dispersion is inferior, the mechanical properties of the obtained elastic composition are inferior, which is not preferable. The time required for performing the dynamic heat treatment at the same time as the sufficient dispersing is different depending on the type and amount of the dehydrochlorinated scavenger, vulcanizing agent and / or vulcanization accelerator used, and the type of the kneader, and is limited. Although it is not something, for example, using a roll kneader, the rubber kneaded material is CSM1
When dynamic heat treatment is performed by adding 50% by weight of 20 parts by weight of PP per 100 parts by weight, a kneading time of 2 to 20 minutes at 180 ° C is required.
The obtained kneaded material (hereinafter referred to as PP kneaded material) is then added and kneaded to the remaining PP.
本発明で云う動的熱処理とは、CSM又はCPEを該記の混
練機中で流動させながらゲルを作ることである。そして
そのゲル量は特に制限されるものではないが、弾性体組
成物のCSM又はCPEのゲル量は20重量％以上が好ましい。
20重量％未満では弾性体組成物の機械的性質が劣り好ま
しくない。なお、ここで云うゲルとは部分架橋されたCS
M又はCPEを指し、ゲル量は動的熱処理されたCSM又はCPE
をJIS Ｋ 6388に従い、100メッシュのステンレス製金
網で作ったハリス籠で測定されるベンゼン未抽出残渣を
云う。The dynamic heat treatment referred to in the present invention is to make a gel while flowing CSM or CPE in the above kneader. The amount of the gel is not particularly limited, but the amount of the CSM or CPE gel of the elastic composition is preferably 20% by weight or more.
If the content is less than 20% by weight, the mechanical properties of the elastic composition are inferior, which is not preferable. The gel referred to here is partially cross-linked CS
Refers to M or CPE, and the gel amount is CSM or CPE subjected to dynamic heat treatment.
Is a benzene unextracted residue measured with a Harris basket made of a 100-mesh stainless steel wire mesh according to JIS K 6388.
本発明においてPP混練物を残りのPPに添加混練する混
練は該記の混練機を使用して行なわれる。混練は、残り
のPPが溶融状態となる温度から250℃の範囲内で行われ
る。PPが溶融しない状態で添加混練を行なった場合は得
られる弾性体組成物の機械的性質が劣り好ましくない。In the present invention, kneading for adding and kneading the PP kneaded material to the remaining PP is performed using the kneader described above. The kneading is performed within a temperature range from the temperature at which the remaining PP becomes a molten state to 250 ° C. When the addition and kneading are performed in a state where the PP is not melted, the mechanical properties of the obtained elastic composition are inferior, which is not preferable.
250℃を越えると、得られる弾性体組成物が変色す
る。混練時間は特に制限されるものではないが、ここで
の添加混練はゴム混練物を使用PP量の５〜90％のポリプ
ロピレンに添加して動的熱処理を行なう混練と同様に重
要であって、PP混練物が残りのPPに充分に分散するまで
行なう必要がある。分散が劣ると得られる弾性体組成物
の機械的性質および流動性が劣り好ましくない。When the temperature exceeds 250 ° C., the obtained elastic composition discolors. The kneading time is not particularly limited, but the addition kneading here is as important as the kneading in which the rubber kneaded material is added to 5-90% of the used PP amount of polypropylene to perform dynamic heat treatment, It is necessary to perform the kneading until the kneaded product is sufficiently dispersed in the remaining PP. If the dispersion is poor, the mechanical properties and fluidity of the obtained elastic composition are poor, which is not preferable.
本発明の弾性体組成物の製造過程において、あるいは
得られた弾性体組成物にゴム用配合剤あるいは樹脂用配
合剤、例えば可塑剤、軟化剤、ラジカル禁止剤、老化防
止剤、紫外線吸収剤、カーボンブラック等の補強剤、白
色充填剤、発泡剤、滑剤、帯電防止剤、着色剤等を混練
することも出来る。そして本発明の熱可塑性エラストマ
ー組成物は成形機、例えば押出成形機、射出成形機、カ
レンダーロール、プレス成形機、吹込成形機あるいは真
空成形機等を使用し成形される。In the manufacturing process of the elastic composition of the present invention, or in the obtained elastic composition, a compounding agent for rubber or a compounding agent for resin, for example, a plasticizer, a softener, a radical inhibitor, an antioxidant, an ultraviolet absorber, A reinforcing agent such as carbon black, a white filler, a foaming agent, a lubricant, an antistatic agent, a coloring agent, and the like can be kneaded. The thermoplastic elastomer composition of the present invention is molded using a molding machine, for example, an extrusion molding machine, an injection molding machine, a calender roll, a press molding machine, a blow molding machine or a vacuum molding machine.
（実施例） 以下、実施例および比較例により、本発明を具体的に
説明するが、本発明はこれらになんら制限されるもので
はない。(Examples) Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
実施例−１ 表−１に示す配合のCSM100重量部と脱塩酸捕捉剤であ
る酸化マグネシウム10重量部、可塑剤のDOS20重量部、
白色充填剤の酸化チタン10重量部、加硫剤及び／又は加
硫促進剤であるPM1重量部を、予めロール混練機で50
℃、10分間混練を行ないゴム混練物を得た。温度が180
℃のロール混練機でPP20重量部の50％を溶融し、得られ
たゴム混練物を添加して５分間の動的熱処理を行ないPP
混練物を得た。次に温度が180℃のロール混練機で残り
のPPを溶融し、これにPP混練物を添加し10分間混練を行
なった。Example-1 100 parts by weight of CSM having the composition shown in Table 1, 10 parts by weight of magnesium oxide as a dehydrochlorination scavenger, 20 parts by weight of DOS of a plasticizer,
10 parts by weight of titanium oxide as a white filler and 1 part by weight of PM as a vulcanizing agent and / or a vulcanization accelerator are previously mixed in a roll kneader with a 50 kneader.
Kneading was performed at 10 ° C. for 10 minutes to obtain a rubber kneaded material. 180 temperature
Melt 50% of PP 20 parts by weight with a roll kneader at ℃, add the obtained rubber kneaded material and perform dynamic heat treatment for 5 minutes to PP
A kneaded product was obtained. Next, the remaining PP was melted with a roll kneader at a temperature of 180 ° C., and the PP kneaded material was added thereto and kneaded for 10 minutes.
得られた弾性組成物の色をゴム混練物の色と比較し、
肉眼により変色の有無を判定した。次に弾性体組成物を
180℃の圧縮成形機で予熱４分間、加圧成形２分間を行
なった後、10℃の圧縮冷却機で４分間冷却を行ない、厚
さ2mmのシートを得た。得られたシートから、JIS Ｋ
6301に従って永久伸び試験を行なった。なおこの永久伸
び試験での伸張は100％伸張とした。また得られた弾性
体組成物を、180℃の圧縮成形機で予熱６分間、加圧成
形３分間を行った後、10℃の圧縮冷却機で６分間冷却を
行ない、厚さ12.7mmのシートを得た。得られたシートか
ら、JIS Ｋ 6301に従って圧縮永久歪試験を70℃、22
時間の試験条件で行なった。Compare the color of the obtained elastic composition with the color of the rubber kneaded material,
The presence or absence of discoloration was determined with the naked eye. Next, the elastic composition
After preheating for 4 minutes and compression molding for 2 minutes in a compression molding machine at 180 ° C., cooling was performed for 4 minutes in a compression cooling machine at 10 ° C. to obtain a sheet having a thickness of 2 mm. From the obtained sheet, JIS K
A permanent elongation test was performed according to 6301. The elongation in this permanent elongation test was 100% elongation. The obtained elastic composition was preheated in a compression molding machine at 180 ° C. for 6 minutes and pressed for 3 minutes, and then cooled in a compression cooling machine at 10 ° C. for 6 minutes to obtain a sheet having a thickness of 12.7 mm. I got From the obtained sheet, a compression set test was performed at 70 ° C and 22 ° C in accordance with JIS K6301.
The test was performed under the test conditions of time.
一方において、弾性体組成物中のCSMのゲル量を知る
ために、CSM100重量部、酸化マグネシウム10重量部、PM
1重量部を、予めロール混練機で50℃、10分間混練を行
ないゴム混練物を得た。次に温度が180℃のロール混練
機でPP20重量部の50％を溶融し、これに予め得たゴム混
練物を添加して５分間の動的熱処理を行ないPP混練物を
得た。次に温度が180℃のロール混練機で残りのPPを溶
融し、これにPP混練物を添加して10分間混練を行なっ
た。これをJIS Ｋ 6388 に従い、100メッシュのステ
ンレス製金網で作ったハリス篭で23℃のベンゼンに未抽
出の残渣を測定した。CSM又はCPEのゲル量は次式により
計算した。On the other hand, in order to know the gel amount of CSM in the elastic composition, CSM 100 parts by weight, magnesium oxide 10 parts by weight, PM
One part by weight was previously kneaded with a roll kneader at 50 ° C. for 10 minutes to obtain a rubber kneaded material. Next, 50% by weight of PP was melted by a roll kneader at a temperature of 180 ° C., and the rubber kneaded material obtained in advance was added thereto and subjected to dynamic heat treatment for 5 minutes to obtain a kneaded PP material. Next, the remaining PP was melted by a roll kneader at a temperature of 180 ° C., and the PP kneaded material was added thereto and kneaded for 10 minutes. In accordance with JIS K 6388, the unextracted residue in benzene at 23 ° C. was measured using a Harris basket made of a 100-mesh stainless steel wire mesh. The gel amount of CSM or CPE was calculated by the following equation.
但し、 L0:ベンゼン抽出前の試料重量 L1:ベンゼン抽出前の試料中の混練で添加したPPと酸化
マグネシウムあるいは水酸化カルシウムの合計重量 L2:ベンゼンに未抽出の残渣重量 試験結果は表−１に示した。 However, L0: Weight of sample before benzene extraction L1: Total weight of PP and magnesium oxide or calcium hydroxide added by kneading in sample before benzene extraction L2: Weight of residue not extracted in benzene Table 1 shows the test results. Indicated.
実施例−２ 実施例−２は実施例−１のPP20重量部の50％をPP20重
量部の70％に変えた以外、実施例−１従った。Example-2 Example-2 followed Example-1 except that 50% of PP20 parts by weight of Example-1 was changed to 70% of PP20 parts by weight.
実施例−３ 実施例−３は実施例−１のPM1重量部をPM2重量部に変
え、５分間の動的熱処理を３分間の動的熱処理に変えた
以外実施例−１に従った。Example-3 Example-3 followed Example-1 except that 1 part by weight of PM in Example-1 was changed to 2 parts by weight of PM and dynamic heat treatment for 5 minutes was changed to dynamic heat treatment for 3 minutes.
実施例−４ 実施例−４は実施例−１のCSMをCPEに変え、酸化マグ
ネシウムを水酸化カルシウムに変えた以外実施例−１に
従った。Example-4 Example-4 followed Example-1 except that the CSM of Example-1 was changed to CPE and magnesium oxide was changed to calcium hydroxide.
比較例−１ 比較例−１は180℃のロール混練機で、表−１に示すP
P20重量部を投入して溶融し、これCSM100重量部、酸化
マグネシウム10重量部、DOS20重量部、酸化チタン10重
量部、PM1重量部を同時に添加し、20分間混練しながら
動的熱処理を行ない弾性体組成物を得た。得られた弾性
体組成物の変色の判定は実施例−１のゴム混練物と比較
して行なった。永久伸び試験および圧縮永久歪試験の試
料作製、試験方法および試験条件は実施例−１に従っ
た。弾性体組成物中のCSMのゲル量を知るために、180℃
のロール混練機でPP20重量部を投入して溶融し、これに
CSM100重量部、酸化マグネシウム10重量部、PM1重量部
を同時に添加し、20分間混練しながら動的熱処理を行な
った。ゲル量の測定方法、測定条件およびゲル量の計算
は実施例−１に従った。Comparative Example-1 Comparative Example-1 is a roll kneader at 180 ° C.
Add 20 parts by weight of P, melt it, add 100 parts by weight of CSM, 10 parts by weight of magnesium oxide, 20 parts by weight of DOS, 10 parts by weight of titanium oxide, and 1 part by weight of PM at the same time. A body composition was obtained. The determination of discoloration of the obtained elastic body composition was performed in comparison with the rubber kneaded product of Example-1. The sample preparation, test method and test conditions for the permanent elongation test and compression set test were in accordance with Example-1. In order to know the amount of CSM gel in the elastic body composition,
20 parts by weight of PP with a roll kneading machine
100 parts by weight of CSM, 10 parts by weight of magnesium oxide, and 1 part by weight of PM were simultaneously added, and dynamic heat treatment was performed while kneading for 20 minutes. The method for measuring the gel amount, the measurement conditions, and the calculation of the gel amount were in accordance with Example 1.
試験結果は表−１に示した。 The test results are shown in Table 1.
比較例−２ 50℃のロール混練機でCSM100重量部、酸化マグネシウ
ム10重量部、DOS20重量部、酸化チタン10重量部、PM1重
量部を10分間混練し混練物を得た。次に180℃のロール
混練機にPP20重量部を投入して溶融し、これに予め得た
ゴム混練物を添加し15分間動的熱処理を行い弾性体組成
物を得た。弾性体組成物の変色の判定は実施例−１のゴ
ム混練物と比較して行なった。永久伸び試験および圧縮
永久歪試験の試料作製、試験方法および試験条件は実施
例−１に従った。弾性体組成物中のCSMのゲル量を知る
ために、50℃のロール混練機でCSM100重量部、酸化マグ
ネシウム10重量部、PM1重量部を10分間混練し混練物を
得た。次に180℃のロール混練機にPP20重量部を投入し
て溶融し、これに予め得たゴム混練物を添加し15分間動
的熱処理を行なった。ゲル量の測定方法、測定条件およ
びゲル量の計算は実施例−１に従った。Comparative Example-2 100 parts by weight of CSM, 10 parts by weight of magnesium oxide, 20 parts by weight of DOS, 10 parts by weight of titanium oxide and 1 part by weight of PM were kneaded with a roll kneader at 50 ° C. for 10 minutes to obtain a kneaded product. Next, 20 parts by weight of PP was charged into a roll kneader at 180 ° C. and melted. The rubber kneaded material obtained in advance was added thereto and subjected to dynamic heat treatment for 15 minutes to obtain an elastic body composition. The determination of the discoloration of the elastic composition was performed in comparison with the rubber kneaded product of Example-1. The sample preparation, test method and test conditions for the permanent elongation test and compression set test were in accordance with Example-1. In order to know the gel amount of CSM in the elastic composition, 100 parts by weight of CSM, 10 parts by weight of magnesium oxide, and 1 part by weight of PM were kneaded with a roll kneader at 50 ° C. for 10 minutes to obtain a kneaded product. Next, 20 parts by weight of PP was charged into a roll kneader at 180 ° C. and melted. The rubber kneaded material obtained in advance was added thereto, and dynamic heat treatment was performed for 15 minutes. The method for measuring the gel amount, the measurement conditions, and the calculation of the gel amount were in accordance with Example 1.
試験結果は表−１に示した。 The test results are shown in Table 1.
比較例−３ 50℃のロール混練機でCPE100重量部、水酸化カルシウ
ム10重量部、DOS20重量部、酸化チタン10重量部、PM1重
量部を10分間混練しゴム混練物を得た後、180℃のロー
ル混練機で、該ゴム混練物を３分間動的熱処理を行なっ
た。次に180℃のロール混練機にPP20重量部を投入して
溶融し、これに動的熱処理した該混練物を添加し15分間
混練を行い弾性体組成物を得た。弾性体組成物の変色の
判定は実施例−１のゴム混練物と比較して行なった。永
久伸び試験および圧縮永久歪試験の試料作製、試験方法
および試験条件は実施例−１に従った。弾性体組成物中
のCPEのゲル量を知るために、50℃のロール混練機でCPE
100重量部、水酸化カルシウム10重量部、PM1重量部を10
分間混練しゴム混練物を得た後、180℃のロール混練機
で該ゴム混練物を３分間動的熱処理を行なった。次に18
0℃のロール混練機にPPを投入して溶融し、これに動的
熱処理した該混練物を添加し15分間混練を行った。ゲル
量の測定方法、測定条件およびゲル量の計算は実施例−
１に従った。Comparative Example-3 100 parts by weight of CPE, 10 parts by weight of calcium hydroxide, 20 parts by weight of DOS, 10 parts by weight of titanium oxide and 1 part by weight of PM were kneaded with a roll kneader at 50 ° C. for 10 minutes to obtain a rubber kneaded product, and then 180 ° C. The rubber kneaded material was subjected to a dynamic heat treatment for 3 minutes by a roll kneader. Next, 20 parts by weight of PP was charged into a roll kneader at 180 ° C. and melted. The kneaded material subjected to dynamic heat treatment was added thereto and kneaded for 15 minutes to obtain an elastic body composition. The determination of the discoloration of the elastic composition was performed in comparison with the rubber kneaded product of Example-1. The sample preparation, test method and test conditions for the permanent elongation test and compression set test were in accordance with Example-1. In order to know the amount of CPE gel in the elastic composition, use a 50 ° C roll kneader to
100 parts by weight, 10 parts by weight of calcium hydroxide, 10 parts by weight of PM
After kneading the mixture for 1 minute to obtain a rubber mixture, the rubber mixture was subjected to dynamic heat treatment with a roll kneader at 180 ° C. for 3 minutes. Then 18
PP was put into a roll kneader at 0 ° C. and melted, and the kneaded material subjected to dynamic heat treatment was added thereto and kneaded for 15 minutes. The method for measuring the amount of gel, the measurement conditions and the calculation of the amount of gel are described in Example-.
I followed 1.
試験結果は表−１に示した。 The test results are shown in Table 1.
以上、表−１から、本発明の製法によつて得られる実
施例１〜４の弾性体組成物は比較例１〜３と比較し機械
的性質である圧縮永久歪および永久伸びの点が優れ、且
つ、変色がないことが分る。As described above, from Table 1, the elastic body compositions of Examples 1 to 4 obtained by the production method of the present invention are superior to Comparative Examples 1 to 3 in terms of mechanical properties such as compression set and permanent elongation. It can be seen that there is no discoloration.
（発明の効果） 以上の説明から明らかなように、本発明の製法によれ
ば、得られる弾性体組成物は機械的性質である圧縮永久
歪および永久伸びの点が優れ、且つ、変色がないという
ことが分る。即ち、本発明の弾性体組成物の製法は、ゲ
ルを含有するCSM又はCPEとPPを主原料とする弾性体組成
物を実用可能ならしめるものである。 (Effects of the Invention) As is clear from the above description, according to the production method of the present invention, the obtained elastic composition has excellent mechanical properties such as compression set and permanent elongation, and has no discoloration. You can see that. That is, the method for producing an elastic body composition of the present invention makes it possible to use an elastic body composition containing CSM or CPE containing gel and PP as main raw materials.
フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｌ 23:10） (Ｃ０８Ｌ 23/34 23:10） (58)調査した分野(Int.Cl.6，ＤＢ名) C08L 23/28 C08L 23/34 C08J 3/20 - 3/22 C08J 3/24 - 3/26Continuation of the front page (51) Int.Cl. 6 identification code FI C08L 23:10) (C08L 23/34 23:10) (58) Investigated field (Int.Cl. 6 , DB name) C08L 23/28 C08L 23/34 C08J 3/20-3/22 C08J 3/24-3/26
Claims (1)
化ポリエチレン100重量部当り脱塩酸捕捉剤0.5〜30重量
部、加硫剤及び／又は加硫促進剤0.01〜10重量部、ポリ
プロピレン10〜50重量部から成る弾性体組成物の製法に
おいて、予めクロロスルフオン化ポリエチレン又は塩素
化ポリエチレンに脱塩酸捕捉剤と加硫剤及び／又は加硫
促進剤を混練し、次いで該混練物を使用ポリプロピレン
量の５〜90％のポリプロピレンに添加して動的熱処理を
行なった後、残りのポリプロピレンに添加混練すること
を特徴とする弾性体組成物の製法。1. 0.5 to 30 parts by weight of a dehydrochlorination scavenger, 0.01 to 10 parts by weight of a vulcanizing agent and / or a vulcanization accelerator, and 10 to 50 parts by weight of polypropylene per 100 parts by weight of chlorosulfonated polyethylene or chlorinated polyethylene. In a method for producing an elastic composition comprising: a chlorosulfonated polyethylene or a chlorinated polyethylene, a dehydrochlorination scavenger and a vulcanizing agent and / or a vulcanization accelerator are kneaded in advance, and the kneaded product is used in an amount of 5% of the polypropylene used. A method for producing an elastic composition, comprising adding to 90% of polypropylene, performing a dynamic heat treatment, and adding and kneading the remaining polypropylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21071789A JP2817241B2 (en) | 1989-08-17 | 1989-08-17 | Method for producing elastic composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21071789A JP2817241B2 (en) | 1989-08-17 | 1989-08-17 | Method for producing elastic composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0374450A JPH0374450A (en) | 1991-03-29 |
| JP2817241B2 true JP2817241B2 (en) | 1998-10-30 |
Family
ID=16593935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21071789A Expired - Fee Related JP2817241B2 (en) | 1989-08-17 | 1989-08-17 | Method for producing elastic composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2817241B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101354989B (en) * | 2007-03-28 | 2013-01-02 | 伊顿公司 | Electrical switching apparatus, and accessory module and electrical conductor mount thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100436117C (en) * | 2005-05-31 | 2008-11-26 | 蒋亨雷 | Automobile power steering tube and its production technology |
| JP2008029133A (en) * | 2006-07-21 | 2008-02-07 | Nitto Electric Works Ltd | Electrical distribution panel |
-
1989
- 1989-08-17 JP JP21071789A patent/JP2817241B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101354989B (en) * | 2007-03-28 | 2013-01-02 | 伊顿公司 | Electrical switching apparatus, and accessory module and electrical conductor mount thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0374450A (en) | 1991-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0428153B1 (en) | Thermoplastic elastomer of propylene Polymer Material and Crosslinked Ethylene-Propylene Rubber | |
| KR100418018B1 (en) | Thermoplastic elastomer composition and method of making same | |
| EP0247580B1 (en) | Thermoplastic composition of crystalline polyolefin and ethylene-containing copolymer | |
| EP1384752B1 (en) | Insulated electric wire | |
| JPS62230838A (en) | Elastic plastic composition | |
| US4782110A (en) | Thermoplastic compositions of crystalline polyolefin, and ethylene/alkyl acrylate copolymer elastomer | |
| JPS5846138B2 (en) | Thermoplastic elastomeric blend | |
| KR920001792B1 (en) | Elastomeric composition and products | |
| DE10105671A1 (en) | Thermoplastic elastomer material for calender-forming to sheet products, e.g. vehicle panels, obtained by dynamic thermal treatment of a mixture of oil-extended EPDM rubber and special polypropylene resin | |
| JP2817241B2 (en) | Method for producing elastic composition | |
| EP3502187B1 (en) | Toughened polyamide moulding masses | |
| BR112013029720B1 (en) | method for mixing a solid phenolic thio-bis antioxidant with polyethylene | |
| EP0624622B1 (en) | Propylene polymers grafted with polyalkenylenes and process for their preparation | |
| JP3306757B2 (en) | Thermoplastic elastomer composition | |
| JP2884606B2 (en) | Thermoplastic elastomer composition | |
| JP3044255B2 (en) | Thermoplastic rubber composition | |
| EP3503122A1 (en) | Polymer composition for insulation layer of power cable, insulation layer including the same and power cable including the same | |
| JP2817240B2 (en) | Thermoplastic elastomer composition | |
| JP2001123027A (en) | Thermoplastic elastomer composition for extrusion molding and process for its preparation | |
| JP2775638B2 (en) | Thermoplastic elastomer composition | |
| JP2838311B2 (en) | Elastic composition and method for producing the same | |
| JP3254799B2 (en) | Thermoplastic elastomer composition | |
| JPH04255742A (en) | Thermoplastic elastomer composition | |
| JP3008514B2 (en) | Thermoplastic elastomer composition | |
| JP3284209B2 (en) | Thermoplastic elastomer composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |