WO2011010615A1 - ハロゲン含有アクリルゴム組成物及びその加硫物 - Google Patents
ハロゲン含有アクリルゴム組成物及びその加硫物 Download PDFInfo
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- WO2011010615A1 WO2011010615A1 PCT/JP2010/062090 JP2010062090W WO2011010615A1 WO 2011010615 A1 WO2011010615 A1 WO 2011010615A1 JP 2010062090 W JP2010062090 W JP 2010062090W WO 2011010615 A1 WO2011010615 A1 WO 2011010615A1
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- halogen
- acrylic rubber
- containing acrylic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/378—Thiols containing heterocyclic rings
Definitions
- the present invention relates to a halogen-containing acrylic rubber composition and a vulcanized product thereof, and more specifically, a vulcanization accelerator having excellent scorch stability, high vulcanization speed, excellent compression set characteristics, and no generation of carcinogenic nitrosamines.
- the present invention relates to a halogen-containing acrylic rubber composition and a vulcanized product thereof.
- the halogen-containing acrylic rubber composition when the halogen-containing acrylic rubber is to be crosslinked with trithiocyanuric acid, it contains a dithiocarbamate metal salt and thiuram sulfide as in Patent Document 1 and Patent Document 2, and is within a preferable range.
- vulcanization speed, scorch stability, and mechanical properties such as tensile strength and compression set (CS) have been satisfied.
- a compound composed of a secondary amine is generally used as a vulcanization accelerator from the viewpoint of physical properties and vulcanization speed.
- vulcanization accelerators that generate nitrosamines include thiazole, sulfenamide, thiuram, and dithiocarbamate.
- Patent Document 3 discloses a vulcanization system comprising sulfur or a sulfur donor compound and a higher fatty acid metal salt for vulcanization of a halogen-containing acrylic rubber.
- sulfur donating compound include 2,4,6-trimercaptotriazine and polymer sulfur.
- the higher fatty acid metal salt is a compound known as a vulcanization accelerator.
- Patent Document 3 discloses as a higher fatty acid metal salt, for example, sodium stearate, potassium stearate, potassium myristate, sodium palmitate, calcium stearate. , Magnesium stearate, sodium oleate, potassium oleate, barium oleate.
- a vulcanization accelerator that does not generate nitrosamine can be selected for the vulcanizing system of halogen-containing acrylic rubber. This is an important issue.
- potassium stearate or sodium stearate is used as a vulcanization accelerator, but the scorch stability (T5) is poor (see Comparative Examples 8 and 9 of this application), and calcium stearate as a vulcanization accelerator. Is used, the vulcanization rate (T90) is slow and the compression set (CS) is inferior (see Comparative Example 10).
- Comparative Example 8 using potassium stearate as a vulcanization accelerator a problem of foaming during vulcanization was also confirmed.
- Example 1 of Patent Document 3 is a vulcanization system formulation in which the vulcanizing agent is sulfur and the vulcanization accelerator is sodium stearate.
- the vulcanizing agent is sulfur
- the vulcanization accelerator is sodium stearate.
- compression set ( CS) is considerably inferior (see Comparative Example 7).
- nitrosamines are used in vulcanization-based formulations using a sulfur donor compound such as 2,4,6-trimercaptotriazine as a vulcanizing agent and zinc diethyldithiocarbamate as a vulcanization accelerator.
- a sulfur donor compound such as 2,4,6-trimercaptotriazine
- zinc diethyldithiocarbamate as a vulcanization accelerator.
- the object of the present invention is to realize a substitution of a halogen-containing acrylic rubber with a vulcanization accelerator that does not generate carcinogenic nitrosamine in a vulcanization system using trithiocyanuric acid as a vulcanizing agent, and scorch stability.
- An object of the present invention is to provide a halogen-containing acrylic rubber composition and a vulcanized product thereof, which can provide a vulcanized product which is excellent in resistance, has a high vulcanization speed and is excellent in compression set.
- the invention according to claim 1 is a halogen-containing acrylic rubber composition containing a halogen-containing acrylic rubber, a vulcanizing agent containing a sulfur donor compound, and a vulcanization accelerator, and using trithiocyanuric acid as a vulcanizing agent.
- Calcium hydroxide is used as a sulfur accelerator and contains 0.1 to 3.0 parts by weight of trithiocyanuric acid and 0.1 to 9 parts by weight of calcium hydroxide with respect to 100 parts by weight of the halogen-containing acrylic rubber. This is a halogen-containing acrylic rubber composition.
- the invention according to claim 2 is the halogen-containing acrylic rubber composition according to claim 1, wherein the calcium hydroxide is contained in an amount of 1 to 5 parts by weight with respect to 100 parts by weight of the halogen-containing acrylic rubber. is there.
- the invention described in claim 3 is characterized in that the vulcanized product obtained by vulcanizing the halogen-containing acrylic rubber composition described in claim 1 or 2 has a compression set (%) of less than 30%. Halogen-containing acrylic rubber vulcanizate.
- the halogen-containing acrylic rubber is replaced with a vulcanization accelerator that does not generate carcinogenic nitrosamine in a vulcanization system using trithiocyanuric acid as a vulcanizing agent, and has excellent scorch stability. It is possible to provide a halogen-containing acrylic rubber composition and a vulcanized product thereof from which a vulcanized product having a high vulcanization rate and excellent compression set can be obtained.
- the halogen-containing acrylic rubber used in the halogen-containing acrylic rubber composition of the present invention is mainly composed of at least one of alkyl acrylate, alkoxyalkyl acrylate, alkylthioalkyl acrylate, cyanoalkyl acrylate and the like (about 60 to 99.8% by weight).
- an addition reaction product of glycidyl compound such as vinyl chloroacetate, allyl chloroacetate or glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ester and monochloroacetic acid is about 0.1 to 10% by weight, preferably about 1%.
- a copolymer obtained by copolymerization of ⁇ 5% by weight is used, and other vinyl compounds can be copolymerized in the copolymer within a range of 30% by weight or less.
- halogen-containing acrylic rubber examples include halogen and / or carboxyl group-containing acrylic rubber, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and maleic acid, and mono-lower alkyl maleates.
- unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and maleic acid
- mono-lower alkyl maleates A product obtained by copolymerizing about 0.1 to 10% by weight, preferably about 1 to 5% by weight of a saturated dicarboxylic acid monoester is used.
- ⁇ Vulcanizing agent> trithiocyanuric acid is used as the vulcanizing agent, and specifically, 2,4,6-trimercaptotriazine is used.
- the blending amount is in the range of 0.1 to 3.0 parts by weight, preferably 0.2 to 1.0 parts by weight with respect to 100 parts by weight of the halogen-containing acrylic rubber. If it is less than 0.1 parts by weight, the effect as a vulcanizing agent cannot be obtained effectively, and if it exceeds 3.0 parts by weight, the compression set (CS) characteristics and the scorch stability (T5) are significantly impaired.
- the vulcanizing agent is preferably 2,4,6-trimercaptotriazine alone.
- the compression set (CS) characteristics and the scorch stability (T5) are impaired. No (see Comparative Example 12).
- Calcium hydroxide is effective as a vulcanization accelerator used in the present invention, and should normally be used alone.
- a vulcanization accelerator such as sodium stearate or potassium stearate may be used in combination with calcium hydroxide within a range not inhibiting the effects of the present invention. That is, when a very small amount (for example, 0.01 parts by weight or less) of these is added, there is almost no adverse effect on vulcanization characteristics and compression set (CS) characteristics, so when calcium hydroxide is used alone. The same effect can be demonstrated. By adding a very small amount of a vulcanization accelerator other than calcium hydroxide, an effective effect does not occur. On the other hand, when the addition amount is increased, naturally vulcanization characteristics and compression set (CS) characteristics are inferior.
- CS compression set
- the calcium hydroxide may be solid or liquid, but usually a commercially available powder is preferred.
- the amount of calcium hydroxide added is in the range of 0.1 to 9 parts by weight, preferably 1 to 5 parts by weight with respect to 100 parts by weight of the halogen-containing acrylic rubber. Within such a range, the vulcanization rate (T90) is fast, the scorch stability (T5) is excellent, and the compression set (CS) is excellent.
- halogen-containing acrylic composition having the above components as essential components, other necessary compounding agents are appropriately blended.
- fillers and reinforcing agents for example, when used as vulcanized moldings of various sealing materials, carbon black is mainly blended for uses such as O-rings and packings, and white carbon and diatomaceous earth for uses such as oil seals.
- Etc. are suitably blended, and inorganic silica and the like are blended and used appropriately for the metal laminated parts.
- anti-aging agents general anti-aging agents such as amines, phenols, and benzimidazoles, and antioxidants are used.
- 4 ′, 4′-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine, 2-mercaptobenzimidazole and its zinc salt are used.
- processing aids stearic acid, fatty acid WAXs, and plasticizers such as mineral oil and PAO are used to improve kneadability, improve handling of rubber compounds, and improve mold release during vulcanization molding. .
- the composition is prepared by using a sealed kneader such as a pressure kneader or a Banbury mixer or an open kneader such as an open roll.
- the vulcanization is generally performed at about 150 to 250 ° C. for about 1 to 30 minutes are preferable, and it is performed by heat compression such as press vulcanization, injection molding vulcanization, injection molding vulcanization, or the like, and further, if necessary, oven vulcanization or steam at about 150 ° C. to 200 ° C. for about 1 to 24 hours.
- Vulcanization is performed as secondary vulcanization.
- composition and vulcanizate The halogen-containing acrylic rubber composition and the vulcanized product thereof according to the present invention are characterized by having the following characteristics.
- the halogen-containing acrylic rubber composition of the present invention is excellent in vulcanization speed.
- the vulcanization rate was measured at T90 and T5.
- T90 is measured in accordance with JIS K6300-2 using a rotorless rheometer to measure the vulcanization speed at 180 ° C., and the minimum torque ML and the maximum torque MH are obtained from the vulcanization curve. The time (minutes) required to reach the% torque value was determined.
- the halogen-containing acrylic rubber composition of the present invention has a T90 of less than 7 minutes, preferably less than 5 minutes.
- T5 was measured according to JIS K6300-1 using a Mooney viscometer (L rotor) at 125 ° C. to measure the time (minutes) required to increase 5 points (T5) from the minimum value of the Mooney viscometer.
- the halogen-containing acrylic rubber composition of the present invention has a scorch stability (Mooney scorch) T5 of 4 minutes or longer.
- the halogen-containing acrylic rubber vulcanizate of the present invention has excellent compression set (CS) characteristics.
- CS compression set
- the test piece was evaluated for compression set (%) after 150 ° C. ⁇ 70 hours in accordance with JIS K 6262.
- the halogen-containing acrylic rubber vulcanizate of the present invention has a compression set (CS) (%) of less than 30%.
- Example 1 Active halogen-containing acrylic rubber (Unimatec Co. product Knox tight PA404K) 100 parts by weight, FEF carbon black (Tokai Carbon Co. product SEAST SO, Nitrogen adsorption specific surface area: 42m 2 / g, DBP absorption amount (A method): 115cm 3 / 100g ) 60 parts by weight, 20 parts by weight of surface-treated natural silica (actifil VM56 manufactured by Hoffman Mineral Co., Ltd.), 2 parts by weight of an amine anti-aging agent (Onouchi Shinko Co., Ltd., product knock rack CD), wax-based processing aid (product of Seiko Chemical Co., Ltd.) Halogen containing 1 part by weight of Santite R, 0.5 part by weight of 2,4,6-trimercaptotriazine (Noxeller TCA manufactured by Ouchi Shinsei Co., Ltd.) and 1 part by weight of calcium hydroxide (Caldic # 1000 manufactured by Omi Chemical Co.
- Each component of the containing acrylic rubber composition is kneaded with an open roll, 180 ° C., 5 minutes
- the test piece (22.5 mm ⁇ 12.5 mm ⁇ 2.0 mm) was produced by press vulcanization of the above and oven vulcanization at 175 ° C. for 15 hours.
- Table 1 shows the results of evaluation based on the following evaluation methods.
- Rubber hardness Hs Measured with a type A durometer according to JIS K6253.
- Compression set (CS) The test piece (22.5 mm ⁇ 12.5 mm ⁇ 2.0 mm) was evaluated for compression set (CS) (%) after 150 ° C. ⁇ 70 hours (25% compression) in accordance with JIS K 6262. . If the compression set (CS) (%) is less than 30%, it indicates that the compression set (CS) characteristics are excellent.
- Vulcanization rate characteristics For the above halogen-containing acrylic rubber composition, in accordance with JIS K6300-2, the vulcanization speed at 180 ° C. is measured using a rotorless rheometer, and the minimum torque ML and the maximum torque MH are obtained from the vulcanization curve. T90 (time (minute) until reaching 90% torque value of maximum torque value) was obtained. If T90 is less than 7 minutes, it is the range of the present invention, and if it is less than 5 minutes, it is a more preferable range. Evaluation criteria ⁇ : Less than 5 minutes ⁇ : Less than 7 minutes ⁇ : Less than 10 minutes ⁇ : More than 10 minutes
- Scorch stability About the above halogen-containing acrylic rubber composition, in accordance with JIS K6300, using a Mooney viscometer (L rotor) at 125 ° C., the time required to increase 5 points (T5) from the minimum value of the Mooney viscometer (minutes) Was measured. Evaluation criteria ⁇ : 4 minutes or more ⁇ : 3-4 minutes ⁇ : Less than 3 minutes
- N-nitrosamine is detected by preparing a rubber sheet of 10 mm ⁇ 10 mm ⁇ 0.5 mm from the above test piece, adsorbing N-nitrosamine gas released from the sheet on an adsorbent, and performing gas chromatography. Detected with. The case where N-nitrosamine was not detected was indicated as “-”, and the case where N-nitrosamine was detected was indicated as “x”.
- Example 2 In Example 1, it evaluated similarly except having changed the compounding quantity of calcium hydroxide into 3 weight part. The results are shown in Table 1.
- Example 3 In Example 1, it evaluated similarly except having changed the compounding quantity of calcium hydroxide into 5 weight part. The results are shown in Table 1.
- Example 4 In Example 2, instead of FEF carbon (Tokai Carbon Co. product seast SO), special carbon (Asahi Carbon Co., Ltd. product Asahi # 50H, Nitrogen adsorption specific surface area: 20 m 2 / g, DBP absorption compared to FEF carbon) the amount (a method): 110cm 3 / 100g) except for using was evaluated in the same manner. The results are shown in Table 1.
- Example 1 Comparative Example 1 In Example 1, it evaluated similarly except not using calcium hydroxide. The results are shown in Table 1.
- Example 2 Comparative Example 2 In Example 1, it evaluated similarly except having used zinc diethyl dithiocarbamate (Ouchi Shinsei Co., Ltd. product Noxeller EZ) instead of calcium hydroxide. The results are shown in Table 1.
- Example 3 Comparative Example 3 In Example 1, it evaluated similarly except having used zinc dibenzyldithiocarbamate (Ouchi Shinsei Co., Ltd. product Noxeller ZTC) instead of calcium hydroxide. The results are shown in Table 1.
- Example 4 Comparative Example 4 In Example 1, it evaluated similarly except having used tetrabenzyl thiuram disulfide (Ouchi Shinsei Co., Ltd. product Noxeller TBZTD) instead of calcium hydroxide. The results are shown in Table 1.
- Example 1 evaluation was carried out in the same manner except that tetrakis (2-ethylhexyl) thiuram disulfide (Ouchi Shinsei Co., Ltd. product Noxeller TOT-N) was used instead of calcium hydroxide. The results are shown in Table 1.
- Example 6 Comparative Example 6 In Example 1, it evaluated similarly except having used magnesium hydroxide instead of calcium hydroxide. The results are shown in Table 1.
- Comparative Example 7 The same procedure as in Example 1 was performed except that sulfur (colloidal sulfur) was used instead of 2,4,6-trimercaptotriazine and alkaline soap (sodium stearate) was used instead of calcium hydroxide. And evaluated. The results are shown in Table 1.
- Example 8 Comparative Example 8 In Example 1, it evaluated similarly except having used alkaline soap (potassium stearate) instead of calcium hydroxide. The results are shown in Table 1.
- Example 9 Comparative Example 9 In Example 1, it evaluated similarly except having used alkaline soap (sodium stearate) instead of calcium hydroxide. The results are shown in Table 1.
- Example 10 Comparative Example 10 In Example 1, it evaluated similarly except having used alkali soap (calcium stearate) instead of calcium hydroxide. The results are shown in Table 1.
- Example 12 In Example 1, instead of 2,4,6-trimercaptotriazine alone as a vulcanizing agent, 0.45 part by weight of 2,4,6-trimercaptotriazine and 0.05 part by weight of sulfur (colloidal sulfur) were added. Evaluation was performed in the same manner except that it was added together. The results are shown in Table 1.
- Example 13 Comparative Example 13 In Example 1, it evaluated similarly except having changed the compounding quantity of calcium hydroxide into 10 weight part. The results are shown in Table 1.
- Comparative Examples 1 and 6 were partially unmeasurable due to insufficient vulcanization, and Comparative Example 8 was partially unmeasurable due to foaming during vulcanization.
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Abstract
Description
本発明のハロゲン含有アクリルゴム組成物に用いられるハロゲン含有アクリルゴムとしては、アルキルアクリレート、アルコキシアルキルアクリレート、アルキルチオアルキルアクリレート、シアノアルキルアクリレートなどの少なくとも一種を主成分(約60~99.8重量%)とし、これにビニルクロロアセテート、アリルクロロアセテートあるいはグリシジルアクリレート、グリシジルメタクリレート、アリルグリジジルエステルなどのグリシジル化合物とモノクロロ酢酸との付加反応生成物などを約0.1~10重量%、好ましくは約1~5重量%共重合させた共重合体が用いられ、この共重合体中には他のビニル化合物を30重量%以下の範囲で共重合させることができる。
本発明において、加硫剤としては、トリチオシアヌル酸が用いられ、具体的には2,4,6-トリメルカプトトリアジンが用いられる。
本発明に用いる加硫促進剤として有効であるのは、水酸化カルシウムであり、通常は単独で使用すべきものである。
以上の各成分を必須成分とするハロゲン含有アクリル組成物中には、他の必要な配合剤が適切に配合される。充填剤、補強剤についていえば、例えば各種シール材の加硫成形物として用いる場合、Oリング、パッキンなどの用途には主としてカーボンブラックが配合され、またオイルシール等の用途にはホワイトカーボンや珪藻土などが適度に配合され、金属積層部品には適度に無機シリカなどが配合されて用いられる。老化防止剤についていえば、アミン系、フェノール系、ベンツイミダゾール系などの一般的な老化防止剤、酸化防止剤が用いられ、中でも4’,4’-ビス(α,α-ジメチルベンジル)ジフェニルアミンや2-メルカプトベンゾイミダゾールやその亜鉛塩が用いられる。加工助剤についていえば、ステアリン酸や脂肪酸WAX類、そして鉱油やPAOなどの可塑剤などが混練性の向上、ゴムコンパウンドの取り扱い性の向上、加硫成形時の離型性の向上から用いられる。
組成物の調製は、加圧式ニーダー、バンバリーミキサー等の密封式混練機あるいはオープンロール等の開放式混練機を用いて行われ、その加硫は一般的に約150℃~250℃で約1~30分が好ましく、プレス加硫または射出成型加硫、注入成形加硫などの加熱圧縮によって行われ、更に必要に応じて、約150℃~200℃で約1~24時間のオーブン加硫あるいは蒸気加硫が二次加硫として行われる。
本発明のハロゲン含有アクリルゴム組成物及びその加硫物は、以下の特性を有する点に特徴がある。
活性ハロゲン含有アクリルゴム(ユニマテック社製品ノックスタイトPA404K)100重量部、FEFカーボンブラック(東海カーボン社製品シーストSO、窒素吸着比表面積:42m2/g、DBP吸収量(A法):115cm3/100g)60重量部、表面処理天然シリカ(ホフマンミネラル社製品アクチジルVM56)20重量部、アミン系老化防止剤(大内新興社製品ノックラックCD)2重量部、ワックス系加工助剤(精工化学社製品サンタイトR)1重量部、2,4,6-トリメルカプトトリアジン(大内新興社製品ノクセラーTCA)0.5重量部、水酸化カルシウム(近江化学社製品カルディック#1000)1重量部を含むハロゲン含有アクリルゴム組成物の各成分をオープンロールで混練し、180℃、5分間のプレス加硫および175℃、15時間のオーブン加硫を行い、試験片(22.5mm×12.5mm×2.0mm)を作製した。
以下の評価方法に基づき評価した結果を表1に示す。
(1)ゴム硬度Hs;JIS K6253に準拠し、タイプAデュロメーターで測定した。
(2)引張強さTB(MPa);JIS K6251に準拠。
(3)伸びEB(%);JIS K6251に準拠。
上記の試験片(22.5mm×12.5mm×2.0mm)について、JIS K 6262に準拠して150℃×70時間(25%圧縮)後の圧縮永久歪(CS)(%)を評価した。圧縮永久歪(CS)(%)が30%未満であれば、圧縮永久歪(CS)特性が優れていることを示している。
上記のハロゲン含有アクリルゴム組成物について、JIS K6300-2に準拠して、ロータレスレオメーターを用いて180℃の加硫速度を測定し、加硫曲線から最低トルクMLおよび最高トルクMHを求め、T90(最大トルク値の90%トルク値に到達する迄の時間(分))を求めた。T90が7分未満であれば本発明の範囲であり、5分未満であればさらに好ましい範囲であることを示している。
評価基準
◎:5分未満
○:7分未満
△:10分未満
×:10分以上
上記のハロゲン含有アクリルゴム組成物について、JIS K6300に準拠して、125℃でムーニー粘度計(Lローター)を用いてムーニー粘度計の最低値から5ポイント(T5)増加するまでの時間(分)を測定した。
評価基準
○:4分以上
△:3~4分
×:3分未満
N-ニトロソアミンの検出は、上記試験片から10mm×10mm×0.5mmのゴムシートを作成し、そのシートから放出されるN-ニトロソアミンガスを吸着材に吸着させ、ガスクロマトグラフィーで検出した。N-ニトロソアミンが検出されなかったものを「-」、検出されたものを「×」とした。
実施例1において、水酸化カルシウムの配合量を3重量部に代えた以外は、同様にして評価した。その結果を表1に示す。
実施例1において、水酸化カルシウムの配合量を5重量部に代えた以外は、同様にして評価した。その結果を表1に示す。
実施例2において、FEFカーボン(東海カーボン社製品シーストSO)に代えて、FEFカーボン対比で粒子径の小さな特殊カーボン(旭カーボン社製品旭#50H、窒素吸着比表面積:20m2/g、DBP吸収量(A法):110cm3/100g)を用いた以外は、同様にして評価した。その結果を表1に示す。
実施例1において、水酸化カルシウムを用いない以外は、同様にして評価した。その結果を表1に示す。
実施例1において、水酸化カルシウムの代わりに、ジエチルジチオカルバミン酸亜鉛(大内新興社製品ノクセラーEZ)を用いた以外は、同様にして評価した。その結果を表1に示す。
実施例1において、水酸化カルシウムの代わりに、ジベンジルジチオカルバミン酸亜鉛(大内新興社製品ノクセラーZTC)を用いた以外は、同様にして評価した。その結果を表1に示す。
実施例1において、水酸化カルシウムの代わりに、テトラベンジルチウラムジスルフィド(大内新興社製品ノクセラーTBZTD)を用いた以外は、同様にして評価した。その結果を表1に示す。
実施例1において、水酸化カルシウムの代わりに、テトラキス(2-エチルヘキシル)チウラムジスルフィド(大内新興社製品ノクセラーTOT-N)を用いた以外は、同様にして評価した。その結果を表1に示す。
実施例1において、水酸化カルシウムの代わりに、水酸化マグネシウムを用いた以外は、同様にして評価した。その結果を表1に示す。
実施例1において、加硫剤を2,4,6-トリメルカプトトリアジンに代えて硫黄(コロイド硫黄)を用い、水酸化カルシウムに代えてアルカリ石鹸(ステアリン酸ナトリウム)を用いた以外は、同様にして評価した。その結果を表1に示す。
実施例1において、水酸化カルシウムの代わりに、アルカリ石鹸(ステアリン酸カリウム)を用いた以外は、同様にして評価した。その結果を表1に示す。
実施例1において、水酸化カルシウムの代わりに、アルカリ石鹸(ステアリン酸ナトリウム)を用いた以外は、同様にして評価した。その結果を表1に示す。
実施例1において、水酸化カルシウムの代わりに、アルカリ石鹸(ステアリン酸カルシウム)を用いた以外は、同様にして評価した。その結果を表1に示す。
実施例1において、加硫剤である2,4,6-トリメルカプトトリアジンの代わりに硫黄(コロイド硫黄)を用いた以外は、同様にして評価した。その結果を表1に示す。
実施例1において、加硫剤として、2,4,6-トリメルカプトトリアジン単独に代えて、2,4,6-トリメルカプトトリアジン0.45重量部と硫黄(コロイド硫黄)0.05重量部を併用添加した以外は、同様にして評価した。その結果を表1に示す。
実施例1において、水酸化カルシウムの配合量を10重量部に代えた以外は、同様にして評価した。その結果を表1に示す。
2,4,6-トリメルカプトトリアジンを加硫剤としたハロゲン含有アクリルゴムを加硫させる場合、ニトロソアミンの発生を防ぎ、且つスコーチ安定性を保ちながら十分な加硫速度を得るためには、水酸化カルシウムの配合が優れていることがわかる。
Claims (3)
- ハロゲン含有アクリルゴムと、硫黄供与化合物を含む加硫剤と、加硫促進剤とを含有するハロゲン含有アクリルゴム組成物において、
加硫剤としてトリチオシアヌル酸を用い、加硫促進剤として水酸化カルシウムを用い、該ハロゲン含有アクリルゴム100重量部に対して、トリチオシアヌル酸を0.1~3.0重量部、水酸化カルシウムを0.1~9重量部含有してなることを特徴とするハロゲン含有アクリルゴム組成物。 - 水酸化カルシウムが、ハロゲン含有アクリルゴム100重量部に対して、1~5重量部含有してなることを特徴とする請求項1記載のハロゲン含有アクリルゴム組成物。
- 請求項1又は2記載のハロゲン含有アクリルゴム組成物を加硫して得られる加硫物が、圧縮永久歪(%)が30%未満であることを特徴とするハロゲン含有アクリルゴム加硫物。
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EP3150664A4 (en) * | 2014-05-08 | 2017-12-06 | NOK Corporation | Ethylene acrylic rubber composition, ethylene acrylic rubber, rubber-metal composite, and bonded piston seal |
WO2019044592A1 (ja) * | 2017-08-31 | 2019-03-07 | Nok株式会社 | アクリルゴム組成物 |
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US11407879B2 (en) | 2017-08-31 | 2022-08-09 | Nok Corporation | Acrylic rubber composition |
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