WO2015163066A1 - 2-メルカプトイミダゾリン含有マスターバッチ - Google Patents
2-メルカプトイミダゾリン含有マスターバッチ Download PDFInfo
- Publication number
- WO2015163066A1 WO2015163066A1 PCT/JP2015/058617 JP2015058617W WO2015163066A1 WO 2015163066 A1 WO2015163066 A1 WO 2015163066A1 JP 2015058617 W JP2015058617 W JP 2015058617W WO 2015163066 A1 WO2015163066 A1 WO 2015163066A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mercaptoimidazoline
- compound
- masterbatch
- mass
- master batch
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
-
- 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
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
- C08K5/405—Thioureas; Derivatives thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2319/00—Characterised by the use of rubbers not provided for in groups C08J2307/00 - C08J2317/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2310/00—Masterbatches
Definitions
- the present invention relates to a masterbatch containing 2-mercaptoimidazoline.
- 2-Mercaptoimidazoline is mainly used as a crosslinking accelerator for chloroprene rubber (CR, hereinafter referred to as “CR” where appropriate) (see, for example, Patent Document 1 and Patent Document 2).
- CR chloroprene rubber
- the remarkable effect of applying 2-mercaptoimidazoline to CR material is that the crosslinking time can be shortened as a crosslinking accelerator, and excellent properties such as low compression set and high tensile strength can be obtained in the crosslinking compound. There is something you can do.
- the CR compound may be produced by kneading using a closed kneader or two rolls in the production process, depending on the use of the product.
- 2-mercaptoimidazoline has a high melting point of 190 ° C. or higher, so that it is difficult to melt in the kneading step in the temperature range of 80 to 150 ° C. usually used in kneading. Therefore, 2-mercaptoimidazoline is required to be present in a good dispersion state as a powder in the CR compound.
- 2-mercaptoimidazoline is a cross-linking accelerator, so that a partial cross-linking reaction proceeds during the kneading step, and an appropriate CR compound is obtained. There was no problem. For such problems, it is necessary to disperse 2-mercaptoimidazoline promptly before the crosslinking reaction proceeds during kneading.
- a master batch in which 2-mercaptoimidazoline is previously dispersed at a high concentration in a binder material is used.
- An EPDM / EVA system is used as a main component of a binder material of a masterbatch containing 75 to 95% by mass of 2-mercaptoimidazoline that is commercially available.
- the main component of such a binder material is not sufficiently compatible with the CR compound, and the master batch component adheres to the mold in the process of repeated molding processing, and finally molding defects due to mold contamination occur. A problem that occurred.
- an object of the present invention is to provide a 2-mercaptoimidazoline-containing masterbatch having excellent dispersibility of 2-mercaptoimidazoline in a CR compound and improved mold contamination during molding.
- NBR nitrile rubber
- the present invention is a 2-mercaptoimidazoline-containing masterbatch using nitrile rubber as a binder material.
- the nitrile rubber is preferably a nitrile rubber having an acrylonitrile content of 15 to 40% by mass.
- the 2-mercaptoimidazoline-containing masterbatch of the present invention is excellent in dispersibility of 2-mercaptoimidazoline in a CR compound, and can improve mold contamination during molding.
- 2-mercaptoimidazoline is a white powder, also called ethylenethiourea, and is used as a crosslinking accelerator for CR materials.
- Binder material The inventors of the present invention have investigated a binder material excellent in compatibility with CR, and found that NBR is more dispersible in CR than EPDM / EVA. Furthermore, it has been found that by using a master batch in which 2-mercaptoimidazoline is previously dispersed in NBR, rapid dispersion can be obtained at the time of kneading with CR, and mold contamination can be reduced. These results are presumed that NBR has an SP value closer to the SP value of CR than EPDM / EVA.
- NBR of the binder material NBR with an acrylonitrile content of 15 to 40% by mass is preferable, and NBR with 18 to 35% by mass is more preferable.
- the content of acrylonitrile in NBR is in this range, the dispersibility in CR is excellent. The reason is not clear, but it is presumed that the compatibility with CR increases.
- NBR of a binder material NBR of low viscosity is preferable.
- the Mooney viscosity of NBR is preferably in the range of 15 to 75M in ML 1 + 4 (100 ° C.), and more preferably in the range of 25 to 65M. When the Mooney viscosity of NBR is within this range, the dispersibility in CR is excellent.
- the content of 2-mercaptoimidazoline in the master batch is preferably 50 to 90% by mass, and the content of NBR in the master batch is preferably 10 to 50% by mass.
- the content of 2-mercaptoimidazoline is 65 to 85% by mass, and the content of NBR is more preferably 15 to 35% by mass.
- the dispersibility of 2-mercaptoimidazoline in the masterbatch is excellent, and the dispersibility in CR is also excellent. Moreover, it can be set to have no trouble at the time of manufacturing and processing of the master batch.
- additives can be added to the master batch as necessary. For example, by adding 0.1 to 5% by mass of a general processing aid such as stearic acid, a plasticizer, a filler, etc., the processability and handleability when producing a masterbatch can be improved. .
- a general processing aid such as stearic acid, a plasticizer, a filler, etc.
- a kneading apparatus such as a hermetic kneader, a two-roll, a feeder ruder, a single or twin screw extruder, and a ram type extruder can be used. These kneading apparatuses can be processed into a required shape and produced by using a single machine or a plurality of machines.
- 2-mercaptoimidazoline powder is added in portions, and the content is gradually increased to a predetermined content.
- the temperature at the time of kneading depends on the kind of the binder material, but is preferably 80 to 150 ° C.
- the kneading time is preferably 5 to 30 minutes.
- the material is discharged from the kneading apparatus (the dough is removed) and cut into small particles to form cylindrical or square pellets. If necessary, other additives such as processing aids and plasticizers can be appropriately blended at the beginning of kneading or during kneading as long as the object of the present invention is not impaired.
- 2-mercaptoimidazoline-containing masterbatch which uses NBR as a binder material, so that it is more quickly dispersed in the CR compound than the conventional masterbatch binder material, and the mold contamination during molding is improved. And became possible.
- ⁇ Master batch composition> As shown in Table 1, a masterbatch was produced using 40 parts by mass of the following various binder materials with respect to 60 parts by mass of 2-mercaptoimidazoline.
- NBR1 is N240S (manufactured by JSR), Mooney viscosity ML 1 + 4 (100 ° C.) is 56 M, and acrylonitrile content (bound acrylonitrile) is 26 mass%.
- Example 2 NBR2 is N225SH (manufactured by JSR), Mooney viscosity ML 1 + 4 (100 ° C.) is 85 M, and acrylonitrile content (bonded acrylonitrile) is 43 mass%.
- Comparative Example 1 EPDM / EVA is such that EPDM: EVA is 50:50 by mass ratio.
- EPDM is EPT4045 (made by Mitsui Chemicals), Mooney viscosity ML1 + 4 (100 degreeC) is 45M, ethylene content is 54 mass%, and diene content is 8.1 mass%.
- EVA is Ultrasen 684 (manufactured by Tosoh Corporation) and has a vinyl acetate content of 20% by mass.
- ⁇ Master batch kneading process> The binder material was kneaded for 1 minute with a sealed 1 L kneader preheated to 100 ° C. in advance, and kneaded in 3 times so that 2-mercaptoimidazoline was 60% by mass to obtain a kneaded product.
- the sheet was taken out from the hermetic 1 L kneader and formed into an approximately 5 mm thick sheet with an open roll.
- crosslinkability of master batch x Inactivates by reacting with binder material, crosslinkability decreases ⁇ : Does not react with binder material and maintains crosslinkability
- CR compound preparation procedure > CR polymer (B-30, manufactured by Tosoh Corporation), SRF carbon, rapeseed oil, ZnO, MgO, stearic acid, accelerator TT (Noxeller TT, manufactured by Ouchi Shinsei Chemical Co., Ltd.), anti-aging agent (3C, manufactured by Seiko Chemical Co., Ltd.) ) was kneaded with a 1 L kneader at the compounding ratio shown in Table 2, and then taken out as a CR compound.
- a 6-inch open roll of 6 inches at room temperature had a gap of 3 mm, a front roll 14 rpm, a rear roll 18 rpm, and a guide width 300 mm.
- Table 2 shows the master batches (M1 to M5) of 2-mercaptoimidazoline having a thickness of about 5 mm prepared in Examples 1 and 2 and Comparative Examples 1 to 3, which were wound with a CR compound produced with a 1 L kneader. A lump of the amount was added and roll kneading was performed.
- CR compounds C1 to C5 in which the master batch was dispersed.
- Crosslinking molding was performed by performing compression molding at 180 ° C. for 10 minutes using a chromium-plated 120 ⁇ 120 ⁇ 2 mm mold.
- ⁇ CR compound evaluation method> 1 Dispersibility A CR compound kneaded in a 1 L kneader was wound around a 6-inch roll, a batch of master batches of the amount shown in Table 2 was added to the bank, and the dough was peeled from the roll after 30 seconds. The apparent dispersion state of the white masterbatch was evaluated. In addition, since a soft masterbatch is immediately stretched and quickly kneaded into the CR compound to reduce unevenness, the presence or absence of unevenness was also evaluated.
- the evaluation results as a master batch are shown in Table 1, and the evaluation results as a CR compound are shown in Table 2.
- the master batch of Example 1 was roll processable, and both had excellent performance in terms of crosslinkability and ease of cutting. Further, the master batch of Example 2 was slightly hard because the Mooney viscosity ML 1 + 4 (100 ° C.) of NBR was slightly high, but it could be cut and roll-processed, and the master batch was excellent in crosslinkability. .
- the binder material was EPDM / EVA, and the roll adhesiveness and the crosslinkability of the master batch were inferior.
- the binder material was EPDM, and it was easy to crosslink, and the crosslinkability of the master batch was poor.
- the binder material was epichlorohydrin rubber, and the roll adhesiveness was poor.
- the CR compound using the master batch of Example 1 had excellent performance in dispersibility (white), dispersibility (unevenness), and mold contamination. .
- the CR compound using the master batch of Example 2 was slightly inferior in compatibility with CR, but was usable.
- the CR compound using the masterbatch of Comparative Example 1 was inferior in mold contamination because of the progress of crosslinking.
- the CR compound using the master batch of Comparative Example 2 was slightly inferior in dispersibility and mold contamination.
- the CR compound using the master batch of Comparative Example 3 was inferior in mold contamination.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
2-メルカプトイミダゾリンは、エチレンチオ尿素とも称される白色粉体であり、CR材の架橋促進剤として使用される。
本発明者らは、CRと相溶性に優れたバインダー材について検討を進めたところ、NBRが、EPDM/EVAよりもCRへの分散性に優れていることを見出した。さらに、2-メルカプトイミダゾリンをNBRへ予め分散させたマスターバッチとすることで、CRとの混練時に速やかな分散が得られること、型汚染を低減させることが可能となることを見出した。これらの結果は、NBRが、EPDM/EVAよりもCRの持つSP値に近いSP値を有しているためと推定される。
マスターバッチ中の2-メルカプトイミダゾリンの含有量は50~90質量%であり、マスターバッチ中のNBRの含有量が10~50質量%であることが好ましい。2-メルカプトイミダゾリンの含有量は65~85質量%であり、NBRの含有量は15~35質量%であることがより好ましい。これらの含有量の範囲内にあると、マスターバッチ中の2-メルカプトイミダゾリンの分散性に優れ、CRへの分散性にも優れたものとなる。また、マスターバッチの製造加工時においても支障のないものとすることができる。
マスターバッチの製造方法としては、密閉式ニーダー、二本ロール、フィーダールーダー、一軸または二軸押し出し機、ラム型押し出し機等の混練装置を用いることができる。これらの混練装置を単独で、または複数機を使用することによって、要求される形状に加工して製造することができる。
表1に示すように、2-メルカプトイミダゾリン60質量部に対して、下記の各種バインダー材40質量部を用いて、マスターバッチを製造した。
2-メルカプトイミダゾリン:SANCELER22C(三新化学工業社製)
バインダー材:
(1)実施例1:NBR1は、N240S(JSR社製)であり、ムーニー粘度ML1+4(100℃)が56M、アクリロニトリル含有量(結合アクリロニトリル)が26質量%である。
(2)実施例2:NBR2は、N225SH(JSR社製)であり、ムーニー粘度ML1+4(100℃)が85M、アクリロニトリル含有量(結合アクリロニトリル)が43質量%である。
(3)比較例1:EPDM/EVAは、EPDM:EVAが質量比で50:50である。EPDMは、EPT4045(三井化学社製)であり、ムーニー粘度ML1+4(100℃)が45M、エチレン含有量が54質量%、ジエン含有量が8.1質量%である。EVAは、ウルトラセン684(東ソー社製)であり、酢酸ビニル含有量が20質量%である。
(4)比較例2:EPDMは、EPT4045(三井化学社製)である。
(5)比較例3:ECOは、エピクロルヒドリンゴム(ヒドリンT3100、日本ゼオン社製)であり、ムーニー粘度ML1+4(100℃)が70Mである。
予め100℃に予熱した密閉式1Lニーダーでバインダー材を1分混練し、2-メルカプトイミダゾリンが60質量%となるように3回に分けて各3分間混練し、混練物を得た。密閉式1Lニーダーから取り出し、オープンロールにて約5mm厚のシート状とした。
1.ロール粘着性
×:ロール加工時におけるロールへの生地粘着が激しいもの
△:ロール加工時におけるロールへの生地粘着が少しあるが、加工が可能なもの
○:ロール加工時におけるロールへの生地粘着が殆ど無く加工性が良好なもの
×:バインダー材と反応して失活し、架橋性が低下するもの
○:バインダー材と反応せず、架橋性が維持されるもの
調製した厚さ約5mmのシート状である各マスターバッチを室温で1日放置後、ハサミを用いて裁断することによる計量のし易さを評価した。
×:硬くて裁断が困難
△:やや硬いが裁断可能
○:やわらかく裁断が容易に可能
CRポリマー(B-30、東ソー社製)にSRFカーボン、菜種油、ZnO、MgO、ステアリン酸、促進剤TT(ノクセラーTT、大内新興化学工業社製)、老化防止剤(3C、精工化学社製)を表2に記載した配合比で1Lニーダーにて混練した後に、CRコンパウンドとして取り出した。常温の6インチの二本オープンロールを間隙3mmとし、前ロール14rpm、後ろロール18rpm、ガイド幅300mmに設定した。1Lニーダーで作製したCRコンパウンドを巻き付かせ、実施例1~2および比較例1~3で調製した厚さ約5mmの2-メルカプトイミダゾリンのマスターバッチ(M1~M5)を、表2に記載した量の一塊りを添加して、ロール混練を行った。
1.分散性
1Lニーダーにて混練したCRコンパウンドを6インチロールに巻き付かせ、表2に示す量の一塊りのマスターバッチをバンクに添加し、30秒後にロールから生地を剥がした。白色であるマスターバッチの見た目の分散状態を評価した。また、やわらかいマスターバッチであれば即座に引き伸ばされて、CRコンパウンドに速やかに練り込まれ凹凸が少なくなることから、凹凸の有無についても評価した。
×:マスターバッチの白色が黒色CRコンパウンドに数多く存在する
△:マスターバッチの白色が黒色CRコンパウンドに少し存在する
○:マスターバッチの白色が黒色CRコンパウンドに見られない
×:CRコンパウンドに凹凸が多く存在する
△:CRコンパウンドに凹凸が少なく存在する
○:CRコンパウンドに凹凸は殆ど確認されない
クロムメッキを施した120×120×2mmの型を用いて、180℃×10分でCRコンパウンドの圧縮成形を行った。この操作を表2に記載した各CRコンパウンド(C1~C5)を用いて各20回行い、型表面に付着したカスの状態から、型汚染性を評価した。
×:型への付着物が顕著に多く、型で連続成形した架橋物の表面は滑らかでない
△:型への付着物は確認されるが、型で連続成形した架橋物の表面は殆ど滑らかである
○:型への付着物は無く、型で連続成形した架橋物の表面はどれも滑らかである
Claims (3)
- ニトリルゴムをバインダー材として用いた2-メルカプトイミダゾリン含有マスターバッチ。
- 2-メルカプトイミダゾリン:50~90質量%およびニトリルゴム:10~50質量%を含有する請求項1に記載の2-メルカプトイミダゾリン含有マスターバッチ。
- 前記ニトリルゴムが、アクリロニトリル含有量15~40質量%のニトリルゴムである請求項1または請求項2に記載の2-メルカプトイミダゾリン含有マスターバッチ。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201580012745.2A CN106068298A (zh) | 2014-04-23 | 2015-03-20 | 含有2‑咪唑烷硫酮的母料 |
EP15782827.8A EP3135713A4 (en) | 2014-04-23 | 2015-03-20 | 2-mercaptoimidazoline-containing masterbatch |
US15/304,902 US20170183458A1 (en) | 2014-04-23 | 2015-03-20 | 2-mercaptoimidazoline-containing masterbatch |
JP2015538181A JP6009090B2 (ja) | 2014-04-23 | 2015-03-20 | クロロプレンゴムコンパウンド用2−メルカプトイミダゾリン含有マスターバッチ |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-089108 | 2014-04-23 | ||
JP2014089108 | 2014-04-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015163066A1 true WO2015163066A1 (ja) | 2015-10-29 |
Family
ID=54332236
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/058617 WO2015163066A1 (ja) | 2014-04-23 | 2015-03-20 | 2-メルカプトイミダゾリン含有マスターバッチ |
Country Status (5)
Country | Link |
---|---|
US (1) | US20170183458A1 (ja) |
EP (1) | EP3135713A4 (ja) |
JP (1) | JP6009090B2 (ja) |
CN (1) | CN106068298A (ja) |
WO (1) | WO2015163066A1 (ja) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04261445A (ja) * | 1991-01-22 | 1992-09-17 | Erasuto Mitsukusu:Kk | ゴム用配合剤組成物 |
JP2003183494A (ja) * | 2001-12-25 | 2003-07-03 | Sumitomo Rubber Ind Ltd | ポリマー組成物及び該組成物を用いた導電性ローラ、導電性ベルト |
CN103159990A (zh) * | 2011-12-08 | 2013-06-19 | 中国石油化工股份有限公司 | 一种母炼胶及其制备方法和硫化橡胶及其应用 |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4048261A (en) * | 1975-11-10 | 1977-09-13 | The B. F. Goodrich Company | Vulcanizable compositions of a halogen-containing polymer and a diene-nitrile rubber having active halogen cure sites |
US4743656A (en) * | 1985-02-20 | 1988-05-10 | Uniroyal Chemical Company, Inc. | Elastomeric composition of EPDM and ethylene-nitrile polymers |
WO2008156178A1 (ja) * | 2007-06-21 | 2008-12-24 | Kao Corporation | 形状記憶ゴム成形体、その製造方法及びその中間混練物 |
-
2015
- 2015-03-20 CN CN201580012745.2A patent/CN106068298A/zh active Pending
- 2015-03-20 EP EP15782827.8A patent/EP3135713A4/en not_active Withdrawn
- 2015-03-20 JP JP2015538181A patent/JP6009090B2/ja active Active
- 2015-03-20 WO PCT/JP2015/058617 patent/WO2015163066A1/ja active Application Filing
- 2015-03-20 US US15/304,902 patent/US20170183458A1/en not_active Abandoned
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04261445A (ja) * | 1991-01-22 | 1992-09-17 | Erasuto Mitsukusu:Kk | ゴム用配合剤組成物 |
JP2003183494A (ja) * | 2001-12-25 | 2003-07-03 | Sumitomo Rubber Ind Ltd | ポリマー組成物及び該組成物を用いた導電性ローラ、導電性ベルト |
CN103159990A (zh) * | 2011-12-08 | 2013-06-19 | 中国石油化工股份有限公司 | 一种母炼胶及其制备方法和硫化橡胶及其应用 |
Non-Patent Citations (2)
Title |
---|
See also references of EP3135713A4 * |
SHIN GOMU GIJUTSU NYUMON, 1969, Japan, pages 135 - 137, XP008185164 * |
Also Published As
Publication number | Publication date |
---|---|
JPWO2015163066A1 (ja) | 2017-04-13 |
EP3135713A1 (en) | 2017-03-01 |
JP6009090B2 (ja) | 2016-10-19 |
US20170183458A1 (en) | 2017-06-29 |
CN106068298A (zh) | 2016-11-02 |
EP3135713A4 (en) | 2017-11-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102344590A (zh) | 渣罐车用电缆护套料及其制造方法 | |
JPH11236465A (ja) | ゴム組成物、該ゴム組成物を用いたゴムローラ及び該ゴム組成物の製造方法 | |
DE112010001327T5 (de) | Thermoplastische Harzzusammensetzung | |
CN109651799A (zh) | 吸波贴片、其制备方法及其应用 | |
TWI625352B (zh) | 橡膠組成物及其硫化成形體 | |
CN103804882A (zh) | 一种高性能氯醇橡胶及制备方法 | |
WO2016104384A1 (ja) | ゴム又は熱可塑性エラストマー組成物及び当該組成物からなる成形体 | |
JP6009090B2 (ja) | クロロプレンゴムコンパウンド用2−メルカプトイミダゾリン含有マスターバッチ | |
CN110054853A (zh) | 一种柔性拖链磨砂高弹聚氯乙烯料及其制备方法 | |
CN105694152B (zh) | 一种打印纸输纸胶辊专用混炼胶及其制备方法 | |
CN104513429A (zh) | 一种耐磨pp材料及其制备方法 | |
JP6401551B2 (ja) | 樹脂複合材料及びその製造方法 | |
JP2007204645A (ja) | タイヤインナーライナー用ゴム組成物 | |
CN110591261B (zh) | 一种丙烯酸酯类橡胶的硫化交联活性剂预分散母胶粒及其制备方法 | |
CN109233152B (zh) | 一种表面处理碳酸钙补强pvc地板砖生产工艺 | |
CN107841072B (zh) | 一种氟橡胶油封组合物及其制备方法 | |
CN110183691A (zh) | 氢化丁腈橡胶用交联剂母炼胶、氢化丁腈橡胶组合物及氢化丁腈橡胶交联成形品 | |
JP2019143041A (ja) | エピクロロヒドリンゴム用架橋剤マスターバッチ | |
JP6870367B2 (ja) | ゴム組成物、コンパウンド、加硫物及びゴムロール | |
JP2006318783A (ja) | ハロゲンフリーポリプロピレン樹脂電線絶縁体 | |
US10717860B2 (en) | Polyvinyl chloride-based resin molded product and method for manufacturing the same | |
CN114437427B (zh) | 热塑性硫化橡胶组合物和热塑性硫化橡胶及其制备方法与应用 | |
CN109401177B (zh) | 一种耐高温耐磨苯乙烯弹性体 | |
CN110157134A (zh) | 一种改性苯乙烯-丁二烯-苯乙烯嵌段共聚物材料及其制备方法 | |
CN115873323B (zh) | 汽车油箱箍带衬垫用丁腈橡胶混炼胶及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2015538181 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15782827 Country of ref document: EP Kind code of ref document: A1 |
|
REEP | Request for entry into the european phase |
Ref document number: 2015782827 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015782827 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15304902 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |