JP4155718B2 - Continuous production method and continuous production apparatus for liquid silicone rubber base - Google Patents
Continuous production method and continuous production apparatus for liquid silicone rubber base Download PDFInfo
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- JP4155718B2 JP4155718B2 JP2001040348A JP2001040348A JP4155718B2 JP 4155718 B2 JP4155718 B2 JP 4155718B2 JP 2001040348 A JP2001040348 A JP 2001040348A JP 2001040348 A JP2001040348 A JP 2001040348A JP 4155718 B2 JP4155718 B2 JP 4155718B2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
- B29B7/487—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws with consecutive casings or screws, e.g. for feeding, discharging, mixing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/60—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material
- B29B7/603—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material in measured doses, e.g. proportioning of several materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7466—Combinations of similar mixers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/748—Plants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/375—Plasticisers, homogenisers or feeders comprising two or more stages
- B29C48/385—Plasticisers, homogenisers or feeders comprising two or more stages using two or more serially arranged screws in separate barrels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/405—Intermeshing co-rotating screws
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/57—Screws provided with kneading disc-like elements, e.g. with oval-shaped elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
【0001】
【産業上の利用分野】
本発明は同方向回転型2軸連続押出機を使用して液状シリコーンゴムベースを連続的に製造する方法および装置に関する。
【0002】
【従来の技術】
液状シリコーンゴムベースは,付加反応硬化型型液状シリコーンゴム組成物の主剤であり,通常液状アルケニル基含有ジオルガノポリシロキサンと補強性シリカフィラーと加工助剤とからなる。これにオルガノハイドロジェンポリシロキサンと白金系触媒を加えて硬化させる。付加反応硬化型型液状シリコーンゴム組成物は、成形性と硬化性が優れているので,種々のシリコーンゴム成形品の製造に使用されている。
【0003】
液状シリコーンゴムベースは、通常バッチ式で製造されるが、需要が増えて迅速に大量生産する必要が出てきたので、連続生産方式がいくつか提案されている。例えば、特公平4−28008号では、2軸連続押出混練機を用いてアルケニル基含有オルガノポロシロキサンと無機質充填剤とから液状シリコーンゴムベースを製造するため、2軸連続押出混練機の混練部を200〜300℃に加熱しておき、アルケニル基含有オルガノポロシロキサンの100〜30重量%および無機質充填剤を前記混練部に供給し、アルケニル基含有オルガノポロシロキサンの0〜70重量%を混練機の中途部に供給して混練している。しかしながら、可塑剤、すなわち、シリカフィラー処理剤を添加することなく液状シリコーンゴムベースを製造することを意図しており、保存安定性に欠けるという問題がある。
【0004】
特開平9−3332では、液状アルケニル基含有オルガノポリシロキサンの一部と混合助剤及びアンモニアを特定比率で予め混合し、これに粉末状シリカ充填剤を混合して混合粉体を製造し、この混合粉体をアルケニル基含有オルガノポリシロキサンの残部と特定比率で連続混練機によって均一に混合させるという、液状シリコーンゴムベースの製造方法が提案されている。しかし、アンモニアは刺激臭があり有毒であるので作業上問題がある。また、均一な混合粉体を連続的に製造しにくく、且つ得られた混合粉体を連続混練機に一定量づつ供給するのは容易でないという問題がある。
【0005】
特開平9−155950では、2軸連続押出混練機の原料投入口に液状オルガノポリシロキサン、微粉末状シリカ,液状オルガノシラザン,水を連続的に投入し混練することにより、液状オルガノポリシロキサンと微粉末状シリカの混合物を連続的に製造している。その際,2軸連続押出混練機のL/D:1〜13の領域では,冷却して50℃以下に保ち,L/D:13〜47の領域では80〜280℃、50〜280℃、あるいは50〜200℃に昇温させている。しかし、冷却領域と昇温領域が隣接しているので、温度制御が容易でないという問題がある。また、スクリューの回転速度を冷却領域と昇温領域で変えることができないので,領域ごとの混練条件の設定が困難であるという問題がある。
【0006】
【発明が解決しようとする課題】
本発明者らは上記問題点を解決するために鋭意検討した結果、本発明に至った。即ち本発明は混練条件の設定が容易であり、生産性に優れ,保存安定性が良好な液状シリコーンゴムベースの連続的製造方法および連続的製造装置を提供することを目的とする。
【0007】
【課題を解決するための手段及びその作用】
上記目的は、L/Dが6〜13である同方向回転型2軸連続混練押出機に、(A)液状アルケニル基含有ジオルガノポリシロキサン、(B)補強性シリカフィラーおよび(C)シリカフィラー処理剤を、(A)成分が100重量部、(B)成分が5〜100重量部、(C)成分が(B)成分の1〜30重量%の割合で連続的に供給し、0〜100℃の温度範囲で混練する第1工程と、第1工程で得られた混練物を別のL/Dが20〜50である同方向回転型2軸連続混練押出機に連続的に供給し、150℃〜300℃の温度範囲で混練する第2工程とからなることを特徴とする液状シリコーンゴムベースの連続的製造方法、および、上記連続的製造方法に使用するための液状シリコーンゴムベースの連続的製造装置であって、L/Dが6〜13である同方向回転型2軸連続混練押出機とL/Dが20〜50である同方向回転型2軸連続混練押出機とからなり、L/Dが6〜13である同方向回転型2軸連続混練押出機の排出口の真下にL/Dが20〜50である同方向回転型2軸連続混練押出機の混練物投入口が位置するように配置されている、あるいは、L/Dが6〜13である同方向回転型2軸連続混練押出機の排出口から配管がL/Dが20〜50である同方向回転型2軸連続混練押出機の混練物投入口に延伸しており、かつ、L/Dが6〜13である同方向回転型2軸連続混練押出機は上記連続的製造方法の第1工程用であり、L/Dが20〜50である同方向回転型2軸連続混練押出機は、上記連続的製造方法の第2工程用であることを特徴とする、液状シリコーンゴムベースの連続的製造装置により達成される。
【0008】
本発明の製造方法では,第1工程の同方向回転型2軸連続混練押出機内での混練温度が0〜100℃と低く抑えられているので、シリカフィラー処理剤がヘキサメチルジシラザンや1,3-ジビニルテトラメチルジシラザンのように揮発性が比較的大きいものであっても、その揮発を防止して補強性シリカフィラーを充分に疎水化処理することができる。また、第2工程の同方向回転型2軸連続混練押出機内での混練温度が150℃〜300℃と高く設定されているので,第1工程からきた各成分の均一混合物の加熱処理を確実に行うことができる。そのため、補強性シリカフィラーの含有量の割に粘度が小さく、流動性が大きく,しかも保存安定性に優れた液状シリコーンゴムベースを生産性よく連続的に製造することができる。
【0009】
また、同一の混練押出機を使用して種々の組成や性状の液状シリコーンゴムベースを生産する場合、品種切り替え時の洗浄性が問題となるが、第1工程,第2工程ともに同方向回転型2軸連続混練押出機というセルフクリーニング性がある混練押出機を使用するので、品種切り替え時間を短縮でき、廃棄物を削減することができる。したがって、作業性、生産性が優れている。
【0010】
【発明の実施の形態】
第1工程で使用する同方向回転型2軸連続混練押出機は、通常市販されているものを使用することができる。例えば(株)栗本鉄工所製のKRC、(株)神戸製鋼所製のMIXTRONが挙げられる。
同方向回転型2軸連続混練押出機は、そのバレル内に2本のスクリューが平行に配置され、その基端部は駆動部に接続しており、同一方向に同調回転する。スクリューは通常2条ネジか3条ネジを有する。基端部の上面に原料投入口が開口しており,バレルの末端部には混練物を排出するための排出口が存在する。
【0011】
原料である(A)成分〜(C)成分はそれぞれ貯槽に貯蔵しておき、液状の原料は配管を通して一定量づつ原料投入口に送り込むとよい。その際、ギヤポンプなどのポンプを使用するとよい。粉末状の原料は、テーブル式、ベルト式あるいはスクリュー式の連続供給機を使用して一定量づつ原料投入口に送り込むとよい。また、原料である(A)成分〜(C)成分は原料投入口からバレル内に直接投入してもよいが,(A)成分は液状であり,(B)成分は粉末状であるので、特開平9−155950で提案されているように二重管を使用して投入することが好ましい。すなわち、(A)成分は二重管の外管を通して投入し、(B)成分は内管を通して投入することが好ましい。(C)成分は通常液状であり、(B)成分の処理剤であるので内管に開口した配管を通して投入することが好ましい。バレル内の排出口の手前には異物ろ過用の金網を取り付けておくことが好ましい。
【0012】
原料投入口と排出口の間には、任意成分(例えば,追加用の(A)成分や(C)成分)の注入口、混練物中の揮発性成分の脱気口、混練物の温度を測定するための温度センサー、その他の計装用センサー等を設置してもよい。
混練時における滞留時間を長くするために、スクリュー径Dに対する軸長L、すなわち、L/Dは大きいほうが好ましく、6〜13が好ましく、7〜10がより好ましい。スクリューの周速度は、好ましくは0.2〜1.7m/s、より好ましくは0.5〜1.5m/sである。
混練中に摩擦熱が発生して混練物の温度が高くなるので、混練物を100℃以下に保つために、バレルの外周面は冷媒を通したジャケットで包囲しておくことが好ましい。
【0013】
第2工程で使用する同方向回転型2軸連続混練押出機も通常市販されているものを使用することができる。例えば(株)東芝機械製のTEM、ウェルナー・フレイドラー社製のZSKが挙げられる。第2工程で使用する同方向回転型2軸連続混練押出機は、第1工程で使用する同方向回転型2軸連続混練押出機と原則として同様の構成でよい。しかし、混練物投入口は,第1工程の同方向回転型2軸連続混練押出機から排出された混練物をバレル内に導入できればよく,特に限定されない。第1工程で使用する同方向回転型2軸連続混練押出機の排出口の真下に第2工程で使用する同方向回転型2軸連続混練押出機の混練物投入口が位置するように配置する。あるいは、第1工程で使用する同方向回転型2軸連続混練押出機の排出口から配管を延伸して第2工程で使用する同方向回転型2軸連続混練押出機の混練物投入口に導入してもよい。
【0014】
混練物投入口と排出口の間には、混練物中の揮発性成分の脱気口、混練物の温度を測定するための温度センサー、その他の計装用センサー等を設置してもよい。混練時における滞留時間を長くして十分に熱処理するために、スクリュー径Dに対する軸長L、すなわち、L/Dは大きいほうが好ましく、20〜50が好ましく、45〜50がより好ましい。
スクリューの周速度は、好ましくは0.2〜1.7m/s、より好ましくは0.5〜1.5m/sである。バレル内の混練物の温度を150〜300℃の温度範囲に保つために,バレルの外周面はヒーターを内蔵したジャケットで包囲することが好ましい。
【0015】
本発明の製造方法の第1工程では、上記のような同方向回転型2軸連続混練押出機に(A)液状アルケニル基含有ジオルガノポリシロキサン、(B)補強性シリカフィラー、および(C)シリカフィラー処理剤を導入する。
ここで、(A)液状アルケニル基含有ジオルガノポリシロキサンは、液状シリコーンゴムベースの主剤である。このジオルガノポリシロキサンの代表例は、一般式R3SiO(R2SiO)nSiR3(式中、Rは1価炭化水素基またはハロゲン化1価炭化水素基であり、そのうちの少なくとも2個はアルケニル基であり、nは25℃における粘度が0.5〜1000Pa・sとなる正数である)で表される。Rとしてはメチル基、エチル基、プロピル基、ブチル基等のアルキル基;シクロヘキシル基のようなシクロアルキル基;ビニル基、アリル基、ヘキセニル基等のアルケニル基;フェニル基、トリル基等のアリール基;ベンジル基、フェニルエチル基等のアラルキル基及びこれらの基の水素原子の一部をハロゲン原子(例えばフッ素原子)で置換した炭化水素基が例示される。アルケニル基以外の1価炭化水素基は、メチル基、ついでフェニル基が好ましい。アルケニル基は架橋点となるので、一分子中に少なくとも2個存在する必要がある。アルケニル基は分子鎖の両末端のみ,側鎖のみ、末端と側鎖の両方に存在していても良い。末端封鎖基としてトリメチルシロキシ基、ジメチルビニルシロキシ基が例示され、主鎖としてジメチルポリシロキサン、ジメチルシロキサン・メチルフェニルシロキサンコポリマー、ジメチルシロキサン・メチルビニルシロキサンコポリマー、ジメチルシロキサン・メチルビニルシロキサン・メチルフェニルシロキサンコポリマー、ジメチルシロキサン・(3,3,3−トリフルオロプロピルシロキサン)コポリマーが例示される。液状アルケニル基含有ジオルガノポリシロキサンは25℃における粘度は、好ましくは0.5〜1000Pa・sの範囲である。粘度が0.5Pa・s未満では液状シリコーンゴムベース硬化物の硬度が大きくなりすぎ、粘度が1000Pa・sを超えると補強性シリカフィラーを配合したときに粘稠になりすぎるからである。液状アルケニル基含有ジオルガノポリシロキサンは少々分岐していてもよい。
【0016】
(B)補強性シリカフィラーは、微細な粉末状であり、シリコーンゴムの補強効果があれば何れのものも使用可能である。その代表例は、乾式法シリカ、すなわち、フュームドシリカ、および、湿式法シリカ,すなわち,沈降シリカである。好ましい比表面積は50m2/g以上である。(B)成分の配合量が少なすぎると補強効果が不充分であり,多すぎると粘ちゅうになりすぎて成形加工が困難になるので,(A)成分100重量部に対して5〜100重量部であり、好ましくは5〜60重量部である。
【0017】
(C)シリカフィラー処理剤は(B)成分を疎水化処理して(A)成分と混ざりやすくする作用をする。シラノール基やケイ素原子結合加水分解性基を含有する有機ケイ素化合物が好適であり,(B)成分の表面に存在するシラノール基と縮合反応して疎水化するので、(A)成分と混ざりやすくなる。具体例として,ヘキサメチルジシラザン、ジビニルテトラメチルジシラザンなどのヘキサオルガノジシラザン;トリメチルシラノール、α,ω-ジヒドロキシジメチルシロキサンオリゴマー、α,ω-ジヒドロキシメチルフェニルシロキサンオリゴマー、α,ω-ジヒドロキシメチルビニルシロキサンオリゴマーなどのシラノール基を有するオルガノシランもしくはオルガノシロキサンオリゴマー、ケイ素原子結合加水分解性基含有オルガノシランもしくはオルガノシロキサンオリゴマーがある。ヘキサメチルジシラザン、ジビニルテトラメチルジシラザンなどのヘキサオルガノジシラザンは、補強性シリカフィラーとの反応性が良好であり,疎水化作用が大きいので好適である。(B)成分の含水量,比表面積,シラノール基含有量や、(C)成分シラノール基やケイ素原子結合加水分解性基含有量によって(C)成分の配合量は変わってくるが,通常(B)成分の1〜30重量%である。なお、(B)成分がヘキサオルガノジシラザンである場合は、その加水分解を促進して処理効果をあげるために少量の水を並存させることが好ましい。液状シリコーンゴムベースを製造するには(A)成分〜(C)成分を混合するだけでよいが、その他に非反応性のジオルガノポリシロキサン、アルケニル基含有オルガノポリシロキサンレジン、顔料,耐熱剤などを配合してもよい。
【0018】
第1工程の同方向回転型2軸連続混練押出機から排出された混練物は,別の同方向回転型2軸連続混練押出機に導入され,加熱下混練されて排出口から液状シリコーンゴムベースとして排出される。放置して冷却するか,強制的に冷却して所定の容器に入れて貯蔵する。この液状シリコーンゴムベースにオルガノハイドロジェンポリシロキサンと白金系触媒を均一に混合するとヒドロシリル化反応が起こって架橋し,シリコーンゴムになる。ヒドロシリル化反応抑制剤を同時に混合すると室温下での架橋反応が遅延して、貯蔵可能となり、加熱すると硬化するようになる。
【0019】
【実施例】
次に本発明を実施例によって説明する。第1工程の同方向回転型2軸連続混練押出機8は、2本のスクリュー9の各直径が100mm、2本のスクリュー9の各回転数が350rpm、L/Dが7.2であった。第2工程の同方向回転型2軸連続混練押出機は、2本のスクリュー14の各直径が58mm、2本のスクリュー14の各回転数は500rpm、L/Dが45であった。
下記の各成分を下記の重量比で同方向回転連続2軸混練機8に原料投入口7から連続的に供給した。
(A)25℃における粘度が40Pa・sである両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン100重量部、
(B)比表面積250m2/gのフュームドシリカ43.3重量部
(C)ヘキサメチルジシラザン7.88重量部
【0020】
該両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサンは貯槽1に貯蔵されており、ギアポンプ4により原料投入口7から同方向回転型2軸連続混練押出機8に定量的に供給した。ヘキサメチルジシラザンは貯槽2に貯蔵されており、ギヤポンプ5により原料投入口7から同方向回転型2軸連続混練押出機8に定量的に供給した。比表面積250m2/gのフュームドシリカは貯槽3に貯蔵されており、テーブル式連続供給機6により原料投入口7から同方向回転型2軸連続混練押出機8に定量的に供給した。同方向回転型2軸連続混練押出機8のバレル10の外周面は冷却水が流れているジャケット(図示していない)で包囲して、摩擦による混練物の昇温を抑制した。バレル10の混練部における混練物の温度は50℃であり、排出口11における混練物の温度は70℃であった。供給された原料が混練物として排出されるまでの時間,すなわち、平均滞留時間は60秒であった。
【0021】
排出口11から排出された混練物は配管を介して別の同方向回転型2軸連続混練押出機13に混練物投入口12から連続的に供給した。該同方向回転型2軸連続混練押出機13のバレル15の外周面は熱媒が流れているジャケット(図示していない)で包囲して、混練物の温度を150〜300℃の温度範囲内に保つようにした。バレル15の混練部における混練物の温度は約280℃であり、排出口16における混練物の温度は200℃であった。混練物の平均滞留時間は90秒であった。
【0022】
かくして製造された液状シリコーンゴムベースを室温になるまで放冷し、その100重量部に粘度0.50Pa・Sの両末端トリメチルシロキシ基封鎖メチルハイドロジェンポリシロキサン0.83重量部、塩化白金酸と1,3-ジビニルテトラメチルジシロキサンの錯塩0.000275重量部および3,5−ジメチル−1−ヘキシン−3−オール0.014重量部を添加して均一になるまで混合し、加圧下150℃で10分間加熱してシート状に硬化させた。このシート状シリコーンゴムの物性を表1に示した。なお、硬さはJIS K6249(タイプAデユロメータ使用)に従い、引張強さと伸びと引裂強さはJIS K6249に従って室温で測定した。
また、放冷して室温になった液状シリコーンゴムベースを卓上ミキサーで練り戻し脱泡してから、粘度測定用シリンダーに圧入し、プランジャーを押してノズルから一定時間内に吐出された液状シリコーンゴムベースの重量を測定し、ハーゲンポアズイユの計算式により見掛け粘度を算出した。上記液状シリコーンゴムベースをシリンダーに圧入した状態で1ヶ月放置した後の見掛け粘度を同様に測定して、これらの結果を表1に示した。
【0023】
比較のため、(A)25℃における粘度が40Pa・sである両末端ジメチルビニルシロキシ基封鎖ジメチルポリシロキサン100重量部、(B)比表面積250m2/gのフュームドシリカ43.3重量部および(C)ヘキサメチルジシラザン7.88重量部をブレードミキサーに投入し、25℃で60分間混練して液状シリコーンゴムベースを調製した。上記と同様にしてシリコーンゴムの物性と液状シリコーンゴムベースの見掛け粘度を測定して表1に示した。
【0024】
【表1】
【0025】
【発明の効果】
本発明の製造方法では、同方向回転型2軸連続混練押出機により所定比率の(A)アルケニル基含有ジオルガノポリシロキサン、(B)補強性シリカフィラー、(C)シリカフィラー処理剤を0〜100℃で混練し、その混練物を別の同方向回転型2軸連続混練押出機に導入して150〜300℃で混練するので、粘度が低く、流動性と保存安定性に優れた液状シリコーンゴムベースを生産性よく連続的に製造することができる。
【0026】
【図面の簡単な説明】
【図1】 本発明の実施例に使用した第1工程の同方向回転型2軸連続混練押出機8、第2工程の同方向回転型2軸連続混練押出機13、貯槽、ギヤポンプおよびテーブル式連続供給装置の概略断面図である。
【符号の説明】
1 貯槽
2 貯槽
3 貯槽
4 ギヤポンプ
5 ギヤポンプ
6 テーブル式連続供給機
7 原料投入口
8 第1工程の同方向回転型2軸連続混練押出機
9 スクリュー
10 バレル
11 排出口
12 混練物投入口
13 第2工程の同方向回転型2軸連続混練押出機
14 スクリュー
15 バレル
16 排出口[0001]
[Industrial application fields]
The present invention relates to a method and apparatus for continuously producing a liquid silicone rubber base using a co-rotating twin screw continuous extruder.
[0002]
[Prior art]
The liquid silicone rubber base is the main component of the addition reaction curable liquid silicone rubber composition, and usually comprises a liquid alkenyl group-containing diorganopolysiloxane, a reinforcing silica filler, and a processing aid. An organohydrogenpolysiloxane and a platinum-based catalyst are added to this and cured. Addition reaction curable liquid silicone rubber compositions are excellent in moldability and curability, and are therefore used in the production of various silicone rubber molded articles.
[0003]
The liquid silicone rubber base is usually manufactured in a batch system. However, since the demand has increased and it has become necessary to rapidly mass-produce, several continuous production systems have been proposed. For example, in Japanese Patent Publication No. 4-28008 , a biaxial continuous extrusion kneader is used to produce a liquid silicone rubber base from an alkenyl group-containing organoporosiloxane and an inorganic filler. The mixture is heated to 200 to 300 ° C., 100 to 30% by weight of the alkenyl group-containing organoporosiloxane and the inorganic filler are supplied to the kneading part, and 0 to 70% by weight of the alkenyl group-containing organoporosiloxane is added to the kneading machine. It is fed to the middle part and kneaded. However, it is intended to produce a liquid silicone rubber base without adding a plasticizer, that is, a silica filler treatment agent, and there is a problem that storage stability is lacking.
[0004]
In JP-A-9-3332, a part of a liquid alkenyl group-containing organopolysiloxane, a mixing aid and ammonia are mixed in advance at a specific ratio, and a powdered silica filler is mixed therewith to produce a mixed powder. There has been proposed a method for producing a liquid silicone rubber base in which the mixed powder is uniformly mixed with the remainder of the alkenyl group-containing organopolysiloxane at a specific ratio by a continuous kneader. However, since ammonia has an irritating odor and is toxic, there is a problem in work. In addition, there is a problem that it is difficult to continuously produce a uniform mixed powder, and it is not easy to supply the obtained mixed powder to a continuous kneader in a constant amount.
[0005]
In JP-A-9-155950, liquid organopolysiloxane, fine powdered silica, liquid organosilazane, and water are continuously charged into the raw material charging port of a biaxial continuous extrusion kneader to knead the liquid organopolysiloxane and fine powder. A mixture of powdered silica is continuously produced. At that time, in the region of L / D: 1 to 13 of the biaxial continuous extrusion kneader, it is cooled and kept at 50 ° C. or lower, and in the region of L /
[0006]
[Problems to be solved by the invention]
As a result of intensive studies to solve the above problems, the present inventors have reached the present invention. That is, an object of the present invention is to provide a continuous production method and a continuous production apparatus for a liquid silicone rubber base in which the kneading conditions are easily set, the productivity is excellent, and the storage stability is good.
[0007]
[Means for Solving the Problem and Action]
The object is to provide a co-rotating biaxial continuous kneading extruder having an L / D of 6 to 13 with (A) a liquid alkenyl group-containing diorganopolysiloxane, (B) a reinforcing silica filler, and (C) a silica filler. The treatment agent is continuously supplied at a ratio of 100 parts by weight of the component (A), 5 to 100 parts by weight of the component (B), and 1 to 30% by weight of the component (C) of the component (B). The first step of kneading in the temperature range of 100 ° C. and the kneaded product obtained in the first step are continuously fed to a co-rotating biaxial continuous kneading extruder having another L / D of 20 to 50 And a second step of kneading in a temperature range of 150 ° C. to 300 ° C., and a continuous production method of a liquid silicone rubber base, and a liquid silicone rubber base for use in the continuous production method Continuous production equipment, L / D is 6 to 1 3 and the same direction rotation type biaxial continuous kneading extruder with L / D 20-50, the same direction rotation type with L / D 6-13 The biaxial continuous kneading extruder is disposed so that the kneaded product inlet of the same-direction rotating biaxial continuous kneading extruder having an L / D of 20 to 50 is located directly under the discharge port of the biaxial continuous kneading extruder, or L / D The pipe extends from the discharge port of the co-rotating biaxial continuous kneading extruder with D of 6 to 13 to the kneaded product inlet of the co-rotating biaxial continuous kneading extruder with L / D of 20 to 50. In addition , the same-direction rotating biaxial continuous kneading and extruding machine having an L / D of 6 to 13 is for the first step of the above continuous production method, and the L / D is 20 to 50. type biaxial continuous kneading extruder, characterized in that it is used for the second step of the continuous manufacturing method, the liquid silicone rubber It is achieved by successive manufacturing apparatus over scan.
[0008]
In the production method of the present invention, the kneading temperature in the first-direction rotating twin-screw continuous kneading extruder in the first step is kept as low as 0 to 100 ° C., so that the silica filler treatment agent is hexamethyldisilazane, 1, Even if the volatility is relatively large, such as 3-divinyltetramethyldisilazane, the volatilization can be prevented and the reinforcing silica filler can be sufficiently hydrophobized. Moreover, since the kneading temperature in the same-direction rotating biaxial continuous kneading and extruding machine in the second step is set as high as 150 ° C. to 300 ° C., the heat treatment of the uniform mixture of each component from the first step is ensured. It can be carried out. Therefore, it is possible to continuously produce a liquid silicone rubber base having a small viscosity, a large fluidity and excellent storage stability for the content of the reinforcing silica filler.
[0009]
In addition, when liquid silicone rubber bases of various compositions and properties are produced using the same kneading extruder, there is a problem with the cleanability at the time of product type change. Since a kneading extruder having a self-cleaning property called a biaxial continuous kneading extruder is used, the time for changing the type can be shortened and waste can be reduced. Therefore, workability and productivity are excellent.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
As the co-rotating biaxial continuous kneading extruder used in the first step, a commercially available one can be used. For example, KRC manufactured by Kurimoto Iron Works Co., Ltd. and MIXTRON manufactured by Kobe Steel Co., Ltd. may be mentioned.
In the same-direction rotating biaxial continuous kneading extruder, two screws are arranged in parallel in the barrel, and the base end portion is connected to the drive unit, and rotates synchronously in the same direction. Screws usually have 2 or 3 threads. A raw material inlet is open on the upper surface of the base end, and an outlet for discharging the kneaded material is present at the end of the barrel.
[0011]
Components (A) to (C), which are raw materials, are each stored in a storage tank, and the liquid raw material is preferably sent to the raw material inlet through a pipe in a certain amount. At that time, a pump such as a gear pump may be used. The powdery raw material may be fed into the raw material charging port by a fixed amount using a table type, belt type or screw type continuous feeder. Moreover, although (A) component-(C) component which is a raw material may be thrown directly into a barrel from a raw material inlet, since (A) component is a liquid and (B) component is a powder form, It is preferable to use a double pipe as proposed in JP-A- 9-155950 . That is, the component (A) is preferably charged through the outer tube of the double tube, and the component (B) is preferably charged through the inner tube. The component (C) is usually in a liquid state, and since it is a treatment agent for the component (B), it is preferably introduced through a pipe opened to the inner pipe. It is preferable to attach a wire net for foreign matter filtration in front of the discharge port in the barrel.
[0012]
Between the raw material inlet and outlet, there are an injection port for optional components (for example, additional component (A) and component (C)), a degassing port for volatile components in the kneaded product, and the temperature of the kneaded product. A temperature sensor for measurement and other instrumentation sensors may be installed.
In order to lengthen the residence time at the time of kneading, the axial length L with respect to the screw diameter D, that is, L / D is preferably larger, preferably 6 to 13, and more preferably 7 to 10. The peripheral speed of the screw is preferably 0.2 to 1.7 m / s, more preferably 0.5 to 1.5 m / s.
Since frictional heat is generated during kneading and the temperature of the kneaded product increases, it is preferable to surround the outer peripheral surface of the barrel with a jacket through which a refrigerant passes in order to keep the kneaded product at 100 ° C. or lower.
[0013]
The same direction rotation type biaxial continuous kneading extruder used at a 2nd process can also use what is marketed normally. Examples thereof include TEM manufactured by Toshiba Machine Co., Ltd. and ZSK manufactured by Werner Fredler. The same direction rotation type biaxial continuous kneading extruder used in the second step may be basically the same configuration as the same direction rotation type biaxial continuous kneading extruder used in the first step. However, the kneaded material inlet is not particularly limited as long as the kneaded material discharged from the same-direction rotating biaxial continuous kneading extruder in the first step can be introduced into the barrel. It arrange | positions so that the kneaded material inlet of the same direction rotation type biaxial continuous kneading extruder used in a 2nd process may be located directly under the discharge port of the same direction rotation type biaxial continuous kneading extruder used in a 1st process. . Alternatively, the pipe is extended from the discharge port of the co-rotating biaxial continuous kneading extruder used in the first step and introduced into the kneaded material inlet of the co-rotating biaxial continuous kneading extruder used in the second step. May be.
[0014]
Between the kneaded product inlet and outlet, a degassing port for volatile components in the kneaded product, a temperature sensor for measuring the temperature of the kneaded product, and other instrumentation sensors may be installed. In order to lengthen the residence time at the time of kneading and sufficiently heat-treat, the axial length L with respect to the screw diameter D, that is, L / D is preferably larger, preferably 20-50, and more preferably 45-50.
The peripheral speed of the screw is preferably 0.2 to 1.7 m / s, more preferably 0.5 to 1.5 m / s. In order to keep the temperature of the kneaded material in the barrel within a temperature range of 150 to 300 ° C., it is preferable to surround the outer peripheral surface of the barrel with a jacket having a built-in heater.
[0015]
In the first step of the production method of the present invention, (A) a liquid alkenyl group-containing diorganopolysiloxane, (B) a reinforcing silica filler, and (C) Silica filler treatment agent is introduced.
Here, (A) the liquid alkenyl group-containing diorganopolysiloxane is a liquid silicone rubber-based main agent. A typical example of this diorganopolysiloxane has the general formula R 3 SiO (R 2 SiO) nSiR 3 (wherein R is a monovalent hydrocarbon group or a halogenated monovalent hydrocarbon group, at least two of which are An alkenyl group, and n is a positive number having a viscosity at 25 ° C. of 0.5 to 1000 Pa · s). R represents an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; a cycloalkyl group such as a cyclohexyl group; an alkenyl group such as a vinyl group, an allyl group or a hexenyl group; an aryl group such as a phenyl group or a tolyl group An aralkyl group such as a benzyl group or a phenylethyl group and a hydrocarbon group obtained by substituting a part of the hydrogen atoms of these groups with a halogen atom (for example, a fluorine atom); The monovalent hydrocarbon group other than the alkenyl group is preferably a methyl group and then a phenyl group. Since the alkenyl group serves as a cross-linking point, at least two alkenyl groups must be present in one molecule. The alkenyl group may be present only at both ends of the molecular chain, only the side chain, or both the terminal and side chains. Examples of the terminal blocking group include trimethylsiloxy group and dimethylvinylsiloxy group, and dimethylpolysiloxane, dimethylsiloxane / methylphenylsiloxane copolymer, dimethylsiloxane / methylvinylsiloxane copolymer, dimethylsiloxane / methylvinylsiloxane / methylphenylsiloxane copolymer as the main chain. And dimethylsiloxane. (3,3,3-trifluoropropylsiloxane) copolymer. The liquid alkenyl group-containing diorganopolysiloxane has a viscosity at 25 ° C. of preferably 0.5 to 1000 Pa · s. This is because if the viscosity is less than 0.5 Pa · s, the hardness of the liquid silicone rubber-based cured product becomes too high, and if the viscosity exceeds 1000 Pa · s, it becomes too viscous when the reinforcing silica filler is blended. The liquid alkenyl group-containing diorganopolysiloxane may be slightly branched.
[0016]
(B) The reinforcing silica filler is in a fine powder form, and any reinforcing silica filler can be used as long as it has a silicone rubber reinforcing effect. Typical examples are dry process silica, ie fumed silica, and wet process silica, ie precipitated silica. A preferred specific surface area is 50 m 2 / g or more. If the blending amount of the component (B) is too small, the reinforcing effect is insufficient, and if it is too large, it becomes too viscous and difficult to mold, so 5 to 100 weights per 100 parts by weight of the component (A). Part, preferably 5 to 60 parts by weight.
[0017]
(C) The silica filler treating agent acts to make the component (B) hydrophobic and to be easily mixed with the component (A). An organosilicon compound containing a silanol group or a silicon atom-bonded hydrolyzable group is suitable, and it is hydrophobized by a condensation reaction with a silanol group present on the surface of the component (B), so that it is easily mixed with the component (A). . Specific examples include hexaorganodisilazanes such as hexamethyldisilazane and divinyltetramethyldisilazane; trimethylsilanol, α, ω-dihydroxydimethylsiloxane oligomer, α, ω-dihydroxymethylphenylsiloxane oligomer, α, ω-dihydroxymethylvinyl. There are organosilanes or organosiloxane oligomers having silanol groups such as siloxane oligomers, and silicon-bonded hydrolyzable group-containing organosilanes or organosiloxane oligomers. Hexaorganodisilazanes such as hexamethyldisilazane and divinyltetramethyldisilazane are preferable because they have good reactivity with the reinforcing silica filler and have a large hydrophobic effect. The blending amount of the component (C) varies depending on the water content, specific surface area, silanol group content of the component (B) and the silanol group or silicon atom bond hydrolyzable group content of the component (C). 1) to 30% by weight of the component. In addition, when (B) component is hexaorganodisilazane, in order to accelerate | stimulate the hydrolysis and to raise a processing effect, it is preferable to coexist a small amount of water. In order to produce a liquid silicone rubber base, it is only necessary to mix components (A) to (C). In addition, non-reactive diorganopolysiloxane, alkenyl group-containing organopolysiloxane resin, pigment, heat-resistant agent, etc. May be blended.
[0018]
The kneaded material discharged from the first-direction rotating biaxial continuous kneading extruder in the first step is introduced into another same-direction rotating biaxial continuous kneading extruder, kneaded under heating, and liquid silicone rubber base from the discharge port. Discharged as. Allow to cool by standing, or forcibly cool and store in a predetermined container. When an organohydrogenpolysiloxane and a platinum-based catalyst are uniformly mixed with this liquid silicone rubber base, a hydrosilylation reaction takes place and the silicone rubber is crosslinked. When the hydrosilylation reaction inhibitor is mixed at the same time, the crosslinking reaction at room temperature is delayed and can be stored, and when heated, it is cured.
[0019]
【Example】
Next, the present invention will be described by way of examples. In the same-direction rotating biaxial continuous kneading extruder 8 in the first step, the diameters of the two screws 9 were 100 mm, the rotational speeds of the two screws 9 were 350 rpm, and L / D was 7.2. . In the same-direction rotating biaxial continuous kneading and extruding machine in the second step, the diameters of the two
The following components were continuously supplied from the raw material charging port 7 to the same direction rotating continuous biaxial kneader 8 at the following weight ratio.
(A) 100 parts by weight of dimethylpolysiloxane blocked with dimethylvinylsiloxy group at both ends having a viscosity at 25 ° C. of 40 Pa · s,
(B) 43.3 parts by weight of fumed silica having a specific surface area of 250 m 2 / g (C) 7.88 parts by weight of hexamethyldisilazane
The both-end dimethylvinylsiloxy-blocked dimethylpolysiloxane is stored in the storage tank 1 and quantitatively supplied from the raw material charging port 7 to the same-direction rotating biaxial continuous kneading extruder 8 by the gear pump 4. Hexamethyldisilazane is stored in the storage tank 2 and quantitatively supplied from the raw material inlet 7 to the same-direction rotating biaxial continuous kneading extruder 8 by the
[0021]
The kneaded material discharged from the discharge port 11 was continuously supplied from the kneaded
[0022]
The liquid silicone rubber base thus produced was allowed to cool to room temperature, 100 parts by weight of which were 0.83 parts by weight of both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane having a viscosity of 0.50 Pa · S, chloroplatinic acid and Add 0.000275 parts by weight of complex salt of 1,3-divinyltetramethyldisiloxane and 0.014 parts by weight of 3,5-dimethyl-1-hexyn-3-ol and mix until uniform, and 150 ° C. under pressure. For 10 minutes to cure into a sheet. The physical properties of this sheet-like silicone rubber are shown in Table 1. The hardness was measured in accordance with JIS K6249 (using type A durometer), and the tensile strength, elongation and tear strength were measured at room temperature in accordance with JIS K6249.
In addition, the liquid silicone rubber base that has been allowed to cool to room temperature is kneaded and defoamed with a desktop mixer, then press-fitted into the viscosity measurement cylinder, and the plunger is pressed to discharge the liquid silicone rubber from the nozzle within a certain period of time. The weight of the base was measured, and the apparent viscosity was calculated by the Hagen Poiseuille formula. The apparent viscosity of the liquid silicone rubber base after being left for 1 month in a state where it was pressed into a cylinder was measured in the same manner, and the results are shown in Table 1.
[0023]
For comparison, (A) 100 parts by weight of dimethylpolysiloxane blocked with dimethylvinylsiloxy at both ends having a viscosity at 25 ° C. of 40 Pa · s, (B) 43.3 parts by weight of fumed silica having a specific surface area of 250 m 2 / g, and (C) 7.88 parts by weight of hexamethyldisilazane was charged into a blade mixer and kneaded at 25 ° C. for 60 minutes to prepare a liquid silicone rubber base. The physical properties of the silicone rubber and the apparent viscosity of the liquid silicone rubber base were measured in the same manner as described above and are shown in Table 1.
[0024]
[Table 1]
[0025]
【The invention's effect】
In the production method of the present invention, (A) an alkenyl group-containing diorganopolysiloxane, (B) a reinforcing silica filler, and (C) a silica filler treating agent are mixed in a predetermined ratio by a co-rotating biaxial continuous kneading extruder. Kneaded at 100 ° C., and the kneaded product is introduced into another co-rotating biaxial continuous kneading extruder and kneaded at 150 to 300 ° C. Therefore, the liquid silicone has low viscosity and excellent fluidity and storage stability. A rubber base can be continuously produced with high productivity.
[0026]
[Brief description of the drawings]
[1] co-rotating biaxial continuous kneading extruder 8 of the first step using the embodiment of the present invention, co-rotating in the second step biaxial
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Storage tank 2 Storage tank 3 Storage tank 4
Claims (5)
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JP2001040348A JP4155718B2 (en) | 2001-02-16 | 2001-02-16 | Continuous production method and continuous production apparatus for liquid silicone rubber base |
GB0201562A GB2384488A (en) | 2001-02-16 | 2002-01-24 | Continuous mixing of silicone rubber base |
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JP2001040348A JP4155718B2 (en) | 2001-02-16 | 2001-02-16 | Continuous production method and continuous production apparatus for liquid silicone rubber base |
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EP2290006A1 (en) | 2009-07-16 | 2011-03-02 | Shin-Etsu Chemical Co., Ltd. | Method for preparing silicone composition |
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JP5110308B2 (en) * | 2008-10-23 | 2012-12-26 | 信越化学工業株式会社 | Method for producing liquid silicone rubber composition and liquid silicone rubber composition |
DE102008054536A1 (en) * | 2008-12-11 | 2010-06-17 | Wacker Chemie Ag | Process for the continuous production of high-viscosity silicone compositions |
DE102008055035A1 (en) * | 2008-12-19 | 2010-07-01 | Wacker Chemie Ag | Continuous process for the preparation of base stocks for silicone compositions with improved stability |
DE102008055041A1 (en) * | 2008-12-19 | 2010-07-29 | Wacker Chemie Ag | Continuous process for the preparation of organopolysiloxane compositions |
JP5465429B2 (en) | 2008-12-24 | 2014-04-09 | 株式会社Shindo | Silicone rubber sponge-forming emulsion composition and method for producing silicone rubber sponge |
US20190091915A1 (en) * | 2015-10-13 | 2019-03-28 | Steer Engineering Private Limited | A process for preparing hydrogels |
KR101760776B1 (en) * | 2017-02-09 | 2017-07-24 | 김형판 | Rubber Extruding Apparatus having Preheat Structure |
US10501657B2 (en) * | 2017-03-08 | 2019-12-10 | Momentive Performance Materials Inc. | Silicone coating composition containing surface sheen modifier |
WO2019023841A1 (en) | 2017-07-31 | 2019-02-07 | Dow Silicones Corporation | Process and apparatus to make liquid silicone rubber compositions |
CN111841421A (en) * | 2020-08-18 | 2020-10-30 | 合盛硅业股份有限公司 | Continuous production line of liquid silicone rubber |
CN112659520A (en) * | 2020-12-08 | 2021-04-16 | 江西蓝星星火有机硅有限公司 | Semi-continuous production process and production device of addition type liquid silicone rubber-based adhesive |
CN114347293A (en) * | 2021-12-08 | 2022-04-15 | 寿光市煜盛汽车配件有限公司 | Open plasticator is used in preparation of vehicle acoustic celotex board |
DE102022210592A1 (en) * | 2022-10-06 | 2024-04-11 | Raumedic Ag | Plant for producing an extruded silicone semi-finished product, use of a co-rotating twin-screw extruder and process for producing a silicone raw extrudate |
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JP3245258B2 (en) * | 1993-04-27 | 2002-01-07 | 東レ・ダウコーニング・シリコーン株式会社 | Continuous production method of heat-curable silicone rubber compound |
JP3259663B2 (en) * | 1997-06-27 | 2002-02-25 | 信越化学工業株式会社 | Method for producing heat-curable silicone rubber compound |
JP3475740B2 (en) * | 1997-09-05 | 2003-12-08 | 信越化学工業株式会社 | Method for producing heat-curable silicone rubber compound |
ATE263801T1 (en) * | 1997-09-25 | 2004-04-15 | Pirelli | CONTINUOUS PROCESS FOR PRODUCING A SILICA-FILLED RUBBER MATERIAL AND TIRES CONTAINING THIS MATERIAL |
EP1110696A3 (en) * | 1999-12-21 | 2001-11-21 | General Electric Company | Continuous process to prepare silicone compositions |
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EP2290006A1 (en) | 2009-07-16 | 2011-03-02 | Shin-Etsu Chemical Co., Ltd. | Method for preparing silicone composition |
US8293835B2 (en) | 2009-07-16 | 2012-10-23 | Shin-Etsu Chemical Co., Ltd. | Method for preparing silicone composition |
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