WO2007091303A1 - Composition de caoutchouc de silicone pour moulage par extrusion - Google Patents

Composition de caoutchouc de silicone pour moulage par extrusion Download PDF

Info

Publication number
WO2007091303A1
WO2007091303A1 PCT/JP2006/302085 JP2006302085W WO2007091303A1 WO 2007091303 A1 WO2007091303 A1 WO 2007091303A1 JP 2006302085 W JP2006302085 W JP 2006302085W WO 2007091303 A1 WO2007091303 A1 WO 2007091303A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicone rubber
mass
group
parts
hose
Prior art date
Application number
PCT/JP2006/302085
Other languages
English (en)
Japanese (ja)
Inventor
Osamu Hayashida
Masayuki Ikeno
Original Assignee
Shin-Etsu Chemical Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shin-Etsu Chemical Co., Ltd. filed Critical Shin-Etsu Chemical Co., Ltd.
Priority to PCT/JP2006/302085 priority Critical patent/WO2007091303A1/fr
Publication of WO2007091303A1 publication Critical patent/WO2007091303A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C08K5/5477—Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the present invention relates to a silicone rubber composition for extrusion molding improved in die swell during extrusion molding.
  • the silicone composition of the present invention is suitable for silicone rubber products to be extruded such as electric wires, extruded tubes, hoses and the like.
  • unvulcanized silicone rubber can be extruded through a die with an extruder, and molded products of various shapes and sizes can be continuously formed. Curing and curing is performed using an organic peroxide or a platinum catalyst in a steam furnace.
  • the cross-sectional dimension of unvulcanized silicone rubber expands more than the die exit dimension immediately after the die force is pushed out. It is strongly required to reduce the expansion coefficient (die swell) at this time as much as possible in order to improve the dimensional accuracy of the obtained molded product and improve the yield of the molded product.
  • Patent Documents 1 and 2 it is widely known that triallyl isocyanurate or a modified product thereof is used as a reaction inhibitor for an addition-curable silicone rubber composition. It is also known to use triallyl isocyanurate modified with an alkoxysilyl group as an adhesion-imparting agent for an addition-curable silicone rubber composition (Patent Documents 3 and 4).
  • Patent Document 5 describes that triallyl isocyanurate is added to an organic peroxide-cured silicone rubber composition capable of atmospheric pressure hot-air vulcanization. With triallyl isocyanurate, the die swell is reduced. There is almost no effect to do! /.
  • Patent Document 1 Japanese Patent Laid-Open No. 5-111981
  • Patent Document 2 Japanese Patent Laid-Open No. 5-140456
  • Patent Document 3 Japanese Patent Laid-Open No. 7-53872
  • Patent Document 4 Japanese Patent Laid-Open No. 2000-136307
  • Patent Document 5 JP-A-10-67936
  • the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a silicone rubber composition for extrusion molding in which die molding in extrusion molding is reduced.
  • the present inventor can reduce die swell during extrusion molding by adding a specific isocyanurate compound to the silicone rubber composition. As a result, the present invention has been completed.
  • the present invention provides a means for solving the above problems as follows:
  • R is the same or different unsubstituted or substituted monovalent hydrocarbon group, a is a positive number from 1.90 to 2.05)
  • the present invention provides a silicone rubber composition for extrusion molding comprising
  • the silicone rubber composition for extrusion molding of the present invention can provide a silicone rubber molding having a small die swell during extrusion molding. For this reason, the dimensional accuracy of the resulting molded product is high and the yield is high.
  • the organopolysiloxane of component (a) is a base component, and an average composition formula (1):
  • R represents the same or different unsubstituted or substituted monovalent hydrocarbon group, and a is a positive number from 1.90 to 2.05)
  • the unsubstituted or substituted monovalent hydrocarbon group represented by R is preferably an unsubstituted or substituted carbon atom having 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms.
  • Monovalent hydrocarbon group for example, alkyl group such as methyl group, ethyl group, propyl group, butyl group, cycloalkyl group such as cyclohexyl group, vinyl group, aryl group, butenyl group, hexenyl group A chloromethyl group, a trifluoro group, etc. in which some or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with halogen atoms, cyan groups, etc.
  • Methyl group, butyl group, phenol group, and trifluoropropyl group are preferable.
  • methyl group is 80 mol% or more, especially 90 mol% or more. Masui.
  • R is an aliphatic unsaturated group, in particular a vinyl group, at least two alkenyl groups such as Ariru groups in one molecule, is good Mashiku 0.001 to 20 Monore 0/0, especially 0.025 to 5 Monore 0/0 that the force element Mashiku including, in particular, (d) when the component of the curing agent is a combination of organohydrogenpolysiloxane and platinum catalyst should contain an aliphatic unsaturated group.
  • A is a positive number of 1.90 to 2.05.
  • the organopolysiloxane of the above average composition formula (1) is preferably linear in nature, but it may be branched after curing so long as the rubber elasticity is not impaired. Or a mixture of two or more of different degrees of polymerization. Those having a molecular chain terminal blocked with a trimethylsilyl group, a dimethylvinylsilyl group, a methyldibulylsilyl group, a tribulylsilyl group, etc. have at least one vinyl group at the molecular terminal end Is preferred.
  • n is an integer of 0 or more.
  • the above-mentioned organopolysiloxane has an average degree of polymerization of 100 to 20,000, particularly 3,000 to 10,000,
  • the reinforcing silica (b) functions as a filler.
  • the specific surface area must be at least 50 m 2 / g, preferably 100 to 400 m, g.
  • silica fumed silica, calcined silica, precipitated silica, etc. may be used alone or in combination of two or more. Fumed silica is preferred, and these silicas may be surface-treated with chain organopolysiloxane, cyclic organopolysiloxane hexamethyldisilazane, dichlorodimethylsilane or the like! /.
  • the silica of (a) component is usually added to 100 parts by mass of the organopolysiloxane of component (a). And 10 to 100 parts by mass, preferably 10 to 50 parts by mass.
  • the isocyanurate compound of component (c) is thought to prevent expansion (die swell) after extrusion by increasing the cohesive strength of the silica filler in the silicone rubber.
  • the isocyanurate compound is a compound represented by the general formulas (2) to (4).
  • the unsubstituted monovalent hydrocarbon group represented by R, R and R in these general formulas As an example
  • alkyl groups such as methyl group, ethyl group and propyl group
  • alkenyl groups such as bur group and allyl group, with allyl group being preferred.
  • the addition amount of the component (c) is 0.1 to 100 parts by mass of the polyorganosiloxane of the component (a) in that good composition handling properties can be obtained while suppressing expansion after extrusion. It is the range of -50 mass parts, Preferably it is 0.5-10 mass parts.
  • any of the catalysts known as those used when silicone rubber is vulcanized at normal pressure or steam can be used.
  • a known organohydrodiene polysiloxane Z platinum-based catalyst or organic peroxide catalyst can be used as a hardener for addition reaction of silicone rubber.
  • organic peroxides are preferred. In either case, it is used in an effective amount.
  • organic peroxide examples include benzoyl peroxide, orthomethyl benzoyl peroxide, paramethyl benzoyl peroxide, dicumyl peroxide, 2,5 dimethyl-2,5 bis (t butyl peroxide) hexane. , Di (2-t-butylperoxyisopropyl) benzene, 2,4-dichlorobenzoyl peroxide, and the like. These can be used alone or in combination of two or more. Of these, organic peroxides that can be vulcanized at normal pressure are preferred, and paramethyl benzoyl peroxide and orthomethyl benzoyl peroxide are particularly preferred. Specifically, the blending amount is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the organopolysiloxane as component (a).
  • a combination of an organohydrogenpolysiloxane and a platinum catalyst is used as a curing agent.
  • platinum-based catalysts include platinum element alone, platinum compounds, platinum complexes, chloroplatinic acid, alcohol compounds of chloroplatinic acid, aldehyde compounds, ether compounds, and complexes with various olefins.
  • the addition amount of the platinum-based catalyst is preferably in the range of 1 to 2, OOOppm as a platinum atom with respect to the organopolysiloxane of component (a).
  • the organohydrogenpolysiloxane may have a linear, branched or cyclic molecular structure, but preferably has a degree of polymerization of 300 or less.
  • H (CH) SiO units dimethylhydrogensiloxane units (H (CH) SiO units) and SiO units
  • the amount of addition of the organohydropolyene polysiloxane is such that the hydrogen atom directly bonded to the silicon atom is compared to the aliphatic unsaturated group (for example, alkenyl group) of the organopolysiloxane of component (a). It is desirable to use 50 to 500 mol%, particularly 70 to 300 mol%.
  • composition of the present invention may contain various additives such as fillers such as quartz powder and diatomaceous earth, colorants, heat resistance improvers, reaction control agents, mold release agents, and hydroxyl group-containing polymerization degree as necessary. It is possible to add a dispersant such as a silicone oil of 100 or less or a silazane compound such as hexamethyldisilazane.
  • a dispersant such as a silicone oil of 100 or less or a silazane compound such as hexamethyldisilazane.
  • silicone rubber composition according to the present invention required components are uniformly mixed using a rubber kneader such as a two-roll mill, a Banbury mixer, or a dough mixer (kneader). It can be obtained by heating at about ⁇ 200 ° C.
  • a rubber kneader such as a two-roll mill, a Banbury mixer, or a dough mixer (kneader). It can be obtained by heating at about ⁇ 200 ° C.
  • the silicone rubber composition obtained as described above can be molded into a use required by extrusion molding.
  • the curing temperature can be appropriately selected depending on the type of the curing agent, the extrusion method, and the desired thickness of the molded body, but can be usually performed at 80 to 500 ° C for 10 seconds to 30 days. .
  • a product produced by extrusion molding of the silicone rubber composition of the present invention is not particularly limited, and examples thereof include an electric wire, an extruded tube, a hose, a knocker, and a seal member.
  • the hose may be a single-layer hose in which the tubular wall constituting the hose is a single layer or a multi-layer hose consisting of a plurality of layers (usually 2 to 5 layers).
  • the single layer or at least one layer of the plurality of layers Is formed of a cured product of the above silicone rubber composition (hereinafter also referred to as a silicone rubber material).
  • the tubular wall body is formed of a plurality of layers, it is preferable to arrange the layer formed of the silicone material of the present invention as the innermost layer or a layer closer to the innermost layer.
  • the outer layer is formed on the outer peripheral surface of the inner layer using the rubber material.
  • the rubber material include silicone rubber, acrylic rubber, ethylene acrylic rubber and the like according to the present invention or other than the present invention.
  • the inner layer is formed using fluororubber on the inner peripheral surface of the outer layer, and the rubber material exemplified above is further used on the outer peripheral surface of the outer layer.
  • the outermost layer may be formed.
  • a fiber reinforcing layer may be provided in any or all of the respective layers.
  • the fiber reinforcing layer those used in ordinary hoses can be used as they are.
  • yarns mainly composed of synthetic fibers such as polyester fibers and aramid fibers can be used by blade knitting, spiral knitting, knit knitting, etc. It is formed.
  • the single-layer hose or the multi-layer hose is preferably used as a hose for automobiles, but can also be used as hoses other than automobiles such as heavy machinery, ships, and tillers. Particularly preferably, it is used as a heat-resistant air hose for the transport vehicle.
  • Example 1 instead of tris [3 (trimethoxysilyl) propyl] isocyanurate, N allyl-N, N bis [3- (trimethoxysilyl) propyl] isocyanurate represented by the following formula (6) was used.
  • a silicone rubber composition was obtained in the same manner as in Example 1 except that the same amount of 5.0 parts by mass was used.
  • a silicone rubber composition was obtained in the same manner as in Example 1, except that tris [3- (trimethoxysilinole) propinole] isocyanurate) was not added.
  • Each composition of Examples 1 and 2 and Comparative Example 1 was extruded into a cylindrical shape from a circular die having a diameter of 2.5 mm using an extruder having a diameter of 60 mm, and then at 250 ° C in a dryer. It was vulcanized by hot air vulcanization for 10 minutes.
  • the cross-sectional area of the cylindrical molded body obtained in each example is S and the cross-sectional area of the die is S.
  • Example 1 instead of tris (3- (trimethoxysilyl) propyl) isocyanurate, N, N-diaryl-N-trimethoxysilylpropylisocyanurate represented by the following formula (7) was replaced with 3 A silicone rubber composition was obtained in the same manner as in Example 1, except for adding part by mass.
  • ⁇ , ⁇ -Gialyl represented by formula (7) A silicone rubber composition was obtained in the same manner as in Example 1 except that 05 parts by mass was added.
  • Example 1 In Example 1, except that 3 parts by mass of triallyl isocyanurate represented by the following formula (8) was added instead of tris (3- (trimethoxysilyl) propyl) isocyanurate, Example 1 In the same manner, a silicone rubber composition was obtained.
  • Example 3 After molding the compositions of Example 3 and Comparative Examples 2 and 3 in the same manner as in Example 1, the die swell was measured. The results are shown in Table 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de caoutchouc de silicone pour moulage par extrusion, comprenant: (a) 100 parties en masse d'organopolysiloxane représenté par la formule de composition moyenne RaSiO(4-a)/2 (dans laquelle les groupes R sont des groupes hydrocarbonés monovalents non substitués ou substitués lesquels peuvent être identiques ou différents les uns des autres, et a est un nombre positif de 1,90 à 2,05); (b) de 10 à 100 parties en masse de silice de renfort ayant une surface spécifique d'au moins 50 m2/g; (c) de 0,1 à 50 parties en masse d'un composé isocyanurate de structure spécifique; et (d) une quantité efficace d'agent du durcissement. En utilisant cette composition, on réduit le gonflement de la matrice au cours du moulage par extrusion et on obtient un moulage avec une grande précision dimensionnelle.
PCT/JP2006/302085 2006-02-07 2006-02-07 Composition de caoutchouc de silicone pour moulage par extrusion WO2007091303A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/JP2006/302085 WO2007091303A1 (fr) 2006-02-07 2006-02-07 Composition de caoutchouc de silicone pour moulage par extrusion

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/JP2006/302085 WO2007091303A1 (fr) 2006-02-07 2006-02-07 Composition de caoutchouc de silicone pour moulage par extrusion

Publications (1)

Publication Number Publication Date
WO2007091303A1 true WO2007091303A1 (fr) 2007-08-16

Family

ID=38344911

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/302085 WO2007091303A1 (fr) 2006-02-07 2006-02-07 Composition de caoutchouc de silicone pour moulage par extrusion

Country Status (1)

Country Link
WO (1) WO2007091303A1 (fr)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54130658A (en) * 1978-03-31 1979-10-11 Nippon Kasei Chem Curable composition
JPH0314838A (ja) * 1989-03-28 1991-01-23 Shin Etsu Chem Co Ltd ゴム組成物用シリコーン変性加硫助剤及びその製造方法
JPH06100779A (ja) * 1992-09-21 1994-04-12 Shin Etsu Chem Co Ltd シリコーンゴム成形物を得る方法
JPH08333456A (ja) * 1995-03-31 1996-12-17 General Electric Co <Ge> 延長された工作時間をもつ一液型アルコキシ硬化性ｒｔｖシリコーンシーラント組成物
JP2000136307A (ja) * 1998-08-24 2000-05-16 Shin Etsu Chem Co Ltd 高電圧電気絶縁体用シリコ―ンゴム組成物、ポリマ―碍子用シ―ル材及びポリマ―碍子用補修材
JP2000351901A (ja) * 1999-06-09 2000-12-19 Shin Etsu Chem Co Ltd 液状付加硬化型シリコーンゴム組成物
JP2005162974A (ja) * 2003-12-05 2005-06-23 Ge Toshiba Silicones Co Ltd 室温硬化性オルガノポリシロキサン組成物
JP2006036987A (ja) * 2004-07-28 2006-02-09 Shin Etsu Chem Co Ltd 押出成型用シリコーンゴム組成物

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54130658A (en) * 1978-03-31 1979-10-11 Nippon Kasei Chem Curable composition
JPH0314838A (ja) * 1989-03-28 1991-01-23 Shin Etsu Chem Co Ltd ゴム組成物用シリコーン変性加硫助剤及びその製造方法
JPH06100779A (ja) * 1992-09-21 1994-04-12 Shin Etsu Chem Co Ltd シリコーンゴム成形物を得る方法
JPH08333456A (ja) * 1995-03-31 1996-12-17 General Electric Co <Ge> 延長された工作時間をもつ一液型アルコキシ硬化性ｒｔｖシリコーンシーラント組成物
JP2000136307A (ja) * 1998-08-24 2000-05-16 Shin Etsu Chem Co Ltd 高電圧電気絶縁体用シリコ―ンゴム組成物、ポリマ―碍子用シ―ル材及びポリマ―碍子用補修材
JP2000351901A (ja) * 1999-06-09 2000-12-19 Shin Etsu Chem Co Ltd 液状付加硬化型シリコーンゴム組成物
JP2005162974A (ja) * 2003-12-05 2005-06-23 Ge Toshiba Silicones Co Ltd 室温硬化性オルガノポリシロキサン組成物
JP2006036987A (ja) * 2004-07-28 2006-02-09 Shin Etsu Chem Co Ltd 押出成型用シリコーンゴム組成物

Similar Documents

Publication Publication Date Title
US4714734A (en) Rubber compounds
JP5090524B2 (ja) 硬化性フルオロシリコーンエラストマー組成物、硬化フルオロシリコーンエラストマーの製造方法、硬化フルオロシリコーンエラストマー、それを含む製品、ホース構造物、および硬化フルオロシリコーンエラストマーの熱安定性または耐熱性を改良する方法
JP5240150B2 (ja) フルオロシリコーンゴム組成物およびその硬化物
JP5108092B2 (ja) 硬化性シリコーンエラストマー組成物、硬化シリコーンエラストマーの製造方法、硬化シリコーンエラストマー、それを含む製品、およびシリコーンエラストマーの熱安定性または耐熱性を改良する方法
MX2008011937A (es) Vejiga para produccion de neumaticos.
JP4704987B2 (ja) 押出成型用シリコ−ンゴム組成物
JPH09286920A (ja) シリコーンゴム中空糸及びその製造方法
JPH0420569A (ja) シリコーンゴム組成物およびその製造方法
JP2013035890A (ja) 耐熱性に優れたシリコーンゴム組成物
JP7256803B2 (ja) フロロシリコーンゴムとシリコーンゴムとの積層体の製造方法
WO2007091303A1 (fr) Composition de caoutchouc de silicone pour moulage par extrusion
JP6389340B2 (ja) 黄酸化鉄を含むフルオロシリコーンエラストマー
JP4421408B2 (ja) 押出成型用シリコーンゴム組成物
JPH10130504A (ja) シリコーンゴム組成物
JP4798375B2 (ja) 押し出し成型用シリコーンゴム組成物及びその製造方法
JPH0480264A (ja) 付加加硫型シリコーンゴム組成物およびその硬化物
JP2010221504A (ja) タイヤ加硫用ブラダー
JP5083564B2 (ja) フロロシリコーンゴム組成物及びフロロシリコーンゴムとジメチルシリコーンゴムとの積層体
JP7434827B2 (ja) シリコーンゴム系硬化性組成物、及びそれを用いた流体駆動型アクチュエータ
JP2011161766A (ja) タイヤ製造用ブラダー
JP2002338809A (ja) オイルブリード性シリコーンゴム組成物
JP7434826B2 (ja) シリコーンゴム系硬化性組成物、及びそれを用いた流体駆動型アクチュエータ
JP7467938B2 (ja) シリコーンゴム系硬化性組成物、及び流体駆動型アクチュエータ
JP7490966B2 (ja) シリコーンゴム系硬化性組成物、及びアクチュエータ
JP2021081029A (ja) シリコーンゴム系硬化性組成物、及びそれを用いた流体駆動型アクチュエータ

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06713228

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP