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WO2009048162A1 - Composition de caoutchouc de silicone pour matrice modèle et matrice modèle - Google Patents

Composition de caoutchouc de silicone pour matrice modèle et matrice modèle Download PDF

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Publication number
WO2009048162A1
WO2009048162A1 PCT/JP2008/068802 JP2008068802W WO2009048162A1 WO 2009048162 A1 WO2009048162 A1 WO 2009048162A1 JP 2008068802 W JP2008068802 W JP 2008068802W WO 2009048162 A1 WO2009048162 A1 WO 2009048162A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicone rubber
silicon atom
weight
rubber composition
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2008/068802
Other languages
English (en)
Japanese (ja)
Inventor
Hideo Takahashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Momentive Performance Materials Japan LLC
Momentive Performance Materials Inc
Original Assignee
Momentive Performance Materials Japan LLC
Momentive Performance Materials Inc
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 Momentive Performance Materials Japan LLC, Momentive Performance Materials Inc filed Critical Momentive Performance Materials Japan LLC
Priority to CN200880110742.2A priority Critical patent/CN101821340A/zh
Publication of WO2009048162A1 publication Critical patent/WO2009048162A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/60—Releasing, lubricating or separating agents
    • B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
    • B29C33/64—Silicone
    • 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
    • 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
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

  • the present invention relates to a silicone rubber composition excellent in releasability used as an inversion matrix for mold making and a mold taking mold obtained therefrom.
  • Silicone rubber molds used as molds for mold reversal require mold release durability.
  • a hydrophobized reinforcing siliceous filler using a silazane compound or a compound having an additional functional group is used in combination.
  • Techniques such as combining those treated with strong hydrophilic silica have been proposed. According to these methods, although improvement in mold release durability of silicone rubber molds is recognized, mold release for resins such as epoxy resins having high physical properties and urethane resins, which are the mainstream of current cast resin materials. Sex is not enough.
  • JP-A 7-1 1 8 5 3 4 proposes to add a non-crosslinkable silicone polymer having a chain length longer than the base polymer to be bridged for the purpose of further improving the releasability.
  • the organopolysiloxane base polymer forming the silicone rubber mold has a refractive index difference with this base polymer of not less than 0.01, It has been proposed to add a non-crosslinkable oily substance with a melting point of less than 100 ° C, which has greatly improved mold release properties.
  • the present invention has been made in view of the above circumstances, and is a silicone rubber composition for a mold master that is excellent in releasability, has little fouling of a duplicate, and has excellent defoaming properties of a material before curing.
  • the purpose is to provide.
  • the present inventors have a liquid silicone rubber composition having an alkoxy group having 1 to 3 carbon atoms bonded to a silicon atom at the molecular end, and an average polymerization. Silicone rubber composition for mold-making mold with excellent releasability, less fouling of replicated products, and excellent defoaming property of the material before curing. The inventors have found that a product can be obtained and have completed the present invention.
  • (A) component is 1 to 200 ppm by weight in terms of platinum atom
  • the alkenyl group-containing polyorganosiloxane ( ⁇ ) used in the present invention has two or more alkenyl groups bonded to a silicon atom in one molecule, and the siloxane skeleton is either linear or branched. It may also be a mixture thereof.
  • Examples of the alkenyl group include vinyl, allyl, 1-butenyl, and 1-hexenyl. A vinyl group is preferable because of ease of synthesis.
  • Substituents bonded to a key atom other than an alkenyl group examples thereof include: an aralkyl group such as methyl, ethyl, propyl, butyl, hexyl and dodecyl; an aryl group such as phenyl; an aralkyl group such as 2-phenylethynyl and 2-phenylpropyl; chloromethyl; 3, 3, 3-trifluoro Examples thereof include substituted carbon hydrogen groups such as isopropyl. Of these, the methyl group is most preferred because it is easily synthesized.
  • component (A) is a base polymer for addition reaction type curable polyorganosiloxane, and 0.01% by mole or more of all organic groups bonded to the silicon atom are alkenyl groups. is required.
  • Its viscosity at 25 ° C is not particularly limited, but it is more preferably 50 centipoise or more, especially for the purpose of rubber elastic bodies with mechanical properties, and it is necessary to have fluidity before curing. Is preferably less than 1 million centipoise.
  • the polyorganohydrogensiloxane of component (B) used in the present invention is cross-linked by addition reaction with (A) component to make the composition into a rubber elastic body or gel, so 3 per molecule.
  • each key atom is an essential component having one or less hydrogen atoms bonded to one key atom.
  • the organic group bonded to the silicon atom other than the hydrogen atom is a group selected from the group consisting of an alkyl group, a phenyl group, and a 3,3,3-trifluoropropyl group. From the viewpoint of easy synthesis, A methyl group is most preferred.
  • the siloxane skeleton may be linear, branched or cyclic.
  • the polyorganohydrogen siloxane of component (B) has 0.4 to 4 hydrogen atoms bonded to the silicon atom for each alkenyl group bonded to the silicon atom in component (A). It is preferable to use in such an amount.
  • the platinum component (C) used in the present invention is a hydrosilylation catalyst.
  • a Lamorrow catalyst platinum-octanol complex, US-A
  • Ashby's catalyst a platinum-vinyl group-containing cyclic siloxane complex, US- A 4288345.
  • An example is a catalyst of KARLSTEST (a platinum-vinyl group-containing disiloxane complex, US-A 3814730).
  • the blending amount of the component (C) in the present invention is a catalyst amount, and specifically, it is used in the range of 1 to 200 ppm by weight in terms of platinum atoms with respect to the component (A).
  • the (D) component polydimethylsiloxane used in the present invention is a characteristic component of the present invention, and imparts excellent release properties to the silicone rubber mold and defoaming properties of the material before curing.
  • the polydimethylsiloxane of component (D) is substantially linear and has at least one alkoxy group having 1 to 3 carbon atoms at both ends of the molecule.
  • the alkoxy group include methyl, ethyl, n-propyl and isopropyl, which may be the same or different, but are preferably the same from the viewpoint of easy synthesis.
  • the average degree of polymerization that is, the average number of key atoms is in the range of 5 to 500, preferably in the range of 10 to 100. If the degree of polymerization is less than 5, the terminal alkoxy group will be hydrolyzed, and it will volatilize during the curing conditions and during use, so that the effects of mold release durability and defoaming will not be obtained. On the other hand, when the degree of polymerization exceeds 500, it is necessary to add a large amount of component (D), and workability is lowered.
  • Siloxane is ring-opened equilibrated; the terminal silanol group of ⁇ , ⁇ -dihydroxypolydimethylsiloxane is alkoxylated with the corresponding alcohol; the terminal silanol group of ⁇ , ⁇ -dihydroxypolydimethylsiloxane is Synthesis using various methods, such as reacting the corresponding dimethyldianoloxysilane, methyltrialkoxysilane, or tetraalkoxysilane to obtain polydimethylsiloxane with 1 to 3 arbitrary alkoxy groups bonded to each terminal it can.
  • Component (D) is added in an amount of 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of polyorganosiloxane of component (D). 0. If less than 1 part by weight, the effect of sustaining mold release durability and defoaming cannot be obtained, exceeding 10 parts by weight As a result, the physical strength of the silicone rubber decreases.
  • the composition of the present invention preferably contains a scavenging filler.
  • Such fillers may be those conventionally used for silicone rubber, and examples thereof include powdered silica and carbon black.
  • fine powder silica include fumed silica and precipitated silica.
  • the specific surface area is 50 m 2 Z g or more, preferably rather is 100 to 400 m 2 Z g or more of finely divided silica are preferred. If it is less than 50 m 2 / g, sufficient reinforcement cannot be obtained.
  • the amount of these fillers used is within the range of 10 to L00 parts by weight per 100 parts by weight of component (A), and if necessary, surface treated with organosilane, organosilazane, etc. May be.
  • the composition of the present invention has good storage stability at room temperature and maintains an appropriate curing time.
  • methylvinylpolysiloxane, acetylene alcohols, benzotriazole, triphenyl phosphite It is desirable to add reaction inhibitors such as organic phosphorus compounds, various triazine compounds, and organic sulfur compounds.
  • the addition amount of this reaction inhibitor is preferably in the range of 1 to 2000 mol per 1 mol of platinum atom in the platinum-based catalyst, although it depends on the inhibitory ability of various inhibitors, and the curing rate and storage of the resulting composition From the viewpoint of stability, a ratio of 10 to 1000 moles is preferable.
  • suitable pigments, dyes, adhesion aids, fungicides, heat resistance improvers, flame retardants or antioxidants can be added.
  • a compound base was produced by mixing (A) component and reinforcing silica in a known mixer such as a single mixer and a loss mixer, followed by heat treatment and uniform mixing. Thereafter, if necessary, the components (B), (C), and (D) can be easily produced by uniformly mixing them with a mixer.
  • a filler surface treatment agent such as organosilazane can be blended when the component (A) and the reinforcing silica are mixed in the production of the base compound.
  • the mold master of the present invention can be obtained by molding and curing the silicone rubber composition with a predetermined mold according to a conventional method.
  • the curing condition of the silicone rubber composition is generally performed around the temperature at which the resin is cured for the purpose of alleviating the shrinkage at the time of curing of the resin used for the replicated product. Usually, it can be carried out at a temperature of 40 to 60 ° C. for about 2 to 20 hours.
  • This mold master can be used effectively for the molding of resin moldings such as epoxy resins and urethane resins.
  • Epoxy resin-102 (manufactured by Nippon Polyurethane Co., Ltd.) is cast into the above mold, cured at 70 ° CX for 2 hours, and the following criteria are used to remove the resulting epoxy resin from the mold: Judged by.
  • the turbidity of the transparent epoxy resin taken out from the matrix was evaluated by visual observation.
  • the turbidity of the concave matrix was evaluated by visual observation.
  • Silicone rubber composition for mold master immediately after stirring for 10 minutes, 20 ml was weighed into a 300 ml 1 disc and immediately deaerated with a vacuum pump. Then, the volume of the most expanded foam was measured, and the magnification with respect to the initial volume was obtained.
  • the cured product obtained from the composition according to the method of the present invention has a good releasability from the well-cast resin, and the material before curing has a good defatting property. Foam was observed
  • Addition-reaction type liquid silicone rubber composition 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Terminal ethoxy group polydimethylpolysiloxane, viscosity 50 c St

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

L'invention concerne une composition de caoutchouc de silicone pour une matrice modèle qui présente une excellente propriété de démoulage, tache moins les produits répliqués et présente d'excellentes propriétés de démoussage d'un matériau avant le durcissement. L'invention concerne plus particulièrement une composition de caoutchouc de silicone pour une matrice modèle qui contient (A) un polyorganosiloxane qui comporte 2 groupes alcényles ou plus reliés à un atome de silicium par molécule et qui présente une viscosité à 25 °C de 500 000 à 1 000 000 centipoises (100 parties par poids) ; (B) un polyorganohydrogénosiloxane qui comporte 3 atomes d'hydrogène ou plus reliés à un atome de silicium par molécule (une quantité telle que le nombre d'atomes d'hydrogène reliés à un atome de silicium par groupe alcényle relié à un atome de silicium dans le composant (A) est de 0,4 à 4) ; (C) un composé de platine (1 à 200 ppm par poids en termes d'atome de platine par rapport au composant (A)) ; et (D) un polydiméthylsiloxane qui contient un groupe alcoxy avec 1 à 3 atomes de carbone reliés à un atome de silicium à son extrémité moléculaire et un degré moyen de polymérisation de 5 à 500 (0,1 à 10 parties en poids).
PCT/JP2008/068802 2007-10-09 2008-10-09 Composition de caoutchouc de silicone pour matrice modèle et matrice modèle Ceased WO2009048162A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200880110742.2A CN101821340A (zh) 2007-10-09 2008-10-09 印模母模用硅酮橡胶组合物以及印模母模

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2007-263005 2007-10-09
JP2007263005A JP5319905B2 (ja) 2007-10-09 2007-10-09 型取り母型用シリコーンゴム組成物及び型取り母型

Publications (1)

Publication Number Publication Date
WO2009048162A1 true WO2009048162A1 (fr) 2009-04-16

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PCT/JP2008/068802 Ceased WO2009048162A1 (fr) 2007-10-09 2008-10-09 Composition de caoutchouc de silicone pour matrice modèle et matrice modèle

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JP (1) JP5319905B2 (fr)
CN (2) CN101821340A (fr)
WO (1) WO2009048162A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4835880B2 (ja) * 2009-03-12 2011-12-14 信越化学工業株式会社 液状硬化性フロロシリコーン組成物の製造方法
CN102490294B (zh) * 2011-11-14 2014-02-12 厦门市豪尔新材料有限公司 一种能多次脱模的离型剂及其制备方法
TWI633157B (zh) * 2013-10-18 2018-08-21 Shin-Etsu Chemical Co., Ltd. 紫外線硬化性有機聚矽氧烷組成物及版材之製造方法
JP6634988B2 (ja) * 2016-09-20 2020-01-22 信越化学工業株式会社 透明液状シリコーンゴム組成物
CN108424652B (zh) * 2018-04-16 2020-10-02 吉林大学 一种加成型硅胶及其制备方法与应用
JP7114510B2 (ja) * 2019-03-06 2022-08-08 信越化学工業株式会社 硬化性有機ケイ素樹脂組成物

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04161459A (ja) * 1990-10-26 1992-06-04 Shin Etsu Chem Co Ltd オルガノポリシロキサン組成物
JPH04236265A (ja) * 1991-01-18 1992-08-25 Shin Etsu Chem Co Ltd 離型性シリコーンゴム組成物及びその硬化物
JPH07118534A (ja) * 1993-10-20 1995-05-09 Shin Etsu Chem Co Ltd 型取り母型用オルガノポリシロキサン組成物の製造方法
JP2000289034A (ja) * 1999-04-05 2000-10-17 Shin Etsu Chem Co Ltd 型取り母型用シリコーンゴム組成物及び型取り母型
JP2002179921A (ja) * 2000-12-18 2002-06-26 Shin Etsu Chem Co Ltd 型取り用オルガノポリシロキサン組成物
JP2006022284A (ja) * 2004-07-09 2006-01-26 Shin Etsu Chem Co Ltd 付加反応硬化型シリコーンゴム組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04161459A (ja) * 1990-10-26 1992-06-04 Shin Etsu Chem Co Ltd オルガノポリシロキサン組成物
JPH04236265A (ja) * 1991-01-18 1992-08-25 Shin Etsu Chem Co Ltd 離型性シリコーンゴム組成物及びその硬化物
JPH07118534A (ja) * 1993-10-20 1995-05-09 Shin Etsu Chem Co Ltd 型取り母型用オルガノポリシロキサン組成物の製造方法
JP2000289034A (ja) * 1999-04-05 2000-10-17 Shin Etsu Chem Co Ltd 型取り母型用シリコーンゴム組成物及び型取り母型
JP2002179921A (ja) * 2000-12-18 2002-06-26 Shin Etsu Chem Co Ltd 型取り用オルガノポリシロキサン組成物
JP2006022284A (ja) * 2004-07-09 2006-01-26 Shin Etsu Chem Co Ltd 付加反応硬化型シリコーンゴム組成物

Also Published As

Publication number Publication date
CN101821340A (zh) 2010-09-01
CN103951982A (zh) 2014-07-30
JP2009091449A (ja) 2009-04-30
JP5319905B2 (ja) 2013-10-16

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