WO2012172917A1 - Matériau composite thermoplastique et article moulé - Google Patents

Matériau composite thermoplastique et article moulé Download PDF

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Publication number
WO2012172917A1
WO2012172917A1 PCT/JP2012/062727 JP2012062727W WO2012172917A1 WO 2012172917 A1 WO2012172917 A1 WO 2012172917A1 JP 2012062727 W JP2012062727 W JP 2012062727W WO 2012172917 A1 WO2012172917 A1 WO 2012172917A1
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WO
WIPO (PCT)
Prior art keywords
silicon oxide
oxide particles
volume
molded article
composite material
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/JP2012/062727
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English (en)
Inventor
Takahiro Kojima
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.)
Canon Inc
Original Assignee
Canon 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 Canon Inc filed Critical Canon Inc
Publication of WO2012172917A1 publication Critical patent/WO2012172917A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]
    • 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
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers

Definitions

  • the present invention relates to a thermoplastic composite material and a molded article that have a low linear expansion coefficient.
  • organic resin materials have high linear expansion coefficients.
  • components composed of organic resin materials are used in, for example, devices
  • component for a precision optical system it desirably has a linear expansion coefficient of 20 x 10 "6 /° C or less.
  • PTL 1 states that a thermosetting resin such as an epoxy resin or a phenolic resin is mixed with an inorganic filler that has an average particle size of 1 nm or more and 100 nm or less and is composed of, for example, Si0 2 , A1 2 0 3 , or MgO. PTL 1 also states that this mixing allows formation of a resin composition having a linear expansion coefficient of 20 x 10 " 6 /° C or less.
  • thermosetting resin such as an epoxy resin or a phenolic resin
  • an organic resin as in PTL 1
  • contraction of the resin due to curing results in severe deformation and misalignment of the molded article.
  • curing generally requires many hours and hence the forming costs incurred by the curing become high.
  • the present invention provides a thermoplastic composite material and a molded article in which deformation and misalignment of the molded article are less likely to occur, the formability is excellent, and the average linear expansion coefficient is very low.
  • thermoplastic composite material contains a cyclic olefin resin and silicon oxide particles whose surfaces are covered with silanol groups; in the thermoplastic composite material, a content of the silicon oxide particles with respect to a total amount of the olefin resin and the silicon oxide particles is 50% by volume or more and 95% by volume or less; and the molded article has a linear expansion
  • the present invention provides a thermoplastic composite material in which deformation and misalignment of the molded article are less likely to occur, the formability is excellent, and the average linear expansion coefficient is very low.
  • An organic-inorganic composite according to the present invention can be suitably used as low-expansion members and temperature-compensated members that are used for optical fibers and precision optical devices such as lenses and mirrors .
  • Figure 1 is a graph illustrating the relationship between the concentration of silicon oxide particles
  • thermoplastic composite material containing a mixture of a cyclic olefin resin and silicon oxide particles whose surfaces are covered with silanol groups; and a molded article, an internal or external component for a device, and an optical element that have a very low linear expansion coefficient by forming the
  • thermoplastic composite material thermoplastic composite material.
  • a cyclic olefin resin used in the present invention will be described.
  • Specific examples of a cyclic olefin resin used in the present invention include a polymer prepared through ring-opening polymerization of a cyclic unsaturated hydrocarbon, and a polymer prepared by
  • ARTON product name
  • TOPAS product name
  • the molecular weight of the cyclic olefin resin is not particularly limited, the cyclic olefin resin can have a number-average molecular weight of 10,000 or more in view of, for example, the formability and the strength of the resultant molded article.
  • a cyclic olefin resin used in the present invention may be a mixture of a plurality of polymers or a copolymer prepared from a plurality of monomers .
  • the repeating structure of the copolymer may be constituted by one of an alternating structure, a random structure, a block structure, and the like.
  • the polymer chain may be constituted by a combination of structures selected from the foregoing.
  • Such a polymer may contain a
  • a cyclic olefin resin used in the present invention preferably has a glass transition temperature of 80° C or more and 300° C or less, more preferably 100° C or more and 200° C or less.
  • the glass transition temperature is 80° C or less, the resultant molded article may have low heat resistance.
  • the glass transition temperature is more than 300° C, the forming process needs to be performed at a high temperature and hence the process is not easily
  • a cyclic olefin resin used in the present invention may contain an additive.
  • the additive include phosphorus -based thermal stabilizers in the processing;
  • antioxidants such as hindered phenols; light stabilizers such as hindered amines; ultraviolet absorbing agents such as benzotriazoles , triazines, benzophenones , and benzoates; plasticizers such as phosphates, phthalates, citrates, and polyesters; release agents such as silicones; flame
  • retardants such as phosphates and melamines
  • antistatic agents such as fatty ester-based surfactants
  • a cyclic olefin resin used in the present invention may further contain, for example, fine particles other than silicon oxide particles and fillers.
  • the fine particles other than silicon oxide particles include fine particles composed of metal oxides such as aluminum oxide, zinc oxide, chromium oxide, cobalt oxide, zirconium oxide, tungsten oxide, titanium oxide, iron oxide, copper oxide, and manganese oxide, and composite oxides of the foregoing.
  • the fillers include clays such as kaolin and montmorillonite , carbon fibers, glass beads. and glass filler.
  • Such additives may be used alone or in combination.
  • the amount of additives added can be adjusted such that the total amount thereof is 20% by weight or less with respect to the resultant thermoplastic composite material.
  • properties of the thermoplastic composite material are considerably changed from original properties of the cyclic olefin resin and the resultant material may have properties that do not satisfy desired properties in terms of, for example, a lightweight property, strength, and a linear expansion coefficient.
  • thermoplastic composite material according to the present invention be lightweight, a large content of a metal atom that has a higher specific gravity than silicon oxide in the particles is not desirable. For this reason, the weight content of silicon oxide particles with respect to the total metal amount is preferably 50% by weight or more, more preferably 80% by weight or more.
  • the surfaces of the fine particles are treated to enhance the dispersibility of the fine particles.
  • the surfaces of the fine particles need to be covered with silanol groups.
  • the surfaces of silicon oxide particles that are not treated with organic surface- treatment agents are covered with silanol groups and such particles are suitably used.
  • the particle size of the silicon oxide particles is not particularly limited, an excessively large particle size results in loss of the low linear expansion property. This is probably because the surface area of the particles is decreased and the effect of the surface interaction is reduced. In addition, a large particle size causes optical scattering, which causes problems in the case of using a thermoplastic composite material according to the present invention in optical devices. When the particle size is excessively small, the contribution of the particles to rigidity is reduced and loss of the low linear expansion property may be caused. Accordingly, the silicon oxide particles preferably have a volume average primary particle size of 1 nm or more and less than 40 nm, more preferably 5 nm or more and less than 30 nm, still more preferably 5 nm or more and less than 15 nm.
  • the method by which the cyclic olefin resin and the silicon oxide particles are mixed is not particularly limited and may be, for example, a direct mixing method in which the powders are mixed, a solution method employing a medium mixture, or a melting method in which the resin is mixed after being heated to equal to or more than the solution temperature.
  • Inorganic fine particles used in the present invention are silicon oxide particles that are not surface- treated and have many silanol groups on the surfaces thereof and hence have hydrophilicity . Accordingly, it is difficult to mix the silicon oxide particles with a cyclic olefin resin having low hydrophilicity in the same medium and, for example, agglomeration tends to occur.
  • the direct mixing method in which fine particles of a cyclic olefin resin formed by a pulverization treatment and the silicon oxide particles are mixed in the form of powders, or a melting-dispersing method in which the resin being melted is mixed can be employed.
  • the pulverization treatment can be performed by mechanically pulverizing the resin into fine particles with a pulverization machine (for example. Wonder Blender [product name], manufactured by OSAKA CHEMICAL Co., Ltd. ) .
  • the agglomerate of the silicon oxide particles and the agglomerate of the resin fine particles desirably have similar particle sizes.
  • these agglomerates desirably have a small particle size, which can be 100 ⁇ or less.
  • An apparatus with which fine particles of the cyclic olefin resin and the silicon oxide particles are mixed may be a publicly known powder-mixing apparatus for mixing powders.
  • suitable examples of the powder-mixing apparatus include stirring apparatuses such as a mortar, a handy mixer, and a laboratory mixer; an air blender, a container blender, and a gravity blender.
  • the resultant mixture may be mixed with a small amount of an organic solvent to enhance adhesion between the fine particles of the cyclic olefin resin; the organic solvent may be then removed by a drying treatment under a reduced pressure, and the resin may be subsequently melted.
  • organic solvent include aliphatic saturated hydrocarbons such as pentane and hexane and aromatic hydrocarbons such as toluene, xylene, and tetralin.
  • the cyclic olefin resin and the silicon oxide particles are mixed such that the content of the silicon oxide particles with respect to the total amount of the cyclic olefin resin and the silicon oxide particles is 50% by volume or more and 95% by volume or less, preferably 70% by volume or more and 95% by volume or less.
  • the content of the silicon oxide particles is 50% by volume or more, the linear expansion coefficient of the molded article becomes very low.
  • the content can be 95% by volume or less.
  • the linear expansion coefficient can be made 0/° C or less.
  • the content of the silicon oxide particles denotes a value determined in the following manner: the composite material is heated to 800° C under a nitrogen atmosphere with a thermogravimetric analysis (TGA) system, and the amount of the residue in percent by weight is measured; and this amount is converted into a value in terms of volume .
  • TGA thermogravimetric analysis
  • the thus-prepared material containing the mixture of a cyclic olefin resin and silicon oxide particles can.be formed into a desired shape by a publicly known method such as injection molding or heat -press forming in which the material is pressed under heating at a temperature equal to or more than the glass transition temperature of the cyclic olefin resin.
  • a publicly known method such as injection molding or heat -press forming in which the material is pressed under heating at a temperature equal to or more than the glass transition temperature of the cyclic olefin resin.
  • the temperature at the time of the forming can be in the range of 150° C to 300° C.
  • the forming pressure is not particularly limited, but it can be 50 MPa or more to achieve the transfer of the shape.
  • the material at the time of the forming need not be uniform and may be non-uniform as long as the content of the silicon oxide particles is locally 50% by volume or more.
  • a molded article in which the content of the silicon oxide particles is locally 50% by volume or more can be obtained by forming a material having two or more
  • the molded article may be produced in various shapes including, a sphere, a rod, a plate, a block, a tube, a weight, a fiber, a grid, a film, and a sheet; and can be used as various internal or external components for devices and optical elements.
  • a molded article according to the present invention preferably has a linear expansion coefficient of, in the range of 20° C to 60° C, -140 x 10 "5 / 0 C or more and 30 x 10 "5 / 0 C or less, more preferably -140 x 10 "6 /° C or more and 20 x 10 " 6 /° C or less, still more preferably -120 x 10 "6 /° C or more and 0/° C or less .
  • a mold for press forming having a diameter of 15 mm was charged with 0.2 g of the mixture of the cyclic olefin resin and the silicon oxide particles.
  • the mold was placed in a small heat-pressing machine (AH-2003 [product name], manufactured by AS ONE Corporation) and heated to 200° C. After temperatures at the upper and lower surfaces of the small heat-pressing machine reached 200° C, the mold was pressed under a load of 200 MPa; while the mold was air- cooled to 100° C, the load was allowed to decrease naturally; at 100° C, the load was completely removed and the composite material was released from the mold to provide a coin-shaped molded article.
  • AH-2003 product name
  • Example 2 Conditions as in Example 1 to provide a coin-shaped molded article .
  • Example 2 Conditions as in Example 1 to provide a coin-shaped molded article .
  • Example 2 Conditions as in Example 1 to provide a coin-shaped molded article.
  • a mold for press forming having a diameter of 15 mm was charged with 0.2 g of particles of a cyclic olefin resin ( ZEONEX E48R [product name], manufactured by ZEON
  • the mold was placed in a small heat-pressing machine (AH-2003 [product name], manufactured by AS ONE Corporation) and heated to 200° C. After temperatures at the upper and lower surfaces of the small heat -pressing machine reached 200° C, the mold was pressed under a load of 200 MPa; while the mold was air-cooled to 100° C, the load was allowed to decrease naturally; at 100° C, the load was completely- removed and the material was released from the mold to provide a coin- shaped molded article.
  • AH-2003 product name
  • Example 2 Conditions as in Example 1 to provide a coin-shaped molded article .
  • Example 2 conditions as in Example 1 to provide a coin- shaped molded article .
  • Example 2 conditions as in Example 1 to provide a coin- shaped formed product .
  • a mold for press forming having a diameter of 15 mm was charged with 0.2 g of silicon oxide particles (AEROSIL 300 [product name], volume average primary particle size: 7 nm, manufactured by NIPPON AEROSIL CO., LTD.).
  • the mold was placed in a small heat-pressing machine (AH-2003 [product name], manufactured by AS ONE Corporation) and heated to 200° C. After temperatures at the upper and lower surfaces of the small heat-pressing machine reached 200° C, the mold was pressed under a load of 200 MPa; while the mold was air- cooled to 100° C, the load was allowed to decrease naturally; at 100° C, the load was completely removed and the material was released from the mold to provide a molded article.
  • AEROSIL 300 product name
  • volume average primary particle size 7 nm
  • This molded article was brittle and obtained in the form of broken pieces .
  • Particles of a cyclic olefin resin (ZEONEX E48R [product name] , manufactured by ZEON CORPORATION) and silicon oxide particles (AEROSIL 200 [product name], volume average primary particle size: 12 nm, manufactured by NIPPON AEROSIL CO., LTD.) were mixed such that the silicon oxide concentration became 61% by volume.
  • the resultant mixture was stirred so as to become uniform.
  • the resultant material was subjected to heat -press forming under the same
  • Example 2 conditions as in Example 1 to provide a coin- shaped molded article .
  • Example 2 Conditions as in Example 1 to provide a coin-shaped molded article .
  • This molded article had a particle-concentration gradient in which the concentration of the silicon oxide particles decreased from the lower layer to the upper layer.
  • NIPPON AEROSIL CO., LTD. were placed as a lower layer.
  • 0.24 g of particles of a cyclic olefin resin (ZEONEX E48R [product name], manufactured by ZEON CORPORATION) were placed as a layer without being mixed with the silicon oxide particles.
  • 0.01 g of silicon oxide particles (AEROSIL 300 [product name], volume average primary particle size: 7 nm, manufactured by NIPPON AEROSIL CO., LTD.) were placed as a layer.
  • the mold was placed in a small heat-pressing machine (AH-2003 [product name], manufactured by AS ONE Corporation) and heated to 200° C.
  • This molded article had a particle-concentration gradient in which the concentration of the silicon oxide particles was the highest in the lower layer and decreased to the middle layer.
  • NIPPON AEROSIL CO., LTD. were placed as a lower layer.
  • 0.24 g of particles of a cyclic olefin resin (ZEONEX E48R [product name], manufactured by ZEON CORPORATION) were placed as a layer without being mixed with the silicon oxide particles.
  • 0.02 g of silicon oxide particles (AEROSIL 300 [product name] , volume average primary particle size: 7 nm, manufactured by NIPPON AEROSIL CO., LTD.) were placed as a layer.
  • the mold was placed in a small heat-pressing machine (AH-2003 [product name], manufactured by AS ONE Corporation) and heated to 200° C.
  • the mold was pressed under a load of 200 MPa; while the mold was air- cooled to 100° C, the load was allowed to decrease naturally; at 100° C, the load was completely removed and the composite material was released from the mold to provide a coin-shaped molded article.
  • This molded article had a particle-concentration gradient in which the concentration of the silicon oxide particles was the highest in the upper and lower layers and decreased to the middle layer.
  • TMA TMA Q400 [product name], manufactured by TA Instruments
  • TMA Q500 TGA Q500 [product name], manufactured by TA Instruments
  • the results of Examples 3 to 8 indicate decrease in the linear expansion coefficient due to various combinations of cyclic olefin resins and silicon oxide particles, though the decrease varies depending on the type of the cyclic olefin resins and the size of the silicon oxide particles.
  • the results of Examples 9 to 11 indicate that the material at the time of the forming need not be uniform; and a considerable decrease in the linear expansion coefficient is achieved even when the material at the time of the forming is non-uniform as long as the content of the silicon oxide particles is locally high.
  • thermoplastic composite material and a molded article according to the present invention have a very low linear expansion coefficient of -135 x 10 "6 /° C at the minimum at least in a temperature range of 20* C to 60° C, and hence are suitably used for low-expansion members and temperature compensated members that are used for optical fibers and precision optical devices such as lenses and mirrors.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention a pour objet un article moulé produit par la formation d'un matériau composite thermoplastique, le matériau composite thermoplastique contenant une résine oléfinique cyclique et des particules d'oxyde de silicium dont les surfaces sont recouvertes de groupes silanol ; dans le matériau composite thermoplastique, une teneur des particules d'oxyde de silicium par rapport à une quantité totale de la résine oléfinique et des particules d'oxyde de silicium étant de 50 % en volume ou plus et de 95 % en volume ou moins ; et l'article moulé possédant un coefficient d'expansion linéaire de -140 X 10-6/°C ou plus et de 30 X 10-6/°C ou moins dans une gamme allant de 20 °C à 60 °C.
PCT/JP2012/062727 2011-06-15 2012-05-11 Matériau composite thermoplastique et article moulé Ceased WO2012172917A1 (fr)

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JP2011-133484 2011-06-15
JP2011133484A JP5836657B2 (ja) 2011-06-15 2011-06-15 成形品

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WO2012172917A1 true WO2012172917A1 (fr) 2012-12-20

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WO2020066529A1 (fr) * 2018-09-27 2020-04-02 三井化学株式会社 Composition de résine à base d'oléfine cyclique, corps moulé et composant optique

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WO1994020575A1 (fr) * 1993-03-01 1994-09-15 Nippon Zeon Co., Ltd. Composition de resine et moulage produit a partir de cette composition
JP2000230102A (ja) * 1999-02-12 2000-08-22 Cosmo Research Inst 低誘電性樹脂組成物
WO2003068842A1 (fr) * 2002-02-15 2003-08-21 Sekisui Chemical Co., Ltd. Composition polymerisable et composition de resine durcie
JP2007077235A (ja) * 2005-09-13 2007-03-29 Konica Minolta Opto Inc 熱可塑性樹脂組成物及び光学素子
JP2007088172A (ja) * 2005-09-21 2007-04-05 Sumitomo Bakelite Co Ltd 樹脂組成物、積層体、配線板および配線板の製造方法
JP2007161980A (ja) * 2005-11-18 2007-06-28 Konica Minolta Opto Inc マスターバッチ、光学素子、マスターバッチの製造方法及び光学素子の製造方法
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JP2008001895A (ja) * 2006-05-25 2008-01-10 Konica Minolta Opto Inc 光学用樹脂材料及び光学素子
WO2009054255A1 (fr) * 2007-10-24 2009-04-30 Konica Minolta Opto, Inc. Matériau à base de résine optique et éléments optiques fabriqués au moyen de ladite résine

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JP2013001780A (ja) 2013-01-07

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