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WO2012172917A1 - Thermoplastic composite material and molded article - Google Patents

Thermoplastic composite material and molded article 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
Authority
WO
WIPO (PCT)
Prior art keywords
silicon oxide
oxide particles
volume
molded article
composite material
Prior art date
Application number
PCT/JP2012/062727
Other languages
French (fr)
Inventor
Takahiro Kojima
Original Assignee
Canon Kabushiki Kaisha
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 Kabushiki Kaisha filed Critical Canon Kabushiki Kaisha
Publication of WO2012172917A1 publication Critical patent/WO2012172917A1/en

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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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Abstract

Provided is a molded article produced by forming a thermoplastic composite material, wherein the 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 coefficient of -140 X10-6/ °C or more and 30 X 10-6/ °C or less in a range of 20 °C to 60 °C.

Description

DESCRIPTION
THERMOPLASTIC COMPOSITE MATERIAL AND MOLDED ARTICLE
Technical Field
[0001] The present invention relates to a thermoplastic composite material and a molded article that have a low linear expansion coefficient.
Background Art
[0002] In general, many substances expand upon heating. In particular, organic resin materials have high linear expansion coefficients. When components composed of organic resin materials are used in, for example, devices
represented by precision optical systems, large dimensional variations of the components in response to temperature change can cause misalignment of the optical systems. When an organic resin material alone is used to produce a
component for a precision optical system, it desirably has a linear expansion coefficient of 20 x 10"6/° C or less.
[0003] To meet such a condition, there is a method for producing an organic-inorganic composite material in which an inorganic material such as inorganic fine particles is added to an organic resin material to decrease the linear expansion coefficient of the resultant composite material.
[0004] 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, Si02, A1203, 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.
Citation List
Patent Literature
[ 0005 ] PTL 1 Japanese Patent Laid-Open No. 2006-291197
Summary of Invention
Technical Problem
[ 0006 ] However, when a thermosetting resin such as an epoxy resin or a phenolic resin is used as an organic resin as in PTL 1, contraction of the resin due to curing results in severe deformation and misalignment of the molded article. In addition, curing generally requires many hours and hence the forming costs incurred by the curing become high.
[ 0007 ] Accordingly, 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.
Solution to Problem
[ 0008 ] Provided is a molded article produced by forming a thermoplastic composite material, wherein the 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
coefficient of -140 x 10"6/° C or more and 30 x 10"6/° C or less in a range of 20° C to 60° C.
Advantageous Effects of Invention
[0009] 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.
[0010] 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 .
Brief Description of Drawings
[0011] Figure 1 is a graph illustrating the relationship between the concentration of silicon oxide particles
(percent by volume) and the linear expansion coefficient of the molded article. Description of Embodiments
[0012] Hereinafter, embodiments according to the present invention will be described in detail. The present
invention provides a 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.
Cyclic olefin resin
[0013] 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
copolymerizing a cyclic unsaturated hydrocarbon and an - unsaturated hydrocarbon and subjecting the resultant
copolymer to hydrogen reduction (for example, ZEONEX
[product name], manufactured by ZEON CORPORATION; APEL
[product name], manufactured by Mitsui Chemicals, Inc.;
ARTON [product name] , manufactured by JSR Corporation; and TOPAS [product name], manufactured by Topas Advanced
Polymers GmbH) . Although 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.
[0014] 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 . When such a
copolymer is used, the manner in which the repeating units constitute the copolymer is not particularly limited. The repeating structure of the copolymer may be constituted by one of an alternating structure, a random structure, a block structure, and the like. Alternatively, the polymer chain may be constituted by a combination of structures selected from the foregoing. Such a polymer may contain a
crosslinking structure.
[0015] 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. When the glass transition temperature is 80° C or less, the resultant molded article may have low heat resistance. When 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
performed and problems such as tinting of a resin
composition may also be caused. [0016] A cyclic olefin resin used in the present invention may contain an additive. Examples of the additive include phosphorus -based thermal stabilizers in the processing;
thermal stabilizers in the processing of hydroxylamines;
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; organic coloring agents; and impact modifiers.
[0017] To further improve optical characteristics such as a refractive index and an absorption wavelength range and physical characteristics such as a linear expansion
coefficient, a cyclic olefin resin used in the present invention may further contain, for example, fine particles other than silicon oxide particles and fillers. Examples of 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. Examples of the fillers include clays such as kaolin and montmorillonite , carbon fibers, glass beads. and glass filler.
[0018] 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. When the amount of additives added is more than 20% by weight, 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.
Silicon oxide particles
[0019] Silicon oxide particles used in the present
invention contain silicon oxide as a main component and may further contain another metal. However, to make a
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.
[0020] In general, when fine particles are added to an organic resin material, the surfaces of the fine particles are treated to enhance the dispersibility of the fine particles. However, to considerably decrease the linear expansion coefficient, 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.
[0021] It is well known that the linear expansion
coefficient of an organic resin material is decreased by adding silicon oxide particles to the material. The
inventor of the present invention has found that the amount of decrease in the linear expansion coefficient in a
particle high-concentration range varies depending on the type of the surface modification group of silicon oxide particles. This is probably caused by surface interaction between an organic resin material and silicon oxide
particles or between silicon oxide particles, or by
difference in the mixing state of silicon oxide particles depending on the type of the surface modification group.
[0022] Although 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.
Mixing of cyclic olefin resin and silicon oxide particles
[0023] 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.
[0024] 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. Thus, 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. ) .
[0025] In the direct mixing method in which powders are mixed, to suppress sedimentation of the silicon oxide particles having a higher specific gravity than the resin, the agglomerate of the silicon oxide particles and the agglomerate of the resin fine particles desirably have similar particle sizes. To achieve uniformity of the material, these agglomerates desirably have a small particle size, which can be 100 μπι or less.
[0026] 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.
[0027] After fine particles of the cyclic olefin resin and the silicon oxide particles are mixed, 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. Examples of the organic solvent include aliphatic saturated hydrocarbons such as pentane and hexane and aromatic hydrocarbons such as toluene, xylene, and tetralin.
[0028] In the present invention, 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. When the content of the silicon oxide particles is 50% by volume or more, the linear expansion coefficient of the molded article becomes very low. To decrease the linear expansion coefficient, it is effective to increase the content of the silicon oxide particles; however, as this content increases , the material becomes brittle and the formability is degraded; in addition, when the content is beyond a certain value, the effect of decreasing the linear expansion coefficient is not provided. Accordingly, the content can be 95% by volume or less. When the content of the silicon oxide particles is made 70% by volume or more and 95% by volume or less, the linear expansion coefficient can be made 0/° C or less.
[0029] Even in the cases where the content of the silicon oxide particles is the same, the linear expansion
coefficient may be different depending on the dispersion state of the silicon oxide particles. In the present invention, 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 .
Forming
[0030] 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. When the temperature at the time of the forming is excessively low, the intended shape is not formed; when the temperature is excessively high, thermal decomposition proceeds and the molded article may turn yellow or have a high linear expansion coefficient.
Accordingly, 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.
[0031] 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. For example, 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
different concentrations of the silicon oxide particles, or by stacking a layer of the particles of the cyclic olefin resin and a layer of the silicon oxide particles without mixing these layers and forming the stacked layers.
[0032] 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.
[0033] 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 .
Examples
[0034] Hereinafter, the present invention will be
described in further detail with reference to Examples and Comparative examples. However, the present invention is not restricted to these Examples at all.
Example 1
[0035] Particles of a cyclic olefin resin (ZEONEX E48R
[product name], manufactured by ZEON CORPORATION) and silicon oxide particles (AEROSIL 300 [product name], volume average primary particle size: 7 nm, manufactured by NIPPON AEROSIL CO., LTD.) were mixed such that the silicon oxide concentration became 53% by volume. The resultant mixture was stirred so as to become uniform.
[0036] 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.
Example 2
[0037] Particles of a cyclic olefin resin (ZEONEX E48R [product name] , manufactured by ZEON CORPORATION) and silicon oxide particles (AEROSIL 300 [product name], volume average primary particle size: 7 nm, manufactured by NIPPON AEROSIL CO., LTD.) were mixed such that the silicon oxide concentration became 56% by volume. The resultant mixture was stirred so as to become uniform. The resultant material was subjected to heat-press forming under the same
conditions as in Example 1 to provide a coin-shaped molded article .
Example 3
[0038] Particles of a cyclic olefin resin (ZEONEX E48R [product name], manufactured by ZEON CORPORATION) and silicon oxide particles (AEROSIL 300 [product name] , volume average primary particle size: 7 nm, manufactured by NIPPON AEROSIL CO., LTD.) were mixed such that the silicon oxide concentration became 77% by volume. The resultant mixture was stirred so as to become uniform. The resultant material was subjected to heat -press forming under the same
conditions as in Example 1 to provide a coin-shaped molded article .
Example 4
[0039] Particles of a cyclic olefin resin (ZEONEX E48R [product name], manufactured by ZEON CORPORATION) and silicon oxide particles (AEROSIL 300 [product name] , volume average primary particle size: 7 nm, manufactured by NIPPON AEROSIL CO., LTD.) were mixed such that the silicon oxide concentration became 93% by volume. The resultant mixture was stirred so as to become uniform. The resultant material was subjected to heat-press forming under the same
conditions as in Example 1 to provide a coin-shaped molded article.
Comparative example 1
[0040] 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
CORPORATION) . 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.
Comparative example 2
[0041] Particles of a cyclic olefin resin ( ZEONEX E48R [product name] , manufactured by ZEON CORPORATION) and silicon oxide particles (AEROSIL 300 [product name] , volume average primary particle size: 7 nm, manufactured by NIPPON AEROSIL CO., LTD.) were mixed such that the silicon oxide concentration became 4% by volume. The resultant mixture was stirred so as to become uniform. The resultant material was subjected to heat-press forming under the same
conditions as in Example 1 to provide a coin-shaped molded article .
Comparative example 3
[0042] Particles of a cyclic olefin resin (ZEONEX E48R [product name], manufactured by ZEON CORPORATION) and silicon oxide particles (AEROSIL 300 [product name] , volume average primary particle size: 7 nm, manufactured by NIPPON AEROSIL CO., LTD.) were mixed such that the silicon oxide concentration became 17% by volume. The resultant mixture was stirred so as to become uniform. The resultant material was subjected to heat -press forming under the same
conditions as in Example 1 to provide a coin- shaped molded article .
Comparative example 4
[0043] Particles of a cyclic olefin resin ( ZEONEX E48R [product name], manufactured by ZEON CORPORATION) and silicon oxide particles (AEROSIL 300 [product name] , volume average primary particle size: 7 nm, manufactured by NIPPON AEROSIL CO., LTD.) were mixed such that the silicon oxide concentration became 29% by volume. The resultant mixture was stirred so as to become uniform. The resultant material was subjected to heat-press forming under the same
conditions as in Example 1 to provide a coin- shaped formed product .
Comparative example 5
[0044] 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.
This molded article was brittle and obtained in the form of broken pieces .
Example 5
[0045] 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
conditions as in Example 1 to provide a coin- shaped molded article .
Example 6
[0046] Particles of a cyclic olefin resin (ZEONEX E48R [product name], manufactured by ZEON CORPORATION) and silicon oxide particles (AEROSIL OX50 [product name], volume average primary particle size: 20 nm, manufactured by NIPPON AEROSIL CO., LTD.) were mixed such that the silicon oxide concentration became 78% by volume. The resultant mixture was stirred so as to become uniform. The resultant material was subjected to heat-press forming under the same
conditions as in Example 1 to provide a coin-shaped molded article .
Example 7
[0047] Particles of a cyclic olefin resin ( ZEONEX E48R [product name], manufactured by ZEON CORPORATION) and silicon oxide particles (NIPGEL CX-200 [product name], manufactured by TOSOH SILICA CORPORATION) were mixed such that the silicon oxide concentration became 65% by volume. The resultant mixture was stirred so as to become uniform. The resultant material was subjected to heat -press forming under the same conditions as in Example 1 to provide a coin- shaped molded article.
Example 8
[0048] Particles of a cyclic olefin copolymer resin (APEL APL5014DP [product name], manufactured by Mitsui Chemicals, Inc.) and silicon oxide particles (AEROSIL 300 [product name], volume average primary particle size: 7 nm. manufactured by NIPPON AEROSIL CO., LTD.) were mixed such that the silicon oxide concentration became 62% by volume. The resultant mixture was stirred so as to become uniform. The resultant material was subjected to heat-press forming under the same conditions as in Example 1 to provide a coin- shaped molded article.
Example 9
[0049] In a mold for press forming having a diameter of 15 mm, 0.04 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 lower layer. On this layer, 0.16 g of particles of a cyclic olefin resin (ZEONEX E48R [product name], manufactured by ZEON CORPORATION) were placed without being mixed with 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 . [0050] 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.
Example 10
[0051] In a mold for press forming having a diameter of 15 mm, 0.03 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 lower layer. On this 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. On this layer, 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. 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. [0052] 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.
Example 11
[0053] In a mold for press forming having a diameter of 15 mm, 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 lower layer. On this 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. On this layer, 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. 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.
[0054] 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.
Evaluation
[0055] Evaluation results of the molded articles of
Examples 1 to 11 and Comparative examples 1 to 5 are
summarized in Table 1. Based on the results of Examples 1 to 4 and Comparative examples 1 to 5 , a graph illustrating the relationship between the concentration of silicon oxide particles (percent by volume) and the linear expansion coefficient in the pressing direction is indicated in Figure 1.
Method of measuring average linear expansion
coefficient and content of inorganic fine particles [0056] Each molded article was subjected to a three-cycle temperature load in a range of 0° C to 80° C with a TMA (TMA Q400 [product name], manufactured by TA Instruments) and an average linear expansion coefficient in the thickness direction in a range of 20° C to 60° C was calculated. The measurement was performed in the plate-thickness direction of the coin (pressing direction) and displacement was measured with an expansion probe. The content of the silicon oxide particles was measured with a TGA (TGA Q500 [product name], manufactured by TA Instruments). In the conversion of the content of the silicon oxide particles from percent by weight (wt%) to percent by volume (vol%), the specific gravity of the cyclic olefin resin used was 1.01 and the specific gravity of the silica fine particles used was 2.00. In the evaluation, each molded article was cut into a suitable size.
[ 0057 ]
[ Table 1 ]
Cyclic olefin Silicon oxide Powder mixing Particle Linear resin particles state at the time concentration expansion of forming coefficient
Example ZEONEX AEROSIL Uniform 53 vol.% 29.4 ppm/°C 1 E48R 300
Example ZEONEX AEROSIL Uniform 56 vol.% 27.0 ppm/°C 2 E48R 300
Example ZEONEX AEROSIL Uniform 77 vol.% -59.7 ppm/°C 3 E48R 300
Example ZEONEX AEROSIL Uniform 93 vol.% -1.4 ppm/°C 4 E48R 300
Example ZEONEX AEROSIL Uniform 61 vol.% -103 ppm/°C 5 E48R 200
Example ZEONEX AEROSIL Uniform 78 vol.% 1.5 ppm/°C 6 E48R OX50
Example ZEONEX NIPGEL CX- Uniform 65 vol.% 6.9 ppm/°C 7 E48R 200
Example APEL AEROSIL Uniform 82 vol.% -21.9 ppm/°C 8 APL5014DP 300
Example ZEONEX AEROSIL Bilayer Concentration -135 ppm/°C 9 E48R 300 gradient
Example ZEONEX AEROSIL Trilayer Concentration -52.4 ppm/°C 10 E48R 300 (Silica upper gradient
layer : lower
layer = 1 :3)
Example ZEONEX AEROSIL Trilayer Concentration -18.0 ppm/X 11 E48R 300 (Silica upper gradient
layer : lower
layer = 1 :1)
Comparative ZEONEX None Uniform 0 vol.% 57.7 ppm/X example E48R
1
Comparative ZEONEX AEROSIL Uniform 4 vol.% 54.7 ppm/X example E48R 300
2
Comparative ZEONEX AEROSIL Uniform 17 vol.% 29.7 ppm/X example E48R 300
3
Comparative ZEONEX AEROSIL Uniform 29 vol.% 47.6 ppm/°C example E48R 300
4
Comparative None AEROSIL Uniform 100 vol.% 5.2 ppm/°C example 300
5 [0058] As is clear from Figure 1, a considerable decrease in the linear expansion coefficient was observed when the concentration of the silicon oxide particles in the
composite material exceeded 50% by volume. 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.
[0059] The molded articles in Examples 1 to 11 have lower linear expansion coefficients than the molded articles in Comparative examples 1 to 4. Accordingly, it has been demonstrated that materials according to the present
invention are suitable for forming low-expansion members and temperature compensated members . Comparison between the molded articles in Examples 1 to 11 and the molded article in Comparative example 5 in which the powder composed only of the silicon oxide particles was formed indicates that the molded articles in Examples 1 to 11 have less fractures due to cracks at the time of forming and hence the materials are useful as forming materials.
[0060] A 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.
[0061] While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.
[0062] This application claims the benefit of Japanese Patent Application No. 2011-133484, filed June 15, 2011, which is hereby incorporated by reference herein in its entirety.

Claims

[1] A molded article produced by forming a thermoplastic composite material, wherein
the 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 coefficient of -140 x 10"6/0 C or more and 30 x 10"6/° C or less in a range of 20° C to 60° C.
[2] The molded article according to Claim 1,
wherein the molded article has a linear expansion
coefficient of -140 x 10"6/° C or more and 0/° C or less in the range of 20° C to 60° C.
[3] The molded article according to Claim 1,
wherein, in the thermoplastic composite material, the content of the silicon oxide particles with respect to the total amount of the olefin resin and the silicon oxide particles is 70% by volume or more and 95% by volume or less, and
the silicon oxide particles have a volume average primary particle size of 5 nm or more and less than 15 nm.
[4] A thermoplastic composite material comprising:
a cyclic olefin resin; and silicon oxide particles whose surfaces are covered with silanol groups ,
wherein 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.
[5] The thermoplastic composite material according to Claim 4,
wherein the silicon oxide particles have a volume
average primary particle size of 1 nm or more and less than 40 nm.
[6] The thermoplastic composite material according to Claim 4,
wherein the silicon oxide particles have a volume
average primary particle size of 5 nm or more and less than 15 nm.
[7] The thermoplastic composite material according to any one of Claims 4 to 6,
wherein, in the thermoplastic composite material, the content of the silicon oxide particles with respect to the total amount of the olefin resin and the silicon oxide particles is 70% by volume or more and 95% by volume or less.
PCT/JP2012/062727 2011-06-15 2012-05-11 Thermoplastic composite material and molded article WO2012172917A1 (en)

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