WO2014087842A1 - Liquid crystal resin composition for camera module and camera module using same - Google Patents

Liquid crystal resin composition for camera module and camera module using same Download PDF

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Publication number
WO2014087842A1
WO2014087842A1 PCT/JP2013/081324 JP2013081324W WO2014087842A1 WO 2014087842 A1 WO2014087842 A1 WO 2014087842A1 JP 2013081324 W JP2013081324 W JP 2013081324W WO 2014087842 A1 WO2014087842 A1 WO 2014087842A1
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Prior art keywords
camera module
resin composition
component
liquid crystalline
conductive filler
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PCT/JP2013/081324
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French (fr)
Japanese (ja)
Inventor
智明 横田
淳一郎 杉浦
吉昭 田口
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ポリプラスチックス株式会社
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Application filed by ポリプラスチックス株式会社 filed Critical ポリプラスチックス株式会社
Priority to KR1020157015230A priority Critical patent/KR101625009B1/en
Priority to CN201380062895.5A priority patent/CN104822775B/en
Priority to JP2014551029A priority patent/JP5826411B2/en
Publication of WO2014087842A1 publication Critical patent/WO2014087842A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0869—Acids or derivatives thereof
    • C08L23/0884—Epoxide containing esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3804—Polymers with mesogenic groups in the main chain
    • C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B7/00—Mountings, adjusting means, or light-tight connections, for optical elements
    • G02B7/02—Mountings, adjusting means, or light-tight connections, for optical elements for lenses

Definitions

  • the present invention relates to a liquid crystal resin composition for a camera module and a camera module using the same.
  • Liquid crystalline resins typified by liquid crystalline polyester resins have excellent mechanical strength, heat resistance, chemical resistance, electrical properties, etc. in a well-balanced manner and have excellent dimensional stability. It's being used. Recently, liquid crystal resins have been used for precision equipment parts by taking advantage of these features.
  • a small amount of dust, dust, etc. will affect the performance of the equipment.
  • a part used in an optical device such as a camera module
  • the optical characteristics of the camera module are significantly deteriorated.
  • the parts that make up the camera module (hereinafter sometimes referred to as “camera module parts”) are ultrasonically cleaned before being assembled and attached to the surface. Small dust, oil, dust, etc. are removed.
  • the molded body formed by molding the liquid crystalline resin composition is easy to peel off because the molecular orientation of the polymer is particularly large in the surface portion.
  • the fluffing phenomenon of peeling and fluffing occurs, and the fluffed raised portion causes small dust.
  • liquid crystalline resin composition when used as a raw material for camera module parts, a special liquid crystalline resin composition that does not raise the surface of the molded body even when the molded body is subjected to ultrasonic cleaning is used.
  • a special liquid crystalline resin composition a liquid crystalline resin composition for a camera module containing a liquid crystalline resin, a specific talc, and carbon black is disclosed (see Patent Document 1).
  • the liquid crystalline resin composition for a camera module described in Patent Document 1 has insufficient suppression of raising of the surface of the molded article, and the molded article is more difficult to raise the surface of the molded article.
  • a liquid crystalline resin composition for a camera module for manufacturing the above is required.
  • the lens holder moves up and down on the guide that becomes the base of the lens holder by the action of the magnetic force generated by the coil wound around the lens holder and the permanent magnet arranged around the coil, Adjust the focus of the lens.
  • the lens holder is usually made of a material containing a liquid crystalline resin
  • the guide is made of a resin other than the liquid crystalline resin, for example, a material containing nylon.
  • the present invention has been made to solve the above-mentioned problems, and its object is to provide a liquid crystalline resin composition for a camera module for producing a camera module component that is less likely to be raised and charged. There is to do.
  • the inventors of the present invention have made extensive studies to solve the above problems. As a result, by using a liquid crystalline resin composition for a camera module containing a liquid crystalline resin, a specific non-conductive filler, a specific copolymer and a specific conductive filler in a specific ratio, The present inventors have found that the problem can be solved and have completed the present invention. More specifically, the present invention provides the following.
  • the (C2) styrene copolymer is composed of styrenes and a glycidyl ester of ⁇ , ⁇ -unsaturated acid, and the (D1) fibrous conductive filler is an average fiber.
  • the length is 50 ⁇ m or more, and the (D2) non-fibrous conductive filler is at least one selected from a plate-like filler and a granular filler having an average particle diameter of 20 nm to 50 ⁇ m, and has a volume resistivity.
  • a camera module part comprising the liquid crystalline resin composition for a camera module described in (1).
  • a camera module comprising a lens holder and a guide serving as a pedestal of the lens holder, wherein the lens holder is made of the liquid crystalline resin composition for camera modules described in (1), A camera module made of a material other than a liquid crystalline resin composition for a camera module.
  • a camera module component is produced using the liquid crystalline resin composition for a camera module of the present invention as a raw material, a camera module component that is less likely to be raised and charged is obtained.
  • the liquid crystalline resin composition for a camera module of the present invention contains (A) a liquid crystalline resin, (B) a nonconductive filler, (C) a copolymer, and (D) a conductive filler.
  • the (A) liquid crystalline resin used in the present invention refers to a melt processable polymer having a property capable of forming an optically anisotropic molten phase.
  • the property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a molten sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times.
  • the liquid crystalline polymer applicable to the present invention is inspected between crossed polarizers, the polarized light is normally transmitted even in the molten stationary state, and optically anisotropic.
  • the type of the above (A) liquid crystalline resin is not particularly limited, but is preferably an aromatic polyester or an aromatic polyester amide.
  • the polyester which partially contains aromatic polyester or aromatic polyester amide in the same molecular chain is also in that range. They preferably have a logarithmic viscosity (IV) of at least about 2.0 dl / g, more preferably 2.0-10.0 dl / g when dissolved in pentafluorophenol at 60 ° C. at a concentration of 0.1% by weight. .) Are preferably used.
  • the aromatic polyester or aromatic polyester amide as the liquid crystalline resin (A) applicable to the present invention is particularly preferably at least one selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines.
  • Aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and 2,6-dihydroxy.
  • Aromatic diols such as naphthalene, 1,4-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcin, compounds represented by the following general formula (I), and compounds represented by the following general formula (II)
  • Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and compounds represented by the following general formula (III); p-aminophenol, p- Aromatic amines such as phenylenediamine are listed.
  • X a group selected from alkylene (C 1 -C 4 ), alkylidene, —O—, —SO—, —SO 2 —, —S—, and —CO—
  • the (A) liquid crystalline resin used in the present invention can be prepared by a known method using a direct polymerization method or a transesterification method from the above monomer compound (or a mixture of monomers). A combination method or a slurry polymerization method is used.
  • the above compounds having ester-forming ability may be used for polymerization as they are, or may be modified from a precursor to a derivative having ester-forming ability in the previous stage of polymerization.
  • various catalysts can be used. Typical examples include dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, and alkali of carboxylic acid.
  • the amount of the catalyst used is generally about 0.001 to 1% by mass, particularly about 0.01 to 0.2% by mass, based on the total weight of the monomers. If the polymer produced by these polymerization methods is further necessary, the molecular weight can be increased by solid-phase polymerization by heating in a reduced pressure or an inert gas.
  • the melt viscosity of the (A) liquid crystalline resin obtained by the above method is not particularly limited. In general, those having a melt viscosity at a molding temperature of 10 MPa or more and 600 MPa or less at a shear rate of 1000 sec ⁇ 1 can be used. However, those having a very high viscosity are not preferable because the fluidity is extremely deteriorated.
  • the (A) liquid crystalline resin may be a mixture of two or more liquid crystalline resins.
  • the content of (A) liquid crystal resin is 55 to 91% by mass. If the content of component (A) is 55% by mass or more, it is preferable for fluidity and suppression of raising of the surface of the molded body, and if the content of component (A) is 91% by mass or less, it is preferable for heat resistance. .
  • the preferable content of component (A) is 60 to 80% by mass.
  • Non-conductive filler comprises: (B1) a fibrous non-conductive filler having an average fiber diameter of 1.0 ⁇ m or less and an average fiber length of 5 to 50 ⁇ m; and (B2) a plate having an average particle diameter of 50 ⁇ m or less. At least one selected from at least one non-fibrous non-conductive filler selected from particulate fillers and particulate fillers.
  • the average fiber diameter of the fibrous nonconductive filler is 1.0 ⁇ m or less, and the preferable average fiber diameter is 0.3 to 0.6 ⁇ m.
  • the average fiber diameter a value obtained by capturing a stereoscopic microscope image from a CCD camera into a PC and measuring the image by an image processing method is employed.
  • the average fiber length of (B1) fibrous nonconductive filler is 5 to 50 ⁇ m, and the preferable average fiber length is 7 to 30 ⁇ m.
  • the average fiber length is 5 ⁇ m or more, the mechanical strength and the deflection temperature under load necessary for the camera module are easily maintained, and when the average fiber length is 50 ⁇ m or less, the raising effect on the surface of the molded body is likely to increase.
  • the average fiber length a value obtained by taking a stereoscopic microscope image from a CCD camera into a PC and measuring by an image processing method using an image measuring machine is adopted.
  • any fiber can be used as long as it is a fibrous non-conductive filler that satisfies the above shape, but examples of (B1) fibrous non-conductive filler include glass fiber, asbestos fiber, and silica fiber. Inorganic fibrous materials such as silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, and potassium titanate fiber.
  • As the component (B1) two or more kinds of fibrous nonconductive fillers may be used.
  • potassium titanate fibers are preferably used as the component (B1).
  • the non-fibrous non-conductive filler is at least one selected from a plate-like filler and a granular filler having an average particle diameter of 50 ⁇ m or less.
  • the average particle diameter is preferably 10 to 20 ⁇ m. In this specification, the value measured by the laser diffraction / scattering particle size distribution measurement method is adopted as the average particle size.
  • any filler can be used as long as it is a non-fibrous non-conductive filler that satisfies the above shape, and examples of the plate-like filler include talc, mica, and glass flakes.
  • particulate fillers include silica, quartz powder, glass beads, glass powder, calcium oxalate, aluminum oxalate, kaolin, clay, diatomaceous earth, wollastonite, etc .; iron oxide, titanium oxide, zinc oxide And metal oxides such as alumina; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; silicon carbide; silicon nitride;
  • the component (B2) two or more kinds may be used.
  • the component (B2) it is preferable to use talc and mica of plate-like filler and silica of granular filler, and it is more preferable to use talc and mica of plate-like filler.
  • the content of the component (B) (the sum of the content of the component (B1) and the content of the component (B2)) is 5 to 20% by mass in the liquid crystal composition for a camera module of the present invention. is there.
  • the content of the component (B) is 5% by mass or more, the mechanical strength and the deflection temperature under load necessary for the camera module are easily secured, and when the content is 20% by mass or less, the effect of suppressing the raising of the surface of the molded article is increased.
  • Cheap A more preferable content is 10 to 20% by mass.
  • the (C) copolymer is at least one selected from (C1) an olefin copolymer and (C2) a styrene copolymer.
  • Mixing the component (C) with the liquid crystalline resin composition for a camera module contributes to suppressing raising of the surface of the molded product when the molded product obtained by molding the composition is subjected to ultrasonic cleaning. The reason for suppressing the raising is not clarified, but it is considered that by adding a certain amount, the surface state of the molded body is changed, and the change contributes to suppressing the raising.
  • Examples of the olefin copolymer include a copolymer composed of a repeating unit derived from an ⁇ -olefin and a repeating unit derived from a glycidyl ester of an ⁇ , ⁇ -unsaturated acid.
  • the ⁇ -olefin is not particularly limited and includes, for example, ethylene, propylene, butene, etc. Among them, ethylene is preferably used.
  • the glycidyl ester of ⁇ , ⁇ -unsaturated acid is represented by the following general formula (IV). Examples of the glycidyl ester of ⁇ , ⁇ -unsaturated acid include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl methacrylate is particularly preferable.
  • the content of repeating units derived from ⁇ -olefin is 87 to 98% by mass, and the content of repeating units derived from glycidyl ester of ⁇ , ⁇ -unsaturated acid is 13 It is preferably 2% by mass.
  • the (C1) olefin copolymer used in the present invention is a third component other than the above two components within the scope of the present invention, such as acrylonitrile, acrylic ester, methacrylic ester, ⁇ -methylstyrene, maleic anhydride, etc.
  • a repeating unit derived from one or more olefinic unsaturated esters may be contained in an amount of 0 to 48 parts by mass with respect to 100 parts by mass of the two components.
  • the olefin copolymer as the component (C1) of the present invention can be easily prepared by a normal radical polymerization method using a monomer and a radical polymerization catalyst corresponding to each component. More specifically, the presence of a suitable solvent or chain transfer agent is usually obtained by mixing ⁇ -olefin and glycidyl ester of ⁇ , ⁇ -unsaturated acid in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C. It can be produced by a method of copolymerization under or in the absence.
  • It can also be produced by a method in which an ⁇ -olefin, a glycidyl ester of ⁇ , ⁇ -unsaturated acid and a radical generator are mixed and melt graft copolymerized in an extruder.
  • Examples of the (C2) styrenic copolymer include a copolymer composed of a repeating unit derived from styrene and a repeating unit derived from a glycidyl ester of an ⁇ , ⁇ -unsaturated acid. Since the glycidyl ester of ⁇ , ⁇ -unsaturated acid is the same as that described for the component (C1), description thereof is omitted.
  • styrenes examples include styrene, ⁇ -methylstyrene, brominated styrene, divinylbenzene and the like, and styrene is preferably used.
  • the (C2) styrenic copolymer used in the present invention may be a multi-component copolymer containing a repeating unit derived from one or more of the other vinyl monomers as the third component in addition to the above two components.
  • Suitable as the third component is a repeating unit derived from one or more olefinic unsaturated esters such as acrylonitrile, acrylic acid ester, methacrylic acid ester, and maleic anhydride.
  • a styrene copolymer containing 40% by mass or less of these repeating units in the styrene copolymer is preferred as the component (C2).
  • the content of the repeating unit derived from the glycidyl ester of ⁇ , ⁇ -unsaturated acid is 2 to 20% by mass, and the content of the repeating unit derived from styrene is 80 to It is preferably 98% by weight.
  • the styrene copolymer can be prepared by a normal radical polymerization method using a monomer corresponding to each component and a radical polymerization catalyst. More specifically, styrenes and glycidyl esters of ⁇ , ⁇ -unsaturated acids are usually present in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C. in the presence of a suitable solvent or chain transfer agent. Or it can manufacture by the method of copolymerizing in absence.
  • It can also be produced by a method in which styrenes, an ⁇ , ⁇ -unsaturated glycidyl ester and a radical generator are mixed and subjected to melt graft copolymerization in an extruder.
  • the (C) copolymer is preferably an (C1) olefin copolymer in terms of heat resistance, but the ratio of the (C1) component to the (C2) component is in accordance with the required characteristics as appropriate. Can be selected.
  • the content of the (C) copolymer (total amount of the (C1) component and the (C2) component) is 2 to 10% by mass in the camera module resin composition of the present invention.
  • the content of the component (C) is 2% by mass or more from the viewpoint of suppressing raising of the surface of the molded body, and being 10% by mass or less obtains a good molded body without impairing fluidity. It is necessary for the reason.
  • a more preferable content is 2 to 7% by mass.
  • the conductive filler is selected from (D1) a fibrous conductive filler having an average fiber length of 50 ⁇ m or more, and (D2) a plate-like filler and a granular filler having an average particle diameter of 20 nm to 50 ⁇ m. And at least one non-fibrous conductive filler.
  • the average fiber length of the fibrous conductive filler is 50 ⁇ m or more.
  • the average fiber length of 50 ⁇ m or more is necessary from the viewpoint of developing antistatic properties.
  • the upper limit of the said average fiber length is not specifically limited, For example, 10 mm is mentioned practically.
  • any fiber can be used as long as it is a fibrous conductive filler satisfying the above shape.
  • fibrous conductive filler include carbon fibers; conductive fibers such as metal fibers. Glass fibers, whiskers, inorganic fibers, ore fibers, and the like are coated with a metal such as nickel or copper to impart conductivity.
  • carbon fibers examples include PAN-based carbon fibers made from polyacrylonitrile and pitch-based carbon fibers made from pitch.
  • metal fibers examples include fibers made of mild steel, stainless steel, steel and alloys thereof, copper, brass, aluminum and alloys thereof, titanium, lead and the like. As these metal fibers, those coated with other metals can be used in order to impart further conductivity if necessary due to their conductivity.
  • whisker examples include silicon nitride whisker, silicon trinitride whisker, basic magnesium sulfate whisker, barium titanate whisker, silicon carbide whisker, and boron whisker.
  • inorganic fiber examples include fibers made of rock wool, zirconia, alumina silica, potassium titanate, barium titanate, titanium oxide, silicon carbide, alumina, silica, blast furnace slag, and the like.
  • ore fiber examples include fibers made of asbestos.
  • (D1) Two or more kinds of fibrous conductive fillers may be used as the component.
  • the content of the component is 1 to 5% by mass in the resin composition for a camera module of the present invention. It is necessary for the content of the component (D1) to be 1% by mass or more from the viewpoint of developing antistatic properties, and 5% by mass or less means that the conductivity is adjusted to a semiconductive region and flow. It is necessary in terms of suppressing the deterioration of the sex and the raising of the hair raising property. A more preferable content is 2 to 4% by mass.
  • the non-fibrous conductive filler is at least one selected from a plate-like filler and a granular filler having an average particle diameter of 20 nm to 50 ⁇ m.
  • the average particle size of 20 nm or more is necessary from the viewpoint of suppressing a decrease in fluidity.
  • the average particle diameter of 50 ⁇ m or less is necessary in terms of suppressing deterioration of surface smoothness.
  • any filler can be used as long as it is a non-fibrous conductive filler satisfying the above shape, but as the plate-like filler, graphite, plate-like metal powder (for example, aluminum, iron, copper) Etc.
  • the particulate filler include carbon black, particulate metal powder (for example, aluminum, iron, copper), particulate conductive ceramics (for example, zinc oxide, tin oxide, indium tin oxide) and the like.
  • the component (D2) two or more kinds may be used. In the present invention, graphite and carbon black are preferably used as the component (D2).
  • the average particle size is preferably 5 to 50 ⁇ m and the thickness is preferably 0.5 to 10 ⁇ m.
  • the average particle size is preferably 20 to 100 nm.
  • the content of the component is 1 to 15% by mass in the resin composition for a camera module of the present invention.
  • the content of the component (D2) is 1% by mass or more, which is necessary in terms of suppressing variation in conductivity and exhibiting stable antistatic properties, and being 15% by mass or less This is necessary in terms of suppressing the decrease.
  • a more preferable content is 2 to 10% by mass.
  • the liquid crystalline resin composition for a camera module of the present invention includes other polymers, known substances generally added to synthetic resins, that is, antioxidants, ultraviolet absorbers, etc., as long as the effects of the present invention are not impaired.
  • Stabilizers, antistatic agents other than component (D), flame retardants, colorants such as dyes and pigments, lubricants, mold release agents, crystallization accelerators, crystal nucleating agents, etc. are added as appropriate according to the required performance. be able to.
  • the preparation of the resin composition for a camera module of the present invention is not particularly limited. For example, by blending the above components (A), (B), (C), and (D), and melt-kneading these using a single screw or twin screw extruder, a liquid crystalline resin for a camera module Preparation of the composition takes place.
  • the shape of the component (B) in the liquid crystalline resin composition for a camera module of the present invention is different from the shape of the component (B) before blending.
  • the shape of the above component (B) is the shape before blending. If the shape before blending is as described above, a camera module component that is less prone to raising the surface can be obtained.
  • the shape of the component (D) in the liquid crystalline resin composition for a camera module of the present invention is different from the shape of the component (D) before blending.
  • the shape of the above component (D) is the shape before blending. If the shape before blending is as described above, a camera module component that is difficult to be charged can be obtained.
  • the liquid crystalline resin composition for a camera module of the present invention obtained as described above preferably has a melt viscosity of 50 Pa ⁇ sec or less.
  • One of the characteristics of the liquid crystalline resin composition for camera modules of the present invention is that it has high fluidity and excellent moldability.
  • the melt viscosity a value obtained by a measurement method based on ISO 11443 under conditions of a cylinder temperature of 350 ° C. and a shear rate of 1000 sec ⁇ 1 is adopted.
  • the liquid crystalline resin composition for a camera module of the present invention preferably has a deflection temperature under load of 200 ° C. or higher.
  • the point which is excellent in heat resistance is also one of the characteristics of the liquid crystalline resin composition for camera modules of this invention.
  • For the deflection temperature under load a value measured by a method based on ISO 75-1 or 2 is adopted.
  • the liquid crystalline resin composition for a camera module of the present invention has a volume resistivity of 1 ⁇ 10 4 to 1 ⁇ 10 14 ⁇ ⁇ cm. That is, the conductivity of the volume resistivity is adjusted to a semiconductive region, thereby exhibiting excellent antistatic properties. If the volume resistivity is less than 1 ⁇ 10 4 ⁇ ⁇ cm, the electrical conductivity may be too high and a short circuit may occur. If the volume resistivity exceeds 1 ⁇ 10 14 ⁇ ⁇ cm, the electrical conductivity may be too low to exhibit antistatic properties.
  • a camera module component is manufactured using the liquid crystalline resin composition for a camera module. If the resin composition of the present invention is used as a raw material, the camera module component is less likely to be charged. Therefore, the camera module component comprising the resin composition of the present invention is less likely to cause malfunction due to static electricity.
  • the surface of the camera module component is hardly raised. Since the camera module component is ultrasonically cleaned, it is required that the surface is not easily raised even if the ultrasonic cleaning is performed. If the resin composition of the present invention is used, even if the ultrasonic cleaning of camera module parts is performed under stronger conditions, there will be no or almost no dropouts causing dust and the like. Accordingly, after the camera module parts are incorporated into the finished product, the dust generated by raising the surface of the camera module parts hardly affects the quality of the finished product.
  • the camera module 1 includes a substrate 10, an optical element 11, a lead wire 12, a lens holder 13, a barrel 14, a lens 15, an IR filter 16, and a guide 17.
  • the optical element 11 is disposed on the substrate 10, and the optical element 11 and the substrate 10 are electrically connected by a lead wiring 12.
  • the guide 17 is disposed on the substrate 10
  • the lens holder 13 is disposed on the guide 17, and the guide 17 and the lens holder 13 cover the optical element 11.
  • the lens holder 13 has an opening at the top, and a spiral groove is formed on the wall surface of the opening.
  • the barrel 14 has a cylindrical shape, and the lens 15 is held inside the cylindrical shape so as to be substantially horizontal.
  • a spiral convex portion is formed on the side wall of one end of the cylinder, and this spiral convex portion and the spiral groove portion formed on the opening wall surface of the lens holder 13 are screwed together,
  • the barrel 14 is connected to the lens holder 13.
  • An IR filter 16 is disposed at one end of the barrel 14 so as to close one end of the cylindrical barrel 14. As shown in FIG. 1, the IR filter 16 and the lens 15 are arranged substantially in parallel.
  • the lens holder 13 includes a magnetic force generated by a coil (not shown) wound around the lens holder 13 and a permanent magnet (not shown) arranged around the coil.
  • the distance between the lens 15 and the optical element 11 changes by moving up and down on the guide 17 by the action of.
  • the focus of the camera can be adjusted by adjusting this distance.
  • the lens holder 13 which is a camera module component can be manufactured using the liquid crystalline resin composition for a camera module of the present invention as a raw material.
  • a general liquid crystalline resin composition is not suitable as a raw material for producing these parts.
  • the lens holder 13 is manufactured using a general liquid crystalline resin composition as a raw material, the following problems occur.
  • Molded products made of general liquid crystalline resin compositions are easily charged negatively, and generate static electricity between molded products made of materials that easily charge positively, such as nylon. However, this causes a malfunction in the camera module.
  • a molded body formed by molding a general liquid crystalline resin composition is likely to raise the surface of the molded body because the molecular orientation of the polymer is particularly large in the surface portion, and this raising causes generation of small dust. . If this small dust adheres to the lens 15 or the like, the performance of the camera module is degraded.
  • the camera module parts such as the lens holder 13 are ultrasonically cleaned before being incorporated into the camera module 1 for the purpose of removing dust and small dust on the surface.
  • the surface of a molded product formed by molding a general liquid crystalline resin composition is easily raised, the surface becomes fluffy when ultrasonically cleaned. Since such a problem arises, the molded object formed by shape
  • the focus adjustment is performed on the guide 17 by the action of the magnetic force generated by the coil (not shown) wound around the lens holder 13 and the permanent magnet (not shown) arranged around the coil. It is done by moving up and down. At this time, first, static electricity is generated between the lens holder 13 formed of a molded body formed by molding the liquid crystalline resin composition and the guide 17 formed of a molded body formed of a material containing nylon or the like. The lens holder 13 is liable to malfunction. Secondly, as described above, the molded body obtained by molding a general liquid crystalline resin composition is likely to have a raised surface, and thus the surface may be peeled off to produce a peeled product. There is a high possibility that the peeled material becomes small dust and adheres to the lens 15 or the like, thereby reducing the performance of the camera module.
  • the liquid crystalline resin composition for a camera module of the present invention is difficult to be charged when formed into a molded body, Further, since the surface state of the molded body has been improved so that even if the molded body is ultrasonically cleaned, the problem of raising the hair hardly occurs, it can be preferably used as a raw material for the lens holder 13.
  • examples of the material for the guide 17 include materials other than the liquid crystalline resin composition for a camera module of the present invention. Etc.
  • ⁇ Material> -Liquid crystalline resin liquid crystalline polyester amide resin: Vectra (registered trademark) E950i (manufactured by Polyplastics Co., Ltd.) ⁇ Olefin copolymer: Bond First 2C (ethylene-glycidyl methacrylate copolymer (containing 6% by mass of glycidyl methacrylate)) manufactured by Sumitomo Chemical Co., Ltd. -Fibrous conductive filler: manufactured by Toho Tenax Co., Ltd.
  • HTC432 PAN-based carbon fiber, average fiber diameter 10 ⁇ m, average fiber length 6 mm
  • -Non-fibrous conductive filler 1 CP manufactured by Nippon Graphite Industry Co., Ltd. (graphite, average particle size 10 ⁇ m, plate-like)
  • Non-fibrous conductive filler 2 VULCAN XC305 (carbon black, average particle size 20 nm, granular) manufactured by Cabot Japan Co., Ltd.
  • -Fibrous non-conductive filler Tismo N-102 (potassium titanate fiber, average fiber diameter 0.3 to 0.6 ⁇ m, average fiber length 10 to 20 ⁇ m) manufactured by Otsuka Chemical Co., Ltd.
  • -Non-fibrous non-conductive filler Crown Talc PP (Talc, average particle diameter 12.8 ⁇ m, average aspect ratio 6, plate shape) manufactured by Matsumura Sangyo Co., Ltd.
  • melt viscosity of the liquid crystalline resin compositions for camera modules of Examples and Comparative Examples was measured using the pellets. Specifically, the apparent melt viscosity under conditions of a cylinder temperature of 350 ° C. and a shear rate of 1000 sec ⁇ 1 was measured according to ISO 11443 using a capillary rheometer (Capillograph 1D manufactured by Toyo Seiki: piston diameter 10 mm). For the measurement, an orifice having an inner diameter of 1 mm and a length of 20 mm was used. The results are shown in Table 1.
  • ⁇ Load deflection temperature> The pellets of Examples and Comparative Examples were molded under the following molding conditions using a molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.) to obtain test specimens (4 mm ⁇ 10 mm ⁇ 80 mm). Thereafter, the deflection temperature under load was measured by a method in accordance with ISO 75-1 and 2. Note that 1.8 MPa was used as the bending stress. The results are shown in Table 1. ⁇ Molding condition ⁇ Cylinder temperature: 350 ° C Mold temperature: 80 °C Back pressure: 2.0MPa Injection speed: 33mm / sec
  • the molded bodies before and after being subjected to an ultrasonic cleaning machine were compared, and the area (raised area) of the fluffed portion on the surface of the molded body was evaluated with an image measuring instrument (LUZEXFS manufactured by Nireco Corporation).
  • the evaluation area was 750 mm 2 (12.5 mm ⁇ 60 mm), and the ratio (%) of the raised area to the evaluation area was used as a result.
  • the results are shown in Table 1. The smaller the raising area, the higher the raising suppression effect.
  • the molded body produced using the pellets of the examples had a volume resistivity in the range of 1 ⁇ 10 4 to 1 ⁇ 10 14 ⁇ ⁇ cm. It was. Moreover, it was confirmed that the surface of the molded body was not fluffed even after ultrasonic cleaning. From these results, the molded body formed by molding the pellets of the examples is superior in antistatic property and surface state compared to the molded body formed by molding normal liquid crystalline resin composition pellets such as comparative examples. Can be said to be very different.
  • the molded body produced using the pellets of the examples was excellent in heat resistance and impact resistance.

Abstract

Provided is a liquid crystal resin composition for a camera module that is to be used for producing a camera module component the surface of which is neither easily raised nor easily charged. The resin composition comprises a liquid crystal resin (A), at least one kind of a non-conductive filler (B) selected from a fibrous nonconductive filler (B1) and a non-fibrous non-conductive filler (B2), at least one kind of a copolymer (C) selected from an olefin-based copolymer (C1) and a styrene-based copolymer (C2), and conductive fillers (D) comprising a fibrous conductive filler (D1) and a non-fibrous conductive filler (D2), each in a definite amount, wherein the components (B1), (B2), (C1), (C2), (D1) and (D2) are respectively configured from specific components and the volume resistivity is 1×104-1×1014 Ω cm.

Description

カメラモジュール用液晶性樹脂組成物及びそれを用いたカメラモジュールLiquid crystalline resin composition for camera module and camera module using the same
　本発明は、カメラモジュール用液晶性樹脂組成物及びそれを用いたカメラモジュールに関する。 The present invention relates to a liquid crystal resin composition for a camera module and a camera module using the same.
　液晶性ポリエステル樹脂に代表される液晶性樹脂は、優れた機械的強度、耐熱性、耐薬品性、電気的性質等をバランス良く有し、優れた寸法安定性も有するため高機能エンジニアリングプラスチックとして広く利用されている。最近では、液晶性樹脂は、これらの特長を生かして、精密機器部品に使用されるようになっている。 Liquid crystalline resins typified by liquid crystalline polyester resins have excellent mechanical strength, heat resistance, chemical resistance, electrical properties, etc. in a well-balanced manner and have excellent dimensional stability. It's being used. Recently, liquid crystal resins have been used for precision equipment parts by taking advantage of these features.
　精密機器、特にレンズがあるような光学機器の場合、わずかなゴミ、埃等が機器性能に影響を与える。例えばカメラモジュールのような光学機器に用いられる部品においては、小さなゴミ、油分、埃がレンズに付着すると、カメラモジュールの光学特性が著しく低下する。このような光学特性の低下を防ぐ目的で、通常、カメラモジュールを構成する部品（以下、「カメラモジュール用部品」という場合がある。）は、組み立て前に超音波洗浄され、表面に付着している小さなゴミ、油分、埃等が除去される。 In the case of precision equipment, especially optical equipment with a lens, a small amount of dust, dust, etc. will affect the performance of the equipment. For example, in a part used in an optical device such as a camera module, if small dust, oil, or dust adheres to the lens, the optical characteristics of the camera module are significantly deteriorated. In order to prevent such deterioration of optical characteristics, the parts that make up the camera module (hereinafter sometimes referred to as “camera module parts”) are ultrasonically cleaned before being assembled and attached to the surface. Small dust, oil, dust, etc. are removed.
　上記のように、液晶性樹脂組成物を成形してなる成形体は、高分子の分子配向が表面部分で特に大きいため成形体表面が剥離しやすいので、この成形体を超音波洗浄すると表面が剥離して毛羽立ちという起毛現象が生じ、この毛羽立った起毛部分は小さなゴミが発生する原因となる。 As described above, the molded body formed by molding the liquid crystalline resin composition is easy to peel off because the molecular orientation of the polymer is particularly large in the surface portion. The fluffing phenomenon of peeling and fluffing occurs, and the fluffed raised portion causes small dust.
　したがって、液晶性樹脂組成物をカメラモジュール用部品の原料として用いる場合には、成形体を超音波洗浄しても成形体表面が起毛しないような特殊な液晶性樹脂組成物を用いる。特殊な液晶性樹脂組成物としては、液晶性樹脂と特定のタルクとカーボンブラックとを含むカメラモジュール用液晶性樹脂組成物が開示されている（特許文献１参照）。 Therefore, when the liquid crystalline resin composition is used as a raw material for camera module parts, a special liquid crystalline resin composition that does not raise the surface of the molded body even when the molded body is subjected to ultrasonic cleaning is used. As a special liquid crystalline resin composition, a liquid crystalline resin composition for a camera module containing a liquid crystalline resin, a specific talc, and carbon black is disclosed (see Patent Document 1).
特開２００９－２４２４５３号公報JP 2009-242453 A
　しかし、本発明者らの検討では、特許文献１に記載されるカメラモジュール用液晶性樹脂組成物では成形体表面の起毛抑制が不十分であり、より一層、成形体表面が起毛しにくい成形体を製造するためのカメラモジュール用液晶性樹脂組成物が求められる。 However, according to the study by the present inventors, the liquid crystalline resin composition for a camera module described in Patent Document 1 has insufficient suppression of raising of the surface of the molded article, and the molded article is more difficult to raise the surface of the molded article. A liquid crystalline resin composition for a camera module for manufacturing the above is required.
　ところで、カメラモジュールにおいて、レンズホルダーは、レンズホルダーに巻かれたコイルが発生する磁力とコイルの周囲に配置された永久磁石との作用によって、レンズホルダーの台座となるガイド上を上下することで、レンズの焦点を合わせる。ここで、通常、レンズホルダーは、液晶性樹脂を含む材料から構成されているのに対し、ガイドは、液晶性樹脂以外の樹脂、例えば、ナイロンを含む材料から構成されている。このように、通常、レンズホルダーとガイドは異種材料から構成されているため、レンズホルダーがガイド上を上下する際に静電気が発生しやすく、レンズホルダーの動作不良の原因となっている。 By the way, in the camera module, the lens holder moves up and down on the guide that becomes the base of the lens holder by the action of the magnetic force generated by the coil wound around the lens holder and the permanent magnet arranged around the coil, Adjust the focus of the lens. Here, the lens holder is usually made of a material containing a liquid crystalline resin, while the guide is made of a resin other than the liquid crystalline resin, for example, a material containing nylon. As described above, since the lens holder and the guide are usually made of different materials, static electricity is likely to be generated when the lens holder moves up and down on the guide, causing a malfunction of the lens holder.
　本発明は、上記課題を解決するためになされたものであり、その目的は、表面が起毛しにくく、帯電しにくいカメラモジュール用部品を製造するための、カメラモジュール用液晶性樹脂組成物を提供することにある。 The present invention has been made to solve the above-mentioned problems, and its object is to provide a liquid crystalline resin composition for a camera module for producing a camera module component that is less likely to be raised and charged. There is to do.
　本発明者らは、上記課題を解決するために鋭意研究を重ねた。その結果、液晶性樹脂と特定の非導電性充填剤と特定の共重合体と特定の導電性充填剤とを、特定の割合で含有するカメラモジュール用液晶性樹脂組成物を用いることで、上記課題を解決できることを見出し、本発明を完成するに至った。より具体的には本発明は以下のものを提供する。 The inventors of the present invention have made extensive studies to solve the above problems. As a result, by using a liquid crystalline resin composition for a camera module containing a liquid crystalline resin, a specific non-conductive filler, a specific copolymer and a specific conductive filler in a specific ratio, The present inventors have found that the problem can be solved and have completed the present invention. More specifically, the present invention provides the following.
　（１）　（Ａ）液晶性樹脂、（Ｂ１）繊維状非導電性充填剤及び（Ｂ２）非繊維状非導電性充填剤から選択される少なくとも１種の（Ｂ）非導電性充填剤、（Ｃ１）オレフィン系共重合体及び（Ｃ２）スチレン系共重合体から選択される少なくとも１種の（Ｃ）共重合体、並びに（Ｄ１）繊維状導電性充填剤及び（Ｄ２）非繊維状導電性充填剤からなる（Ｄ）導電性充填剤を含有し、（Ａ）成分の含有量が５５～９１質量％、（Ｂ）成分の含有量が５～２０質量％、（Ｃ）成分の含有量が２～１０質量％、（Ｄ１）成分の含有量が１～５質量％、（Ｄ２）成分の含有量が１～１５質量％であり、前記（Ｂ１）繊維状非導電性充填剤は、平均繊維径が１．０μｍ以下、且つ平均繊維長が５～５０μｍであり、前記（Ｂ２）非繊維状非導電性充填剤は、平均粒子径が５０μｍ以下の、板状充填剤及び粒状充填剤から選択される少なくとも１種であり、前記（Ｃ１）オレフィン系共重合体は、α－オレフィンとα，β－不飽和酸のグリシジルエステルとから構成され、前記（Ｃ２）スチレン系共重合体は、スチレン類とα，β－不飽和酸のグリシジルエステルとから構成され、前記（Ｄ１）繊維状導電性充填剤は、平均繊維長が５０μｍ以上であり、前記（Ｄ２）非繊維状導電性充填剤は、平均粒子径が２０ｎｍ～５０μｍの、板状充填剤及び粒状充填剤から選択される少なくとも１種であり、体積抵抗率が１×１０４～１×１０１４Ω・ｃｍであるカメラモジュール用液晶性樹脂組成物。 (1) at least one (B) non-conductive filler selected from (A) liquid crystalline resin, (B1) fibrous non-conductive filler, and (B2) non-fibrous non-conductive filler, ( At least one (C) copolymer selected from C1) olefin copolymer and (C2) styrene copolymer, and (D1) fibrous conductive filler and (D2) non-fibrous conductive Containing (D) conductive filler comprising filler, (A) component content is 55 to 91% by mass, (B) component content is 5 to 20% by mass, (C) component content Is 2 to 10% by mass, the content of the component (D1) is 1 to 5% by mass, the content of the component (D2) is 1 to 15% by mass, and the (B1) fibrous non-conductive filler is: (B2) Non-fibrous non-conductive filler having an average fiber diameter of 1.0 μm or less and an average fiber length of 5 to 50 μm And (C1) the olefin copolymer is an α-olefin and an α, β-unsaturated acid, which is at least one selected from a plate-like filler and a granular filler having an average particle size of 50 μm or less. The (C2) styrene copolymer is composed of styrenes and a glycidyl ester of α, β-unsaturated acid, and the (D1) fibrous conductive filler is an average fiber. The length is 50 μm or more, and the (D2) non-fibrous conductive filler is at least one selected from a plate-like filler and a granular filler having an average particle diameter of 20 nm to 50 μm, and has a volume resistivity. Is a liquid crystalline resin composition for a camera module, having a value of 1 × 10 4 to 1 × 10 14 Ω · cm.
　（２）　（１）記載のカメラモジュール用液晶性樹脂組成物からなるカメラモジュール用部品。 (2) A camera module part comprising the liquid crystalline resin composition for a camera module described in (1).
　（３）　レンズホルダーである（２）記載のカメラモジュール用部品。 (3) The camera module component according to (2), which is a lens holder.
　（４）　レンズホルダーと、前記レンズホルダーの台座となるガイドとを備えるカメラモジュールであって、前記レンズホルダーは、（１）記載のカメラモジュール用液晶性樹脂組成物からなり、前記ガイドは、前記カメラモジュール用液晶性樹脂組成物以外の材料からなるカメラモジュール。 (4) A camera module comprising a lens holder and a guide serving as a pedestal of the lens holder, wherein the lens holder is made of the liquid crystalline resin composition for camera modules described in (1), A camera module made of a material other than a liquid crystalline resin composition for a camera module.
　本発明のカメラモジュール用液晶性樹脂組成物を原料として、カメラモジュール用部品を製造すれば、表面が起毛しにくく、帯電しにくいカメラモジュール用部品が得られる。 If a camera module component is produced using the liquid crystalline resin composition for a camera module of the present invention as a raw material, a camera module component that is less likely to be raised and charged is obtained.
一般的なカメラモジュールを模式的に示す断面図である。It is sectional drawing which shows a common camera module typically.
　以下、本発明の実施形態について説明する。なお、本発明は以下の実施形態に限定されない。 Hereinafter, embodiments of the present invention will be described. In addition, this invention is not limited to the following embodiment.
＜カメラモジュール用液晶性樹脂組成物＞
　本発明のカメラモジュール用液晶性樹脂組成物は、（Ａ）液晶性樹脂、（Ｂ）非導電性充填剤、（Ｃ）共重合体、及び（Ｄ）導電性充填剤を含有する。 <Liquid crystal resin composition for camera module>
The liquid crystalline resin composition for a camera module of the present invention contains (A) a liquid crystalline resin, (B) a nonconductive filler, (C) a copolymer, and (D) a conductive filler.
［（Ａ）液晶性樹脂］
　本発明で使用する（Ａ）液晶性樹脂とは、光学異方性溶融相を形成し得る性質を有する溶融加工性ポリマーを指す。異方性溶融相の性質は、直交偏光子を利用した慣用の偏光検査法により確認することが出来る。より具体的には、異方性溶融相の確認は、Ｌｅｉｔｚ偏光顕微鏡を使用し、Ｌｅｉｔｚホットステージに載せた溶融試料を窒素雰囲気下で４０倍の倍率で観察することにより実施できる。本発明に適用できる液晶性ポリマーは直交偏光子の間で検査したときに、たとえ溶融静止状態であっても偏光は通常透過し、光学的に異方性を示す。 [(A) Liquid crystalline resin]
The (A) liquid crystalline resin used in the present invention refers to a melt processable polymer having a property capable of forming an optically anisotropic molten phase. The property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a molten sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times. When the liquid crystalline polymer applicable to the present invention is inspected between crossed polarizers, the polarized light is normally transmitted even in the molten stationary state, and optically anisotropic.
　上記のような（Ａ）液晶性樹脂の種類としては特に限定されないが、芳香族ポリエステル又は芳香族ポリエステルアミドであることが好ましい。また、芳香族ポリエステル又は芳香族ポリエステルアミドを同一分子鎖中に部分的に含むポリエステルもその範囲にある。これらは６０℃でペンタフルオロフェノールに濃度０．１重量％で溶解したときに、好ましくは少なくとも約２．０ｄｌ／ｇ、更に好ましくは２．０～１０．０ｄｌ／ｇの対数粘度（Ｉ．Ｖ．）を有するものが好ましく使用される。 The type of the above (A) liquid crystalline resin is not particularly limited, but is preferably an aromatic polyester or an aromatic polyester amide. Moreover, the polyester which partially contains aromatic polyester or aromatic polyester amide in the same molecular chain is also in that range. They preferably have a logarithmic viscosity (IV) of at least about 2.0 dl / g, more preferably 2.0-10.0 dl / g when dissolved in pentafluorophenol at 60 ° C. at a concentration of 0.1% by weight. .) Are preferably used.
　本発明に適用できる（Ａ）液晶性樹脂としての芳香族ポリエステル又は芳香族ポリエステルアミドは、特に好ましくは、芳香族ヒドロキシカルボン酸、芳香族ヒドロキシアミン、及び芳香族ジアミンからなる群より選ばれる少なくとも１種の化合物に由来する繰り返し単位を構成成分として有する芳香族ポリエステル又は芳香族ポリエステルアミドである。 The aromatic polyester or aromatic polyester amide as the liquid crystalline resin (A) applicable to the present invention is particularly preferably at least one selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines. An aromatic polyester or aromatic polyester amide having a repeating unit derived from a seed compound as a constituent component.
　より具体的には、
（１）主として芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上からなるポリエステル；
（２）主として（ａ）芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上と、（ｂ）芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の１種又は２種以上と、（ｃ）芳香族ジオール、脂環族ジオール、脂肪族ジオール、及びそれらの誘導体の少なくとも１種又は２種以上、とからなるポリエステル；
（３）主として（ａ）芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上と、（ｂ）芳香族ヒドロキシアミン、芳香族ジアミン、及びそれらの誘導体の１種又は２種以上と、（ｃ）芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の１種又は２種以上、とからなるポリエステルアミド；
（４）主として（ａ）芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上と、（ｂ）芳香族ヒドロキシアミン、芳香族ジアミン、及びそれらの誘導体の１種又は２種以上と、（ｃ）芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の１種又は２種以上と、（ｄ）芳香族ジオール、脂環族ジオール、脂肪族ジオール、及びそれらの誘導体の少なくとも１種又は２種以上、とからなるポリエステルアミド等が挙げられる。更に上記の構成成分に必要に応じ分子量調整剤を併用してもよい。 More specifically,
(1) A polyester mainly composed of one or more aromatic hydroxycarboxylic acids and derivatives thereof;
(2) Mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, and (b) one or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof (C) a polyester comprising at least one or more of aromatic diol, alicyclic diol, aliphatic diol, and derivatives thereof;
(3) Mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, and (b) one or more aromatic hydroxyamines, aromatic diamines, and derivatives thereof; c) Polyesteramide comprising one or more of aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and derivatives thereof;
(4) Mainly (a) one or more aromatic hydroxycarboxylic acids and derivatives thereof; and (b) one or more aromatic hydroxyamines, aromatic diamines and derivatives thereof; c) one or more of aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and derivatives thereof; and (d) at least one of aromatic diol, alicyclic diol, aliphatic diol, and derivatives thereof. Or the polyesteramide which consists of 2 or more types is mentioned. Furthermore, you may use a molecular weight modifier together with said structural component as needed.
　本発明に適用できる（Ａ）液晶性樹脂を構成する具体的化合物の好ましい例としては、ｐ－ヒドロキシ安息香酸、６－ヒドロキシ－２－ナフトエ酸等の芳香族ヒドロキシカルボン酸、２，６－ジヒドロキシナフタレン、１，４－ジヒドロキシナフタレン、４，４’－ジヒドロキシビフェニル、ハイドロキノン、レゾルシン、下記一般式（Ｉ）で表される化合物、及び下記一般式（ＩＩ）で表される化合物等の芳香族ジオール；テレフタル酸、イソフタル酸、４，４’－ジフェニルジカルボン酸、２，６－ナフタレンジカルボン酸、及び下記一般式（ＩＩＩ）で表される化合物等の芳香族ジカルボン酸；ｐ－アミノフェノール、ｐ－フェニレンジアミン等の芳香族アミン類が挙げられる。
Figure JPOXMLDOC01-appb-C000001
 （Ｘ：アルキレン（Ｃ１～Ｃ４）、アルキリデン、－Ｏ－、－ＳＯ－、－ＳＯ２－、－Ｓ－、及び－ＣＯ－より選ばれる基である）
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
 （Ｙ：－（ＣＨ２）ｎ－（ｎ＝１～４）及び－Ｏ（ＣＨ２）ｎＯ－（ｎ＝１～４）より選ばれる基である。） Specific examples of the specific compound constituting the liquid crystalline resin (A) applicable to the present invention include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, and 2,6-dihydroxy. Aromatic diols such as naphthalene, 1,4-dihydroxynaphthalene, 4,4′-dihydroxybiphenyl, hydroquinone, resorcin, compounds represented by the following general formula (I), and compounds represented by the following general formula (II) Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and compounds represented by the following general formula (III); p-aminophenol, p- Aromatic amines such as phenylenediamine are listed.
Figure JPOXMLDOC01-appb-C000001
 (X: a group selected from alkylene (C 1 -C 4 ), alkylidene, —O—, —SO—, —SO 2 —, —S—, and —CO—)
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
 (Y: a group selected from — (CH 2 ) n — (n = 1 to 4) and —O (CH 2 ) n O— (n = 1 to 4).
　本発明に用いられる（Ａ）液晶性樹脂の調製は、上記のモノマー化合物（又はモノマーの混合物）から直接重合法やエステル交換法を用いて公知の方法で行うことができるが、通常は溶融重合法やスラリー重合法等が用いられる。エステル形成能を有する上記化合物類はそのままの形で重合に用いても良く、また、重合の前段階で前駆体から該エステル形成能を有する誘導体に変性されたものでもよい。これらの重合に際しては種々の触媒の使用が可能であり、代表的なものとしては、ジアルキル錫酸化物、ジアリール錫酸化物、２酸化チタン、アルコキシチタンけい酸塩類、チタンアルコラート類、カルボン酸のアルカリ及びアルカリ土類金属塩類、ＢＦ３の如きルイス酸塩等があげられる。触媒の使用量は一般にはモノマーの全重量に対して約０．００１～１質量％、特に約０．０１～０．２質量％が好ましい。これらの重合方法により製造されたポリマーは更に必要があれば、減圧又は不活性ガス中で加熱する固相重合により分子量の増加を図ることができる。 The (A) liquid crystalline resin used in the present invention can be prepared by a known method using a direct polymerization method or a transesterification method from the above monomer compound (or a mixture of monomers). A combination method or a slurry polymerization method is used. The above compounds having ester-forming ability may be used for polymerization as they are, or may be modified from a precursor to a derivative having ester-forming ability in the previous stage of polymerization. In the polymerization, various catalysts can be used. Typical examples include dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, and alkali of carboxylic acid. And alkaline earth metal salts, Lewis acid salts such as BF 3 and the like. The amount of the catalyst used is generally about 0.001 to 1% by mass, particularly about 0.01 to 0.2% by mass, based on the total weight of the monomers. If the polymer produced by these polymerization methods is further necessary, the molecular weight can be increased by solid-phase polymerization by heating in a reduced pressure or an inert gas.
　上記のような方法で得られた（Ａ）液晶性樹脂の溶融粘度は特に限定されない。一般には成形温度での溶融粘度が剪断速度１０００ｓｅｃ－１で１０ＭＰａ以上６００ＭＰａ以下のものが使用可能である。しかし、それ自体あまり高粘度のものは流動性が非常に悪化するため好ましくない。なお、上記（Ａ）液晶性樹脂は２種以上の液晶性樹脂の混合物であってもよい。 The melt viscosity of the (A) liquid crystalline resin obtained by the above method is not particularly limited. In general, those having a melt viscosity at a molding temperature of 10 MPa or more and 600 MPa or less at a shear rate of 1000 sec −1 can be used. However, those having a very high viscosity are not preferable because the fluidity is extremely deteriorated. The (A) liquid crystalline resin may be a mixture of two or more liquid crystalline resins.
　本発明のカメラモジュール用液晶性樹脂組成物において、（Ａ）液晶性樹脂の含有量は、５５～９１質量％である。（Ａ）成分の含有量が５５質量％以上であれば流動性、成形体表面の起毛抑制という理由で好ましく、（Ａ）成分の含有量が９１質量％以下であれば耐熱性という理由で好ましい。また、（Ａ）成分の好ましい含有量は、６０～８０質量％である。 In the liquid crystal resin composition for a camera module of the present invention, the content of (A) liquid crystal resin is 55 to 91% by mass. If the content of component (A) is 55% by mass or more, it is preferable for fluidity and suppression of raising of the surface of the molded body, and if the content of component (A) is 91% by mass or less, it is preferable for heat resistance. . The preferable content of component (A) is 60 to 80% by mass.
［（Ｂ）非導電性充填剤］
　（Ｂ）非導電性充填剤は、（Ｂ１）平均繊維径１．０μｍ以下、且つ平均繊維長が５～５０μｍの繊維状非導電性充填剤と、（Ｂ２）平均粒子径５０μｍ以下の、板状充填剤及び粒状充填剤から選択される少なくとも１種の非繊維状非導電性充填剤とから選択される少なくとも１種である。 [(B) Non-conductive filler]
(B) Non-conductive filler comprises: (B1) a fibrous non-conductive filler having an average fiber diameter of 1.0 μm or less and an average fiber length of 5 to 50 μm; and (B2) a plate having an average particle diameter of 50 μm or less. At least one selected from at least one non-fibrous non-conductive filler selected from particulate fillers and particulate fillers.
　（Ｂ１）繊維状非導電性充填剤の平均繊維径は１．０μｍ以下であり、好ましい平均繊維径は０．３～０．６μｍである。上記平均繊維径が１．０μｍ以下であると、成形体表面の起毛抑制効果が高くなりやすい。なお、本明細書において、平均繊維径としては、実体顕微鏡画像をＣＣＤカメラからＰＣに取り込み、画像測定機によって画像処理手法により測定された値を採用する。 (B1) The average fiber diameter of the fibrous nonconductive filler is 1.0 μm or less, and the preferable average fiber diameter is 0.3 to 0.6 μm. When the average fiber diameter is 1.0 μm or less, the effect of suppressing napping on the surface of the molded body tends to be high. In the present specification, as the average fiber diameter, a value obtained by capturing a stereoscopic microscope image from a CCD camera into a PC and measuring the image by an image processing method is employed.
　また、（Ｂ１）繊維状非導電性充填剤の平均繊維長は５～５０μｍであり、好ましい平均繊維長は７～３０μｍである。上記平均繊維長が５μｍ以上であると、カメラモジュールとして必要な機械強度、荷重たわみ温度が保持されやすく、５０μｍ以下であると、成形体表面の起毛抑制効果が高くなりやすい。なお、本明細書において、平均繊維長としては、実体顕微鏡画像をＣＣＤカメラからＰＣに取り込み、画像測定機によって画像処理手法により測定された値を採用する。 In addition, the average fiber length of (B1) fibrous nonconductive filler is 5 to 50 μm, and the preferable average fiber length is 7 to 30 μm. When the average fiber length is 5 μm or more, the mechanical strength and the deflection temperature under load necessary for the camera module are easily maintained, and when the average fiber length is 50 μm or less, the raising effect on the surface of the molded body is likely to increase. In this specification, as the average fiber length, a value obtained by taking a stereoscopic microscope image from a CCD camera into a PC and measuring by an image processing method using an image measuring machine is adopted.
　以上の形状を満足する繊維状非導電性充填剤であれば、何れの繊維を用いることもできるが、（Ｂ１）繊維状非導電性充填剤としては、例えば、ガラス繊維、アスベスト繊維、シリカ繊維、シリカ・アルミナ繊維、ジルコニア繊維、窒化硼素繊維、窒化硅素繊維、硼素繊維、チタン酸カリウム繊維等の無機質繊維状物質が挙げられる。（Ｂ１）成分として２種以上の繊維状非導電性充填剤を用いてもよい。本発明においては（Ｂ１）成分として、チタン酸カリウム繊維を使用することが好ましい。 Any fiber can be used as long as it is a fibrous non-conductive filler that satisfies the above shape, but examples of (B1) fibrous non-conductive filler include glass fiber, asbestos fiber, and silica fiber. Inorganic fibrous materials such as silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, and potassium titanate fiber. As the component (B1), two or more kinds of fibrous nonconductive fillers may be used. In the present invention, potassium titanate fibers are preferably used as the component (B1).
　（Ｂ２）非繊維状非導電性充填剤は、平均粒子径が５０μｍ以下の、板状充填剤及び粒状充填剤から選択される少なくとも１種である。上記平均粒子径が５０μｍ以下であると、成形体表面の起毛抑制効果が高くなりやすい。好ましい上記平均粒子径は１０～２０μｍである。なお、本明細書において、平均粒子径としては、レーザ回折／散乱式粒度分布測定法で測定した値を採用する。 (B2) The non-fibrous non-conductive filler is at least one selected from a plate-like filler and a granular filler having an average particle diameter of 50 μm or less. When the average particle size is 50 μm or less, the effect of suppressing napping on the surface of the molded body tends to increase. The average particle diameter is preferably 10 to 20 μm. In this specification, the value measured by the laser diffraction / scattering particle size distribution measurement method is adopted as the average particle size.
　以上の形状を満足する非繊維状非導電性充填剤であれば、何れの充填剤を用いることができるが、板状充填剤としては、タルク、マイカ、ガラスフレーク等が挙げられる。また、粒状充填剤としては、シリカ、石英粉末、ガラスビーズ、ガラス粉、硅酸カルシウム、硅酸アルミニウム、カオリン、クレー、珪藻土、ウォラストナイト等の硅酸塩；酸化鉄、酸化チタン、酸化亜鉛、アルミナ等の金属酸化物；炭酸カルシウム、炭酸マグネシウム等の金属炭酸塩；硫酸カルシウム、硫酸バリウム等の金属硫酸塩；炭化硅素；窒化硅素；窒化硼素等が挙げられる。（Ｂ２）成分として２種以上を用いてもよい。本発明においては（Ｂ２）成分として、板状充填剤のタルク、マイカ、粒状充填剤のシリカを使用することが好ましく、板状充填剤のタルク、マイカを使用することがより好ましい。 Any filler can be used as long as it is a non-fibrous non-conductive filler that satisfies the above shape, and examples of the plate-like filler include talc, mica, and glass flakes. In addition, particulate fillers include silica, quartz powder, glass beads, glass powder, calcium oxalate, aluminum oxalate, kaolin, clay, diatomaceous earth, wollastonite, etc .; iron oxide, titanium oxide, zinc oxide And metal oxides such as alumina; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; silicon carbide; silicon nitride; As the component (B2), two or more kinds may be used. In the present invention, as the component (B2), it is preferable to use talc and mica of plate-like filler and silica of granular filler, and it is more preferable to use talc and mica of plate-like filler.
　（Ｂ）成分の含有量（上記（Ｂ１）成分の含有量と、上記（Ｂ２）成分の含有量との合計）は、本発明のカメラモジュール用液晶性組成物において、５～２０質量％である。（Ｂ）成分の含有量が５質量％以上であると、カメラモジュールとして必要な機械強度、荷重たわみ温度が確保されやすく、２０質量％以下であると、成形体表面の起毛抑制効果が高くなりやすい。より好ましい上記含有量は１０～２０質量％である。 The content of the component (B) (the sum of the content of the component (B1) and the content of the component (B2)) is 5 to 20% by mass in the liquid crystal composition for a camera module of the present invention. is there. When the content of the component (B) is 5% by mass or more, the mechanical strength and the deflection temperature under load necessary for the camera module are easily secured, and when the content is 20% by mass or less, the effect of suppressing the raising of the surface of the molded article is increased. Cheap. A more preferable content is 10 to 20% by mass.
［（Ｃ）共重合体］
　（Ｃ）共重合体は、（Ｃ１）オレフィン系共重合体及び（Ｃ２）スチレン系共重合体から選択される少なくとも１種である。（Ｃ）成分をカメラモジュール用液晶性樹脂組成物に配合させることが、当該組成物を成形してなる成形体を超音波洗浄したときの、成形体表面の起毛を抑えることに寄与する。
　起毛を抑える理由については明確になっておるわけではないが、ある一定量配合させることにより、成形体表面状態を変化させ、その変化が起毛を抑えることに寄与していると考えられる。 [(C) Copolymer]
The (C) copolymer is at least one selected from (C1) an olefin copolymer and (C2) a styrene copolymer. Mixing the component (C) with the liquid crystalline resin composition for a camera module contributes to suppressing raising of the surface of the molded product when the molded product obtained by molding the composition is subjected to ultrasonic cleaning.
The reason for suppressing the raising is not clarified, but it is considered that by adding a certain amount, the surface state of the molded body is changed, and the change contributes to suppressing the raising.
　（Ｃ１）オレフィン系共重合体としては、例えば、α－オレフィンに由来する繰り返し単位とα，β－不飽和酸のグリシジルエステルに由来する繰り返し単位とから構成される共重合体が挙げられる。 (C1) Examples of the olefin copolymer include a copolymer composed of a repeating unit derived from an α-olefin and a repeating unit derived from a glycidyl ester of an α, β-unsaturated acid.
　α－オレフィンは特に限定されず、例えば、エチレン、プロピレン、ブテン等が挙げられるが、中でもエチレンが好ましく用いられる。α，β－不飽和酸のグリシジルエステルは下記一般式（ＩＶ）で示されるものである。α，β－不飽和酸のグリシジルエステルは、例えばアクリル酸グリシジルエステル、メタクリル酸グリシジルエステル、エタクリル酸グリシジルエステル、イタコン酸グリシジルエステル等であるが、特にメタクリル酸グリシジルエステルが好ましい。
Figure JPOXMLDOC01-appb-C000004
 The α-olefin is not particularly limited and includes, for example, ethylene, propylene, butene, etc. Among them, ethylene is preferably used. The glycidyl ester of α, β-unsaturated acid is represented by the following general formula (IV). Examples of the glycidyl ester of α, β-unsaturated acid include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl methacrylate is particularly preferable.
Figure JPOXMLDOC01-appb-C000004
　（Ｃ１）オレフィン系共重合体において、α－オレフィンに由来する繰り返し単位の含有量は８７～９８質量％であり、α，β－不飽和酸のグリシジルエステルに由来する繰り返し単位の含有量は１３～２質量％であることが好ましい。 (C1) In the olefin copolymer, the content of repeating units derived from α-olefin is 87 to 98% by mass, and the content of repeating units derived from glycidyl ester of α, β-unsaturated acid is 13 It is preferably 2% by mass.
　本発明で用いる（Ｃ１）オレフィン系共重合体は、本発明を損なわない範囲で上記２成分以外に第３成分としてアクリロニトリル、アクリル酸エステル、メタクリル酸エステル、α－メチルスチレン、無水マレイン酸等のオレフィン系不飽和エステルの１種又は２種以上に由来する繰り返し単位を、上記２成分１００質量部に対し０～４８質量部含有してもよい。 The (C1) olefin copolymer used in the present invention is a third component other than the above two components within the scope of the present invention, such as acrylonitrile, acrylic ester, methacrylic ester, α-methylstyrene, maleic anhydride, etc. A repeating unit derived from one or more olefinic unsaturated esters may be contained in an amount of 0 to 48 parts by mass with respect to 100 parts by mass of the two components.
　本発明の（Ｃ１）成分であるオレフィン系共重合体は、各成分に対応するモノマー及びラジカル重合触媒を用いて通常のラジカル重合法により容易に調製することができる。より具体的には、通常、α－オレフィンとα，β－不飽和酸のグリシジルエステルとをラジカル発生剤の存在下、５００～４０００気圧、１００～３００℃で適当な溶媒や連鎖移動剤の存在下又は不存在下に共重合させる方法により製造できる。また、α－オレフィンとα，β－不飽和酸のグリシジルエステル及びラジカル発生剤とを混合し、押出機の中で溶融グラフト共重合させる方法によっても製造できる。 The olefin copolymer as the component (C1) of the present invention can be easily prepared by a normal radical polymerization method using a monomer and a radical polymerization catalyst corresponding to each component. More specifically, the presence of a suitable solvent or chain transfer agent is usually obtained by mixing α-olefin and glycidyl ester of α, β-unsaturated acid in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C. It can be produced by a method of copolymerization under or in the absence. It can also be produced by a method in which an α-olefin, a glycidyl ester of α, β-unsaturated acid and a radical generator are mixed and melt graft copolymerized in an extruder.
　（Ｃ２）のスチレン系共重合体としては、例えば、スチレン類に由来する繰り返し単位とα，β－不飽和酸のグリシジルエステルに由来する繰り返し単位とから構成される共重合体が挙げられる。α，β－不飽和酸のグリシジルエステルについては、（Ｃ１）成分で説明したものと同様であるため説明を省略する。 Examples of the (C2) styrenic copolymer include a copolymer composed of a repeating unit derived from styrene and a repeating unit derived from a glycidyl ester of an α, β-unsaturated acid. Since the glycidyl ester of α, β-unsaturated acid is the same as that described for the component (C1), description thereof is omitted.
　スチレン類としては、スチレン、α－メチルスチレン、ブロム化スチレン、ジビニルベンゼン等が挙げられるが、スチレンが好ましく用いられる。 Examples of styrenes include styrene, α-methylstyrene, brominated styrene, divinylbenzene and the like, and styrene is preferably used.
　本発明で用いる（Ｃ２）スチレン系共重合体は、上記２成分以外に第３成分として他のビニルモノマーの１種又は２種以上に由来する繰り返し単位を含有する多元共重合体であってもよい。第３成分として好適なものは、アクリロニトリル、アクリル酸エステル、メタクリル酸エステル、無水マレイン酸等のオレフィン系不飽和エステルの１種又は２種以上に由来する繰り返し単位である。これらの繰り返し単位をスチレン系共重合体中に４０質量％以下含有するスチレン系共重合体が（Ｃ２）成分として好ましい。 The (C2) styrenic copolymer used in the present invention may be a multi-component copolymer containing a repeating unit derived from one or more of the other vinyl monomers as the third component in addition to the above two components. Good. Suitable as the third component is a repeating unit derived from one or more olefinic unsaturated esters such as acrylonitrile, acrylic acid ester, methacrylic acid ester, and maleic anhydride. A styrene copolymer containing 40% by mass or less of these repeating units in the styrene copolymer is preferred as the component (C2).
　（Ｃ２）スチレン系共重合体において、α，β－不飽和酸のグリシジルエステルに由来する繰り返し単位の含有量は２～２０質量％であり、スチレン類に由来する繰り返し単位の含有量は８０～９８重量％であることが好ましい。 (C2) In the styrene copolymer, the content of the repeating unit derived from the glycidyl ester of α, β-unsaturated acid is 2 to 20% by mass, and the content of the repeating unit derived from styrene is 80 to It is preferably 98% by weight.
　（Ｃ２）スチレン系共重合体は、各成分に対応するモノマー及びラジカル重合触媒を用いて通常のラジカル重合法により調製することができる。より具体的には、通常、スチレン類とα，β－不飽和酸のグリシジルエステルとをラジカル発生剤の存在下、５００～４０００気圧、１００～３００℃で適当な溶媒や連鎖移動剤の存在下又は不存在下に共重合させる方法により製造できる。また、スチレン類とα，β－不飽和酸のグリシジルエステル及びラジカル発生剤とを混合し、押出機の中で溶融グラフト共重合させる方法によっても製造できる。 (C2) The styrene copolymer can be prepared by a normal radical polymerization method using a monomer corresponding to each component and a radical polymerization catalyst. More specifically, styrenes and glycidyl esters of α, β-unsaturated acids are usually present in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C. in the presence of a suitable solvent or chain transfer agent. Or it can manufacture by the method of copolymerizing in absence. It can also be produced by a method in which styrenes, an α, β-unsaturated glycidyl ester and a radical generator are mixed and subjected to melt graft copolymerization in an extruder.
　なお、（Ｃ）共重合体としては、（Ｃ１）オレフィン系共重合体が耐熱性の点で好ましいが、（Ｃ１）成分と（Ｃ２）成分との割合は、適宜、要求される特性に沿って選択することができる。 The (C) copolymer is preferably an (C1) olefin copolymer in terms of heat resistance, but the ratio of the (C1) component to the (C2) component is in accordance with the required characteristics as appropriate. Can be selected.
　（Ｃ）共重合体の含有量（（Ｃ１）成分と（Ｃ２）成分との合計量）は、本発明のカメラモジュール用樹脂組成物において、２～１０質量％である。（Ｃ）成分の含有量が２質量％以上であることは、成形体表面の起毛抑制の点で必要であり、１０質量％以下であることは流動性を損なわず、良好な成形体を得るという理由で必要である。より好ましい上記含有量は２～７質量％である。 The content of the (C) copolymer (total amount of the (C1) component and the (C2) component) is 2 to 10% by mass in the camera module resin composition of the present invention. The content of the component (C) is 2% by mass or more from the viewpoint of suppressing raising of the surface of the molded body, and being 10% by mass or less obtains a good molded body without impairing fluidity. It is necessary for the reason. A more preferable content is 2 to 7% by mass.
［（Ｄ）導電性充填剤］
　（Ｄ）導電性充填剤は、（Ｄ１）平均繊維長が５０μｍ以上の繊維状導電性充填剤と、（Ｄ２）平均粒子径が２０ｎｍ～５０μｍの、板状充填剤及び粒状充填剤から選択される少なくとも１種の非繊維状導電性充填剤と、からなる。 [(D) conductive filler]
(D) The conductive filler is selected from (D1) a fibrous conductive filler having an average fiber length of 50 μm or more, and (D2) a plate-like filler and a granular filler having an average particle diameter of 20 nm to 50 μm. And at least one non-fibrous conductive filler.
　また、（Ｄ１）繊維状導電性充填剤の平均繊維長は５０μｍ以上である。上記平均繊維長が５０μｍ以上であることは、帯電防止性を発現させる点で必要である。なお、上記平均繊維長の上限は特に限定されないが、実用上は、例えば、１０ｍｍが挙げられる。 (D1) The average fiber length of the fibrous conductive filler is 50 μm or more. The average fiber length of 50 μm or more is necessary from the viewpoint of developing antistatic properties. In addition, although the upper limit of the said average fiber length is not specifically limited, For example, 10 mm is mentioned practically.
　以上の形状を満足する繊維状導電性充填剤であれば、何れの繊維を用いることができるが、（Ｄ１）繊維状導電性充填剤としては、例えば、炭素繊維；金属繊維等の導電性繊維；ガラス繊維、ウィスカー、無機系繊維、鉱石系繊維等にニッケル、銅等の金属をコートし、導電性を付与したものが挙げられる。 Any fiber can be used as long as it is a fibrous conductive filler satisfying the above shape. Examples of (D1) fibrous conductive filler include carbon fibers; conductive fibers such as metal fibers. Glass fibers, whiskers, inorganic fibers, ore fibers, and the like are coated with a metal such as nickel or copper to impart conductivity.
　炭素繊維としては、ポリアクリロニトリルを原料とするＰＡＮ系炭素繊維、ピッチを原料とするピッチ系炭素繊維が挙げられる。 Examples of carbon fibers include PAN-based carbon fibers made from polyacrylonitrile and pitch-based carbon fibers made from pitch.
　金属繊維としては、軟鋼、ステンレス、鋼及びその合金、銅、黄銅、アルミニウム及びその合金、チタン、鉛等からなる繊維が挙げられる。これらの金属繊維は、その導電性により必要であれば更に導電性を付与するために他の金属をコートしたものも使用可能である。 Examples of the metal fibers include fibers made of mild steel, stainless steel, steel and alloys thereof, copper, brass, aluminum and alloys thereof, titanium, lead and the like. As these metal fibers, those coated with other metals can be used in order to impart further conductivity if necessary due to their conductivity.
　上記ウィスカーとしては、窒化珪素ウィスカー、三窒化珪素ウィスカー、塩基性硫酸マグネシウムウィスカー、チタン酸バリウムウィスカー、炭化珪素ウィスカー、ボロンウィスカー等が挙げられる。上記無機系繊維としては、ロックウール、ジルコニア、アルミナシリカ、チタン酸カリウム、チタン酸バリウム、酸化チタン、炭化珪素、アルミナ、シリカ、高炉スラグ等からなる繊維が挙げられる。上記鉱石系繊維としては、アスベスト等からなる繊維が挙げられる。 Examples of the whisker include silicon nitride whisker, silicon trinitride whisker, basic magnesium sulfate whisker, barium titanate whisker, silicon carbide whisker, and boron whisker. Examples of the inorganic fiber include fibers made of rock wool, zirconia, alumina silica, potassium titanate, barium titanate, titanium oxide, silicon carbide, alumina, silica, blast furnace slag, and the like. Examples of the ore fiber include fibers made of asbestos.
　（Ｄ１）成分として２種以上の繊維状導電性充填剤を用いてもよい。本発明においては（Ｄ１）成分として、ＰＡＮ系炭素繊維、ピッチ系炭素繊維を使用することが好ましい。 (D1) Two or more kinds of fibrous conductive fillers may be used as the component. In the present invention, it is preferable to use PAN-based carbon fibers and pitch-based carbon fibers as the component (D1).
　（Ｄ１）成分の含有量は、本発明のカメラモジュール用樹脂組成物において、１～５質量％である。（Ｄ１）成分の含有量が１質量％以上であることは、帯電防止性を発現させる点で必要であり、５質量％以下であることは、導電性を半導電域に調整する点と流動性の低下や起毛性の悪化を抑制する点で必要である。より好ましい上記含有量は２～４質量％である。 (D1) The content of the component is 1 to 5% by mass in the resin composition for a camera module of the present invention. It is necessary for the content of the component (D1) to be 1% by mass or more from the viewpoint of developing antistatic properties, and 5% by mass or less means that the conductivity is adjusted to a semiconductive region and flow. It is necessary in terms of suppressing the deterioration of the sex and the raising of the hair raising property. A more preferable content is 2 to 4% by mass.
　（Ｄ２）非繊維状導電性充填剤は、平均粒子径が２０ｎｍ～５０μｍの、板状充填剤及び粒状充填剤から選択される少なくとも１種である。上記平均粒子径が２０ｎｍ以上であることは、流動性の低下を抑制する点で必要である。上記平均粒子径が５０μｍ以下であることは、表面の平滑性の悪化を抑制する点で必要である。 (D2) The non-fibrous conductive filler is at least one selected from a plate-like filler and a granular filler having an average particle diameter of 20 nm to 50 μm. The average particle size of 20 nm or more is necessary from the viewpoint of suppressing a decrease in fluidity. The average particle diameter of 50 μm or less is necessary in terms of suppressing deterioration of surface smoothness.
　以上の形状を満足する非繊維状導電性充填剤であれば、何れの充填剤を用いることができるが、板状充填剤としては、黒鉛、板状金属粉（例えば、アルミ、鉄、銅）等が挙げられる。また、粒状充填剤としては、カーボンブラック、粒状金属粉（例えば、アルミ、鉄、銅）、粒状導電性セラミックス（例えば、酸化亜鉛、酸化スズ、酸化インジウムスズ）等が挙げられる。（Ｄ２）成分として２種以上を用いてもよい。本発明においては（Ｄ２）成分として、黒鉛、カーボンブラックを使用することが好ましい。 Any filler can be used as long as it is a non-fibrous conductive filler satisfying the above shape, but as the plate-like filler, graphite, plate-like metal powder (for example, aluminum, iron, copper) Etc. Examples of the particulate filler include carbon black, particulate metal powder (for example, aluminum, iron, copper), particulate conductive ceramics (for example, zinc oxide, tin oxide, indium tin oxide) and the like. As the component (D2), two or more kinds may be used. In the present invention, graphite and carbon black are preferably used as the component (D2).
　（Ｄ２）成分が黒鉛である場合、平均粒子径は５～５０μｍであることが好ましく、厚みは０．５～１０μｍであることが好ましい。
　（Ｄ２）成分がカーボンブラックである場合、平均粒子径は２０～１００ｎｍであることが好ましい。 When the component (D2) is graphite, the average particle size is preferably 5 to 50 μm and the thickness is preferably 0.5 to 10 μm.
When the component (D2) is carbon black, the average particle size is preferably 20 to 100 nm.
　（Ｄ２）成分の含有量は、本発明のカメラモジュール用樹脂組成物において、１～１５質量％である。（Ｄ２）成分の含有量が１質量％以上であることは、導電性のばらつきを抑え、安定した帯電防止性を発現させる点で必要であり、１５質量％以下であることは、流動性の低下を抑制する点で必要である。より好ましい上記含有量は２～１０質量％である。 (D2) The content of the component is 1 to 15% by mass in the resin composition for a camera module of the present invention. The content of the component (D2) is 1% by mass or more, which is necessary in terms of suppressing variation in conductivity and exhibiting stable antistatic properties, and being 15% by mass or less This is necessary in terms of suppressing the decrease. A more preferable content is 2 to 10% by mass.
［その他の成分］
　本発明のカメラモジュール用液晶性樹脂組成物には、本発明の効果を害さない範囲で、その他の重合体、一般に合成樹脂に添加される公知の物質、即ち、酸化防止剤や紫外線吸収剤等の安定剤、（Ｄ）成分以外の帯電防止剤、難燃剤、染料や顔料等の着色剤、潤滑剤、離型剤、及び結晶化促進剤、結晶核剤等も要求性能に応じ適宜添加することができる。 [Other ingredients]
The liquid crystalline resin composition for a camera module of the present invention includes other polymers, known substances generally added to synthetic resins, that is, antioxidants, ultraviolet absorbers, etc., as long as the effects of the present invention are not impaired. Stabilizers, antistatic agents other than component (D), flame retardants, colorants such as dyes and pigments, lubricants, mold release agents, crystallization accelerators, crystal nucleating agents, etc. are added as appropriate according to the required performance. be able to.
［カメラモジュール用液晶性樹脂組成物の調製］
　本発明のカメラモジュール用樹脂組成物の調製は特に限定されない。例えば、上記（Ａ）、（Ｂ）、（Ｃ）、及び（Ｄ）成分を配合して、これらを１軸又は２軸押出機を用いて溶融混練処理することで、カメラモジュール用液晶性樹脂組成物の調製が行われる。 [Preparation of liquid crystalline resin composition for camera module]
The preparation of the resin composition for a camera module of the present invention is not particularly limited. For example, by blending the above components (A), (B), (C), and (D), and melt-kneading these using a single screw or twin screw extruder, a liquid crystalline resin for a camera module Preparation of the composition takes place.
［カメラモジュール用液晶性樹脂組成物］
　本発明のカメラモジュール用液晶性樹脂組成物中の（Ｂ）成分の形状と、配合される前の（Ｂ）成分の形状とは異なる。上述の（Ｂ）成分の形状は配合される前の形状である。配合される前の形状が上述の通りであれば、表面が起毛しにくいカメラモジュール用部品が得られる。 [Liquid crystalline resin composition for camera modules]
The shape of the component (B) in the liquid crystalline resin composition for a camera module of the present invention is different from the shape of the component (B) before blending. The shape of the above component (B) is the shape before blending. If the shape before blending is as described above, a camera module component that is less prone to raising the surface can be obtained.
　同様に、本発明のカメラモジュール用液晶性樹脂組成物中の（Ｄ）成分の形状と、配合される前の（Ｄ）成分の形状とは異なる。上述の（Ｄ）成分の形状は配合される前の形状である。配合される前の形状が上述の通りであれば、帯電しにくいカメラモジュール用部品が得られる。 Similarly, the shape of the component (D) in the liquid crystalline resin composition for a camera module of the present invention is different from the shape of the component (D) before blending. The shape of the above component (D) is the shape before blending. If the shape before blending is as described above, a camera module component that is difficult to be charged can be obtained.
　上記のようにして得られた本発明のカメラモジュール用液晶性樹脂組成物は、溶融粘度が５０Ｐａ・ｓｅｃ以下であることが好ましい。流動性が高く、成形性に優れる点も本発明のカメラモジュール用液晶性樹脂組成物の特徴の一つである。ここで、溶融粘度は、シリンダー温度３５０℃、せん断速度１０００ｓｅｃ－１の条件で、ＩＳＯ　１１４４３に準拠した測定方法で得られた値を採用する。 The liquid crystalline resin composition for a camera module of the present invention obtained as described above preferably has a melt viscosity of 50 Pa · sec or less. One of the characteristics of the liquid crystalline resin composition for camera modules of the present invention is that it has high fluidity and excellent moldability. Here, as the melt viscosity, a value obtained by a measurement method based on ISO 11443 under conditions of a cylinder temperature of 350 ° C. and a shear rate of 1000 sec −1 is adopted.
　本発明のカメラモジュール用液晶性樹脂組成物は、荷重たわみ温度が２００℃以上であることが好ましい。耐熱性に優れる点も本発明のカメラモジュール用液晶性樹脂組成物の特徴の一つである。なお、荷重たわみ温度はＩＳＯ　７５－１，２に準拠した方法で測定された値を採用する。 The liquid crystalline resin composition for a camera module of the present invention preferably has a deflection temperature under load of 200 ° C. or higher. The point which is excellent in heat resistance is also one of the characteristics of the liquid crystalline resin composition for camera modules of this invention. For the deflection temperature under load, a value measured by a method based on ISO 75-1 or 2 is adopted.
　本発明のカメラモジュール用液晶性樹脂組成物は、体積抵抗率が１×１０４～１×１０１４Ω・ｃｍである。即ち、上記体積抵抗率の導電性は半導電域に調整され、これにより、優れた帯電防止性が発現する。上記体積抵抗率が１×１０４Ω・ｃｍ未満であると、導電性が高くなりすぎて短絡が生じる場合がある。前記体積抵抗率が１×１０１４Ω・ｃｍを超えると、導電性が低くなりすぎて帯電防止性が発現しない場合がある。 The liquid crystalline resin composition for a camera module of the present invention has a volume resistivity of 1 × 10 4 to 1 × 10 14 Ω · cm. That is, the conductivity of the volume resistivity is adjusted to a semiconductive region, thereby exhibiting excellent antistatic properties. If the volume resistivity is less than 1 × 10 4 Ω · cm, the electrical conductivity may be too high and a short circuit may occur. If the volume resistivity exceeds 1 × 10 14 Ω · cm, the electrical conductivity may be too low to exhibit antistatic properties.
＜カメラモジュール用部品及びカメラモジュール＞
　上記カメラモジュール用液晶性樹脂組成物を用いて、カメラモジュール用部品を製造する。本発明の樹脂組成物を原料として用いれば、カメラモジュール用部品が帯電しにくくなる。したがって、本発明の樹脂組成物からなるカメラモジュール用部品は、静電気による動作不良を起こしにくい。 <Camera module parts and camera module>
A camera module component is manufactured using the liquid crystalline resin composition for a camera module. If the resin composition of the present invention is used as a raw material, the camera module component is less likely to be charged. Therefore, the camera module component comprising the resin composition of the present invention is less likely to cause malfunction due to static electricity.
　また、本発明の樹脂組成物を原料として用いれば、カメラモジュール用部品の表面が起毛しにくくなる。カメラモジュール用部品は、超音波洗浄されるため、超音波洗浄されても表面が起毛しにくいことが求められる。本発明の樹脂組成物を用いれば、カメラモジュール用部品の超音波洗浄をより強い条件で行っても、ゴミ等の原因となる脱落物が生じないか、ほとんど生じない。したがって、カメラモジュール用部品が完成品に組み込まれた後に、このカメラモジュール用部品の表面が起毛することにより生じるゴミで、完成品の品質に影響を与えることはほとんど無い。 Further, when the resin composition of the present invention is used as a raw material, the surface of the camera module component is hardly raised. Since the camera module component is ultrasonically cleaned, it is required that the surface is not easily raised even if the ultrasonic cleaning is performed. If the resin composition of the present invention is used, even if the ultrasonic cleaning of camera module parts is performed under stronger conditions, there will be no or almost no dropouts causing dust and the like. Accordingly, after the camera module parts are incorporated into the finished product, the dust generated by raising the surface of the camera module parts hardly affects the quality of the finished product.
　本発明のカメラモジュール用液晶性樹脂組成物を成形してなるカメラモジュール用部品について説明する。一般的なカメラモジュールの断面を図１に模式的に示した。図１に示す通り、カメラモジュール１は、基板１０と、光学素子１１と、リード配線１２と、レンズホルダー１３と、バレル１４と、レンズ１５と、ＩＲフィルター１６と、ガイド１７とを備える。 The camera module component formed by molding the liquid crystalline resin composition for a camera module of the present invention will be described. A cross section of a general camera module is schematically shown in FIG. As shown in FIG. 1, the camera module 1 includes a substrate 10, an optical element 11, a lead wire 12, a lens holder 13, a barrel 14, a lens 15, an IR filter 16, and a guide 17.
　光学素子１１は基板１０上に配置されており、光学素子１１と基板１０との間はリード配線１２で電気的に接続されている。 The optical element 11 is disposed on the substrate 10, and the optical element 11 and the substrate 10 are electrically connected by a lead wiring 12.
　ガイド１７は、基板１０上に配置され、レンズホルダー１３は、ガイド１７上に配置されており、ガイド１７及びレンズホルダー１３は、光学素子１１を覆う。レンズホルダー１３は頂部に開口が形成されており、この開口壁面には螺旋状の溝部が形成されている。 The guide 17 is disposed on the substrate 10, the lens holder 13 is disposed on the guide 17, and the guide 17 and the lens holder 13 cover the optical element 11. The lens holder 13 has an opening at the top, and a spiral groove is formed on the wall surface of the opening.
　バレル１４は円筒状であり、円筒状の内部にレンズ１５が略水平になるように保持されている。また、円筒の一端の側壁には螺旋状の凸部が形成されており、この螺旋状の凸部と、レンズホルダー１３の開口壁面に形成された螺旋状の溝部とが螺合することで、バレル１４はレンズホルダー１３と連結する。また、円筒状のバレル１４の一端を閉じるように、ＩＲフィルター１６が、バレル１４の一端に配置される。図１に示すように、ＩＲフィルター１６とレンズ１５は略平行に並ぶ。 The barrel 14 has a cylindrical shape, and the lens 15 is held inside the cylindrical shape so as to be substantially horizontal. In addition, a spiral convex portion is formed on the side wall of one end of the cylinder, and this spiral convex portion and the spiral groove portion formed on the opening wall surface of the lens holder 13 are screwed together, The barrel 14 is connected to the lens holder 13. An IR filter 16 is disposed at one end of the barrel 14 so as to close one end of the cylindrical barrel 14. As shown in FIG. 1, the IR filter 16 and the lens 15 are arranged substantially in parallel.
　図１に示すようなカメラモジュール１においては、レンズホルダー１３が、レンズホルダー１３に巻かれたコイル（図示せず）が発生する磁力とコイルの周囲に配置された永久磁石（図示せず）との作用によってガイド１７上を上下することで、レンズ１５と光学素子１１との間の距離が変化する。この距離を調整することでカメラのフォーカス調整を行うことができる。 In the camera module 1 as shown in FIG. 1, the lens holder 13 includes a magnetic force generated by a coil (not shown) wound around the lens holder 13 and a permanent magnet (not shown) arranged around the coil. The distance between the lens 15 and the optical element 11 changes by moving up and down on the guide 17 by the action of. The focus of the camera can be adjusted by adjusting this distance.
　上記のようなカメラモジュール１において、カメラモジュール用部品であるレンズホルダー１３を、本発明のカメラモジュール用液晶性樹脂組成物を原料として製造することができる。一般的な液晶性樹脂組成物はこれらの部品を製造するための原料として適さない。一般的な液晶性樹脂組成物を原料としてレンズホルダー１３を製造すると以下の問題を生じる。 In the camera module 1 as described above, the lens holder 13 which is a camera module component can be manufactured using the liquid crystalline resin composition for a camera module of the present invention as a raw material. A general liquid crystalline resin composition is not suitable as a raw material for producing these parts. When the lens holder 13 is manufactured using a general liquid crystalline resin composition as a raw material, the following problems occur.
　一般的な液晶性樹脂組成物を成形してなる成形体は、マイナスに帯電しやすく、プラスに帯電しやすい樹脂、例えば、ナイロンを含む材料から成形してなる成形体との間で静電気を発生し、カメラモジュールにおいては動作不良の原因となる。また、一般的な液晶性樹脂組成物を成形してなる成形体は、高分子の分子配向が表面部分で特に大きいため成形体表面が起毛しやすく、この起毛は小さなゴミが発生する原因となる。この小さなゴミがレンズ１５等に付着するとカメラモジュールの性能が低下する。 Molded products made of general liquid crystalline resin compositions are easily charged negatively, and generate static electricity between molded products made of materials that easily charge positively, such as nylon. However, this causes a malfunction in the camera module. In addition, a molded body formed by molding a general liquid crystalline resin composition is likely to raise the surface of the molded body because the molecular orientation of the polymer is particularly large in the surface portion, and this raising causes generation of small dust. . If this small dust adheres to the lens 15 or the like, the performance of the camera module is degraded.
　レンズホルダー１３等のカメラモジュール用部品は、表面の埃や小さなゴミを除去する目的で、カメラモジュール１に組み込まれる前に超音波洗浄される。しかし、一般的な液晶性樹脂組成物を成形してなる成形体の表面は起毛しやすいため、超音波洗浄すると表面が毛羽立つ。このような問題が生じることから、通常、液晶性樹脂組成物を成形してなる成形体を超音波洗浄することはできない。 The camera module parts such as the lens holder 13 are ultrasonically cleaned before being incorporated into the camera module 1 for the purpose of removing dust and small dust on the surface. However, since the surface of a molded product formed by molding a general liquid crystalline resin composition is easily raised, the surface becomes fluffy when ultrasonically cleaned. Since such a problem arises, the molded object formed by shape | molding a liquid crystalline resin composition cannot usually be ultrasonically cleaned.
　上記のフォーカス調整は、レンズホルダー１３が、レンズホルダー１３に巻かれたコイル（図示せず）が発生する磁力とコイルの周囲に配置された永久磁石（図示せず）との作用によってガイド１７上を上下することで行われる。このとき、第一に、液晶性樹脂組成物を成形してなる成形体からなるレンズホルダー１３と、ナイロン等を含む材料を成形してなる成形体からなるガイド１７との間では静電気が発生し、レンズホルダー１３が動作不良を起こしやすい。そして、第二に、一般的な液晶性樹脂組成物を成形してなる成形体は、上記の通り、表面が起毛しやすいため、表面が剥離して剥離物が生じる可能性がある。この剥離物は小さなゴミとなりレンズ１５等に付着してカメラモジュールの性能を低下させる可能性が高い。 The focus adjustment is performed on the guide 17 by the action of the magnetic force generated by the coil (not shown) wound around the lens holder 13 and the permanent magnet (not shown) arranged around the coil. It is done by moving up and down. At this time, first, static electricity is generated between the lens holder 13 formed of a molded body formed by molding the liquid crystalline resin composition and the guide 17 formed of a molded body formed of a material containing nylon or the like. The lens holder 13 is liable to malfunction. Secondly, as described above, the molded body obtained by molding a general liquid crystalline resin composition is likely to have a raised surface, and thus the surface may be peeled off to produce a peeled product. There is a high possibility that the peeled material becomes small dust and adheres to the lens 15 or the like, thereby reducing the performance of the camera module.
　以上の通り、通常、液晶性樹脂組成物をレンズホルダー１３の原料として用いると不具合が生じやすいが、本発明のカメラモジュール用液晶性樹脂組成物は、成形体としたときに、帯電しにくく、また、この成形体を超音波洗浄しても起毛の問題がほとんど生じないほど成形体の表面状態が改良されているため、レンズホルダー１３の原料として好ましく用いることができる。 As described above, normally, when the liquid crystalline resin composition is used as a raw material for the lens holder 13, problems are likely to occur, but the liquid crystalline resin composition for a camera module of the present invention is difficult to be charged when formed into a molded body, Further, since the surface state of the molded body has been improved so that even if the molded body is ultrasonically cleaned, the problem of raising the hair hardly occurs, it can be preferably used as a raw material for the lens holder 13.
　本発明のカメラモジュール用液晶性樹脂組成物をレンズホルダー１３に用いる場合、ガイド１７の材料としては、本発明のカメラモジュール用液晶性樹脂組成物以外のものが挙げられ、具体的には、ナイロン等が挙げられる。 When the liquid crystalline resin composition for a camera module of the present invention is used for the lens holder 13, examples of the material for the guide 17 include materials other than the liquid crystalline resin composition for a camera module of the present invention. Etc.
　以下に実施例を挙げて、本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
＜材料＞
・液晶性樹脂（液晶性ポリエステルアミド樹脂）：ベクトラ（登録商標）Ｅ９５０ｉ（ポリプラスチックス（株）製）
・オレフィン系共重合体：住友化学（株）製　ボンドファースト２Ｃ（エチレン－グリシジルメタクリレート共重合体（グリシジルメタクリレートを６質量％含有））
・繊維状導電性充填剤：東邦テナックス（株）製　ＨＴＣ４３２（ＰＡＮ系炭素繊維、平均繊維径１０μｍ、平均繊維長６ｍｍ）
・非繊維状導電性充填剤１：日本黒鉛工業（株）製　ＣＰ（黒鉛、平均粒子径１０μｍ、板状）
・非繊維状導電性充填剤２：キャボットジャパン(株)製　ＶＵＬＣＡＮ　ＸＣ３０５（カーボンブラック、平均粒子径２０ｎｍ、粒状）
・繊維状非導電性充填剤：大塚化学（株）製　ティスモＮ－１０２（チタン酸カリウム繊維、平均繊維径０．３～０．６μｍ、平均繊維長１０～２０μｍ）
・非繊維状非導電性充填剤：松村産業（株）製　クラウンタルクＰＰ（タルク、平均粒子径１２．８μｍ、平均アスペクト比６、板状） <Material>
-Liquid crystalline resin (liquid crystalline polyester amide resin): Vectra (registered trademark) E950i (manufactured by Polyplastics Co., Ltd.)
・ Olefin copolymer: Bond First 2C (ethylene-glycidyl methacrylate copolymer (containing 6% by mass of glycidyl methacrylate)) manufactured by Sumitomo Chemical Co., Ltd.
-Fibrous conductive filler: manufactured by Toho Tenax Co., Ltd. HTC432 (PAN-based carbon fiber, average fiber diameter 10 μm, average fiber length 6 mm)
-Non-fibrous conductive filler 1: CP manufactured by Nippon Graphite Industry Co., Ltd. (graphite, average particle size 10 μm, plate-like)
・ Non-fibrous conductive filler 2: VULCAN XC305 (carbon black, average particle size 20 nm, granular) manufactured by Cabot Japan Co., Ltd.
-Fibrous non-conductive filler: Tismo N-102 (potassium titanate fiber, average fiber diameter 0.3 to 0.6 μm, average fiber length 10 to 20 μm) manufactured by Otsuka Chemical Co., Ltd.
-Non-fibrous non-conductive filler: Crown Talc PP (Talc, average particle diameter 12.8 μm, average aspect ratio 6, plate shape) manufactured by Matsumura Sangyo Co., Ltd.
＜カメラモジュール用液晶性樹脂組成物の製造＞
　上記成分を、表１に示す割合で二軸押出機（（株）日本製鋼所製ＴＥＸ３０α型）を用いて、シリンダー温度３５０℃にて溶融混練し、カメラモジュール用液晶性樹脂組成物ペレットを得た。 <Manufacture of liquid crystalline resin composition for camera module>
The above components were melt-kneaded at a cylinder temperature of 350 ° C. using a twin-screw extruder (TEX30α type, manufactured by Nippon Steel Works) at the ratio shown in Table 1 to obtain a liquid crystalline resin composition pellet for a camera module. It was.
＜溶融粘度＞
　実施例及び比較例のカメラモジュール用液晶性樹脂組成物の溶融粘度を、上記ペレットを用いて測定した。具体的には、キャピラリー式レオメーター（東洋精機製キャピログラフ１Ｄ：ピストン径１０ｍｍ）により、シリンダー温度３５０℃、せん断速度１０００ｓｅｃ－１の条件での見かけの溶融粘度をＩＳＯ　１１４４３に準拠して測定した。測定には、内径１ｍｍ、長さ２０ｍｍのオリフィスを用いた。結果を表１に示す。 <Melt viscosity>
The melt viscosity of the liquid crystalline resin compositions for camera modules of Examples and Comparative Examples was measured using the pellets. Specifically, the apparent melt viscosity under conditions of a cylinder temperature of 350 ° C. and a shear rate of 1000 sec −1 was measured according to ISO 11443 using a capillary rheometer (Capillograph 1D manufactured by Toyo Seiki: piston diameter 10 mm). For the measurement, an orifice having an inner diameter of 1 mm and a length of 20 mm was used. The results are shown in Table 1.
＜曲げ試験＞
　上記ペレットから１３０ｍｍ×１３ｍｍ×０．８ｍｍの曲げ試験片を作製し、これを用いて、ＡＳＴＭ　Ｄ７９０に準拠し、曲げ強度及び曲げ弾性率を測定した。結果を表１に示す。 <Bending test>
A bending test piece of 130 mm × 13 mm × 0.8 mm was prepared from the above pellets, and the bending strength and bending elastic modulus were measured using the bending test piece in accordance with ASTM D790. The results are shown in Table 1.
＜荷重たわみ温度＞
　実施例及び比較例のペレットを、成形機（住友重機械工業社製　「ＳＥ１００ＤＵ」）を用いて、以下の成形条件で成形し、測定用試験片（４ｍｍ×１０ｍｍ×８０ｍｍ）を得た。その後、ＩＳＯ　７５－１，２に準拠した方法で荷重たわみ温度を測定した。なお、曲げ応力としては、１．８ＭＰａを用いた。結果を表１に示す。
〔成形条件〕
シリンダー温度：　３５０℃
金型温度：　８０℃
背圧：　２．０ＭＰａ
射出速度：　３３ｍｍ／ｓｅｃ <Load deflection temperature>
The pellets of Examples and Comparative Examples were molded under the following molding conditions using a molding machine (“SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.) to obtain test specimens (4 mm × 10 mm × 80 mm). Thereafter, the deflection temperature under load was measured by a method in accordance with ISO 75-1 and 2. Note that 1.8 MPa was used as the bending stress. The results are shown in Table 1.
〔Molding condition〕
Cylinder temperature: 350 ° C
Mold temperature: 80 ℃
Back pressure: 2.0MPa
Injection speed: 33mm / sec
＜体積抵抗率＞
　φ１００ｍｍ×３ｍｍｔの平板試験片を用い、ＡＳＴＭ　Ｄ２５７に準拠して、体積抵抗率を測定した。結果を表１に示す。 <Volume resistivity>
Volume resistivity was measured according to ASTM D257 using a flat test piece of φ100 mm × 3 mmt. The results are shown in Table 1.
＜成形体表面の起毛状態（表面起毛抑制効果）の評価＞
　実施例及び比較例のペレットを、成形機（住友重機械工業社製　「ＳＥ３０ＤＵＺ」）を用いて、以下の成形条件で成形し、１２．５ｍｍ×１２０ｍｍ×０．８ｍｍの成形体を得た。この成形体を半分に切断したものを試験片として使用した。
〔成形条件〕
シリンダー温度：　３５０℃
金型温度：　９０℃
射出速度：　８０ｍｍ／ｓｅｃ
〔評価〕
　半分に切断した成形体を３分間、室温の水中で超音波洗浄機（出力３００Ｗ、周波数４５ｋＨｚ）にかけた。その後、超音波洗浄機にかける前後の成形体を比較して、成形体表面の毛羽立った部分の面積（起毛面積）を画像測定器（（株）ニレコ製ＬＵＺＥＸＦＳ）にて評価した。なお、評価面積は７５０ｍｍ２（１２．５ｍｍ×６０ｍｍ）であり、上記評価面積に対する上記起毛面積の割合（％）を結果として用いた。結果を表１に示す。
　起毛面積が少ないほど、起毛抑制効果が高い評価となる。 <Evaluation of napping state (surface napping suppression effect) on the surface of the molded body>
The pellets of Examples and Comparative Examples were molded under the following molding conditions using a molding machine (“SE30DUZ” manufactured by Sumitomo Heavy Industries, Ltd.) to obtain a molded body of 12.5 mm × 120 mm × 0.8 mm. What cut | disconnected this molded object in half was used as a test piece.
〔Molding condition〕
Cylinder temperature: 350 ° C
Mold temperature: 90 ℃
Injection speed: 80mm / sec
[Evaluation]
The molded body cut in half was subjected to an ultrasonic cleaner (output 300 W, frequency 45 kHz) in water at room temperature for 3 minutes. Thereafter, the molded bodies before and after being subjected to an ultrasonic cleaning machine were compared, and the area (raised area) of the fluffed portion on the surface of the molded body was evaluated with an image measuring instrument (LUZEXFS manufactured by Nireco Corporation). The evaluation area was 750 mm 2 (12.5 mm × 60 mm), and the ratio (%) of the raised area to the evaluation area was used as a result. The results are shown in Table 1.
The smaller the raising area, the higher the raising suppression effect.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表１に記載の結果から明らかなように、実施例のペレットを用いて製造した成形体は、体積抵抗率が１×１０４～１×１０１４Ω・ｃｍの範囲内にあることが確認された。また、上記成形体は、超音波洗浄しても表面が毛羽立たないことが確認された。これらの結果から、実施例のペレットを成形してなる成形体は、比較例等の通常の液晶性樹脂組成物ペレットを成形してなる成形体と比較して、帯電防止性に優れ、表面状態が大きく異なるといえる。 As is apparent from the results shown in Table 1, it was confirmed that the molded body produced using the pellets of the examples had a volume resistivity in the range of 1 × 10 4 to 1 × 10 14 Ω · cm. It was. Moreover, it was confirmed that the surface of the molded body was not fluffed even after ultrasonic cleaning. From these results, the molded body formed by molding the pellets of the examples is superior in antistatic property and surface state compared to the molded body formed by molding normal liquid crystalline resin composition pellets such as comparative examples. Can be said to be very different.
　また、実施例のペレットを用いて製造した成形体は、耐熱性及び耐衝撃性に優れることが確認された。 Also, it was confirmed that the molded body produced using the pellets of the examples was excellent in heat resistance and impact resistance.
　１　　　カメラモジュール
　１０　　基板
　１１　　光学素子
　１２　　リード配線
　１３　　レンズホルダー
　１４　　バレル
　１５　　レンズ
　１６　　ＩＲフィルター
　１７　　ガイド DESCRIPTION OF SYMBOLS 1 Camera module 10 Board | substrate 11 Optical element 12 Lead wiring 13 Lens holder 14 Barrel 15 Lens 16 IR filter 17 Guide

Claims (4)

  1. 　（Ａ）液晶性樹脂、
    　（Ｂ１）繊維状非導電性充填剤及び（Ｂ２）非繊維状非導電性充填剤から選択される少なくとも１種の（Ｂ）非導電性充填剤、
    　（Ｃ１）オレフィン系共重合体及び（Ｃ２）スチレン系共重合体から選択される少なくとも１種の（Ｃ）共重合体、並びに
    　（Ｄ１）繊維状導電性充填剤及び（Ｄ２）非繊維状導電性充填剤からなる（Ｄ）導電性充填剤
    を含有し、
    　（Ａ）成分の含有量が５５～９１質量％、（Ｂ）成分の含有量が５～２０質量％、（Ｃ）成分の含有量が２～１０質量％、（Ｄ１）成分の含有量が１～５質量％、（Ｄ２）成分の含有量が１～１５質量％であり、
    　前記（Ｂ１）繊維状非導電性充填剤は、平均繊維径が１．０μｍ以下、且つ平均繊維長が５～５０μｍであり、
    　前記（Ｂ２）非繊維状非導電性充填剤は、平均粒子径が５０μｍ以下の、板状充填剤及び粒状充填剤から選択される少なくとも１種であり、
    　前記（Ｃ１）オレフィン系共重合体は、α－オレフィンとα，β－不飽和酸のグリシジルエステルとから構成され、
    　前記（Ｃ２）スチレン系共重合体は、スチレン類とα，β－不飽和酸のグリシジルエステルとから構成され、
    　前記（Ｄ１）繊維状導電性充填剤は、平均繊維長が５０μｍ以上であり、
    　前記（Ｄ２）非繊維状導電性充填剤は、平均粒子径が２０ｎｍ～５０μｍの、板状充填剤及び粒状充填剤から選択される少なくとも１種であり、
    　体積抵抗率が１×１０４～１×１０１４Ω・ｃｍであるカメラモジュール用液晶性樹脂組成物。     (A) liquid crystalline resin,
    At least one (B) non-conductive filler selected from (B1) fibrous non-conductive filler and (B2) non-fibrous non-conductive filler,
    (C1) an olefin copolymer and (C2) at least one (C) copolymer selected from styrene copolymers, and (D1) fibrous conductive filler and (D2) non-fibrous conductive Containing a conductive filler (D) composed of a conductive filler,
    The content of component (A) is 55 to 91% by mass, the content of component (B) is 5 to 20% by mass, the content of component (C) is 2 to 10% by mass, and the content of component (D1) is 1 to 5% by mass, the content of component (D2) is 1 to 15% by mass,
    The (B1) fibrous nonconductive filler has an average fiber diameter of 1.0 μm or less and an average fiber length of 5 to 50 μm.
    The (B2) non-fibrous non-conductive filler is at least one selected from a plate-like filler and a granular filler having an average particle diameter of 50 μm or less,
    The (C1) olefin copolymer is composed of an α-olefin and a glycidyl ester of an α, β-unsaturated acid,
    The (C2) styrene copolymer is composed of styrenes and glycidyl ester of α, β-unsaturated acid,
    The (D1) fibrous conductive filler has an average fiber length of 50 μm or more,
    The (D2) non-fibrous conductive filler is at least one selected from a plate-like filler and a granular filler having an average particle diameter of 20 nm to 50 μm,
    A liquid crystalline resin composition for a camera module having a volume resistivity of 1 × 10 4 to 1 × 10 14 Ω · cm.
  2. 　請求項１記載のカメラモジュール用液晶性樹脂組成物からなるカメラモジュール用部品。 A camera module part comprising the liquid crystalline resin composition for a camera module according to claim 1.
  3. 　レンズホルダーである請求項２記載のカメラモジュール用部品。 3. The camera module component according to claim 2, wherein the camera module component is a lens holder.
  4. 　レンズホルダーと、前記レンズホルダーの台座となるガイドとを備えるカメラモジュールであって、
    　前記レンズホルダーは、請求項１記載のカメラモジュール用液晶性樹脂組成物からなり、
    　前記ガイドは、前記カメラモジュール用液晶性樹脂組成物以外の材料からなるカメラモジュール。
          A camera module comprising a lens holder and a guide serving as a base for the lens holder,
    The lens holder is made of a liquid crystalline resin composition for a camera module according to claim 1,
    The guide is a camera module made of a material other than the liquid crystalline resin composition for the camera module.
PCT/JP2013/081324 2012-12-03 2013-11-20 Liquid crystal resin composition for camera module and camera module using same WO2014087842A1 (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017038421A1 (en) * 2015-09-01 2017-03-09 ポリプラスチックス株式会社 Liquid crystalline resin composition for camera module and camera module using same
US9862809B2 (en) 2015-07-31 2018-01-09 Ticona Llc Camera module
KR20180041156A (en) * 2015-08-17 2018-04-23 티코나 엘엘씨 Liquid crystal polymer composition for camera module
JP2019015855A (en) * 2017-07-06 2019-01-31 ミツミ電機株式会社 Lens drive device, camera module, and camera mounting device
US10407605B2 (en) 2015-07-31 2019-09-10 Ticona Llc Thermally conductive polymer composition
US10633535B2 (en) 2017-02-06 2020-04-28 Ticona Llc Polyester polymer compositions
US10829634B2 (en) 2017-12-05 2020-11-10 Ticona Llc Aromatic polymer composition for use in a camera module
US11086200B2 (en) 2019-03-20 2021-08-10 Ticona Llc Polymer composition for use in a camera module
US11084925B2 (en) 2018-02-20 2021-08-10 Ticona Llc Thermally conductive polymer composition
US11098173B2 (en) 2016-07-27 2021-08-24 Sumitomo Chemical Company, Limited Prepreg, prepreg laminate and method for producing prepreg
US11384238B2 (en) 2018-02-08 2022-07-12 Celanese Sales Germany Gmbh Polymer composite containing recycled carbon fibers
US11722759B2 (en) 2019-03-20 2023-08-08 Ticona Llc Actuator assembly for a camera module

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101907100B1 (en) * 2015-12-24 2018-10-11 포리프라스틱 가부시키가이샤 Liquid crystalline resin composition for camera module, production method thereof, and camera module using the composition
CN110079058A (en) 2018-01-26 2019-08-02 上野制药株式会社 Liquid crystal polyester resin compositions
KR102461065B1 (en) 2020-12-29 2022-11-01 세양폴리머주식회사 Liquid crystal polyester resin composition and electronic component material containing the same

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08134334A (en) * 1994-11-10 1996-05-28 Sumitomo Chem Co Ltd Liquid crystal polyester resin composition
JPH08183910A (en) * 1994-12-28 1996-07-16 Toray Ind Inc Thermoplastic resin composition
JP2002509573A (en) * 1997-07-09 2002-03-26 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Liquid crystalline polymer-poly (phenylene oxide) blend
WO2007043701A1 (en) * 2005-10-13 2007-04-19 Polyplastics Co., Ltd. Liquid crystalline resin composition for use in injection molding
JP2007254717A (en) * 2006-02-27 2007-10-04 Toray Ind Inc Liquid crystalline resin composition and molded article consisting of the same
JP2009030044A (en) * 2007-07-02 2009-02-12 Asahi Kasei Chemicals Corp Resin composition having specific morphology
WO2009119863A1 (en) * 2008-03-28 2009-10-01 新日本石油株式会社 Liquid-crystal polyester resin composition for camera modules
WO2009119864A1 (en) * 2008-03-28 2009-10-01 新日本石油株式会社 Liquid-crystal polyester resin composition for camera modules
JP2009242453A (en) * 2008-03-28 2009-10-22 Nippon Oil Corp Liquid crystal polyester resin composition for camera module
WO2011036927A1 (en) * 2009-09-28 2011-03-31 新日本石油株式会社 Liquid-crystal polyester resin composition
WO2012050082A1 (en) * 2010-10-15 2012-04-19 Ｊｘ日鉱日石エネルギー株式会社 Liquid crystal polyester resin composition and camera module component
JP2012241089A (en) * 2011-05-18 2012-12-10 Teijin Chem Ltd High-cycle moldable thermoplastic resin composition
WO2013129338A1 (en) * 2012-02-29 2013-09-06 ポリプラスチックス株式会社 Liquid crystal resin composition for camera modules

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW340130B (en) 1993-12-28 1998-09-11 Toray Industries Shaped article of liquid crystalline resin
WO2006030951A1 (en) 2004-09-17 2006-03-23 Toray Industries, Inc. Resin composition and molded article comprising the same

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08134334A (en) * 1994-11-10 1996-05-28 Sumitomo Chem Co Ltd Liquid crystal polyester resin composition
JPH08183910A (en) * 1994-12-28 1996-07-16 Toray Ind Inc Thermoplastic resin composition
JP2002509573A (en) * 1997-07-09 2002-03-26 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー Liquid crystalline polymer-poly (phenylene oxide) blend
WO2007043701A1 (en) * 2005-10-13 2007-04-19 Polyplastics Co., Ltd. Liquid crystalline resin composition for use in injection molding
JP2007254717A (en) * 2006-02-27 2007-10-04 Toray Ind Inc Liquid crystalline resin composition and molded article consisting of the same
JP2009030044A (en) * 2007-07-02 2009-02-12 Asahi Kasei Chemicals Corp Resin composition having specific morphology
WO2009119863A1 (en) * 2008-03-28 2009-10-01 新日本石油株式会社 Liquid-crystal polyester resin composition for camera modules
WO2009119864A1 (en) * 2008-03-28 2009-10-01 新日本石油株式会社 Liquid-crystal polyester resin composition for camera modules
JP2009242453A (en) * 2008-03-28 2009-10-22 Nippon Oil Corp Liquid crystal polyester resin composition for camera module
WO2011036927A1 (en) * 2009-09-28 2011-03-31 新日本石油株式会社 Liquid-crystal polyester resin composition
WO2012050082A1 (en) * 2010-10-15 2012-04-19 Ｊｘ日鉱日石エネルギー株式会社 Liquid crystal polyester resin composition and camera module component
JP2012241089A (en) * 2011-05-18 2012-12-10 Teijin Chem Ltd High-cycle moldable thermoplastic resin composition
WO2013129338A1 (en) * 2012-02-29 2013-09-06 ポリプラスチックス株式会社 Liquid crystal resin composition for camera modules

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9862809B2 (en) 2015-07-31 2018-01-09 Ticona Llc Camera module
US10407605B2 (en) 2015-07-31 2019-09-10 Ticona Llc Thermally conductive polymer composition
US10767049B2 (en) 2015-08-17 2020-09-08 Ticona Llc Liquid crystalline polymer composition for camera modules
KR20180041156A (en) * 2015-08-17 2018-04-23 티코나 엘엘씨 Liquid crystal polymer composition for camera module
US11214683B2 (en) 2015-08-17 2022-01-04 Ticona Llc Liquid crystalline polymer composition for camera modules
US10106682B2 (en) 2015-08-17 2018-10-23 Ticona Llc Liquid crystalline polymer composition for camera modules
KR102571509B1 (en) * 2015-08-17 2023-08-25 티코나 엘엘씨 Liquid crystal polymer composition for camera module
JPWO2017038421A1 (en) * 2015-09-01 2018-07-12 ポリプラスチックス株式会社 Liquid crystalline resin composition for camera module and camera module using the same
WO2017038421A1 (en) * 2015-09-01 2017-03-09 ポリプラスチックス株式会社 Liquid crystalline resin composition for camera module and camera module using same
US11098173B2 (en) 2016-07-27 2021-08-24 Sumitomo Chemical Company, Limited Prepreg, prepreg laminate and method for producing prepreg
US10633535B2 (en) 2017-02-06 2020-04-28 Ticona Llc Polyester polymer compositions
JP2019015855A (en) * 2017-07-06 2019-01-31 ミツミ電機株式会社 Lens drive device, camera module, and camera mounting device
JP6989759B2 (en) 2017-07-06 2022-01-12 ミツミ電機株式会社 Lens drive device, camera module, and camera mount device
US10829634B2 (en) 2017-12-05 2020-11-10 Ticona Llc Aromatic polymer composition for use in a camera module
US11725106B2 (en) 2017-12-05 2023-08-15 Ticona Llc Aromatic polymer composition for use in a camera module
US11384238B2 (en) 2018-02-08 2022-07-12 Celanese Sales Germany Gmbh Polymer composite containing recycled carbon fibers
US11725105B2 (en) 2018-02-20 2023-08-15 Ticona Llc Thermally conductive polymer composition
US11084925B2 (en) 2018-02-20 2021-08-10 Ticona Llc Thermally conductive polymer composition
US11722759B2 (en) 2019-03-20 2023-08-08 Ticona Llc Actuator assembly for a camera module
US11086200B2 (en) 2019-03-20 2021-08-10 Ticona Llc Polymer composition for use in a camera module

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