WO2017110424A1 - カメラモジュール用液晶性樹脂組成物、その製造方法、及び上記組成物を用いたカメラモジュール - Google Patents

カメラモジュール用液晶性樹脂組成物、その製造方法、及び上記組成物を用いたカメラモジュール Download PDF

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WO2017110424A1
WO2017110424A1 PCT/JP2016/085909 JP2016085909W WO2017110424A1 WO 2017110424 A1 WO2017110424 A1 WO 2017110424A1 JP 2016085909 W JP2016085909 W JP 2016085909W WO 2017110424 A1 WO2017110424 A1 WO 2017110424A1
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Prior art keywords
crystalline resin
liquid crystalline
camera module
epoxy group
component
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PCT/JP2016/085909
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English (en)
French (fr)
Japanese (ja)
Inventor
不二 酒井
博樹 深津
青藤　宏光
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ポリプラスチックス株式会社
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Priority to CN201680062626.2A priority Critical patent/CN108350278B/zh
Priority to JP2017523563A priority patent/JP6190089B1/ja
Priority to KR1020187012357A priority patent/KR101907100B1/ko
Publication of WO2017110424A1 publication Critical patent/WO2017110424A1/ja

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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
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
    • B29B7/06—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices
    • B29B7/10—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type with movable mixing or kneading devices rotary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • B29B11/10—Extrusion moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B17/00—Details of cameras or camera bodies; Accessories therefor
    • G03B17/02—Bodies
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B30/00—Camera modules comprising integrated lens units and imaging units, specially adapted for being embedded in other devices, e.g. mobile phones or vehicles

Definitions

  • the present invention relates to a liquid crystalline resin composition for a camera module, a method for producing the same, and a camera module using the composition.
  • 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 present invention has been made in order to solve the above-mentioned problems, and its purpose is to produce a camera module component in which the surface is less likely to be raised, is excellent in low dust generation, and warpage deformation is suppressed. It is providing the liquid crystalline resin composition for camera modules.
  • the inventors of the present invention have made extensive studies to solve the above problems.
  • the liquid crystalline resin, the particulate filler having an average primary particle size in a specific range, and an epoxy group-containing copolymer are contained in a specific ratio, and the number of aggregates having a particle size of 10 ⁇ m or more is within a specific range.
  • the present inventors have found that the above problems can be solved by using a certain liquid crystalline resin composition for a camera module, and have completed the present invention. More specifically, the present invention provides the following.
  • the content of component (A) is 35 to 79% by mass
  • the content of component (B) is 20 to 60% by mass
  • the content of component (C) is 1 to 5% by mass
  • the average primary particle size of the component is 5 ⁇ m or less
  • a liquid crystalline resin composition for a camera module wherein the number of aggregates having a particle diameter of 10 ⁇ m or more is 5 or less per cross-sectional area of 0.1 mm 2 .
  • the (C) epoxy group-containing copolymer is at least one selected from the group consisting of (C1) an epoxy group-containing olefin copolymer and (C2) an epoxy group-containing styrene copolymer.
  • the composition according to (1) is at least one selected from the group consisting of (C1) an epoxy group-containing olefin copolymer and (C2) an epoxy group-containing styrene copolymer.
  • a camera module part comprising the composition according to (1) or (2).
  • a camera module provided with the components described in (5).
  • a camera module part is produced using the liquid crystalline resin composition for a camera module of the present invention as a raw material, a camera module part having a surface that is less likely to be raised, excellent in low dust generation, and suppressed in warpage is obtained. .
  • FIG. 1 is a cross-sectional view schematically showing a general camera module.
  • FIG. 2 is a view showing two of the electron micrographs used in Example 1.
  • FIG. 3 is a diagram showing two of the electron micrographs used in Comparative Example 1.
  • the liquid crystalline resin composition for a camera module of the present invention contains (A) a liquid crystalline resin, (B) a particulate filler, and (C) an epoxy group-containing copolymer.
  • 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 (A) liquid crystalline resin as described above is not particularly limited, and is preferably an aromatic polyester and / or an aromatic polyester amide. Moreover, the polyester which partially contains aromatic polyester and / or aromatic polyester amide in the same molecular chain is also within the range.
  • the liquid crystalline resin is preferably at least about 2.0 dl / g, more preferably 2.0 to 10.0 dl / g when dissolved in pentafluorophenol at a concentration of 0.1% by mass at 60 ° C. Those having a logarithmic viscosity (IV) of 1 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 is 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 from the above monomer compound (or a mixture of monomers) by a known method using a direct polymerization method or a transesterification method, and usually a melt polymerization method. Or a slurry polymerization method.
  • the above compounds having ester-forming ability may be used for polymerization in the form 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 weight, particularly about 0.01 to 0.2% by weight, based on the total weight of 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 35 to 79% by mass. If the content of component (A) is 35% 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 79% by mass or less, it is preferable for reasons of heat resistance. .
  • the preferable content of the component (A) is 40 to 73% by mass, and the more preferable content of the component (A) is 45 to 67% by mass.
  • the component (B) is a granular filler, and the average primary particle size of the component (B) is 5 ⁇ m or less.
  • the average primary particle diameter is preferably 0.25 to 4.5 ⁇ m, more preferably 0.5 to 4 ⁇ m. In this specification, a value measured by a laser diffraction / scattering particle size distribution measurement method is employed as the average primary particle size.
  • Examples of the particulate filler of component (B) include silica, quartz powder, glass beads, glass powder, calcium oxalate, aluminum oxalate, kaolin, clay, diatomaceous earth, wollastonite and other oxalates; iron oxide, Metal oxides such as titanium oxide, zinc oxide, and alumina; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; silicon carbide; silicon nitride; boron nitride and the like.
  • the component (B) two or more kinds may be used.
  • silica, alumina, and titanium oxide are used as the component (B) from the viewpoint of raising effect on the surface of the molded body, low dust generation of the molded body, and warping deformation suppressing effect of the molded body.
  • silica and alumina are more preferred.
  • the content of the component (B) is 20 to 60% by mass in the liquid crystal composition for a camera module of the present invention.
  • the content of the component (B) is 20% by mass or more, the mechanical strength and the deflection temperature under load necessary for the camera module can be easily secured. Low dust generation is likely to be high.
  • a preferable content of the component (B) is 25 to 55% by mass, and a more preferable content of the component (B) is 30 to 50% by mass.
  • the epoxy group-containing copolymer can be used alone or in combination of two or more.
  • the (C) epoxy group-containing copolymer is not particularly limited. For example, at least selected from the group consisting of (C1) an epoxy group-containing olefin copolymer and (C2) an epoxy group-containing styrene copolymer.
  • One type is mentioned.
  • 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 (C1) epoxy group-containing olefin copolymer include a copolymer composed of a structural unit derived from an ⁇ -olefin and a structural unit derived from a glycidyl ester of an ⁇ , ⁇ -unsaturated acid. It is done.
  • 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).
  • R ′ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • the glycidyl ester of ⁇ , ⁇ -unsaturated acid is, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, etc., and glycidyl methacrylate is particularly preferable.
  • the content of the structural unit derived from ⁇ -olefin is 87 to 98% by mass, and the content of the structural unit derived from the glycidyl ester of ⁇ , ⁇ -unsaturated acid The amount is preferably 13 to 2% by mass.
  • Epoxy group-containing olefin copolymer is an olefin such as acrylonitrile, acrylic acid ester, methacrylic acid ester, ⁇ -methylstyrene, maleic anhydride, etc. as a third component in addition to the above two components within the range not impairing the present invention.
  • a structural unit derived from one or more of the 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 epoxy group-containing olefin copolymer can be easily prepared by a normal radical polymerization method using a monomer and a radical polymerization catalyst corresponding to each component. More specifically, for example, the presence of a suitable solvent or chain transfer agent at 500 to 4000 atm and 100 to 300 ° C. in the presence of a radical generator such as ⁇ -olefin and glycidyl ester of ⁇ , ⁇ -unsaturated acid. 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) epoxy group-containing styrene copolymer include a copolymer composed of a structural unit derived from styrenes and a structural 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 epoxy group-containing styrene-based copolymer may be a multi-component copolymer containing structural units derived from one or more other vinyl monomers as the third component in addition to the above two components. .
  • Suitable as the third component is a structural unit derived from one or more olefinic unsaturated esters such as acrylonitrile, acrylic acid ester, methacrylic acid ester, and maleic anhydride.
  • An epoxy group-containing styrene copolymer containing 40% by mass or less of these structural units in the copolymer is preferred as the component (C2).
  • the content of the structural unit derived from the glycidyl ester of ⁇ , ⁇ -unsaturated acid is 2 to 20% by mass, and the content of the structural unit derived from styrenes Is preferably 80 to 98% by mass.
  • the epoxy group-containing styrenic 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) epoxy group-containing copolymer is preferably (C1) an epoxy group-containing olefin copolymer from the viewpoint of heat resistance.
  • the ratio between these components can be appropriately selected according to the required characteristics.
  • the content of the epoxy group-containing copolymer is 1 to 5% by mass in the camera module resin composition of the present invention.
  • the content of the component (C) is 1% by mass or more from the viewpoint of suppressing raising of the surface of the molded body, and being 5% by mass or less does not impair the fluidity and obtains a good molded body. It is necessary for the reason.
  • a more preferable content is 2 to 4% by mass.
  • the (D) carbon black used as an optional component in the present invention is not particularly limited as long as it is generally available for use in resin coloring.
  • (D) carbon black contains a lump formed by agglomeration of primary particles, but the resin composition of the present invention is molded unless a large amount of lump having a size of 50 ⁇ m or more is contained.
  • Many bumps fine bumpy projections (fine irregularities) in which carbon black is aggregated) hardly occur on the surface of the molded body.
  • a preferable content rate is 5 ppm or less.
  • the blending amount of carbon black is preferably in the range of 0.5 to 5% by mass in the liquid crystalline resin composition for camera modules.
  • the blending amount of the carbon black is 0.5% by mass or more, the jetness of the obtained resin composition is not easily lowered, and the light shielding property is less likely to be anxious.
  • the blending amount of the carbon black is 5% by mass or less, it is difficult to be uneconomical, and it is difficult to generate bumps.
  • the liquid crystalline resin composition for a camera module of the present invention includes other polymers, other fillers, known substances generally added to synthetic resins, that is, antioxidants, as long as the effects of the present invention are not impaired.
  • Stabilizers such as UV absorbers, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, mold release agents, crystallization accelerators, crystal nucleating agents, etc. may be added as appropriate according to the required performance. it can.
  • fillers refer to fillers other than (B) particulate filler, and examples include plate-like fillers such as talc.
  • the liquid crystalline resin composition for a camera module of the present invention does not contain a plate-like filler.
  • the number of aggregates having a particle diameter of 10 ⁇ m or more is 5 or less per cross-sectional area of 0.1 mm 2 , preferably 3 or less, and 2 or less. More preferably.
  • the component (B) and the component (C) tend to form aggregates in the liquid crystalline resin composition, and if the degree of aggregation of these components is large, It was found that the effect of suppressing the raising of the surface and the low dusting property of the molded body are not sufficiently exhibited.
  • the number of the aggregates is 5 or less per cross-sectional area of 0.1 mm 2 , the effect of suppressing the raising of the surface of the molded body and the low dust generation property of the molded body tend to be high.
  • the number of aggregates having a particle diameter of 10 ⁇ m or more in the liquid crystalline resin composition is measured as follows. Using a microtome, a molded body obtained by injection molding a liquid crystalline resin composition under the conditions shown in the examples below is trimmed in a cross section perpendicular to the flow direction during molding, and randomly obtained from the obtained sample. The cross section selected in (1) is observed with a scanning electron microscope, the number of aggregates having a particle diameter of 10 ⁇ m or more is measured, and this number is divided by the area of the cross section to be observed. The number of the aggregates per 1 mm 2 is determined. The longest diameter on the cross section is adopted as the particle diameter of the aggregate.
  • 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 liquid crystalline resin composition for a camera module of the present invention obtained as described above preferably has a melt viscosity of 90 Pa ⁇ sec or less from the viewpoint of fluidity at the time of melting, the viewpoint of moldability, and the like. -More preferably, it is sec or less.
  • the melt viscosity is a value obtained by a measurement method based on ISO 11443 under conditions of a cylinder temperature 10 to 20 ° C. higher than the melting point of the liquid crystalline resin and a shear rate of 1000 sec ⁇ 1 .
  • liquid crystalline resin composition for camera module Since the liquid crystalline resin composition for a camera module according to the present invention easily suppresses the formation of an aggregate of (B) the particulate filler and (C) the epoxy group-containing copolymer, (A) the liquid crystalline resin, (B) obtaining a mixture containing a particulate filler, (C) an epoxy group-containing copolymer, (A) mixing of a liquid crystalline resin and (B) particulate filler, and (A) liquid crystalline It is preferable to produce the resin by a method that does not simultaneously mix the resin and the (C) epoxy group-containing copolymer.
  • (B) the particulate filler and (C) the epoxy group-containing copolymer separately to (A) the liquid crystalline resin.
  • (C) an epoxy group-containing copolymer is mixed in a mixture containing (A) liquid crystalline resin and (B) particulate filler, and / or (A) liquid crystalline resin and ( C)
  • a method is used which comprises mixing (B) a particulate filler into a mixture containing an epoxy group-containing copolymer.
  • Other components are mixed with (A) liquid crystalline resin together with (B) particulate filler and / or (C) epoxy group-containing copolymer.
  • the above components are mixed by, for example, melt kneading using a single screw or twin screw extruder.
  • (A) liquid crystalline resin and (B) particulate filler are supplied from the main feed port of the extruder, and the rear side in the extrusion direction from the main feed port.
  • the (C) epoxy group-containing copolymer is supplied from a side feed port provided in the above, or (A) a liquid crystalline resin and (C) an epoxy group-containing copolymer are supplied from the main feed port, It is preferable to supply the particulate filler (B) from the side feed port.
  • a camera module component is manufactured using the liquid crystalline resin composition for a camera module. If the resin composition of this invention is used as a raw material, it will become difficult to raise the surface of the components for camera modules. 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 and / or the barrel 14 which are parts for the camera module 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.
  • 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 at 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 and the barrel 14 are ultrasonically cleaned before being assembled 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.
  • the surface of the molded body formed by molding a general liquid crystalline resin composition is likely to be raised as described above, the surface may be peeled off to produce a peeled material. 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 formed into a molded body, 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 and / or the barrel 14.
  • 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.
  • the stirring torque reached a predetermined value, nitrogen was introduced and the pressure was changed from the reduced pressure state to the normal pressure state, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized to obtain pellets.
  • the obtained pellets were heat-treated at 300 ° C. for 2 hours under a nitrogen stream to obtain the target polymer.
  • the obtained polymer had a melting point of 334 ° C. and a melt viscosity of 14.0 Pa ⁇ s.
  • the melt viscosity of the polymer was measured in the same manner as the melt viscosity measurement method described later.
  • -Granular filler 1 Admafine SO-C2 (manufactured by Admatechs, silica, average primary particle size 0.5 ⁇ m)
  • -Granular filler 2 Admafine AO-502 (manufactured by Admatechs, Alumina, average primary particle size 0.7 ⁇ m)
  • -Granular filler 3 Denka fused silica FB-5SDC (manufactured by Denki Kagaku Kogyo Co., Ltd., silica, average primary particle size 4.0 ⁇ m)
  • -Granular filler 4 EGB731 (Potters Ballotini Co., Ltd., glass beads, average primary particle size 20.0 ⁇ m)
  • Plate filler GH3 (manufactured by Hayashi Kasei Co., Ltd., talc, average primary particle size 3.0 ⁇ m)
  • Carbon black VULCAN XC305 (manufactured by Cabot Japan Co
  • 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 the conditions of a cylinder temperature of 350 ° C. and a shear rate of 1000 sec ⁇ 1 is measured according to ISO 11443 using a capillary rheometer (Capillograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd .: piston diameter 10 mm). Measured. 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 Tables 1 and 2.
  • Example 1 As is clear from the comparison between Example 1 and Comparative Example 1, when the particulate filler and the epoxy group-containing copolymer are simultaneously supplied to the extruder, the number of aggregates having a particle diameter of 10 ⁇ m or more is increased, and dust is generated. While the number increases, when the particulate filler and the epoxy group-containing copolymer are separately supplied to the extruder, the number of aggregates having a particle diameter of 10 ⁇ m or more is greatly reduced, and the number of dusts generated is also reduced. It was confirmed.

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PCT/JP2016/085909 2015-12-24 2016-12-02 カメラモジュール用液晶性樹脂組成物、その製造方法、及び上記組成物を用いたカメラモジュール WO2017110424A1 (ja)

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US10106682B2 (en) 2015-08-17 2018-10-23 Ticona Llc Liquid crystalline polymer composition for camera modules
WO2019054187A1 (ja) * 2017-09-12 2019-03-21 ポリプラスチックス株式会社 耐摺動摩耗部材用液晶性樹脂組成物及びそれを用いた耐摺動摩耗部材
WO2019065063A1 (ja) * 2017-09-29 2019-04-04 ポリプラスチックス株式会社 耐摺動摩耗部材用液晶性樹脂組成物及びそれを用いた耐摺動摩耗部材
WO2020071495A1 (ja) * 2018-10-05 2020-04-09 ポリプラスチックス株式会社 耐ボールベアリング摺動摩耗部材用液晶性樹脂組成物及びそれを用いた耐ボールベアリング摺動摩耗部材
US10829634B2 (en) 2017-12-05 2020-11-10 Ticona Llc Aromatic polymer composition for use in a camera module
WO2020230890A1 (ja) * 2019-05-16 2020-11-19 ポリプラスチックス株式会社 液晶性樹脂組成物及びそれを用いた成形体

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KR20210145184A (ko) 2019-03-20 2021-12-01 티코나 엘엘씨 카메라 모듈용 액추에이터 어셈블리
CN113993937A (zh) 2019-03-20 2022-01-28 提克纳有限责任公司 用于相机模块的聚合物组合物
KR102532937B1 (ko) * 2020-09-29 2023-05-16 포리프라스틱 가부시키가이샤 내 볼베어링 접동 마모 부재용 액정성 수지 조성물 및 이를 이용한 내 볼베어링 접동 마모 부재

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US10106682B2 (en) 2015-08-17 2018-10-23 Ticona Llc Liquid crystalline polymer composition for camera modules
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CN110997820B (zh) * 2017-09-12 2021-05-11 宝理塑料株式会社 耐滑动摩耗构件用液晶性树脂组合物和使用了其的耐滑动摩耗构件
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CN110997820A (zh) * 2017-09-12 2020-04-10 宝理塑料株式会社 耐滑动摩耗构件用液晶性树脂组合物和使用了其的耐滑动摩耗构件
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WO2019065063A1 (ja) * 2017-09-29 2019-04-04 ポリプラスチックス株式会社 耐摺動摩耗部材用液晶性樹脂組成物及びそれを用いた耐摺動摩耗部材
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JPWO2020071495A1 (ja) * 2018-10-05 2021-02-15 ポリプラスチックス株式会社 耐ボールベアリング摺動摩耗部材用液晶性樹脂組成物及びそれを用いた耐ボールベアリング摺動摩耗部材
WO2020071495A1 (ja) * 2018-10-05 2020-04-09 ポリプラスチックス株式会社 耐ボールベアリング摺動摩耗部材用液晶性樹脂組成物及びそれを用いた耐ボールベアリング摺動摩耗部材
WO2020230890A1 (ja) * 2019-05-16 2020-11-19 ポリプラスチックス株式会社 液晶性樹脂組成物及びそれを用いた成形体
JPWO2020230890A1 (ja) * 2019-05-16 2021-05-20 ポリプラスチックス株式会社 液晶性樹脂組成物及びそれを用いた成形体
JP7026842B2 (ja) 2019-05-16 2022-02-28 ポリプラスチックス株式会社 液晶性樹脂組成物及びそれを用いた成形体

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