CN107924039B - Liquid crystalline resin composition for camera module and camera module using same - Google Patents
Liquid crystalline resin composition for camera module and camera module using same Download PDFInfo
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- CN107924039B CN107924039B CN201680050644.9A CN201680050644A CN107924039B CN 107924039 B CN107924039 B CN 107924039B CN 201680050644 A CN201680050644 A CN 201680050644A CN 107924039 B CN107924039 B CN 107924039B
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- 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
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- 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
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- 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
- C08K7/10—Silicon-containing compounds
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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
- 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
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- 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
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- 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
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Abstract
Provided is a liquid crystalline resin composition for camera modules, which is used for producing a component for camera modules, which is less prone to surface fuzzing, has high mechanical strength, and is excellent in heat resistance, and which has high fluidity during melting. The liquid crystal resin composition for camera modules comprises (A) a liquid crystal resin, (B) fibrous wollastonite, (C) an epoxy group-containing copolymer, and (D) a platy filler, wherein the content of the component (A) is 55-95.5% by mass, the content of the component (B) is 2.5-25% by mass, the content of the component (C) is 1.0-4.5% by mass, the content of the component (D) is 10-35% by mass, and the total content of the component (B) and the component (D) is 20-37.5% by mass.
Description
Technical Field
The present invention relates to a liquid crystalline resin composition for a camera module and a camera module using the same.
Background
Liquid crystalline resins represented by liquid crystalline polyester resins are widely used as high-performance engineering plastics because they have excellent mechanical strength, heat resistance, chemical resistance, electrical properties, and the like in a well-balanced manner, and also have excellent dimensional stability. Recently, liquid crystalline resins have been used for precision instrument parts by effectively utilizing these characteristics.
In the case of precision instruments, especially optical instruments with lenses and the like, slight dirt (rubbishh), dust, and the like also have an influence on instrument performance. For example, in a component used in an optical device such as a camera module, when minute dirt, oil, or dust adheres to a lens, optical characteristics of the camera module are significantly degraded. In order to prevent such a decrease in optical characteristics, components constituting the camera module (hereinafter, sometimes referred to as "camera module components") are usually subjected to ultrasonic cleaning before assembly to remove fine dirt, oil, dust, and the like adhering to the surface.
As described above, in the molded article obtained by molding the liquid crystalline resin composition, since the molecular orientation of the polymer is particularly large in the surface portion, the surface of the molded article is easily peeled, and therefore, when the molded article is subjected to ultrasonic cleaning, a fluffing phenomenon called fuzzing occurs due to the surface peeling, and the fluffed portion causes the generation of fine dirt.
Therefore, when the liquid crystalline resin composition is used as a raw material for a camera module member, a special liquid crystalline resin composition is used which does not cause surface fuzzing of a molded article even when the molded article is subjected to ultrasonic cleaning. As a specific liquid crystalline resin composition, a liquid crystalline resin composition for a camera module containing a liquid crystalline resin, specific talc and carbon black is disclosed (see patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2009 and No. 242453
Disclosure of Invention
Problems to be solved by the invention
However, according to the studies of the present inventors, the suppression of the fluffing on the surface of the molded article of the liquid crystal resin composition for camera modules described in patent document 1 is not sufficient, and a liquid crystal resin composition for camera modules for producing a molded article having a molded article surface which is less prone to fluffing has been demanded.
Further, according to the studies of the present inventors, when a molded body such as a lens holder is produced by molding a conventional liquid crystal resin composition for a camera module, warpage and deformation are large, which may cause a problem in assembling the camera module.
In recent years, mobile phones equipped with a camera module and with functions equivalent to those of a non-contact IC card have become widespread. Such a mobile phone reads and writes information by a non-contact reader. In this case, the mobile phone may collide with the non-contact reader with a strong force, and therefore, in order to prevent a camera module in the mobile phone from being easily defective, a liquid crystal resin composition for a camera module for producing a molded body having high mechanical strength is required.
In addition, from the viewpoint that defects are less likely to occur during processing and use of the camera module, a liquid crystal resin composition for a camera module is required for producing a molded article having excellent heat resistance.
In addition, the liquid crystalline resin composition for a camera module is required to have high fluidity when melted from the viewpoint of moldability.
The present invention has been made to solve the above problems, and an object of the present invention is to provide a liquid crystal resin composition for a camera module, which is used for producing a part for a camera module having a surface which is less likely to have fluffs or warp deformation, has high mechanical strength, and has excellent heat resistance, and has high fluidity during melting.
Means for solving the problems
The present inventors have made extensive studies to solve the above problems. As a result, the present inventors have found that the above problems can be solved by using a liquid crystalline resin composition for camera modules containing a liquid crystalline resin, fibrous wollastonite, an epoxy group-containing copolymer and a platy filler at a specific ratio, and have completed the present invention. More specifically, the present invention provides the following.
(1) A liquid crystalline resin composition for a camera module, comprising:
(A) a liquid crystalline resin,
(B) Fibrous wollastonite,
(C) An epoxy group-containing copolymer, and
(D) a plate-shaped filler, wherein the filler is a filler,
(A) the content of the component (B) is 55-95.5% by mass, the content of the component (B) is 2.5-25% by mass, the content of the component (C) is 1.0-4.5% by mass, the content of the component (D) is 10-35% by mass, and the total content of the component (B) and the component (D) is 20-37.5% by mass.
(2) The composition according to (1), wherein the epoxy-containing copolymer (C) is at least 1 selected from the group consisting of an epoxy-containing olefin copolymer (C1) and an epoxy-containing styrene copolymer (C2).
(3) A component for a camera module, which is formed from the composition of (1) or (2).
(4) A camera module comprising the member according to (3).
ADVANTAGEOUS EFFECTS OF INVENTION
The liquid crystalline resin composition for camera modules of the present invention has high fluidity when melted, and when a component for camera modules is produced using the composition as a raw material, a component for camera modules having a suppressed surface fuzzing and warping deformation, high mechanical strength, and excellent heat resistance can be obtained.
Drawings
Fig. 1 is a sectional view schematically showing a general camera module.
Detailed Description
Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments.
< liquid Crystal resin composition for Camera Module >
The liquid crystalline resin composition for camera modules comprises (A) a liquid crystalline resin, (B) fibrous wollastonite, (C) an epoxy group-containing copolymer, and (D) a platy filler.
[ (A) liquid crystalline resin ]
The liquid crystalline resin (a) used in the present invention is a melt-processable polymer having a property of forming an optically anisotropic melt phase. The properties of the anisotropic molten phase can be confirmed by a conventional polarization examination method using a crossed polarizing plate. More specifically, the anisotropic molten phase can be confirmed by observing a molten sample placed on a Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere using a Leitz polarizing microscope. When the liquid crystalline polymer applicable to the present invention is examined between crossed polarizers, polarized light is generally transmitted even in a molten static state, and optically shows anisotropy.
The type of the liquid crystalline resin (a) is not particularly limited, but is preferably an aromatic polyester and/or an aromatic polyester amide. In addition, a polyester partially containing an aromatic polyester and/or an aromatic polyester amide in the same molecular chain is also within the range. As the liquid crystalline resin (A), a resin having a logarithmic viscosity (I.V.) of preferably at least about 2.0dl/g, more preferably 2.0 to 10.0dl/g when dissolved in pentafluorophenol at a concentration of 0.1% by mass at 60 ℃ is preferably used.
As the aromatic polyester or aromatic polyester amide which is the liquid crystalline resin (a) applicable in the present invention, particularly preferred are aromatic polyesters and aromatic polyester amides having a repeating unit derived from at least 1 compound selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines as a constituent component.
More specifically, there may be mentioned:
(1) a polyester mainly composed of 1 or 2 or more kinds of repeating units derived from an aromatic hydroxycarboxylic acid or a derivative thereof;
(2) a polyester mainly comprising (a) 1 or 2 or more kinds of repeating units derived from an aromatic hydroxycarboxylic acid or a derivative thereof, (b) 1 or 2 or more kinds of repeating units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, or a derivative thereof, and (c) at least 1 or 2 or more kinds of repeating units derived from an aromatic diol, an alicyclic diol, an aliphatic diol, or a derivative thereof;
(3) a polyesteramide mainly comprising (a) 1 or 2 or more kinds of repeating units derived from an aromatic hydroxycarboxylic acid or a derivative thereof, (b) 1 or 2 or more kinds of repeating units derived from an aromatic hydroxylamine, an aromatic diamine, or a derivative thereof, and (c) 1 or 2 or more kinds of repeating units derived from an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, or a derivative thereof;
(4) polyesteramides mainly comprising (a) 1 or 2 or more kinds of repeating units derived from aromatic hydroxycarboxylic acids and derivatives thereof, (b) 1 or 2 or more kinds of repeating units derived from aromatic hydroxyamines, aromatic diamines, and derivatives thereof, (c) 1 or 2 or more kinds of repeating units derived from aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and derivatives thereof, and (d) at least 1 or 2 or more kinds of repeating units derived from aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof, and the like. Further, the above-mentioned components may be used in combination with a molecular weight modifier, if necessary.
Preferred 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; aromatic diols such as 2, 6-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 4' -dihydroxybiphenyl, hydroquinone, resorcinol, a compound represented by the following general formula (I), and a compound represented by the following general formula (II); aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4' -diphenyldicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, and compounds represented by the following general formula (III); aromatic amines such as p-aminophenol and p-phenylenediamine.
(X is selected from the group consisting of alkylene (C)1～C4) Alkylidene, -O-, -SO2Radicals in-S-, and-CO-)
(Y is selected from- (CH)2)n- (n-1-4) and-O (CH)2)nAnd O- (n is 1 to 4). )
The liquid crystalline resin (a) used in the present invention can be produced by a known method from the above-mentioned monomer compound (or mixture of monomers) by a direct polymerization method or an ester exchange method, and a melt polymerization method, a slurry polymerization method, or the like can be usually used. The above-mentioned compounds having an ester-forming ability may be used in the polymerization in the original form, or may be modified from a precursor to a derivative having the ester-forming ability in a stage prior to the polymerization. In the polymerization, various catalysts can be used, and typical catalysts include dialkyltin oxide, diaryltin oxide, titanium dioxide, alkoxytitanosilicate, titanium alkoxide, alkali metal salt and alkaline earth metal salt of carboxylic acid, and BF3Such as Lewis acid salts, and the like. The amount of the catalyst used is usually about 0.001 to 1% by mass, particularly preferably about 0.01 to 0.2% by mass, based on the total mass of the monomers. The polymer produced by these polymerization methods can further realize an increase in molecular weight by solid-phase polymerization by heating under reduced pressure or in an inert gas, as required.
The melt viscosity of the liquid crystalline resin (a) obtained by the above-described method is not particularly limited. In general, a melt viscosity at the molding temperature of 1000 seconds can be used-1The shear rate of (3) is 10MPa or more and 600MPa or less. However, a resin having an excessively high viscosity is not preferable because the fluidity is extremely deteriorated. The liquid crystalline resin (a) may be a mixture of 2 or more liquid crystalline resins.
The liquid crystalline resin composition for a camera module of the present invention contains (A) a liquid crystalline resin in an amount of 55 to 95.5% by mass. (A) When the content of the component (A) is 55% by mass or more, it is preferable for the reasons of fluidity and suppression of fuzz on the surface of the molded article, and when the content of the component (A) is 95.5% by mass or less, it is preferable for the reason of heat resistance. The preferable content of the component (A) is 60 to 80% by mass, and the more preferable content of the component (A) is 62 to 70% by mass.
[ (B) fibrous wollastonite ]
In the present specification, the fibrous wollastonite (B) is a wollastonite having an aspect ratio, that is, a value of an average fiber length/an average fiber diameter of 8 or more. The aspect ratio is preferably 10to 25, and more preferably 15 to 20, from the viewpoint of the effect of suppressing fuzz on the surface of the molded article. In the present specification, wollastonite having an aspect ratio of less than 8 is referred to as particulate wollastonite.
The fibrous wollastonite (B) is not particularly limited, and for example, a known fibrous wollastonite can be used. (B) The fibrous wollastonite may be used alone in 1 kind, or 2 or more kinds different in aspect ratio, average fiber length, average fiber diameter and the like may be used in combination.
(B) The fibrous wollastonite preferably has an average fiber diameter of 3.0 to 50 μm, and more preferably has an average fiber diameter of 4.5 to 40 μm. When the average fiber diameter is 3.0 μm or more, the mechanical strength and the load deflection temperature required for a camera module can be easily secured. When the average fiber diameter is 50 μm or less, the effect of suppressing the surface fuzzing of the molded article tends to be high. In the present specification, as the average fiber diameter, a value obtained by reading a physical microscope image from a CCD camera to a Personal Computer (PC) and measuring the image by an image processing method using an image measuring instrument is used.
(B) The fibrous wollastonite preferably has an average fiber length of 30 to 800 μm, more preferably 50 to 600 μm. When the average fiber length is 30 μm or more, the mechanical strength and the load deflection temperature required for a camera module can be easily secured. When the average fiber length is 800 μm or less, the effect of suppressing the surface fuzzing of the molded article tends to be high. In the present specification, as the average fiber length, a value obtained by reading a solid microscope image from a CCD camera to a PC and measuring the image by an image processing method using an image measuring instrument is used.
(B) The content of the component (B) is 2.5 to 25% by mass in the liquid crystalline composition for a camera module of the present invention. (B) When the content of the component is 2.5% by mass or more, the mechanical strength and the load deflection temperature required for the camera module can be easily secured. (B) When the content of the component (b) is 25% by mass or less, the fluidity of the composition at the time of melting is easily improved, the effect of suppressing the surface fuzz of the molded article is easily increased, and the effect of suppressing the warp deformation of the molded article is easily increased. More preferably, the content is 5 to 20% by mass.
[ (C) epoxy group-containing copolymer ]
(C) The epoxy group-containing copolymer may be used alone in 1 kind or in combination of 2 or more kinds. The epoxy group-containing copolymer (C) is not particularly limited, and examples thereof include at least 1 selected from the group consisting of (C1) epoxy group-containing olefin copolymers and (C2) epoxy group-containing styrene copolymers. The blending of component (C) in the liquid crystal resin composition for camera modules contributes to suppression of fuzzing of the surface of a molded article obtained by molding the composition when the molded article is subjected to ultrasonic cleaning.
The reason for the inhibition of fuzz is not clear, but it is considered that: when the amount of the additive is in a certain range, the surface state of the molded article changes, and the change contributes to suppression of fuzz.
(C1) Examples of the epoxy group-containing 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.
The α -olefin is not particularly limited, and examples thereof include ethylene, propylene, butene, and the like, and among them, ethylene is preferably used. The glycidyl ester of an α, β -unsaturated acid is a compound represented by the following general formula (IV). Examples of the glycidyl ester of α, β -unsaturated acid include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate, and glycidyl methacrylate is particularly preferable.
Preferably, in the epoxy group-containing olefin copolymer (C1), the content of repeating units derived from an α -olefin is 87 to 98% by mass, and the content of repeating units derived from a glycidyl ester of an α, β -unsaturated acid is 13 to 2% by mass.
The epoxy group-containing olefin copolymer (C1) used in the present invention may contain, in addition to the two components, 0to 48 parts by mass of 1 or 2 or more repeating units derived from an ethylenically unsaturated ester such as acrylonitrile, an acrylic acid ester, a methacrylic acid ester, α -methylstyrene, maleic anhydride, or the like as a third component, per 100 parts by mass of the two components, within a range not impairing the present invention.
The epoxy group-containing olefin copolymer as the component (C1) of the present invention can be easily produced by a general radical polymerization method using a monomer and a radical polymerization catalyst corresponding to each component. More specifically, the alpha-olefin is usually produced by copolymerizing an alpha-olefin and a glycidyl ester of an alpha, beta-unsaturated acid in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ℃ in the presence or absence of a suitable solvent or a chain transfer agent. Further, the copolymer can be produced by a method in which an α -olefin, a glycidyl ester of an α, β -unsaturated acid, and a radical generator are mixed and melt graft-copolymerized in an extruder.
Examples of the (C2) epoxy group-containing styrenic copolymer include a copolymer composed of a repeating unit derived from a styrenic compound and a repeating unit derived from a glycidyl ester of an α, β -unsaturated acid. The glycidyl ester of an α, β -unsaturated acid is the same as that described for the component (C1), and therefore, the description thereof is omitted.
Examples of the styrene include styrene, α -methylstyrene, bromostyrene, and divinylbenzene, and styrene is preferably used.
The (C2) epoxy group-containing styrenic copolymer used in the present invention may be a multipolymer comprising 1 or 2 or more repeating units derived from other vinyl monomers in addition to the above two components as a third component. Preferably, the third component is a repeating unit derived from 1 or 2 or more species of an ethylenically unsaturated ester such as acrylonitrile, an acrylic acid ester, a methacrylic acid ester, and maleic anhydride. An epoxy group-containing styrenic copolymer containing 40 mass% or less of these repeating units in the copolymer is preferable as the (C2) component.
(C2) In the epoxy group-containing styrenic copolymer, the content of the repeating unit derived from the glycidyl ester of an α, β -unsaturated acid is preferably 2 to 20 mass% and the content of the repeating unit derived from the styrenic is preferably 80 to 98 mass%.
(C2) The epoxy group-containing styrenic copolymer can be produced by a general radical polymerization method using a monomer and a radical polymerization catalyst corresponding to each component. More specifically, the copolymer is usually produced by copolymerizing a styrene and a glycidyl ester of an α, β -unsaturated acid in the presence of a radical generator, at 500 to 4000 atmospheres at 100 to 300 ℃, in the presence or absence of a suitable solvent or a chain transfer agent. Further, the copolymer can be produced by a method in which glycidyl esters of styrenes and α, β -unsaturated acids and a radical generator are mixed and melt graft copolymerized in an extruder.
As the (C) epoxy group-containing copolymer, (C1) epoxy group-containing olefin copolymer is preferable in terms of heat resistance. When the component (C1) and the component (C2) are used in combination, the ratio of these components to each other can be appropriately selected depending on the desired properties.
(C) The content of the epoxy group-containing copolymer in the resin composition for a camera module of the present invention is 1.0 to 4.5% by mass. (C) The content of the component (b) is 1.0% by mass or more is necessary in order to suppress surface fuzzing of the molded article, and 4.5% by mass or less is necessary for obtaining a good molded article without impairing the flowability. More preferably, the content is 2.0 to 4.0 mass%.
[ (D) plate Filler ]
(D) The average particle diameter of the plate-like filler is preferably 20 to 50 μm. When the average particle size is 20 μm or more, the mechanical strength and the load deflection temperature required for a camera module can be easily secured, and the effect of suppressing warping deformation of the molded article can be easily increased. When the average particle diameter is 50 μm or less, the effect of suppressing the surface fuzzing of the molded article tends to be high. The average particle diameter is preferably 23 to 30 μm. In the present specification, a value measured by a laser diffraction/scattering particle size distribution measurement method is used as the average particle diameter.
The plate-like filler (D) is not particularly limited, and examples thereof include mica, talc, glass flake, graphite, and various metal foils (e.g., aluminum foil, iron foil, and copper foil). As the component (D), 2 or more species can be used. In the present invention, mica and talc are preferably used as the component (D), and mica is more preferably used.
(D) The content of the component (B) is 10to 35% by mass in the liquid crystal composition for a camera module of the present invention. (D) When the content of the component is 10% by mass or more, the mechanical strength and the load deflection temperature required for a camera module are easily ensured, and the effect of suppressing the warp deformation of the molded article is easily increased. (D) When the content of the component is 35% by mass or less, the effect of suppressing the surface fuzzing of the molded article tends to be high. The content is preferably 15 to 30% by mass.
The total content of the component (B) and the component (D) is 20 to 37.5% by mass, preferably 25 to 35% by mass, in the liquid crystal composition for a camera module of the present invention. When the total content is 20% by mass or more, the mechanical strength and the load deflection temperature required for the camera module can be easily ensured. When the total content is 37.5% by mass or less, the fluidity of the composition at the time of melting is easily improved, the effect of suppressing the surface fuzzing of the molded article is easily increased, and the impact resistance of the molded article is easily increased.
[ (E) carbon Black ]
The carbon black (E) used as an optional component in the present invention is not particularly limited as long as it is a generally available carbon black used for coloring a resin. In general, (E) carbon black contains a lump of aggregated primary particles, and as long as it does not contain a large amount of a lump having a size of 50 μm or more, a large amount of projections (fine uneven projections (fine irregularities) of aggregated carbon black) are not easily generated on the surface of a molded article obtained by molding the resin composition of the present invention. When the content of the particles having a lump particle diameter of 50 μm or more is 20ppm or less, the effect of suppressing the surface fuzzing of the molded article tends to be high. The content is preferably 5ppm or less.
The amount of carbon black (E) to be blended is preferably in the range of 0.5 to 5% by mass in the liquid crystal resin composition for camera modules. When the amount of carbon black is 0.5% by mass or more, the resultant resin composition is less likely to have reduced paint black properties and is less likely to have light-blocking properties. When the amount of carbon black is 5% by mass or less, it is not likely to be uneconomical and also to cause protrusion.
[ other ingredients ]
Other polymers, other fillers, known substances added to general synthetic resins, that is, antioxidants, stabilizers such as ultraviolet absorbers, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, mold release agents, crystallization accelerators, crystallization nucleating agents, and the like may be added to the liquid crystal resin composition for camera modules according to the present invention as needed in accordance with the required performance within a range not to impair the effects of the present invention.
The other filler is a filler other than (B) fibrous wollastonite, (D) plate-like filler, and (E) carbon black, and examples thereof include wollastonite having an aspect ratio of less than 8, other than (B) fibrous wollastonite; fibrous fillers other than (B) fibrous wollastonite, such as glass fibers; and a particulate filler such as silica.
[ preparation of liquid Crystal resin composition for Camera Module ]
The preparation of the resin composition for camera modules of the present invention is not particularly limited. For example, the liquid crystal resin composition for a camera module is prepared by blending the above-mentioned components (a), (B), (C) and (D) and melt-kneading them using a single-screw or twin-screw extruder.
[ liquid Crystal resin composition for Camera Module ]
The shape of the component (B) in the liquid crystalline resin composition for camera modules of the present invention is different from the shape of the component (B) before blending. The shape of the component (B) is the shape before blending. When the shape before blending is as described above, a camera module member whose surface is less likely to be raised can be obtained.
Similarly, the shape of the component (D) in the liquid crystal resin composition for camera modules of the present invention is different from the shape of the component (D) before blending. The shape of the component (D) is the shape before blending. When the shape before blending is as described above, a camera module component in which warping deformation is suppressed can be obtained.
The melt viscosity of the liquid crystal resin composition for camera modules of the present invention obtained as described above is preferably less than 50Pa · sec. The liquid crystal resin composition for a camera module of the present invention is also characterized by high fluidity when melted and excellent moldability. In the present specification, the melt viscosity is a barrel temperature 10to 20 ℃ higher than the melting point of the liquid crystalline resin, and a shear rate is 1000sec-1The value obtained by using a measurement method based on ISO 11443 under the conditions of (1).
The liquid crystalline resin composition for a camera module of the present invention preferably has a deflection temperature under load of 240 ℃ or higher. The liquid crystalline resin composition for a camera module of the present invention is also one of the characteristics of excellent heat resistance. The deflection temperature under load was measured by the method according to ISO75-1 or ISO 2.
< parts for camera module and camera module >
A component for a camera module is produced by using the liquid crystalline resin composition for a camera module. When the resin composition of the present invention is used as a raw material, the surface of the camera module member is less likely to be fluffed. The components for camera modules are required to be cleaned by ultrasonic waves, and therefore, it is required that the surfaces thereof are not easily roughened even by ultrasonic cleaning. When the resin composition of the present invention is used, even if the ultrasonic cleaning of the camera module member is performed under stronger conditions, no or substantially no detached objects causing dirt or the like are generated. Therefore, the finished product quality is not substantially affected by the dirt generated by the surface fuzzing of the camera module member after the camera module member is assembled to the finished product.
A description will be given of a camera module member obtained by molding the liquid crystal resin composition for a camera module of the present invention. Fig. 1 schematically shows a cross-sectional view of a typical camera module. 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 lens barrel 14, a lens 15, an IR filter 16, and a guide (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 wire 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 formed in the top portion, and a spiral groove is formed in the wall surface of the opening.
The lens barrel 14 is cylindrical, and the lens 15 is held substantially horizontally inside the cylindrical shape. Further, a spiral convex portion is formed on one side wall of the cylinder, and the spiral convex portion is screwed with a spiral groove portion formed on an opening wall surface of the lens holder 13, so that the lens barrel 14 is connected to the lens holder 13. The IR filter 16 is disposed at one end of the barrel 14, and closes one end of the cylindrical barrel 14. As shown in fig. 1, the IR filter 16 is arranged substantially in parallel with the lens 15.
In the camera module 1 shown in fig. 1, the lens holder 13 moves up and down on the guide 17 by the action of a magnetic force generated by a coil (not shown) wound around the lens holder 13 and a permanent magnet (not shown) disposed around the coil, and the distance between the lens 15 and the optical element 11 changes. By adjusting this distance, focusing of the camera can be performed.
In the camera module 1 as described above, the lens holder 13 and/or the lens barrel 14, which are components for a camera module, can be manufactured using the liquid crystal resin composition for a camera module of the present invention as a raw material. The conventional liquid crystalline resin composition is not suitable as a raw material for producing these parts. When the lens holder 13 and/or the lens barrel 14 are manufactured using a normal liquid crystalline resin composition as a raw material, the following problems occur.
In a molded article obtained by molding a general liquid crystalline resin composition, the molecular orientation of a polymer is particularly large in the surface portion, and therefore, the surface of the molded article is likely to have fuzz, which causes generation of small stains. The performance of the camera module is degraded when the small dirt adheres to the lens 15 or the like.
The components for camera modules such as the lens holder 13 and the lens barrel 14 are ultrasonically cleaned before being assembled to the camera module 1 for the purpose of removing dust and small dirt on the surface. However, since a molded article obtained by molding a general liquid crystalline resin composition is apt to have fuzz on its surface, the surface is fuzz when ultrasonic cleaning is performed. Since such a problem occurs, ultrasonic cleaning of a molded article obtained by molding a liquid crystalline resin composition is generally impossible.
The above-described focusing is performed by moving the lens holder 13 up and down on the guide 17 by the action of a magnetic force generated by a coil (not shown) wound around the lens holder 13 and a permanent magnet (not shown) disposed around the coil. In this case, as described above, the surface of the molded article obtained by molding the general liquid crystalline resin composition is easily fluffed, and thus, there is a possibility that the surface is separated to generate a detachable substance. The peeled off material becomes small dirt and adheres to the lens 15 or the like, and there is a high possibility that the performance of the camera module is lowered.
As described above, in general, when the liquid crystal resin composition is used as a raw material for the lens holder 13 and/or the lens barrel 14, defects are likely to occur, but when the liquid crystal resin composition for a camera module of the present invention is used as a molded body, the surface state of the molded body can be improved to such an extent that the problem of fuzz is not substantially caused even when the molded body is subjected to ultrasonic cleaning, and therefore, the liquid crystal resin composition can be preferably used as a raw material for the lens holder 13 and/or the lens barrel 14.
When the liquid crystal resin composition for camera modules of the present invention is used for the lens holder 13, the material of the guide 17 may be other than the liquid crystal resin composition for camera modules of the present invention, and specifically, nylon or the like may be used.
[ examples ]
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the examples.
< liquid Crystal resin >
Liquid crystalline polyester amide resin
After the following raw materials were charged into a polymerization vessel, the temperature of the reaction system was raised to 140 ℃ and the reaction was carried out at 140 ℃ for 1 hour. Thereafter, the temperature was raised to 340 ℃ over 4.5 hours, and from this temperature, the pressure was reduced to 10Torr (1330 Pa) over 15 minutes, and melt polymerization was carried out while distilling off acetic acid, excess acetic anhydride, and other low-boiling components. After the stirring torque reached a predetermined value, nitrogen gas was introduced, the pressure was increased from a reduced pressure state to a pressurized state under normal pressure, and the polymer was discharged from the lower part of the polymerization vessel, and the strand was granulated to obtain pellets. The resultant particles were subjected to heat treatment at 300 ℃ for 2 hours under a nitrogen gas stream to obtain the objective polymer. The obtained polymer had a melting point of 334 ℃ and a melt viscosity of 14.0 pas. The melt viscosity of the polymer is measured in the same manner as the method for measuring the melt viscosity described later.
(I) 4-hydroxybenzoic acid; 188.4g (60 mol%)
(II) 2-hydroxy-6-naphthoic acid; 21.4g (5 mol%)
(III) terephthalic acid; 66.8g (17.7 mol%)
(IV)4, 4' -dihydroxybiphenyl; 52.2g (12.3 mol%)
(V) 4-acetoxyaminophenol; 17.2g (5 mol%)
Metal catalysts (potassium acetate catalysts); 15mg of
An acylating agent (acetic anhydride); 226.2g
< materials other than liquid Crystal resin >
Fibrous wollastonite: NYGLOS 8(NYCO Materials, Inc., aspect ratio 17, average fiber length 136 μm, average fiber diameter 8 μm)
Granular wollastonite: NYAD 325(NYCO Materials, Inc., aspect ratio 5, average fiber length 50 μm, average fiber diameter 5 μm)
Glass fibers: PF70E-001(Nitto Boseki Co., Ltd., manufactured by Ltd., milled fibers, average fiber diameter 10 μm, average fiber length 70 μm)
Epoxy group-containing olefin copolymer: BONDFAST 2C (product of Sumitomo chemical Co., Ltd., ethylene-glycidyl methacrylate copolymer, glycidyl methacrylate content 6% by mass)
Epoxy-free copolymers: tuftec M1913 (maleic anhydride-modified hydrogenated styrene-ethylene-butadiene-styrene Block copolymer, manufactured by Asahi Kasei corporation)
Plate-like filler 1: AB-25S (manufactured by Shankou mica industries Co., Ltd., mica, average particle diameter 24 μm)
Plate-like filler 2: クラウンタルク PP (Talc, manufactured by Sonmura industries, Ltd., average particle diameter 12.8 μm, average aspect ratio 6)
Carbon black: VULCANXC305 (manufactured by キャボットジャパン Co., Ltd., average particle diameter 20nm, proportion of particles having a particle diameter of 50 μm or more is 20ppm or less)
< production of liquid Crystal resin composition for Camera Module >
The components were melt-kneaded at a barrel temperature of 350 ℃ in the proportions shown in Table 1 or Table 2 using a twin-screw extruder (TEX 30. alpha. model, made by Nippon Steel works) to obtain liquid crystalline resin composition pellets for camera modules.
< melt viscosity >
The melt viscosity of the liquid crystalline resin compositions for camera modules of examples and comparative examples was measured using the above-described pellets. Specifically, a barrel temperature of 350 ℃ and a shear rate of 1000 seconds were measured in accordance with ISO 11443 using a capillary rheometer (Capilograph 1D manufactured by Toyo Seiki Seisaku-sho, Ltd.: piston diameter of 10mm)-1The apparent melt viscosity under the conditions of (1). An orifice (orifice) having an inner diameter of 1mm and a length of 20mm was used for the measurement. The results are shown in tables 1 and 2.
< deflection temperature under load >
The pellets of examples and comparative examples were molded under the following molding conditions using a molding machine ("SE 100 DU" manufactured by Sumitomo gravity Industries, Ltd.) to obtain test pieces (4 mm. times.10 mm. times.80 mm) for measurement. Using the test piece, the deflection temperature under load was measured by a method according to ISO75-1 and ISO 2. As the bending stress, 1.8MPa was used. The results are shown in tables 1 and 2.
[ Forming Condition ]
Barrel temperature: 350 deg.C
Temperature of the die: 80 deg.C
Back pressure: 2.0MPa
Injection speed: 33 mm/sec
< bending test >
Pellets of examples and comparative examples were molded under the following molding conditions using a molding machine ("SE 100 DU" by Sumitomo gravity Industries, Ltd.) to prepare a bending test piece of 130 mm. times.13 mm. times.0.8 mm. Using the test piece, the flexural strength, flexural modulus, and strain at break were measured according to astm d 790. The results are shown in tables 1 and 2.
[ Forming Condition ]
Barrel temperature: 350 deg.C
Temperature of the die: 90 deg.C
Injection speed: 33 mm/sec
Pressure maintaining: 50MPa
< Charpy impact test >
The pellets of examples and comparative examples were molded into test pieces (4 mm. times.10 mm. times.80 mm) for measurement using a molding machine ("SE 100 DU" manufactured by Sumitomo gravity Industries, Ltd.) under the following molding conditions. Using the test piece, the Charpy impact strength was measured by a method based on ISO 179-1. The results are shown in tables 1 and 2.
[ Forming Condition ]
Barrel temperature: 350 deg.C
Temperature of the die: 80 deg.C
Back pressure: 2.0MPa
Injection speed: 33 mm/sec
< flatness >
The pellets of examples and comparative examples were molded under the following molding conditions using a molding machine ("SE-100 DU" by Sumitomo gravity Industries, Ltd.) to prepare 5-piece flat test pieces of 80 mm. times.80 mm. times.1 mm. The 1 st flat plate-like test piece was left to stand on a horizontal surface, and the height from the horizontal surface was measured at 9 places on the flat plate-like test piece using a CNC image measuring instrument (model: QVBHU404-PRO1F) manufactured by Mitutoyo Corporation, and the average height was calculated from the measured values. The positions of the measuring height are as follows: when a square having one side of 74mm was placed on the principal plane of a flat plate-like test piece so that the distance from each side of the principal plane was 3mm, the position corresponded to the intersection of each vertex of the square, the midpoint of each side of the square, and 2 diagonal lines of the square. And a plane having the same height from the horizontal plane as the average height and being parallel to the horizontal plane is set as a reference plane. The maximum height and the minimum height from the reference plane were selected from the heights measured at the above 9 positions, and the difference between the two heights was calculated. Similarly, the above-mentioned difference was calculated for the other 4 flat plate-like test pieces, and the obtained 5 values were averaged to obtain a flatness value. The results are shown in tables 1 and 2.
[ Forming Condition ]
Barrel temperature: 350 deg.C
Temperature of the die: 80 deg.C
Injection speed: 33 mm/sec
Pressure maintaining: 60MPa
< dust (dust) generation number >
Pellets of examples and comparative examples were molded using a molding machine ("SE 30 DUZ" manufactured by Sumitomo gravity Industries, Ltd.) under the following molding conditions to obtain molded articles of 12.5 mm. times.120 mm. times.0.8 mm. The molded article was used as a test piece.
[ Forming Condition ]
Barrel temperature: 350 deg.C
Temperature of the die: 90 deg.C
Injection speed: 80 mm/sec
[ evaluation ]
The test piece was left in water at room temperature for 3 minutes in an ultrasonic cleaner (output 300W, frequency 45 kHz). Thereafter, the number of particles having a particle size of 2 μm or more present in the water was measured by a particle counter (particle counter KL-11A (PARTICLEUTOUNTER) manufactured by RION corporation), and the number of generated dust was evaluated. The results are shown in tables 1 and 2.
[ Table 1]
[ Table 2]
As is clear from the results shown in tables 1 and 2, it was confirmed that the molded articles produced using the pellets of examples had a small amount of dust generation even when they were subjected to ultrasonic cleaning. In addition, the molded article has a small flatness value. From the above results, it can be said that the molded article obtained by molding the particles of the examples has a significantly different surface state and is suppressed in warpage from the molded article obtained by molding the particles of the general liquid crystalline resin composition of comparative example or the like.
In addition, it was confirmed that the molded article produced using the pellets of the examples was excellent in heat resistance.
Further, it was confirmed that the molded articles produced using the pellets of examples had high mechanical strength such as flexural strength and impact resistance. Therefore, by molding the particles of the embodiment, it is possible to manufacture a component for a camera module, which has high mechanical strength, and which is less likely to be broken by, for example, an impact at the time of collision with a non-contact reader or the like or an impact of driving.
Further, it was confirmed that the pellets of examples had high fluidity during melting and excellent moldability.
Description of the reference numerals
1 Camera Module
10 base plate
11 optical element
12 lead wire
13 lens holder
14 lens barrel
15 lens
16 IR filter
17 guide member
Claims (4)
1. A liquid crystalline resin composition for a camera module, comprising:
(A) a liquid crystalline resin,
(B) Fibrous wollastonite,
(C) An epoxy group-containing copolymer, and
(D) a plate-shaped filler, wherein the filler is a filler,
(A) 55 to 95.5 mass% of component (A), 2.5 to 25 mass% of component (B), 1.0 to 4.5 mass% of component (C), 10to 35 mass% of component (D), and 20 to 37.5 mass% of the total of component (B) and component (D);
the average fiber diameter of the component (B) is 3.0-50 μm, and the average fiber length of the component (B) is 30-800 μm;
the component (D) has an average particle diameter of 20 to 50 μm.
2. The composition according to claim 1, wherein the (C) epoxy-containing copolymer is at least 1 selected from the group consisting of (C1) epoxy-containing olefin-based copolymer and (C2) epoxy-containing styrenic copolymer.
3. A part for a camera module formed from the composition of claim 1 or 2.
4. A camera module provided with the member according to claim 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2015171981 | 2015-09-01 | ||
| JP2015-171981 | 2015-09-01 | ||
| PCT/JP2016/073623 WO2017038421A1 (en) | 2015-09-01 | 2016-08-10 | Liquid crystalline resin composition for camera module and camera module using same |
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| CN107924039A CN107924039A (en) | 2018-04-17 |
| CN107924039B true CN107924039B (en) | 2020-10-16 |
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| JP (1) | JP6581659B2 (en) |
| KR (1) | KR102081231B1 (en) |
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| KR102627886B1 (en) | 2017-12-05 | 2024-01-19 | 티코나 엘엘씨 | Aromatic polymer compositions for use in camera modules |
| JP7353288B2 (en) | 2018-02-20 | 2023-09-29 | ティコナ・エルエルシー | thermally conductive polymer composition |
| MY187836A (en) * | 2018-11-15 | 2021-10-26 | Polyplastics Co | Liquid crystalline resin composition and connector including molded article of said liquid crystalline resin composition |
| KR20210145184A (en) | 2019-03-20 | 2021-12-01 | 티코나 엘엘씨 | Actuator assembly for camera module |
| WO2020190569A1 (en) | 2019-03-20 | 2020-09-24 | Ticona Llc | Polymer composition for use in a camera module |
| WO2021065417A1 (en) * | 2019-09-30 | 2021-04-08 | ポリプラスチックス株式会社 | Liquid crystalline resin composition and electronic component comprising molded article of said liquid crystalline resin composition |
| JP6895032B1 (en) * | 2019-10-28 | 2021-06-30 | ポリプラスチックス株式会社 | A connector containing a liquid crystal resin composition and a molded product of the liquid crystal resin composition. |
| KR102501091B1 (en) * | 2020-05-13 | 2023-02-17 | 포리프라스틱 가부시키가이샤 | Liquid crystalline resin composition for surface mount relay and surface mount relay using the same |
| CN116438245A (en) * | 2020-10-29 | 2023-07-14 | 大塚化学株式会社 | Liquid crystal polymer composition, liquid crystal polymer molded body, and electric and electronic device |
| KR20230031545A (en) * | 2021-08-27 | 2023-03-07 | 롯데케미칼 주식회사 | Liquid crystalline polymer composition and article produced therefrom |
| CN115651368B (en) * | 2022-11-08 | 2023-12-19 | 珠海万通特种工程塑料有限公司 | Antistatic liquid crystal polyester composition and preparation method and application thereof |
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| CN1727437A (en) * | 2004-07-30 | 2006-02-01 | 汎塑料株式会社 | Liquid crystalline polyester resin composition |
| CN101240106A (en) * | 2006-02-13 | 2008-08-13 | 住友化学株式会社 | Liquid-crystalline polymer composition, method for producing the same and molded article using the same |
| CN104341721A (en) * | 2013-07-23 | 2015-02-11 | 宝理塑料株式会社 | A liquid crystal resin composition used for a camera module |
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| JP5951167B2 (en) | 2008-03-28 | 2016-07-13 | Ｊｘエネルギー株式会社 | Liquid crystalline polyester resin composition for camera modules |
| 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 |
| CN104736672B (en) * | 2012-10-16 | 2017-10-24 | 提克纳有限责任公司 | Liquid antistatic crystalline polymer composition |
| CN104822775B (en) * | 2012-12-03 | 2017-12-05 | 宝理塑料株式会社 | Camera module use liquid crystalline resin composition and use its camera module |
| US9512293B2 (en) * | 2013-03-13 | 2016-12-06 | Ticona Llc | Antistatic liquid crystalline polymer composition |
| EP2816083B1 (en) * | 2013-06-19 | 2019-02-20 | 3M Innovative Properties Company | Component made of a polymer boron nitride compound, polymer boron nitride compound for producing such a component and its use |
| US20150104165A1 (en) * | 2013-10-16 | 2015-04-16 | Ticona Llc | Polymer Composition for Use in a Compact Camera Module |
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| CN1727437A (en) * | 2004-07-30 | 2006-02-01 | 汎塑料株式会社 | Liquid crystalline polyester resin composition |
| CN101240106A (en) * | 2006-02-13 | 2008-08-13 | 住友化学株式会社 | Liquid-crystalline polymer composition, method for producing the same and molded article using the same |
| CN104341721A (en) * | 2013-07-23 | 2015-02-11 | 宝理塑料株式会社 | A liquid crystal resin composition used for a camera module |
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| KR102081231B1 (en) | 2020-02-25 |
| WO2017038421A1 (en) | 2017-03-09 |
| TW201726809A (en) | 2017-08-01 |
| KR20180044343A (en) | 2018-05-02 |
| JPWO2017038421A1 (en) | 2018-07-12 |
| TWI689550B (en) | 2020-04-01 |
| CN107924039A (en) | 2018-04-17 |
| JP6581659B2 (en) | 2019-09-25 |
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