CN104040422B - Camera module use liquid crystalline resin composition - Google Patents
Camera module use liquid crystalline resin composition Download PDFInfo
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- CN104040422B CN104040422B CN201380004759.0A CN201380004759A CN104040422B CN 104040422 B CN104040422 B CN 104040422B CN 201380004759 A CN201380004759 A CN 201380004759A CN 104040422 B CN104040422 B CN 104040422B
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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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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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
- C08K3/02—Elements
- C08K3/04—Carbon
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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
- C08K3/346—Clay
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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
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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
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
- C08L23/0884—Epoxide containing esters
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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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
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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
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
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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
- G03B17/00—Details of cameras or camera bodies; Accessories therefor
- G03B17/02—Bodies
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Dispersion Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Camera Bodies And Camera Details Or Accessories (AREA)
Abstract
The invention provides for the manufacture of formed body surface not easily fluff camera module use parts, camera module use liquid crystalline resin composition.Described resin combination is compounding in (A) liquid-crystalline resin at least one (B) inorganic filler being selected from (B1) fibrous filler and (B2) Non-fibrous filling agent, be selected from least one (C) multipolymer of (C1) olefin copolymer and (C2) styrene based copolymer, (A) composition is made to be 65 ~ 93 quality %, (B) composition is 5 ~ 20 quality %, (C) composition is 2 ~ 10 quality %, (B1) fiber diameter of composition is less than 1.0 μm, and average fiber length is 5 ~ 50 μm, (B2) composition is selected from mean grain size is less than 50 μm, at least one in sheet filling agent and particulate fillers, (C1) composition and (C2) composition are made up of specific composition.
Description
Technical field
The present invention relates to camera module (cameramodule) and use liquid crystalline resin composition.
Background technology
The liquid-crystalline resin taking liquid crystalline polyester resin as representative, owing to balancing the physical strength, thermotolerance, chemical proofing, electrical property etc. well with excellence, also has excellent dimensional stability, is therefore widely used as high function engineering plastics.Recently, apply flexibly these characteristics of liquid-crystalline resin, and use it for precision equipment parts.
At precision equipment, when particularly having a such optical device of lens, a small amount of dirt, dust etc. just can impact equipment performance.For such as camera module for the parts of optical device, when small dirt, oil content, dust are attached to lens, the optical characteristics of camera module significantly reduces.In order to prevent the reduction of this optical characteristics, usually, the parts (hereinafter sometimes referred to " camera module use parts ") forming camera module carry out Ultrasonic Cleaning before assembling, remove the small dirt, oil content, dust etc. that are attached to surface.
As mentioned above, by formed body shaping for liquid crystalline resin composition because high molecular molecular orientation is large especially in surface portion, therefore formed body surface is easily peeled off, when therefore Ultrasonic Cleaning being carried out to this formed body, surface is peeled off, produce the fluffiness being called as fluffing, the fluffing part of this fluffing causes small dirt to produce.
Therefore, when liquid crystalline resin composition is used as the raw material of camera module use parts, even if use, the special liquid crystalline resin composition that Ultrasonic Cleaning also can not make formed body wildness such is carried out to formed body.As special liquid crystalline resin composition, disclose the camera module use liquid crystalline resin composition (with reference to patent documentation 1) comprising liquid-crystalline resin and specific talcum and carbon black.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2009-242453 publication
Summary of the invention
the problem that invention will solve
But, in the research of the present inventor etc., the suppression of camera module use liquid crystalline resin composition to formed body wildness recorded in patent documentation 1 is insufficient, needs the camera module use liquid crystalline resin composition of the formed body more not easily fluffed for the manufacture of formed body surface.
The present invention makes to solve the problem, its object is to be provided for manufacture the camera module use parts not easily fluffed on surface, camera module use liquid crystalline resin composition.
for the scheme of dealing with problems
The present inventor etc. conduct in-depth research repeatedly in order to solve the problem.Its result, manufacture liquid-crystalline resin and specific inorganic filler and the compounding camera module use liquid crystalline resin composition of specific multipolymer if find according to the mode contained with specific ratio, then can solve the problem, thus complete the present invention.More specifically, the invention provides following technical scheme.
(1) a kind of camera module use liquid crystalline resin composition, it is compounding in (A) liquid-crystalline resin at least one (B) inorganic filler being selected from (B1) fibrous filler and (B2) Non-fibrous filling agent, be selected from least one (C) multipolymer of (C1) olefin copolymer and (C2) styrene based copolymer, (A) composition is made to be 65 ~ 93 quality %, (B) composition is 5 ~ 20 quality %, (C) composition is 2 ~ 10 quality %, the fiber diameter of aforementioned (B1) fibrous filler is less than 1.0 μm, and average fiber length is 5 ~ 50 μm, it is less than 50 μm that aforementioned (B2) Non-fibrous filling agent is selected from mean grain size, at least one in sheet filling agent and particulate fillers, aforementioned (C1) olefin copolymer is by alpha-olefin and α, the ethylene oxidic ester of beta-unsaturated acid is formed, aforementioned (C2) styrene based copolymer is by phenylethylene and α, the ethylene oxidic ester of beta-unsaturated acid is formed.
(2) the camera module use liquid crystalline resin composition Gen Ju (1), wherein, the mean grain size of aforementioned (B2) Non-fibrous filling agent is 10 ~ 20 μm.
(3) according to (1) or the camera module use liquid crystalline resin composition described in (2), it is also that the mode of 1 ~ 5 quality % is compounding with content (D) carbon black.
the effect of invention
If using camera module use liquid crystalline resin composition of the present invention as raw material, manufacture camera module use parts, then can obtain the camera module use parts not easily fluffed in surface.
Accompanying drawing explanation
Fig. 1 is the sectional view schematically showing common camera module.
Embodiment
Below, embodiments of the present invention are described.It should be noted that, the present invention is not limited to following embodiment.
< camera module use liquid crystalline resin composition >
In camera module use liquid crystalline resin composition of the present invention, compounding (A) liquid-crystalline resin, (B) inorganic filler, (C) multipolymer are as required composition.
[(A) liquid-crystalline resin]
(A) liquid-crystalline resin used in the present invention refers to have the melt processable polymkeric substance of the character that can form optical anisotropy melting behaviors.The character of anisotropy melting behaviors can confirm by utilizing the usual polarisation inspection technique of cross polarization sheet.More specifically, anisotropy melting behaviors is approved to implement as follows really: by using Leitz polarizing microscope, observe the melting sample be positioned in Leitz thermal station in a nitrogen atmosphere with the multiplying power of 40 times, thus implements.When in the present invention, adaptable liquid-crystalline polymer checks between cross polarization sheet, even if under melting stationary state, polarisation also normal through, optically demonstrate anisotropy.
As the kind of (A) liquid-crystalline resin as above, be not particularly limited, be preferably aromatic polyester or aromatic polyester acid amides.In addition, the polyester that local comprises aromatic polyester or aromatic polyester acid amides in same strand is also within the scope of this.Preferred use has when they are dissolved in Pentafluorophenol with concentration 0.1 % by weight at 60 DEG C preferably at least about the material of 2.0dl/g, the further preferred log viscosities (I.V.) of 2.0 ~ 10.0dl/g.
About as the aromatic polyester of adaptable in the present invention (A) liquid-crystalline resin or aromatic polyester acid amides, particularly preferably be and there is aromatic polyester, the aromatic polyester acid amides of the above compound of at least one in the group being selected from aromatic hydroxy-carboxylic, aromatic series azanol, aromatic diamine as constituent.
More specifically, can list:
(1) primarily of the polyester that one or more in aromatic hydroxy-carboxylic and derivant thereof are formed;
(2) primarily of the polyester more than at least one or two in one or more in one or more in (a) aromatic hydroxy-carboxylic and derivant thereof, (b) aromatic dicarboxylic acid, alicyclic dicarboxylic acid and derivant thereof, (c) aromatic diol, alicyclic diol, aliphatic diol and derivant thereof formed;
(3) primarily of the polyesteramide that one or more in one or more in one or more in (a) aromatic hydroxy-carboxylic and derivant thereof, (b) aromatic series azanol, aromatic diamine and derivant thereof, (c) aromatic dicarboxylic acid, alicyclic dicarboxylic acid and derivant thereof are formed;
(4) primarily of the polyesteramide the etc. more than at least one or two in one or more in one or more in one or more in (a) aromatic hydroxy-carboxylic and derivant thereof, (b) aromatic series azanol, aromatic diamine and derivant thereof, (c) aromatic dicarboxylic acid, alicyclic dicarboxylic acid and derivant thereof, (d) aromatic diol, alicyclic diol, aliphatic diol and derivant thereof formed.And then, in above-mentioned constituent, molecular weight regulator can also be combinationally used as required.
As the preferred example of the concrete compound of adaptable (A) liquid-crystalline resin in formation the present invention, the aromatic hydroxy-carboxylic such as P-hydroxybenzoic acid, 6-Hydroxy-2-naphthoic acid, 2 can be listed, 6-dihydroxy naphthlene, 1,4-dihydroxy naphthlene, 4, the aromatic diols such as 4 '-dihydroxybiphenyl, quinhydrones, resorcinol, the compound shown in following general formula (I) and following general formula (II); The aromatic dicarboxylic acids such as terephthalic acid (TPA), m-phthalic acid, 4,4'-diphenyldicarboxylic acids, the compound shown in 2,6-naphthalene dicarboxylic acids and following general formula (III); The aromatic amine such as para-aminophenol, p-phenylenediamine (PPD).
(X: for being selected from alkylidene (C1 ~ C4), alkylidene radical ,-O-,-SO-,-SO
2-, group in-S-,-CO-.)
(Y: for being selected from-(CH
2) n-(n=1 ~ 4) ,-O (CH
2) group in nO-(n=1 ~ 4).)
The preparation of (A) liquid-crystalline resin used in the present invention can use direct polymerization method, ester-interchange method to be undertaken by known method by above-mentioned monomeric compound (or potpourri of monomer), usually uses melt phase polycondensation, slurry polymerization process etc.The above-claimed cpd class with ester Forming ability can be directly used in polymerization with form originally, or also can become have the derivant of this ester Forming ability in the last stage of polymerization from precursor modification.During their polymerization, various catalyzer can be used, representatively example, dialkyltin, diaryl tin oxide, titania, alkoxytitanium silicates, Titanium alkoxides class, the alkali metal salt of carboxylic acid and earth alkali metal salt can be listed, as BF
3such lewis acid etc.The consumption of catalyzer is usually about 0.001 ~ 1 quality % relative to the general assembly (TW) of monomer, is particularly preferably about 0.01 ~ 0.2 quality %.The polymkeric substance manufactured by these polymerizations if necessary can by the incompatible increase seeking molecular weight of solid polycondensation of heating in decompression or non-active gas.
The melt viscosity of (A) liquid-crystalline resin obtained by method as above is not particularly limited.Usually melt viscosity under forming temperature can be used at shear rate 1000sec
-1it is down the liquid-crystalline resin of more than 10MPa and below 600MPa.But, the mobility extreme degradation of the liquid-crystalline resin that oneself viscosity is too high, thus not preferred.It should be noted that, above-mentioned (A) liquid-crystalline resin also can be the potpourri of two or more liquid-crystalline resins.
The content of (A) liquid-crystalline resin in camera module use liquid crystalline resin composition of the present invention is 65 ~ 93 quality %.(A) when the content of composition is more than 65 quality %, for mobility, suppress shaping surface to be fluffed reason and preferably, when the content of (A) composition is below 93 quality %, for the reason of thermotolerance preferably.In addition, the preferred content of (A) composition is 80 ~ 93 quality %.
[(B) inorganic filler]
(B) inorganic filler is for being selected from (B1) fiber diameter less than 1.0 μm and average fiber length is at least one in the Non-fibrous filling agent of the fibrous filler of 5 ~ 50 μm and (B2) mean grain size less than 50 μm.
(B1) fiber diameter of fibrous filler is less than 1.0 μm, and preferred fiber diameter is 0.3 ~ 0.6 μm.Above-mentioned fiber diameter is less than 1.0 μm is necessary in suppressing shaping surface to be fluffed.It should be noted that, fiber diameter adopts and stereomicroscope image is imported PC from CCD camera, utilizes determining image machine to be measured the value obtained by image processing method.
In addition, the average fiber length of (B1) fibrous filler is 5 ~ 50 μm, and preferred average fiber length is 5 ~ 30 μm, and preferred average fiber length is 7 ~ 30 μm.Above-mentioned average fiber length for more than 5 μm keep as the physical strength needed for camera module, deflection temperature under load in be necessary, be less than 50 μm be necessary in suppressing shaping surface to be fluffed.It should be noted that, average fiber length adopts and stereomicroscope image is imported PC from CCD camera, utilizes determining image machine to be measured the value obtained by image processing method.
If meet the fibrous filler of above shape, then can use arbitrary fiber, as (B1) fibrous filler, include, for example out the inorganic fibrous materials such as the fibrous material of the metals such as glass fibre, carbon fiber, fibrous asbestos, silicon dioxide fibre, silica alumina fiber, Zirconium oxide fibre, boron nitride fiber, silicon nitride fiber, boron fibre, potassium titanate fibre and stainless steel, aluminium, titanium, copper, brass.As (B1) composition, also two or more fibrous fillers can be used.In the present invention, as (B1) composition, preferably use potassium titanate fibre.
(B2) Non-fibrous filling agent is that to be selected from mean grain size be at least one in the sheet filling agent of less than 50 μm and particulate fillers.Above-mentioned mean grain size is less than 50 μm is necessary in suppressing shaping surface to be fluffed.Preferred above-mentioned mean grain size is 10 ~ 20 μm.It should be noted that, mean grain size adopts and measures by the method for laser diffraction/diffuse transmission type particle size distribution the value obtained.
If meet the Non-fibrous filling agent of above shape, then can use arbitrary filling agent, as sheet filling agent, talcum, mica, glass flake, various metal formings etc. can be listed.In addition, as particulate fillers, sulfate and silit, silicon nitride, boron nitride, the various metal powders etc. of the such metal of the carbonate of the such metal of the oxide of the such metal of the such silicate of silicon dioxide, quartz powder, glass microballoon, glass dust, calcium silicate, alumina silicate, porcelain earth, clay, zeyssatite, wollastonite, iron oxide, titanium dioxide, zinc paste, aluminium oxide, calcium carbonate, magnesium carbonate, calcium sulphate, barium sulphate can be listed.As (B2) composition, also can use two or more.In the present invention, as (B2) composition, preferably use the silicon dioxide of the talcum of sheet filling agent, mica, particulate fillers, more preferably use talcum, the mica of sheet filling agent.
(B) content (summation of the content of above-mentioned (B1) composition and the content of above-mentioned (B2) composition) of composition is 5 ~ 20 quality % in camera module use liquid crystalline composition of the present invention.(B) composition content for more than 5 quality % guarantee as the physical strength needed for camera module, deflection temperature under load in be necessary, be below 20 quality % suppress the fluffing of shaping surface in be necessary.Preferred above-mentioned content is 5 ~ 15 quality %.
[(C) multipolymer]
(C) multipolymer is for being selected from least one of (C1) olefin copolymer and (C2) styrene based copolymer.When (C) composition is compounded in camera module use liquid crystalline resin composition, be conducive to suppressing to when formed body shaping for said composition being carried out Ultrasonic Cleaning, the fluffing on formed body surface.
About the reason suppressing fluffing, and indefinite, but can think, by compounding with certain constant basis, thus formed body surface state is changed, this change contributes to suppressing fluffing.
(C1) olefin copolymer is by alpha-olefin and α, and the ethylene oxidic ester of beta-unsaturated acid is formed.
Alpha-olefin is not particularly limited, include, for example out ethene, propylene, butylene etc., wherein preferably use ethene.α, the ethylene oxidic ester of beta-unsaturated acid is represented by following general formula (IV).α, the diglycidyl ester units of beta-unsaturated acid such as has glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itoconate etc., particularly preferably glycidyl methacrylate.
(C1) content in olefin copolymer, alpha-olefin is preferably 87 ~ 98 quality %, α, and the content of the ethylene oxidic ester of beta-unsaturated acid is preferably 13 ~ 2 quality %.
(C1) olefin copolymer used in the present invention is not damaging in scope of the present invention, except above-mentioned two kinds of compositions, as the 3rd composition, the amount that can be 0 ~ 48 mass parts with two kind compositions above-mentioned relative to 100 mass parts contains one or more of the ethylene series beta-unsaturated esters of vinyl cyanide, acrylate, methacrylate, α-methyl styrene, maleic anhydride etc.
Olefin copolymer as (C1) of the present invention composition can use the monomer of each composition, catalysts for radical polymerization easily to be prepared by common radical polymerization.More specifically, usually can by by alpha-olefin and α, the ethylene oxidic ester of beta-unsaturated acid under the existence of free-radical generating agent, at 500 ~ 4000 air pressure, at 100 ~ 300 DEG C, under the existence of suitable solvent, chain-transferring agent or not in the presence of carry out copolymerization method manufacture.In addition, also can pass through alpha-olefin and α, the ethylene oxidic ester of beta-unsaturated acid and free-radical generating agent mixing, the method for carrying out fusion-grafting copolymerization in an extruder manufactures.
(C2) styrene based copolymer is by phenylethylene and α, and the ethylene oxidic ester of beta-unsaturated acid is formed.About α, the ethylene oxidic ester of beta-unsaturated acid, due to identical with the material illustrated in (C1) composition, therefore omits the description.
As phenylethylene, styrene, α-methyl styrene, bromostyrene, divinylbenzene etc. can be listed, preferably use styrene.
The multiple copolymer that (C2) styrene based copolymer used in the present invention can be assigned to carry out copolymerization as the three one-tenth for also using except above-mentioned two kinds of compositions more than one other vinyl monomer and be obtained.Suitable ternary as the, one or more in the ethylene series beta-unsaturated esters of vinyl cyanide, acrylate, methacrylate, maleic anhydride etc.The repetitive being derived from them of below 40 quality % and the multipolymer that obtains is imported preferably as (C2) composition in (C2) styrene based copolymer.
(C2) α in styrene based copolymer, the diglycidyl ester content of beta-unsaturated acid is preferably 2 ~ 20 quality %, and phenylethylene is preferably 80 ~ 98 % by weight.
(C2) styrene based copolymer can be prepared by common radical polymerization by using the monomer of each composition, catalysts for radical polymerization.More specifically, usually can by by phenylethylene and α, the ethylene oxidic ester of beta-unsaturated acid under the existence of free-radical generating agent, at 500 ~ 4000 air pressure, at 100 ~ 300 DEG C, under the existence of suitable solvent, chain-transferring agent or not in the presence of carry out copolymerization method manufacture.In addition, also can pass through phenylethylene and α, the ethylene oxidic ester of beta-unsaturated acid and free-radical generating agent mixing, the method for carrying out fusion-grafting copolymerization in an extruder manufactures.
It should be noted that, as (C) multipolymer, (C1) olefin copolymer in thermotolerance preferably, suitably can select according to required characteristic with the ratio of (C2) composition by (C1) composition.
(C) content (total amount of (C1) composition and (C2) composition) of multipolymer is 2 ~ 10 quality % in camera module use resin combination of the present invention.(C) content of composition be more than 2 quality % suppress the fluffing of shaping surface in be necessary, be below 10 quality % be necessary for not damaging mobility, the reason of good formed body can being obtained.Preferred above-mentioned content is 2 ~ 7 quality %.
[(D) carbon black]
(D) that use in the present invention is as long as carbon black is the usual retrievable carbon black for coloring resin; just be not particularly limited; but usually can comprise primary particle to assemble and the block of formation; if obviously more comprise the block of the size of more than 50 μm; then the surface of formed body shaping for resin combination of the present invention will produce sometimes a large amount of hard spot (the fine fash shape thrust (fine is concavo-convex) that carbon black is assembled), not preferably.Above-mentioned block particle diameter to be the particle of more than 50 μm be below 20ppm suppress the fluffing of shaping surface in be necessary.Preferred containing ratio is below 5ppm.
As the compounding amount of (D) carbon black, be preferably the scope of 1 ~ 5 quality % in camera module use liquid crystalline resin composition.During compounding quantity not sufficient 1 mass parts of carbon black, the pitch-dark property of the resin combination obtained reduces, and can worry light-proofness, during more than 5 mass parts, uneconomical, and the possibility producing hard spot uprises.
[other composition]
In camera module use liquid crystalline resin composition of the present invention, in the scope not damaging effect of the present invention, suitably can also add colorant, lubricant, release agent and crystallization promoter, the crystallization nucleating agent etc. such as other polymkeric substance, the known material usually added in synthetic resin, the i.e. stabilizing agent such as antioxidant, ultraviolet light absorber, antistatic agent, fire retardant, dyestuff, pigment according to desired properties.
[preparation of camera module use liquid crystalline resin composition]
The preparation of camera module use resin combination of the present invention is not particularly limited.Such as, add compounding above-mentioned (A), (B), (C) composition, use singe screw or double screw extrusion machine to carry out melting mixing process them, thus carry out the preparation of camera module use liquid crystalline resin composition.
[camera module use liquid crystalline resin composition]
The shape of (B) composition in camera module use liquid crystalline resin composition of the present invention is different from the shape of compounding front (B) composition.The shape of above-mentioned (B) composition is compounding front shape.As long as the shape before compounding is described above, the camera module use parts not easily fluffed in surface just can be obtained.
The melt viscosity of the camera module use liquid crystalline resin composition of the present invention obtained as mentioned above is preferably below 50Pasec.Mobility is high, the excellent this point of mouldability is also one of feature of camera module use liquid crystalline resin composition of the present invention.Herein, melt viscosity adopts at barrel zone temperature 350 DEG C, shear rate 1000sec
-1condition under, value by obtaining according to the assay method of ISO11443.
The deflection temperature under load of camera module use liquid crystalline resin composition of the present invention is preferably more than 200 DEG C.Excellent heat resistance this point is also one of feature of camera module use liquid crystalline resin composition of the present invention.It should be noted that, deflection temperature under load adopt by according to ISO75-1,2 method measure the value obtained.
< camera module use parts >
Use above-mentioned camera module use liquid crystalline resin composition, manufacture camera module use parts.If use resin combination of the present invention as raw material, then the surface of camera module use parts becomes and not easily fluffs.Camera module use parts are owing to carrying out Ultrasonic Cleaning, even if therefore require to carry out Ultrasonic Cleaning, also not easily fluff in surface.Use resin combination of the present invention, even if carry out the Ultrasonic Cleaning of camera module use parts under stronger condition, also can not produce or produce the cast causing dirt etc. hardly.Therefore, after camera module use parts are assembled into finished goods, the dirt produced because of the wildness of these camera module use parts hardly and quality of finished goods is impacted.
Be described by camera module use parts shaping for camera module use liquid crystalline resin composition of the present invention.The cross-sectional schematic of common camera module is shown in Fig. 1.As shown in Figure 1, camera module 1 possesses: substrate 10, optical element 11, lead-in wire 12, keeper 13, bucket 14, lens 15, IR optical filter 16.
Optical element 11 configures on the substrate 10, is electrically connected between optical element 11 with substrate 10 with lead-in wire 12.
Keeper 13 configures on the substrate 10, covers optical element 11.Keeper 13 is formed with opening at top, is formed with spiral helicine ditch portion on the surface at this perforated wall.
Bucket 14 is cylindric, and lens 15 remain on cylindric inside in a generally horizontal fashion.In addition, the sidewall of one end of cylinder is formed with spiral helicine protuberance, this spiral helicine protuberance screws with the spiral helicine ditch portion on the perforated wall surface being formed at keeper 13, thus is connected with keeper 13 by bucket 14.In addition, IR optical filter 16 is configured at one end of bucket 14 by the mode closed with one end of the bucket 14 by cylindrical shape.As shown in Figure 1, IR optical filter 16 and lens 15 arrange substantially in parallel.
In camera module 1 as shown in Figure 1, rotated by bucket 14, thus the distance between lens 15 and optical element 11 changes.By adjusting this distance, the focal adjustments of camera can be carried out.
In camera module 1 as above, camera module use liquid crystalline resin composition of the present invention can be used to manufacture keeper 13, the bucket 14 as camera module use parts as raw material.Common liquid crystalline resin composition is not suitable for as the raw material for the manufacture of these parts.When manufacturing keeper 13, bucket 14 using common liquid crystalline resin composition as raw material, following problem can be produced.
By formed body shaping for common liquid crystalline resin composition because high molecular molecular orientation is large especially in surface portion, therefore formed body surface easily fluffing, this fluffing causes little dirt to produce.When this little dirt is attached to lens 15 grade, the performance of camera module reduces.
The camera module use parts such as keeper 13, bucket 14 are in order to remove dust, the little dirt and carried out Ultrasonic Cleaning before being assembled in camera module 1 on surface.But easily fluffed on the surface of formed body shaping for common liquid crystalline resin composition, therefore during Ultrasonic Cleaning, fluff in surface.Owing to producing this problem, usually Ultrasonic Cleaning cannot be carried out to by formed body shaping for liquid crystalline resin composition.
Above-mentioned focal adjustments is undertaken by the spiral helicine protuberance moving the sidewall of the end being formed at bucket 14 in the spiral helicine ditch portion on the perforated wall surface being formed at keeper 13.Now, above-mentioned spiral helicine ditch portion rubs at surface of contact mutually with above-mentioned spiral helicine protuberance.By formed body shaping for common liquid crystalline resin composition as mentioned above owing to easily fluffing in surface, therefore may sur-face peeling and be peeling thing.This overburden forms little dirt and is attached to lens 15 etc., may reduce the performance of camera module.
As mentioned above, usually liquid crystalline resin composition cannot be used as the raw material of keeper 13, bucket 14, even if carry out to this formed body the surface state that level that Ultrasonic Cleaning also produces the problem of fluffing hardly improves formed body when camera module use liquid crystalline resin composition of the present invention is to make formed body, the raw material of keeper 13, bucket 14 therefore preferably can be used as.
Embodiment
Below enumerate embodiment, in further detail the present invention is described, but the present invention is not limited to these embodiments.
< material >
Liquid-crystalline resin (liquid crystalline polyester amide resin): VECTRA (registered trademark) E950i (Polyplastics Co., Ltd.'s manufacture)
Fibrous filler 1: Otsuka Chemical Co., Ltd manufactures TISMON-102 (potassium titanate fibre, fiber diameter 0.3 ~ 0.6 μm, average fiber length 10 ~ 20 μm)
Fibrous filler 2: Nitto Boseki Co. Ltd manufactures PF70E-001 (milled glass fiber, fibre diameter 10 μm, weight average length 70 μm)
Non-fibrous filling agent 1: Ishihara Sangyo Kaisha, Ltd. manufactures CrownTalcPP (talcum, mean grain size 12.8 μm, average aspect ratio 6)
Non-fibrous filling agent 2: mica industry in mountain pass manufactures AB-25S (mica, mean grain size 24 μm)
Non-fibrous filling agent 3: mica industry in mountain pass manufactures A-41S (mica, mean grain size 47 μm)
Olefin copolymer: Sumitomo Chemical Co manufactures Bondfast2C (ethylene-methyl methacrylate glycidyl ester copolymer (glycidyl methacrylate containing 6 % by weight))
Carbon black: CabotJapanK.K manufactures VULCANXC305 (ratio of carbon black, mean grain size 20nm, particle diameter more than 50 μm be below 20ppm, granular)
The manufacture > of < camera module use liquid crystalline resin composition
Use biaxial extruder (the TEX30 α type that Corporation Japan Steel Works manufactures) to carry out melting mixing at barrel zone temperature 350 DEG C with the ratio shown in table 1 mentioned component, obtain camera module use liquid crystalline resin composition pellet.
< melt viscosity >
Above-mentioned pellet is used to measure the melt viscosity of the camera module use liquid crystalline resin composition of embodiment and comparative example.Specifically, utilize capillary rheometer (CAPIROGRAPH1D: the diameter of plunger 10mm of the manufacture of Toyo Seiki Co., Ltd.), be determined at barrel zone temperature 350 DEG C, shear rate 1000sec according to ISO11443
-1condition under apparent melt viscosity.The hole of internal diameter 1mm, length 20mm is used in mensuration.It should be noted that, measurement result is shown in table 1.
< rod fluidity test >
Use the mobility of the camera module use liquid crystalline resin composition of above-mentioned pellet Evaluation operation example and comparative example.Specifically, forming machine (Sumitomo Heavy Industries, Ltd manufactures " SE30DUZ ") above-mentioned pellet is used to be the test film of thickness 0.3mm at following condition of molding compacted under.Mobility is evaluated by the length measuring the formed body obtained.It should be noted that, evaluation result is shown in table 1.
(condition of molding)
Barrel zone temperature: 350 DEG C
Mold temperature: 80 DEG C
Injection pressure: 100MPa
Injection moulding speed: 200mm/sec
The evaluation > of the fluffing state (wildness inhibition) on < formed body surface
Forming machine (Sumitomo Heavy Industries, Ltd manufactures " SE30DUZ ") is used at following condition of molding compacted under, to obtain the formed body of 12.5mm × 120mm × 0.8mm the pellet of embodiment and comparative example.This formed body is cut into half use as test film.
(condition of molding)
Barrel zone temperature: 350 DEG C
Mold temperature: 90 DEG C
Injection moulding speed: 80mm/sec
(evaluation)
In the water of room temperature, supersonic wave cleaning machine (output power 300W, frequency 45kHz) is placed in 3 minutes by cutting into the formed body after half.Then, compare the formed body be placed in before and after supersonic wave cleaning machine, utilize image determiner (LUZEXFS that NirecoCorporation manufactures) to evaluate the area (playing gross area) of the part of the fluffing on formed body surface.It should be noted that, evaluation area is 750mm
2(12.5mm × 60mm).Evaluation result is shown in table 1.
Play gross area fewer, be evaluated as feathering inhibition effect higher.
< deflection temperature under load >
Forming machine (Sumitomo Heavy Industries, Ltd manufactures " SE100DU ") is used by the pellet of embodiment and comparative example to be mensuration test film (4mm × 10mm × 80mm) at following condition of molding compacted under.Then, by according to ISO75-1,2 method measuring load deflection temperature.Measurement result is shown in table 1.
(condition of molding)
Barrel zone temperature: 350 DEG C
Mold temperature: 80 DEG C
Back pressure: 2.0MPa
Injection moulding speed: 33mm/sec
< Charpy-type test >
Forming machine (Sumitomo Heavy Industries, Ltd manufactures " SE100DU ") is used by the pellet of embodiment and comparative example to be mensuration test film (4mm × 10mm × 80mm) at following condition of molding compacted under.Then, charp impact value is measured by the method according to ISO179-1.Show the result in table 1.
(condition of molding)
Barrel zone temperature: 350 DEG C
Mold temperature: 80 DEG C
Back pressure: 2.0MPa
Injection moulding speed: 33mm/sec
[table 1]
[table 1]
Obviously confirmed by the result recorded in table 1, even if use the formed body of the pellet manufacture of embodiment to carry out Ultrasonic Cleaning, also do not fluff in surface.Can say according to this result, by formed body shaping for the pellet of embodiment with the surface state of formed body shaping for the common liquid crystalline resin composition pellets such as comparative example is differed widely.
In addition, confirm the excellent heat resistance of the formed body using the pellet of embodiment to manufacture, mobility is excellent, excellent impact resistance.
description of reference numerals
1 camera module
10 substrates
11 optical elements
12 lead-in wires
13 keepers
14 barrels
15 lens
16IR optical filter
Claims (3)
1. a camera module use liquid crystalline resin composition, it is compounding in liquid-crystalline resin A has
Be selected from least one inorganic filler B of fibrous filler B1 and Non-fibrous filling agent B2,
Be selected from least one multipolymer C of olefin copolymer C1 and styrene based copolymer C2,
Make that composition A is 65 ~ 93 quality %, composition B is 5 ~ 20 quality %, composition C is 2 ~ 10 quality %,
The fiber diameter of described fibrous filler B1 is less than 1.0 μm, and average fiber length is 5 ~ 50 μm,
Described Non-fibrous filling agent B2 be selected from that mean grain size is less than 50 μm, at least one in sheet filling agent and particulate fillers,
Described olefin copolymer C1 is by alpha-olefin and α, and the ethylene oxidic ester of beta-unsaturated acid is formed,
Described styrene based copolymer C2 is by the phenylethylene be selected from group that styrene, α-methyl styrene, bromostyrene and divinylbenzene form and α, and the ethylene oxidic ester of beta-unsaturated acid is formed.
2. camera module use liquid crystalline resin composition according to claim 1, wherein, the mean grain size of described Non-fibrous filling agent B2 is 10 ~ 20 μm.
3. camera module use liquid crystalline resin composition according to claim 1 and 2, it is also that the mode of 1 ~ 5 quality % is compounding with content carbon black D.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012044660 | 2012-02-29 | ||
| JP2012-044660 | 2012-02-29 | ||
| PCT/JP2013/054822 WO2013129338A1 (en) | 2012-02-29 | 2013-02-25 | Liquid crystal resin composition for camera modules |
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| Publication Number | Publication Date |
|---|---|
| CN104040422A CN104040422A (en) | 2014-09-10 |
| CN104040422B true CN104040422B (en) | 2016-04-13 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201380004759.0A Active CN104040422B (en) | 2012-02-29 | 2013-02-25 | Camera module use liquid crystalline resin composition |
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| Country | Link |
|---|---|
| JP (1) | JP5680788B2 (en) |
| KR (1) | KR101537109B1 (en) |
| CN (1) | CN104040422B (en) |
| TW (2) | TWI608037B (en) |
| WO (1) | WO2013129338A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5826411B2 (en) * | 2012-12-03 | 2015-12-02 | ポリプラスチックス株式会社 | Liquid crystalline resin composition for camera module and camera module using the same |
| JP2016510831A (en) | 2013-03-13 | 2016-04-11 | ティコナ・エルエルシー | Liquid crystal polymer composition |
| JP6174406B2 (en) * | 2013-07-23 | 2017-08-02 | ポリプラスチックス株式会社 | Liquid crystalline resin composition for camera modules |
| JP6165608B2 (en) * | 2013-12-03 | 2017-07-19 | Ｊｘｔｇエネルギー株式会社 | Camera module parts comprising a wholly aromatic liquid crystal polyester resin composition and an injection molded product thereof as constituent members |
| US9822254B2 (en) | 2014-04-09 | 2017-11-21 | Ticona Llc | Camera module |
| US10407605B2 (en) | 2015-07-31 | 2019-09-10 | Ticona Llc | Thermally conductive polymer composition |
| US9862809B2 (en) | 2015-07-31 | 2018-01-09 | Ticona Llc | Camera module |
| TWI708806B (en) | 2015-08-17 | 2020-11-01 | 美商堤康那責任有限公司 | Liquid crystalline polymer composition for camera modules |
| CN107924039B (en) * | 2015-09-01 | 2020-10-16 | 宝理塑料株式会社 | Liquid crystalline resin composition for camera module and camera module using same |
| US10633535B2 (en) | 2017-02-06 | 2020-04-28 | Ticona Llc | Polyester polymer compositions |
| JP6878149B2 (en) * | 2017-05-30 | 2021-05-26 | 上野製薬株式会社 | Liquid crystal polymer composition |
| TW201922862A (en) * | 2017-11-15 | 2019-06-16 | 日商住友化學股份有限公司 | Liquid crystal polyester composition and resin molded article |
| KR102627886B1 (en) | 2017-12-05 | 2024-01-19 | 티코나 엘엘씨 | Aromatic polymer compositions for use in camera modules |
| TW201932533A (en) * | 2017-12-18 | 2019-08-16 | 日商住友化學股份有限公司 | Liquid crystal polyester composition and molded article |
| WO2019155419A1 (en) | 2018-02-08 | 2019-08-15 | Celanese Sales Germany Gmbh | Polymer composite containing recycled carbon fibers |
| EP3755515A4 (en) | 2018-02-20 | 2021-11-10 | Ticona LLC | Thermally conductive polymer composition |
| WO2019201010A1 (en) * | 2018-04-16 | 2019-10-24 | Oppo广东移动通信有限公司 | Laser projector, camera module and electronic device |
| CN113015765B (en) * | 2018-11-15 | 2022-04-26 | 宝理塑料株式会社 | Liquid crystalline resin composition and connector of molded article comprising same |
| US11086200B2 (en) | 2019-03-20 | 2021-08-10 | Ticona Llc | Polymer composition for use in a camera module |
| WO2020190568A1 (en) | 2019-03-20 | 2020-09-24 | Ticona Llc | Actuator assembly for a camera module |
| US11702539B2 (en) | 2020-02-26 | 2023-07-18 | Ticona Llc | Polymer composition for an electronic device |
| KR20220146567A (en) | 2020-02-26 | 2022-11-01 | 티코나 엘엘씨 | electronic device |
| KR20220145385A (en) | 2020-02-26 | 2022-10-28 | 티코나 엘엘씨 | circuit structure |
| US11728065B2 (en) | 2020-07-28 | 2023-08-15 | Ticona Llc | Molded interconnect device |
| WO2024122582A1 (en) * | 2022-12-08 | 2024-06-13 | ポリプラスチックス株式会社 | Liquid crystal resin composition and camera module using same |
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- 2013-02-25 KR KR1020147017399A patent/KR101537109B1/en active IP Right Grant
- 2013-02-25 CN CN201380004759.0A patent/CN104040422B/en active Active
- 2013-02-25 WO PCT/JP2013/054822 patent/WO2013129338A1/en active Application Filing
- 2013-02-25 JP JP2014502219A patent/JP5680788B2/en active Active
- 2013-02-27 TW TW102106848A patent/TWI608037B/en active
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| CN101305056A (en) * | 2005-10-13 | 2008-11-12 | 宝理塑料株式会社 | Liquid crystalline resin composition for use in injection molding |
| CN101981123A (en) * | 2008-03-28 | 2011-02-23 | 吉坤日矿日石能源株式会社 | Liquid-crystal polyester resin composition for camera modules |
Also Published As
| Publication number | Publication date |
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| TW201639908A (en) | 2016-11-16 |
| KR20140141570A (en) | 2014-12-10 |
| TWI608038B (en) | 2017-12-11 |
| WO2013129338A1 (en) | 2013-09-06 |
| JP5680788B2 (en) | 2015-03-04 |
| KR101537109B1 (en) | 2015-07-15 |
| JPWO2013129338A1 (en) | 2015-07-30 |
| TW201402664A (en) | 2014-01-16 |
| CN104040422A (en) | 2014-09-10 |
| TWI608037B (en) | 2017-12-11 |
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