CN104040422A - Liquid crystal resin composition for camera modules - Google Patents
Liquid crystal resin composition for camera modules Download PDFInfo
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- CN104040422A CN104040422A CN201380004759.0A CN201380004759A CN104040422A CN 104040422 A CN104040422 A CN 104040422A CN 201380004759 A CN201380004759 A CN 201380004759A CN 104040422 A CN104040422 A CN 104040422A
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
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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
Abstract
Provided is a liquid crystal resin composition for camera modules, which is used for the purpose of producing a camera module component. The surface of a molded body of this liquid crystal resin composition for camera modules is not easily raised. This resin composition is obtained by blending at least one kind of (B) an inorganic filler that is selected from among (B1) fibrous fillers and (B2) non-fibrous fillers and at least one kind of (C) a copolymer that is selected from among (C1) olefin copolymers and (C2) styrene copolymers into (A) a liquid crystal resin, so that the component (A) is 65-93% by mass, the component (B) is 5-20% by mass and the component (C) is 2-10% by mass. The component (B1) has an average fiber diameter of 1.0 mum or less and an average fiber length of 5-50 mum, and the component (B2) is at least one filler that is selected from among plate-like fillers and granular fillers having an average particle diameter of 50 mum or less. The component (C1) and the component (C2) are respectively configured of specific components.
Description
Technical field
The present invention relates to camera module (camera module) and use liquid crystalline resin composition.
Background technology
Liquid-crystalline resin taking liquid crystalline polyester resin as representative, because balance has excellent physical strength, thermotolerance, chemical proofing, electrical property etc. well, 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, particularly have the such optical device of lens, a small amount of dirt, dust etc. just can impact equipment performance.For for example as camera module for the parts of optical device, when small dirt, oil content, dust is attached to lens, the optical characteristics of camera module significantly reduces.In order to prevent the reduction of this optical characteristics, conventionally, the parts (being sometimes referred to as below " camera module use parts ") that form camera module carry out Ultrasonic Cleaning before assembling, remove and are attached to surperficial small dirt, oil content, dust etc.
As mentioned above, the formed body that liquid crystalline resin composition moulding is formed is because high molecular molecular orientation divides large especially at surface element, therefore easily peel off on formed body surface, therefore while this formed body being carried out to Ultrasonic Cleaning, peel off on surface, generation is called as the fluffiness of fluffing, and the fluffing part that this fluffing forms causes small dirt to produce.
Therefore,, when liquid crystalline resin composition is used as to the raw material of camera module use parts, even if carrying out Ultrasonic Cleaning to formed body, use can not make the such special liquid crystalline resin composition of formed body wildness yet.As special liquid crystalline resin composition, the camera module use liquid crystalline resin composition (with reference to patent documentation 1) that comprises liquid-crystalline resin and specific talcum and carbon black is disclosed.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2009-242453 communique
Summary of the invention
the problem that invention will solve
But, in the inventor's etc. research, the camera module use liquid crystalline resin composition of recording in patent documentation 1 is insufficient to the inhibition of formed body wildness, need to more be difficult for for the manufacture of formed body surface the camera module use liquid crystalline resin composition of the formed body of fluffing.
The present invention makes in order to address the above problem, its object be to be provided for to manufacture camera module use parts that surface is difficult for fluffing, camera module use liquid crystalline resin composition.
for the scheme of dealing with problems
The inventor etc. conduct in-depth research repeatedly in order to address the above problem.Its result, manufacture camera module use liquid crystalline resin composition liquid-crystalline resin and specific inorganic filler and specific multipolymer compounding being formed according to the mode containing with specific ratio if find, can address the above problem, thereby complete the present invention.More specifically, the invention provides following technical scheme.
(1) a kind of camera module use liquid crystalline resin composition, its compounding in (A) liquid-crystalline resin has and is selected from (B1) fibrous filler and (B2) at least one (B) inorganic filler of non-fibrous filler, be selected from (C1) olefin copolymer and (C2) at least one (C) multipolymer of styrene based copolymer, making (A) composition is 65～93 quality %, (B) composition is 5～20 quality %, (C) composition is 2～10 quality %, the fiber diameter of aforementioned (B1) fibrous filler is below 1.0 μ m, and average fiber length is 5～50 μ m, it is below 50 μ m that aforementioned (B2) non-fibrous filler is selected from mean grain size, at least one in sheet filling agent and granular filling agent, aforementioned (C1) olefin copolymer is by alpha-olefin and α, the ethylene oxidic ester of beta-unsaturated acid forms, aforementioned (C2) styrene based copolymer is by phenylethylene and α, the ethylene oxidic ester of beta-unsaturated acid forms.
(2) according to the camera module use liquid crystalline resin composition (1) described, wherein, the mean grain size of aforementioned (B2) non-fibrous filler is 10～20 μ m.
(3) according to the camera module use liquid crystalline resin composition (1) or (2) described, it also has (D) carbon black taking content as the mode compounding of 1～5 quality %.
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, can obtain the camera module use parts that surface is difficult for fluffing.
Brief description of the drawings
Fig. 1 is the sectional view of schematically illustrated 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 essential composition.
[(A) liquid-crystalline resin]
(A) liquid-crystalline resin using in the present invention refers to have the melt processable polymkeric substance of the character that can form optical anisotropy melting phase.The character of anisotropy melting phase can be confirmed by the usual polarisation inspection technique of utilizing cross polarization sheet.More specifically, anisotropy melting is approved to implement as follows mutually really: by using Leitz polarizing microscope, the multiplying power with 40 times under nitrogen atmosphere is observed the melting sample being positioned on the hot platform of Leitz, thereby implements.When in the present invention, adaptable liquid-crystalline polymer checks between cross polarization sheet, even under melting stationary state, polarisation also normally sees through, and optically demonstrates anisotropy.
As the kind of (A) as above liquid-crystalline resin, be not particularly limited, be preferably aromatic polyester or aromatic polyester acid amides.In addition, the polyester that part comprises aromatic polyester or aromatic polyester acid amides in same strand is also within the scope of this.Preferably use and when they are dissolved in to Pentafluorophenol with concentration 0.1 % by weight at 60 DEG C, have preferably at least about 2.0dl/g, the further preferred material of the logarithm viscosity (I.V.) of 2.0～10.0dl/g.
About aromatic polyester or aromatic polyester acid amides as adaptable in the present invention (A) liquid-crystalline resin, particularly preferably be at least one above compound of having in the group that is selected from aromatic hydroxy-carboxylic, aromatic series azanol, aromatic diamine aromatic polyester, aromatic polyester acid amides as constituent.
More specifically, can list:
(1) main by one or more polyester that form in aromatic hydroxy-carboxylic and derivant thereof;
(2) mainly by (a) aromatic hydroxy-carboxylic and derivant thereof one or more, in (b) aromatic dicarboxylic acid, alicyclic dicarboxylic acid and derivant thereof one or more, at least one or two above polyester that form in (c) aromatic diol, alicyclic diol, aliphatic diol and derivant thereof;
(3) mainly by (a) aromatic hydroxy-carboxylic and derivant thereof one or more, in (b) aromatic series azanol, aromatic diamine and derivant thereof one or more, one or more polyesteramides that form in (c) aromatic dicarboxylic acid, alicyclic dicarboxylic acid and derivant thereof;
(4) mainly by (a) aromatic hydroxy-carboxylic and derivant thereof one or more, in (b) aromatic series azanol, aromatic diamine and derivant thereof one or more, in (c) aromatic dicarboxylic acid, alicyclic dicarboxylic acid and derivant thereof one or more, at least one or two above polyesteramides that form in (d) aromatic diol, alicyclic diol, aliphatic diol and derivant thereof etc.And then, can also in above-mentioned constituent, be used in combination as required molecular weight regulator.
As the preferred example that forms the concrete compound of adaptable (A) liquid-crystalline resin in the present invention, can list the aromatic hydroxy-carboxylic such as P-hydroxybenzoic acid, 6-Hydroxy-2-naphthoic acid, 2,6-dihydroxy naphthlene, 1,4-dihydroxy naphthlene, 4, the aromatic diols such as the compound shown in 4 '-dihydroxybiphenyl, quinhydrones, resorcinol, following general formula (I) and following general formula (II); Terephthalic acid (TPA), m-phthalic acid, 4,4'-diphenyldicarboxylic acids, 2, the aromatic dicarboxylic acids such as the compound shown in 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: be selected from-(CH
2) n-(n=1～4) ,-O (CH
2) group in nO-(n=1～4).)
The preparation of (A) liquid-crystalline resin using in the present invention can be used direct polymerization method, ester-interchange method to be undertaken by known method by above-mentioned monomeric compound (or potpourri of monomer), conventionally uses melt phase polycondensation, slurry polymerization process etc.The above-claimed cpd class with ester formation ability can be directly used in polymerization with form originally, or also can become have in the last stage of polymerization the derivant of this ester formation ability from precursor modification.When their polymerization, various catalyzer can be used, as representational example, the alkali metal salt of dialkyltin, diaryl tin oxide, titania, alkoxytitanium silicates, titanium alcohol salt, carboxylic acid and earth alkali metal salt can be listed, as BF
3such lewis acid etc.The consumption of catalyzer is conventionally about 0.001～1 quality %, is particularly preferably about 0.01～0.2 quality % with respect to the general assembly (TW) of monomer.The polymkeric substance of manufacturing by these polymerizations if necessary can be by the incompatible increase of seeking molecular weight of solid polycondensation of heating in decompression or non-active gas.
Melt viscosity to (A) liquid-crystalline resin obtaining by method as above is not particularly limited.Conventionally can use melt viscosity under forming temperature at shear rate 1000sec
-1it is down the liquid-crystalline resin more than 10MPa and below 600MPa.But the mobility of the too high liquid-crystalline resin of oneself viscosity extremely worsens, therefore not preferred.It should be noted that, above-mentioned (A) liquid-crystalline resin can be also the potpourri of two or more liquid-crystalline resin.
The content of (A) liquid-crystalline resin in camera module use liquid crystalline resin composition of the present invention is 65～93 quality %.(A) content of composition is 65 quality % when above, for mobility, suppress the reason of moulding surface fluffing and preferably, (A) content of composition is that 93 quality % are when following, for stable on heating reason preferably.In addition, (A) the preferred content of composition is 80～93 quality %.
[(B) inorganic filler]
(B) inorganic filler is for being selected from below (B1) fiber diameter 1.0 μ m and average fiber length is the fibrous filler of 5～50 μ m and (B2) at least one in the non-fibrous filler below mean grain size 50 μ m.
(B1) fiber diameter of fibrous filler is below 1.0 μ m, and preferred fiber diameter is 0.3～0.6 μ m.Above-mentioned fiber diameter is that 1.0 μ m are being necessary aspect the fluffing of inhibition moulding surface below.It should be noted that, fiber diameter adopts stereomicroscope image is imported to PC from CCD camera, utilizes determining image machine to measure the value obtaining by image processing method.
In addition, (B1) average fiber length of fibrous filler is 5～50 μ m, and preferred average fiber length is 5～30 μ m, and preferred average fiber length is 7～30 μ m.Above-mentioned average fiber length be 5 μ m above aspect the required physical strength of camera module, deflection temperature under load, be necessary keeping, be 50 μ m following suppress the fluffing of moulding surface aspect be necessary.It should be noted that, average fiber length adopts stereomicroscope image is imported to PC from CCD camera, utilizes determining image machine to measure the value obtaining by image processing method.
If meet the fibrous filler of above shape, can use fiber arbitrarily, as (B1) fibrous filler, for example, can list 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 can use two or more fibrous fillers.In the present invention, as (B1) composition, preferably use potassium titanate fibre.
(B2) non-fibrous filler is that to be selected from mean grain size be at least one in sheet filling agent and the granular filling agent below 50 μ m.Above-mentioned mean grain size is that 50 μ m are being necessary aspect the fluffing of inhibition moulding surface below.Preferred above-mentioned mean grain size is 10～20 μ m.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 obtaining.
If meet the non-fibrous filler of above shape, can use filling agent arbitrarily, as sheet filling agent, can list talcum, mica, glass flake, various metal formings etc.In addition, as granular filling agent, can list the sulfate of the such metal of carbonate, calcium sulphate, the barium sulphate of the such metal of oxide, calcium carbonate, the magnesium carbonate of the such metal of silicon dioxide, quartz powder, glass microballoon, glass dust, calcium silicate, alumina silicate, porcelain earth, clay, zeyssatite, wollastonite such silicate, iron oxide, titanium dioxide, zinc paste, aluminium oxide and silit, silicon nitride, boron nitride, various metal powders etc.As (B2) composition, also can use two or more.In the present invention, as (B2) composition, preferably use talcum, the mica of sheet filling agent, the silicon dioxide of granular filling agent, more preferably use talcum, the mica of sheet filling agent.
(B) content of composition (summation of the content of the content of above-mentioned (B1) composition and above-mentioned (B2) composition) is 5～20 quality % in camera module use liquid crystalline composition of the present invention.(B) content of composition be 5 quality % above guarantee the physical strength required as camera module, deflection temperature under load aspect be necessary, be 20 quality % following suppress the fluffing of moulding surface aspect be necessary.Preferred above-mentioned content is 5～15 quality %.
[(C) multipolymer]
(C) multipolymer is for being selected from (C1) olefin copolymer and (C2) at least one of styrene based copolymer.When (C) composition is compounded in camera module use liquid crystalline resin composition, fluffing when being conducive to be suppressed at formed body to said composition moulding is formed and carrying out Ultrasonic Cleaning, formed body surface.
About the reason that suppresses fluffing, and indefinite, but can think, by with certain constant basis compounding, thereby formed body surface state is changed, this variation contributes to suppress fluffing.
(C1) olefin copolymer is by alpha-olefin and α, and the ethylene oxidic ester of beta-unsaturated acid forms.
Alpha-olefin is not particularly limited, for example, can lists 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 for example has glycidyl acrylate, glycidyl methacrylate, ethyl propylene acid glycidyl ester, 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 using in the present invention is not damaging in scope of the present invention, except above-mentioned two kinds of compositions, as the 3rd composition, can be taking one or more of the ethylene series beta-unsaturated esters that contains vinyl cyanide, acrylate, methacrylate, α-methyl styrene, maleic anhydride etc. as the amount of 0～48 mass parts with respect to the above-mentioned two kinds of compositions of 100 mass parts.
Can use monomer, catalysts for radical polymerization easily preparation by common radical polymerization of each composition as the olefin copolymer of (C1) of the present invention composition.More specifically, conventionally can be 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, 100～300 DEG C, under the existence of suitable solvent, chain-transferring agent or the method for carrying out copolymerization not manufacture.In addition, also can pass through alpha-olefin and α, the ethylene oxidic ester of beta-unsaturated acid and free-radical generating agent are mixed, and carry out the method for fusion-grafting copolymerization and manufacture in extruder.
(C2) styrene based copolymer is by phenylethylene and α, and the ethylene oxidic ester of beta-unsaturated acid forms.About α, the ethylene oxidic ester of beta-unsaturated acid, due to identical with the material illustrating in (C1) composition, therefore description thereof is omitted.
As phenylethylene, can list styrene, α-methyl styrene, bromostyrene, divinylbenzene etc., preferably use styrene.
(C2) styrene based copolymer using in the present invention can be for also using more than one other vinyl monomer to assign to carry out as the three one-tenth the multiple copolymer that copolymerization obtains except above-mentioned two kinds of compositions.Suitable to ternary, one or more in the ethylene series beta-unsaturated esters of vinyl cyanide, acrylate, methacrylate, maleic anhydride etc.The multipolymer that imports the repetitive that is derived from them below 40 quality % and obtain in (C2) styrene based copolymer is preferably as (C2) composition.
(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 the monomer with each composition, catalysts for radical polymerization.More specifically, conventionally can be 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, 100～300 DEG C, under the existence of suitable solvent, chain-transferring agent or the method for carrying out copolymerization not manufacture.In addition, also can pass through phenylethylene and α, the ethylene oxidic ester of beta-unsaturated acid and free-radical generating agent are mixed, and carry out the method for fusion-grafting copolymerization and manufacture in extruder.
It should be noted that, as (C) multipolymer, (C1) olefin copolymer is preferred aspect stable on heating, and (C1) composition can suitably be selected according to required characteristic with (C2) ratio of composition.
(C) content of multipolymer ((C1) composition and (C2) total amount of composition) is 2～10 quality % in camera module use resin combination of the present invention.(C) content of composition be 2 quality % above suppress the fluffing of moulding surface aspect be necessary, be 10 quality % following for not damaging mobility, the reason that can obtain good formed body is necessary.Preferred above-mentioned content is 2～7 quality %.
[(D) carbon black]
(D) carbon black using in the present invention is as long as be the common retrievable carbon black for coloring resin; just be not particularly limited; but conventionally can comprise primary particle assembles and the block of formation; if obviously more comprise the block of sizes more than 50 μ m; on the surface of the formed body that resin combination moulding of the present invention is formed, sometimes produce a large amount of hard spots (carbon black is assembled the fine fash shape thrust (fine is concavo-convex) forming), not preferred.Above-mentioned block particle diameter is that particles more than 50 μ m is that 20ppm is being necessary aspect the fluffing of inhibition moulding surface below.Preferred containing ratio is below 5ppm.
As the compounding amount of (D) carbon black, it in camera module use liquid crystalline resin composition, is preferably the scope of 1～5 quality %.When compounding quantity not sufficient 1 mass parts of carbon black, the pitch-dark property of the resin combination obtaining reduces, and can worry light-proofness, while exceeding 5 mass parts, uneconomical, and the possibility that produces hard spot uprises.
[other composition]
In camera module use liquid crystalline resin composition of the present invention, in the scope of not damaging effect of the present invention, can also suitably add other polymkeric substance, the known material, i.e. colorant, lubricant, release agent and crystallization promoter, the crystallization nucleating agent etc. such as the stabilizing agent such as antioxidant, ultraviolet light absorber, antistatic agent, fire retardant, dyestuff, pigment that in synthetic resin, add conventionally according to desired properties.
[preparation of camera module use liquid crystalline resin composition]
Preparation to camera module use resin combination of the present invention is not particularly limited.For example, add compounding above-mentioned (A), (B), (C) composition, use single screw rod or double screw extrusion machine to carry out melting mixing processing them, thereby 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 (B) composition before compounding.Above-mentioned (B) composition be shaped as the shape before compounding.As long as the shape before compounding is described above, just can obtain the camera module use parts that surface is difficult for fluffing.
The melt viscosity of the camera module use liquid crystalline resin composition of the present invention obtaining is as mentioned above 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 350 DEG C of barrel zone temperatures, shear rate 1000sec
-1condition under, by the value 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 adopts by measuring according to ISO75-1,2 method the value obtaining.
< 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, the surface of camera module use parts becomes and is difficult for fluffing.Camera module use parts are owing to will carrying out Ultrasonic Cleaning, even if therefore require to carry out Ultrasonic Cleaning, surface is also difficult for fluffing.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 hardly the cast that causes dirt etc.Therefore, camera module use parts have been assembled into after product, can impact the quality that completes product because of the dirt that the wildness of these camera module use parts produces hardly.
The camera module use parts that camera module use liquid crystalline resin composition of the present invention moulding is formed are described.The cross section of common camera module is schematically shown in to 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 is configured on substrate 10, between optical element 11 and substrate 10, is electrically connected with lead-in wire 12.
Keeper 13 is configured on substrate 10, covers optical element 11.Keeper 13 is formed with opening at top, is formed with spiral helicine ditch portion on this perforated wall surface.
Bucket 14 is cylindric, and lens 15 remain on inside cylindraceous in the mode of approximate horizontal.In addition, on the sidewall of one end of cylinder, be formed with spiral helicine protuberance, this spiral helicine protuberance screws with the spiral helicine ditch portion on the perforated wall surface that is formed at keeper 13, thereby bucket 14 is connected with keeper 13.In addition, the mode of one end sealing of bucket 14 cylindraceous is disposed at IR optical filter 16 to one end of bucket 14.As shown in Figure 1, IR optical filter 16 is arranged substantially in parallel with lens 15.
In camera module 1 as shown in Figure 1, rotate by bucket 14, thus the change of distance between lens 15 and optical element 11.By adjusting this distance, can carry out the focal adjustments of camera.
In camera module 1 as above, can manufacture keeper 13, the bucket 14 as camera module use parts as raw material with camera module use liquid crystalline resin composition of the present invention.Common liquid crystalline resin composition is not suitable for as the raw material for the manufacture of these parts.Manufacture keeper 13, bucket using common liquid crystalline resin composition as raw material at 14 o'clock, can produce following problem.
The formed body that common liquid crystalline resin composition moulding is formed is large especially because high molecular molecular orientation divides at surface element, therefore easily fluffing of formed body surface, and this fluffing causes little dirt to produce.When this little dirt is attached to lens 15 grade, the performance of camera module reduces.
Keeper 13, the bucket camera module use parts such as 14 carried out Ultrasonic Cleaning in order to remove surperficial dust, little dirt before being assembled in camera module 1.But easily fluff in the surface of the formed body that common liquid crystalline resin composition moulding is formed, therefore when Ultrasonic Cleaning, fluff in surface.Owing to producing this problem, conventionally cannot carry out Ultrasonic Cleaning to the formed body that liquid crystalline resin composition moulding is formed.
Above-mentioned focal adjustments is undertaken by the spiral helicine protuberance that moves the sidewall of the end that is formed at bucket 14 in the spiral helicine ditch portion on perforated wall surface that is formed at keeper 13.Now, above-mentioned spiral helicine ditch portion rubs at surface of contact mutually with above-mentioned spiral helicine protuberance.The formed body that common liquid crystalline resin composition moulding is formed is as mentioned above owing to easily fluffing in surface, therefore may sur-face peeling and produce overburden.This overburden forms little dirt and is attached to lens 15 etc., may reduce the performance of camera module.
As mentioned above, conventionally liquid crystalline resin composition cannot be used as to the raw material of keeper 13, bucket 14, even if camera module use liquid crystalline resin composition of the present invention carries out level that Ultrasonic Cleaning also can produce the problem of fluffing hardly and improved the surface state of formed body when making formed body to this formed body, therefore can preferably be used as the raw material of keeper 13, bucket 14.
Embodiment
Below enumerate embodiment, the present invention is described in further detail, but the present invention is not limited to these embodiment.
< 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 TISMO N-102, and (potassium titanate fibre, fiber diameter 0.3～0.6 μ m, average fiber length 10～20 μ are m)
Fibrous filler 2: Nitto Boseki Co. Ltd manufactures PF70E-001, and (milled glass fiber, fibre diameter 10 μ m, weight average length 70 μ are m)
Non-fibrous filler 1: Ishihara Sangyo Kaisha, Ltd. manufactures Crown Talc PP (talcum, mean grain size 12.8 μ m, average aspect ratio 6)
Non-fibrous filler 2: AB-25S is manufactured in mica industry in mountain pass, and (mica, mean grain size 24 μ are m)
Non-fibrous filler 3: A-41S is manufactured in mica industry in mountain pass, and (mica, mean grain size 47 μ are m)
Olefin copolymer: Sumitomo Chemical Co manufactures Bondfast2C (ethylene-methyl methacrylate glycidyl ester copolymer (glycidyl methacrylate that contains 6 % by weight))
Carbon black: Cabot Japan K.K manufactures VULCAN XC305 (carbon black, mean grain size 20nm, more than particle diameter 50 μ m ratio are that 20ppm is following, 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 350 DEG C of barrel zone temperatures with ratio shown in table 1 mentioned component, obtain camera module use liquid crystalline resin composition pellet.
< melt viscosity >
Use above-mentioned pellet to measure the melt viscosity of the camera module use liquid crystalline resin composition of embodiment and comparative example.Particularly, utilize capillary rheometer (CAPIROGRAPH1D that Jing Ji Co., Ltd. of Japan manufactures: diameter of plunger 10mm), be determined at 350 DEG C of barrel zone temperatures, shear rate 1000sec according to ISO11443
-1condition under apparent melt viscosity.In mensuration, use the hole of internal diameter 1mm, length 20mm.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.Particularly, above-mentioned pellet being used to forming machine (Sumitomo Heavy Industries, Ltd manufactures " SE30DUZ ") is the test film of thickness 0.3mm at following condition of molding compacted under.Length by the formed body that measures is evaluated mobility.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
Use forming machine (Sumitomo Heavy Industries, Ltd manufactures " SE30DUZ ") 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 to be used as test film.
(condition of molding)
Barrel zone temperature: 350 DEG C
Mold temperature: 90 DEG C
Injection moulding speed: 80mm/sec
(evaluation)
The formed body cutting into after half is placed in to supersonic wave cleaning machine (output power 300W, frequency 45kHz) 3 minutes in the water of room temperature.Then, be relatively placed in the formed body of supersonic wave cleaning machine front and back, utilize determining image device (LUZEXFS that Nireco Corporation 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 fluffing inhibition higher.
< deflection temperature under load >
Use forming machine (Sumitomo Heavy Industries, Ltd manufactures " SE100DU ") to use test film (4mm × 10mm × 80mm) at following condition of molding compacted under for measuring the pellet of embodiment and comparative example.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 >
Use forming machine (Sumitomo Heavy Industries, Ltd manufactures " SE100DU ") to use test film (4mm × 10mm × 80mm) at following condition of molding compacted under for measuring the pellet of embodiment and comparative example.Then, by measuring charp impact value according to the method for 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 of recording 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, the formed body that the pellet moulding of embodiment is formed differs widely with the surface state of the formed body that the common liquid crystalline resin composition pellet moulding such as comparative example are formed.
In addition, confirm the excellent heat resistance of the formed body of the pellet manufacture that uses embodiment, mobility excellence, resistance to impact excellence.
description of reference numerals
1 camera module
10 substrates
11 optical elements
12 lead-in wires
13 keepers
14 barrels
15 lens
16 IR optical filters
Claims (3)
1. a camera module use liquid crystalline resin composition, its compounding in (A) liquid-crystalline resin has
Be selected from (B1) fibrous filler and (B2) non-fibrous filler at least one (B) inorganic filler,
Be selected from (C1) olefin copolymer and (C2) at least one (C) multipolymer of styrene based copolymer,
Making (A) composition is that 65～93 quality %, (B) composition are that 5～20 quality %, (C) composition are 2～10 quality %,
The fiber diameter of described (B1) fibrous filler is below 1.0 μ m, and average fiber length is 5～50 μ m,
Described (B2) non-fibrous filler be selected from mean grain size be below 50 μ m, in sheet filling agent and granular filling agent at least one,
Described (C1) olefin copolymer is by alpha-olefin and α, and the ethylene oxidic ester of beta-unsaturated acid forms,
Described (C2) styrene based copolymer is by phenylethylene and α, and the ethylene oxidic ester of beta-unsaturated acid forms.
2. camera module use liquid crystalline resin composition according to claim 1, wherein, the mean grain size of described (B2) non-fibrous filler is 10～20 μ m.
3. camera module use liquid crystalline resin composition according to claim 1 and 2, it also has (D) carbon black taking content as the mode compounding of 1～5 quality %.
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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104040422A true CN104040422A (en) | 2014-09-10 |
| CN104040422B CN104040422B (en) | 2016-04-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380004759.0A Active CN104040422B (en) | 2012-02-29 | 2013-02-25 | Camera module use liquid crystalline resin composition |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5680788B2 (en) |
| KR (1) | KR101537109B1 (en) |
| CN (1) | CN104040422B (en) |
| TW (2) | TWI608038B (en) |
| WO (1) | WO2013129338A1 (en) |
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| 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 |
| CN111417680A (en) * | 2017-11-15 | 2020-07-14 | 住友化学株式会社 | Liquid crystal polyester composition and resin molded article |
| US11084925B2 (en) | 2018-02-20 | 2021-08-10 | Ticona Llc | Thermally conductive polymer composition |
| CN113897036A (en) * | 2015-08-17 | 2022-01-07 | 提克纳有限责任公司 | Liquid crystal polymer composition for camera module |
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| JP6616322B2 (en) | 2014-04-09 | 2019-12-04 | ティコナ・エルエルシー | The camera module |
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| WO2017038421A1 (en) * | 2015-09-01 | 2017-03-09 | ポリプラスチックス株式会社 | Liquid crystalline resin composition for camera module and camera module using same |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08183910A (en) * | 1994-12-28 | 1996-07-16 | Toray Ind Inc | Thermoplastic resin composition |
| JPH10330602A (en) * | 1997-05-29 | 1998-12-15 | Sumitomo Chem Co Ltd | Liquid crystal polyester resin composition, injection molding product and film comprising the same |
| JP2007254717A (en) * | 2006-02-27 | 2007-10-04 | Toray Ind Inc | Liquid crystalline resin composition and molded article consisting of the same |
| 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 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3399120B2 (en) * | 1994-11-10 | 2003-04-21 | 住友化学工業株式会社 | Liquid crystal polyester resin composition |
| JP2002509573A (en) * | 1997-07-09 | 2002-03-26 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Liquid crystalline polymer-poly (phenylene oxide) blend |
| WO2005085348A1 (en) * | 2004-03-10 | 2005-09-15 | Matsushita Electric Works, Ltd. | Metal-coated resin molded article and production method therefor |
| JP2009030045A (en) * | 2007-07-02 | 2009-02-12 | Asahi Kasei Chemicals Corp | Liquid crystal polyester-based resin composition |
| JP5752990B2 (en) * | 2011-05-18 | 2015-07-22 | 帝人株式会社 | High cycle moldable thermoplastic resin composition |
-
2013
- 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
- 2013-02-25 KR KR1020147017399A patent/KR101537109B1/en active IP Right Grant
- 2013-02-27 TW TW105125254A patent/TWI608038B/en not_active IP Right Cessation
- 2013-02-27 TW TW102106848A patent/TWI608037B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08183910A (en) * | 1994-12-28 | 1996-07-16 | Toray Ind Inc | Thermoplastic resin composition |
| JPH10330602A (en) * | 1997-05-29 | 1998-12-15 | Sumitomo Chem Co Ltd | Liquid crystal polyester resin composition, injection molding product and film comprising the same |
| 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 |
| JP2007254717A (en) * | 2006-02-27 | 2007-10-04 | Toray Ind Inc | Liquid crystalline resin composition and molded article consisting of the same |
| 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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104341721B (en) * | 2013-07-23 | 2017-07-28 | 宝理塑料株式会社 | Camera module use liquid crystalline resin composition |
| CN113897036A (en) * | 2015-08-17 | 2022-01-07 | 提克纳有限责任公司 | Liquid crystal polymer composition for camera module |
| CN111417680A (en) * | 2017-11-15 | 2020-07-14 | 住友化学株式会社 | Liquid crystal polyester composition and resin molded article |
| US11084925B2 (en) | 2018-02-20 | 2021-08-10 | Ticona Llc | Thermally conductive polymer composition |
| US11725105B2 (en) | 2018-02-20 | 2023-08-15 | Ticona Llc | Thermally conductive polymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201402664A (en) | 2014-01-16 |
| TWI608038B (en) | 2017-12-11 |
| KR101537109B1 (en) | 2015-07-15 |
| KR20140141570A (en) | 2014-12-10 |
| CN104040422B (en) | 2016-04-13 |
| TWI608037B (en) | 2017-12-11 |
| WO2013129338A1 (en) | 2013-09-06 |
| JP5680788B2 (en) | 2015-03-04 |
| TW201639908A (en) | 2016-11-16 |
| JPWO2013129338A1 (en) | 2015-07-30 |
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