WO2015083759A1 - 全芳香族液晶ポリエステル樹脂組成物およびその射出成形品を構成部材として含むカメラモジュール部品 - Google Patents

全芳香族液晶ポリエステル樹脂組成物およびその射出成形品を構成部材として含むカメラモジュール部品 Download PDF

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WO2015083759A1
WO2015083759A1 PCT/JP2014/082054 JP2014082054W WO2015083759A1 WO 2015083759 A1 WO2015083759 A1 WO 2015083759A1 JP 2014082054 W JP2014082054 W JP 2014082054W WO 2015083759 A1 WO2015083759 A1 WO 2015083759A1
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liquid crystal
crystal polyester
resin composition
polyester resin
wholly aromatic
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PCT/JP2014/082054
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English (en)
French (fr)
Japanese (ja)
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智 江原
中山　敏雄
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Ｊｘ日鉱日石エネルギー株式会社
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Priority to KR1020167014940A priority Critical patent/KR101831543B1/ko
Priority to CN201480066356.3A priority patent/CN105764988B/zh
Publication of WO2015083759A1 publication Critical patent/WO2015083759A1/ja

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B17/00—Details of cameras or camera bodies; Accessories therefor
    • G03B17/02—Bodies
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B30/00—Camera modules comprising integrated lens units and imaging units, specially adapted for being embedded in other devices, e.g. mobile phones or vehicles

Definitions

  • Smart built-in digital cameras such as smartphones and tablet terminals have been positioned as one of the main functional units from the additional functional units as the performance of the number of pixels and image quality has improved.
  • the present invention relates to a liquid crystal polyester resin composition suitably used for such a camera module component, and further relates to a camera module component including a molded body obtained by injection molding the liquid crystal polyester resin composition as a constituent member.
  • an object of the present invention is to provide a wholly aromatic liquid crystal polyester resin composition capable of obtaining an injection-molded product excellent in particle detachment resistance required for recent camera module parts.
  • the present inventors have conducted injection molding of a wholly aromatic liquid crystal polyester resin composition containing a specific liquid crystal polyester resin, whiskers, and carbon black. It has been found that an injection-molded product having “detachment resistance” can be obtained, and the present invention has been completed. That is, the first of the present invention is a wholly aromatic liquid crystalline polyester 50 to 80% by weight, whiskers 10 to 30% by weight, carbon black 0.5 to 5% by weight, talc 0 to 20 parts by weight, precipitated barium sulfate 3 to 20 parts by mass (totally 100% by mass) obtained by melt-kneading, the deflection temperature under load is 220 ° C.
  • the second aspect of the present invention is the wholly aromatic liquid crystal polyester according to claim 1, wherein the whisker is at least one of calcium silicate and calcium carbonate having a true specific gravity of 3.0 or less.
  • the present invention relates to a resin composition.
  • a third aspect of the present invention relates to a camera module component comprising an injection molded product of the wholly aromatic liquid crystal polyester resin composition described in the first or second aspect of the present invention as a constituent member.
  • the wholly aromatic liquid crystalline polyester resin composition according to the present invention has good molded product rigidity, heat resistance, mechanical strength, thin-wall processability of the resin composition, mold shape transferability, surface mount of molded product (SMT). It is possible to provide a camera module member that has excellent resistance and “particle detachment resistance” and has extremely excellent characteristics by injection molding.
  • FIG. 1 is a plan view and a side view of a test piece for measuring weld strength.
  • FIG. 2 is a plan view and a side view of a test piece for measuring particle desorption resistance.
  • the wholly aromatic liquid crystal polyester resin used in the present invention exhibits melt anisotropy.
  • the molded product in order to have excellent heat resistance and rigidity, the molded product has an anisotropy based on the rigidity of the molecular structure and is used during injection molding (melting). It is necessary to provide a strong liquid crystal alignment property during molding. For this reason, among liquid crystal polyesters, wholly aromatic liquid crystal polyesters obtained by polycondensation reaction of only aromatic compounds mainly have so-called “mesogens” (rigid sites that exhibit liquid crystallinity), melting points and molding processing. It has liquid crystallinity excellent in the balance of temperature and rigidity of molecular chain, which is preferable.
  • the structural unit of the liquid crystal polyester resin constituting the liquid crystal polyester resin composition of the present invention includes, for example, a combination of an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid, or a heterogeneous aromatic hydroxycarboxylic acid.
  • Specific structural units such as those comprising a combination of an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid and an aromatic diol, and a polyester such as polyethylene terephthalate reacted with an aromatic hydroxycarboxylic acid. For example, the following may be mentioned.
  • a preferable liquid crystal polyester resin has a structural unit (A1) of 30 mol% or more, and more preferably (A1) and (B1) together. It has more than mol%.
  • Particularly preferred liquid crystal polyesters are p-hydroxybenzoic acid (I), terephthalic acid (II), 4,4′-dihydroxybiphenyl (III) (including these derivatives) in an amount of 80 to 100 mol% (provided that (I ) And (II) is 60 mol% or more), and (I), (II), or (III) is condensed with any other aromatic compound capable of decondensation reaction with 0 to 20 mol%.
  • the heat resistance tends to decrease, which is not preferable.
  • the composition of the liquid crystal polyester resin is in the range of 50 to 80% by mass. If it deviates from this range, it becomes difficult to obtain sufficient injection molding characteristics (melt flowability, short cycle time, etc.).
  • a method for producing the liquid crystal polyester resin used in the present invention a known method can be adopted, and a production method by only melt polymerization or a production method by two-stage polymerization of melt polymerization and solid phase polymerization can be used.
  • acetic anhydride is added to acetylate the hydroxyl group of the monomer, Produced by deacetic acid polycondensation reaction.
  • p-hydroxybenzoic acid, terephthalic acid, isophthalic acid, and 4,4′-dihydroxybiphenyl are charged into a reactor under a nitrogen atmosphere, acetic anhydride is added, and acetoxylation is performed under acetic anhydride reflux, followed by ascending.
  • a method for producing a polyester resin by performing deacetic acid melt polycondensation while heating and distilling acetic acid in a temperature range of 150 to 350 ° C. can be mentioned.
  • the polymerization time can be selected in the range of 1 hour to several tens of hours.
  • the moisture in the monomer may or may not be dehydrated before production.
  • solid phase polymerization is further performed on the polymer obtained by melt polymerization, the polymer obtained by melt polymerization is solidified and then pulverized into powder or flakes, and then a known solid phase polymerization method such as nitrogen
  • a method such as heat treatment at 200 to 350 ° C. in an inert gas atmosphere for 1 to 30 hours is preferably selected.
  • the solid phase polymerization may be performed with stirring, or may be performed in a standing state without stirring.
  • a catalyst may or may not be used.
  • those conventionally known as polyester polycondensation catalysts can be used, such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, and antimony trioxide. Examples thereof include metal salt catalysts and organic compound catalysts such as N-methylimidazole.
  • the polymerization reaction apparatus in melt polymerization is not particularly limited, but a reaction apparatus used for reaction of a general high viscosity fluid is preferably used.
  • reaction apparatuses examples include, for example, a stirring tank type polymerization reaction apparatus having a stirring apparatus having stirring blades of various shapes, such as a vertical type, a multistage type, a spiral band type, a helical shaft type, etc. And a kneader, a roll mill, a Banbury mixer, and the like, which are generally used for resin kneading.
  • the shape of the liquid crystalline polyester resin used in the present invention may be any of powder, granule, and pellet, but is preferably powder or granule from the viewpoint of dispersibility when mixed with a filler.
  • Liquid crystal polyester resin compositions may contain a wide variety of fibrous fillers, and are known to exhibit excellent heat resistance, rigidity, and the like due to their shape factors. In the present invention, it is necessary to include so-called “whiskers” which are needle-like single crystals as the fibrous filler, and to further contain a filler different from this in a specific blending ratio. “Particle detachment resistance” of the liquid crystal polyester resin composition for camera modules is remarkably improved by adding whiskers as the fibrous filler in the resin composition having the specific composition. The present inventors have not yet clarified the reason for this, but can make assumptions in comparison with glass fibers as typical examples of fibrous fillers.
  • particles in a drop impact of a liquid crystal polyester resin composition containing various fillers are mainly fibrils derived from fragments of various fibrous fillers and destruction of the liquid crystal polyester matrix. It is considered that the generation of particles is largely caused by the fracture mode of interfacial peeling between the fibrous filler having a large aspect ratio and size (length) and the liquid crystalline polyester among the fillers.
  • a matrix It is expected that the interface structure with the liquid crystal polyester is different microscopically, and the fracture mode of the interface is different.
  • the needle-like single crystal interface having a relatively smooth surface and the liquid crystal polyester resin are easily peeled to form a large number of minute voids, and the impact energy is absorbed by the formation of these voids. It is considered that the destruction of the matrix part that leads to the generation of fibrils (one of the main components of “particles”) is suppressed.
  • whiskers there are no restrictions on the whiskers that can be used in the present invention.
  • an average diameter of 5 ⁇ m or less having toughness is suitable.
  • potassium titanate chemical formula: K2O.nTiO2 (n is 6 or 8, true specific gravity 3.4 to 3.6, average fiber diameter 0.3 to 0.6 ⁇ m.
  • the fiber diameter is relatively large.
  • (Ii) and (iii) are preferable because they have a small specific gravity difference and easy good dispersion, and these may be used alone or in admixture of two or more.
  • the whisker content is preferably in the range of 10 to 30% by mass, and if it is less than 10% by mass, the effect of addition is not sufficient, and if it exceeds 30% by mass, the content is good. It may be difficult to obtain fluidity.
  • the liquid crystal polyester resin composition in the present invention contains precipitated barium sulfate.
  • Barium sulfate is an almost spherical filler, and has a low probability of adopting an interfacial debonding failure mode that leads to particle generation. Also, due to its specific high specific gravity (about 4.5), the impact energy of liquid crystal polyester composition It is considered that the absorption efficiency is improved and the effect of suppressing particle generation is given. In addition, the fact that it is amorphous, very thin, soft, and difficult to break is considered to have led to the suppression of particle generation.
  • the content is preferably in the range of 3 to 20% by mass.
  • the liquid crystal polyester resin composition preferably contains talc.
  • Talc is an oval-shaped filler with a relatively smooth surface, and provides dimensional stability to molded products by reducing anisotropy. It is possible to improve the reliability.
  • the content is preferably in the range of 5 to 20% by mass. If it is less than 5% by mass, the effect of addition is not sufficient. If it exceeds 20% by mass, it may be difficult to obtain good fluidity.
  • the carbon black used in the present invention is used for the purpose of ensuring the light shielding property of the camera module parts, and is not particularly limited as long as it is generally available for use in resin coloring.
  • the carbon black content is preferably in the range of 0.5 to 5% by mass. More preferably, it is 2 to 4% by mass. If the blending amount of the carbon black is less than 0.5% by mass, the jet blackness of the resulting resin composition is lowered, and sufficient light-shielding properties cannot be secured. The possibility of generation of fine bumpy projections with agglomerated carbon black is increased.
  • the composition of the present invention includes an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites and substituted products thereof), an ultraviolet absorber (in the range not impairing the object of the present invention).
  • a heat stabilizer for example, hindered phenol, hydroquinone, phosphites and substituted products thereof
  • an ultraviolet absorber in the range not impairing the object of the present invention.
  • resorcinol, salicylate, benzotriazole, benzophenone, etc. lubricant and mold release agent (montanic acid and its salt, its ester, its partial ester, higher fatty acid and its salt such as stearic acid, its ester, higher alcohol such as stearyl alcohol, stearyl Amide and polyethylene wax (polyolefin wax, etc.), plasticizers, antistatic agents, flame retardants and other normal additives, other fillers and other thermoplastic resins other than those mentioned above, and the addition of the specified characteristics Can
  • the liquid crystal polyester resin composition according to the present invention can be obtained by melting the liquid crystal polyester and kneading it with other components.
  • the equipment and operation method used for the melt kneading are generally those used for melt kneading of the liquid crystal polyester.
  • liquid crystal polyester, whisker, carbon black, precipitated barium sulfate is added from a popper, and further, talc is added as necessary, and melt-kneaded and pelletized. Is preferred.
  • the liquid crystal polyester resin composition thus obtained has a melt viscosity of 20 to 100 Pa ⁇ S, preferably 30 to 80 Pa ⁇ S, measured at a shear rate of 100 sec ⁇ 1 and a melting point + 10 ° C. There is. If the resin viscosity is out of this range, the surface properties of the injection-molded product are deteriorated, and there is a risk of generation of particles due to this.
  • the melt viscosity is a capillary rheometer (Model 2010) manufactured by Intesco Corporation, a capillary having a diameter of 1.00 mm, a length of 40 mm and an inflow angle of 90 °, a melting point of ⁇ 40 ° C. to + 4 ° C. at a shear rate of 100 sec ⁇ 1.
  • the apparent viscosity is measured while heating at a constant rate at a heating rate of 1 min / min, and the apparent viscosity at the melting point + 10 ° C. is determined by rounding off to the first decimal place.
  • the deflection temperature under load of the injection-molded product of the liquid crystal polyester resin composition thus obtained is 220 ° C. or higher.
  • the deflection temperature under load means the deflection temperature under load (DTUL) measured according to ASTM D648. If the deflection temperature under load is less than 220 ° C., there is a possibility that a problem arises in heat resistance during solder reflow in surface mounting, which is not suitable.
  • the resin composition according to the present invention individual characteristics of these constituent materials and good fluidity are comprehensively exhibited in the injection molding process, and in particular, a thickness in the range of 0.3 to 0.9 mm.
  • a camera module component having excellent “particle detachment resistance” is supplied.
  • the injection molding machine used for injection molding is not particularly limited as long as it is a known machine that is generally used for molding liquid crystal polyester.
  • thermotropic liquid crystal polyester A P-Hydroxybenzoic acid (manufactured by Ueno Pharmaceutical Co., Ltd.) 298 kg (2.16 kgol), 4,4′- in a 1700 L polymerization tank (manufactured by Kobe Steel Co., Ltd.) having a double helical stirring blade made of SUS316.
  • Dihydroxybiphenyl (Honshu Chemical Industry Co., Ltd.) 134 kg (0.72 kgmol), terephthalic acid (Mitsui Chemicals Co., Ltd.) 90 kg (0.54 kgmol), Isophthalic acid (Ai International Chemical Co., Ltd.) 30 kg ( 0.18 kgmol), 0.04 kg of potassium acetate (manufactured by Kishida Chemical Co., Ltd.) as a catalyst, and 0.10 kg of magnesium acetate (manufactured by Kishida Chemical Co., Ltd.) were charged. After that, 386 kg (3.78 kgol) of acetic anhydride was added, and the rotating speed of the stirring blade was 45 r. The temperature was raised to 150 ° C.
  • the obtained polymer was pulverized by a pulverizer manufactured by Hosokawa Micron Co., Ltd. into a size passing through a sieve having an opening of 2.0 mm to obtain a prepolymer.
  • the obtained prepolymer was subjected to solid phase polymerization using a rotary kiln manufactured by Takasago Industry Co., Ltd.
  • the prepolymer was filled in the kiln, nitrogen was passed at a flow rate of 16 Nm 3 / hr, the heater temperature was raised from room temperature to 350 ° C. in 1 hour at a rotation speed of 2 rpm, and the temperature was maintained at 350 ° C. for 10 hours. After confirming that the temperature of the resin powder in the kiln reached 295 ° C., the heating was stopped and the rotary kiln was rotated and cooled for 4 hours to obtain a powdery liquid crystal polyester. The melting point was 360 ° C. and the melt viscosity was 70 Pa ⁇ S. The melting point was measured according to ISO11357-3 and ASTM D3418 (hereinafter the same).
  • thermotropic liquid crystal polyester B A prepolymer was obtained in the same manner as the thermotropic liquid crystal polyester A. The obtained prepolymer was subjected to solid phase polymerization using a rotary kiln manufactured by Takasago Industry Co., Ltd. The prepolymer was filled in the kiln, nitrogen was passed at a flow rate of 16 Nm 3 / hr, the heater temperature was raised from room temperature to 350 ° C. in 1 hour at a rotation speed of 2 rpm, and held at 350 ° C. for 9 hours.
  • thermotropic liquid crystal polyester C A prepolymer was obtained in the same manner as the thermotropic liquid crystal polyester A. The obtained prepolymer was subjected to solid phase polymerization using a rotary kiln manufactured by Takasago Industry Co., Ltd.
  • the prepolymer was filled in the kiln, nitrogen was passed at a flow rate of 16 Nm 3 / hr, the heater temperature was raised from room temperature to 350 ° C. in 1 hour at a rotation speed of 2 rpm, and the temperature was maintained at 350 ° C. for 11 hours. After confirming that the temperature of the resin powder in the kiln reached 300 ° C., the heating was stopped and the rotary kiln was rotated and cooled for 4 hours to obtain a powdery liquid crystalline polyester. The melting point was 370 ° C. and the melt viscosity was 140 Pa ⁇ S.
  • thermotropic liquid crystal polyester D P-Hydroxybenzoic acid (Ueno Pharmaceutical Co., Ltd.) 97.5 kg (1.43 kgol), 4, 4 in a 1700 L polymerization vessel (Kobe Steel Co., Ltd.) having a double helical stirring blade made of SUS316.
  • the obtained prepolymer was subjected to solid phase polycondensation using a rotary kiln manufactured by Takasago Industry Co., Ltd.
  • the shape of the kiln inner cylinder is generally a regular hexagon, and has a side length of 500 mm and a total length of 3500 mm.
  • 150 kg of the prepolymer was charged in the kiln, nitrogen was circulated for 15 Nm3 hours, the temperature in the 2 rpm rotation heater was raised from room temperature to 400 ° C. over 5 hours, and maintained at 400 ° C. for 12 hours.
  • Whisker (I) Potassium titanate: Chemical formula; K2O.nTiO2: n is 6 or 8, true specific gravity 3.4 to 3.6, fiber diameter 0.3 to 0.6 ⁇ m (trade name “Tismo”, Otsuka Chemical Co., Ltd.) Made) (Ii) Calcium silicate: chemical formula; CaSiO3, true specific gravity 2.5 to 2.6, average fiber diameter 1 to 5 ⁇ m (available from the market under the name “Wollastonite”) (Iii) Calcium carbonate: Chemical formula; CaCO 3, true specific gravity 2.8, average fiber diameter 0.5-1 ⁇ m (trade name “Wiscal”, manufactured by Maruo Calcium Co., Ltd.) (Iv) Zinc oxide: (Chemical formula; ZnO True specific gravity 5.78 Average fiber diameter 0.2-3 ⁇ m (trade name “Panatetra”, manufactured by Amtec Co., Ltd.) (2) Carbon black (CB): “REGAL 660” (primary particle size: 24 nm), manufactured by Cabot Corporation (3)
  • the melt viscosity of the thermotropic liquid crystal polyester resin composition is a capillary rheometer (2010 manufactured by Intesco Corporation), and has a diameter of 1.00 mm, a length of 40 mm, and an inflow angle of 90 °.
  • the apparent viscosity is measured while heating at a constant rate from (melting point ⁇ 40) ° C. to + 4 ° C./min at a shear rate of 100 sec-1 and rounded to one decimal place. The viscosity was determined and used as the test value.
  • a resin composition dried in advance in an air oven at 150 ° C. for 4 hours was used.
  • Weld strength measurement (molding of test pieces) The pellets of the resin composition thus obtained were tested using an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., UH-1000) at a cylinder maximum temperature of 370 ° C., an injection speed of 300 mm / sec, and a mold temperature of 80 ° C. Obtained.
  • Resin was injected by a two-point gate.
  • the mold used was a mold having a cavity of 48 mm ⁇ 15 mm ⁇ 0.3 mm, in which a melt front of resin injected from different gates collided at the center to generate a weld crossing the molded product.
  • FIG. 1 shows a plan view and a side view of the test piece obtained with this mold. (Evaluation of weld strength) For each brand, five test pieces were arranged on a resin frame so that both ends were arranged in a frame frame and a central portion having a weld was arranged in a frame window, and both ends on the frame were fixed to the frame with an adhesive tape.
  • the deflection temperature under load was measured based on ASTM D648.
  • ⁇ indicates that the temperature is 220 ° C. or higher
  • X indicates that the temperature is less than 220 ° C.
  • the pellets of the resin composition thus obtained were tested using an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., UH-1000) at a cylinder maximum temperature of 370 ° C., an injection speed of 300 mm / sec, and a mold temperature of 80 ° C. Obtained.
  • FIG. 2 shows a plan view and a side view of the test piece obtained with this mold. (Evaluation of particle detachment resistance) 50 test pieces were placed in a SUS container and closed.
  • the storage container was dropped 50 times from a height of 1.5 m, then the lid was opened, the test piece and the particles dropped from the test piece were separated, and the number of particles was counted with “FPIA-3000” manufactured by Sysmex. .
  • Evaluation of anti-degradation particles is made in three stages, “ ⁇ ” means that the number of generated particles is in the range of less than 100, “ ⁇ ” means that the number of generated particles is in the range of 100 to less than 200, and “200”. It was set as “x”. (5) Evaluation of anisotropy Evaluation was performed based on a difference in molding shrinkage between the TD direction and the MD direction.
  • the camera module component comprising an injection molded product of the wholly aromatic liquid crystal polyester resin composition according to the present invention as a constituent member has heat resistance to withstand solder reflow, and can be applied to injection molding of a component having a thin-walled portion.
  • a component having a thin-walled portion has heat resistance to withstand solder reflow, and can be applied to injection molding of a component having a thin-walled portion.
  • CMOS image sensor

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Polyesters Or Polycarbonates (AREA)
PCT/JP2014/082054 2013-12-03 2014-11-27 全芳香族液晶ポリエステル樹脂組成物およびその射出成形品を構成部材として含むカメラモジュール部品 WO2015083759A1 (ja)

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JP2017014357A (ja) * 2015-06-30 2017-01-19 上野製薬株式会社 電子部品用液晶ポリマー
US10377851B2 (en) 2014-09-19 2019-08-13 Ueno Fine Chemicals Industry, Ltd. Liquid crystal polymer
US10640648B2 (en) 2014-04-09 2020-05-05 Ticona Llc Camera module
US10829634B2 (en) 2017-12-05 2020-11-10 Ticona Llc Aromatic polymer composition for use in a camera module
US11086200B2 (en) 2019-03-20 2021-08-10 Ticona Llc Polymer composition for use in a camera module
WO2023276698A1 (ja) * 2021-06-30 2023-01-05 大塚化学株式会社 液晶ポリマー組成物および液晶ポリマー成形体
WO2023276699A1 (ja) * 2021-06-30 2023-01-05 大塚化学株式会社 液晶ポリマー組成物および液晶ポリマー成形体
US11722759B2 (en) 2019-03-20 2023-08-08 Ticona Llc Actuator assembly for a camera module

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KR102545958B1 (ko) * 2020-06-30 2023-06-22 포리프라스틱 가부시키가이샤 내 볼베어링 접동 마모 부재용 액정성 수지 조성물 및 이를 이용한 내 볼베어링 접동 마모 부재
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KR102461065B1 (ko) 2020-12-29 2022-11-01 세양폴리머주식회사 액정 폴리에스테르 수지 조성물 및 이를 포함하는 저분진 특성의 전자부품 소재

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US10640648B2 (en) 2014-04-09 2020-05-05 Ticona Llc Camera module
US11208556B2 (en) 2014-04-09 2021-12-28 Ticona Llc Camera module
US10377851B2 (en) 2014-09-19 2019-08-13 Ueno Fine Chemicals Industry, Ltd. Liquid crystal polymer
JP2017014357A (ja) * 2015-06-30 2017-01-19 上野製薬株式会社 電子部品用液晶ポリマー
US10829634B2 (en) 2017-12-05 2020-11-10 Ticona Llc Aromatic polymer composition for use in a camera module
US11725106B2 (en) 2017-12-05 2023-08-15 Ticona Llc Aromatic polymer composition for use in a camera module
US11086200B2 (en) 2019-03-20 2021-08-10 Ticona Llc Polymer composition for use in a camera module
US11722759B2 (en) 2019-03-20 2023-08-08 Ticona Llc Actuator assembly for a camera module
WO2023276698A1 (ja) * 2021-06-30 2023-01-05 大塚化学株式会社 液晶ポリマー組成物および液晶ポリマー成形体
WO2023276699A1 (ja) * 2021-06-30 2023-01-05 大塚化学株式会社 液晶ポリマー組成物および液晶ポリマー成形体

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KR20160096086A (ko) 2016-08-12
JP6165608B2 (ja) 2017-07-19
CN105764988A (zh) 2016-07-13

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