JP2009242454A - Liquid crystal polyester resin composition for camera module - Google Patents
Liquid crystal polyester resin composition for camera module Download PDFInfo
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- JP2009242454A JP2009242454A JP2008087490A JP2008087490A JP2009242454A JP 2009242454 A JP2009242454 A JP 2009242454A JP 2008087490 A JP2008087490 A JP 2008087490A JP 2008087490 A JP2008087490 A JP 2008087490A JP 2009242454 A JP2009242454 A JP 2009242454A
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 32
- 239000004645 polyester resin Substances 0.000 title claims abstract description 32
- 229920000728 polyester Polymers 0.000 claims abstract description 28
- 229910052623 talc Inorganic materials 0.000 claims abstract description 27
- 239000003365 glass fiber Substances 0.000 claims abstract description 26
- 239000000454 talc Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 15
- 239000006229 carbon black Substances 0.000 claims abstract description 12
- 239000000835 fiber Substances 0.000 claims abstract description 12
- 238000001746 injection moulding Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 11
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 5
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 abstract description 19
- 238000004299 exfoliation Methods 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 12
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- -1 aromatic diol Chemical class 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000008188 pellet Substances 0.000 description 8
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 7
- 229910000679 solder Inorganic materials 0.000 description 7
- 239000007790 solid phase Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229920000106 Liquid crystal polymer Polymers 0.000 description 6
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 0 C*C(C1)C1c(cc1)ccc1C(*(C)C)=O Chemical compound C*C(C1)C1c(cc1)ccc1C(*(C)C)=O 0.000 description 5
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 150000001491 aromatic compounds Chemical class 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 2
- 229940069446 magnesium acetate Drugs 0.000 description 2
- 235000011285 magnesium acetate Nutrition 0.000 description 2
- 239000011654 magnesium acetate Substances 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- BKBJDABPWGQNDZ-UHFFFAOYSA-N 4-(4-hydroxyphenyl)phenol;terephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C=C1.C1=CC(O)=CC=C1C1=CC=C(O)C=C1 BKBJDABPWGQNDZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 238000006137 acetoxylation reaction Methods 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- IMHDGJOMLMDPJN-UHFFFAOYSA-N dihydroxybiphenyl Natural products OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Lens Barrels (AREA)
- Structure And Mechanism Of Cameras (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明はカメラモジュール向け材料に関するものであり、さらに詳しく言うと、耐熱性が高く、ハンダリフローに耐えることができ、(ハンダペーストを印刷等で塗布した基板上に材料をのせ、リフロー炉でハンダを溶融させ基板と固定する)表面実装(Surface Mount Technology,略してSMT)加工が可能な「レンズバレル部」(レンズが乗る部分)及び「マウントホルダー部」(バレルを装着し、基板に固定する部分)、更には、「CMOS(イメージセンサー)の枠」、「シャッター及び、シャッターボビン部」などの、生産工程中、使用中に発塵し、その塵がCMOS(イメージセンサー)に乗っかる可能性がある全てのブラスチック部分に使用する液晶ポリエステル樹脂組成物に関するものである。 The present invention relates to a material for a camera module. More specifically, the present invention has high heat resistance and can withstand solder reflow. (The material is placed on a substrate coated with solder paste by printing or the like and soldered in a reflow furnace. "Lens barrel part" (the part on which the lens is mounted) and "Mount holder part" (mounting the barrel) that can be surface-mounted (SMT) and surface mount technology (SMT for short) Part), and further, “CMOS (image sensor) frame”, “shutter and shutter bobbin part”, etc., may generate dust during production process and use, and the dust may get on the CMOS (image sensor) The present invention relates to a liquid crystal polyester resin composition used for all plastic parts.
AV情報をデジタル形式で伝達する時、情報の入出力に用いる主要な装置としてカメラモジュールがある。携帯電話、ラップトップコンピューター、デジタルカメラ、デジタルビデオカメラ等に搭載されており、撮影の機能として静的なスチール撮影機能のみでなく、動的なモニタリング機能(例えば自動車の後部モニター等)を有するものもある。
これまで携帯電話に搭載するカメラモジュールは、ハンダリフローに耐えられるプラスチックレンズがなかったため、(カメラモジュール全体として)表面実装することはできなかった。このため、これまでの基板(への)組立工程は、レンズ部分を除いたモジュール部品を表面実装し、その後レンズを装着するか、あるいは、カメラモジュール全体を組立てた後、他の方法により基板に装着することで対応していた。
近年、ハンダリフローに耐えられる安価なプラスチックレンズが開発され、カメラモジュール全体の表面実装対応が可能な環境になった。そこで、耐熱性が高く薄肉成形が可能な液晶ポリマーを「レンズバレル部」(レンズが乗る部分)及び「マウントホルダー部」(バレルを装着し、基板に固定する部分)、更には、「CMOS(イメージセンサー)の枠」、「シャッター及び、シャッターボビン部」に使用するようになってきた(特許文献1参照)。
When transmitting AV information in a digital format, there is a camera module as a main device used for inputting and outputting information. Installed in mobile phones, laptop computers, digital cameras, digital video cameras, etc., which have not only a static still shooting function but also a dynamic monitoring function (for example, the rear monitor of a car) as a shooting function There is also.
Until now, camera modules mounted on mobile phones could not be surface mounted (as a whole camera module) because there was no plastic lens that could withstand solder reflow. For this reason, the conventional board assembly process is to mount the module parts excluding the lens surface and then mount the lens, or assemble the entire camera module and then mount it on the board by other methods. It was supported by wearing.
In recent years, an inexpensive plastic lens that can withstand solder reflow has been developed, and an environment in which the entire camera module can be mounted on the surface is now available. Therefore, a liquid crystal polymer that has high heat resistance and can be molded thinly is made up of “lens barrel part” (the part on which the lens is mounted) and “mount holder part” (the part where the barrel is mounted and fixed to the substrate), and further, “CMOS ( It has come to be used for “frame of image sensor” and “shutter and shutter bobbin portion” (see Patent Document 1).
一般的な固定焦点の光学系を搭載したカメラモジュールでは、CMOS(イメージセンサー)が信号処理チップ上に積層チップを搭載した構成となっており、その組立工程において、光学部品系の手動焦点調整(ネジでマウントホルダー部に螺合されたレンズバレル部を螺動し、レンズとイメージセンサー間距離を変化させ、焦点距離を最適化する調整)が必要となる(特許文献1参照)。ところが、従来の液晶ポリマー組成物では、この焦点調整工程において、レンズバレル部の螺動時にレンズバレル、マウントホルダー両部のネジ摩り合わせ部分、及び両成形品表面からの樹脂組成物からなる粉(パーティクル)が脱落し、それが、CMOS(イメージセンサー)上、あるいは(IRカット)フィルター上に乗り、画像不良を起こす大きな原因の1つとなっている。粉の脱落は該部材を組み込んだ製品の使用中にも生じるおそれがある。従って、カメラモジュールのレンズバレル部、マウントホルダー部、CMOS(イメージセンサー)の枠、シャッター及び、シャッターボビン部などに使用する材料として、粉(パーティクル)の脱落の少ない液晶ポリマー組成物の提供が求められていた。 A camera module equipped with a general fixed-focus optical system has a configuration in which a CMOS (image sensor) has a multilayer chip mounted on a signal processing chip. In the assembly process, manual focus adjustment ( It is necessary to adjust the focal length by changing the distance between the lens and the image sensor by screwing the lens barrel portion screwed into the mount holder portion with a screw (see Patent Document 1). However, in the conventional liquid crystal polymer composition, in this focus adjustment step, when the lens barrel portion is screwed, a powder composed of a resin composition from the lens barrel, the screw-attached portions of both mount holders, and the surfaces of both molded products ( Particles fall off, and this is one of the major causes of image defects on CMOS (image sensor) or (IR cut) filters. Powder fall-off may occur during use of a product incorporating the member. Therefore, it is required to provide a liquid crystal polymer composition with less powder (particle) dropout as a material used for the lens barrel part, mount holder part, CMOS (image sensor) frame, shutter and shutter bobbin part of the camera module. It was done.
上述したカメラモジュール部品に使用する材料として、液晶ポリマーを使用する例としては、上記特許文献1の他に数例挙げられるが(特許文献2及び3、参照)、
上記組立工程中の粉(パーティクル)の発生を抑制する方法、あるいは発生の少ない樹脂組成物の開発等については、まったく触れられていない。
As an example of using the liquid crystal polymer as the material used for the camera module component described above, there are several examples in addition to the above-mentioned Patent Document 1 (see Patent Documents 2 and 3).
There is no mention of a method for suppressing the generation of powder (particles) during the assembly process or the development of a resin composition that generates little.
従来、液晶ポリエステル樹脂の機械的特性、異方性、反り、耐熱性の改良を目的として、タルク等の板状物質とガラス繊維等の繊維状物質を配合することが知られている。ガラス繊維等の繊維状物質を配合すると、強度や弾性率は向上するが、異方性の改善効果が小さく、タルク等の板状物質を配合すると異方性は改善するが、強度や弾性率の改善効果は小さいという欠点があるため、ガラス繊維等繊維状物質とタルク等の板状物質とを組み合わせて配合することにより、強度や弾性率、異方性等をバランスよく改良することが試みられている(例えば、特許文献4−8参照)。その表面外観について言及した文献(特許文献9参照)もあるが、本用途のような厳しい成形体の表面転写性―表面(から)の脱落物発生を極力減少させる―を有する樹脂組成物作成に関する好ましいタルク等の板状物質、及びガラス繊維等の繊維状物質については、まったく述べられていない。
以上述べたように従来の液晶ポリマー樹脂組成物からなるカメラモジュールのレンズバレル部材、マウントホルダー部材等で、液晶ポリマー樹脂組成物の持つ良好な物性としての、剛性、耐熱性、薄肉加工性、機械強度を維持しながら、カメラモジュール組立工程中および使用中に、製品合格率および製品性能を低下させる原因となる粉(パーティクル)の発生を制御することは、現在のところ、できていない。 As described above, the lens barrel member, mount holder member, etc. of a camera module made of a conventional liquid crystal polymer resin composition, such as rigidity, heat resistance, thin-wall processability, machine, etc. as good physical properties possessed by the liquid crystal polymer resin composition While maintaining strength, it is not currently possible to control the generation of powder (particles) that cause the product acceptance rate and product performance to deteriorate during the camera module assembly process and during use.
本発明は、このような現在未解決であるが、重要な問題を解決しようとするものであり、良好な剛性、耐熱性、薄肉加工性、機械強度をバランスよく有し、しかも、カメラモジュール組立工程中および使用中の粉(パーティクル)の発生量の少ない、カメラモジュール部材に適した液晶ポリエステル樹脂組成物からなる成形材料を提供することを目的とするものである。 The present invention is currently unsolved, but is intended to solve an important problem, and has a good balance of rigidity, heat resistance, thin-wall processability, and mechanical strength, and is a camera module assembly. An object of the present invention is to provide a molding material comprising a liquid crystal polyester resin composition suitable for a camera module member, which generates a small amount of powder (particles) during and during use.
本発明者らは、上記問題を解決するため、種々検討した結果、特定粘度範囲の液晶ポリエステル樹脂に特定粒径のタルクを特定量及び特定のガラス繊維を特定量併せ添加することで、射出成形品の表面転写性に優れ、モジュールの組立加工時、使用時において、表面の脱落物の発生が少ない材料を得ることができ、該組成物から形成されたカメラモジュール部材は、組立工程中粉塵の発生が少なく、かつ、ウェルド部分においても充分な機械強度を持つこと、を見出し、本発明に至った。 As a result of various investigations in order to solve the above problems, the inventors of the present invention added a specific amount of talc having a specific particle diameter and a specific amount of specific glass fiber to a liquid crystal polyester resin having a specific viscosity range, thereby injection molding. It is possible to obtain a material that has excellent surface transferability of the product and is less likely to cause surface dropout during module assembly and use, and the camera module member formed from the composition is free from dust during the assembly process. The inventors have found that the generation is small and that the weld portion has sufficient mechanical strength, and the present invention has been achieved.
本発明の第1は、液晶ポリエステル100質量部に対して、数平均粒径が10〜50μmのタルク15〜60質量部、数平均繊維長が100〜200μmのガラス繊維25〜50質量部、カーボンブラック2〜10質量部配合してなり、荷重たわみ温度が220℃以上、せん断速度100sec−1、370℃における溶融粘度が10〜100Pa・Sであることを特徴とするカメラモジュール用液晶ポリエステル樹脂組成物に関するものである。 The first of the present invention is based on 100 to 50 parts by mass of liquid crystalline polyester, 15 to 60 parts by mass of talc having a number average particle diameter of 10 to 50 μm, 25 to 50 parts by mass of glass fibers having a number average fiber length of 100 to 200 μm, carbon A liquid crystal polyester resin composition for a camera module, comprising 2 to 10 parts by mass of black, having a deflection temperature under load of 220 ° C. or higher, a shear viscosity of 100 sec −1 and a melt viscosity at 370 ° C. of 10 to 100 Pa · S. It is about things.
本発明の第2は、本発明の第1の樹脂組成物を射出成形により成形した時、その成形品表面からの以下の定義による脱落物数が280個以下であることを特徴とする液晶ポリエステル樹脂組成物に関するものである。
脱落物数:外径70mm、内径60mm、高さ0.5mmの円筒の内面に0.3mmピッチ、溝深さ0.2mmのねじ切り構造を有する射出成形体を、純水266mL中で40kHz、480Wの出力にて30秒間超音波洗浄後に、純水10mL中に含まれる最大径が2μm以上の範囲にある粒子の数
A second aspect of the present invention is a liquid crystalline polyester characterized in that when the first resin composition of the present invention is molded by injection molding, the number of fallen objects from the surface of the molded product is 280 or less as defined below. The present invention relates to a resin composition.
Number of falling objects: An injection molded body having a threaded structure with a pitch of 0.3 mm and a groove depth of 0.2 mm on the inner surface of a cylinder having an outer diameter of 70 mm, an inner diameter of 60 mm, and a height of 0.5 mm is obtained at 40 kHz, 480 W in 266 mL of pure water. Of particles having a maximum diameter in the range of 2 μm or more in 10 mL of pure water after ultrasonic cleaning for 30 seconds at an output of
本発明の第3は、本発明の第1または第2の樹脂組成物を射出成形により成形した時、その成形品のウェルド強度が30MPa以上であることを特徴とする液晶ポリエステル樹脂組成物に関するものである。 According to a third aspect of the present invention, there is provided a liquid crystal polyester resin composition characterized in that when the first or second resin composition of the present invention is molded by injection molding, the weld strength of the molded product is 30 MPa or more. It is.
本発明の第4は、本発明の第1、第2または第3のいずれかの液晶ポリエステル樹脂組成物から射出成形により製造されたカメラモジュール部品に関するものである。 The fourth aspect of the present invention relates to a camera module component manufactured by injection molding from any one of the first, second or third liquid crystal polyester resin compositions of the present invention.
本発明に係る液晶ポリエステル樹脂組成物からなる成形体は、良好な剛性、耐熱性、薄肉加工性、機械強度を有し、かつ、表面転写性、表面脱落物特性にも優れるため、表面実装(SMT)可能な、しかも工程中の粉(パーティクル)の発生量の少ない最適なカメラモジュール用部材を提供できる。 The molded body made of the liquid crystalline polyester resin composition according to the present invention has good rigidity, heat resistance, thin-wall processability, mechanical strength, and excellent surface transferability and surface dropout characteristics. It is possible to provide an optimal member for a camera module that is capable of SMT) and that generates a small amount of powder (particle) during the process.
本発明で用いる液晶ポリエステル樹脂とは、異方性溶融体を形成するものであり、これらの中で、実質的に芳香族化合物のみの重縮合反応によって得られる全芳香族液晶ポリエステルが好ましい。 The liquid crystal polyester resin used in the present invention forms an anisotropic melt, and among these, a wholly aromatic liquid crystal polyester obtained by a polycondensation reaction of substantially only an aromatic compound is preferable.
本発明の液晶ポリエステル樹脂組成物を構成する液晶ポリエステル樹脂の構造単位としては、例えば、芳香族ジカルボン酸と芳香族ジオールと芳香族ヒドロキシカルボン酸との組み合わせからなるもの、異種の芳香族ヒドロキシカルボン酸からなるもの、芳香族ヒドロキシカルボン酸と芳香族ジカルボン酸と芳香族ジオールとの組み合わせからなるもの、ポリエチレンテレフタレートなどのポリエステルに芳香族ヒドロキシカルボン酸を反応させたもの等が挙げられ、具体的構造単位としては、例えば下記のものが挙げられる。 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.
芳香族ヒドロキシカルボン酸に由来する構造単位:
芳香族ジカルボン酸に由来する構造単位:
芳香族ジオールに由来する繰り返し構造単位:
耐熱性、機械的物性、加工性のバランスの観点から、好ましい液晶ポリエステル樹脂は、上記構造単位(A1)を30モル%以上有するもの、更に好ましくは(A1)と(B1)をあわせて60モル%以上有するものである。 From the viewpoint of the balance of heat resistance, mechanical properties, and processability, a preferable liquid crystal polyester resin has a structural unit (A1) of 30 mol% or more, more preferably 60 mol in total of (A1) and (B1). % Or more.
特に好ましい液晶ポリエステルは、p−ヒドロキシ安息香酸(I)、テレフタル酸(II)、4,4’−ジヒドロキシビフェニル(III)(これらの誘導体を含む。)を80〜100モル%(但し、(I)と(II)の合計を60モル%以上とする。)、および、(I)(II)(III)のいずれかと脱縮合反応可能な他の芳香族化合物0〜20モル%を重縮合してなる融点320℃以上の全芳香族液晶ポリエステル、または、p−ヒドロキシ安息香酸(I)、テレフタル酸(II)、4,4’−ジヒドロキシビフェニル(III)(これらの誘導体を含む。)を90〜99モル%(但し、(I)と(II)の合計を60モル%以上とする。)、および、(I)(II)(III)と脱縮合反応可能な他の芳香族化合物1〜10モル%(両者をあわせて100モル%とする。)を重縮合してなる融点320℃以上の全芳香族液晶ポリエステルである。 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 any other aromatic compound capable of decondensation reaction with (III) is further polycondensed in an amount of 0 to 20 mol%. 90 of a wholly aromatic liquid crystal polyester having a melting point of 320 ° C. or higher, or p-hydroxybenzoic acid (I), terephthalic acid (II), 4,4′-dihydroxybiphenyl (III) (including these derivatives). -99 mol% (provided that the total of (I) and (II) is 60 mol% or more) and (I) (II) (III) and other aromatic compounds capable of decondensation with 1 10 mol% (both are 100 mol%. ) Is a wholly aromatic liquid crystal polyester having a melting point of 320 ° C. or higher.
上記構造単位の組み合わせとしては、
(A1)
(A1)、(B1)、(C1)
(A1)、(B1)、(B2)、(C1)
(A1)、(B1)、(B2)、(C2)
(A1)、(B1)、(B3)、(C1)
(A1)、(B1)、(B3)、(C2)
(A1)、(B1)、(B2)、(C1)、(C2)
(A1)、(A2)、(B1)、(C1)
が好ましく、特に好ましいモノマー組成比としては、p−ヒドロキシ安息香酸、テレフタル酸、4,4’−ジヒドロキシビフェニル(これらの誘導体を含む。)を80〜100モル%と、これら以外の芳香族ジオール、芳香族ヒドロキシジカルボン酸及び芳香族ジカルボン酸からなる群から選択される芳香族化合物0〜20モル%(両者を合わせて100モル%とする。)とを重縮合してなる全芳香族液晶ポリエステル樹脂である。p−ヒドロキシ安息香酸、テレフタル酸4,4’−ジヒドロキシビフェニルが80モル%以下になると、耐熱性が低下する傾向にあり、好ましくない。
As a combination of the above structural units,
(A1)
(A1), (B1), (C1)
(A1), (B1), (B2), (C1)
(A1), (B1), (B2), (C2)
(A1), (B1), (B3), (C1)
(A1), (B1), (B3), (C2)
(A1), (B1), (B2), (C1), (C2)
(A1), (A2), (B1), (C1)
As a particularly preferable monomer composition ratio, p-hydroxybenzoic acid, terephthalic acid, 4,4′-dihydroxybiphenyl (including these derivatives) is 80 to 100 mol%, and other aromatic diols, A wholly aromatic liquid crystalline polyester resin obtained by polycondensation of 0 to 20 mol% of an aromatic compound selected from the group consisting of aromatic hydroxydicarboxylic acid and aromatic dicarboxylic acid (both are 100 mol% in total). It is. When p-hydroxybenzoic acid and terephthalic acid 4,4′-dihydroxybiphenyl are 80 mol% or less, the heat resistance tends to decrease, which is not preferable.
本発明で用いる液晶ポリエステル樹脂の製造方法としては、公知の方法を採用することができ、溶融重合のみによる製造方法、あるいは溶融重合と固相重合の2段重合による製造方法を用いることができる。具体的な例示としては、芳香族ジヒドロキシ化合物、芳香族ヒドロキシカルボン酸化合物、及び芳香族ジカルボン酸化合物から選択されたモノマーを反応器に仕込み、無水酢酸を投入してモノマーの水酸基をアセチル化した後、脱酢酸重縮合反応によって製造する。例えば、p−ヒドロキシ安息香酸、テレフタル酸、イソフタル酸、及び4,4’−ジヒドロキシビフェニルを窒素雰囲気下の反応器に投入し、無水酢酸を加えて無水酢酸還流下にアセトキシ化を行い、その後昇温して150〜350℃の温度範囲で酢酸を留出しながら脱酢酸溶融重縮合を行うことにより、ポリエステル樹脂を製造する方法が挙げられる。重合時間は、1時間から数十時間の範囲で選択することができる。本発明で用いる液晶ポリエステル樹脂の製造においては、製造前にモノマーの乾燥を行ってもよく、行わなくてもよい。 As a method for producing the liquid crystal polyester resin used in the present invention, a known method can be adopted, and a production method only by melt polymerization or a production method by two-stage polymerization of melt polymerization and solid phase polymerization can be used. As a specific example, after a monomer selected from an aromatic dihydroxy compound, an aromatic hydroxycarboxylic acid compound, and an aromatic dicarboxylic acid compound is charged into a reactor, acetic anhydride is added to acetylate the hydroxyl group of the monomer , Produced by deacetic acid polycondensation reaction. For example, 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. The method of manufacturing a polyester resin is mentioned by performing a deacetic acid melt polycondensation, heating and distilling acetic acid in the temperature range of 150-350 degreeC. The polymerization time can be selected in the range of 1 hour to several tens of hours. In the production of the liquid crystalline polyester resin used in the present invention, the monomer may or may not be dried before the production.
溶融重合により得られた重合体についてさらに固相重合を行う場合は、溶融重合により得られたポリマーを固化後に粉砕してパウダー状もしくはフレーク状にした後、公知の固相重合方法、例えば、窒素などの不活性雰囲気下において200〜350℃の温度範囲で1〜30時間熱処理するなどの方法が好ましく選択される。固相重合は、攪拌しながら行ってもよく、また攪拌することなく静置した状態で行ってもよい。 When 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. for 1 to 30 hours under an inert atmosphere is preferably selected. The solid phase polymerization may be performed with stirring, or may be performed in a standing state without stirring.
重合反応において触媒は使用してもよいし、また使用しなくてもよい。使用する触媒としては、ポリエステルの重縮合用触媒として従来公知のものを使用することができ、酢酸マグネシウム、酢酸第一錫、テトラブチルチアネート、酢酸鉛、酢酸ナトリウム、酢酸カリウム、三酸化アンチモンなどの金属塩触媒、N−メチルイミダゾールなどの有機化合物触媒等が挙げられる。 In the polymerization reaction, a catalyst may or may not be used. As the catalyst to be used, those conventionally known as polyester polycondensation catalysts can be used, such as magnesium acetate, stannous acetate, tetrabutylthiocyanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, etc. And an organic compound catalyst such as N-methylimidazole.
溶融重合における重合反応装置は特に限定されるものではないが、一般の高粘度流体の反応に用いられる反応装置が好ましく使用される。これらの反応装置の例としては、例えば、錨型、多段型、螺旋帯型、螺旋軸型等、あるいはこれらを変形した各種形状の攪拌翼をもつ攪拌装置を有する攪拌槽型重合反応装置、又は、ニーダー、ロールミル、バンバリーミキサー等の、一般に樹脂の混練に使用される混合装置などが挙げられる。 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. Examples of these reaction apparatuses 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.
本発明で用いる液晶ポリエステル樹脂の形状は、粉末状、顆粒状、ペレット状のいずれでもよいが、充填材との混合時の分散性の観点から、粉末状あるいは顆粒状が好ましい。 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.
<タルクについて>
本発明に用いるタルクは、樹脂組成物を構成する材料として使用されている公知のタルクであれば化学組成上、特別な制限は無い。
ただし、理論上の化学構造は含水ケイ酸マグネシウムであるが、特に天然物である場合は、酸化鉄、酸化アルミニウム等の不純物を含むことがあり、タルクに含有される不純物の合計が、10質量%未満であるタルクが本発明に用いるタルクとしては、好ましい。
本発明においては、鱗片状でなめらかな物理的形状が剛性、低摩耗性に係る特性バランスに関与していると考えるが、これらのバランスが最も効果的に発揮できるのは、レーザー回折法による数平均粒径が10〜50μmの範囲の範囲にあるものである。10μm未満であると、コンパウンド時のハンドリングが難しく、かつ、成形品表面からの脱落物が多くなる。また、50μmを超えると、成形品中での分散性が悪くなると共に、その表面が粗くなり、成形品表面からの脱落物が多くなる。このため、平均粒径としては、10〜50μmであることが好ましい。
タルク、及びガラス繊維を必須材料として共に配合する本発明の場合、ガラス繊維配合量とのバランスにもよるが、タルクの配合量としては、液晶ポリエステル100質量部に対して15〜60質量部の範囲が好ましい。タルクの配合量が60質量部を超えると、本発明組成物から得られる成形品の強度及び耐衝撃性が低下する。また、タルクの配合量が、15質量部未満の場合は、配合効果が不十分であり、表面転写性の改善による成形品表面からの脱落物低減という本発明の目的を達成することができない。
<About talc>
If the talc used for this invention is a well-known talc used as a material which comprises a resin composition, there will be no special restriction | limiting on a chemical composition.
However, although the theoretical chemical structure is hydrous magnesium silicate, particularly a natural product, it may contain impurities such as iron oxide and aluminum oxide, and the total amount of impurities contained in talc is 10 mass. Talc that is less than% is preferable as the talc used in the present invention.
In the present invention, it is considered that the flaky and smooth physical shape is involved in the balance of characteristics relating to rigidity and low wear, but these balances can be most effectively exhibited by the number of laser diffraction methods. The average particle diameter is in the range of 10 to 50 μm. If it is less than 10 μm, handling at the time of compounding is difficult, and the amount of falling off from the surface of the molded product increases. On the other hand, if it exceeds 50 μm, the dispersibility in the molded product is deteriorated and the surface becomes rough, resulting in an increase in the amount of falling off from the surface of the molded product. For this reason, as an average particle diameter, it is preferable that it is 10-50 micrometers.
In the case of the present invention in which talc and glass fiber are blended together as essential materials, depending on the balance with the glass fiber blending amount, the talc blending amount is 15-60 parts by mass with respect to 100 parts by mass of the liquid crystalline polyester. A range is preferred. When the blending amount of talc exceeds 60 parts by mass, the strength and impact resistance of the molded product obtained from the composition of the present invention are lowered. Moreover, when the compounding quantity of talc is less than 15 mass parts, the compounding effect is inadequate and the objective of this invention called the fallen substance reduction from the surface of a molded article by the improvement of surface transferability cannot be achieved.
<ガラス繊維について>
本発明に用いるガラス繊維としては、樹脂組成物を構成する材料として使用されている公知のガラス繊維であり、その数平均繊維径には特に制限はないが8μmを超えるものが好ましい、数平均繊維長は、100〜200μmであることが好ましい。タルク配合量とのバランスにもよるが、数平均繊維長が、100μm以上であれば、比較的少ない配合量で、強度や弾性率を向上させることができるため、タルク、及びガラス繊維を必須材料として共に配合する本発明の場合には、これらの成形品中での均一分散性のため好ましいが、200μmを超えると、その表面が粗くなり、表面転写性の改善による成形品表面からの脱落物低減という本発明の目的を達成することができないばかりか、流動性、耐熱性の改良効果が不十分となる。
タルク、及びガラス繊維を必須材料として共に配合する本発明の場合、タルク配合量とのバランスにもよるが、ガラス繊維の配合量としては、液晶ポリエステル100質量部に対して25〜50質量部の範囲が好ましい。ガラス繊維の配合量が25質量部未満の場合は、強度や耐熱性の改良効果が不十分であり、ガラス繊維の配合量が60質量部を超えると場合は、その表面が粗くなり、表面転写性の改善による成形品表面からの脱落物低減という本発明の目的を達成することができない。
<About glass fiber>
The glass fiber used in the present invention is a known glass fiber used as a material constituting the resin composition, and the number average fiber diameter is not particularly limited, but a number average fiber of more than 8 μm is preferable. The length is preferably 100 to 200 μm. Although depending on the balance with the amount of talc, if the number average fiber length is 100 μm or more, the strength and elastic modulus can be improved with a relatively small amount, so talc and glass fiber are essential materials. In the case of the present invention to be blended together, it is preferable because of the uniform dispersibility in these molded products, but when it exceeds 200 μm, the surface becomes rough, and the fallen product from the surface of the molded product due to improved surface transferability. Not only can the object of the present invention of reduction not be achieved, but also the effect of improving fluidity and heat resistance becomes insufficient.
In the case of the present invention in which talc and glass fiber are blended together as essential materials, depending on the balance with the amount of talc, the amount of glass fiber is 25 to 50 parts by mass with respect to 100 parts by mass of the liquid crystalline polyester. A range is preferred. When the blending amount of the glass fiber is less than 25 parts by mass, the effect of improving the strength and heat resistance is insufficient, and when the blending amount of the glass fiber exceeds 60 parts by mass, the surface becomes rough and surface transfer is performed. Therefore, the object of the present invention, that is, reduction of falling off the surface of the molded product due to improvement of the property cannot be achieved.
<カーボンブラックについて>
本発明に用いるカーボンブラックは、樹脂着色に用いられる一般的に入手可能なものであれば特に限定されるものではないが、その一次粒子径が20nm未満の場合には、得られる成形品の表面にブツ(カーボンブラックが凝集した細かいブツブツ状突起物)が多く発生し、その表面が粗くなる傾向にあり、好ましくない。
カーボンブラックの配合量としては、液晶ポリエステル100質量部に対して2〜10質量部の範囲が好ましい。カーボンブラックの配合量が2質量部未満であると、得られる樹脂組成物の漆黒性が低下し、遮光性に不安が出てくることになり、10質量部を超えると不経済であり、またブツ発生の可能性が高くなる。
<About carbon black>
The carbon black used in the present invention is not particularly limited as long as it is generally available for use in resin coloring, but when the primary particle diameter is less than 20 nm, the surface of the obtained molded product In this case, a large amount of bumps (fine bumpy projections with agglomerated carbon black) are generated and the surface tends to become rough, which is not preferable.
As a compounding quantity of carbon black, the range of 2-10 mass parts is preferable with respect to 100 mass parts of liquid crystalline polyester. If the blending amount of the carbon black is less than 2 parts by mass, the jet blackness of the resulting resin composition will be lowered, and the light-shielding property will be uneasy, and if it exceeds 10 parts by mass, it will be uneconomical. The possibility of occurrence of irregularities increases.
さらに、本発明の組成物には、本発明の目的を損なわない範囲で、酸化防止剤および熱安定剤(たとえばヒンダードフェノール、ヒドロキノン、ホスファイト類およびこれらの置換体など)、紫外線吸収剤(たとえばレゾルシノール、サリシレート、ベンゾトリアゾール、ベンゾフェノンなど)、滑剤および離型剤(モンタン酸およびその塩、そのエステル、そのハーフエステル、ステアリルアルコール、ステアラミドおよびポリエチレンワックスなど)、可塑剤、帯電防止剤、難燃剤などの通常の添加剤や他の熱可塑性樹脂を添加して、所定の特性を付与することができる。 Further, 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). Resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and mold release agents (such as montanic acid and salts thereof, esters thereof, half esters thereof, stearyl alcohol, stearamide and polyethylene wax), plasticizers, antistatic agents, flame retardants Ordinary additives such as these and other thermoplastic resins can be added to impart predetermined characteristics.
本発明に係る液晶ポリエステル樹脂組成物は液晶ポリエステルを溶融して他の成分と混練して得られるが、溶融混練に用いる機器および運転方法は、一般に液晶ポリエステルの溶融混練に使用するものであれば特に制限はない。
好ましくは、一対のスクリュをする混練機で、ポッパーから液晶ポリエステル、タルクおよび(ペレット状)カーボンブラックを投入し、溶融混練し押し出してペレット化する方法が好ましい。
これらは、2軸混練機と呼ばれるもので、これらの中でも、切り替えし機構を有することで充填材の均一分散を可能とする異方向回転式であるもの、食い込みが容易となるバレル−スクリュウ間の空隙が大きい40mmφ以上のシリンダー径を有するもの、2条タイプのもの、および、スクリュウ間の噛合いが大きいもの、具体的には、噛合い率が1.45以上のものが好ましい。
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. There is no particular limitation.
It is preferable to use a method in which liquid crystal polyester, talc, and (pellet-like) carbon black are introduced from a popper, melt-kneaded, extruded, and pelletized with a kneader having a pair of screws.
These are called twin-screw kneaders. Among these, a rotating mechanism that enables uniform dispersion of the filler by switching and having a mechanism, and between the barrel and the screw that makes it easy to bite. Those having a large air gap and a cylinder diameter of 40 mmφ or more, those having a two-row type, and those having a large mesh between the screws, specifically, having a mesh rate of 1.45 or more are preferable.
<溶融粘度範囲について>
本発明においては、このようにして得られた液晶ポリエステル樹脂組成物の剪断速度100sec−1、370℃で測定される溶融粘度が10〜100(Pa・S)の範囲にあることが必要である。樹脂粘度がこの範囲を外れると、射出成形品の表面性状が悪くなり、脱落物が増えるためである。溶融粘度は、インテスコ株式会社製キャピラリーレオメーター(Model2010)を用い、キャピラリーとして径1.00mm、長さ40mm、流入角90°のものを用い、せん断速度100sec−1で320℃から+4℃/分の昇温速度で等速加熱をしながら見掛け粘度測定を行い、370℃における見かけ粘度を求める。
<荷重たわみ温度について>
また、本発明においては、このようにして得られた液晶ポリエステル樹脂組成物の射出成形品の荷重たわみ温度が220℃以上であることが必要である。ここで、荷重たわみ温度とは、ASTM D648に準拠して測定された荷重たわみ温度(DTUL)を意味する。荷重たわみ温度がこの範囲を外れると、表面実装におけるハンダリフロー時の耐熱性に問題が生じるおそれがあるためである。
<About melt viscosity range>
In the present invention, the liquid crystal polyester resin composition thus obtained needs to have a melt viscosity measured at a shear rate of 100 sec −1 and 370 ° C. in the range of 10 to 100 (Pa · S). . This is because if the resin viscosity is out of this range, the surface properties of the injection-molded product are deteriorated and the amount of fallen substances increases. 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 °, and a shear rate of 100 sec −1 from 320 ° C. to + 4 ° C./min. The apparent viscosity is measured while heating at a constant rate at a constant heating rate, and the apparent viscosity at 370 ° C. is obtained.
<About deflection temperature under load>
In the present invention, it is necessary that the deflection temperature under load of the injection-molded product of the liquid crystal polyester resin composition thus obtained is 220 ° C. or higher. Here, the deflection temperature under load means the deflection temperature under load (DTUL) measured according to ASTM D648. This is because if the deflection temperature under load is out of this range, there may be a problem in heat resistance during solder reflow in surface mounting.
本発明のカメラモジュール用部材は上記組成物から射出成形で得られるが、成形品に目的とする剛性、摺動性能を発揮させるにも、上記の溶融粘度範囲が必須である。
部材の最小厚みが0.2〜0.8mmのような薄肉の場合、上記範囲の溶融粘度範囲にある樹脂組成物を用いることにより、金型内の0.2〜0.8mmの厚みの空間に高速で射出充填されたときに、金型内で均一に流動して、組成の偏りがない成形品を得ることができる。このようにして得られたカメラモジュール用部材は、機械強度、剛性にすぐれ、成形品表面からの脱落物が抑制されたものである。また、成形品に目的とするハンダリフロー性能発揮させるためにも、上記の荷重たわみ温度範囲が必須である。
The camera module member of the present invention can be obtained from the above composition by injection molding, but the above melt viscosity range is essential for the molded product to exhibit the desired rigidity and sliding performance.
In the case where the minimum thickness of the member is as thin as 0.2 to 0.8 mm, a space having a thickness of 0.2 to 0.8 mm in the mold is obtained by using the resin composition in the melt viscosity range of the above range. When the product is injected and filled at a high speed, a molded product that flows uniformly in the mold and has no compositional deviation can be obtained. The camera module member thus obtained is excellent in mechanical strength and rigidity, and is prevented from falling off from the surface of the molded product. In addition, the above-mentioned deflection temperature range of load is essential for exhibiting the desired solder reflow performance in the molded product.
なお、本発明に用いる射出成形条件あるいは射出成形機は、液晶ポリエステルの成形に一般に使用されている公知のものであれば特に制限は無い。 The injection molding conditions or injection molding machine used in the present invention is not particularly limited as long as it is a known one generally used for molding liquid crystal polyester.
以下、実施例および比較例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to a following example.
(試験方法)
実施例及び比較例におけるサーモトロピック液晶ポリエステル樹脂組成物及びそれから得られる成形体の性能の測定方法および評価方法を以下に示す。
(1)溶融粘度の測定
サーモトロピック液晶ポリエステル樹脂組成物の溶融粘度は、キャピラリーレオメーター(インテスコ(株)社製2010)を用い、キャピラリーとして径1.00mm、長さ40mm、流入角90°のものを用い、せん断速度100sec −1 で300℃から+4℃/分の昇温速度で等速加熱をしながら見掛け粘度測定を行い、370℃における見掛け粘度を求め、試験値とした。なお、試験には、予めエアーオーブン中、150℃、4時間乾燥した樹脂組成物を用いた。
(2)ウェルド強度の測定
得られた樹脂組成物のペレットを射出成形機(日精樹脂工業株式会社製、UH−1000)を使用し、シリンダー最高温度370℃、射出速度300mm/sec、金型温度80℃にて射出成形し、13mm(幅)×80mm(長さ)×1.0mm(厚み)の中央部にウェルドのある射出成形体をウェルド部強度測定用の試験片とした。各試験片について、スパン間隔25mmでASTM D790に準拠してウェルド部の曲げ強度を測定した。
(3)荷重たわみ温度(DTUL)の測定
得られた樹脂組成物のペレットを射出成形機(住友重機械工業(株)製SG−25)を用いて、シリンダー最高温度370℃、射出速度100mm/sec、金型温度80℃で、13mm(幅)×130mm(長さ)×3mm(厚み)の射出成形体を得て、荷重たわみ温度測定の試験片とした。各試験片について、ASTM D648に準拠し、荷重たわみ温度を測定した。
4)脱落物数の測定
得られた樹脂組成物のペレットを射出成形機(日精樹脂工業株式会社製、UH−1000)を用いて、シリンダー最高温度370℃、射出速度300mm/sec、金型温度80℃で、7mm(外径)×4mm(高さ)×6mm(内径)の内側に0.3mmピッチ、溝深さ0.2mmのねじ切り構造を有する、円筒状の射出成形体(キャリアと称する)を得て、脱落物数測定の試験片とした。各試験片2個を純水中266mLに投入し、40kHz、480Wの出力にて30秒間超音波洗浄を実施した。超音波洗浄後の純水10mL中に含まれる試験片脱落物のうち、最大径が2μm以上の範囲にあるものの数を、ソナック(株)社製SURFEX200を使用して測定し、3回の測定の平均値を測定結果とした。
(Test method)
The measuring methods and evaluation methods for the performance of the thermotropic liquid crystal polyester resin compositions and molded products obtained therefrom in Examples and Comparative Examples are shown below.
(1) Measurement of melt viscosity 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 was measured while heating at a constant rate from 300 ° C. to + 4 ° C./min at a shear rate of 100 sec −1 , and the apparent viscosity at 370 ° C. was determined as a test value. In the test, a resin composition dried in advance in an air oven at 150 ° C. for 4 hours was used.
(2) Measurement of weld strength Using an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd., UH-1000), the pellets of the obtained resin composition were used, the maximum cylinder temperature was 370 ° C., the injection speed was 300 mm / sec, and the mold temperature. Injection molding was performed at 80 ° C., and an injection molded body having a weld at the center of 13 mm (width) × 80 mm (length) × 1.0 mm (thickness) was used as a test piece for measuring the strength of the weld. About each test piece, the bending strength of the weld part was measured based on ASTM D790 with a span interval of 25 mm.
(3) Measurement of deflection temperature under load (DTUL) Using an injection molding machine (SG-25, manufactured by Sumitomo Heavy Industries, Ltd.), pellets of the resin composition obtained were subjected to a maximum cylinder temperature of 370 ° C. and an injection speed of 100 mm / An injection-molded body of 13 mm (width) × 130 mm (length) × 3 mm (thickness) was obtained at a mold temperature of 80 ° C., and used as a test piece for measuring the deflection temperature under load. About each test piece, the deflection temperature under load was measured based on ASTM D648.
4) Measurement of the number of omissions The pellets of the resin composition obtained were subjected to an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., UH-1000), a cylinder maximum temperature of 370 ° C., an injection speed of 300 mm / sec, and a mold temperature. Cylindrical injection-molded body (referred to as a carrier) having a threaded structure with a pitch of 0.3 mm and a groove depth of 0.2 mm inside a 7 mm (outer diameter) × 4 mm (height) × 6 mm (inner diameter) at 80 ° C. ) To obtain a test piece for the number of fallen objects. Two test pieces were put into 266 mL of pure water and subjected to ultrasonic cleaning for 30 seconds at an output of 40 kHz and 480 W. The number of specimens that fall within the range of 2 μm or more in the test piece dropout contained in 10 mL of pure water after ultrasonic cleaning is measured using SURFEX200 manufactured by Sonac Co., Ltd., and measured three times. The average value was taken as the measurement result.
液晶ポリエステル(LCP)の製造例を以下に示す。
(製造例 サーモトロピック液晶ポリエステルAの製造)
SUS316を材質とし、ダブルヘリカル攪拌翼を有する内容積1700Lの重合槽(神戸製鋼株式会社製)にp−ヒドロキシ安息香酸(上野製薬株式会社製)298kg(2.16キロモル)、4,4‘−ジヒドロキシビフェニル(本州化学工業株式会社製)134kg(0.72キロモル)、テレフタル酸(三井化学株式会社製)90kg(0.54キロモル)、イソフタル酸(エイ・ジ・インターナショナルケミカル株式会社製)30kg(0.18キロモル)、触媒として酢酸カリウム(キシダ化学株式会社製)0.04kg、酢酸マグネシウム(キシダ化学株式会社製)0.10kgを仕込み、重合槽の減圧−窒素注入を2回行って窒素置換を行った後、無水酢酸386kg(3.78キロモル)を添加し、攪拌翼の回転速度45rpmで150℃まで1.5時間で昇温して還流状態で2時間アセチル化反応を行った。アセチル化終了後、酢酸留出状態にして0.5℃/分で昇温して、リアクター温度が305℃になったところで重合物をリアクター下部の抜き出し口から取り出し、冷却装置で冷却固化した。得られた重合物をホソカワミクロン株式会社製の粉砕機により目開き2.0mmの篩を通過する大きさに粉砕してプレポリマーを得た。
得られたプレポリマーを高砂工業株式会社製のロータリーキルンを用いて固相重合を行った。プレポリマーを該キルンに充填し、窒素を16Nm3/hrの流速にて流通し、回転速度2rpmでヒーター温度を室温から350℃まで1時間で昇温し、350℃で10時間保持した。キルン内の樹脂粉末温度が295℃に到達したことを確認し、加熱を停止してロータリーキルンを回転しながら4時間かけて冷却し、粉末状の液晶ポリエステルを得た。融点は360℃、溶融粘度は70Pa・Sであった。
(製造例 サーモトロピック液晶ポリエステルBの製造)
サーモトロピック液晶ポリエステルAと同様の方法にて、プレポリマーを得た。
得られたプレポリマーを高砂工業株式会社製のロータリーキルンを用いて固相重合を行った。プレポリマーを該キルンに充填し、窒素を16Nm3/hrの流速にて流通し、回転速度2rpmでヒーター温度を室温から350℃まで1時間で昇温し、350℃で9時間保持した。キルン内の樹脂粉末温度が290℃に到達したことを確認し、加熱を停止してロータリーキルンを回転しながら4時間かけて冷却し、粉末状の液晶ポリエステルを得た。融点は350℃、溶融粘度は20Pa・Sであった。
(製造例 サーモトロピック液晶ポリエステルCの製造)
サーモトロピック液晶ポリエステルAと同様の方法にて、プレポリマーを得た。
得られたプレポリマーを高砂工業株式会社製のロータリーキルンを用いて固相重合を行った。プレポリマーを該キルンに充填し、窒素を16Nm3/hrの流速にて流通し、回転速度2rpmでヒーター温度を室温から350℃まで1時間で昇温し、350℃で11時間保持した。キルン内の樹脂粉末温度が300℃に到達したことを確認し、加熱を停止してロータリーキルンを回転しながら4時間かけて冷却し、粉末状の液晶ポリエステルを得た。融点は370℃、溶融粘度は140Pa・Sであった。
A production example of liquid crystal polyester (LCP) is shown below.
(Production example Production of 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. 2 hours acetylation reaction was carried out at a Atsushi Nobori to reflux for 1.5 hours 0.99 ° C. by m. After completion of acetylation, acetic acid was distilled off and the temperature was raised at 0.5 ° C./min. When the reactor temperature reached 305 ° C., the polymer was taken out from the outlet at the bottom of the reactor and solidified by cooling with a cooling device. 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.
(Production example Production of 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. After confirming that the temperature of the resin powder in the kiln reached 290 ° 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 350 ° C. and the melt viscosity was 20 Pa · S.
(Production example Production of thermotropic liquid crystal polyester C)
A prepolymer was obtained in the same manner as in 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.
以下の実施例で使用した無機充填材を示す。
(1)タルク:日本タルク(株)社製、「MS−KY」(数平均粒径23μm)
(2)ガラスファイバー(GF)A:日東紡績(株)社製、PF100E−001SC(数平均繊維長100μm、数平均繊維径10μm)
(3)ガラスファイバー(GF)B:セントラルグラスファイバー(株)社製、EFH150−01(平均繊維長150μm、数平均繊維径10μm)
(4)ガラスファイバー(GF)C:オーゥエンスコーニング(株)社製、PX−1(数平均繊維長3mm、数平均繊維径10μm)
(5)カーボンブラック(CB):キャボット(株)社製、「REGAL 660」(1次粒子径24nm)
The inorganic filler used in the following examples is shown.
(1) Talc: “MS-KY” manufactured by Nippon Talc Co., Ltd. (number average particle size 23 μm)
(2) Glass fiber (GF) A: manufactured by Nitto Boseki Co., Ltd., PF100E-001SC (number average fiber length 100 μm, number average fiber diameter 10 μm)
(3) Glass fiber (GF) B: manufactured by Central Glass Fiber Co., Ltd., EFH150-01 (average fiber length 150 μm, number average fiber diameter 10 μm)
(4) Glass fiber (GF) C: manufactured by Owens Corning Co., Ltd., PX-1 (number average fiber length 3 mm, number average fiber diameter 10 μm)
(5) Carbon black (CB): “REGAL 660” (primary particle diameter: 24 nm), manufactured by Cabot Corporation
(実施例1)
前記製造例にて得た粉末状の液晶ポリエステルAを100質量部、タルクを34質量部、ガラスファイバーAを34質量部、カーボンブラック3質量部をリボンブレンダーを用いて混合し、その混合物をエアーオーブン中で150℃にて2時間乾燥した。この乾燥した混合物を、シリンダーの最高温度380℃に設定したシリンダー径30mmの2軸押出機((株)池貝社製PCM−30)を用い、押出速度140kg/hrにて溶融混練して目的の液晶ポリエステル樹脂組成物のペレットを得た。得られたペレットを用い、前記の試験方法にて、各物性の測定を行った。結果を表1に示す。
(実施例2〜4及び比較例1〜7)
Example 1
100 parts by mass of powdered liquid crystalline polyester A obtained in the above production example, 34 parts by mass of talc, 34 parts by mass of glass fiber A, and 3 parts by mass of carbon black were mixed using a ribbon blender, and the mixture was aired. Dried in an oven at 150 ° C. for 2 hours. This dried mixture was melt kneaded at an extrusion speed of 140 kg / hr using a twin screw extruder (PCM-30 manufactured by Ikegai Co., Ltd.) with a cylinder diameter of 30 mm set at a maximum temperature of 380 ° C. A pellet of the liquid crystal polyester resin composition was obtained. Each physical property was measured by the test method using the obtained pellet. The results are shown in Table 1.
(Examples 2 to 4 and Comparative Examples 1 to 7)
実施例1と同様に粉末状の液晶ポリエステル、タルク、ガラスファイバー、カーボンブラックを、表1に記載した組成とした以外は、実施例1と同様の設備、操作方法により、それぞれの液晶ポリエステル樹脂組成物のペレットを製造した。また実施例1と同様に得られたペレットを用い、前記の試験方法にて、各物性の測定を行った。結果を表1に示す。 Similar to Example 1, except that powdered liquid crystal polyester, talc, glass fiber, and carbon black have the compositions described in Table 1, the same liquid crystal polyester resin composition as in Example 1 was used. Product pellets were produced. Moreover, each physical property was measured with the said test method using the pellet obtained similarly to Example 1. FIG. The results are shown in Table 1.
*注)
1.全ての測定において、30μm以上のものは検出されなかった。
2.実施例組成物の脱落試験後のサンプルを再度同条件で超音波洗浄した場合、脱落物の発生はほとんど認められなかったのに対し、比較例組成物では、同様に再度同条件で超音波洗浄した時、更に脱落物の発生(多いものでは30個以上の発生)が認められた。
*note)
1. In all the measurements, those of 30 μm or more were not detected.
2. When the sample after the dropout test of the example composition was ultrasonically cleaned again under the same conditions, almost no dropout was observed, whereas in the comparative composition, the sample was again superheated under the same conditions. When sonic cleaning was performed, the generation of fallen objects (occurrence of 30 or more in many cases) was observed.
表1に示したように、本発明の液晶ポリエステル樹脂組成物(実施例1〜4)は、溶融粘度が本発明の規定範囲に入っており、その結果、良好な成形性を示し、脱落物が少なく、荷重たわみ温度、ウェルド強度が高いという良好な結果が得られた。
それに対し、比較例1〜7のごとく本発明の規定範囲から外れる樹脂組成物の場合は、成形性、脱落物、荷重たわみ温度、ウェルド強度、の少なくとも一つが劣っている結果となった。
As shown in Table 1, the liquid crystal polyester resin compositions (Examples 1 to 4) of the present invention have a melt viscosity within the specified range of the present invention, and as a result, exhibit good moldability and fall off. Good results were obtained in that the deflection temperature under load and the weld strength were high.
On the other hand, in the case of the resin composition deviating from the specified range of the present invention as in Comparative Examples 1 to 7, at least one of moldability, dropout, deflection temperature under load, and weld strength was inferior.
本発明のカメラモジュール用樹脂組成物およびこの組成物から得られるカメラモジュール部品は、耐熱性が高く、ハンダリフローに耐えることができ、かつ該部品からの落下物が極めて少ないので、携帯電話、ラップトップコンピューター、デジタルカメラ、デジタルビデオカメラ等における、表面実装加工が可能なレンズバレル部、マウントホルダー部、更には、「CMOS(イメージセンサー)の枠」、「シャッター及び、シャッターボビン部」などの各種用途に利用することができる。 The resin composition for a camera module of the present invention and the camera module component obtained from the composition have high heat resistance, can withstand solder reflow, and have very few falling objects from the component. Lens barrels and mount holders that can be surface-mounted in top computers, digital cameras, digital video cameras, etc. In addition, various types such as “CMOS (image sensor) frame” and “shutter and shutter bobbin” Can be used for applications.
Claims (4)
脱落物数:外径70mm、内径60mm、高さ0.5mmの円筒の内面に0.3mmピッチ、溝深さ0.2mmのねじ切り構造を有する射出成形体を、純水266mL中で40kHz、480Wの出力にて30秒間超音波洗浄後に、純水10mL中に含まれる最大径が2μm以上の範囲にある粒子の数 2. The liquid crystal polyester resin composition according to claim 1, wherein the number of fallen articles from the surface of the molded article molded by injection molding is 280 or less.
Number of falling objects: An injection molded body having a threaded structure with a pitch of 0.3 mm and a groove depth of 0.2 mm on the inner surface of a cylinder having an outer diameter of 70 mm, an inner diameter of 60 mm, and a height of 0.5 mm is obtained at 40 kHz, 480 W in 266 mL of pure water. Of particles having a maximum diameter in the range of 2 μm or more in 10 mL of pure water after ultrasonic cleaning for 30 seconds at an output of
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CN2009801113254A CN101981123B (en) | 2008-03-28 | 2009-03-24 | Liquid-crystal polyester resin composition for camera modules |
TW098109567A TWI444427B (en) | 2008-03-28 | 2009-03-24 | Camera module with liquid crystal polyester resin composition |
US12/933,967 US8192645B2 (en) | 2008-03-28 | 2009-03-24 | Liquid crystal polyester resin composition for camera module |
PCT/JP2009/056410 WO2009119863A1 (en) | 2008-03-28 | 2009-03-24 | Liquid-crystal polyester resin composition for camera modules |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009242453A (en) * | 2008-03-28 | 2009-10-22 | Nippon Oil Corp | Liquid crystal polyester resin composition for camera module |
JP2009242455A (en) * | 2008-03-28 | 2009-10-22 | Nippon Oil Corp | Liquid crystal polyester resin composition for camera module |
JP2012193343A (en) * | 2011-02-28 | 2012-10-11 | Sumitomo Chemical Co Ltd | Liquid crystal polyester composition |
KR20160096086A (en) | 2013-12-03 | 2016-08-12 | 제이엑스 에네루기 가부시키가이샤 | Wholly aromatic liquid crystal polyester resin composition and camera module component including injection-molded article of same as constituent member |
KR20160096087A (en) | 2013-12-03 | 2016-08-12 | 제이엑스 에네루기 가부시키가이샤 | Liquid crystal polyester amide resin composition and camera module component including injection-molded article of same as constituent member |
US10941275B2 (en) | 2013-03-13 | 2021-03-09 | Ticona Llc | Compact camera module |
US11702539B2 (en) | 2020-02-26 | 2023-07-18 | Ticona Llc | Polymer composition for an electronic device |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09297256A (en) * | 1996-04-30 | 1997-11-18 | Toray Ind Inc | Camera lens barrel and its production |
JP2009242453A (en) * | 2008-03-28 | 2009-10-22 | Nippon Oil Corp | Liquid crystal polyester resin composition for camera module |
-
2008
- 2008-03-28 JP JP2008087490A patent/JP5951168B2/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH09297256A (en) * | 1996-04-30 | 1997-11-18 | Toray Ind Inc | Camera lens barrel and its production |
JP2009242453A (en) * | 2008-03-28 | 2009-10-22 | Nippon Oil Corp | Liquid crystal polyester resin composition for camera module |
Cited By (14)
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JP2009242455A (en) * | 2008-03-28 | 2009-10-22 | Nippon Oil Corp | Liquid crystal polyester resin composition for camera module |
JP2009242453A (en) * | 2008-03-28 | 2009-10-22 | Nippon Oil Corp | Liquid crystal polyester resin composition for camera module |
JP2012193343A (en) * | 2011-02-28 | 2012-10-11 | Sumitomo Chemical Co Ltd | Liquid crystal polyester composition |
JP2017066412A (en) * | 2011-02-28 | 2017-04-06 | 住友化学株式会社 | Liquid crystal polyester composition |
KR101867623B1 (en) * | 2011-02-28 | 2018-06-15 | 스미또모 가가꾸 가부시끼가이샤 | Liquid crystal polyester composition and process for producing the same |
US10941275B2 (en) | 2013-03-13 | 2021-03-09 | Ticona Llc | Compact camera module |
US11725095B2 (en) | 2013-03-13 | 2023-08-15 | Ticona Llc | Compact camera module |
KR20160096086A (en) | 2013-12-03 | 2016-08-12 | 제이엑스 에네루기 가부시키가이샤 | Wholly aromatic liquid crystal polyester resin composition and camera module component including injection-molded article of same as constituent member |
KR20160096087A (en) | 2013-12-03 | 2016-08-12 | 제이엑스 에네루기 가부시키가이샤 | Liquid crystal polyester amide resin composition and camera module component including injection-molded article of same as constituent member |
US11702539B2 (en) | 2020-02-26 | 2023-07-18 | Ticona Llc | Polymer composition for an electronic device |
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US11728065B2 (en) | 2020-07-28 | 2023-08-15 | Ticona Llc | Molded interconnect device |
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