JP2009242453A - Liquid crystal polyester resin composition for camera module - Google Patents

Liquid crystal polyester resin composition for camera module Download PDF

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JP2009242453A
JP2009242453A JP2008087485A JP2008087485A JP2009242453A JP 2009242453 A JP2009242453 A JP 2009242453A JP 2008087485 A JP2008087485 A JP 2008087485A JP 2008087485 A JP2008087485 A JP 2008087485A JP 2009242453 A JP2009242453 A JP 2009242453A
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liquid crystal
resin composition
crystal polyester
polyester resin
camera module
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JP2009242453A5 (en
JP5951167B2 (en
Inventor
Satoshi Murouchi
聡士 室内
Toshio Nakayama
敏雄 中山
Tooru Kitai
徹 北居
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Eneos Corp
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Nippon Oil Corp
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Priority to JP2008087485A priority Critical patent/JP5951167B2/en
Application filed by Nippon Oil Corp filed Critical Nippon Oil Corp
Priority to US12/933,967 priority patent/US8192645B2/en
Priority to TW098109567A priority patent/TWI444427B/en
Priority to KR1020107024246A priority patent/KR101591541B1/en
Priority to PCT/JP2009/056410 priority patent/WO2009119863A1/en
Priority to CN2009801113254A priority patent/CN101981123B/en
Publication of JP2009242453A publication Critical patent/JP2009242453A/en
Publication of JP2009242453A5 publication Critical patent/JP2009242453A5/ja
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition, which is excellent in the balance between heat resistance, rigidity, moldability and surface exfoliation characteristics, for a surface-mountable (SMT) camera module. <P>SOLUTION: The liquid crystal polyester resin composition comprises 50-110 pts.mass of talc having a number-mean particle diameter of 10-50 μm, and 2-10 pts.mass of carbon black based on 100 pts.mass of a liquid crystal polyester. The liquid crystal polyester resin composition exhibits melt viscosity of 10-150 Pa s as determined at a shear rate of 100 sec<SP>-1</SP>at 370°C and a deflection temperature under load of 220°C or above. <P>COPYRIGHT: (C)2010,JPO&INPIT

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)、「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” (Surface Mount Technology, abbreviated as SMT), “Lens Barrel” (the part on which the lens is mounted), “Mount Holder” (Mount the barrel and fix it on the board) 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)、「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 where the lens is placed), “mount holder part” (the part where the barrel is mounted and fixed to the substrate), and “CMOS ( It has come to be used for “frame of image sensor”, “shutter and shutter bobbin portion” and the like (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一つとなっている。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, which is one of the major causes of image defects on the CMOS image sensor or (IR cut) filter. 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 a material used for the camera module parts 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 at all about the method for suppressing the occurrence of the above, or the development of a resin composition with little occurrence.

従来、液晶ポリエステル樹脂成形品の異方性、反り、耐熱性の改良のためにタルクを充填することが知られており(例えば、特許文献4−6参照)、その表面外観について言及した文献(特許文献7参照)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については、まったく述べられていない。
特開2006−246461号公報 特開2008−028838号公報 特開2008−034453号公報 特開平04−13758号公報 特開2001−207054号公報 特開平06−207083号公報 特開2003−128893号公報
Conventionally, it has been known that talc is filled to improve the anisotropy, warpage, and heat resistance of a liquid crystal polyester resin molded product (see, for example, Patent Documents 4-6), and a document that mentions its surface appearance ( Although there is also a patent document 7), there is no description at all about a resin composition having a severe surface transferability of a molded article as in the present application—reducing generation of falling off of the surface as much as possible.
JP 2006-246461 A JP 2008-028838 A JP 2008-034453 A Japanese Patent Laid-Open No. 04-13758 JP 2001-207054 A Japanese Patent Laid-Open No. 06-207083 JP 2003-128893 A

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、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 have excellent physical properties of the liquid crystal polymer resin composition, such as rigidity, heat resistance, and thin-wall processability. While maintaining, 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、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, which is currently unsolved, is intended to solve an important problem, has a good balance of rigidity, heat resistance, and thin wall workability, and is in the process of assembling the camera module. Another object of the present invention is to provide a molding material made of a liquid crystal polyester resin composition suitable for a camera module member with a small amount of generated powder (particles).

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、特定粒径のタルクを特定粘度範囲の液晶ポリエステル樹脂に特定量添加することで、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、粉塵の発生の少ないことを見出し、本発明に至った。   As a result of various investigations to solve the above problems, the inventors have added a specific amount of talc having a specific particle size to a liquid crystal polyester resin having a specific viscosity range, so that the surface transferability of an injection-molded product is excellent. During assembly and use, it was possible to obtain a material with less surface dropout, and the camera module member formed from the composition was found to generate less dust, leading to the present invention. .

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50〜110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10〜150Pa・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 comprises 50 to 110 parts by mass of talc having a number average particle size of 10 to 50 μm and 2 to 10 parts by mass of carbon black with respect to 100 parts by mass of the liquid crystalline polyester, and the deflection temperature under load is 220 ° C. As described above, the present invention relates to a liquid crystal polyester resin composition for a camera module, which has a melt viscosity of 10 to 150 Pa · S at a shear rate of 100 sec −1 and 370 ° C.

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200個以下であることを特徴とする請求項1記載の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
According to a second aspect of the present invention, 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 according to the following definition is 200 or less. 1. The liquid crystal polyester resin composition according to 1.
Number of fallen 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, in pure water of 266 mL, 40 kHz, 480 W 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 third aspect of the present invention relates to a camera module component manufactured by injection molding from the first or second liquid crystal polyester resin composition 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、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, and excellent surface transferability and surface dropout characteristics. It is possible to provide an optimal member for a camera module that is possible and that generates a small amount of powder (particles) during the assembly process and in use.

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:

Figure 2009242453
Structural units derived from aromatic hydroxycarboxylic acids:
Figure 2009242453

芳香族ジカルボン酸に由来する構造単位:

Figure 2009242453
Structural units derived from aromatic dicarboxylic acids:
Figure 2009242453

芳香族ジオールに由来する繰り返し構造単位:

Figure 2009242453
Figure 2009242453
Repeating structural units derived from aromatic diols:
Figure 2009242453
Figure 2009242453

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 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 the 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 stirrer having various types of stirrer blades, a vertical type, a multistage type, a spiral band type, a helical shaft type, or the like, or 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、特に制限は無い。
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%未満であるタルクを用いることが好ましい。
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。
タルクの配合量としては、液晶ポリエステル100質量部に対して50〜110質量部の範囲が好ましい。タルクの配合量が110質量部を超えると場合は、本発明組成物の強度及び耐衝撃性が低下する。また、タルクの配合量が、50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 restriction | limiting in particular 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. It is preferable to use talc that is less than%.
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.
As a compounding quantity of talc, the range of 50-110 mass parts is preferable with respect to 100 mass parts of liquid crystalline polyester. When the amount of talc exceeds 110 parts by mass, the strength and impact resistance of the composition of the present invention are lowered. Moreover, when the compounding quantity of talc is less than 50 mass parts, the compounding effect is inadequate and the objective of this invention of the fallen substance reduction from the surface of a molded article by the improvement of surface transferability 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 and is generally available for use in resin coloring. However, when the primary particle diameter is less than 20 nm, the surface of the resulting molded product has a rough surface (carbon A large number of fine protrusions with agglomerated 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10〜150(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 150 (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、耐磨耗性能、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 wear resistance and rigidity, and is prevented from falling off the surface of the molded product. In addition, the above-mentioned deflection temperature range of load is indispensable 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 obtained resin composition were molded using an injection molding machine (Nissei Resin Co., Ltd., UH-1000), the cylinder maximum temperature 370 ° C., the injection speed 300 mm / sec, the mold Cylindrical injection-molded body (carrier and carrier) having a threaded structure of 0.3 mm pitch and groove depth of 0.2 mm inside 7 mm (outer diameter) × 4 mm (height) × 6 mm (inner diameter) at a temperature of 80 ° C. To obtain a test piece for measuring 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 falling in the range of the maximum diameter of 2 μm or more included 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 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A:日本タルク(株)社製、「MS−KY」(数平均粒径23μm)
(2)タルクB:林化成(株)社製、「5000S」(数平均粒径4μm)
(3)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 A: “MS-KY” manufactured by Nippon Talc Co., Ltd. (number average particle size 23 μm)
(2) Talc B: “5000S” manufactured by Hayashi Kasei Co., Ltd. (number average particle size 4 μm)
(3) Carbon black (CB): “REGAL 660” (primary particle size: 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Aを69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。
Example 1
100 parts by mass of powdered liquid crystalline polyester A obtained in the above production example, 69 parts by mass of talc A, and 3 parts by mass of carbon black were mixed using a ribbon blender, and the mixture was mixed at 150 ° C. in an air oven. Dried 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.

(実施例2〜3及び比較例1〜5)
実施例1と同様に粉末状の液晶ポリエステル、タルク、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。

Figure 2009242453
(Examples 2-3 and Comparative Examples 1-5)
Similar to Example 1, except that powdered liquid crystal polyester, talc, and carbon black have the compositions described in Table 1, pellets of each liquid crystal polyester resin composition were prepared by the same equipment and operation method as in Example 1. Manufactured. 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.
Figure 2009242453

*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20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 occurrence of further fallen objects (in many cases, generation of 20 or more) 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1〜3)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1〜5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、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 3) of the present invention have a melt viscosity that falls 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 was high and the deflection temperature under load was high.
On the other hand, in the case of a resin composition that deviates from the specified range of the present invention as in Comparative Examples 1 to 5, at least one of the moldability, dropout, and deflection temperature under load 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 (3)

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50〜110質量部、カーボンブラック2〜100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10〜150Pa・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。 It is composed of 50 to 110 parts by mass of talc having a number average particle size of 10 to 50 μm and 2 to 100 parts by mass of carbon black with respect to 100 parts by mass of the liquid crystalline polyester, the deflection temperature under load is 220 ° C. or higher, and the shear rate is 100 sec −1. A liquid crystal polyester resin composition for a camera module, having a melt viscosity at 370 ° C. of 10 to 150 Pa · s. 射出成形により成形した成形品表面からの以下の定義による脱落物数が200個以下であることを特徴とする請求項1記載の液晶ポリエステル樹脂組成物。
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 objects from the surface of the molded product molded by injection molding is 200 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
請求項1または2記載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。   A camera module component produced by injection molding from the liquid crystal polyester resin composition according to claim 1 or 2.
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JP2011157422A (en) * 2010-01-29 2011-08-18 Sumitomo Chemical Co Ltd Liquid crystalline polyester composition, method for producing the same, and connector
JP2012107221A (en) * 2010-10-29 2012-06-07 Sumitomo Chemical Co Ltd Liquid crystal polyester composition
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