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JP3487656B2 - Electronic components for surface mounting - Google Patents

Electronic components for surface mounting

Info

Publication number
JP3487656B2
JP3487656B2 JP28632794A JP28632794A JP3487656B2 JP 3487656 B2 JP3487656 B2 JP 3487656B2 JP 28632794 A JP28632794 A JP 28632794A JP 28632794 A JP28632794 A JP 28632794A JP 3487656 B2 JP3487656 B2 JP 3487656B2
Authority
JP
Japan
Prior art keywords
phenylene
electronic component
surface mounting
mol
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
JP28632794A
Other languages
Japanese (ja)
Other versions
JPH08143654A (en
Inventor
達也 斉藤
幸彦 影山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Polyplastics Co Ltd
Original Assignee
Polyplastics Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Polyplastics Co Ltd filed Critical Polyplastics Co Ltd
Priority to JP28632794A priority Critical patent/JP3487656B2/en
Publication of JPH08143654A publication Critical patent/JPH08143654A/en
Application granted granted Critical
Publication of JP3487656B2 publication Critical patent/JP3487656B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481Disposition
    • H01L2224/48151Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48225Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H01L2224/48227Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation connecting the wire to a bond pad of the item
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/28Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H01L23/3107Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape the device being completely enclosed
    • H01L23/3135Double encapsulation or coating and encapsulation
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/19Details of hybrid assemblies other than the semiconductor or other solid state devices to be connected
    • H01L2924/191Disposition
    • H01L2924/19101Disposition of discrete passive components
    • H01L2924/19105Disposition of discrete passive components in a side-by-side arrangement on a common die mounting substrate

Landscapes

  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Polyamides (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は、半田耐熱性に優れた表
面実装用電子部品に関し、更に詳しくは、溶融時に光学
異方性を示す特定の共重合ポリエステルからなる、表面
実装する際の赤外線リフロー或いは半田浴浸漬時におけ
る膨れ(以後、ブリスター変形と言う)が少ない表面実
装用電子部品であり、更に本発明の共重合ポリエステル
は高温下での使用における接点汚染が少ないため、特に
表面実装用電子部品の中でもリレー用やスイッチ用とし
て好適に使用される。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electronic component for surface mounting having excellent solder heat resistance, and more specifically, an infrared ray for surface mounting which is made of a specific copolyester showing optical anisotropy when melted. It is an electronic component for surface mounting that has little swelling (hereinafter referred to as blister deformation) during reflow or immersion in a solder bath. Furthermore, since the copolyester of the present invention has little contact contamination during use at high temperatures, it is especially for surface mounting. Among electronic components, it is preferably used for relays and switches.

【0002】[0002]

【従来の技術及び発明が解決しようとする課題】表面実
装技術は、プリント基板等の基体に半導体、抵抗、コン
デンサー、コイル、スイッチ、リレー、コネクター等の
電子部品を固定し電子回路を形成する際に、固定および
回路形成の機能を持つ半田付けを電子部品のある基体の
表面より行うもので、これは赤外線リフロー炉に通した
り、溶融した半田浴に浸漬することで実現される。この
表面実装技術は、近年の電子回路の高集積化及び自動化
による省力化に伴い急激に採用が増加している。又、プ
リント基板、半導体、コネクター、リレー、スイッチ等
の電子部品は、成形性に優れる熱可塑性樹脂が多く使わ
れ、特に表面実装用電子部品には、成形性に加え耐熱性
に優れる溶融時に光学異方性を示す共重合ポリエステル
(液晶性ポリエステル)が用いられるようになってき
た。しかしながら、耐熱性に優れる液晶性ポリエステル
であっても、回路形成を行うために電子部品を赤外線リ
フロー炉に通したり、溶融した高温の半田浴に浸漬した
場合、電子部品を構成する液晶性ポリエステルの表面が
1mm2 〜数十cm2 の範囲で膨れ、いわゆるブリスター変
形を生じるという問題があった。それに加え、接点部分
の存在するスイッチ部品或いは密閉容器で構成されるリ
レー部品は、液晶性ポリエステルから発生する比較的高
温のガスが金属接点を汚染する原因となり、導通不良を
起こすことがしばしばあった。この問題を避けるため成
形後にパッケージ部品を高温条件下におきガスを揮発さ
せる方法等が行われているが、省力化の要請から高温乾
燥の必要のない表面実装リレー用等の電子部品が望まれ
ていた。
2. Description of the Related Art Surface mounting technology is used when an electronic circuit is formed by fixing electronic components such as semiconductors, resistors, capacitors, coils, switches, relays and connectors to a substrate such as a printed circuit board. In addition, soldering having a function of fixing and forming a circuit is performed from the surface of a substrate having an electronic component, which is realized by passing it through an infrared reflow furnace or immersing it in a molten solder bath. This surface mounting technology is rapidly increasing in adoption with the recent trend toward higher integration of electronic circuits and labor saving due to automation. Electronic components such as printed circuit boards, semiconductors, connectors, relays, switches, etc. are often made of thermoplastic resin with excellent moldability. Especially for surface mount electronic components, optical characteristics during melting, which has excellent heat resistance as well as moldability, are used. Copolyesters exhibiting anisotropy (liquid crystalline polyesters) have come to be used. However, even if the liquid crystalline polyester is excellent in heat resistance, if the electronic component is passed through an infrared reflow furnace to form a circuit or immersed in a molten high-temperature solder bath, the liquid crystalline polyester of the electronic component There is a problem that the surface swells in the range of 1 mm 2 to several tens of cm 2 and so-called blister deformation occurs. In addition, switch parts that have contact points or relay parts that consist of closed containers often cause metal contacts to be contaminated by the relatively high-temperature gas generated from liquid crystalline polyester, often causing poor conduction. . In order to avoid this problem, a method of volatilizing the gas by placing the package parts under high temperature conditions after molding has been performed, but due to the demand for labor saving, electronic parts for surface mount relays etc. that do not require high temperature drying are desired. Was there.

【0003】[0003]

【課題を解決するための手段】本発明者らは上記問題点
を解決し、半田耐熱性に優れる表面実装用電子部品を提
供するために鋭意研究努力した結果、通常液晶性ポリエ
ステルに必須と考えられていたp−ヒドロキシ安息香酸
を特定量以下に限定し、更に特定のモノマーを含む芳香
族共重合ポリエステルからなる電子部品を用いれば、表
面実装する際の赤外線リフロー処理時或いは半田浴浸漬
時におけるブリスター変形が少なく、且つ高温使用下で
の使用における接点汚染が少なく、表面実装スイッチあ
るいは表面実装リレー用部品として用いることが可能で
あることを見出し、本発明を完成するに至った。即ち本
発明は、構成成分として、下記一般式(1) 、(2) 、(3)
、(4) で表される構成単位を含み、全構成単位に対し
て、(1) の構成成分が0〜10mol %、(2)の構成成分が
0〜80 mol%、(3) の構成成分が2〜50 mol%、(4) の
構成成分が2〜50 mol%である溶融時に光学異方性を示
す共重合ポリエステルからなる表面実装用電子部品であ
る。 (1) -OC-Ar1-O- (2) -OC-Ar2-O- (3) -OC-Ar3-CO- (4) -O-Ar4-X- (ここでAr1 は、1,4 −フェニレンである。Ar2 は、2,
6 −ナフタレン、及びパラ位でつながるフェニレン数2
以上の化合物から選ばれた1種若しくは2種以上であ
る。Ar3 は、1,2 −フェニレン、1,3 −フェニレン、1,
4 −フェニレン、4,4'−ビフェニレン、2,6 −ナフタレ
ンより選ばれた1種若しくは2種以上である。Ar4 は、
1,3 −フェニレン、1,4 −フェニレン、2,6 −フェニレ
ン、及びフェニレン基がパラ位で結合したフェニレン数
2以上の化合物の残基から選ばれた1種若しくは2種以
上、又はパラ位のフェニレン間を-O- 、-CH2- 、-CO-、
-S- 、-SO-、-SO2- 、-CH3CCH3- 、-CF3CCF3- 及び-O-
(CH2)m-O- {m=2〜6}により結合された化合物から
選ばれた1種若しくは2種以上である。又、-X-は、-O-
及び-NH-より選ばれた1種若しくは2種以上であ
る。)上記(1) 〜(4) の構成単位を具現化するには、通
常のエステル形成能を有する種々の化合物が使用され
る。以下に本発明の表面実装用電子部品を構成する共重
合ポリエステルを形成するために必要な原料化合物につ
いて、順を追って詳しく説明する。
The inventors of the present invention have found that the liquid crystal polyester is usually essential as a result of diligent research efforts to solve the above problems and provide an electronic component for surface mounting having excellent solder heat resistance. By limiting the amount of p-hydroxybenzoic acid used to a specified amount to a specific amount or less and further using an electronic component made of an aromatic copolyester containing a specific monomer, it is possible to perform infrared reflow treatment during surface mounting or dipping in a solder bath. The inventors have found that they can be used as parts for surface-mounting switches or surface-mounting relays, with little blister deformation and little contact contamination during use at high temperatures, and have completed the present invention. That is, the present invention, as a constituent, the following general formula (1), (2), (3)
, Including the constitutional unit represented by (4), 0 to 10 mol% of the constitutional component of (1), 0 to 80 mol% of the constitutional component of (2), and (3) An electronic component for surface mounting comprising a copolyester having optical anisotropy when melted, wherein the constituent component is 2 to 50 mol% and the constituent component (4) is 2 to 50 mol%. (1) -OC-Ar 1 -O- (2) -OC-Ar 2 -O- (3) -OC-Ar 3 -CO- (4) -O-Ar 4 -X- (where Ar 1 is , 1,4-phenylene, and Ar 2 is 2,
6-naphthalene and phenylene number 2 connected in para position
One or more selected from the above compounds. Ar 3 is 1,2-phenylene, 1,3-phenylene, 1,
One or more selected from 4-phenylene, 4,4′-biphenylene and 2,6-naphthalene. Ar 4
1,3-phenylene, 1,4-phenylene, 2,6-phenylene, and one or more kinds selected from the residue of a compound having a phenylene group of 2 or more and having a phenylene group bonded at the para position, or the para position Between phenylene of -O-, -CH 2- , -CO-,
-S-, -SO-, -SO 2- , -CH 3 CCH 3- , -CF 3 CCF 3 -and -O-
(CH 2) is m -O- {m = 2~6} 1 kind or 2 or more selected from the combined compound. Also, -X- is -O-
And one or more selected from -NH-. In order to embody the constitutional units (1) to (4), various compounds having ordinary ester forming ability are used. The raw material compounds necessary for forming the copolyester constituting the surface mount electronic component of the present invention will be described in detail below in order.

【0004】上記構造単位(1) は、p−ヒドロキシ安息
香酸から生成したポリエステルの構成単位であり、全構
成単位に対して0〜10mol %配合される。驚くべきこと
に、この量が10mol %を越えると、適正な融点と十分な
熱変形温度を具備しているにもかかわらず、ブリスター
変形が著しくなり、また高温使用下での金属接点汚染性
が悪化する。構造単位(2) は、全構成単位に対して0〜
80mol %使用される。この量が80mol %を越えると融点
が上昇し、また著しいときはポリマー中に不溶不融物が
でき通常の成形機で目的の電子部品を成形するのが困難
となる。(2) 成分を構成するAr2 は、2,6 −ナフタレ
ン、及びパラ位でつながるフェニレン数2以上の化合物
から選ばれた1種若しくは2種以上である。構造単位
(3) は、全構成単位に対して2〜50mol %使用される。
この量が2mol %未満であると、(1) 及び(2) の構成成
分が上記の範囲、つまり構成単位(1)が全構成単位に対
して0〜10mol %、構成単位(2) が全構成単位に対して
0〜80mol %においては融点が上昇し通常の成形機で目
的の電子部品を成形するのが困難となる。またこの量が
50mol %を越えると構造単位(4) と実質的に等量でなく
なるため重合度が著しく低下するため好ましくない。
(3) 成分を構成するAr3 は、1,2 −フェニレン、1,3 −
フェニレン、1,4 −フェニレン、4,4'−ビフェニレン、
2,6 −ナフタレンより選ばれた1種若しくは2種以上で
ある。構造単位(4) は、全構成単位に対して2〜50mol
%使用される。この量が2mol %未満であると、(1) 及
び(2) の構成成分が上記の範囲、つまり構成単位(1)が
全構成単位に対して0〜10mol %、構成単位(2) が全構
成単位に対して0〜80mol %においては融点が上昇し通
常の成形機で目的の電子部品を成形するのが困難とな
る。またこの量が50mol %を越えると構造単位(3) と実
質的に等量でなくなるため重合度が著しく低下するため
好ましくない。(4) 成分を構成するAr4 は、1,3 −フェ
ニレン、1,4 −フェニレン、2,6 −フェニレン、及びフ
ェニレン基がパラ位で結合したフェニレン数2以上の化
合物の残基(例えば4,4'−ビフェニレン)から選ばれた
1種若しくは2種以上、又はパラ位のフェニレン間を-O
- (例えば4,4'−ジヒドロキシジフェニルエーテル)、
-CH2- (例えば4,4'−ジヒドロキシジフェニルメタ
ン)、-CO-(例えば4,4'−ジヒドロキシジフェニルケト
ン)、-S- (例えば4,4'−ジヒドロキシジフェニルスル
フィド)、-SO2- (例えば4,4'−ジヒドロキシジフェニ
ルスルホン)、-CH3CCH3- (例えば4,4'−イソプロピリ
デンジフェノール)、-CF3CCF3- (例えば4,4'−ヘキサ
フロロイソプロピリデンジフェノール)及び-O-(CH2)m-
O- {m =2〜6}(例えば4,4'−(エチレンジオキ
シ)ジフェノール)により結合された化合物から選ばれ
た1種若しくは2種以上である。また-X- は、-O- 及び
-NH-より選ばれた1種若しくは2種以上である。構造単
位(3) と構造単位(4) の夫々のモル比は上記の通り実質
的に等量でなくてはならないが、意図的に僅かに量を変
えることで共重合ポリエステルの重合度を制御すること
もできる。
[0004] The structural unit (1) is a structural unit of polyester produced from p- hydroxybenzoic acid, it is 0 10 mol% blended with respect to all the structural units. Surprisingly, when this amount exceeds 10 mol%, blister deformation becomes remarkable even though it has a proper melting point and sufficient heat distortion temperature, and the metal contact contamination property under high temperature use is high. Becomes worse. Structural unit (2) is 0 to all structural units.
Used at 80 mol%. When this amount exceeds 80 mol%, the melting point rises, and when it is remarkable, an insoluble and infusible substance is formed in the polymer, which makes it difficult to mold the intended electronic component with a normal molding machine. (2) Ar 2 constituting the component is one or two or more selected from 2,6-naphthalene and a compound having a phenylene number of 2 or more connected in the para position. Structural unit
(3) is used in an amount of 2 to 50 mol% based on all the constituent units.
When this amount is less than 2 mol%, the constituent components of (1) and (2) are in the above range, that is, the constituent unit (1) is 0 to 10 mol% based on all constituent units, and the constituent unit (2) is When the content is 0 to 80 mol% with respect to all the constituent units, the melting point rises, and it becomes difficult to mold the intended electronic component with a normal molding machine. Also this amount
When it exceeds 50 mol%, it is not substantially equivalent to the structural unit (4) and the degree of polymerization remarkably decreases, which is not preferable.
(3) Ar 3 constituting the component is 1,2-phenylene, 1,3-
Phenylene, 1,4-phenylene, 4,4'-biphenylene,
One or more selected from 2,6-naphthalene. Structural unit (4) is 2 to 50 mol based on all structural units
%used. When this amount is less than 2 mol%, the constituent components of (1) and (2) are in the above range, that is, the constituent unit (1) is 0 to 10 mol% based on all constituent units, and the constituent unit (2) is When the content is 0 to 80 mol% with respect to all the constituent units, the melting point rises, and it becomes difficult to mold the intended electronic component with a normal molding machine. On the other hand, if this amount exceeds 50 mol%, the amount is not substantially the same as that of the structural unit (3) and the degree of polymerization remarkably decreases, which is not preferable. (4) Ar 4 constituting the component is 1,3-phenylene, 1,4-phenylene, 2,6-phenylene, and a residue of a compound having a phenylene number of 2 or more in which a phenylene group is bonded at the para position (for example, 4 , 4'-biphenylene), or one or more kinds selected from (4'-biphenylene), or -O between para-phenylenes.
-(For example 4,4'-dihydroxydiphenyl ether),
-CH 2 - (e.g. 4,4'-dihydroxydiphenyl methane), - CO- (such as 4,4'-dihydroxydiphenyl ketone), - S- (such as 4,4'-dihydroxydiphenyl sulfide), - SO 2 - ( For example, 4,4′-dihydroxydiphenyl sulfone), —CH 3 CCH 3 — (eg 4,4′-isopropylidenediphenol), —CF 3 CCF 3 — (eg 4,4′-hexafluoroisopropylidenediphenol) And -O- (CH 2 ) m-
One or more selected from compounds bound by O- {m = 2 to 6} (for example, 4,4 '-(ethylenedioxy) diphenol). Also, -X- is -O- and
One or more selected from -NH-. The molar ratio of each of the structural unit (3) and the structural unit (4) must be substantially equal as described above, but the degree of polymerization of the copolyester can be controlled by intentionally changing the amount slightly. You can also do it.

【0005】 以上述べたように、本発明は構成単位
(1) の量を0〜10mol %に限定することにより、表面実
装する際のブリスター変形を抑制したものであるが、こ
の範囲において工業的に入手が容易な構成成分(2) 、
(3) 及び(4) の割合を限定することにより溶融加工性、
耐熱性及び機械的特性の全てに優れる共重合ポリエステ
ル及びその組成物を提供できたのである。たとえ、構成
成分(2) が80mol %以下であっても、構成成分(3) 及び
(4) が夫々2mol %未満であると、融点が著しく上昇
し、加工特性が非常に悪いものとなる。
As described above, the present invention is a structural unit
By limiting the amount of (1) to 0 to 10 mol%, the blister deformation during surface mounting is suppressed, but within this range industrially easily available component (2),
By limiting the proportions of (3) and (4), melt processability,
It was possible to provide a copolyester having excellent heat resistance and mechanical properties and a composition thereof. Even if the constituent component (2) is 80 mol% or less, the constituent component (3) and
If each of (4) is less than 2 mol%, the melting point remarkably rises and the processing characteristics become very poor.

【0006】本発明の共重合ポリエステルは、直接重合
法やエステル交換法を用いて重合され、重合に際して
は、通常、溶媒重合法や溶融重合法、スラリー重合法等
が用いられる。これらの重合に際しては、種々の触媒の
使用が可能であり、代表的なものは、ジアルキル錫酸化
物、ジアリール錫酸化物、二酸化チタン、アルコキシチ
タン珪酸塩類、チタンアルコラート類、カルボン酸のア
ルカリ及びアルカリ土類金属塩類、BF3 の如きルイス酸
塩等が挙げられる。触媒の使用量は、一般にはモノマー
全重量に基づいて、約 0.001乃至1重量%が好ましい。
これらの重合法により製造されたポリマーは、更に減圧
又は不活性ガス中で加熱する固相重合により分子量の増
加を図ることができる。
The copolyester of the present invention is polymerized by a direct polymerization method or a transesterification method, and in the polymerization, a solvent polymerization method, a melt polymerization method, a slurry polymerization method or the like is usually used. In these polymerizations, various catalysts can be used, and typical ones are dialkyl tin oxide, diaryl tin oxide, titanium dioxide, alkoxy titanium silicates, titanium alcoholates, carboxylic acid alkali and alkali. Examples thereof include earth metal salts and Lewis acid salts such as BF 3 . The amount of catalyst used is generally preferably about 0.001 to 1% by weight, based on the total weight of the monomers.
The polymers produced by these polymerization methods can be further increased in molecular weight by solid phase polymerization in which the polymer is further heated under reduced pressure or in an inert gas.

【0007】溶融時に、光学的異方性を示す液晶性ポリ
マーであることは、本発明において熱安定性と易加工性
を併せ持つ上で不可欠な要素である。溶融異方の性質
は、直交偏光子を利用した慣用の偏光検査方法により確
認することができる。より具体的には、溶融異方性の確
認は、オリンパス社製偏光顕微鏡を使用し、リンカム社
製ホットステージに載せた試料を溶融し、窒素雰囲気下
で 150倍の倍率で観察することにより実施できる。上記
ポリマーは、光学的に異方性であり、直交偏光子間に挿
入したとき光を透過させる。試料が光学的に異方性であ
ると、例えば溶融静止状態であっても偏光は透過する。
本発明の加工性の指標としては液晶性及び融点(液晶性
発現温度)が考えられる。液晶性を示すか否かは溶融時
の流動性に深く関わり、本願のポリエステルは溶融状態
で液晶性を示すことが不可欠である。ネマチックな液晶
性ポリマーは融点以上で著しく粘性低下を生じるので、
一般的に融点またはそれ以上の温度で液晶性を示すこと
が加工性の指標となる。融点(液晶転移温度)は、出来
得る限り高い方が耐熱性の観点からは好ましいが、ポリ
マーの溶融加工時の熱劣化や成形機の加工能力を考慮す
ると、350 ℃以下であることが望ましい目安となる。
又、少なくとも融点に10℃を加えた温度以上で樹脂の溶
融粘度が 1000sec-1の剪断速度下で1×105 ポイズ以下
であることが好ましい。更に好ましくは1×104 ポイズ
以下である。これらの溶融粘度は液晶性を具備すること
で概ね実現される。
A liquid crystalline polymer exhibiting optical anisotropy when melted is an essential element in the present invention for having both thermal stability and easy processability. The fused anisotropic property can be confirmed by a conventional polarization inspection method using a crossed polarizer. More specifically, the melt anisotropy is confirmed by using a polarizing microscope manufactured by Olympus, melting the sample placed on the hot stage manufactured by Rincom, and observing it under a nitrogen atmosphere at a magnification of 150 times. it can. The polymer is optically anisotropic and transmits light when inserted between crossed polarizers. If the sample is optically anisotropic, polarized light will be transmitted even if it is in a stationary state, for example.
Liquid crystallinity and melting point (liquid crystallinity manifesting temperature) are considered as indices of the processability of the present invention. Whether or not it exhibits liquid crystallinity is deeply related to the fluidity at the time of melting, and it is essential that the polyester of the present invention exhibits liquid crystalline property in the molten state. Since nematic liquid crystalline polymers cause a significant decrease in viscosity above the melting point,
Generally, the liquid crystallinity at the melting point or higher is an index of processability. The melting point (liquid crystal transition temperature) is preferably as high as possible from the viewpoint of heat resistance, but in consideration of thermal deterioration during polymer melt processing and the processing capacity of the molding machine, it is desirable that it be 350 ° C or less. Becomes
Further, it is preferable that the melt viscosity of the resin is 1 × 10 5 poise or less at a shear rate of 1000 sec −1 at a temperature equal to or higher than the temperature obtained by adding 10 ° C. to the melting point. More preferably, it is 1 × 10 4 poise or less. These melt viscosities are generally realized by having liquid crystallinity.

【0008】又、本発明では、使用目的に応じて、上記
共重合ポリエステルに各種の繊維状、粉粒状、板状の無
機及び有機の充填剤を配合することが望ましい。充填剤
の配合は、液晶性ポリエステルの異方性の低減、機械的
物性、耐熱性の向上等に優れた効果を示すが、従来の液
晶性ポリエステルでは充填剤を配合することによってか
えってブリスター変形は悪化していた。この問題を解決
した本発明の上記共重合ポリエステルは、ブリスター変
形もなく、各種物性を向上させる充填剤の配合を可能と
し、充填剤を配合した場合により顕著な効果を示す。繊
維状充填剤としてはガラス繊維、炭素繊維、アスベスト
繊維、シリカ繊維、シリカ・アルミナ繊維、ジルコニア
繊維、窒化硼素繊維、窒硅素繊維、硼素繊維、チタン酸
カリ繊維、更にステンレス繊維、アルミニウム、チタ
ン、銅、真鍮等、金属繊維状物などの無機質繊維状物質
が挙げられる。特に代表的な繊維状充填剤はガラス繊維
である。尚、ポリアミド、フッ素樹脂、ポリエステル樹
脂、アクリル樹脂等の高融点有機質繊維状物質も使用す
ることが出来る。一方、粉粒状充填剤としては、カーボ
ンブラック、黒鉛、シリカ、石英粉末、ガラスビーズ、
ミルドガラスファイバー、ガラスバルーン、ガラス粉、
硅素カルシウム、カオリン、タルク、クレー、硅藻土、
ウォラストナイトの如く硅素酸塩、酸化鉄、酸化チタ
ン、酸化亜鉛、三酸化アンチモン、アルミナの如く金属
の酸化物、炭酸カルシウム、炭酸マグネシウムの如く金
属の炭酸塩、硫酸カルシウム、硫酸バリウムの如く金属
の硫酸塩、その他フェライト、炭化珪素、窒化硅素、窒
化硼素、各種金属粉末等が挙げられる。又、板状充填剤
としては、マイカ、ガラスフレーク、各種の金属箔等が
挙げられる。有機充填剤の例を示せば芳香族ポリエステ
ル繊維、液晶性ポリマー繊維、芳香族ポリアミド繊維、
ポリイミド繊維等の耐熱性高強度合成繊維である。これ
らの無機及び有機充填剤は1種又は2種以上併用するこ
とが出来る。繊維状充填剤と粒状又は板状充填剤との併
用には特に機械的強度と寸法精度、電気的性質を兼備す
る上で好ましい組み合わせである。無機充填剤の配合量
は、組成物全量に対して80重量%以下、好ましくは1〜
60重量%である。これらの充填剤の使用にあたっては、
必要ならば収束剤又は表面処理剤を使用することが望ま
しい。
Further, in the present invention, it is desirable to add various fibrous, powdery or plate-like inorganic and organic fillers to the above-mentioned copolyester according to the purpose of use. The compounding of the filler shows an excellent effect in reducing the anisotropy of the liquid crystalline polyester, improving the mechanical properties, the heat resistance, etc., but in the conventional liquid crystalline polyester, the blister deformation is rather caused by the compounding of the filler. It was getting worse. The above-mentioned copolyester of the present invention, which has solved this problem, allows the blending of a filler to improve various physical properties without blister deformation, and exhibits a remarkable effect when the filler is blended. As the fibrous filler, glass fiber, carbon fiber, asbestos fiber, silica fiber, silica-alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate fiber, stainless steel fiber, aluminum, titanium, Inorganic fibrous substances such as copper and brass and metallic fibrous substances can be mentioned. A particularly representative fibrous filler is glass fiber. In addition, high-melting-point organic fibrous substances such as polyamide, fluororesin, polyester resin, and acrylic resin can also be used. On the other hand, as the particulate filler, carbon black, graphite, silica, quartz powder, glass beads,
Milled glass fiber, glass balloon, glass powder,
Calcium silicon, kaolin, talc, clay, diatomaceous earth,
Wollastonite such as silicate, iron oxide, titanium oxide, zinc oxide, antimony trioxide, metal oxide such as alumina, metal carbonate such as calcium carbonate and magnesium carbonate, metal such as calcium sulfate and barium sulfate. And other ferrites, silicon carbide, silicon nitride, boron nitride, various metal powders, and the like. Examples of the plate-shaped filler include mica, glass flakes, various metal foils and the like. Aromatic polyester fiber, liquid crystalline polymer fiber, aromatic polyamide fiber,
It is a heat-resistant and high-strength synthetic fiber such as polyimide fiber. These inorganic and organic fillers can be used alone or in combination of two or more. The combined use of the fibrous filler and the granular or plate-like filler is a preferable combination particularly in terms of mechanical strength, dimensional accuracy and electrical properties. The content of the inorganic filler is 80% by weight or less based on the total amount of the composition, preferably 1 to
60% by weight. When using these fillers,
If desired, it is desirable to use a sizing agent or a surface treatment agent.

【0009】更に本発明のポリエステルには、本発明の
企図する目的を損なわない範囲で他の熱可塑性樹脂を補
助的に添加してもよい。この場合に使用する熱可塑性樹
脂の例を示すと、ポリエチレン、ポリプロピレンなどの
ポリオレフィン、ポリエチレンテレフタレート、ポリブ
チレンテレフタレート等の芳香族ジカルボン酸とジオー
ル等からなる芳香族ポリエステル、ポリアセタール(ホ
モ又はコポリマー)、ポリスチレン、ポリ塩化ビニル、
ポリアミド、ホリカーボネート、ABS、ポリフェニレ
ンオキシド、ポリフェニレンスルフィド、フッ素樹脂等
を挙げることが出来る。又、これらの熱可塑性樹脂は2
種以上混合して使用することが出来る。又、熱可塑性ポ
リマーに通常用いられる酸化防止剤(例えばトリデシル
フォスファイト等のリン化合物、又は商品名イルガノッ
クス1010等のヒンダードフェノールを含む化合物
等)、滑剤(例えばステアリルアルコール、ポリエチレ
ンワックス等)、難燃剤(例えば臭素化ビスフェノール
A等のハロゲン化合物や、有機リン化合物からなるポリ
マーや、三酸化アンチモンなどのアンチモン化合物等)
等の当業界周知な添加物の使用は目的に応じて選択使用
することができる。
Further, to the polyester of the present invention, other thermoplastic resin may be supplementarily added within a range not impairing the intended purpose of the present invention. Examples of thermoplastic resins used in this case include polyolefins such as polyethylene and polypropylene, aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate, and aromatic polyesters such as diols, polyacetals (homo or copolymers), and polystyrene. ,PVC,
Examples thereof include polyamide, polycarbonate, ABS, polyphenylene oxide, polyphenylene sulfide, and fluororesin. In addition, these thermoplastic resins are
A mixture of two or more species can be used. In addition, antioxidants (for example, phosphorus compounds such as tridecyl phosphite, or compounds containing hindered phenol such as trade name Irganox 1010) commonly used for thermoplastic polymers, lubricants (for example, stearyl alcohol, polyethylene wax, etc.) Flame retardants (for example, halogen compounds such as brominated bisphenol A, polymers composed of organic phosphorus compounds, antimony compounds such as antimony trioxide, etc.)
The use of additives well known in the art such as can be selected and used according to the purpose.

【0010】[0010]

【発明の効果】本発明で得られる特定の構成単位よりな
る共重合ポリエステルからなる、例えばプリント基板、
半導体、抵抗、コンデンサー、コイル、スイッチ、リレ
ー、コネクター等の電子部品は、表面実装の赤外線リフ
ロー処理時或いは半田浴浸漬時のブリスター変形が少な
く、良好な回路部品を構成できる。本発明の共重合ポリ
エステルを用いた表面実装用電子部品は、高温下での使
用における接点汚染が少ないため、特にリレー用やスイ
ッチ用として好適である。
EFFECTS OF THE INVENTION A copolyester comprising a specific constitutional unit obtained in the present invention, such as a printed circuit board,
Electronic parts such as semiconductors, resistors, capacitors, coils, switches, relays and connectors are less likely to be blister-deformed during surface mounting infrared reflow treatment or immersion in a solder bath, and can form good circuit parts. The surface-mounting electronic component using the copolyester of the present invention is particularly suitable for relays and switches because it has less contact contamination when used at high temperatures.

【0011】[0011]

【実施例】以下に実施例をもって本発明を更に詳しく説
明するが、本発明はこれらに限定されるものではない。 実施例1 表1に示す如く、パラヒドロキシ安息香酸1343g、テレ
フタル酸 889g、1,4−ジヒドロキシベンゼン 589g、
無水酢酸1822g及び最終理論ポリマー収量2500gに対し
て0.05重量%の酢酸カリウムを、攪拌機、窒素導入管及
び留出管を備えた反応器に仕込み、反応器内を窒素にて
置換した後、窒素気流下で、この混合物を 140℃にて1
時間反応させた。この後 2.5時間で 270℃まで加熱し
た。この時酢酸が約2020g留出した。次に、更に300 ℃
まで2時間で昇温した。その時までに、理論酢酸留出量
の95%以上が留出した。次に 350℃まで1時間で昇温し
た後、反応容器内を徐々に減圧し、さらに0.5 時間で1
mmHg以下に減圧し、この圧力にて35粉間反応を行った。
この減圧中に、少量の酢酸が留出した。そして、反応終
了後窒素を導入し、内容物を取り出したところ得られた
重合物は淡黄白色であり、パーキンエルマー社製DSC
にて測定した融点は、329 ℃であった。又、オリンパス
社製偏光顕微鏡にて、リンカム社製ホットステージ上で
重合物をクロスニコル下で加熱観察したところ融点以上
ではネマチック性液晶パターンを示した。次に得られた
重合体を押出機にてガラス繊維30重量%と常法に従って
混合押出し、ペレット化した樹脂組成物を調製した。こ
のペレットから、射出成形及び一般的なコネクター用金
型によりコネクター部品を成形した。このコネクターサ
ンプルを250 ℃から340 ℃まで、10℃おきに設定された
溶融半田浴にそれぞれ10秒間浸漬した後、表面を観察
し、ブリスター変形が確認された温度またはコネクター
部品の変形した温度より10℃低い温度を半田耐熱温度と
した。この実施例で得た部品は、ブリスター変形は発生
せず、330 ℃で変形したので半田耐熱温度は320 ℃であ
った。又、上記の如く調製したペレットから、射出成形
及び一般的なIC封止用金型でIC封止を行いICを作
成し、同様に半田耐熱温度を調べた。次に、上記の如く
調製したペレットから、射出成形及び一般的なリレー用
金型によりリレー部品を作成した。金属接点には、銀−
パラジウム合金を使用した。このサンプルを160 ℃の恒
温槽におき、金属接点の汚染状況を観察した。汚染状況
は5点満点法で評価し、3日後、1週間後、2週間後の
状況を観察したところ、表1に示す如く、それぞれ5
点、4点、4点と殆ど汚染されなかった。
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 As shown in Table 1, 1343 g of para-hydroxybenzoic acid, 889 g of terephthalic acid, 589 g of 1,4-dihydroxybenzene,
1822 g of acetic anhydride and 0.05 g of potassium acetate based on the final theoretical polymer yield of 2500 g were charged into a reactor equipped with a stirrer, a nitrogen introducing pipe and a distilling pipe, and the inside of the reactor was replaced with nitrogen, and then a nitrogen stream was supplied. Under this mixture at 140 ℃ 1
Reacted for hours. This was followed by heating to 270 ° C in 2.5 hours. At this time, about 2020 g of acetic acid was distilled. Then another 300 ° C
Up in 2 hours. By that time, more than 95% of the theoretical acetic acid distillate had distilled. Next, after raising the temperature to 350 ° C in 1 hour, the pressure inside the reaction vessel was gradually reduced, and the temperature was increased to 1 hour in 0.5 hour.
The pressure was reduced to less than mmHg, and 35 powder reaction was performed at this pressure.
During this vacuum, a small amount of acetic acid distilled out. Then, after the reaction was completed, nitrogen was introduced, and the content was taken out. The obtained polymer was pale yellowish white, and DSC manufactured by Perkin Elmer Co., Ltd.
The melting point measured by C. was 329.degree. Further, when the polymer was heated and observed under a crossed Nicol on a hot stage manufactured by Rincom under a polarizing microscope manufactured by Olympus, a nematic liquid crystal pattern was exhibited at a melting point or higher. Next, the obtained polymer was mixed and extruded with 30% by weight of glass fiber in an extruder according to a conventional method to prepare a pelletized resin composition. Connector parts were molded from the pellets by injection molding and a general connector mold. After immersing this connector sample in a molten solder bath set at 10 ° C intervals from 250 ° C to 340 ° C for 10 seconds, observe the surface and check the temperature at which blister deformation was confirmed or the temperature at which connector parts were deformed for 10 seconds. The temperature lower by ℃ was used as the solder heat resistance temperature. The parts obtained in this example did not undergo blister deformation and were deformed at 330 ° C., so the solder heat resistance temperature was 320 ° C. Further, the pellets prepared as described above were injection-molded and IC-sealed with a general IC-sealing die to prepare an IC, and the soldering heat resistance temperature was similarly examined. Next, relay parts were prepared from the pellets prepared as described above by injection molding and a general relay mold. For metal contacts, silver-
A palladium alloy was used. This sample was placed in a constant temperature bath at 160 ° C. and the state of contamination of metal contacts was observed. The pollution situation was evaluated by a 5-point scale, and the situation after 3 days, 1 week, and 2 weeks was observed.
There was almost no contamination with points, 4 points and 4 points.

【0012】実施例2〜6 実施例1と同様の方法で表1に記載の原料モノマーと構
成比率にて共重合ポリエステルを合成し、更に組成物に
対し30重量%となるようにガラス繊維を配合し、実施例
1と同様にコネクター部品、IC、リレー部品を作成
し、評価した。半田耐熱試験では、表1に示すように何
れも融点とほぼ同じ温度で変形が起きるが、ブリスター
変形は発生しなかった、又、接点汚染試験においても、
いずれも優れていた。
Examples 2 to 6 Copolyesters were synthesized in the same manner as in Example 1 with the raw material monomers shown in Table 1 in the composition ratio, and glass fibers were further added so that the content of the composition was 30% by weight. The components were blended, and connector parts, ICs, and relay parts were prepared and evaluated in the same manner as in Example 1. In the solder heat resistance test, as shown in Table 1, in all cases, deformation occurred at almost the same temperature as the melting point, but no blister deformation occurred. Also, in the contact contamination test,
Both were excellent.

【0013】比較例1〜6 実施例1と同様の方法で表2に記載の原料モノマーと構
成比率にて共重合ポリエステルを合成し、更に組成物に
対し30重量%となるようにガラス繊維を配合し、実施例
1と同様にコネクター部品、IC、リレー部品を作成
し、評価した。表2に示すように何れも融点よりかなり
低い温度でブリスター変形が発生し、接点汚染性も劣っ
ていた。また、比較例5及び6では、共重合ポリエステ
ルの重合中に高融点化により著しく粘度が上昇し、良好
な重合体が得られず評価できなかった。
Comparative Examples 1 to 6 Copolyesters were synthesized in the same manner as in Example 1 with the raw material monomers shown in Table 2 in the compositional ratio, and glass fibers were further added so as to be 30% by weight with respect to the composition. The components were blended, and connector parts, ICs, and relay parts were prepared and evaluated in the same manner as in Example 1. As shown in Table 2, in all cases, blister deformation occurred at a temperature considerably lower than the melting point, and contact contamination was inferior. Further, in Comparative Examples 5 and 6, the viscosity was remarkably increased due to the increase in the melting point during the polymerization of the copolyester, and a good polymer was not obtained, which could not be evaluated.

【0014】[0014]

【表1】 [Table 1]

【0015】[0015]

【表2】 [Table 2]

【0016】(表の注) TPA :テレフタル酸 NDA :2,6 −ナフタレンジカルボン酸 BBA :4,4'−ビフェニルジカルボン酸 HQ :1,4 −ジヒドロキシベンゼン BP :4,4'−ジヒドロキシビフェニル PAP :4−アミノフェノール HBA :4−ヒドロキシ安息香酸 HNA :2−ヒドロキシ6−ナフトエ酸 N/A :融点が高すぎ成形体が得られず評価できない。(Note to table) TPA: terephthalic acid NDA: 2,6-naphthalenedicarboxylic acid BBA: 4,4'-biphenyldicarboxylic acid HQ: 1,4-dihydroxybenzene BP: 4,4'-dihydroxybiphenyl PAP: 4-aminophenol HBA: 4-hydroxybenzoic acid HNA: 2-hydroxy 6-naphthoic acid N / A: Melting point is too high to obtain a molded product, which cannot be evaluated.

───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7,DB名) C08G 63/00 - 63/91 C08G 69/44 ─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. 7 , DB name) C08G 63/00-63/91 C08G 69/44

Claims (5)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 構成成分として、下記一般式(1) 、(2)
、(3) 、(4) で表される構成単位を含み、全構成単位
に対して、(1) の構成成分が0〜10mol %、(2) の構成
成分が0〜80 mol%、(3) の構成成分が2〜50 mol%、
(4) の構成成分が2〜50 mol%である溶融時に光学異方
性を示す共重合ポリエステルからなる表面実装用電子部
品。 (1) -OC-Ar1-O- (2) -OC-Ar2-O- (3) -OC-Ar3-CO- (4) -O-Ar4-X- (ここでAr1 は、1,4 −フェニレンである。Ar2 は、2,
6 −ナフタレン、及びパラ位でつながるフェニレン数2
以上の化合物から選ばれた1種若しくは2種以上であ
る。Ar3 は、1,2 −フェニレン、1,3 −フェニレン、1,
4 −フェニレン、4,4'−ビフェニレン、2,6 −ナフタレ
ンより選ばれた1種若しくは2種以上である。Ar4 は、
1,3 −フェニレン、1,4 −フェニレン、2,6 −フェニレ
ン、及びフェニレン基がパラ位で結合したフェニレン数
2以上の化合物の残基から選ばれた1種若しくは2種以
上、又はパラ位のフェニレン間を-O- 、-CH2- 、-CO-、
-S- 、-SO-、-SO2- 、-CH3CCH3- 、-CF3CCF3- 及び-O-
(CH2)m-O- {m=2〜6}により結合された化合物から
選ばれた1種若しくは2種以上である。又、-X-は、-O-
及び-NH-より選ばれた1種若しくは2種以上であ
る。)
1. The following general formulas (1) and (2) are used as constituent components.
, (3), including the structural units represented by (4), the composition of (1) is 0 to 10 mol%, the composition of (2) is 0 to 80 mol% with respect to all the structural units. The component of (3) is 2 to 50 mol%,
An electronic component for surface mounting comprising a copolyester which exhibits optical anisotropy when melted, wherein the constituent component of (4) is 2 to 50 mol%. (1) -OC-Ar 1 -O- (2) -OC-Ar 2 -O- (3) -OC-Ar 3 -CO- (4) -O-Ar 4 -X- (where Ar 1 is , 1,4-phenylene, and Ar 2 is 2,
6-naphthalene and phenylene number 2 connected in para position
One or more selected from the above compounds. Ar 3 is 1,2-phenylene, 1,3-phenylene, 1,
One or more selected from 4-phenylene, 4,4′-biphenylene and 2,6-naphthalene. Ar 4
1,3-phenylene, 1,4-phenylene, 2,6-phenylene, and one or more kinds selected from the residue of a compound having a phenylene group of 2 or more and having a phenylene group bonded at the para position, or the para position Between phenylene of -O-, -CH 2- , -CO-,
-S-, -SO-, -SO 2- , -CH 3 CCH 3- , -CF 3 CCF 3 -and -O-
(CH 2) is m -O- {m = 2~6} 1 kind or 2 or more selected from the combined compound. Also, -X- is -O-
And one or more selected from -NH-. )
【請求項2】 (2) の構成成分において、Ar2が2,6 −
ナフタレンである請求項1記載の表面実装用電子部品。
2. In the constituent component (2), Ar 2 is 2,6-
Surface mount electronic component according to claim 1 Symbol placement is naphthalene.
【請求項3】 請求項1又は2記載の共重合ポリエステ
ルに無機充填剤 80 重量%以下(対組成物全量)を配合し
たポリエステル樹脂組成物からなる表面実装用電子部
品。
3. The copolymerized polyester according to claim 1 or 2.
80 % by weight or less of inorganic filler (based on the total amount of the composition)
Electronic component for surface mounting comprising the polyester resin composition .
【請求項4】 表面実装用電子部品がリレー用電子部品
である請求項1〜3の何れか1項記載の表面実装用電子
部品。
4. The surface mounting electronic component is a relay electronic component.
The electronic component for surface mounting according to any one of claims 1 to 3 .
【請求項5】 表面実装用電子部品がスイッチ用電子部
品である請求項1〜3の何れか1項記載の表面実装用電
子部品。
5. The surface mounting electronic component is an electronic part for a switch.
The electronic component for surface mounting according to any one of claims 1 to 3, which is a product .
JP28632794A 1994-11-21 1994-11-21 Electronic components for surface mounting Expired - Fee Related JP3487656B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP28632794A JP3487656B2 (en) 1994-11-21 1994-11-21 Electronic components for surface mounting

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP28632794A JP3487656B2 (en) 1994-11-21 1994-11-21 Electronic components for surface mounting

Publications (2)

Publication Number Publication Date
JPH08143654A JPH08143654A (en) 1996-06-04
JP3487656B2 true JP3487656B2 (en) 2004-01-19

Family

ID=17702958

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JP3487656B2 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6132884A (en) * 2000-01-14 2000-10-17 Ticona Llc Process for producing amorphous anisotrophic melt-forming polymers having a high degree of stretchability and polymers produced by same
TWI359159B (en) 2003-11-05 2012-03-01 Sumitomo Chemical Co Aromatic liquid-crystalline polyester
JP4302508B2 (en) * 2003-12-26 2009-07-29 ポリプラスチックス株式会社 Conductive resin composition
JP2005213418A (en) * 2004-01-30 2005-08-11 Sumitomo Chemical Co Ltd Liquid crystal polyester resin composition
JP4625340B2 (en) * 2005-01-31 2011-02-02 上野製薬株式会社 Liquid crystal polyester resin and method for producing the same
JP4950441B2 (en) * 2005-05-31 2012-06-13 住友化学株式会社 Liquid crystal polyester, liquid crystal polyester solution, method for improving solubility of liquid crystal polyester, liquid crystal polyester film, and method for producing the same.
JP5230122B2 (en) * 2007-05-14 2013-07-10 上野製薬株式会社 Electronic components for surface mounting
JP5032958B2 (en) * 2007-11-28 2012-09-26 ポリプラスチックス株式会社 Totally aromatic polyester and polyester resin composition
JP2009280831A (en) * 2009-08-31 2009-12-03 Sumitomo Chemical Co Ltd Liquid-crystalline polyester solution composition
JP6626358B2 (en) * 2016-02-04 2019-12-25 Jxtgエネルギー株式会社 Wholly aromatic liquid crystal polyester resin and method for producing the same
CN110177821B (en) * 2017-01-26 2020-03-24 宝理塑料株式会社 Wholly aromatic polyester and polyester resin composition
WO2022210967A1 (en) * 2021-03-30 2022-10-06 ポリプラスチックス株式会社 Wholly aromatic polyester and polyester resin composition

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