TW202028365A - Liquid crystalline resin composition and connector including molded article of said liquid crystalline resin composition - Google Patents

Liquid crystalline resin composition and connector including molded article of said liquid crystalline resin composition Download PDF

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TW202028365A
TW202028365A TW108140944A TW108140944A TW202028365A TW 202028365 A TW202028365 A TW 202028365A TW 108140944 A TW108140944 A TW 108140944A TW 108140944 A TW108140944 A TW 108140944A TW 202028365 A TW202028365 A TW 202028365A
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resin composition
liquid crystalline
crystalline resin
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深津博樹
松村卓馬
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日商寶理塑料股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/10—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/46—Bases; Cases

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Abstract

Provided are: a liquid crystalline resin composition having good fluidity, whereby it is possible to manufacture a connector which has excellent heat resistance and mechanical strength, and in which warpage is suppressed; and a connector including a molded article of the liquid crystalline resin composition. The liquid crystalline resin composition pertaining to the present invention includes a liquid crystalline resin (A), fibrous wollastonite (B), and mica (C), the aspect ratio of the fibrous wollastonite (B) being at least 8, the content of the liquid crystalline resin (A) being 62.5-72.5% by mass, the content of the fibrous wollastonite (B) being 2.5-15% by mass, the content of the mica (C) being 17.5-30% by mass, and the total content of the fibrous wollastonite (B) and the mica (C) being 27.5-37.5% by mass with respect to the liquid crystalline resin composition as a whole.

Description

液晶性樹脂組合物及包含該液晶性樹脂組合物的成型品的連接器Liquid crystal resin composition and connector of molded article containing the liquid crystal resin composition

本發明係有關於液晶性樹脂組合物、及包含該液晶性樹脂組合物的成型品的連接器。The present invention relates to a connector of a liquid crystal resin composition and a molded article containing the liquid crystal resin composition.

液晶性樹脂係具有優異的尺寸精度、流動性等的熱塑性樹脂。由於具有上述特性，因此液晶性樹脂以往經常用來作為各種電子部件的材料。The liquid crystalline resin is a thermoplastic resin having excellent dimensional accuracy and fluidity. Because of the above characteristics, liquid crystalline resins have been used as materials for various electronic components.

特別是，近年來隨著電子設備的小型化及薄型化，構成電子設備的電子部件（連接器（connector）等）產生了薄化及截距窄化的需求。例如，專利文獻1公開了一種由利用雲母（Mica）及玻璃纖維使之強化的液晶性樹脂組合物所構成並成型的連接器。上述連接器，使用作為要求耐熱性、翹曲變形的抑制、流動性、尺寸穩定性等之基板對基板連接器、或連接可撓性印刷電路板（Flexible printed circuit，FPC）和可撓性扁平電纜（Flexible flat cable，FFC）所使用的可撓性印刷電路板用連接器等。 [現有技術文獻] [專利文獻]In particular, with the miniaturization and thinning of electronic devices in recent years, there has been a demand for thinning and narrowing of the intercept of electronic components (connectors, etc.) constituting the electronic devices. For example, Patent Document 1 discloses a connector formed and molded of a liquid crystalline resin composition reinforced with Mica and glass fibers. The above-mentioned connector is used as a board-to-board connector that requires heat resistance, suppression of warpage deformation, fluidity, dimensional stability, etc., or for connecting flexible printed circuit (FPC) and flexible flat Connectors for flexible printed circuit boards used in cables (Flexible flat cable, FFC). [Prior Art Literature] [Patent Literature]

[專利文獻1] 日本專利特開第2006-37061號公報[Patent Document 1] Japanese Patent Laid-Open No. 2006-37061

[發明所欲解決的課題][The problem to be solved by the invention]

然而，當試圖利用以往的液晶性樹脂組合物進行成型以作為連接器時，組合物的耐熱性、機械強度、翹曲變形的抑制、及流動性並不足，而且加工性差，因此難以製造出滿足對於薄化及截距窄化的需求之薄化窄截距連接器。However, when trying to use the conventional liquid crystalline resin composition for molding as a connector, the composition has insufficient heat resistance, mechanical strength, suppression of warpage deformation, and fluidity, and poor processability, so it is difficult to produce satisfactory products. Thinned and narrow-intercept connectors for thinning and narrowing of the intercept.

本發明係有鑑於上述情況而完成的，目的在於提供一種具有優異的耐熱性及機械強度、能夠實現在製造連接器的期間可抑制翹曲變形、流動性良好之液晶性樹脂組合物，以及提供包括該液晶性樹脂組合物的成型品的連接器。 [用於解決課題的手段]The present invention has been completed in view of the above circumstances, and aims to provide a liquid crystalline resin composition with excellent heat resistance and mechanical strength, capable of suppressing warpage and good fluidity during connector manufacturing, and providing A connector including a molded article of the liquid crystal resin composition. [Means used to solve the problem]

本發明人發現以預定的含量組合液晶性樹脂、纖維狀矽灰石、和雲母，且將纖維狀矽灰石的長寬比設定為介於預定的範圍內，能夠解決上述的問題。具體而言，本發明提供以下等內容。The inventors found that combining the liquid crystal resin, fibrous wollastonite, and mica at a predetermined content and setting the aspect ratio of the fibrous wollastonite within a predetermined range can solve the above-mentioned problem. Specifically, the present invention provides the following contents.

（1）一種液晶性樹脂組合物，其係包括（A）液晶性樹脂、（B）纖維狀矽灰石及（C）雲母之液晶性樹脂組合物，其中前述（B）纖維狀矽灰石的長寬比為8以上，且其中相對於前述液晶性樹脂組合物的整體，前述（A）液晶性樹脂的含量為62.5～72.5質量％，前述（B）纖維狀矽灰石的含量為2.5～15質量％，前述（C）雲母的含量為17.5～30質量％，且前述（B）纖維狀矽灰石及前述（C）雲母的總含量為27.5～37.5質量％。(1) A liquid crystal resin composition comprising (A) liquid crystal resin, (B) fibrous wollastonite and (C) mica, wherein the aforementioned (B) fibrous wollastonite The aspect ratio is 8 or more, and the content of the liquid crystal resin (A) is 62.5 to 72.5% by mass relative to the whole liquid crystal resin composition, and the content of the fibrous wollastonite (B) is 2.5 ~15% by mass, the content of the aforementioned (C) mica is 17.5 to 30% by mass, and the total content of the aforementioned (B) fibrous wollastonite and the aforementioned (C) mica is 27.5 to 37.5% by mass.

（2）如（1）所述之液晶性樹脂組合物，其係用於產品總長度未滿30mm、產品高度未滿5mm之連接器。(2) The liquid crystal resin composition as described in (1), which is used for connectors with a total product length of less than 30mm and a product height of less than 5mm.

（3）一種連接器，其包括如（1）或（2）所述之液晶性樹脂組合物的成型品，且產品總長度未滿30mm、產品高度未滿5mm。(3) A connector comprising a molded product of the liquid crystal resin composition as described in (1) or (2), and the total product length is less than 30 mm and the product height is less than 5 mm.

（4）如（3）所述之連接器，其係薄化窄截距連接器。(4) The connector described in (3), which is a thinner and narrow-intercept connector.

（5）如（3）或（4）所述之連接器，其係基板對基板的連接器或可撓性刷電路板用連接器之薄化窄截距連接器，其中截距之間的距離為0.5mm以下，產品總長度為3.5mm以上未滿30mm，且產品高度為1.5mm以下。 [本發明的效果](5) The connector as described in (3) or (4), which is a substrate-to-substrate connector or a thinned narrow-intercept connector of a flexible brushed circuit board connector, where the distance between the intercepts The distance is 0.5mm or less, the total product length is 3.5mm or more but less than 30mm, and the product height is 1.5mm or less. [Effects of the invention]

根據本發明，提供了一種具有優異的耐熱性及機械強度、能夠實現在製造連接器的期間可抑制翹曲變形、流動性良好之液晶性樹脂組合物，以及提供包括該液晶性樹脂組合物的成型品的連接器。According to the present invention, there is provided a liquid crystalline resin composition having excellent heat resistance and mechanical strength, capable of suppressing warpage and good fluidity during connector manufacturing, and providing a liquid crystalline resin composition comprising the liquid crystalline resin composition Connectors for molded products.

以下，對於本發明的實施形態進行具體的說明。Hereinafter, the embodiment of the present invention will be specifically described.

[液晶性樹脂組合物] 根據本發明的液晶性樹脂組合物，包括各自為預定含量的液晶性樹脂、纖維狀矽灰石、和雲母，且纖維狀矽灰石的長寬比為8以上。以下，針對構成根據本發明的液晶性樹脂組合物之成分進行說明。[Liquid crystal resin composition] The liquid crystalline resin composition according to the present invention includes a liquid crystalline resin, fibrous wollastonite, and mica each in a predetermined content, and the aspect ratio of the fibrous wollastonite is 8 or more. Hereinafter, the components constituting the liquid crystal resin composition according to the present invention will be described.

[（A）液晶性樹脂] 在本發明中所使用的（A）液晶性樹脂，係指具有能夠形成光學異向性熔融相的性質之熔融加工性聚合物。異向性熔融相的性質，能夠藉由常用的使用正交偏振器之偏振檢查方法進行確認。更具體而言，能夠藉由使用萊茲（Leitz）偏振顯微鏡，在氮氣氣氛中以40倍的放大倍率觀察放置於萊茲熱載台（hot stage）上的熔融樣品，以確認異向性熔融相。當適用於本發明的液晶性樹脂在正交偏振器之間進行檢查時，即使在熔融的靜止狀態下，偏振光也會正常地透射，表現出光學異向性。[(A) Liquid crystal resin] The (A) liquid crystalline resin used in the present invention refers to a melt processable polymer having the property of forming an optically anisotropic melt phase. The properties of the anisotropic melt phase can be confirmed by the commonly used polarization inspection method using crossed polarizers. More specifically, by using a Leitz polarizing microscope, the molten sample placed on the Leitz hot stage can be observed at 40 times magnification in a nitrogen atmosphere to confirm anisotropic melting phase. When the liquid crystalline resin suitable for the present invention is inspected between crossed polarizers, even in a molten static state, polarized light is normally transmitted and exhibits optical anisotropy.

作為如以上述之（A）液晶性樹脂的種類，並沒有特別限定，以芳香族聚酯及/或芳香族聚酯醯胺為佳。再者，在同一分子鏈中局部地含有芳香族聚酯及/或芳香族聚酯醯胺之聚酯也可列於上述範圍內。作為（A）液晶性樹脂，以使用當在60°C下以0.1質量％的濃度溶於五氟苯酚（pentafluorophenol）中時具有至少大約為2.0dl/g的對數黏度（I V ）之液晶性樹脂為佳，且以使用具有2.0～10.0dl/g的對數黏度（I V ）之液晶性樹脂為更佳。The type of the liquid crystal resin (A) mentioned above is not particularly limited, but aromatic polyester and/or aromatic polyester amide is preferred. Furthermore, polyesters partially containing aromatic polyester and/or aromatic polyesteramide in the same molecular chain may also be included in the above range. As (A) the liquid crystal resin, a liquid crystal resin having a logarithmic viscosity (IV) of at least about 2.0dl/g when dissolved in pentafluorophenol at a concentration of 0.1% by mass at 60°C is used Preferably, it is more preferable to use a liquid crystal resin having a logarithmic viscosity (IV) of 2.0 to 10.0 dl/g.

作為適用於本發明的（A）液晶性樹脂之芳香族聚酯或芳香族聚酯醯胺，以具有衍生自芳香族羥基羧酸的重複單元作為構成成分之芳香族聚酯或芳香族聚酯醯胺為特佳。As the aromatic polyester or aromatic polyester amide suitable for the liquid crystal resin (A) of the present invention, an aromatic polyester or aromatic polyester having a repeating unit derived from an aromatic hydroxycarboxylic acid as a constituent component Amide is particularly preferred.

更具體而言，可列舉出 （1）主要為由衍生自1種或2種以上的芳香族羥基羧酸及其衍生物之重複單元所構成的聚酯； （2）主要為由（a）衍生自1種或2種以上的芳香族羥基羧酸及其衍生物之重複單元、和（b）衍生自1種或2種以上的芳香族二羧酸、脂環族二羧酸及其衍生物之重複單元所構成的聚酯； （3）主要為由（a）衍生自1種或2種以上的芳香族羥基羧酸及其衍生物之重複單元、（b）衍生自1種或2種以上的芳香族二羧酸、脂環族二羧酸及其衍生物之重複單元、和（c）衍生自至少1種或2種以上的芳香族二醇、脂環族二醇、脂肪族二醇及其衍生物之重複單元所構成的聚酯； （4）主要為由（a）衍生自1種或2種以上的芳香族羥基羧酸及其衍生物之重複單元、（b）衍生自1種或2種以上的芳香族羥基胺、芳香族二胺及其衍生物之重複單元、和（c）衍生自至少1種或2種以上的芳香族二羧酸、脂環族二羧酸及其衍生物之重複單元所構成的聚酯醯胺； （5）主要為由（a）衍生自1種或2種以上的芳香族羥基羧酸及其衍生物之重複單元、（b）衍生自1種或2種以上的芳香族羥基胺、芳香族二胺及其衍生物之重複單元、（c）衍生自1種或2種以上的芳香族二羧酸、脂環族二羧酸及其衍生物之重複單元、和（d）衍生自至少1種或2種以上的芳香族二醇、脂環族二醇、脂肪族二醇及其衍生物之重複單元所構成的聚酯醯胺等。進一步而言，也可以根據需求將分子量調節劑與上述的組成成分組合使用。More specifically, one can cite (1) Polyester mainly composed of repeating units derived from one or more aromatic hydroxycarboxylic acids and their derivatives; (2) It is mainly composed of (a) repeating units derived from one or more kinds of aromatic hydroxycarboxylic acids and their derivatives, and (b) derived from one or more kinds of aromatic dicarboxylic acids, Polyester composed of repeating units of alicyclic dicarboxylic acid and its derivatives; (3) It is mainly composed of (a) repeating units derived from one or more kinds of aromatic hydroxycarboxylic acids and their derivatives, (b) derived from one or more kinds of aromatic dicarboxylic acids, lipids The repeating unit of cyclic dicarboxylic acid and its derivatives, and (c) the repeating unit derived from at least one or more of aromatic diols, alicyclic diols, aliphatic diols and their derivatives Constituted polyester; (4) It is mainly composed of (a) repeating units derived from one or more kinds of aromatic hydroxycarboxylic acids and their derivatives, (b) derived from one or more kinds of aromatic hydroxyamines, aromatic Repeating units of diamines and their derivatives, and (c) polyester amides composed of repeating units derived from at least one or more of aromatic dicarboxylic acids, alicyclic dicarboxylic acids and their derivatives ； (5) Mainly composed of (a) repeating units derived from one or more kinds of aromatic hydroxycarboxylic acids and their derivatives, (b) derived from one or more kinds of aromatic hydroxyamines, aromatic Repeating units of diamines and their derivatives, (c) repeating units derived from one or more kinds of aromatic dicarboxylic acids, alicyclic dicarboxylic acids and their derivatives, and (d) derived from at least one Polyesteramide composed of repeating units of one or more kinds of aromatic diols, alicyclic diols, aliphatic diols and derivatives thereof. Furthermore, a molecular weight modifier can also be used in combination with the above-mentioned components as required.

作為構成可適用於本發明的（A）液晶性樹脂之具體的化合物的較佳例，可以列舉出對羥基苯甲酸、6-羥基-2-萘甲酸等的芳香族羥基羧酸；2,6-二羥基萘、1,4-二羥基萘、4,4'-二羥基聯苯、對苯二酚、間苯二酚、以下通式（I）所表示的化合物、及以下通式（II）所表示的化合物等的芳香族二醇；對苯二甲酸、間苯二甲酸、4,4'-二苯基二羧酸、2,6-萘二羧酸、及以下通式（III）所表示的化合物等的芳香族二羧酸；對氨基苯酚、對苯二胺等的芳香族胺類。 [化學式1]

Figure 02_image001
（X：係選自伸烷基（C1 至C4 ）、亞烷基、-O-、-SO-、-SO2 -、-S-、及-CO-的基團） [化學式2]
Figure 02_image003
[化學式3]
Figure 02_image005
（Y係選自-（CH2 ）n -（n=1～4）及-O（CH2 ）n O-（n=1～4）的基團。）Preferable examples of specific compounds constituting the (A) liquid crystalline resin applicable to the present invention include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; 2,6 -Dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, hydroquinone, resorcinol, the compound represented by the following general formula (I), and the following general formula (II) ) Aromatic diols such as the compound represented; terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and the following general formula (III) Aromatic dicarboxylic acids such as the compounds shown; aromatic amines such as p-aminophenol and p-phenylenediamine. [Chemical formula 1]
Figure 02_image001
(X: a group selected from alkylene (C 1 to C 4 ), alkylene, -O-, -SO-, -SO 2 -, -S-, and -CO-) [Chemical formula 2]
Figure 02_image003
[Chemical formula 3]
Figure 02_image005
(Y is a group selected from -(CH 2 ) n -(n=1～4) and -O(CH 2 ) n O-(n=1～4).)

適用於本發明的（A）液晶性樹脂以包括以下的結構單元（I）～（VI）作為必要的組成成分為最佳， 相對於整體結構單元，結構單元（I）的含量為50〜70莫耳％， 相對於整體結構單元，結構單元（II）的含量為0.5莫耳％以上且未滿4.5莫耳％， 相對於整體結構單元，結構單元（III）的含量為10.25〜22.25莫耳％，相對於整體結構單元，結構單元（IV）的含量為0.5莫耳％以上且未滿4.5莫耳％， 相對於整體結構單元，結構單元（V）的含量為5.75〜23.75莫耳％， 相對於整體結構單元，結構單元（VI）的含量為1〜7莫耳％， 相對於整體結構單元，結構單元（II）和結構單元（IV）的總含量為1莫耳％以上且未滿5莫耳％， 相對於整體結構單元，結構單元（I）～（VI）的總含量為100莫耳％， 相對於結構單元（V）和結構單元（VI）的總含量，結構單元（VI）的莫耳比為0.04～0.37，係在熔融時表現出光學異向性之全芳香族聚酯醯胺。The (A) liquid crystalline resin suitable for the present invention preferably includes the following structural units (I) to (VI) as essential components, Relative to the overall structural unit, the content of structural unit (I) is 50 to 70 mol%, Relative to the overall structural unit, the content of structural unit (II) is 0.5 mol% or more and less than 4.5 mol%, Relative to the overall structural unit, the content of structural unit (III) is 10.25-22.25 mol%, relative to the overall structural unit, the content of structural unit (IV) is 0.5 mol% or more and less than 4.5 mol%, Relative to the overall structural unit, the content of structural unit (V) is 5.75 to 23.75 mol%, Relative to the overall structural unit, the content of structural unit (VI) is 1-7 mol%, Relative to the overall structural unit, the total content of structural unit (II) and structural unit (IV) is 1 mol% or more and less than 5 mol%, Relative to the overall structural unit, the total content of structural units (I) to (VI) is 100 mol%, Relative to the total content of the structural unit (V) and the structural unit (VI), the molar ratio of the structural unit (VI) is 0.04 to 0.37, which is a wholly aromatic polyester amide that exhibits optical anisotropy when melted.

[化學式4]

Figure 02_image007
[Chemical formula 4]
Figure 02_image007

在本發明中所使用的（A）液晶性樹脂，能夠藉由使用直接聚合法或酯交換法之已知的方法，利用上述單體化合物（或單體的混合物）進行製備，通常使用熔融聚合法、溶液聚合法、漿料（slurry）聚合法、固相聚合法等，或者將上述2種以上的方法組合使用，其中以使用熔融聚合法、或將熔融聚合法和固相聚合法組合使用為佳。具有酯形成能力的上述化合物可以直接用於聚合反應，或者也可以在聚合的前階段，從前驅體改性成為具有上述酯形成能力的衍生物。在這些材料的聚合反應中可以使用各種催化劑，可列舉出乙酸鉀、乙酸鎂、乙酸亞錫、鈦酸四丁酯、乙酸鉛、乙酸鈉、三氧化銻、参（2,4-戊二酮酸）鈷(III) (tris(2,4-pentanedionato) cobalt (III))等的金屬鹽催化劑、N-甲基咪唑、4-二甲基氨基吡啶等的有機化合物類催化劑作為典型的範例。相對於單體的總重量，催化劑的用量通常大約為0.001～1質量％，以大約為0.01～0.2質量％為特佳。如果需要更多的藉由這些聚合方法所製造出的聚合物，則可以藉由在減壓下或在惰性氣體中進行加熱之固相聚合方法，以增加分子量。The (A) liquid crystalline resin used in the present invention can be prepared by using known methods such as direct polymerization or transesterification using the above-mentioned monomer compounds (or mixtures of monomers), usually by melt polymerization Method, solution polymerization method, slurry polymerization method, solid phase polymerization method, etc., or a combination of two or more of the above methods, among which melt polymerization method or a combination of melt polymerization method and solid phase polymerization method are used Better. The above-mentioned compound having ester-forming ability may be directly used in the polymerization reaction, or it may be modified from a precursor to a derivative having the above-mentioned ester-forming ability in the pre-polymerization stage. Various catalysts can be used in the polymerization of these materials, including potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, ginseng (2,4-pentanedione Acid) cobalt (III) (tris(2,4-pentanedionato) cobalt (III)) and other metal salt catalysts, N-methylimidazole, 4-dimethylaminopyridine and other organic compound catalysts are typical examples. Relative to the total weight of the monomers, the amount of the catalyst is usually about 0.001 to 1% by mass, and about 0.01 to 0.2% by mass is particularly preferred. If more polymers produced by these polymerization methods are needed, the molecular weight can be increased by a solid-phase polymerization method of heating under reduced pressure or in an inert gas.

藉由以上所述之方法所得到的（A）液晶性樹脂的熔體黏度並沒有特別限定。 通常，可以使用在1000sec-1 的剪切速率之下成型溫度下的熔體黏度為3Pa·s以上500Pa·s以下的液晶性樹脂。然而，本身的黏度太高的液晶性樹脂由於流動性極度惡化因此並不建議使用。另外，上述（A）液晶性樹脂也可以是2種以上的液晶性樹脂之混合物。The melt viscosity of the (A) liquid crystalline resin obtained by the method described above is not particularly limited. Generally, a liquid crystalline resin having a melt viscosity of 3 Pa·s or more and 500 Pa·s or less at a molding temperature at a shear rate of 1000 sec -1 can be used. However, liquid crystalline resins whose viscosity is too high are not recommended because of their extremely deteriorated fluidity. In addition, the above-mentioned (A) liquid crystal resin may be a mixture of two or more liquid crystal resins.

根據本發明的液晶性樹脂組合物，相對於液晶性樹脂組合物的整體，（A）液晶性樹脂在液晶性樹脂組合物中的含量為62.5〜72.5質量％。當（A）液晶性樹脂的含量相對於液晶性樹脂組合物的整體未滿62.5質量％時，液晶性樹脂組合物的流動性容易變差，且由液晶性樹脂組合物所得到的連接器等的成型品之彎曲應變有變小的疑慮，因此並不建議此含量。 當（A）液晶性樹脂的含量相對於液晶性樹脂組合物的整體超過72.5質量％時，由液晶性樹脂組合物所得到的連接器等的成型品之彎曲彈性模量及翹曲變形的抑制效果降低，因此並不建議此含量。根據本發明的液晶性樹脂組合物，相對於液晶性樹脂組合物的整體，（A）液晶性樹脂在液晶性樹脂組合物中的含量以63.5〜71.5質量％為佳，且以65〜70質量％為較佳。According to the liquid crystal resin composition of the present invention, the content of the (A) liquid crystal resin in the liquid crystal resin composition is 62.5 to 72.5% by mass relative to the entire liquid crystal resin composition. (A) When the content of the liquid crystalline resin is less than 62.5% by mass relative to the entire liquid crystalline resin composition, the fluidity of the liquid crystalline resin composition tends to deteriorate, and connectors etc. obtained from the liquid crystalline resin composition There is a concern that the bending strain of the molded product becomes smaller, so this content is not recommended. (A) When the content of the liquid crystalline resin exceeds 72.5% by mass relative to the entire liquid crystalline resin composition, the bending elastic modulus and warpage deformation of molded products such as connectors obtained from the liquid crystalline resin composition are suppressed The effect is reduced, so this content is not recommended. According to the liquid crystalline resin composition of the present invention, the content of (A) the liquid crystalline resin in the liquid crystalline resin composition is preferably 63.5 to 71.5% by mass, and 65 to 70 mass% relative to the entire liquid crystalline resin composition. % Is better.

[（B）纖維狀矽灰石] （B）纖維狀矽灰石的長徑（aspect）比，亦即，平均纖維長度/平均纖維直徑的值為8以上。從由根據本發明的液晶性樹脂組合物所得到的連接器等的成型品之彎曲彈性模量及翹曲變形的抑制效果的觀點來看，上述長徑比以10〜25為佳，且以15〜20為較佳。[(B) Fibrous Wollastonite] (B) The aspect ratio of fibrous wollastonite, that is, the value of the average fiber length/average fiber diameter is 8 or more. From the viewpoint of the bending elastic modulus and the effect of suppressing warpage deformation of molded products such as connectors obtained from the liquid crystalline resin composition of the present invention, the aspect ratio is preferably 10 to 25, and preferably 15-20 is preferable.

作為（B）纖維狀矽灰石，並沒有特別限定，例如可以使用公知的纖維狀矽灰石。 （B）纖維矽灰石可以單獨使用1種，也可以將不同的長徑比、平均纖維長度、平均纖維直徑等組合2種以上使用。The (B) fibrous wollastonite is not particularly limited, and, for example, a known fibrous wollastonite can be used. (B) Fibrous wollastonite can be used alone or in combination of two or more different aspect ratios, average fiber lengths, average fiber diameters, etc.

（B）纖維狀矽灰石的平均纖維直徑以3.0〜50μm為佳，且以4.5〜40μm為較佳。當上述平均纖維直徑為3.0μm以上時，易於確保由根據本發明的液晶性樹脂組合物所得到的連接器等的成型品具有充分的機械強度及負載撓曲溫度。當上述平均纖維直徑為50μm以下時，上述成型品的表面易於具有較優異的起毛抑制效果。另外，在本說明書中，使用掃描電子顯微鏡觀察纖維狀矽灰石且針對100根纖維狀矽灰石測量出纖維直徑並取得平均值，以作為平均纖維直徑。(B) The average fiber diameter of fibrous wollastonite is preferably 3.0-50 μm, and more preferably 4.5-40 μm. When the average fiber diameter is 3.0 μm or more, it is easy to ensure that molded articles such as connectors obtained from the liquid crystalline resin composition of the present invention have sufficient mechanical strength and deflection temperature under load. When the above-mentioned average fiber diameter is 50 μm or less, the surface of the above-mentioned molded article is likely to have a relatively excellent fluffing suppression effect. In addition, in this specification, the fibrous wollastonite is observed using a scanning electron microscope, and the fiber diameter is measured for 100 fibrous wollastonite, and the average value is obtained as the average fiber diameter.

（B）纖維狀矽灰石的平均纖維長度以30〜800μm為佳，且以50〜600μm為較佳。當上述平均纖維長度為30μm以上時，易於確保由根據本發明的液晶性樹脂組合物所得到的連接器等的成型品具有充分的機械強度及負載撓曲溫度。當平均纖維長度為800μm以下時，上述成型品的表面易於具有較優異的起毛抑制效果。另外，在本說明書中，從CCD照相機將10張纖維狀矽灰石的立體顯微鏡圖像擷取至PC中，且藉由使用圖像測量裝置的圖像處理方法，對每1張立體顯微鏡圖像中的100根纖維狀矽灰石，亦即總共1000根的纖維狀矽灰石，測量出纖維長度並取得平均值，以作為平均纖維長度。(B) The average fiber length of fibrous wollastonite is preferably 30 to 800 μm, and more preferably 50 to 600 μm. When the above-mentioned average fiber length is 30 μm or more, it is easy to ensure that molded articles such as connectors obtained from the liquid crystalline resin composition of the present invention have sufficient mechanical strength and load deflection temperature. When the average fiber length is 800 μm or less, the surface of the above-mentioned molded article is likely to have a relatively excellent fuzz suppressing effect. In addition, in this manual, 10 stereo microscope images of fibrous wollastonite are captured from a CCD camera to a PC, and by the image processing method using an image measuring device, each stereo microscope image For the 100 fibrous wollastonite in the image, that is, a total of 1000 fibrous wollastonite, the fiber length is measured and the average value is obtained as the average fiber length.

根據本發明的液晶性樹脂組合物，相對於液晶性樹脂組合物的整體，（B）纖維狀矽灰石在液晶性樹脂組合物中的含量為2.5～15質量％。當（B）纖維狀矽灰石的含量相對於液晶性樹脂組合物的整體未滿2.5質量％時，由液晶性樹脂組合物所得到的連接器等的成型品之翹曲變形，特別是回流後的翹曲變形，有變大的疑慮，因此並不建議此含量。當（B）纖維狀矽灰石的含量相對於液晶性樹脂組合物的整體超過15質量％時，液晶性樹脂組合物的流動性易於變差，而且，由液晶性樹脂組合物所得到的連接器等的成型品之彎曲應變有變小的疑慮，因此並不建議此含量。在本發明中，相對於液晶性樹脂組合物的整體，（B）纖維狀矽灰石在液晶性樹脂組合物中的含量以3〜13質量％為佳，且以5〜10質量％為較佳。According to the liquid crystal resin composition of the present invention, the content of (B) fibrous wollastonite in the liquid crystal resin composition is 2.5 to 15% by mass relative to the entire liquid crystal resin composition. (B) When the content of fibrous wollastonite is less than 2.5% by mass relative to the entire liquid crystalline resin composition, the molded products such as connectors obtained from the liquid crystalline resin composition will warp and deform, especially reflow There is a concern that the subsequent warpage will become larger, so this content is not recommended. When the content of (B) fibrous wollastonite exceeds 15% by mass relative to the entire liquid crystal resin composition, the fluidity of the liquid crystal resin composition is likely to deteriorate, and the connection obtained from the liquid crystal resin composition There is a concern that the bending strain of molded products such as instruments will become smaller, so this content is not recommended. In the present invention, relative to the entire liquid crystal resin composition, the content of (B) fibrous wollastonite in the liquid crystal resin composition is preferably 3-13% by mass, and more preferably 5-10% by mass good.

[（C）雲母] 根據本發明的液晶性樹脂組合物包括雲母。藉由根據本發明的液晶性樹脂組合物包括雲母，能夠得到具有充分的彎曲彈性模量且抑制了翹曲變形之成型品。雲母可以單獨使用1種或者組合2種以上使用。[(C) Mica] The liquid crystalline resin composition according to the present invention includes mica. When the liquid crystalline resin composition according to the present invention includes mica, it is possible to obtain a molded article having a sufficient flexural modulus and suppressed warpage deformation. Mica can be used individually by 1 type or in combination of 2 or more types.

相對於液晶性樹脂組合物的整體，雲母的含量為17.5～30質量％。當雲母的含量相對於液晶性樹脂組合物的整體未滿17.5質量％時，由液晶性樹脂組合物所得到的成型品之彎曲彈性模量並不能充分地提升且不能充分地抑制翹曲，因此並不建議此含量。當雲母的含量相對於液晶性樹脂組合物的整體超過30質量％時，液晶性樹脂組合物的流動性變差，且液晶性樹脂組合物有可能變得難以成型，因此並不建議此含量。相對於液晶性樹脂組合物的整體，雲母在液晶性樹脂組合物中的含量以18.5～27.5質量％為佳，且以20～25質量％為較佳。The content of mica is 17.5 to 30% by mass with respect to the entire liquid crystal resin composition. When the content of mica is less than 17.5% by mass with respect to the entire liquid crystalline resin composition, the flexural modulus of the molded article obtained from the liquid crystalline resin composition cannot be sufficiently increased and warpage cannot be sufficiently suppressed. This content is not recommended. When the content of mica exceeds 30% by mass with respect to the entire liquid crystalline resin composition, the fluidity of the liquid crystalline resin composition deteriorates, and the liquid crystalline resin composition may become difficult to mold, so this content is not recommended. The content of mica in the liquid crystal resin composition is preferably 18.5 to 27.5 mass%, and more preferably 20 to 25 mass% with respect to the entire liquid crystal resin composition.

[雲母] 所謂雲母係含有鋁、鉀、鎂、鈉、鐵等的矽酸鹽礦物之粉狀物。作為可使用於本發明的雲母，可列舉出白雲母、金雲母、黑雲母、人造雲母等，其中，考量到良好的色調和較低的價格，以白雲母為佳。[Mica] The so-called mica is a powdery substance containing silicate minerals such as aluminum, potassium, magnesium, sodium, and iron. The mica that can be used in the present invention includes muscovite, phlogopite, biotite, artificial mica, etc. Among them, in consideration of good color tone and low price, muscovite is preferred.

再者，在雲母的製造中，作為將礦物粉碎的方法，已知有濕式粉碎法及乾式粉碎法。所謂濕式粉碎法係指用乾式粉碎機將生雲母進行粗粉碎之後加水，並在漿料的狀態下利用濕式粉碎進行主要粉碎，然後進行脫水、乾燥的方法。相較於濕式粉碎法，乾式粉碎法為較低成本的常見方法，然而使用濕式粉碎法時更容易將礦物粉碎得薄且細。由於可以得到後續描述的具有較佳的平均粒徑及厚度之雲母，因此在本發明中以使用薄且細的粉碎物為佳。因此，在本發明中，以使用藉由濕式粉碎法製造出的雲母為佳。Furthermore, in the production of mica, as a method of pulverizing minerals, a wet pulverization method and a dry pulverization method are known. The so-called wet pulverization method refers to a method in which raw mica is coarsely pulverized by a dry pulverizer and then water is added, and the main pulverization is performed in the state of slurry by wet pulverization, and then dehydrated and dried. Compared with the wet pulverization method, the dry pulverization method is a common method with lower cost. However, it is easier to pulverize the minerals into thin and fine particles when the wet pulverization method is used. Since mica with better average particle size and thickness described later can be obtained, it is better to use thin and fine crushed products in the present invention. Therefore, in the present invention, it is preferable to use mica produced by a wet pulverization method.

再者，在濕式粉碎法中，由於需要進行將待粉碎物分散於水中的步驟，因此通常會在待粉碎物中加入凝集沉降劑及/或沉降助劑，以提高待粉碎物的分散效率。作為使用於本發明的凝集沉降劑及沉降助劑，可列舉出聚合氯化鋁、硫酸鋁、硫酸亞鐵、硫酸鐵、氯化水綠礬、聚合硫酸鐵、聚合氯化鐵、鐵-二氧化矽無機高分子凝集劑、氯化鐵-二氧化矽無機高分子凝集劑、熟石灰（Ca（OH）2 ），苛性鈉（NaOH）、純鹼（Na2 CO3 ）(soda ash)等。這些凝集沉降劑及沉降助劑的pH值為鹼性或酸性。在本發明中所使用的雲母，以在進行濕式粉碎時不使用凝集沉降劑及/或沉降助劑的雲母為佳。當使用未經過凝集沉降劑及/或沉降助劑處理的雲母時，液晶性樹脂組合物中的聚合物幾乎不會分解，且不大可能會發生產生大量的氣體或聚合物的分子量降低等的情形，因此容易更加良好地維持所得到的連接器等的成型品之性能。Furthermore, in the wet pulverization method, since the step of dispersing the material to be pulverized in water is required, an agglomeration settling agent and/or sedimentation aid is usually added to the material to be pulverized to improve the dispersion efficiency of the material to be pulverized . As the flocculation and sedimentation agents and sedimentation aids used in the present invention, polyaluminum chloride, aluminum sulfate, ferrous sulfate, ferric sulfate, chlorinated water green vitriol, polyferric sulfate, polyferric chloride, iron-two Silicon oxide inorganic polymer flocculant, iron chloride-silica dioxide inorganic polymer flocculant, slaked lime (Ca(OH) 2 ), caustic soda (NaOH), soda ash (Na 2 CO 3 ) (soda ash), etc. The pH of these flocculation and sedimentation aids is alkaline or acidic. The mica used in the present invention is preferably a mica that does not use a flocculating sedimentation agent and/or a sedimentation aid during wet pulverization. When using mica that has not been treated with a flocculating sedimentation agent and/or sedimentation aid, the polymer in the liquid crystalline resin composition hardly decomposes, and it is unlikely that a large amount of gas will be generated or the molecular weight of the polymer will decrease. Circumstances, therefore, it is easy to maintain the performance of the molded product such as the obtained connector more well.

可使用於本發明的雲母，以藉由微徑雷射（micro track laser）衍射法所測量的平均粒徑為10〜100μm為佳，且以平均粒徑為20〜80μm為特佳。雲母的平均粒徑以10μm以上為佳，係因為易於充分獲得對於成型品的剛性之改良效果的緣故。雲母的平均粒徑以100μm以下為佳，係因為易於充分提高成型品的剛性，且也易於具有充分的焊接強度的緣故。而且，當雲母的平均粒徑為100μm以下時，易於確保將本發明的連接器等成型時具有充分的流動性。The mica that can be used in the present invention preferably has an average particle diameter of 10-100 μm as measured by a micro track laser diffraction method, and particularly preferably an average particle diameter of 20-80 μm. The average particle size of mica is preferably 10 μm or more, because it is easy to sufficiently obtain the effect of improving the rigidity of the molded product. The average particle size of mica is preferably 100 μm or less, because it is easy to sufficiently increase the rigidity of the molded product, and it is easy to have sufficient welding strength. Moreover, when the average particle size of mica is 100 μm or less, it is easy to ensure sufficient fluidity when the connector or the like of the present invention is molded.

可使用於本發明中的雲母的厚度，藉由電子顯微鏡觀察所測量出的厚度以0.01〜1μm為佳，且以0.03〜0.3μm為特佳。雲母的厚度以0.01μm以上為佳，係因為在液晶性樹脂組合物的熔融加工期間雲母幾乎不會破裂，因此可以易於提高成型品的剛性的緣故。雲母的厚度以1μm以下為佳，係因為易於充分獲得對於成型品的剛性之改良效果的緣故。The thickness of the mica that can be used in the present invention is preferably 0.01 to 1 μm as measured by electron microscope observation, and particularly preferably 0.03 to 0.3 μm. The thickness of the mica is preferably 0.01 μm or more, because the mica hardly breaks during the melt processing of the liquid crystalline resin composition, so the rigidity of the molded product can be easily increased. The thickness of the mica is preferably 1 μm or less, because it is easy to sufficiently obtain the effect of improving the rigidity of the molded product.

可使用於本發明中的雲母，也可以利用矽烷偶合劑等進行表面處理及/或也可以利用黏合劑進行造粒而成為顆粒狀。The mica that can be used in the present invention may be surface-treated with a silane coupling agent or the like and/or may be granulated with a binder to be granulated.

在根據本發明的液晶性樹脂組合物中，相對於液晶性樹脂組合物的整體，（B）纖維矽灰石及（C）雲母的總含量為27.5〜37.5質量％。當上述含量相對於液晶性樹脂組合物的整體未滿27.5質量％時，由液晶性樹脂組合物所得到的連接器等的成型品之彎曲彈性模量及翹曲變形的抑制效果降低，因此並不建議此含量。當上述含量相對於液晶性樹脂組合物的整體超過37.5質量％時，液晶性樹脂組合物的流動性易於變差，且由液晶性樹脂組合物所得到的連接器等的成型品之彎曲應變有變小的疑慮，因此並不建議此含量。相對於液晶性樹脂組合物的整體，上述含量以28.0〜36.5質量％為佳，且以28.5〜35質量％為較佳。In the liquid crystal resin composition according to the present invention, the total content of (B) fibrous wollastonite and (C) mica is 27.5 to 37.5% by mass relative to the entire liquid crystal resin composition. When the above content is less than 27.5% by mass relative to the entire liquid crystalline resin composition, the flexural modulus of molded products such as connectors obtained from the liquid crystalline resin composition and the effect of suppressing warpage deformation decrease, and therefore are not This content is not recommended. When the above content exceeds 37.5% by mass with respect to the entire liquid crystal resin composition, the fluidity of the liquid crystal resin composition tends to deteriorate, and the bending strain of molded products such as connectors obtained from the liquid crystal resin composition may be It becomes less doubtful, so this content is not recommended. With respect to the entire liquid crystal resin composition, the above content is preferably 28.0 to 36.5 mass%, and more preferably 28.5 to 35 mass%.

[其他成分] 根據本發明的液晶性樹脂組合物，在不損害本發明的效果的範圍內，可以根據所需的性質適當地添加其他的成分，例如其他的聚合物、其他的填充劑、一般在合成樹脂中所添加的公知物質，亦即抗氧化劑和紫外線吸收劑等的穩定劑、抗靜電劑、阻燃劑、染料和顏料等的著色劑、潤滑劑、剝離劑、結晶化促進劑、晶體成核劑等。上述其他的成分可以單獨使用1種，也可以組合2種以上使用。[Other ingredients] According to the liquid crystalline resin composition of the present invention, within a range that does not impair the effects of the present invention, other components can be appropriately added according to the required properties, such as other polymers, other fillers, and generally synthetic resins. Well-known substances added, namely stabilizers such as antioxidants and ultraviolet absorbers, antistatic agents, flame retardants, coloring agents such as dyes and pigments, lubricants, release agents, crystallization accelerators, crystal nucleating agents Wait. These other components may be used individually by 1 type, and may be used in combination of 2 or more types.

所謂其他的填充劑係指長徑比為8以上的纖維矽灰石、雲母、及碳黑以外的填充劑，例如，可列舉出長徑比為8以上的纖維矽灰石以外的纖維填充劑（例如，長徑比未滿8的纖維狀矽灰石、磨碎纖維(milled fiber)）、雲母以外的板狀填料（例如，滑石）。然而，從提高成型品的機械強度並抑制翹曲變形等的觀點來看，根據本發明的液晶性樹脂組合物以不含有長徑比未滿8的纖維狀矽灰石、研碎纖維、及滑石為佳。The so-called other fillers refer to fillers other than fiber wollastonite, mica, and carbon black with an aspect ratio of 8 or more. For example, fiber fillers other than fiber wollastonite with an aspect ratio of 8 or more can be cited. (For example, fibrous wollastonite with an aspect ratio of less than 8, milled fibers), and plate-shaped fillers other than mica (for example, talc). However, from the viewpoint of improving the mechanical strength of the molded product and suppressing warpage deformation, the liquid crystalline resin composition according to the present invention does not contain fibrous wollastonite with an aspect ratio of less than 8, pulverized fibers, and Talc is better.

根據本發明的液晶性樹脂組合物的製造方法，只要能夠將液晶性樹脂組合物中的各成分均勻地混合，並沒有特別限定，可以從以往公知的樹脂組合物的製造方法中適當地選擇。例如，可列舉出使用單螺桿或雙螺桿擠出機等的熔融混煉機，將各成分熔融混煉並擠出之後，將所得到的液晶性樹脂組合物加工成粉末、薄片、粒料等期望的形式之方法。According to the manufacturing method of the liquid crystalline resin composition of this invention, as long as each component in a liquid crystalline resin composition can be uniformly mixed, it will not specifically limit, It can select suitably from the manufacturing method of a conventionally well-known resin composition. For example, a melt-kneader using a single-screw or twin-screw extruder is used to melt, knead and extrude the components, and then process the obtained liquid crystalline resin composition into powder, flakes, pellets, etc. The method of the desired form.

由於根據本發明的液晶性樹脂組合物具有優異的流動性，在成型時的最小填充壓力幾乎不會變得過高，因此能夠良好地成型出連接器，特別是例如薄化窄截距連接器等的小型且具有複雜形狀的部件等。流動性的程度取決於連接器的最小填充壓力。亦即，將圖1所示之FPC連接器在注射成型時可得到良好的成型品之最小注射填充壓力設定為最小填充壓力。最小填充壓力越低，評價為流動性越優異。Since the liquid crystalline resin composition according to the present invention has excellent fluidity and the minimum filling pressure during molding hardly becomes too high, it is possible to form connectors well, especially for thinner and narrow-intercept connectors. Such as small and complex-shaped parts. The degree of fluidity depends on the minimum filling pressure of the connector. That is, the minimum injection filling pressure at which a good molded product can be obtained during injection molding of the FPC connector shown in FIG. 1 is set as the minimum filling pressure. The lower the minimum filling pressure, the better the fluidity.

在比液晶性樹脂的熔點高10～30℃的高溫、且剪切速率為1000/秒下，根據ISO 11443所測量的液晶性樹脂組合物的熔體黏度以1×105 Pa·s以下為佳，且以5 Pa·s以上1×102 Pa·s以下為較佳。當上述熔體黏度為1×105 Pa·s以下時，在連接器特別是薄化窄截距連接器的成型時，易於確保液晶性樹脂組合物的流動性，填充壓力幾乎不會變得過大。At a high temperature 10-30°C higher than the melting point of the liquid crystalline resin and a shear rate of 1000/sec, the melt viscosity of the liquid crystalline resin composition measured in accordance with ISO 11443 is 1×10 5 Pa·s or less Preferably, it is more preferably 5 Pa·s or more and 1×10 2 Pa·s or less. When the above-mentioned melt viscosity is 1×10 5 Pa·s or less, it is easy to ensure the fluidity of the liquid crystalline resin composition during the molding of connectors, especially thinned and narrow-intercept connectors, and the filling pressure hardly becomes is too big.

（連接器） 藉由根據本發明的液晶性樹脂組合物進行成型，能夠得到根據本發明的連接器。作為本發明的連接器並沒有特別限定，例如可列舉出產品的總長度未滿30mm、產品的高度未滿5mm的連接器。作為產品的總長度未滿30mm、產品的高度未滿5mm的連接器，並沒有特別限定，例如可列舉出薄化窄截距連接器、同軸連接器、微型SIM連接器、微型SD連接器等。其中，薄化窄截距連接器十分適合。作為薄化窄截距連接器並沒有特別限定，例如可列舉出基板對基板連接器（也稱為「BtoB連接器」）、可撓性印刷電路板用連接器（用於連接可撓性印刷電路板（FPC）和可撓性扁平電纜（FFC），也稱為「 FPC連接器」）等。其中，截距之間的距離為0.5mm以下、產品的總長度為3.5mm以上未滿30mm、產品的高度為1.5mm以下且為基板對基板連接器或可撓性印刷電路板用連接器之薄化窄截距連接器十分適合。(Connector) By molding the liquid crystalline resin composition according to the present invention, the connector according to the present invention can be obtained. The connector of the present invention is not particularly limited. For example, a connector having a total product length of less than 30 mm and a product height of less than 5 mm can be cited. There are no particular limitations on the connector whose total length of the product is less than 30mm and the height of the product is less than 5mm. Examples include thinned narrow-intercept connectors, coaxial connectors, micro SIM connectors, and micro SD connectors. . Among them, thinned narrow-intercept connectors are very suitable. There are no particular limitations on the thinned and narrow-intercept connectors, and examples include board-to-board connectors (also called "BtoB connectors"), flexible printed circuit board connectors (used to connect flexible printed circuit boards). Circuit board (FPC) and flexible flat cable (FFC), also known as "FPC connector"), etc. Among them, the distance between the intercepts is 0.5mm or less, the total length of the product is 3.5mm or more but less than 30mm, the height of the product is 1.5mm or less, and it is one of the board-to-board connectors or flexible printed circuit board connectors. Thinned and narrow-intercept connectors are very suitable.

作為用於得到本發明的連接器的成型方法並沒有特別限定，而為了防止所得到的連接器變形等，以選擇不會造成殘留內應力的成型條件為佳。為了降低填充壓力並減少所得到的連接器之殘留內應力，成型機的氣缸（cylinder）溫度以液晶性樹脂的熔點以上的溫度為佳。The molding method for obtaining the connector of the present invention is not particularly limited, but in order to prevent deformation of the obtained connector, etc., it is preferable to select molding conditions that do not cause residual internal stress. In order to reduce the filling pressure and reduce the residual internal stress of the resulting connector, the temperature of the cylinder of the molding machine is preferably above the melting point of the liquid crystal resin.

再者，模具溫度以70～100℃為佳。當模具溫度較低，填充於模具中的液晶性樹脂組合物可能會發生流動不良的情形，因此並不建議。當模具溫度較高，可能會發生毛刺等的問題，因此並不建議。關於注射速度，以150mm/秒以上進行注射為佳。當注射速度較低，有可能僅得到未填充的成型品，且即使得到完全填充的成型品，也會成為填充壓力高、殘留內應力大的成型品，有可能僅得到平坦性差的連接器。Furthermore, the mold temperature is preferably 70-100°C. When the mold temperature is low, the liquid crystalline resin composition filled in the mold may have poor flow, so it is not recommended. When the mold temperature is high, problems such as burrs may occur, so it is not recommended. Regarding the injection speed, it is better to perform injection at 150 mm/sec or more. When the injection speed is low, only an unfilled molded product may be obtained, and even if a completely filled molded product is obtained, a molded product with high filling pressure and large residual internal stress may be obtained, and only a connector with poor flatness may be obtained.

本發明的連接器的翹曲變形得到抑制。連接器翹曲的程度藉由如以下所述的方式判斷。亦即，圖1所示之FPC連接器，在圖2中用黑點表示的複數位置處測量高度，並將最小平方法的最大高度與最小高度之間的差異視為翹曲。本發明的連接器，在進行IR回流之前和之後，翹曲的變化得到抑制。The warpage deformation of the connector of the present invention is suppressed. The degree of connector warpage is judged by the method described below. That is, the FPC connector shown in FIG. 1 measures the height at the multiple positions indicated by the black dots in FIG. 2, and regards the difference between the maximum height and the minimum height of the least square method as warpage. In the connector of the present invention, the change in warpage is suppressed before and after IR reflow.

再者，本發明的連接器具有優異的耐熱性，例如藉由高溫剛性所評價的耐熱性。根據ISO 75-1、ISO 75-2藉由測量負載撓曲溫度來評估高溫剛性。Furthermore, the connector of the present invention has excellent heat resistance, for example, heat resistance evaluated by high-temperature rigidity. According to ISO 75-1 and ISO 75-2, the high temperature rigidity is evaluated by measuring the load deflection temperature.

本發明的連接器具有優異的機械強度。根據ASTM D790的彎曲試驗測量彎曲強度、彎曲應變、及彎曲彈性模量來評估機械強度。 [實施例]The connector of the present invention has excellent mechanical strength. The bending strength, bending strain, and bending elastic modulus are measured according to the bending test of ASTM D790 to evaluate the mechanical strength. [Example]

以下，藉由實施例具體說明本發明，然而本發明並不限於此。Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited thereto.

>實施例1〜5、比較例1〜7> 在以下的實施例及比較例中，液晶性樹脂LCP1及LCP2如以下所述而製造。此時，分別在以下的條件下各自測量粒料的熔點及熔體黏度。>Examples 1~5, Comparative Examples 1~7> In the following Examples and Comparative Examples, the liquid crystal resins LCP1 and LCP2 were produced as described below. At this time, the melting point and melt viscosity of the pellets were measured under the following conditions.

[熔點的測量] 利用TA Instruments公司所製造的DSC，在觀測到在從室溫以20℃/分的升溫條件之下對液晶性樹脂進行測量時所觀測出的吸熱峰溫度（Tm1）之後，在（Tm1 + 40）℃的溫度下保持2分鐘後，在20℃/分的升溫條件之下將其冷卻至室溫，然後再度測量以20℃/分的升溫條件進行測量時所觀測出的吸熱峰溫度。[Melting point measurement] Using the DSC manufactured by TA Instruments, after observing the endothermic peak temperature (Tm1) observed when measuring the liquid crystalline resin at a temperature rise of 20°C/min from room temperature, the temperature (Tm1 + 40 ) After keeping it at a temperature of ℃ for 2 minutes, cool it to room temperature under a heating condition of 20℃/min, and then measure the endothermic peak temperature observed when measuring at a heating condition of 20℃/min.

[熔體黏度的測量] 使用由東洋精機製作所股份公司所製造的Capillograph 1B型，在比液晶性樹脂的熔點高10～30°C的高溫下，使用內徑為1 mm、長度為20 mm的管口（orifice），剪切速率為1000/秒，根據ISO11443測量液晶性樹脂的熔體黏度。另外， LCP1的測量溫度為360°C，而LCP2的測量溫度為380°C。[Measurement of Melt Viscosity] Use Capillograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd., at a high temperature of 10 to 30°C higher than the melting point of liquid crystal resin, use an orifice with an inner diameter of 1 mm and a length of 20 mm, and cut The shear rate is 1000/sec, and the melt viscosity of the liquid crystal resin is measured according to ISO11443. In addition, the measurement temperature of LCP1 is 360°C, and the measurement temperature of LCP2 is 380°C.

（LCP1的製造方法） 在具備攪拌器、回流塔、單體入口、氮氣入口、減壓/流出管線的聚合容器中加入以下原料單體、脂肪酸金屬鹽催化劑、醯化劑，並進行氮置換。 （I）4-羥基苯甲酸：1385g（60莫耳％）（HBA） （II）6-羥基-2-萘甲酸：88 g（2.8莫耳％）（HNA） （III）對苯二甲酸：504 g（18.15莫耳％）（TA） （IV）間苯二甲酸：19 g（0.7莫耳％）（IA） （V）4,4'-二羥基聯苯：415 g（13.35莫耳％）（BP） （VI）N-乙醯基-對氨基苯酚：126g（5莫耳％）（APAP） 醋酸鉀催化劑：120mg 乙酸酐：1662g 將原料加入聚合容器後，將反應體系的溫度升高至140℃，並在140℃下進行反應1小時。之後，在5.5小時內將溫度進一步升高至360℃，然後在20分鐘內將壓力降低至10Torr（亦即，1330Pa），蒸餾出乙酸、過量的乙酸酐、其他低沸點成分的同時進行熔融聚合。在攪拌扭矩（torque）達到預定的值之後，引入氮氣以從減壓狀態經過常壓而變為加壓狀態，聚合物從聚合容器的下部排出，並從線狀變成顆粒狀以完成造粒。所得到的粒料的熔點為345℃，熔體黏度為10Pa·s。(Method of manufacturing LCP1) A polymerization vessel equipped with a stirrer, a reflux tower, a monomer inlet, a nitrogen inlet, and a pressure reduction/outflow line was charged with the following raw material monomers, fatty acid metal salt catalysts, and acylating agents, followed by nitrogen replacement. (I) 4-Hydroxybenzoic acid: 1385g (60 mol%) (HBA) (II) 6-Hydroxy-2-naphthoic acid: 88 g (2.8 mol%) (HNA) (III) Terephthalic acid: 504 g (18.15 mol%) (TA) (IV) Isophthalic acid: 19 g (0.7 mol%) (IA) (V) 4,4'-dihydroxybiphenyl: 415 g (13.35 mol%) (BP) (VI) N-Acetyl-p-Aminophenol: 126g (5 mol%) (APAP) Potassium acetate catalyst: 120mg Acetic anhydride: 1662g After the raw materials were added to the polymerization vessel, the temperature of the reaction system was increased to 140°C, and the reaction was carried out at 140°C for 1 hour. After that, the temperature was further increased to 360°C within 5.5 hours, and then the pressure was reduced to 10 Torr (that is, 1330 Pa) within 20 minutes, and acetic acid, excess acetic anhydride, and other low-boiling components were distilled out while melt polymerization was performed . After the stirring torque (torque) reaches a predetermined value, nitrogen is introduced to pass from a reduced pressure state to a pressurized state through normal pressure, and the polymer is discharged from the lower portion of the polymerization vessel and changed from a linear shape to a granular shape to complete granulation. The melting point of the obtained pellets was 345°C, and the melt viscosity was 10 Pa·s.

（LCP2的製造方法） 在具備攪拌器、回流塔、單體入口、氮氣入口、減壓/流出管線的聚合容器中加入以下原料單體、脂肪酸金屬鹽催化劑、醯化劑，並進行氮置換。 （I）           4-羥基苯甲酸：1040g（48莫耳％）（HBA） （II）         6-羥基-2-萘甲酸：89g（3莫耳％）（HNA） （III）       對苯二甲酸：547g（21莫耳％）（TA） （IV）      間苯二甲酸：91g（3.5莫耳％）（IA） （V）        4,4'-二羥基聯苯：716g（24.5莫耳％）（BP） 醋酸鉀催化劑：110mg 乙酸酐：1644g(Method of manufacturing LCP2) A polymerization vessel equipped with a stirrer, a reflux tower, a monomer inlet, a nitrogen inlet, and a pressure reduction/outflow line was charged with the following raw material monomers, fatty acid metal salt catalysts, and acylating agents, followed by nitrogen replacement. (I) 4-Hydroxybenzoic acid: 1040g (48 mol%) (HBA) (II) 6-Hydroxy-2-naphthoic acid: 89g (3 mol%) (HNA) (III) Terephthalic acid: 547g (21 mol%) (TA) (IV) Isophthalic acid: 91g (3.5 mol%) (IA) (V) 4,4'-dihydroxybiphenyl: 716g (24.5 mol%) (BP) Potassium acetate catalyst: 110mg Acetic anhydride: 1644g

將原料加入聚合容器後，將反應體系的溫度升高至140℃，並在140℃下進行反應1小時。之後，在5.5小時內將溫度進一步升高至360℃，然後在20分鐘內將壓力降低至5Torr（亦即，667Pa），蒸餾出乙酸、過量的乙酸酐、其他低沸點成分的同時進行熔融聚合。在攪拌扭矩（torque）達到預定的值之後，引入氮氣以從減壓狀態經過常壓而變為加壓狀態，聚合物從聚合容器的下部排出，並從線狀變成顆粒狀以完成造粒。所得到的粒料的熔點為355℃，熔體黏度為10Pa·s。After the raw materials were added to the polymerization vessel, the temperature of the reaction system was increased to 140°C, and the reaction was carried out at 140°C for 1 hour. After that, the temperature was further increased to 360°C within 5.5 hours, and then the pressure was reduced to 5 Torr (ie, 667 Pa) within 20 minutes, and the acetic acid, excess acetic anhydride, and other low-boiling components were distilled out while melt polymerization was performed . After the stirring torque (torque) reaches a predetermined value, nitrogen is introduced to pass from a reduced pressure state to a pressurized state through normal pressure, and the polymer is discharged from the lower portion of the polymerization vessel and changed from a linear shape to a granular shape to complete granulation. The melting point of the obtained pellets was 355°C, and the melt viscosity was 10 Pa·s.

（液晶性樹脂以外的成分） ・纖維狀填充劑 矽灰石1：NYGLOS 8（由NYCO Materials公司所製造，長徑比為17，平均纖維長度為136μm，平均纖維直徑為8μm） 矽灰石2：NYAD 325（由NYCO Materials公司所製造，長徑比為5，平均纖維長度為50μm，平均纖維直徑為5μm） 研磨纖維：日東紡股份公司所製造的 PF70E001，纖維直徑為10μm，平均纖維長度為70μm（製造商標稱值） ・板狀填充劑 雲母；山口雲母工業股份公司所製造的AB-25S，平均粒徑為25μm 滑石；松村產業股份公司所製造的Crown Talc PP，平均粒徑為10μm(Ingredients other than liquid crystal resin) ・Fibrous filler Wollastonite 1: NYGLOS 8 (manufactured by NYCO Materials, with aspect ratio of 17, average fiber length of 136μm, average fiber diameter of 8μm) Wollastonite 2: NYAD 325 (manufactured by NYCO Materials, with an aspect ratio of 5, an average fiber length of 50μm, and an average fiber diameter of 5μm) Grinding fiber: PF70E001 manufactured by Nittobo Co., Ltd., with a fiber diameter of 10μm and an average fiber length of 70μm (manufacturing brand name) ・Plate filler Mica: AB-25S manufactured by Yamaguchi Mica Industry Co., Ltd., with an average particle size of 25μm Talc; Crown Talc PP manufactured by Songcun Industry Co., Ltd., with an average particle size of 10μm

使用雙螺桿擠出機，將上述所得到的各種液晶性樹脂、和上述液晶性樹脂以外的成分混合，以得到液晶性樹脂組合物。各成分的調配量如表1及表2所示。另外，在以下的表格中，關於調配量的「％」係表示質量％。再者，得到液晶性樹脂組合物時的擠出條件如下。 [擠出條件] [實施例1〜4、比較例1〜7] 設置於主要進料口的氣缸的溫度設為250°C，所有其他的氣缸的溫度則設為360°C。所有液晶性樹脂均從主要進料口供給。再者，填充劑從側面進料口供給。 [實施例5] 設置於主要進料口的氣缸的溫度設為250°C，所有其他的氣缸的溫度則設為370°C。所有液晶性樹脂均從主要進料口供給。再者，填充劑從側面進料口供給。Using a twin-screw extruder, the various liquid crystalline resins obtained above and components other than the above liquid crystalline resin are mixed to obtain a liquid crystalline resin composition. The blending amount of each component is shown in Table 1 and Table 2. In addition, in the following table, "%" with respect to the compounding amount indicates mass %. In addition, the extrusion conditions when obtaining a liquid crystal resin composition are as follows. [Extrusion conditions] [Examples 1 to 4, Comparative Examples 1 to 7] The temperature of the cylinder set at the main feed port is set to 250°C, and the temperature of all other cylinders is set to 360°C. All liquid crystal resins are supplied from the main feed port. Furthermore, the filler is supplied from the side inlet. [Example 5] The temperature of the cylinder set at the main feed port is set to 250°C, and the temperature of all other cylinders is set to 370°C. All liquid crystal resins are supplied from the main feed port. Furthermore, the filler is supplied from the side inlet.

（液晶性樹脂組合物的熔體黏度的測量） 使用由東洋精機製作所股份公司所製造的Capillograph 1B型，在比液晶性樹脂的熔點高10～30°C的高溫下，使用內徑為1 mm、長度為20 mm的管口，剪切速率為1000/秒，根據ISO11443測量液晶性樹脂的熔體黏度。另外，使用LCP1的液晶性樹脂組合物的測量溫度為360°C，而使用LCP2的液晶性樹脂組合物的測量溫度為380°C。結果如表1及表2所示。(Measurement of melt viscosity of liquid crystalline resin composition) Using Capillograph 1B manufactured by Toyo Seiki Seisakusho Co., Ltd., at a high temperature of 10-30°C higher than the melting point of the liquid crystal resin, a nozzle with an inner diameter of 1 mm and a length of 20 mm is used, and the shear rate is 1000/sec, the melt viscosity of liquid crystal resin is measured according to ISO11443. In addition, the measurement temperature of the liquid crystalline resin composition using LCP1 was 360°C, and the measurement temperature of the liquid crystalline resin composition using LCP2 was 380°C. The results are shown in Table 1 and Table 2.

基於下列方法，測量包括液晶性樹脂組合物的成型品之連接器的物性。各種評估結果如表1及表2所示。Based on the following method, the physical properties of the connector of the molded article including the liquid crystal resin composition were measured. Various evaluation results are shown in Table 1 and Table 2.

（負載撓曲溫度） 在下列成型條件下，將液晶性樹脂組合物注射成型以得到成型品，並根據ISO 75-1、ISO 75-2測量負載撓曲溫度。 [成型條件] 成型機：由住友重機械工業所製造的SE100DU 氣缸溫度： 360℃（實施例1〜4、比較例1〜7） 370°C（實施例5） 模具溫度：80℃ 注射速度：33 mm/sec(Load deflection temperature) Under the following molding conditions, the liquid crystalline resin composition was injection molded to obtain a molded product, and the load deflection temperature was measured according to ISO 75-1 and ISO 75-2. [Molding conditions] Forming machine: SE100DU manufactured by Sumitomo Heavy Industries Cylinder temperature: 360°C (Examples 1 to 4, Comparative Examples 1 to 7) 370°C (Example 5) Mold temperature: 80℃ Injection speed: 33 mm/sec

（彎曲測試） 在下列成型條件下，將液晶性樹脂組合物注射成型以得到厚度為0.8mm的成型品，並根據ASTM D790測量彎曲強度、彎曲應變、及彎曲彈性模量。 [成型條件] 成型機：由住友重機械工業所製造的SE100DU 氣缸溫度： 360℃（實施例1〜4、比較例1〜7） 370°C（實施例5） 模具溫度：80℃ 注射速度：33 mm/sec(Bending test) Under the following molding conditions, the liquid crystalline resin composition was injection molded to obtain a molded article with a thickness of 0.8 mm, and the bending strength, bending strain, and bending elastic modulus were measured in accordance with ASTM D790. [Molding conditions] Forming machine: SE100DU manufactured by Sumitomo Heavy Industries Cylinder temperature: 360°C (Examples 1 to 4, Comparative Examples 1 to 7) 370°C (Example 5) Mold temperature: 80℃ Injection speed: 33 mm/sec

（FPC連接器的翹曲） 在下列成型條件下，將液晶性樹脂組合物注射成型（澆口（gate）：隧道澆口，澆口尺寸：φ0.4mm），以得到整體尺寸為17.6mm×4.00mm×1.16mm、截距之間的距離為0.5mm、針孔數為30×2個針腳、最小壁厚為0.12mm之FPC連接器，如圖1所示。 [成型條件] 成型機：由住友重機械工業所製造的SE30DUZ 氣缸溫度（顯示為從噴嘴之側的溫度）： 360°C－360°C－350°C－340°C（實施例1〜4、比較例1〜7） 370°C－370°C－360°C－350°C（實施例5） 模具溫度：80℃ 注射速度：200mm/sec 保壓壓力：50MPa 保壓時間：0.5秒 冷卻時間：10秒 螺桿轉速：120rpm 螺桿背壓：1.2 MPa(Warpage of FPC connector) Under the following molding conditions, the liquid crystal resin composition was injection molded (gate: tunnel gate, gate size: φ0.4mm) to obtain an overall size of 17.6mm×4.00mm×1.16mm, intercept The distance between the FPC connectors is 0.5mm, the number of pinholes is 30×2 pins, and the minimum wall thickness is 0.12mm, as shown in Figure 1. [Molding conditions] Forming machine: SE30DUZ manufactured by Sumitomo Heavy Industries Cylinder temperature (shown as the temperature from the side of the nozzle): 360°C－360°C－350°C－340°C (Examples 1 to 4, Comparative Examples 1 to 7) 370°C-370°C-360°C-350°C (Example 5) Mold temperature: 80℃ Injection speed: 200mm/sec Holding pressure: 50MPa Holding time: 0.5 seconds Cooling time: 10 seconds Screw speed: 120rpm Screw back pressure: 1.2 MPa

將所得到的連接器放置於水平的桌面上靜置，並使用由三豐公司所製造的Quick Vision 404 PROCNC圖像測量機，測量連接器的高度。此時，在圖2中用黑點表示的複數位置處測量高度，並將最小平方法的最大高度與最小高度之間的差異視為FPC連接器的翹曲。另外，在下列條件之下進行的IR回流之前和之後測量翹曲。 [IR回流條件] 測量儀器：由日本脈衝技術研究所所製造的大型桌面式回流焊設備RF-300（使用遠紅外加熱器） 試料供給速度：140 mm/sec 回流爐通過時間：5分鐘 預熱區的溫度條件：150°C 回流區的溫度條件：190°C 波峰溫度：251°CThe obtained connector was placed on a horizontal table to stand still, and the height of the connector was measured using the Quick Vision 404 PROCNC image measuring machine manufactured by Mitutoyo. At this time, the height is measured at a plurality of positions indicated by black dots in FIG. 2, and the difference between the maximum height and the minimum height of the least square method is regarded as the warpage of the FPC connector. In addition, warpage was measured before and after IR reflow performed under the following conditions. [IR reflow conditions] Measuring instrument: large desktop reflow soldering equipment RF-300 (using far infrared heater) manufactured by Japan Pulse Technology Research Institute Sample supply speed: 140 mm/sec Reflow oven passing time: 5 minutes Temperature condition of preheating zone: 150°C Temperature conditions in the reflux zone: 190°C Peak temperature: 251°C

（FPC連接器的最小填充壓力） 測量出圖1的FPC連接器在注射成型時可得到良好的成型品之最小注射填充壓力，以作為最小填充壓力。(Minimum filling pressure of FPC connector) The minimum injection filling pressure at which the FPC connector of Figure 1 can obtain a good molded product during injection molding is measured as the minimum filling pressure.

[表1]     實施例1 實施例2 實施例3 比較例1 實施例4 比較例2 比較例3 液晶性樹脂（％） LCP1 65 70 70 75 70 60 60 LCP2               纖維狀填充劑（％） 纖維狀矽灰石1 10 5 10 5 7.5 10 20 纖維狀矽灰石2               經研磨的纖維               板狀填充劑（％） 雲母 25 25 20 20 22.5 30 20 滑石               填充劑合（％）   35 30 30 25 30 40 40 合計 （％）   100 100 100 100 100 100 100 熔體黏度 Pa･s 19 12 16 14 16 19 25 負載撓曲溫度 ℃ 267 266 266 262 266 271 268 彎曲強度 MPa 164 174 175 170 176 167 167 彎曲應變 ％ 2.0 2.4 2.4 2.8 2.5 1.6 1.5 彎曲彈性模量 MPa 15800 15300 15100 14000 15200 16700 16600 FPC連接器的翹曲（回流之前） mm 0.019 0.021 0.024 0.028 0.023 0.016 0.018 FPC連接器的翹曲（回流之後） mm 0.060 0.071 0.089 0.106 0.077 0.055 0.082 FPC連接器的最小填充壓力 MPa 73 68 69 65 68 80 82 [Table 1] Example 1 Example 2 Example 3 Comparative example 1 Example 4 Comparative example 2 Comparative example 3 Liquid crystal resin (%) LCP1 65 70 70 75 70 60 60 LCP2 Fibrous filler (%) Fibrous Wollastonite 1 10 5 10 5 7.5 10 20 Fibrous Wollastonite 2 Milled fiber Plate filler (%) Mica 25 25 20 20 22.5 30 20 talc Filler mix (%) 35 30 30 25 30 40 40 total(%) 100 100 100 100 100 100 100 Melt viscosity Pa･s 19 12 16 14 16 19 25 Load deflection temperature °C 267 266 266 262 266 271 268 Bending strength MPa 164 174 175 170 176 167 167 Bending strain % 2.0 2.4 2.4 2.8 2.5 1.6 1.5 Flexural modulus of elasticity MPa 15,800 15300 15100 14000 15200 16,700 16600 Warpage of FPC connector (before reflow) mm 0.019 0.021 0.024 0.028 0.023 0.016 0.018 Warpage of FPC connector (after reflow) mm 0.060 0.071 0.089 0.106 0.077 0.055 0.082 Minimum filling pressure of FPC connector MPa 73 68 69 65 68 80 82

[表2]     比較例4 實施例5 比較例5 比較例6 比較例7 比較例8 比較例9 液晶性樹脂（％） LCP1 80   70 70 65 70 70 LCP2   70           纖維狀填充劑（％） 纖維狀矽灰石1 5 10 5         纖維狀矽灰石2       7.5       經研磨的纖維         10 5 10 板狀填充劑（％） 雲母 15 20   22.5 25 25 20 滑石     25         填充劑合（％）   20 30 30 30 35 30 30 合計 （％）   100 100 100 100 100 100 100 熔體黏度 Pa･s 12 12 11 12 12 8 9 負載撓曲溫度 ℃ 258 245 255 255 266 265 266 彎曲強度 MPa 164 161 160 170 181 178 176 彎曲應變 ％ 3.1 2.6 3.0 3.0 2.6 3.0 2.9 彎曲彈性模量 MPa 13600 14100 13500 13000 16400 15500 15300 FPC連接器的翹曲（回流之前） mm 0.045 0.028 0.035 0.030 0.020 0.029 0.026 FPC連接器的翹曲（回流之後） mm 0.150 0.083 0.110 0.100 0.068 0.084 0.090 FPC連接器的最小填充壓力 MPa 61 70 63 65 91 85 88 [Table 2] Comparative example 4 Example 5 Comparative example 5 Comparative example 6 Comparative example 7 Comparative example 8 Comparative example 9 Liquid crystal resin (%) LCP1 80 70 70 65 70 70 LCP2 70 Fibrous filler (%) Fibrous Wollastonite 1 5 10 5 Fibrous Wollastonite 2 7.5 Milled fiber 10 5 10 Plate filler (%) Mica 15 20 22.5 25 25 20 talc 25 Filler mix (%) 20 30 30 30 35 30 30 total(%) 100 100 100 100 100 100 100 Melt viscosity Pa･s 12 12 11 12 12 8 9 Load deflection temperature °C 258 245 255 255 266 265 266 Bending strength MPa 164 161 160 170 181 178 176 Bending strain % 3.1 2.6 3.0 3.0 2.6 3.0 2.9 Flexural modulus of elasticity MPa 13,600 14100 13,500 13000 16,400 15500 15300 Warpage of FPC connector (before reflow) mm 0.045 0.028 0.035 0.030 0.020 0.029 0.026 Warpage of FPC connector (after reflow) mm 0.150 0.083 0.110 0.100 0.068 0.084 0.090 Minimum filling pressure of FPC connector MPa 61 70 63 65 91 85 88

如表1及表2所示，在實施例中，負載撓曲溫度為245°C以上，彎曲應變為2.0％以上，彎曲彈性模量為14000 MPa以上，回流之前的FPC連接器的翹曲未滿0.030 mm， 回流之後的FPC連接器的翹曲未滿0.090 mm，FPC連接器的最小填充壓力未滿75 MPa。 因此得以確知，根據本發明的液晶性樹脂組合物具有優異的流動性，且包括此液晶性樹脂組合物的成型品之連接器具有優異的耐熱性及機械強度，且翹曲變形也得到抑制。As shown in Table 1 and Table 2, in the examples, the load deflection temperature is 245°C or more, the bending strain is 2.0% or more, and the bending elastic modulus is 14000 MPa or more. The warpage of the FPC connector before reflow is not The warpage of the FPC connector after reflow is less than 0.090 mm, and the minimum filling pressure of the FPC connector is less than 75 MPa. Therefore, it is confirmed that the liquid crystal resin composition according to the present invention has excellent fluidity, and the connector including the molded article of the liquid crystal resin composition has excellent heat resistance and mechanical strength, and warpage deformation is also suppressed.

無。no.

[圖1]係繪示出在實施例中已成型的FPC連接器的圖式。另外，圖中的數值的單位為mm。 [圖2]係繪示出在實施例中進行了FPC連接器的翹曲測量之測量點的圖式。[Fig. 1] A diagram showing the FPC connector formed in the embodiment. In addition, the unit of the numerical value in the figure is mm. [Fig. 2] A diagram showing the measurement points where the warpage measurement of the FPC connector was performed in the embodiment.

Claims (5)

一種液晶性樹脂組合物，其係包括（A）液晶性樹脂、（B）纖維狀矽灰石及（C）雲母之液晶性樹脂組合物， 其中前述（B）纖維狀矽灰石的長寬比為8以上， 且其中相對於前述液晶性樹脂組合物的整體， 前述（A）液晶性樹脂的含量為62.5～72.5質量％， 前述（B）纖維狀矽灰石的含量為2.5～15質量％， 前述（C）雲母的含量為17.5～30質量％， 且前述（B）纖維狀矽灰石及前述（C）雲母的總含量為27.5～37.5質量％。A liquid crystal resin composition, which is a liquid crystal resin composition comprising (A) liquid crystal resin, (B) fibrous wollastonite and (C) mica, The aspect ratio of the aforementioned (B) fibrous wollastonite is 8 or more, And wherein with respect to the whole of the aforementioned liquid crystal resin composition, The content of the aforementioned (A) liquid crystal resin is 62.5 to 72.5% by mass, The content of the aforementioned (B) fibrous wollastonite is 2.5-15 mass%, The content of the aforementioned (C) mica is 17.5-30% by mass, And the total content of the aforementioned (B) fibrous wollastonite and the aforementioned (C) mica is 27.5-37.5 mass%. 如申請專利範圍第1項所述之液晶性樹脂組合物，其係用於產品總長度未滿30mm、產品高度未滿5mm之連接器。The liquid crystal resin composition described in item 1 of the scope of patent application is used for connectors whose total product length is less than 30mm and the product height is less than 5mm. 一種連接器，其包括如申請專利範圍第1或2項所述之液晶性樹脂組合物的成型品，且產品總長度未滿30mm、產品高度未滿5mm。A connector comprising a molded product of a liquid crystal resin composition as described in item 1 or 2 of the scope of patent application, and the total product length is less than 30 mm, and the product height is less than 5 mm. 如申請專利範圍第3項所述之連接器，其係薄化窄截距連接器。The connector described in item 3 of the scope of patent application is a thinner and narrow-intercept connector. 如申請專利範圍第3或4項所述之連接器，其係基板對基板的連接器或可撓性刷電路板用連接器之薄化窄截距連接器， 其中，節距之間的距離為0.5mm以下， 產品總長度為3.5mm以上未滿30mm， 且產品高度為1.5mm以下。For example, the connector described in item 3 or 4 of the scope of patent application is a substrate-to-substrate connector or a thinned narrow-intercept connector for a flexible brush circuit board connector. Among them, the distance between the pitches is 0.5mm or less, The total length of the product is more than 3.5mm and less than 30mm, And the product height is 1.5mm or less.
TW108140944A 2018-11-15 2019-11-12 Liquid crystalline resin composition and connector including molded article of said liquid crystalline resin composition TW202028365A (en)

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