TWI437039B - Liquid-crystalline polymer composition and molded article made of the same - Google Patents

Liquid-crystalline polymer composition and molded article made of the same Download PDF

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TWI437039B
TWI437039B TW096141141A TW96141141A TWI437039B TW I437039 B TWI437039 B TW I437039B TW 096141141 A TW096141141 A TW 096141141A TW 96141141 A TW96141141 A TW 96141141A TW I437039 B TWI437039 B TW I437039B
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crystalline polymer
liquid crystalline
polymer composition
acid
talc
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TW200831584A (en
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Hiroto Uchida
Hitoshi Tsuchiya
Tomoyuki Saito
Hiroyuki Kato
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Ueno Fine Chemical Ind
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L101/00Compositions of unspecified macromolecular compounds
    • C08L101/12Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/04Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38Polymers
    • C09K19/3804Polymers with mesogenic groups in the main chain
    • C09K19/3809Polyesters; Polyester derivatives, e.g. polyamides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00Liquid crystal materials
    • C09K19/52Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54Additives having no specific mesophase characterised by their chemical composition

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Description

液晶性聚合物組成物及其模製物Liquid crystalline polymer composition and molded article thereof

本發明係關於一種液晶性聚合物組成物及其所製成的模製物。The present invention relates to a liquid crystalline polymer composition and a molded article thereof.

熱向性液晶性聚合物(thermotropic liquid-crystalline polymer)(其於後文中稱為液晶性聚合物或LCP)具有良好的性質包括耐熱性、機械性質諸如剛性、抗化學性和尺寸準確性,不僅可用於模製物且亦可用於多種產品諸如纖維和膜。A thermotropic liquid-crystalline polymer (hereinafter referred to as a liquid crystalline polymer or LCP) has good properties including heat resistance, mechanical properties such as rigidity, chemical resistance, and dimensional accuracy, not only It can be used for moldings and can also be used in a variety of products such as fibers and films.

於資訊和電信領域中,有時候需要非常薄的部件。特別地,個人電腦和行動電話採用高度集成的裝置且此項技術領域希望彼等使用尺寸縮小,更薄且更小的部件。建基於LCPs相較於其他熱塑性樹脂的優良模塑性質包括良好的流動性和較低的著火形成(flash development),LCPs的消耗已然增加。In the field of information and telecommunications, sometimes very thin parts are required. In particular, personal computers and mobile phones employ highly integrated devices and the art is expected to use smaller, thinner and smaller components. Based on the excellent molding properties of LCPs compared to other thermoplastic resins, including good fluidity and low flash development, the consumption of LCPs has increased.

不過,於電子組件之領域中,諸如連接器,無鉛焊劑合金,諸如Sn-Ag-Cu合金,於最近都用來裝配產品,且此等合金需要高的廻銲溫度(reflow temperature)。高廻銲溫度可能造成LCPs所製造的模製物之翹曲。However, in the field of electronic components, such as connectors, lead-free solder alloys, such as Sn-Ag-Cu alloys, have recently been used to assemble products, and such alloys require high reflow temperatures. The high soldering temperature may cause warpage of the molded article produced by the LCPs.

為了解決LCPs所製造的模製物之翹曲形成問題,有提出用層狀填充料補充的液晶性聚合物。例如,日本專利JP-A-2001-106923(對應於歐洲專利EP1243620 A1)揭示一種液晶性聚合物組成物,其除了液晶性聚合物之外,包含諸如滑石之層狀填充料,該層狀填充料滿足下述式(1)和(2)且具有0.5至100微米之平均粒徑: 其中“D”為該層狀填充料的最大粒徑且該直徑D的方向係經定義為“x”;“W”為在相對於方向x呈直角的方向y中的粒子之直徑;且“H”為在垂直於xy-平面的z方向中之該粒子的厚度。In order to solve the problem of warpage formation of a molded article produced by LCPs, a liquid crystalline polymer supplemented with a layered filler has been proposed. For example, Japanese Patent No. JP-A-2001-106923 (corresponding to European Patent No. EP 1243620 A1) discloses a liquid crystalline polymer composition comprising, in addition to a liquid crystalline polymer, a layered filler such as talc, the layered filling The material satisfies the following formulas (1) and (2) and has an average particle diameter of 0.5 to 100 μm: Wherein "D" is the maximum particle size of the layered filler and the direction of the diameter D is defined as "x";"W" is the diameter of the particles in the direction y at right angles to the direction x; and H" is the thickness of the particle in the z direction perpendicular to the xy-plane.

針對滑石而言,日本專利JP-A-2001-106923(對應於歐洲專利EP1243620 A1)僅揭示具有1.0至1.3 D/W比例者,亦即幾乎為圓形至正方形的滑石。此等滑石於事實上降低用LCP組成物所製造的物件之翹曲,但是其效用仍屬不足。For the talc, the Japanese patent JP-A-2001-106923 (corresponding to European Patent EP 1243620 A1) only discloses talc having a ratio of 1.0 to 1.3 D/W, that is, almost circular to square. These talc actually reduce the warpage of the articles made with the LCP composition, but their effectiveness is still insufficient.

本發明一目的為提供一種可提供具有低翹曲的模製物之液晶性聚合物組成物。SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystalline polymer composition which can provide a molded article having low warpage.

本發明提供一種液晶性聚合物組成物,其包含:100重量份的液晶性聚合物和1至200重量份的滑石,該滑石具有5至100微米之中間粒子直徑和3.0至5.0的長寬比(aspect ratio)。The present invention provides a liquid crystalline polymer composition comprising: 100 parts by weight of a liquid crystalline polymer and 1 to 200 parts by weight of talc having an intermediate particle diameter of 5 to 100 μm and an aspect ratio of 3.0 to 5.0 (aspect ratio).

本發明液晶性聚合物沒有受到特別地限制且可為展現出各向異性熔融相之任何聚酯或聚醯胺且為熟諳此技藝者稱為熱向性液晶性聚酯或熱向性液晶性聚酯醯胺。The liquid crystalline polymer of the present invention is not particularly limited and may be any polyester or polyamine which exhibits an anisotropic molten phase and is known to be skilled in the art as a thermotropic liquid crystalline polyester or a thermotropic liquid crystalline property. Polyester decylamine.

該各向異性熔融相可利用習用的偏振光系統使用正交偏光器予以確定。更細部而言,於氮環境下放置在Leitz’s熱台上的樣品可使用Leitz’s偏光顯微鏡予以觀察。The anisotropic molten phase can be determined using a conventional polarized light system using a crossed polarizer. In more detail, samples placed on a Leitz's hot stage under a nitrogen atmosphere can be observed using a Leitz's polarizing microscope.

本發明液晶性聚合物係由芳族氧羰基重複單位、芳族二羰基重複單位、芳族二氧基重複單位、芳族胺氧基重複單位、芳族胺基羰基重複單位、芳族二胺基重複單位、芳族氧基二羰基重複單位、脂族二氧基重複單位、和類似者所構成。The liquid crystalline polymer of the present invention is composed of an aromatic oxycarbonyl repeating unit, an aromatic dicarbonyl repeating unit, an aromatic dioxy repeating unit, an aromatic amineoxy repeating unit, an aromatic aminocarbonyl repeating unit, and an aromatic diamine. A repeating unit, an aromatic oxydicarbonyl repeating unit, an aliphatic dioxy repeating unit, and the like.

由上面所述重複單位構成的液晶性聚合物,取決於聚合物的結構成分、其比例、和其序列分布,可包括能給予各向異性熔融相者與不給予者兩者。用在本發明中的液晶性聚合物係限於展現出各向異性熔融相者。The liquid crystalline polymer composed of the repeating units described above may include both an anisotropic molten phase and a non-administrative depending on the structural components of the polymer, the ratio thereof, and the sequence distribution thereof. The liquid crystalline polymer used in the present invention is limited to those exhibiting an anisotropic molten phase.

提供芳族氧羰基重複單位的單體之例子為對-羥基苯甲酸、間-羥基苯甲酸、鄰-羥基苯甲酸、6-羥基-2-萘甲酸、5-羥基-2-萘甲酸、3-羥基-2-萘甲酸、4’-羥基苯基-4-苯甲酸、3’-羥基苯基-4-苯甲酸、4’-羥基苯基-3-苯甲酸、彼等經烷基-、烷氧基-和鹵素-取代之衍生物以及彼等的酯形成性衍生物諸如彼等的醯基、酯和酸鹵化物之衍生物。Examples of the monomer which provides an aromatic oxycarbonyl repeating unit are p-hydroxybenzoic acid, m-hydroxybenzoic acid, o-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 5-hydroxy-2-naphthoic acid, 3 -hydroxy-2-naphthoic acid, 4'-hydroxyphenyl-4-benzoic acid, 3'-hydroxyphenyl-4-benzoic acid, 4'-hydroxyphenyl-3-benzoic acid, these are alkyl- , alkoxy- and halogen-substituted derivatives and their ester-forming derivatives such as their thiol, ester and acid halide derivatives.

於彼等之中,較佳者為對-羥基苯甲酸和6-羥基-2-萘甲酸,因為彼等可促成更容易地控制所得液晶性聚合物的性質和熔點。Among them, p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are preferred because they can contribute to more easily controlling the properties and melting point of the resulting liquid crystalline polymer.

提供芳族二羰基重複單位的單體之例子為芳族二羧酸諸如對苯二甲酸、異酞酸、2,6-萘二羧酸、1,6-萘二羧酸、2,7-萘二羧酸、1,4-萘二羧酸、4,4’-二羧基聯苯,彼等經烷基-、烷氧基-和鹵素-取代之衍生物以及彼等的酯形成性衍生物諸如彼等的酯和酸鹵化物之衍生物。Examples of monomers which provide an aromatic dicarbonyl repeating unit are aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 2,7- Naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 4,4'-dicarboxybiphenyl, alkyl-, alkoxy- and halogen-substituted derivatives and their ester-forming derivatives Such as their esters and derivatives of acid halides.

於彼等之中,較佳者為對苯二甲酸和2,6-萘二羧酸,因為彼等可促成更容易地控制所得液晶性聚合物的機械性質、耐熱性、可模塑性和熔點。Among them, terephthalic acid and 2,6-naphthalene dicarboxylic acid are preferred because they can facilitate the mechanical properties, heat resistance, moldability and the like of the obtained liquid crystalline polymer to be more easily controlled. Melting point.

提供芳族二氧基重複單位的單體之例子為芳族二醇類諸如氫醌、間苯二酚、2,6-二羥基萘、2,7-二羥基萘、1,6-二羥基萘、1,4-二羥基萘、4,4’-二羥基聯苯、3,3’-二羥基聯苯、3,4’-二羥基聯苯、4,4’-二羥基聯苯醚,彼等經烷基-、烷氧基-和鹵素-取代之衍生物以及彼等的酯形成性衍生物諸如彼等的醯基衍生物。Examples of the monomer which provides an aromatic dioxy repeating unit are aromatic diols such as hydroquinone, resorcin, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxyl Naphthalene, 1,4-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl, 3,3'-dihydroxybiphenyl, 3,4'-dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether These are alkyl-, alkoxy- and halogen-substituted derivatives and their ester-forming derivatives such as their mercapto derivatives.

於彼等之中,較佳者為氫醌和4,4’-二羥基聯苯,因為在聚合步驟中有良好的反應性且所得液晶性聚合物有優良的性質。Among them, preferred are hydroquinone and 4,4'-dihydroxybiphenyl because of good reactivity in the polymerization step and the obtained liquid crystalline polymer has excellent properties.

提供芳族胺氧基重複單位的單體之例子為芳族羥基胺類諸如對-胺基酚、間-胺基酚、4-胺基-1-萘酚、5-胺基-1-萘酚、8-胺基-2-萘酚、4-胺基-4-羥基聯苯,彼等經烷基-、烷氧基-和鹵素-取代之衍生物以及彼等的酯或醯胺形成性衍生物諸如彼等的醯基衍生物。Examples of the monomer which provides an aromatic aminooxy repeating unit are aromatic hydroxylamines such as p-aminophenol, m-aminophenol, 4-amino-1-naphthol, 5-amino-1-naphthalene Phenol, 8-amino-2-naphthol, 4-amino-4-hydroxybiphenyl, which are formed by alkyl-, alkoxy- and halogen-substituted derivatives and their esters or decylamines Sex derivatives such as their mercapto derivatives.

提供芳族胺基羰基重複單位的單體之例子為芳族胺基羧酸類諸如對-胺基苯甲酸、間-胺基苯甲酸、6-胺基-2-萘甲酸,彼等經烷基-、烷氧基-和鹵素-取代之衍生物以及彼等的酯或醯胺形成性衍生物諸如彼等的醯基、酯和酸鹵化物之衍生物。Examples of the monomer which provides an aromatic aminocarbonyl repeating unit are aromatic aminocarboxylic acids such as p-aminobenzoic acid, m-aminobenzoic acid, 6-amino-2-naphthoic acid, and the like. - alkoxy- and halogen-substituted derivatives and their ester or guanamine-forming derivatives such as their thiol, ester and acid halide derivatives.

提供芳族二胺基重複單位的單體之例子為芳族胺基二胺類諸如對-苯二胺、間-苯二胺、1,5-二胺基萘、1,8-二胺基萘,彼等經烷基-、烷氧基-和鹵素-取代之衍生物以及彼等的醯胺形成性衍生物諸如彼等的醯基衍生物。Examples of the monomer which provides an aromatic diamine group repeating unit are aromatic amine diamines such as p-phenylenediamine, m-phenylenediamine, 1,5-diaminonaphthalene, 1,8-diamino group. Naphthalenes, such alkyl-, alkoxy- and halogen-substituted derivatives and their guanamine-forming derivatives such as their fluorenyl derivatives.

提供芳族氧基二羰基重複單位的單體之例子為羥基芳族二羧酸諸如3-羥基-2,7-萘二羧酸、4-羥基-異酞酸、5-羥基-異酞酸,彼等經烷基-、烷氧基-和鹵素-取代之衍生物以及彼等的酯形成性衍生物諸如彼等的醯基、酯、酸鹵化物之衍生物。Examples of monomers which provide an aromatic oxydicarbonyl repeating unit are hydroxyaromatic dicarboxylic acids such as 3-hydroxy-2,7-naphthalenedicarboxylic acid, 4-hydroxy-isodecanoic acid, 5-hydroxy-isodecanoic acid. These are alkyl-, alkoxy- and halogen-substituted derivatives and their ester-forming derivatives such as their thiol, ester, acid halide derivatives.

提供脂族二氧基重複單位的單體之例子為脂族二醇類諸如乙二醇、1,4-丁二醇、1,6-己二醇和彼等的醯基衍生物。Examples of the monomer which provides an aliphatic dioxy repeating unit are aliphatic diols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, and the mercapto derivatives thereof.

此外,包含脂族二氧基重複單位的液晶性聚合物可經由使包含脂族二氧基重複單位的聚酯諸如聚對苯二甲酸乙二酯和聚對苯二甲酸丁二酯,與上述諸單體諸如芳族氧基羧酸、芳族二羧酸、芳族二醇、芳族羥基胺、芳族胺基羧酸、芳族二胺、羥基芳族二羧酸、以及彼等的醯基、酯和酸鹵化物之衍生物反應而獲得。Further, the liquid crystalline polymer containing an aliphatic dioxy repeating unit may be obtained by reacting a polyester comprising an aliphatic dioxy repeating unit such as polyethylene terephthalate and polybutylene terephthalate Monomers such as aromatic oxycarboxylic acids, aromatic dicarboxylic acids, aromatic diols, aromatic hydroxylamines, aromatic aminocarboxylic acids, aromatic diamines, hydroxyaromatic dicarboxylic acids, and the like The thiol, ester and acid halide derivatives are obtained by reaction.

另外,本發明液晶性聚合物可包含硫酯鍵結,除非其會損及本發明目的。可提供硫酯鍵結的單體之例子為氫硫基芳族羧酸、芳族二硫醇和羥基芳族硫醇。此等單體相對於提供芳族氧羰基重複單位、芳族二羰基重複單位、芳族二氧基重複單位、芳族胺氧基重複單位、芳族胺基羰基重複單位、芳族二胺基重複單位、芳族氧基二羰基重複單位及脂族二氧基重複單位的總單體之比例較佳地為等於或少於10莫耳%。Further, the liquid crystalline polymer of the present invention may contain a thioester bond unless it would impair the object of the present invention. Examples of thioester-bondable monomers that can be provided are thiosulfanyl aromatic carboxylic acids, aromatic dithiols, and hydroxyaromatic thiols. These monomers are provided with an aromatic oxycarbonyl repeating unit, an aromatic dicarbonyl repeating unit, an aromatic dioxy repeating unit, an aromatic amineoxy repeating unit, an aromatic amine carbonyl repeating unit, and an aromatic diamine group. The proportion of the total monomer of the repeating unit, the aromatic oxydicarbonyl repeating unit and the aliphatic dioxy repeating unit is preferably equal to or less than 10 mol%.

本發明液晶性聚合物較佳地包含,4-氧基苯甲醯基重複單位及/或6-氧基-2-萘甲醯基重複單位,兩者都是芳族氧羰基重複單位。The liquid crystalline polymer of the present invention preferably comprises a 4-oxybenzylidene repeating unit and/or a 6-oxy-2-naphthomethylthiol repeating unit, both of which are aromatic oxycarbonyl repeating units.

於包含4-氧基苯甲醯基重複單位及/或6-氧基-2-萘甲醯基重複單位的液晶性聚合物之中,較佳者為由下列單體成分所構成的共聚物:1)4-羥基苯甲酸/6-羥基-2-萘甲酸共聚物2)4-羥基苯甲酸/對苯二甲酸/4,4’-二羥基聯苯共聚物3)4-羥基苯甲酸/對苯二甲酸/異酞酸/4,4’-二羥基聯苯共聚物4)4-羥基苯甲酸/對苯二甲酸/異酞酸/4,4’-二羥基聯苯/氫醌共聚物5)4-羥基苯甲酸/對苯二甲酸/氫醌共聚物6)6-羥基-2-萘甲酸/對苯二甲酸/氫醌共聚物7)4-羥基苯甲酸/6-羥基-2-萘甲酸/對苯二甲酸/4,4’-二羥基聯苯共聚物8)6-羥基-2-萘甲酸/對苯二甲酸/4,4’-二羥基聯苯共聚物9)4-羥基苯甲酸/6-羥基-2-萘甲酸/對苯二甲酸/氫醌共聚物10)4-羥基苯甲酸/2,6-萘二羧酸/4,4’-二羥基聯苯共聚物11)4-羥基苯甲酸/對苯二甲酸/2,6-萘二羧酸/氫醌共聚物12)4-羥基苯甲酸/2,6-萘二羧酸/氫醌共聚物13)4-羥基苯甲酸/6-羥基-2-萘甲酸/2,6-萘二羧酸/氫醌共聚物14)4-羥基苯甲酸/對苯二甲酸/2,6-萘二羧酸/氫醌/4,4’-二羥基聯苯共聚物15)4-羥基苯甲酸/對苯二甲酸/4-胺基酚共聚物16)6-羥基-2-萘甲酸/對苯二甲酸/4-胺基酚共聚物17)4-羥基苯甲酸/6-羥基-2-萘甲酸/對苯二甲酸/4-胺基酚共聚物18)4-羥基苯甲酸/對苯二甲酸/4,4’-二羥基聯苯/4-胺基酚共聚物19)4-羥基苯甲酸/對苯二甲酸/乙二醇共聚物20)4-羥基苯甲酸/對苯二甲酸/4,4’-二羥基聯苯/乙二醇共聚物21)4-羥基苯甲酸/6-羥基-2-萘甲酸/對苯二甲酸/乙二醇共聚物,和22)4-羥基苯甲酸/6-羥基-2-萘甲酸/對苯二甲酸/4,4’-二羥基聯苯/乙二醇共聚物。Among the liquid crystalline polymers containing a repeating unit of 4-oxybenzhydryl group and/or 6-oxy-2-naphthoquinone group, a copolymer composed of the following monomer components is preferred. :1) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid copolymer 2) 4-hydroxybenzoic acid / terephthalic acid / 4,4 '-dihydroxybiphenyl copolymer 3) 4-hydroxybenzoic acid /terephthalic acid/isophthalic acid/4,4'-dihydroxybiphenyl copolymer 4) 4-hydroxybenzoic acid/terephthalic acid/isodecanoic acid/4,4'-dihydroxybiphenyl/hydroquinone Copolymer 5) 4-hydroxybenzoic acid / terephthalic acid / hydroquinone copolymer 6) 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone copolymer 7) 4-hydroxybenzoic acid / 6-hydroxyl -2-naphthoic acid/terephthalic acid/4,4'-dihydroxybiphenyl copolymer 8) 6-hydroxy-2-naphthoic acid/terephthalic acid/4,4'-dihydroxybiphenyl copolymer 9 ) 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid / terephthalic acid / hydroquinone copolymer 10) 4-hydroxybenzoic acid / 2,6-naphthalenedicarboxylic acid / 4,4 '-dihydroxyl Benzene copolymer 11) 4-hydroxybenzoic acid / terephthalic acid / 2,6-naphthalene dicarboxylic acid / hydroquinone copolymer 12) 4- Benzoic acid/2,6-naphthalene dicarboxylic acid/hydroquinone copolymer 13) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/2,6-naphthalene dicarboxylic acid/hydroquinone copolymer 14)4 -hydroxybenzoic acid/terephthalic acid/2,6-naphthalene dicarboxylic acid/hydroquinone/4,4'-dihydroxybiphenyl copolymer 15) 4-hydroxybenzoic acid/terephthalic acid/4-amino group Phenol Copolymer 16) 6-Hydroxy-2-naphthoic acid/terephthalic acid/4-aminophenol copolymer 17) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/4- Aminophenol copolymer 18) 4-hydroxybenzoic acid/terephthalic acid/4,4'-dihydroxybiphenyl/4-aminophenol copolymer 19) 4-hydroxybenzoic acid/terephthalic acid/ethylene Alcohol copolymer 20) 4-hydroxybenzoic acid/terephthalic acid/4,4'-dihydroxybiphenyl/ethylene glycol copolymer 21) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/p-benzene Dicarboxylic acid/ethylene glycol copolymer, and 22) 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/4,4'-dihydroxybiphenyl/ethylene glycol copolymer.

於上列之中,共聚物1)、9)和13)就良好可模塑性和優良機械性質而言可特別較佳地作為本發明液晶性聚合物。Among the above, copolymers 1), 9) and 13) are particularly preferably used as the liquid crystalline polymer of the present invention in terms of good moldability and excellent mechanical properties.

本發明液晶性聚合物可為經由將二種或多種本發明液晶性聚合物摻合而得者以改良諸如在模塑時的流動性等性質。The liquid crystalline polymer of the present invention may be obtained by blending two or more liquid crystalline polymers of the present invention to improve properties such as fluidity at the time of molding.

本發明液晶性聚合物可用下面所述方法製備。The liquid crystalline polymer of the present invention can be produced by the method described below.

製備本發明液晶性聚合物所用方法沒有受到限制且可以採用任何已知的方法。例如,可以採用慣用的聚合方法諸如熔融酸解法和漿液聚合方法來製備聚合物而給予在上面所述諸單體成分之間的酯或醯胺鍵結。The method for preparing the liquid crystalline polymer of the present invention is not limited and any known method can be employed. For example, a conventional polymerization method such as a melt acidolysis method and a slurry polymerization method can be used to prepare a polymer to impart an ester or a guanamine bond between the monomer components described above.

於本發明中較佳地係使用熔融酸解法。於此方法中,將聚合物單體加熱到給予反應物的熔融溶液且隨後使該溶液反應而給予熔融聚合物。此方法的最後步驟可以在真空下進行以利於揮發性副產物諸如醋酸和水之移除。In the present invention, a melt acidolysis method is preferably used. In this method, a polymer monomer is heated to a molten solution to which a reactant is administered and then the solution is reacted to give a molten polymer. The final step of this process can be carried out under vacuum to facilitate the removal of volatile by-products such as acetic acid and water.

漿液聚合方法的特徵在於該等單體係在熱交換流體中反應而在該該熱交換液體介質內的懸浮液形式中給予固態聚合物。The slurry polymerization process is characterized in that the single systems are reacted in a heat exchange fluid to impart a solid polymer in the form of a suspension in the heat exchange liquid medium.

在熔融酸解法或漿液聚合方法的任一者之中,液晶性聚合物製備所用的聚合單體成分可為變性形式,亦即呈C2-5 醯基酯形式,此可經由將單體的羥基及/或胺基予以醯基化而得。於該等C2-5 醯基之中,較佳者為C2-3 醯基。最佳者為使用醋酸酯來進行反應。In any of the melt acidolysis or slurry polymerization processes, the polymerizable monomer component used in the preparation of the liquid crystalline polymer may be in a denatured form, that is, in the form of a C 2-5 decyl ester, which may be via a monomer The hydroxyl group and/or the amine group are obtained by thiolation. Among these C 2-5 fluorenyl groups, C 2-3 fluorenyl groups are preferred. The best is to use acetate to carry out the reaction.

單體的C2-5 醯基酯可為在事先經由將單體獨立地醯基化而製備者或可為在製備液晶性聚合物之際添加醯基化劑諸如醋酸酐於單體而在反應系統中製成者。The monomeric C 2-5 decyl ester may be prepared by previously thiolation of the monomer independently or may be added to the monomer during the preparation of the liquid crystalline polymer, such as acetic anhydride. Producer in the reaction system.

在熔融酸解法或漿液聚合方法的任一者之中,必要時,可在反應中使用觸媒。In any of the melt acid hydrolysis method or the slurry polymerization method, a catalyst may be used in the reaction if necessary.

觸媒的例子包括有機錫化合物諸如氧化二烷基錫(如氧化二丁基錫)和氧化二芳基錫;三氧化銻;二氧化鈦;有機鈦化合物諸如矽酸烷氧基鈦和烷氧化鈦;羧酸的鹼金屬鹽或鹼土金屬鹽諸如醋酸鉀;無機酸的鹼金屬鹽或鹼土金屬鹽諸如硫酸鉀和路以士酸(Lewis acid)(如BF3 );氣態酸觸媒諸如鹵化氫(如HCl)。Examples of the catalyst include organotin compounds such as dialkyltin oxide (e.g., dibutyltin oxide) and diaryltin oxide; antimony trioxide; titanium dioxide; organotitanium compounds such as titanium alkoxide and titanium alkoxide; carboxylic acid An alkali metal or alkaline earth metal salt such as potassium acetate; an alkali metal or alkaline earth metal salt of an inorganic acid such as potassium sulfate and Lewis acid (such as BF 3 ); a gaseous acid catalyst such as a hydrogen halide (such as HCl) ).

在有使用到觸媒之時,添加到反應中的觸媒之量較佳者可為以總單體為基準之10至1000 ppm,且更佳者為20至200 ppm。The amount of the catalyst added to the reaction may preferably be from 10 to 1000 ppm, and more preferably from 20 to 200 ppm, based on the total monomers, when the catalyst is used.

熔融狀態中的液晶性聚合物係從聚縮合反應容器拉出且予以加工成而給予小粒、薄片或粉末形式。The liquid crystalline polymer in a molten state is drawn from a polycondensation reaction vessel and processed into a pellet, flake or powder form.

其後,在減壓下或在諸如氮氣及氦氣之惰性氣體環境於實質固體狀態中聚合物可接受加熱製程以增加分子量且改良該液晶性聚合物的耐熱性。Thereafter, the polymer may be subjected to a heating process under reduced pressure or in an inert gas atmosphere such as nitrogen and helium in a substantially solid state to increase the molecular weight and improve the heat resistance of the liquid crystalline polymer.

固體狀態中的加熱製程之溫度,除非該液晶性聚合物熔化,否則沒有受到限制,而較佳者為260至350℃且更佳者為280至320℃。The temperature of the heating process in the solid state is not limited unless the liquid crystalline polymer is melted, and is preferably 260 to 350 ° C and more preferably 280 to 320 ° C.

本發明液晶性聚合物組成物可經由將具有5至100微米之中間粒子直徑和約3.0至5.0的長寬比的滑石添加到該液晶性聚合物且使用捏合機器諸如Banbury混合機、捏合機、單螺桿擠壓機、雙螺桿擠壓機和類似者,在靠近聚合物的熔點到該熔點加30℃的溫度將混合物熔融捏合。The liquid crystalline polymer composition of the present invention can be added to the liquid crystalline polymer via a talc having an intermediate particle diameter of 5 to 100 μm and an aspect ratio of about 3.0 to 5.0, and using a kneading machine such as a Banbury mixer, a kneader, A single screw extruder, a twin screw extruder and the like melt-knead the mixture at a temperature close to the melting point of the polymer to the melting point plus 30 °C.

使用差示掃描熱量計(DSC)根據下面所述方法測定的本發明液晶性聚合物之熔點(Tm),較佳者為270至380℃,且更佳者為320至380℃。The melting point (Tm) of the liquid crystalline polymer of the present invention measured by a differential scanning calorimeter (DSC) according to the method described below is preferably 270 to 380 ° C, and more preferably 320 to 380 ° C.

使用差示掃描熱量計Exstar 6000(Seiko Instruments Inc.,Chiba,Japan)或相同類型的DSC裝置。要檢驗的LCP樣品係以20℃/分鐘的速率從室溫加熱且記錄其吸熱峰(Tm1)。其後,將LCP樣品在高於Tm1 20至50℃的溫度保持10分鐘。然後以20℃/分鐘的速率將樣品冷卻到室溫。然後,再以20℃/分鐘的速率加熱該LCP樣品且記錄其放熱峰。將最後步驟所測得之吸熱峰記錄為熔點。A differential scanning calorimeter Exstar 6000 (Seiko Instruments Inc., Chiba, Japan) or a DSC device of the same type was used. The LCP sample to be tested was heated from room temperature at a rate of 20 ° C/min and its endothermic peak (Tm1) was recorded. Thereafter, the LCP sample was held at a temperature of 20 to 50 ° C above Tm1 for 10 minutes. The sample was then cooled to room temperature at a rate of 20 ° C/min. Then, the LCP sample was further heated at a rate of 20 ° C / minute and its exothermic peak was recorded. The endothermic peak measured in the last step was recorded as the melting point.

本發明液晶性聚合物包含具有5至100微米,較佳者5至75微米且更佳者5至50微米的中間粒子直徑之滑石。The liquid crystalline polymer of the present invention comprises talc having an intermediate particle diameter of 5 to 100 μm, preferably 5 to 75 μm, and more preferably 5 to 50 μm.

於本發明中,該滑石的中間粒子直徑係以雷射繞射測定法測定。In the present invention, the intermediate particle diameter of the talc is measured by a laser diffraction measurement.

用於本發明的滑石之長寬比為3.0至5.0,較佳者3.0至4.5,且更佳者3.0至4.0。The aspect ratio of the talc used in the present invention is from 3.0 to 5.0, preferably from 3.0 to 4.5, and more preferably from 3.0 to 4.0.

於本發明中,該滑石的長寬比係使用Multi Image Analyzer(Beckman Coulter,Inc.)根據Coulter原理測定,包括下列諸步驟:i)當滑石粒子通過細孔之時,對應於所產生的電壓脈衝照射閃光燈;ii)拍攝該粒子的投射影像;及iii)分析該投射影像;其中,滑石粒子的長寬比係以公式(A)/(B)來計算;其中(A)為該投射影像外周上的兩隨意點間的最大長度且(B)為與該投射影像接觸且平行於連接用於測定該最大長度(A)的兩點的直線之兩直線間的最小距離。In the present invention, the aspect ratio of the talc is determined according to the Coulter principle using a Multi Image Analyzer (Beckman Coulter, Inc.), and includes the following steps: i) when the talc particles pass through the pores, corresponding to the generated voltage Pulse illuminating the flash; ii) capturing a projected image of the particle; and iii) analyzing the projected image; wherein the aspect ratio of the talc particle is calculated by equation (A)/(B); wherein (A) is the projected image The maximum length between the two random points on the outer circumference and (B) is the minimum distance between the two straight lines that are in contact with the projected image and parallel to the line connecting the two points for measuring the maximum length (A).

於本發明中,滑石的量相對於100重量份的液晶性聚合物為1至200重量份,較佳者5至150重量份且更佳者10至100重量份。In the present invention, the amount of talc is from 1 to 200 parts by weight, preferably from 5 to 150 parts by weight, and more preferably from 10 to 100 parts by weight, per 100 parts by weight of the liquid crystalline polymer.

本發明所用滑石的水分含量,從較不會形成所謂的起泡(blister)(其為模製物的表面突起)及對模製物的性質諸如耐熱性較低不良影響之觀點來看,較佳者為等於或少於0.2重量%。The moisture content of the talc used in the present invention is less from the viewpoint of less formation of a so-called blister, which is a surface protrusion of a molded article, and a bad influence on properties of a molded article such as heat resistance. The best is equal to or less than 0.2% by weight.

滑石的水分含量可以經由使用紅外線水分計(Kett Electric Laboratory)來測定,如下面所述者。The moisture content of the talc can be determined by using an infrared moisture meter (Kett Electric Laboratory) as described below.

<滑石水分含量的測定方法><Method for measuring moisture content of talc>

將10克的滑石樣品加熱到105℃且保持在此溫度直到樣品的重量變成固定為止。於此時所測量到的重量損失量即定義為滑石的水分含量。A 10 gram talc sample was heated to 105 ° C and held at this temperature until the weight of the sample became fixed. The amount of weight loss measured at this time is defined as the moisture content of the talc.

當滑石的水分含量超過0.2重量%之時,其可能要在使用之前在,例如,100至150℃的溫度下乾燥以使水分含量減低到等於或低於0.2重量%。When the moisture content of the talc exceeds 0.2% by weight, it may be dried at a temperature of, for example, 100 to 150 ° C before use to reduce the moisture content to be equal to or lower than 0.2% by weight.

本發明液晶性聚合物組成物可包含除了滑石以外的纖維狀填充料,該纖維狀填充料的量於每100重量份的液晶性聚合物較佳地為1至200重量份,更佳地1至150重量份且最佳者1至100重量份。The liquid crystalline polymer composition of the present invention may contain a fibrous filler other than talc, and the amount of the fibrous filler is preferably from 1 to 200 parts by weight per 100 parts by weight of the liquid crystalline polymer, more preferably 1 To 150 parts by weight and most preferably from 1 to 100 parts by weight.

該纖維狀填充料的平均纖維直徑除非損及本發明的目的,否則沒有受到限制且較佳者為0.1至50微米。在該纖維狀填充料的橫截面不是圓形者時,纖維的直徑係經定義為在該纖維狀填充料橫截面外周上的任意兩點之間的最大長度。The average fiber diameter of the fibrous filler is not limited and is preferably from 0.1 to 50 μm unless it is detrimental to the object of the present invention. Where the cross-section of the fibrous filler is not circular, the diameter of the fiber is defined as the maximum length between any two points on the outer circumference of the cross-section of the fibrous filler.

纖維狀填充料的例子包括玻璃纖維、橢圓形玻璃纖維、繭形玻璃纖維、氧化矽-氧化鋁纖維、氧化鋁纖維、碳纖維、芳綸(aramid)纖維、鈦酸鉀纖維、硼酸鋁纖維、矽灰石(wollastonite)及彼等的組合。Examples of the fibrous filler include glass fiber, elliptical glass fiber, bismuth glass fiber, cerium oxide-alumina fiber, alumina fiber, carbon fiber, aramid fiber, potassium titanate fiber, aluminum borate fiber, bismuth Greystone (wollastonite) and their combination.

於上面所述纖維狀填充料之中,從液晶性聚合物組成物的性質和其成本而論,較佳者為玻璃纖維、橢圓形玻璃纖維、繭形玻璃纖維和彼等的組合。Among the fibrous fillers described above, glass fibers, elliptical glass fibers, scorpion glass fibers, and combinations thereof are preferred from the properties of the liquid crystalline polymer composition and the cost thereof.

於本發明說明書和申請專利範圍之中,術語“玻璃纖維”意指具有圓形橫截面的玻璃纖維。術語“橢圓形玻璃纖維”意指具有橢圓形橫截面的玻璃纖維。術語“繭形玻璃纖維”意指其橫截面為將兩圓形的小部份彼此重疊之時所觀察到形狀之玻璃纖維。此等形狀包括,例如,花生殼的縱向部份。於本發明中,術語“圓形”或“橢圓形”形狀不僅意指幾何圓形或橢圓形之形狀而且也包括顯示為幾乎為圓形或橢圓形的形狀。例如,圓形形狀包括其角落圓化的正方形且該橢圓形的形狀包括其角落圓化的長方形。Within the scope of the present specification and claims, the term "glass fiber" means a glass fiber having a circular cross section. The term "elliptical glass fiber" means a glass fiber having an elliptical cross section. The term "rhodium-shaped glass fiber" means a glass fiber whose cross-section is the shape observed when two small circular portions overlap each other. Such shapes include, for example, the longitudinal portion of the peanut shell. In the present invention, the term "circular" or "elliptical" shape means not only a geometric circular or elliptical shape but also a shape which is shown to be almost circular or elliptical. For example, a circular shape includes a square whose corner is rounded and the shape of the ellipse includes a rectangle whose corner is rounded.

本發明液晶性聚合物組成物中除了滑石之外可包含一種或多種之層狀或粒狀填充料,除非該附加的填充料會損及本發明目的。The liquid crystalline polymer composition of the present invention may comprise one or more layered or granulated fillers in addition to talc unless the additional fillers impair the object of the present invention.

該除了滑石之外的層狀或粒狀填充料之量於每100重量份的液晶性聚合物較佳地為1至200重量份,更佳地1至150重量份且最佳者1至100重量份。The amount of the layered or granular filler other than the talc is preferably from 1 to 200 parts by weight, more preferably from 1 to 150 parts by weight, and most preferably from 1 to 100, per 100 parts by weight of the liquid crystalline polymer. Parts by weight.

該除了滑石之外的層狀或粒狀填充料之例子包括雲母、石墨、碳酸鈣、白雲石、黏土、玻璃薄片、玻璃珠粒、硫酸鋇、氧化鈦、和彼等的組合。Examples of the layered or granular filler other than talc include mica, graphite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, titanium oxide, and combinations thereof.

該滑石和除了滑石之外的纖維狀、層狀或粒狀填充料在本發明液晶性聚合物組成物中之總量於每100重量份的液晶性聚合物較佳地為1至200重量份。The total amount of the talc and the fibrous, layered or granular filler other than talc in the liquid crystalline polymer composition of the present invention is preferably from 1 to 200 parts by weight per 100 parts by weight of the liquid crystalline polymer. .

必要時,根據本發明的液晶性聚合物組成物可以進一步混合一種或多種LCP組成物所慣用的添加劑,例如模塑潤滑劑諸如高碳數脂族酸、高碳數脂族酯、高碳數脂族醯胺、高碳數脂族酸金屬鹽、聚矽氧烷、氟碳樹脂;著色劑諸如染料和顏料;抗氧化劑;熱安定劑;UV吸收劑;抗靜電劑和表面活性劑。If necessary, the liquid crystalline polymer composition according to the present invention may further be mixed with an additive conventionally used for one or more LCP compositions, such as a molding lubricant such as a high carbon number aliphatic acid, a high carbon number aliphatic ester, and a high carbon number. Aliphatic guanamine, high carbon number aliphatic acid metal salt, polyoxyalkylene, fluorocarbon resin; colorants such as dyes and pigments; antioxidants; thermal stabilizers; UV absorbers; antistatic agents and surfactants.

模塑潤滑劑諸如高碳數脂族酸、高碳數脂族酯、高碳數脂族醯胺、高碳數脂族酸金屬鹽和氟碳類型界面活性劑,可以在對液晶性聚合物或液晶性聚合物組成物之小粒接受模塑製程之前,加到該等小粒之中,使得模塑潤滑劑黏附到該等小粒的外表面上。Molding lubricants such as high carbon number aliphatic acids, high carbon number aliphatic esters, high carbon number aliphatic guanamines, high carbon number aliphatic acid metal salts and fluorocarbon type surfactants, which can be used in liquid crystalline polymers Or the pellets of the liquid crystalline polymer composition are added to the pellets prior to being subjected to the molding process so that the molding lubricant adheres to the outer surfaces of the pellets.

術語“高碳數脂族酸”於用在本文中之時係指稱具有10至25個碳原子者。The term "high carbon number aliphatic acid" as used herein refers to those having from 10 to 25 carbon atoms.

於本發明的液晶性聚合物中可以加入一種或多種其他的樹脂成分。該等其他樹脂成分的例子包括熱塑性樹脂諸如聚醯胺、聚酯、聚伸苯硫化物、聚醚酮、聚碳酸酯、聚伸苯醚和其變性衍生物、聚碸、聚醚碸、和聚醚醯亞胺以及熱固性樹脂諸如酚樹脂、環氧樹脂和聚醯亞胺樹脂。包含其他樹脂成分的液晶性聚合物可包括在本發明範圍之內。One or more other resin components may be added to the liquid crystalline polymer of the present invention. Examples of such other resin components include thermoplastic resins such as polyamides, polyesters, polyphenylene sulfides, polyetherketones, polycarbonates, polyphenylene ethers and denatured derivatives thereof, polyfluorenes, polyether oximes, and Polyether sulfimine and thermosetting resins such as phenol resins, epoxy resins and polyimide resins. Liquid crystalline polymers containing other resin components may be included in the scope of the present invention.

該等附加樹脂的量沒有受到限制,且可以根據所欲性質而定。典型地,此等附加樹脂加到液晶性聚合物組成物中的量於每100重量份的液晶性聚合物可為1至200重量份,較佳者10至100重量份。The amount of such additional resins is not limited and may depend on the desired properties. Typically, the amount of such additional resin added to the liquid crystalline polymer composition may be from 1 to 200 parts by weight, preferably from 10 to 100 parts by weight, per 100 parts by weight of the liquid crystalline polymer.

本發明液晶性聚合物組成物可以經由將其他纖維狀、層狀和粒狀填充料、添加劑和其他樹脂成分以及滑石添加到該液晶性聚合物中且在從靠近該聚合物的熔點到該熔點加30℃的溫度使用捏合機器諸如Banbury混合機、捏合機、單螺桿擠壓機、雙螺桿擠壓機和類似者,熔融捏合該混合物而得到。The liquid crystalline polymer composition of the present invention can be added to the liquid crystalline polymer via other fibrous, layered and granular fillers, additives and other resin components, and talc, and from the melting point of the polymer to the melting point The temperature at 30 ° C is obtained by melt kneading the mixture using a kneading machine such as a Banbury mixer, a kneader, a single screw extruder, a twin screw extruder, and the like.

所得到的本發明液晶性聚合物組成物展現出極為低的翹曲。例如,由本發明液晶性聚合物組成物所製造的檢驗碟(test disk)按照下面所述測定展現出的等於或小於6.0毫米,較佳者等於或小於5.5毫米,且更佳者等於或小於5.0毫米之翹曲。The obtained liquid crystalline polymer composition of the present invention exhibited extremely low warpage. For example, a test disk manufactured from the liquid crystalline polymer composition of the present invention exhibits a value equal to or less than 6.0 mm, preferably equal to or less than 5.5 mm, and more preferably equal to or less than 5.0 as measured as described below. Warp of millimeters.

<測定LCP翹曲之方法><Method for measuring LCP warpage>

將使用射出成形機(Nissei Plastic Industrial Co.,Ltd.,UH-1000-110)製造的具有1.0毫米厚度和100毫米直徑之檢驗碟在23℃溫度和50%相對濕度靜置24小時。然後,將該檢驗碟放置在表面板上且使用高度計(height gage;Mitutoyo Corporation,HDM-30)測量從該表面板的平面到檢驗碟邊緣上端之距離。所測量到的距離即定義為該檢驗碟的翹曲。A test dish having a thickness of 1.0 mm and a diameter of 100 mm manufactured using an injection molding machine (Nissei Plastic Industrial Co., Ltd., UH-1000-110) was allowed to stand at a temperature of 23 ° C and a relative humidity of 50% for 24 hours. Then, the test dish was placed on the surface plate and the distance from the plane of the surface plate to the upper end of the edge of the test dish was measured using a height gauge (Mitutoyo Corporation, HDM-30). The measured distance is defined as the warpage of the test disc.

根據本發明的液晶性聚合物組成物可以使用習用的熔融模塑方法諸如射出成形和壓縮成形予以模塑而給予模製物、膜、片和不織物等產品。The liquid crystalline polymer composition according to the present invention can be molded into a molded article, a film, a sheet, and a non-woven fabric using a conventional melt molding method such as injection molding and compression molding.

特別者,可適當地使用本發明液晶性聚合物組成物來製造在高廻銲溫度加工的模製物,例如,開關、繼電器、連接器、晶片、光學讀取器、反相器變換器(inverter trans)和線圈捲線筒,乃是因為本發明液晶性聚合物組成物在模塑時展示出優良的流動性且即使在高溫之下形成較小的翹曲之故。In particular, the liquid crystalline polymer composition of the present invention can be suitably used to manufacture a molded article processed at a high soldering temperature, for example, a switch, a relay, a connector, a wafer, an optical reader, and an inverter converter ( The inverter trans) and the coil bobbin are because the liquid crystalline polymer composition of the present invention exhibits excellent fluidity upon molding and forms small warpage even at high temperatures.

[實施例][Examples]

至此要參照下面的實施例進一步說明本發明。下面該等實施例係要用來示範說明本發明而無意用來限制本發明的範圍。The invention has been further described so far with reference to the following examples. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

於諸實施例和比較實施例中,有用到下列縮寫:<液晶性聚合物>LCP 1:UENO LCP2500(Ueno Fine Chemical Industry,Ltd.,4-羥基苯甲酸/6-羥基-2-萘甲酸/對苯二甲酸/氫醌共聚物,熔化溫度335℃)LCP 2:UENO LCP6700(Ueno Fine Chemical Industry,Ltd.,4-羥基苯甲酸/6-羥基-2-萘甲酸/2,6-萘二羧酸//氫醌共聚物,熔化溫度330℃)In the examples and comparative examples, the following abbreviations are used: <liquid crystalline polymer> LCP 1: UENO LCP2500 (Ueno Fine Chemical Industry, Ltd., 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/ Terephthalic acid/hydroquinone copolymer, melting temperature 335 ° C) LCP 2: UENO LCP6700 (Ueno Fine Chemical Industry, Ltd., 4-hydroxybenzoic acid / 6-hydroxy-2-naphthoic acid/2,6-naphthalene Carboxylic acid / / hydroquinone copolymer, melting temperature 330 ° C)

<滑石>滑石1(Talc 1):FUJI TALC INDUSTRIAL CO.,HK-A(長寬比3.6,中間粒子直徑24.0微米,水分含量0.13重量%)滑石2(Talc 2):FUJI TALC INDUSTRIAL CO.,FG1-A(長寬比3.6,中間粒子直徑26.1微米,水分含量0.07重量%)滑石3(Talc 3):FUJI TALC INDUSTRIAL CO.,DS-34(長寬比2.6,中間粒子直徑19.8微米,水分含量0.24重量%)<Talc> Talc 1: FUJI TALC INDUSTRIAL CO., HK-A (length to width ratio 3.6, intermediate particle diameter 24.0 μm, moisture content 0.13 wt%) Talc 2: FUJI TALC INDUSTRIAL CO., FG1-A (length ratio 3.6, intermediate particle diameter 26.1 μm, moisture content 0.07 wt%) Talc 3: FUJI TALC INDUSTRIAL CO., DS-34 (length to width ratio 2.6, intermediate particle diameter 19.8 μm, moisture Content 0.24% by weight)

<纖維狀填充料>GF 1:玻璃纖維,NSG Vetrotex K.K.,10EC 3MM92C(中間纖維直徑l0微米)GF 2:橢圓玻璃纖維,Nitto Boseki Co.,Ltd.,CSG 3PA 831S(中間截面短軸7微米,中間截面長軸28微米)<Fibrous filler> GF 1: Glass fiber, NSG Vetrotex KK, 10EC 3MM92C (intermediate fiber diameter 10 μm) GF 2: Elliptical glass fiber, Nitto Boseki Co., Ltd., CSG 3PA 831S (intermediate section short axis 7 μm , the middle section has a long axis of 28 microns)

實施例1至5和比較實施例1至3將LCP 1、滑石、和纖維狀填充料(GF 1)混合。每100重量份LCP 1的滑石和纖維狀填充料之重量份數都顯示於表2之中。使用雙螺桿擠壓機(The Japan Steel Works,LTD.,TEX-30 α)將該混合物熔融捏合而給予液晶性聚合物組成物小粒。Examples 1 to 5 and Comparative Examples 1 to 3 mixed LCP 1, talc, and fibrous filler (GF 1). The parts by weight of the talc and fibrous filler per 100 parts by weight of LCP 1 are shown in Table 2. The mixture was melt-kneaded using a twin-screw extruder (The Japan Steel Works, LTD., TEX-30 α) to give pellets of the liquid crystalline polymer composition.

使用所得液晶性聚合物組成物小粒在表1中所示條件下射出成形而得檢驗碟。測量該檢驗碟的翹曲。表2顯示出翹曲測量結果。Using the obtained liquid crystalline polymer composition pellets, injection molding was carried out under the conditions shown in Table 1 to obtain test discs. The warpage of the test disc was measured. Table 2 shows the results of the warpage measurement.

含有滑石但是不含纖維狀填充料的實施例1之液晶性聚合物組成物的翹曲小於3毫米。此翹曲值係極為小者。The liquid crystalline polymer composition of Example 1 containing talc but no fibrous filler had a warpage of less than 3 mm. This warpage value is extremely small.

實施例2和比較實施例1之液晶性聚合物組成物,實施例3和比較實施例2之液晶性聚合物組成物,以及實施例4和比較實施例3之液晶性聚合物組成物分別含有相同量的滑石和纖維狀填充料。實施例和比較實施例之間的差別為滑石類型,前者所含滑石具有比後者所含者為較大的長寬比。比較該等實施例和比較實施例的LCP組成物之翹曲之下,該等實施例2至4的液晶性聚合物組成物展示出分別比該等比較實施例1至3者較為小的翹曲值。The liquid crystalline polymer compositions of Example 2 and Comparative Example 1, the liquid crystalline polymer compositions of Example 3 and Comparative Example 2, and the liquid crystalline polymer compositions of Example 4 and Comparative Example 3 respectively contained The same amount of talc and fibrous filler. The difference between the examples and the comparative examples is the type of talc, and the talc contained in the former has a larger aspect ratio than that contained in the latter. Comparing the warpage of the LCP compositions of the examples and the comparative examples, the liquid crystalline polymer compositions of the above Examples 2 to 4 exhibited smaller warps than those of Comparative Examples 1 to 3, respectively. Curvature.

實施例6至8和比較實施例4將LCP 2、滑石、和纖維狀填充料混合。每100重量份LCP 2的滑石和纖維狀填充料之重量份數都顯示於表4之中。使用雙螺桿擠壓機(The Japan Steel Works,LTD.,TEX-30 α)將該混合物熔融捏合而給予液晶性聚合物組成物丸粒。Examples 6 to 8 and Comparative Example 4 were mixed with LCP 2, talc, and fibrous filler. The parts by weight of the talc and fibrous filler per 100 parts by weight of LCP 2 are shown in Table 4. The mixture was melt-kneaded using a twin-screw extruder (The Japan Steel Works, LTD., TEX-30 α) to give a liquid crystal polymer composition pellet.

使用所得液晶性聚合物組成物小粒在表1中所示條件下射出成形而得檢驗碟。測量該檢驗碟的翹曲。Using the obtained liquid crystalline polymer composition pellets, injection molding was carried out under the conditions shown in Table 1 to obtain test discs. The warpage of the test disc was measured.

另外,使用所得液晶性聚合物組成物小粒在表3中所示條件下射出成形而得具有127毫米長度,12.7毫米寬度和3.2毫米厚度的檢驗條。使用該檢驗條根據ASTM D 648在1.82 MPa之荷重下且使用2℃/分鐘的加熱速率測量荷重下變形溫度(DTUL)。Further, using the obtained liquid crystalline polymer composition pellets, injection molding was carried out under the conditions shown in Table 3 to obtain test strips having a length of 127 mm, a width of 12.7 mm, and a thickness of 3.2 mm. The load deformation temperature (DTUL) was measured using a test strip according to ASTM D 648 under a load of 1.82 MPa and using a heating rate of 2 ° C/min.

表4顯示出翹曲和DTUL的測量結果。Table 4 shows the measurement results of warpage and DTUL.

含有長寬比3.6的滑石之實施例6至8液晶性聚合物組成物的翹曲小於6.0毫米。另一方面,含有長寬比2.6的滑石之比較實施例4液晶性聚合物組成物的翹曲超過6.0毫米。The liquid crystal polymer compositions of Examples 6 to 8 containing talc having an aspect ratio of 3.6 had a warpage of less than 6.0 mm. On the other hand, the liquid crystal polymer composition of Comparative Example 4 containing talc having an aspect ratio of 2.6 had a warpage exceeding 6.0 mm.

此外,含有大的長寬比的滑石和橢圓形玻璃纖維(GF2)之液晶性聚合物組成物的翹曲小於含有滑石和GF1者。Further, the liquid crystal polymer composition containing a large aspect ratio of talc and elliptical glass fiber (GF2) has a smaller warpage than those containing talc and GF1.

再者,含有水分含量為0.24重量%的滑石3之比較實施例4的液晶性聚合物組成物展示出比含有水分含量為等於或少於0.2重量%的滑石1和滑石2之實施例6至8較為低的荷重下變形溫度(DTUL)。Further, the liquid crystalline polymer composition of Comparative Example 4 containing talc 3 having a moisture content of 0.24% by weight exhibited Example 6 to talc 1 and talc 2 having a moisture content of 0.2% by weight or less. 8 lower load deformation temperature (DTUL).

Claims (12)

一種液晶性聚合物組成物,包含:100重量份的液晶性聚合物和1至200重量份的滑石,該滑石具有5至100微米之中間粒子直徑和3.0以上且未達4.0的長寬比。 A liquid crystalline polymer composition comprising: 100 parts by weight of a liquid crystalline polymer and 1 to 200 parts by weight of talc having an intermediate particle diameter of 5 to 100 μm and an aspect ratio of 3.0 or more and less than 4.0. 如申請專利範圍第1項之液晶性聚合物組成物,其中,該滑石具有3.0至3.6的長寬比。 The liquid crystalline polymer composition of claim 1, wherein the talc has an aspect ratio of 3.0 to 3.6. 如申請專利範圍第1或2項之液晶性聚合物組成物,其中,該液晶性聚合物組成物係選自4-羥基苯甲酸/6-羥基-2-萘甲酸/對苯二甲酸/氫醌共聚物及4-羥基苯甲酸/6-羥基-2-萘甲酸/2,6-萘二羧酸/氫醌共聚物所組成群組。 The liquid crystalline polymer composition of claim 1 or 2, wherein the liquid crystalline polymer composition is selected from the group consisting of 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/terephthalic acid/hydrogen A group of rhodium copolymers and 4-hydroxybenzoic acid/6-hydroxy-2-naphthoic acid/2,6-naphthalenedicarboxylic acid/hydroquinone copolymer. 如申請專利範圍第1或2項之液晶性聚合物組成物,其中,該滑石的水分含量為等於或少於0.2重量%。 The liquid crystalline polymer composition of claim 1 or 2, wherein the talc has a moisture content of 0.2% by weight or less. 如申請專利範圍第1或2項之液晶性聚合物組成物,其進一步包含1至200重量份的纖維狀填充料。 The liquid crystalline polymer composition of claim 1 or 2 further comprising 1 to 200 parts by weight of a fibrous filler. 如申請專利範圍第5項之液晶性聚合物組成物,其中,該纖維狀填充料係選自下述所成組群:玻璃纖維、橢圓形玻璃纖維、繭形玻璃纖維、氧化矽-氧化鋁纖維、氧化鋁纖維、碳纖維、芳綸(aramid)纖維、鈦酸鉀纖維、硼酸鋁纖維、矽灰石(wollastonite)及彼等的組合。 The liquid crystalline polymer composition of claim 5, wherein the fibrous filler is selected from the group consisting of glass fiber, elliptical glass fiber, bismuth glass fiber, cerium oxide-alumina Fiber, alumina fiber, carbon fiber, aramid fiber, potassium titanate fiber, aluminum borate fiber, wollastonite, and combinations thereof. 如申請專利範圍第6項之液晶性聚合物組成物,其中,該纖維狀填充料係選自下述所成組群:玻璃纖維、橢圓形玻璃纖維、繭形玻璃纖維及彼等的組合。 The liquid crystalline polymer composition of claim 6, wherein the fibrous filler is selected from the group consisting of glass fibers, elliptical glass fibers, scorpion glass fibers, and combinations thereof. 如申請專利範圍第1或2項之液晶性聚合物組成物,其 進一步包含1至200重量份的除了滑石以外之層狀或粒狀填充料。 A liquid crystalline polymer composition as claimed in claim 1 or 2, Further, 1 to 200 parts by weight of a layered or granular filler other than talc is contained. 如申請專利範圍第8項之液晶性聚合物組成物,其中,該層狀或粒狀填充料係選自下述所成組群:雲母、石墨、碳酸鈣、白雲石、黏土、玻璃薄片、玻璃珠粒、硫酸鋇、氧化鈦及彼等的組合。 The liquid crystalline polymer composition of claim 8, wherein the layered or granular filler is selected from the group consisting of mica, graphite, calcium carbonate, dolomite, clay, glass flakes, Glass beads, barium sulfate, titanium oxide, and combinations thereof. 如申請專利範圍第1或2項之液晶性聚合物組成物,其中經由將該液晶性聚合物組成物模塑所得具有1.0毫米厚度和100毫米直徑的檢驗碟,在該檢驗碟於23℃的溫度和50%的相對濕度靜置24小時之後測定的翹曲值為等於或小於6.0毫米。 The liquid crystalline polymer composition of claim 1 or 2, wherein the test disc having a thickness of 1.0 mm and a diameter of 100 mm is obtained by molding the liquid crystalline polymer composition at 23 ° C The warp value measured after the temperature and 50% relative humidity were allowed to stand for 24 hours was equal to or less than 6.0 mm. 一種模製物,係經由將申請專利範圍第1至10項中任一項之液晶性聚合物組成物模塑而得者。 A molded article obtained by molding the liquid crystalline polymer composition according to any one of claims 1 to 10. 如申請專利範圍第11項之模製物,其係選自下述所成組群:開關、繼電器、連接器、晶片、光學讀取器、反相器變換器(inverter trans)和線圈捲線筒。 The molded article of claim 11 is selected from the group consisting of a switch, a relay, a connector, a wafer, an optical reader, an inverter trans, and a coil reel. .
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Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5935288B2 (en) * 2010-10-29 2016-06-15 住友化学株式会社 Liquid crystalline polyester composition
KR101309914B1 (en) 2011-02-28 2013-09-17 도레이 카부시키가이샤 Liquid crystal polyester resin composition and metal composite molded article using same
KR101763948B1 (en) * 2011-05-06 2017-08-01 심천 워트 어드밴스드 머티리얼즈 주식회사 Reflector and light emitting device having the same
JP5730704B2 (en) * 2011-07-27 2015-06-10 上野製薬株式会社 Liquid crystal polymer composition
JP2016510831A (en) 2013-03-13 2016-04-11 ティコナ・エルエルシー Liquid crystal polymer composition
CN103194078A (en) * 2013-04-27 2013-07-10 苏州正豪塑胶电子有限公司 High-strength and high temperature resistant plug connector
CN103194080A (en) * 2013-04-27 2013-07-10 苏州正豪塑胶电子有限公司 Corrosion-resistant plug connector
CN103194081A (en) * 2013-04-27 2013-07-10 苏州正豪塑胶电子有限公司 Corrosion-resistant and high-strength plug connector
CN103194077A (en) * 2013-04-27 2013-07-10 苏州正豪塑胶电子有限公司 High-strength plug connector
CN103194083A (en) * 2013-04-27 2013-07-10 苏州正豪塑胶电子有限公司 High-temperature-resistant and durable plug connector
CN103194082A (en) * 2013-04-27 2013-07-10 苏州正豪塑胶电子有限公司 High-temperature-resistant plug connector
JP6165553B2 (en) * 2013-08-21 2017-07-19 上野製薬株式会社 Liquid crystal polymer composition
CN103865243B (en) * 2014-03-28 2015-08-19 上海瀚氏模具成型有限公司 Automotive upholstery toughness reinforcing damage resistant PBT plastic and preparation method thereof
JP6774329B2 (en) 2016-12-28 2020-10-21 住友化学株式会社 Liquid crystal polyester resin composition
CN106674929A (en) * 2016-12-29 2017-05-17 江苏沃特特种材料制造有限公司 Liquid crystal polyester composite with enhanced moisture barrier property and preparation method thereof
KR102627886B1 (en) 2017-12-05 2024-01-19 티코나 엘엘씨 Aromatic polymer compositions for use in camera modules
KR20220146567A (en) 2020-02-26 2022-11-01 티코나 엘엘씨 electronic device
KR20220145385A (en) 2020-02-26 2022-10-28 티코나 엘엘씨 circuit structure
US11702539B2 (en) 2020-02-26 2023-07-18 Ticona Llc Polymer composition for an electronic device
US11728065B2 (en) 2020-07-28 2023-08-15 Ticona Llc Molded interconnect device
CN112126244B (en) * 2020-09-09 2022-06-07 金发科技股份有限公司 Liquid crystal polymer composition
CN112552649A (en) * 2020-12-04 2021-03-26 张家港大塚化学有限公司 Preparation method of liquid crystal composite material for LED
CN113512303A (en) * 2021-05-14 2021-10-19 金发科技股份有限公司 Liquid crystal polymer composite material and application thereof
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Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3060110B2 (en) * 1990-05-29 2000-07-10 日本石油化学株式会社 Method for producing a thermotropic liquid crystal polyester resin composition having improved blister resistance
JP4450902B2 (en) * 1999-10-08 2010-04-14 ポリプラスチックス株式会社 Liquid crystalline polymer composition
JP2001207054A (en) * 2000-01-24 2001-07-31 Polyplastics Co Molded article of liquid crystalline polymer
JP2003268252A (en) * 2002-03-19 2003-09-25 Polyplastics Co Liquid crystalline polymer composition
JP4150015B2 (en) * 2004-04-22 2008-09-17 新日本石油株式会社 Totally aromatic liquid crystal polyester resin composition and optical pickup lens holder
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