JPWO2020070903A1 - Liquid crystal polyester resin - Google Patents
Liquid crystal polyester resin Download PDFInfo
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- JPWO2020070903A1 JPWO2020070903A1 JP2018568458A JP2018568458A JPWO2020070903A1 JP WO2020070903 A1 JPWO2020070903 A1 JP WO2020070903A1 JP 2018568458 A JP2018568458 A JP 2018568458A JP 2018568458 A JP2018568458 A JP 2018568458A JP WO2020070903 A1 JPWO2020070903 A1 JP WO2020070903A1
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- 239000004645 polyester resin Substances 0.000 title claims abstract description 100
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 100
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 96
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 238000005452 bending Methods 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 description 28
- 239000000178 monomer Substances 0.000 description 17
- 239000008188 pellet Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- -1 phosphorus compound Chemical class 0.000 description 15
- 238000001746 injection moulding Methods 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002253 acid Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 239000000454 talc Substances 0.000 description 7
- 229910052623 talc Inorganic materials 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 2
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Abstract
本発明は、機械物性に優れるとともに、リフロー時のブリスターの発生が抑制された液晶ポリエステル樹脂を提供することを目的とする。本発明は、式（Ｉ）〜（Ｖ）［式中、ｐ、ｑ、ｒ、ｓおよびｔは、それぞれ、液晶ポリエステル樹脂中での各繰返し単位の組成比（モル％）であり、以下の条件を満たす：１５≦ｐ≦３０、７０≦ｑ≦８５、０．０１≦ｒ＋ｓ＋ｔ＜２、ここで、ｒ、ｓ、ｔは、それぞれ０以上２未満であり、但し、ｒ、ｓ、ｔは同時に０でない］で表される繰返し単位から構成される液晶ポリエステル樹脂に関する。An object of the present invention is to provide a liquid crystal polyester resin having excellent mechanical properties and suppressing the generation of blisters during reflow. In the present invention, the formulas (I) to (V) [in the formula, p, q, r, s and t are composition ratios (mol%) of each repeating unit in the liquid crystal polyester resin, and are as follows. Satisfy the conditions: 15 ≦ p ≦ 30, 70 ≦ q ≦ 85, 0.01 ≦ r + s + t <2, where r, s, t are 0 or more and less than 2, respectively, where r, s, t are It relates to a liquid crystal polyester resin composed of repeating units represented by [not 0 at the same time].
Description
本特許出願は日本国特許出願第２０１８−１８７３９２号（出願日：２０１８年１０月２日）についてパリ条約上の優先権を主張するものであり、ここに参照することによって、その全体が本明細書中へ組み込まれるものとする。
本発明は、リフロー時のブリスターの発生が抑制された液晶ポリエステル樹脂に関する。This patent application claims priority under the Paris Convention for Japanese Patent Application No. 2018-187392 (filed on October 2, 2018), and by reference here in its entirety, this specification. It shall be incorporated into the document.
The present invention relates to a liquid crystal polyester resin in which the generation of blisters during reflow is suppressed.
サーモトロピック液晶ポリエステル樹脂（以下、液晶ポリエステル樹脂またはＬＣＰとも称する）は、耐熱性、剛性等の機械物性、耐薬品性、寸法精度等に優れているため、成形品用途のみならず、繊維やフィルムといった各種用途にその使用が拡大しつつある。 Thermotropic liquid crystal polyester resin (hereinafter, also referred to as liquid crystal polyester resin or LCP) is excellent in mechanical properties such as heat resistance and rigidity, chemical resistance, dimensional accuracy, etc., so it is used not only for molded products but also for fibers and films. Its use is expanding to various uses such as.
特にパーソナル・コンピューターや携帯電話等の情報・通信分野においては、部品の高集積度化、小型化、薄肉化、低背化が急速に進んでおり、非常に薄い肉厚部が形成されるケースが多い。そこで、ＬＣＰはその優れた成形性、すなわち流動性が良好であり、かつバリが出ないという他の樹脂にない特徴を生かして、その使用量が大幅に増大している。電気電子部品として有用な成形品を構成するための液晶ポリエステル樹脂として、特定の構成単位を必須とする全芳香族ポリエステルが提案されている（特許文献１〜２）。 Especially in the information and communication fields such as personal computers and mobile phones, the degree of integration, miniaturization, thinning, and thinning of parts are rapidly progressing, and very thin thick parts are formed. There are many. Therefore, the amount of LCP used has been greatly increased by taking advantage of its excellent moldability, that is, good fluidity and no burrs, which are not found in other resins. As a liquid crystal polyester resin for forming a molded product useful as an electric / electronic component, an all-aromatic polyester that requires a specific structural unit has been proposed (Patent Documents 1 and 2).
しかしながら、近年、はんだの鉛フリー化により、コネクターなどの電子部品用途において、リフロー温度が高温化しており、液晶ポリエステル樹脂の成形品においても高温でのリフロー処理により生じるブリスターと呼ばれる成形品表面の膨れの発生が問題となっている。 However, in recent years, the reflow temperature has become high in electronic component applications such as connectors due to the lead-free soldering, and even in molded products of liquid crystal polyester resin, swelling of the molded product surface called blister caused by the reflow treatment at high temperature has occurred. Is a problem.
かかるブリスターの発生は、金型ないしホッパー内に存在する空気や、樹脂に内包される分解ガス、空気ないし水分が原因であると考えられている。 It is considered that the generation of such blisters is caused by air existing in the mold or hopper, decomposition gas contained in the resin, air or moisture.
また、リフロー温度が高温化した場合には、液晶ポリエステル樹脂の成形品に反りが生じやすくなる問題があり、反りの発生を抑制するために液晶ポリエステル樹脂にタルクなどの充填材を配合することが知られている。 In addition, when the reflow temperature rises, there is a problem that the molded product of the liquid crystal polyester resin tends to warp, and in order to suppress the occurrence of warpage, a filler such as talc may be added to the liquid crystal polyester resin. Are known.
しかし、タルク等の充填材は微量の水分を含有しているために、タルク等の充填材を含有する液晶ポリエステル樹脂組成物においては、成形品の反りの発生は抑制されるものの、ブリスターの発生がより増加しやすくなる問題を有する。 However, since the filler such as talc contains a small amount of water, in the liquid crystal polyester resin composition containing the filler such as talc, the occurrence of warpage of the molded product is suppressed, but the occurrence of blisters is generated. Has a problem that is more likely to increase.
このような、液晶ポリエステル樹脂の成形品のブリスター発生の問題を解消する方法について多数の方法が提案されている。具体的には、シリコーンゴム、リン化合物、ホウ素化合物などを添加剤として配合する方法（特許文献３〜１０）、射出成形時のスクリュー圧縮比を調整する方法（特許文献１１）、または液晶ポリエステル樹脂と無機充填材を溶融混練する場合のスクリュー噛合率を調整する方法（特許文献１２）などが知られている。 A number of methods have been proposed for solving such a problem of blistering in a molded product of a liquid crystal polyester resin. Specifically, a method of blending a silicone rubber, a phosphorus compound, a boron compound or the like as an additive (Patent Documents 3 to 10), a method of adjusting a screw compression ratio during injection molding (Patent Document 11), or a liquid crystal polyester resin. And a method of adjusting the screw meshing ratio when the inorganic filler is melt-kneaded (Patent Document 12) and the like are known.
しかしながら、ブリスターの発生を抑制するために各種の添加剤を配合する方法については、ブリスター発生の抑制効果は改善の余地のあるものであり、添加剤によっては液晶ポリエステル樹脂組成物の機械物性が大きく低下する問題があった。 However, with respect to the method of blending various additives to suppress the generation of blisters, the effect of suppressing the generation of blisters has room for improvement, and depending on the additives, the mechanical properties of the liquid crystal polyester resin composition are large. There was a problem of decline.
また、射出成形時や、液晶ポリエステル樹脂と無機充填材との溶融混練時のスクリューの設定を調整する方法については、添加剤を配合する方法と比較し、大きな作業負担がかかる問題があった。 Further, the method of adjusting the screw setting at the time of injection molding or at the time of melt-kneading the liquid crystal polyester resin and the inorganic filler has a problem that a large work load is applied as compared with the method of blending an additive.
これらの事情から、添加剤の配合や成形時などのスクリューの設定調整などの操作を必要とせずに、耐ブリスター性に優れた液晶ポリエステル樹脂の開発が強く望まれている。 Under these circumstances, it is strongly desired to develop a liquid crystal polyester resin having excellent blister resistance without the need for operations such as blending additives and adjusting screw settings during molding.
本発明の目的は、機械物性に優れるとともに、リフロー時のブリスターの発生が抑制された液晶ポリエステル樹脂を提供することにある。 An object of the present invention is to provide a liquid crystal polyester resin having excellent mechanical properties and suppressing the generation of blisters during reflow.
本発明者等は、上記課題に鑑み、鋭意検討した結果、特定の繰返し単位を与える単量体を縮重合することによって、優れた機械物性を維持しつつ、リフロー時のブリスターの発生が抑制された液晶ポリエステル樹脂が得られることを見出し、本発明を完成させるに至った。 As a result of diligent studies in view of the above problems, the present inventors have suppressed the generation of blister during reflow while maintaining excellent mechanical properties by polycondensing a monomer giving a specific repeating unit. We have found that a liquid polyester resin can be obtained, and have completed the present invention.
すなわち、本発明は、以下の式（Ｉ）〜（Ｖ）で表される繰返し単位から構成される液晶ポリエステル樹脂に関する。
［式中、
ｐ、ｑ、ｒ、ｓおよびｔは、それぞれ、液晶ポリエステル樹脂中での各繰返し単位の組成比（モル％）であり、以下の条件を満たす：
１５≦ｐ≦３０、
７０≦ｑ≦８５、
０．０１≦ｒ＋ｓ＋ｔ＜２、ここで、ｒ、ｓ、ｔは、それぞれ０以上２未満であり、但し、これらは同時に０でない。］
また、本発明の好ましい実施形態は、下記式で表される繰返し単位から構成される液晶ポリエステル樹脂に関する。
ｐ、ｑ、ｓおよびｔは、それぞれ、液晶ポリエステル樹脂中での各繰返し単位の組成比（モル％）であり、以下の条件を満たす：
１５≦ｐ≦３０、
７０≦ｑ≦８５、
０．０１≦ｓ＋ｔ＜２、ここで、ｓ、ｔは、それぞれ０以上２未満であり、但し、これらは同時に０でない。］[During the ceremony,
p, q, r, s and t are composition ratios (mol%) of each repeating unit in the liquid crystal polyester resin, respectively, and satisfy the following conditions:
15 ≦ p ≦ 30,
70 ≤ q ≤ 85,
0.01 ≦ r + s + t <2, where r, s, and t are 0 or more and less than 2, respectively, but they are not 0 at the same time. ]
Further, a preferred embodiment of the present invention relates to a liquid crystal polyester resin composed of a repeating unit represented by the following formula.
p, q, s and t are composition ratios (mol%) of each repeating unit in the liquid crystal polyester resin, respectively, and satisfy the following conditions:
15 ≦ p ≦ 30,
70 ≤ q ≤ 85,
0.01 ≦ s + t <2, where s and t are 0 or more and less than 2, respectively, but they are not 0 at the same time. ]
本発明の液晶ポリエステル樹脂は、引張強度・引張弾性率や曲げ強度・曲げ弾性率などの機械物性に優れ、かつリフロー時のブリスターの発生が著しく抑制される。そのため、本発明の液晶ポリエステル樹脂は、薄層化、高集積化したコネクター、カメラモジュール、アンテナ、基板などの電気電子用部品の材料として好適に使用することができる。 The liquid crystal polyester resin of the present invention is excellent in mechanical properties such as tensile strength / tensile elastic modulus and bending strength / flexural modulus, and the generation of blisters during reflow is remarkably suppressed. Therefore, the liquid crystal polyester resin of the present invention can be suitably used as a material for electrical and electronic parts such as thin-layered and highly integrated connectors, camera modules, antennas, and substrates.
本明細書および請求の範囲において、「液晶ポリエステル樹脂」とは異方性溶融相を形成するポリエステル樹脂であり、当該技術分野においてサーモトロピック液晶ポリエステル樹脂と呼ばれているものである。 In the present specification and claims, the "liquid crystal polyester resin" is a polyester resin that forms an anisotropic molten phase, and is called a thermotropic liquid crystal polyester resin in the art.
液晶ポリエステル樹脂の異方性溶融相の性質は、直交偏向子を利用した通常の偏光検査法により確認することができる。より具体的には、異方性溶融相の確認は、Ｌｅｉｔｚ偏光顕微鏡を使用し、Ｌｅｉｔｚホットステージに載せた試料を窒素雰囲気下で４０倍の倍率で観察することにより実施できる。本発明の液晶ポリエステル樹脂は光学的に異方性を示すもの、すなわち、直交偏光子の間で検査したときに光を透過させるものである。試料が光学的に異方性であると、たとえ静止状態であっても偏光は透過する。 The properties of the anisotropic molten phase of the liquid crystal polyester resin can be confirmed by a normal polarization inspection method using an orthogonal deflector. More specifically, the confirmation of the anisotropic molten phase can be carried out by observing the sample placed on the Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere using a Leitz polarizing microscope. The liquid crystal polyester resin of the present invention is optically anisotropic, that is, it transmits light when inspected between orthogonal polarizers. If the sample is optically anisotropic, polarized light will be transmitted even in the stationary state.
本発明の液晶ポリエステル樹脂は、式（Ｉ）〜（Ｖ）で表される繰返し単位から構成される。
［式中、
ｐ、ｑ、ｒ、ｓおよびｔは、それぞれ、液晶ポリエステル樹脂中での各繰返し単位の組成比（モル％）であり、以下の条件を満たす：
１５≦ｐ≦３０、
７０≦ｑ≦８５、
０．０１≦ｒ＋ｓ＋ｔ＜２、ここで、ｒ、ｓ、ｔは、それぞれ０以上２未満であり、但し、ｒ、ｓ、ｔは同時に０でない。］[During the ceremony,
p, q, r, s and t are composition ratios (mol%) of each repeating unit in the liquid crystal polyester resin, respectively, and satisfy the following conditions:
15 ≦ p ≦ 30,
70 ≤ q ≤ 85,
0.01 ≦ r + s + t <2, where r, s, and t are 0 or more and less than 2, respectively, where r, s, and t are not 0 at the same time. ]
本発明の液晶ポリエステル樹脂において、式（Ｉ）で表される繰返し単位の全繰返し単位に対する組成比ｐは１５〜３０モル％、好ましくは１６〜２５モル％、より好ましくは１７〜２４モル％、さらに好ましくは１８〜２４モル％である。 In the liquid crystal polyester resin of the present invention, the composition ratio p of the repeating unit represented by the formula (I) to all repeating units is 15 to 30 mol%, preferably 16 to 25 mol%, more preferably 17 to 24 mol%. More preferably, it is 18 to 24 mol%.
本発明の液晶ポリエステル樹脂において、式（ＩＩ）で表される繰返し単位の全繰返し単位に対する組成比ｑは７０〜８５モル％、好ましくは７５〜８４モル％、より好ましくは７６〜８３モル％、さらに好ましくは７６〜８２モル％である。 In the liquid crystal polyester resin of the present invention, the composition ratio q of the repeating unit represented by the formula (II) to all repeating units is 70 to 85 mol%, preferably 75 to 84 mol%, more preferably 76 to 83 mol%. More preferably, it is 76 to 82 mol%.
式（Ｉ）に係る組成比ｐが３０モル％超、あるいは式（ＩＩ）に係る組成比ｑが７０モル％未満であると、得られる液晶ポリエステル樹脂の結晶融解温度が低下する。また、式（Ｉ）に係る組成比ｐが１５モル％未満、あるいは式（ＩＩ）に係る組成比ｑが８５モル％超であると、重合が困難となる。 When the composition ratio p according to the formula (I) is more than 30 mol% or the composition ratio q according to the formula (II) is less than 70 mol%, the crystal melting temperature of the obtained liquid crystal polyester resin is lowered. Further, if the composition ratio p according to the formula (I) is less than 15 mol%, or the composition ratio q according to the formula (II) is more than 85 mol%, polymerization becomes difficult.
式（Ｉ）で表される繰返し単位を与える単量体としては、例えば、４−ヒドロキシ安息香酸ならびにこのアシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性の誘導体が挙げられる。 Examples of the monomer giving the repeating unit represented by the formula (I) include 4-hydroxybenzoic acid and ester-forming derivatives such as acylates, ester derivatives and acid halides thereof.
式（ＩＩ）で表される繰返し単位を与える単量体としては、例えば、６−ヒドロキシ−２−ナフトエ酸ならびにこのアシル化物、エステル誘導体、酸ハロゲン化物などのエステル形成性の誘導体が挙げられる。 Examples of the monomer giving the repeating unit represented by the formula (II) include 6-hydroxy-2-naphthoic acid and ester-forming derivatives such as an acylated product, an ester derivative, and an acid halide.
本発明の液晶ポリエステル樹脂において、式（ＩＩＩ）で表される繰返し単位の全繰返し単位に対する組成比ｒ、式（ＩＶ）で表される繰返し単位の全繰返し単位に対する組成比ｓおよび式（Ｖ）で表される繰返し単位の全繰返し単位に対する組成比ｔの合計量（ｒ＋ｓ＋ｔ）は、０．０１モル％以上２モル％未満、好ましくは０．０３〜１．９モル％、より好ましくは０．０５〜１．８モル％、さらに好ましくは０．１〜１．７モル％、特に好ましくは０．２〜１．６である。ここで、ｒ、ｓ、ｔは、それぞれ０以上２未満であり、但し、ｒ、ｓ、ｔは同時に０でない。 In the liquid crystal polyester resin of the present invention, the composition ratio r of the repeating unit represented by the formula (III) to all the repeating units, the composition ratio s of the repeating unit represented by the formula (IV) to all the repeating units, and the formula (V). The total amount (r + s + t) of the composition ratio t with respect to all the repeating units of the repeating unit represented by is 0.01 mol% or more and less than 2 mol%, preferably 0.03 to 1.9 mol%, more preferably 0. It is 05 to 1.8 mol%, more preferably 0.1 to 1.7 mol%, and particularly preferably 0.2 to 1.6. Here, r, s, and t are each 0 or more and less than 2, but r, s, and t are not 0 at the same time.
式（ＩＩＩ）に係る組成比ｒ、式（ＩＶ）に係る組成比ｓおよび式（Ｖ）に係る組成比ｔの合計量（ｒ＋ｓ＋ｔ）が０．０１モル％未満であると、ブリスター発生の抑制効果が不十分となり、２モル％以上であると、引張強度・引張弾性率や曲げ強度・曲げ弾性率などの機械物性が低下するとともに、ブリスター発生の抑制効果も得られ難くなる。 When the total amount (r + s + t) of the composition ratio r according to the formula (III), the composition ratio s according to the formula (IV) and the composition ratio t according to the formula (V) is less than 0.01 mol%, the generation of blister is suppressed. If the effect is insufficient and is 2 mol% or more, mechanical properties such as tensile strength / tensile elastic modulus and bending strength / flexural modulus are lowered, and it is difficult to obtain an effect of suppressing blister generation.
本発明の液晶ポリエステル樹脂において、式（ＩＩＩ）で表される繰返し単位、式（ＩＶ）で表される繰返し単位および式（Ｖ）で表される繰返し単位のうち、少なくとも、いずれか１種が液晶ポリエステル樹脂の構成単位として存在する。式（ＩＩＩ）で表される繰返し単位、式（ＩＶ）で表される繰返し単位および式（Ｖ）で表される繰返し単位は、いずれか１種のみが、液晶ポリエステル樹脂の構成単位として存在してもよく、また２種以上が組み合わさって存在していてもよい。 In the liquid crystal polyester resin of the present invention, at least one of the repeating unit represented by the formula (III), the repeating unit represented by the formula (IV) and the repeating unit represented by the formula (V) is used. It exists as a constituent unit of a liquid crystal polyester resin. Only one of the repeating unit represented by the formula (III), the repeating unit represented by the formula (IV), and the repeating unit represented by the formula (V) exists as a constituent unit of the liquid crystal polyester resin. It may be present, or two or more kinds may be present in combination.
例えば、（１）液晶ポリエステル樹脂に式（ＩＶ）および式（Ｖ）で表される繰返し単位が含まれない場合（ｓおよびｔが０）、式（ＩＩＩ）に係る組成比ｒは、０．０１≦ｒ＜２であり、（２）式（ＩＩＩ）で表される繰返し単位が含まれない場合（ｒが０）、式（ＩＶ）に係る組成比ｓと式（Ｖ）に係る組成比ｔの合計量（ｓ＋ｔ）は、０．０１≦ｓ＋ｔ＜２である。 For example, (1) when the liquid crystal polyester resin does not contain the repeating units represented by the formulas (IV) and (V) (s and t are 0), the composition ratio r according to the formula (III) is 0. When 01 ≦ r <2 and the repeating unit represented by the formula (III) is not included (r is 0), the composition ratio s according to the formula (IV) and the composition ratio according to the formula (V) The total amount of t (s + t) is 0.01 ≦ s + t <2.
また、例えば、（３）液晶ポリエステル樹脂に式（ＩＩＩ）および式（Ｖ）で表される繰返し単位が含まれない場合（ｒおよびｔが０）、式（ＩＶ）に係る組成比ｓは、０．０１≦ｓ＜２であり、（４）式（ＩＶ）で表される繰返し単位が含まれない場合（ｓが０）、式（ＩＩＩ）に係る組成比ｒと式（Ｖ）に係る組成比ｔの合計量（ｒ＋ｔ）は、０．０１≦ｒ＋ｔ＜２である。 Further, for example, when (3) the liquid crystal polyester resin does not contain the repeating units represented by the formulas (III) and (V) (r and t are 0), the composition ratio s according to the formula (IV) is When 0.01 ≦ s <2 and the repeating unit represented by the formula (IV) in (4) is not included (s is 0), the composition ratio r according to the formula (III) and the formula (V) are related. The total amount (r + t) of the composition ratio t is 0.01 ≦ r + t <2.
また、例えば、（５）液晶ポリエステル樹脂に式（ＩＩＩ）および式（ＩＶ）で表される繰返し単位が含まれない場合（ｒおよびｓが０）、式（Ｖ）に係る組成比ｔは、０．０１≦ｔ＜２であり、（６）式（Ｖ）で表される繰返し単位が含まれない場合（ｔが０）、式（ＩＩＩ）に係る組成比ｒと式（ＩＶ）に係る組成比ｓの合計量（ｒ＋ｓ）は、０．０１≦ｒ＋ｓ＜２である。 Further, for example, when the liquid crystal polyester resin (5) does not contain the repeating units represented by the formulas (III) and (IV) (r and s are 0), the composition ratio t according to the formula (V) is When 0.01 ≦ t <2 and the repeating unit represented by the formula (V) in (6) is not included (t is 0), the composition ratio r according to the formula (III) and the composition ratio r according to the formula (IV) are related. The total amount (r + s) of the composition ratio s is 0.01 ≦ r + s <2.
本発明の液晶ポリエステル樹脂において、式（ＩＩＩ）で表される繰返し単位、式（ＩＶ）で表される繰返し単位および式（Ｖ）で表される繰返し単位のうち、２種以上が組み合わさって存在する場合、上記（２）、（４）及び（６）のうち、（２）式（ＩＩＩ）で表される繰返し単位が含まれない場合（ｒが０）であって、式（ＩＶ）に係る組成比ｓと式（Ｖ）に係る組成比ｔの合計量（ｓ＋ｔ）が、０．０１≦ｓ＋ｔ＜２であることが好適である。
すなわち、本発明の好ましい実施形態は、下記式：
ｐ、ｑ、ｓおよびｔは、それぞれ、液晶ポリエステル樹脂中での各繰返し単位の組成比（モル％）であり、以下の条件を満たす：
１５≦ｐ≦３０、
７０≦ｑ≦８５、
０．０１≦ｓ＋ｔ＜２、ここで、ｓ、ｔは、それぞれ０以上２未満であり、但し、これらは同時に０でない］
で表される繰返し単位から構成される液晶ポリエステル樹脂に関する。In the liquid crystal polyester resin of the present invention, two or more of the repeating unit represented by the formula (III), the repeating unit represented by the formula (IV) and the repeating unit represented by the formula (V) are combined. If it exists, of the above (2), (4) and (6), when the repeating unit represented by the formula (2) (III) is not included (r is 0), the formula (IV) It is preferable that the total amount (s + t) of the composition ratio s according to the above and the composition ratio t according to the formula (V) is 0.01 ≦ s + t <2.
That is, a preferred embodiment of the present invention is the following formula:
p, q, s and t are composition ratios (mol%) of each repeating unit in the liquid crystal polyester resin, respectively, and satisfy the following conditions:
15 ≦ p ≦ 30,
70 ≤ q ≤ 85,
0.01 ≦ s + t <2, where s and t are 0 or more and less than 2, respectively, but they are not 0 at the same time]
It relates to a liquid crystal polyester resin composed of a repeating unit represented by.
本発明の液晶ポリエステル樹脂において、式（ＩＩＩ）で表される繰返し単位、式（ＩＶ）で表される繰返し単位および式（Ｖ）で表される繰返し単位は、いずれか１種のみを含むことが好ましい。 In the liquid crystal polyester resin of the present invention, the repeating unit represented by the formula (III), the repeating unit represented by the formula (IV), and the repeating unit represented by the formula (V) include only one of them. Is preferable.
式（ＩＩＩ）で表される繰返し単位を与える単量体としては、例えば、イソフタル酸およびこのアルキル、アルコキシまたはハロゲン置換体、ならびにこれらのエステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が挙げられる。 Examples of the monomer giving the repeating unit represented by the formula (III) include isophthalic acid and its alkyl, alkoxy or halogen substituents, and ester-forming derivatives such as these ester derivatives and acid halides. ..
式（ＩＶ）で表される繰返し単位を与える単量体としては、例えば、２，６−ナフタレンジカルボン酸およびこのアルキル、アルコキシまたはハロゲン置換体、ならびにこれらのエステル誘導体、酸ハロゲン化物などのエステル形成性誘導体が挙げられる。 Examples of the monomer giving the repeating unit represented by the formula (IV) include 2,6-naphthalenedicarboxylic acid and its alkyl, alkoxy or halogen substituents, and ester formation of these ester derivatives and acid halides. Examples include sex derivatives.
式（Ｖ）で表される繰返し単位を与える単量体としては、例えば、ハイドロキノンおよびこのアルキル、アルコキシまたはハロゲン置換体、ならびにこれらのアシル化物などのエステル形成性誘導体が挙げられる。 Examples of the monomer giving the repeating unit represented by the formula (V) include hydroquinone and its alkyl, alkoxy or halogen substituents, and ester-forming derivatives such as acylated products thereof.
本発明の液晶ポリエステル樹脂において、上記各繰返し単位の組成比の合計［ｐ＋ｑ＋ｒ＋ｓ＋ｔ］が１００モル％であることが好ましいが、本発明の目的を損なわない範囲において、他の繰返し単位をさらに含んでもよい。本発明の液晶ポリエステル樹脂が他の繰返し単位をさらに含む場合、他の繰り返し単位の組成比αは、液晶ポリエステル樹脂を構成する繰返し単位の合計１００モル％に対し、１０モル％以下であるのことが好ましく、より好ましくは５モル％以下、さらに好ましくは３モル％以下、特に好ましくは１モル％以下である。 In the liquid crystal polyester resin of the present invention, the total composition ratio [p + q + r + s + t] of each of the above repeating units is preferably 100 mol%, but other repeating units may be further contained as long as the object of the present invention is not impaired. .. When the liquid crystal polyester resin of the present invention further contains other repeating units, the composition ratio α of the other repeating units is 10 mol% or less with respect to a total of 100 mol% of the repeating units constituting the liquid crystal polyester resin. Is preferable, more preferably 5 mol% or less, still more preferably 3 mol% or less, and particularly preferably 1 mol% or less.
他の繰り返し単位を与える単量体としては、芳香族ヒドロキシカルボン酸、芳香族ジオール、芳香族ジカルボン酸、芳香族ヒドロキシジカルボン酸、芳香族ヒドロキシアミン、芳香族ジアミン、芳香族アミノカルボン酸、脂環族ジカルボン酸、脂肪族ジオール、脂環族ジオール、芳香族メルカプトカルボン酸、芳香族ジチオールおよび芳香族メルカプトフェノールなどが例示される。 Examples of the monomer giving another repeating unit include aromatic hydroxycarboxylic acid, aromatic diol, aromatic dicarboxylic acid, aromatic hydroxydicarboxylic acid, aromatic hydroxyamine, aromatic diamine, aromatic aminocarboxylic acid, and alicyclic. Examples thereof include group dicarboxylic acids, aliphatic diols, alicyclic diols, aromatic mercaptocarboxylic acids, aromatic dithiols and aromatic mercaptophenols.
本発明の液晶ポリエステル樹脂の製造方法には特に限定はなく、上記単量体成分間にエステル結合を形成させる公知のポリエステル樹脂の重縮合法、たとえば溶融アシドリシス法、スラリー重合法などを用いることができる。 The method for producing the liquid crystal polyester resin of the present invention is not particularly limited, and a known polycondensation method for polyester resins for forming an ester bond between the above-mentioned monomer components, for example, a molten acidlysis method, a slurry polymerization method, or the like can be used. it can.
溶融アシドリシス法とは、最初に単量体を加熱して反応物質の溶融溶液を形成し、続いて反応を続けて溶融ポリマーを得るものである。なお、縮合の最終段階で副生する揮発物（たとえば酢酸、水など）の除去を容易にするために真空を適用してもよい。この方法は、本発明において特に好適に用いられる。 The molten acidlysis method first heats a monomer to form a molten solution of a reactant, and then continues the reaction to obtain a molten polymer. A vacuum may be applied to facilitate the removal of volatiles (eg, acetic acid, water, etc.) by-produced in the final stage of condensation. This method is particularly preferably used in the present invention.
スラリー重合法とは、熱交換流体の存在下で反応させる方法であって、固体生成物は熱交換媒質中に懸濁した状態で得られる。 The slurry polymerization method is a method of reacting in the presence of a heat exchange fluid, and the solid product is obtained in a state of being suspended in a heat exchange medium.
溶融アシドリシス法およびスラリー重合法のいずれの場合においても、液晶ポリエステル樹脂を製造する際に使用する重合性単量体成分は、ヒドロキシル基をエステル化した変性形態、すなわち低級アシルエステルとして反応に供することもできる。低級アシル基は炭素原子数２〜５のものが好ましく、炭素原子数２または３のものがより好ましい。特に好ましくは前記単量体成分の酢酸エステルを反応に用いる方法が挙げられる。 In both the melt acidlysis method and the slurry polymerization method, the polymerizable monomer component used in producing the liquid crystal polyester resin is subjected to the reaction as a modified form in which a hydroxyl group is esterified, that is, a lower acyl ester. You can also. The lower acyl group preferably has 2 to 5 carbon atoms, and more preferably 2 or 3 carbon atoms. Particularly preferably, a method of using the acetic acid ester of the monomer component in the reaction can be mentioned.
単量体の低級アシルエステルは、別途アシル化して予め合成したものを用いてもよいし、液晶ポリエステル樹脂の製造時にモノマーに無水酢酸等のアシル化剤を加えて反応系内で生成せしめることもできる。 As the lower acyl ester of the monomer, one that is separately acylated and synthesized in advance may be used, or an acylating agent such as acetic anhydride may be added to the monomer during the production of the liquid crystal polyester resin to produce the monomer in the reaction system. it can.
溶融アシドリシス法またはスラリー重合法のいずれにおいても、必要に応じて触媒を用いてもよい。 In either the melt acidlysis method or the slurry polymerization method, a catalyst may be used if necessary.
触媒の具体例としては、ジアルキルスズオキシド（たとえばジブチルスズオキシド）、ジアリールスズオキシドなどの有機スズ化合物；二酸化チタン、三酸化アンチモン、アルコキシチタンシリケート、チタンアルコキシドなどの有機チタン化合物；カルボン酸のアルカリおよびアルカリ土類金属塩（たとえば酢酸カリウム）；無機酸のアルカリおよびアルカリ土類金属塩（たとえば硫酸カリウム）；ルイス酸（たとえばＢＦ３）、ハロゲン化水素（たとえばＨＣｌ）などの気体状酸触媒などが挙げられる。Specific examples of the catalyst include organic tin compounds such as dialkyltin oxide (eg dibutyltin oxide) and diaryltin oxide; organic titanium compounds such as titanium dioxide, antimony trioxide, alkoxytitanium silicate, and titanium alkoxide; alkalis and alkalis of carboxylic acids. Earth metal salts (eg potassium acetate); alkaline and alkaline earth metal salts of inorganic acids (eg potassium sulfate); Lewis acids (eg BF 3 ), gaseous acid catalysts such as hydrogen halides (eg HCl), etc. Be done.
触媒の使用割合は、通常モノマー全量に対し１０〜１０００ｐｐｍ、好ましくは２０〜２００ｐｐｍである。 The ratio of the catalyst used is usually 10 to 1000 ppm, preferably 20 to 200 ppm, based on the total amount of the monomers.
このようにして得られる本発明の液晶ポリエステル樹脂は、後述する示差走査熱量計（ＤＳＣ）により測定される結晶融解温度が、好ましくは２９０〜３４０℃、より好ましくは２９５〜３３５℃、さらに好ましくは３００〜３３０℃、特に好ましくは３０５〜３２５℃である。 The liquid crystal polyester resin of the present invention thus obtained has a crystal melting temperature of preferably 290 to 340 ° C, more preferably 295 to 335 ° C, still more preferably 295 to 335 ° C, as measured by a differential scanning calorimeter (DSC) described later. It is 300 to 330 ° C, particularly preferably 305 to 325 ° C.
また、本発明の液晶ポリエステル樹脂は、３５０℃で測定した溶融粘度が、１〜１０００Ｐａ・ｓであることが好ましく、より好ましくは５〜３００Ｐａ・ｓ、さらに好ましくは８〜２００Ｐａ・ｓ、特に好ましくは１２〜１５０Ｐａ・ｓである。 Further, the liquid crystal polyester resin of the present invention preferably has a melt viscosity measured at 350 ° C. of 1 to 1000 Pa · s, more preferably 5 to 300 Pa · s, still more preferably 8 to 200 Pa · s, and particularly preferably. Is 12 to 150 Pa · s.
また、本発明の液晶ポリエステル樹脂は、長さ６３．５ｍｍ×幅３．５ｍｍ×厚さ２．０ｍｍのダンベル状試験片を用いて、ＡＳＴＭ Ｄ６３８に準拠して測定した引張強度が好ましくは１８０ＭＰａ以上であり、引張弾性率が好ましくは７．７ＧＰａ以上である。 Further, the liquid crystal polyester resin of the present invention has a tensile strength of preferably 180 MPa or more measured in accordance with ASTM D638 using a dumbbell-shaped test piece having a length of 63.5 mm, a width of 3.5 mm and a thickness of 2.0 mm. The tensile elastic modulus is preferably 7.7 GPa or more.
引張強度は、より好ましくは１９０ＭＰａ以上であり、さらに好ましくは２００ＭＰａ以上であり、通常は２８０ＭＰａ以下である。 The tensile strength is more preferably 190 MPa or more, further preferably 200 MPa or more, and usually 280 MPa or less.
引張弾性率は、より好ましくは８．０ＧＰａ以上であり、さらに好ましくは８．２ＧＰａ以上であり、通常は１５．０ＧＰａ以下である。 The tensile elastic modulus is more preferably 8.0 GPa or more, further preferably 8.2 GPa or more, and usually 15.0 GPa or less.
さらに、本発明の液晶ポリエステル樹脂は、長さ６５ｍｍ×幅１２．７ｍｍ×厚さ２．０ｍｍの短冊状試験片を用いて、ＡＳＴＭ Ｄ７９０に準拠して測定した曲げ強度が１６５ＭＰａ以上であり、曲げ弾性率が９．０ＧＰａ以上である。 Further, the liquid crystal polyester resin of the present invention has a bending strength of 165 MPa or more measured in accordance with ASTM D790 using a strip-shaped test piece having a length of 65 mm, a width of 12.7 mm and a thickness of 2.0 mm. The elastic modulus is 9.0 GPa or more.
曲げ強度は、より好ましくは１７０ＭＰａ以上であり、さらに好ましくは１７５ＭＰａ以上であり、通常は２５０ＭＰａ以下である。 The bending strength is more preferably 170 MPa or more, further preferably 175 MPa or more, and usually 250 MPa or less.
曲げ弾性率は、より好ましくは９．５ＧＰａ以上であり、さらに好ましくは１０．０ＧＰａ以上であり、通常は１５．０ＧＰａ以下である。 The flexural modulus is more preferably 9.5 GPa or more, further preferably 10.0 GPa or more, and usually 15.0 GPa or less.
本発明はさらに、本発明の液晶ポリエステル樹脂に繊維状、板状、または粉状の充填剤の１種または２種以上を配合せしめて得られる液晶ポリエステル樹脂組成物を提供する。充填剤としては、従来から樹脂組成物に用いられることが知られている物質から、液晶ポリエステル樹脂組成物の使用目的、用途等に応じて適宜選択すればよい。 The present invention further provides a liquid crystal polyester resin composition obtained by blending one or more of fibrous, plate-like, or powder-like fillers with the liquid crystal polyester resin of the present invention. The filler may be appropriately selected from substances conventionally known to be used in the resin composition, depending on the purpose and use of the liquid crystal polyester resin composition.
繊維状の充填剤としては、例えばガラス繊維、シリカアルミナ繊維、アルミナ繊維、炭素繊維、アラミド繊維、などが挙げられる。これらの中では、ガラス繊維が物性とコストのバランスが優れている点から好ましい。 Examples of the fibrous filler include glass fiber, silica-alumina fiber, alumina fiber, carbon fiber, aramid fiber and the like. Among these, glass fiber is preferable because it has an excellent balance between physical properties and cost.
板状あるいは粉状の充填剤としては、例えばタルク、マイカ、グラファイト、ウォラストナイト、炭酸カルシウム、ドロマイト、クレイ、ガラスフレーク、ガラスビーズ、硫酸バリウム、酸化チタンなどが挙げられる。これらの中では、タルクが物性とコストのバランスが優れている点から好ましい。 Examples of the plate-like or powder-like filler include talc, mica, graphite, wollastonite, calcium carbonate, dolomite, clay, glass flakes, glass beads, barium sulfate, titanium oxide and the like. Among these, talc is preferable because it has an excellent balance between physical properties and cost.
本発明の液晶ポリエステル樹脂組成物において、充填剤はその合計配合量が、液晶ポリエステル樹脂１００質量部に対して、０．１〜２００質量部、特に１０〜１００質量部であるのが好ましい。充填剤の配合量が２００質量部を超える場合、液晶ポリエステル樹脂組成物の成形加工性が低下したり、成形機のシリンダーや金型の磨耗が大きくなる傾向がある。 In the liquid crystal polyester resin composition of the present invention, the total amount of the filler is preferably 0.1 to 200 parts by mass, particularly 10 to 100 parts by mass with respect to 100 parts by mass of the liquid crystal polyester resin. When the blending amount of the filler exceeds 200 parts by mass, the molding processability of the liquid crystal polyester resin composition tends to decrease, and the cylinder and the mold of the molding machine tend to be worn out.
本発明の液晶ポリエステル樹脂または液晶ポリエステル樹脂組成物には、本発明の効果を損なわない範囲で、高級脂肪酸、高級脂肪酸エステル、高級脂肪酸アミド、高級脂肪酸金属塩、ポリシロキサン、フッ素樹脂などの離型剤；染料、顔料などの着色剤；酸化防止剤；熱安定剤；紫外線吸収剤；帯電防止剤；界面活性剤などの従来用いられることが知られている添加剤を、その目的及び用途に応じて１種または２種以上を組み合わせて配合してもよい。 The liquid crystal polyester resin or liquid crystal polyester resin composition of the present invention can be released from higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty acid metal salts, polysiloxanes, fluororesins, etc., as long as the effects of the present invention are not impaired. Agents; Colorants such as dyes and pigments; Antioxidants; Heat stabilizers; UV absorbers; Antistatic agents; Additives known to be used conventionally such as surfactants, depending on the purpose and application. You may mix one kind or a combination of two or more kinds.
高級脂肪酸、高級脂肪酸エステル、高級脂肪酸金属塩、フルオロカーボン系界面活性剤等の外部滑剤効果を有するものについては、成形に際して予め液晶ポリエステル樹脂又は液晶ポリエステル樹脂組成物のペレットに付着させて用いてもよい。 Higher fatty acids, higher fatty acid esters, higher fatty acid metal salts, fluorocarbon-based surfactants, and other substances that have an external lubricant effect may be used by adhering them to the pellets of the liquid crystal polyester resin or the liquid crystal polyester resin composition in advance during molding. ..
本発明の液晶ポリエステル樹脂組成物は、充填剤および添加剤などの全ての成分をポリエステル樹脂中へ添加し、バンバリーミキサー、ニーダー、一軸もしくは二軸押出機などを用いて、液晶ポリエステル樹脂の結晶融解温度近傍から結晶融解温度＋１００℃の温度下で溶融混練して調製することができる。 In the liquid crystal polyester resin composition of the present invention, all components such as fillers and additives are added to the polyester resin, and crystal melting of the liquid crystal polyester resin is performed using a Banbury mixer, a kneader, a uniaxial or biaxial extruder, or the like. It can be prepared by melt-kneading at a temperature of crystal melting temperature + 100 ° C. from near the temperature.
このようにして得られた本発明の液晶ポリエステル樹脂および液晶ポリエステル樹脂組成物は、従来公知の射出成形、圧縮成形、押出成形、ブローなどの成形法によって、射出成形品、フィルム、シートおよび不織布などの成形品に加工することができる。 The liquid crystal polyester resin and the liquid crystal polyester resin composition of the present invention thus obtained can be an injection molded product, a film, a sheet, a non-woven fabric, or the like by a molding method such as injection molding, compression molding, extrusion molding, or blow, which are conventionally known. Can be processed into molded products.
本発明の液晶ポリエステル樹脂および液晶ポリエステル樹脂組成物は、耐ブリスター性に優れるとともに、耐熱性、引張強度・引張弾性率、曲げ強度・曲げ弾性率などの機械物性に優れるため、コネクター、カメラモジュール、アンテナ、基板などの電気電子用部品の材料として好適に使用される。 The liquid crystal polyester resin and the liquid crystal polyester resin composition of the present invention are excellent in blister resistance and mechanical properties such as heat resistance, tensile strength / tensile elastic modulus, and bending strength / flexural modulus. It is suitably used as a material for electrical and electronic parts such as antennas and substrates.
以下、実施例により本発明を詳述するが、本発明はこれに限定されるものではない。
実施例において、下記の略号は以下の化合物を表す。
ＰＯＢ：４−ヒドロキシ安息香酸
ＢＯＮ６：６−ヒドロキシ−２−ナフトエ酸
ＩＰＡ：イソフタル酸
ＮＤＡ：２，６−ナフタレンジカルボン酸
ＨＱ：ハイドロキノンHereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.
In the examples, the following abbreviations represent the following compounds.
POB: 4-Hydroxybenzoic acid BON6: 6-hydroxy-2-naphthoic acid IPA: Isophthalic acid NDA: 2,6-naphthalenedicarboxylic acid HQ: Hydroquinone
〈結晶融解温度の測定〉
示差走査熱量計としてセイコーインスツルメンツ株式会社製Ｅｘｓｔａｒ６０００を用いて測定を行った。液晶ポリエステル樹脂試料を、室温から２０℃／分の昇温条件下で測定し、吸熱ピーク温度（Ｔｍ１）を観測した後、Ｔｍ１より２０〜５０℃高い温度で１０分間保持した。次いで２０℃／分の降温条件で室温まで試料を冷却した後に、再度２０℃／分の昇温条件で測定した際の吸熱ピークを観測し、そのピークトップを示す温度を液晶ポリエステル樹脂の結晶融解温度とした。<Measurement of crystal melting temperature>
The measurement was performed using Exstar6000 manufactured by Seiko Instruments Co., Ltd. as a differential scanning calorimeter. The liquid crystal polyester resin sample was measured under a temperature rising condition of 20 ° C./min from room temperature, and after observing the endothermic peak temperature (Tm1), the sample was held at a temperature 20 to 50 ° C. higher than Tm1 for 10 minutes. Next, after cooling the sample to room temperature under the temperature lowering condition of 20 ° C./min, the endothermic peak when measured again under the temperature rising condition of 20 ° C./min was observed, and the temperature indicating the peak top was defined as the crystal melting of the liquid crystal polyester resin. The temperature was set.
〈溶融粘度の測定〉
溶融粘度測定装置（東洋精機（株）製キャピログラフ１Ｄ）により、０．７ｍｍφ×１０ｍｍのキャピラリーを用いて、剪断速度１０００ｓｅｃ−１、３５０℃の条件下での溶融粘度を測定した。<Measurement of melt viscosity>
A melt viscosity measuring device (Capillary Graph 1D manufactured by Toyo Seiki Co., Ltd.) was used to measure the melt viscosity under the conditions of a shear rate of 1000 sec -1 and 350 ° C. using a capillary of 0.7 mmφ × 10 mm.
〈引張強度および引張弾性率の測定〉
型締め圧１５ｔの射出成形機（住友重機工業（株）製 ＭＩＮＩＭＡＴ Ｍ２６／１５）を用いて結晶融解温度＋２０〜４０℃のシリンダー温度、金型温度７０℃で射出成形し、ダンベル状試験片（長さ６３．５ｍｍ×幅３．５ｍｍ×厚さ２．０ｍｍ）を作成した。引張試験は、ＩＮＳＴＲＯＮ５５６７（インストロンジャパン カンパニイリミテッド社製万能試験機）を用いて、ＡＳＴＭ Ｄ６３８に準拠し、チャック間距離２５．４ｍｍ、引張速度５ｍｍ／分で測定した。<Measurement of tensile strength and tensile elastic modulus>
Using an injection molding machine with a mold clamping pressure of 15 tons (MINIMAT M26 / 15 manufactured by Sumitomo Heavy Industries, Ltd.), injection molding was performed at a crystal melting temperature of + 20 to 40 ° C. and a mold temperature of 70 ° C. Length 63.5 mm × width 3.5 mm × thickness 2.0 mm) was prepared. The tensile test was measured using an INSTRON 5567 (universal testing machine manufactured by Instron Japan Company Limited) in accordance with ASTM D638, with a chuck-to-chuck distance of 25.4 mm and a tensile speed of 5 mm / min.
〈曲げ強度および曲げ弾性率の測定〉
型締め圧１５ｔの射出成形機（住友重機械工業（株）製ＭＩＮＩＭＡＴ Ｍ２６／１５）を用いて結晶融解温度＋２０〜４０℃のシリンダー温度、金型温度７０℃で射出成形し、短冊状試験片（長さ６５ｍｍ×幅１２．７ｍｍ×厚さ２．０ｍｍ）を作製した。曲げ試験は、３点曲げ試験をＩＮＳＴＲＯＮ５５６７（インストロンジャパンカンパニイリミティッド社製万能試験機）を用いて、ＡＳＴＭ Ｄ７９０に準拠し、スパン間距離４０．０ｍｍ、圧縮速度１．３ｍｍ／分で行った。<Measurement of bending strength and flexural modulus>
Using an injection molding machine with a mold clamping pressure of 15 tons (MINIMAT M26 / 15 manufactured by Sumitomo Heavy Industries, Ltd.), injection molding is performed at a cylinder temperature of + 20 to 40 ° C and a mold temperature of 70 ° C to form a strip-shaped test piece. (Length 65 mm × width 12.7 mm × thickness 2.0 mm) was produced. The bending test was performed using an INSTRON5567 (universal testing machine manufactured by Instron Japan Company Limited) at a distance between spans of 40.0 mm and a compression speed of 1.3 mm / min in accordance with ASTM D790.
〈Ｉｚｏｄ衝撃強度の測定〉
型締め圧１５ｔの射出成形機（住友重機械工業（株）製ＭＩＮＩＭＡＴ Ｍ２６／１５）を用いて結晶融解温度＋２０〜４０℃のシリンダー温度、金型温度７０℃で射出成形し、短冊状試験片（長さ６５ｍｍ×幅１２．７ｍｍ×厚さ２．０ｍｍ）を作製した。Ｉｚｏｄ衝撃強度は、ＡＳＴＭ Ｄ２５６に準拠して測定した。Ｉｚｏｄ衝撃強度の値が大きいほど、柔軟性に優れることを示す。<Measurement of Izod impact strength>
Using an injection molding machine with a mold clamping pressure of 15 tons (MINIMAT M26 / 15 manufactured by Sumitomo Heavy Industries, Ltd.), injection molding is performed at a cylinder temperature of + 20 to 40 ° C and a mold temperature of 70 ° C to form a strip-shaped test piece. (Length 65 mm × width 12.7 mm × thickness 2.0 mm) was produced. The Izod impact strength was measured according to ASTM D256. The larger the value of the Izod impact strength, the better the flexibility.
〈ブリスター発生評価〉
射出成形機（日精樹脂株式会社製ＮＥＸ−１５−１Ｅ）を用いて結晶融解温度＋２０〜４０℃のシリンダー温度、金型温度１４０℃で射出成形し、箱形試験片（縦３０ｍｍ×横５ｍｍ×高さ６ｍｍ、厚さ０．２ｍｍ）を作製した。この箱型試験片をギアオーブンにて２６０℃で１０分間加熱処理を行い、冷却後、目視により表面に膨れ（ブリスター）の発生した個数を観察した。一回の試験につきそれぞれ３０本の試験片を評価し、膨れの発生した試験片の数が０〜５の場合は○、６〜１０の場合は△、１１以上の場合は×とした。<Blister generation evaluation>
Using an injection molding machine (NEX-15-1E manufactured by Nissei Resin Co., Ltd.), injection molding is performed at a cylinder temperature of + 20 to 40 ° C. and a mold temperature of 140 ° C., and a box-shaped test piece (length 30 mm x width 5 mm x) (Height 6 mm, thickness 0.2 mm) was produced. This box-shaped test piece was heat-treated at 260 ° C. for 10 minutes in a gear oven, and after cooling, the number of blisters generated on the surface was visually observed. Thirty test pieces were evaluated for each test, and the number of test pieces with swelling was 0 to 5, Δ for 6 to 10, and x for 11 or more.
［実施例１（参考例）］
トルクメーター付き攪拌装置および留出管を備えた反応容器に、ＰＯＢ：２０５．６ｇ（２２．９モル％）、ＢＯＮ６：９３９．４ｇ（７６．８モル％）およびＩＰＡ：３．２ｇ（０．３モル％）を仕込み、さらに全単量体の水酸基量（モル）に対して１.０３倍モルの無水酢酸を仕込み、次の条件で脱酢酸重合を行った。[Example 1 (reference example)]
POB: 205.6 g (22.9 mol%), BON 6: 939.4 g (76.8 mol%) and IPA: 3.2 g (0.) In a reaction vessel equipped with a stirrer with a torque meter and a distillate. 3 mol%) was charged, 1.03 times mol of acetic anhydride was further charged with respect to the amount of hydroxyl groups (mol) of all the monomers, and deacetic acid polymerization was carried out under the following conditions.
窒素ガス雰囲気下に室温から１５０℃まで１時間かけて昇温し、同温度にて３０分間保持した。次いで、副生する酢酸を留去させつつ２１０℃まで速やかに昇温し、同温度にて３０分間保持した。その後、３５０℃まで４時間かけて昇温した後、８０分かけて１０ｍｍＨｇにまで減圧した。所定のトルクを示した時点で重合反応を終了し、反応容器内容物を取り出し、粉砕機により液晶ポリエステル樹脂のペレットを得た。重合時の留出酢酸量は、ほぼ理論値どおりであった。 The temperature was raised from room temperature to 150 ° C. over 1 hour under a nitrogen gas atmosphere, and the temperature was maintained at the same temperature for 30 minutes. Next, the temperature was rapidly raised to 210 ° C. while distilling off acetic acid produced as a by-product, and the temperature was maintained at the same temperature for 30 minutes. Then, the temperature was raised to 350 ° C. over 4 hours, and then the pressure was reduced to 10 mmHg over 80 minutes. When a predetermined torque was exhibited, the polymerization reaction was terminated, the contents of the reaction vessel were taken out, and pellets of liquid crystal polyester resin were obtained by a pulverizer. The amount of distillate acetic acid at the time of polymerization was almost the same as the theoretical value.
得られたペレットを用いて上記の方法により、結晶融解温度、溶融粘度、引張強度、引張弾性率、曲げ強度、曲げ弾性率、Ｉｚｏｄ衝撃強度およびブリスター発生の測定、評価を行った。結果を表１に示す。 Using the obtained pellets, the crystal melting temperature, melt viscosity, tensile strength, tensile elastic modulus, bending strength, bending elastic modulus, Izod impact strength and blister generation were measured and evaluated by the above method. The results are shown in Table 1.
［実施例２〜９（実施例２〜４は参考例）および比較例１〜５］
ＰＯＢ、ＢＯＮ６、ＩＰＡ、ＮＤＡおよびＨＱを表１に示す割合（モル％）となるように変更した以外は、実施例１と同様にして、液晶ポリエステル樹脂のペレットを得た。得られたペレットを用いて上記の方法により、結晶融解温度、溶融粘度、引張強度、引張弾性率、曲げ強度、曲げ弾性率、Ｉｚｏｄ衝撃強度およびブリスター発生の測定、評価を行った。結果を表１に示す。[Examples 2 to 9 (Examples 2 to 4 are reference examples) and Comparative Examples 1 to 5]
Liquid crystal polyester resin pellets were obtained in the same manner as in Example 1 except that POB, BON6, IPA, NDA and HQ were changed to the ratios (mol%) shown in Table 1. Using the obtained pellets, the crystal melting temperature, melt viscosity, tensile strength, tensile elastic modulus, bending strength, bending elastic modulus, Izod impact strength and blister generation were measured and evaluated by the above method. The results are shown in Table 1.
なお、比較例４については、３５０℃まで４時間かけて昇温する際、３０５℃まで昇温した時点で内容物が固化し攪拌が不能になったため反応を中止し、液晶ポリエステル樹脂を得ることができなかった。 In Comparative Example 4, when the temperature was raised to 350 ° C. over 4 hours, the contents solidified and stirring became impossible when the temperature was raised to 305 ° C., so the reaction was stopped to obtain a liquid crystal polyester resin. I couldn't.
［実施例１０（参考例）］
液晶ポリエステル樹脂として実施例１の樹脂を用い、液晶ポリエステル樹脂１００質量部に対して、充填材として、ガラス繊維（繊維径１０．５μｍ、繊維長３ｍｍのチョップドガラス）１０質量部およびタルク（平均粒子径１９μｍ）２０質量部を配合し、２軸押出機（日本製鋼(株)製ＴＥＸ−３０）にて溶融混練したものをペレット化し、液晶樹脂組成物のペレットを得た。得られたペレットを用いて上記の方法により、ブリスター発生評価を行った。結果を表１に示す。[Example 10 (reference example)]
The resin of Example 1 was used as the liquid crystal polyester resin, and 10 parts by mass of glass fiber (chopped glass having a fiber diameter of 10.5 μm and a fiber length of 3 mm) and talc (average particles) were used as a filler with respect to 100 parts by mass of the liquid crystal polyester resin. 20 parts by mass (diameter 19 μm) was blended and melt-kneaded with a twin-screw extruder (TEX-30 manufactured by Nippon Steel Co., Ltd.) and pelletized to obtain pellets of a liquid crystal resin composition. Using the obtained pellets, blister generation was evaluated by the above method. The results are shown in Table 1.
［比較例６］
液晶ポリエステル樹脂として比較例１の樹脂を用いた以外は実施例１０と同様にしてペレットを得、ブリスター発生評価を行った。結果を表１に示す。[Comparative Example 6]
Pellets were obtained in the same manner as in Example 10 except that the resin of Comparative Example 1 was used as the liquid crystal polyester resin, and the generation of blisters was evaluated. The results are shown in Table 1.
［実施例１１］
トルクメーター付き攪拌装置および留出管を備えた反応容器に、ＰＯＢ：２０５．６ｇ（２２．９モル％）、ＢＯＮ６：９３９．４ｇ（７６．８モル％）およびＮＤＡ：４．２ｇ（０．３モル％）を仕込み、さらに全単量体の水酸基量（モル）に対して１.０３倍モルの無水酢酸を仕込み、次の条件で脱酢酸重合を行った。[Example 11]
POB: 205.6 g (22.9 mol%), BON 6: 939.4 g (76.8 mol%) and NDA: 4.2 g (0.) In a reaction vessel equipped with a stirrer with a torque meter and a distillate. 3 mol%) was charged, 1.03 times mol of acetic anhydride was further charged with respect to the amount of hydroxyl groups (mol) of all the monomers, and deacetic acid polymerization was carried out under the following conditions.
窒素ガス雰囲気下に室温から１５０℃まで１時間かけて昇温し、同温度にて３０分間保持した。次いで、副生する酢酸を留去させつつ２１０℃まで速やかに昇温し、同温度にて３０分間保持した。その後、３５０℃まで４時間かけて昇温した後、８０分かけて１０ｍｍＨｇにまで減圧した。所定のトルクを示した時点で重合反応を終了し、反応容器内容物を取り出し、粉砕機により液晶ポリエステル樹脂のペレットを得た。重合時の留出酢酸量は、ほぼ理論値どおりであった。 The temperature was raised from room temperature to 150 ° C. over 1 hour under a nitrogen gas atmosphere, and the temperature was maintained at the same temperature for 30 minutes. Next, the temperature was rapidly raised to 210 ° C. while distilling off acetic acid produced as a by-product, and the temperature was maintained at the same temperature for 30 minutes. Then, the temperature was raised to 350 ° C. over 4 hours, and then the pressure was reduced to 10 mmHg over 80 minutes. When a predetermined torque was exhibited, the polymerization reaction was terminated, the contents of the reaction vessel were taken out, and pellets of liquid crystal polyester resin were obtained by a pulverizer. The amount of distillate acetic acid at the time of polymerization was almost the same as the theoretical value.
得られたペレットを用いて上記の方法により、結晶融解温度、溶融粘度、引張強度、引張弾性率、曲げ強度、曲げ弾性率、Ｉｚｏｄ衝撃強度およびブリスター発生の測定、評価を行った。結果を表２に示す。 Using the obtained pellets, the crystal melting temperature, melt viscosity, tensile strength, tensile elastic modulus, bending strength, bending elastic modulus, Izod impact strength and blister generation were measured and evaluated by the above method. The results are shown in Table 2.
［実施例１２〜１５および比較例７〜１０］
ＰＯＢ、ＢＯＮ６、ＮＤＡおよびＨＱを表２に示す割合（モル％）となるように変更した以外は、実施例１と同様にして、液晶ポリエステル樹脂のペレットを得た。得られたペレットを用いて上記の方法により、結晶融解温度、溶融粘度、引張強度、引張弾性率、曲げ強度、曲げ弾性率、Ｉｚｏｄ衝撃強度およびブリスター発生の測定、評価を行った。結果を表２に示す。[Examples 12 to 15 and Comparative Examples 7 to 10]
Liquid crystal polyester resin pellets were obtained in the same manner as in Example 1 except that POB, BON6, NDA and HQ were changed to the ratios (mol%) shown in Table 2. Using the obtained pellets, the crystal melting temperature, melt viscosity, tensile strength, tensile elastic modulus, bending strength, bending elastic modulus, Izod impact strength and blister generation were measured and evaluated by the above method. The results are shown in Table 2.
なお、比較例９については、３５０℃まで４時間かけて昇温する際、３０５℃まで昇温した時点で内容物が固化し攪拌が不能になったため反応を中止し、液晶ポリエステル樹脂を得ることができなかった。 In Comparative Example 9, when the temperature was raised to 350 ° C. over 4 hours, the contents solidified and stirring became impossible when the temperature was raised to 305 ° C., so the reaction was stopped to obtain a liquid crystal polyester resin. I couldn't.
［実施例１６］
液晶ポリエステル樹脂として実施例１１の樹脂を用い、液晶ポリエステル樹脂１００質量部に対して、充填材として、ガラス繊維（繊維径１０．５μｍ、繊維長３ｍｍのチョップドガラス）１０質量部およびタルク（平均粒子径１９μｍ）２０質量部を配合し、２軸押出機（日本製鋼(株)製ＴＥＸ−３０）にて溶融混練したものをペレット化し、液晶樹脂組成物のペレットを得た。得られたペレットを用いて上記の方法により、ブリスター発生評価を行った。結果を表２に示す。[Example 16]
Using the resin of Example 11 as the liquid crystal polyester resin, 10 parts by mass of glass fiber (chopped glass having a fiber diameter of 10.5 μm and a fiber length of 3 mm) and talc (average particles) were used as a filler with respect to 100 parts by mass of the liquid crystal polyester resin. 20 parts by mass (diameter 19 μm) was blended and melt-kneaded with a twin-screw extruder (TEX-30 manufactured by Nippon Steel Co., Ltd.) and pelletized to obtain pellets of a liquid crystal resin composition. Using the obtained pellets, blister generation was evaluated by the above method. The results are shown in Table 2.
上記各表に示すように、本発明の各実施例による液晶ポリエステル樹脂および液晶ポリエステル樹脂組成物では、いずれも機械物性に優れ、かつ良好なリフロー時の耐ブリスター性が得られた。 As shown in each of the above tables, the liquid crystal polyester resin and the liquid crystal polyester resin composition according to each embodiment of the present invention were both excellent in mechanical properties and had good blister resistance during reflow.
これに対して、本発明によらない場合（各比較例）には、いずれもリフロー時の耐ブリスター性が不十分であり、また、機械物性又はそのバランスが十分と言えない評価結果であった。比較例５では、液晶ポリエステル樹脂の結晶融解温度にも低下が見られた。 On the other hand, in the cases not according to the present invention (each comparative example), the blister resistance at the time of reflow was insufficient, and the mechanical properties or their balance were not sufficient. .. In Comparative Example 5, a decrease was also observed in the crystal melting temperature of the liquid crystal polyester resin.
［実施例２〜９（実施例２〜４及び実施例７〜９は参考例）および比較例１〜５］
ＰＯＢ、ＢＯＮ６、ＩＰＡ、ＮＤＡおよびＨＱを表１に示す割合（モル％）となるように変更した以外は、実施例１と同様にして、液晶ポリエステル樹脂のペレットを得た。得られたペレットを用いて上記の方法により、結晶融解温度、溶融粘度、引張強度、引張弾性率、曲げ強度、曲げ弾性率、Ｉｚｏｄ衝撃強度およびブリスター発生の測定、評価を行った。結果を表１に示す。
[Examples 2 to 9 (Examples 2 to 4 and Examples 7 to 9 are reference examples) and Comparative Examples 1 to 5]
Liquid crystal polyester resin pellets were obtained in the same manner as in Example 1 except that POB, BON6, IPA, NDA and HQ were changed to the ratios (mol%) shown in Table 1. Using the obtained pellets, the crystal melting temperature, melt viscosity, tensile strength, tensile elastic modulus, bending strength, bending elastic modulus, Izod impact strength and blister generation were measured and evaluated by the above method. The results are shown in Table 1.
Claims (6)
ｐ、ｑ、ｓおよびｔは、それぞれ、液晶ポリエステル樹脂中での各繰返し単位の組成比（モル％）であり、以下の条件を満たす：
１５≦ｐ≦３０、
７０≦ｑ≦８５、
０．０１≦ｓ＋ｔ＜２、ここで、ｓ、ｔは、それぞれ０以上２未満であり、但し、これらは同時に０でない］
で表される繰返し単位から構成される液晶ポリエステル樹脂。The following formula:
p, q, s and t are composition ratios (mol%) of each repeating unit in the liquid crystal polyester resin, respectively, and satisfy the following conditions:
15 ≦ p ≦ 30,
70 ≤ q ≤ 85,
0.01 ≦ s + t <2, where s and t are 0 or more and less than 2, respectively, but they are not 0 at the same time]
A liquid crystal polyester resin composed of repeating units represented by.
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