JP4945163B2 - Thermotropic liquid crystal polyester resin composition and electric / electronic component - Google Patents
Thermotropic liquid crystal polyester resin composition and electric / electronic component Download PDFInfo
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- JP4945163B2 JP4945163B2 JP2006106396A JP2006106396A JP4945163B2 JP 4945163 B2 JP4945163 B2 JP 4945163B2 JP 2006106396 A JP2006106396 A JP 2006106396A JP 2006106396 A JP2006106396 A JP 2006106396A JP 4945163 B2 JP4945163 B2 JP 4945163B2
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- crystal polyester
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- thermotropic liquid
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- 239000004974 Thermotropic liquid crystal Substances 0.000 title claims description 23
- 239000000203 mixture Substances 0.000 title claims description 16
- 229920001225 polyester resin Polymers 0.000 title claims description 4
- 239000004645 polyester resin Substances 0.000 title claims description 4
- 229920000728 polyester Polymers 0.000 claims description 29
- 239000010419 fine particle Substances 0.000 claims description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims description 15
- 150000004706 metal oxides Chemical class 0.000 claims description 15
- 239000011342 resin composition Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 238000006640 acetylation reaction Methods 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000004898 kneading Methods 0.000 description 7
- 239000007790 solid phase Substances 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- -1 aromatic hydroxycarboxylic acids Chemical class 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 5
- 230000021736 acetylation Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920000106 Liquid crystal polymer Polymers 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 210000003746 feather Anatomy 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000679 solder Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 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 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 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 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- 238000010943 off-gassing Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、アウトガスの発生量が極めて少ない、特にハンダリフロー等の高温環境下での腐食性のガスの発生量が極めて少ないサーモトロピック液晶ポリエステル樹脂組成物および該樹脂組成物から得られた構造部材を具備する電気電子部品に関するものである。 The present invention relates to a thermotropic liquid crystal polyester resin composition that generates a very small amount of outgas, particularly a corrosive gas generated under a high temperature environment such as solder reflow, and a structural member obtained from the resin composition It is related with the electrical and electronic component which comprises.
サーモトロピック液晶ポリエステルと無機充填材を含む樹脂組成物は、電気電子部品産業分野において、優れた成形加工特性に加え、ハンダリフロー等の高温環境下での耐熱性に優れるので構造部材として使用されている。しかしながら、樹脂組成物自体の材料としての耐熱性が優れていても、含有される揮発性有機物はこれらの環境下では系外に気体(アウトガス)となって放出されることがあり、特に、この気体が金属腐食性のものであると、電気電子部分中の金属部の機能に好ましくない影響をあたえる場合がある。 A resin composition containing a thermotropic liquid crystalline polyester and an inorganic filler is used as a structural member in the electric and electronic parts industry, because of its excellent heat resistance in a high temperature environment such as solder reflow in addition to excellent molding characteristics. Yes. However, even if the heat resistance as a material of the resin composition itself is excellent, the contained volatile organic matter may be released as a gas (outgas) outside the system in these environments. If the gas is corrosive to metal, it may adversely affect the function of the metal part in the electric / electronic part.
金属腐食性のアウトガスの代表例は、酢酸、フェノールであるが、これらの放出量の削減を目的として、いくつかの提案がなされている(たとえば、特許文献1〜5参照)。
しかし、これらの提案は、重合工程における無水酢酸添加量の規制(特許文献1)、末端封止基の特定(特許文献2)、特定の亜リン酸エステルの添加(特許文献3)、特定の吸着剤(ハイドロタルサイト)の添加(特許文献4)および特定の混練機による溶融混練(特許文献5)等、いずれも工程の改変、新たな化合物の添加、新たな混練装置の採用等、従来の製造方法または組成を改変するものであり、その結果、アウトガスの抑制は得られても、サーモトロピック液晶ポリエステルを含む樹脂組成物を使用する利点のいくつかに好ましくない影響を与えるおそれがあるし、経済的にも付加的費用を要する。 However, these proposals are the regulation of the amount of acetic anhydride added in the polymerization process (Patent Document 1), the specification of the terminal blocking group (Patent Document 2), the addition of a specific phosphite (Patent Document 3), the specific Addition of adsorbent (hydrotalcite) (Patent Document 4) and melt-kneading with a specific kneader (Patent Document 5), etc., all of which are conventional processes, addition of a new compound, adoption of a new kneading apparatus, etc. As a result, although outgassing suppression can be obtained, it may adversely affect some of the advantages of using a resin composition containing a thermotropic liquid crystal polyester. Also, additional costs are required economically.
本発明は、極めて簡便かつ効率的な方法で、揮発性有機物の気体放出が抑制された樹脂組成物を提供することを目的とするものである。 An object of the present invention is to provide a resin composition in which gas emission of volatile organic substances is suppressed by an extremely simple and efficient method.
本発明の第1は、サーモトロピック液晶ポリエステル100質量部、平均粒径100nm以下であって溶液中でゾルを形成する金属酸化物微粒子0.1〜5質量部および充填材0〜150質量部を溶融混練してなるサーモトロピック液晶ポリエステル樹脂組成物に関するものである。 The first of the present invention comprises 100 parts by weight of thermotropic liquid crystalline polyester, 0.1 to 5 parts by weight of metal oxide fine particles having an average particle size of 100 nm or less and forming a sol in the solution, and 0 to 150 parts by weight of filler. The present invention relates to a thermotropic liquid crystal polyester resin composition obtained by melt-kneading.
本発明の第2は、本発明の第1の前記樹脂組成物において、前記金属酸化物微粒子が酸化アルミニウムであることを特徴とするものである。 According to a second aspect of the present invention, in the first resin composition of the present invention, the metal oxide fine particles are aluminum oxide.
また、本発明の第3は、本発明の第1または第2の樹脂組成物から得られた構造部材を具備することを特徴とする電気電子部品に関するものである。 A third aspect of the present invention relates to an electric / electronic component comprising a structural member obtained from the first or second resin composition of the present invention.
本発明は、特定の吸着性機能を有する微粒子をサーモトロピック液晶ポリエステルに溶融混練すると、重合工程、溶融混練工程の実質的な改変を伴わずに、サーモトロピック液晶ポリエステルの優れた耐熱性、成形性を維持したままで、金属腐食性気体放出が抑制された樹脂組成物を得ることができる。 The present invention provides excellent heat resistance and moldability of the thermotropic liquid crystal polyester without substantial modification of the polymerization process and the melt kneading process when fine particles having a specific adsorptive function are melt-kneaded into the thermotropic liquid crystal polyester. While maintaining the above, it is possible to obtain a resin composition in which metal corrosive gas release is suppressed.
(サーモトロピック液晶ポリエステル)
本発明に係るサーモトロピック液晶ポリマーに関しては、特に制限はないがハンダリフロー工程等で表面実装される電気電子部品の構成材料として使用される場合は、耐熱性の観点から、融点が320℃以上の全芳香族サーモトロピック液晶ポリエステルであることが好ましい。また、融点が高いことは、必然的に溶融混練温度が高くなり、サーモトロピック液晶ポリエステルと充填材との界面相互作用の活性化の点からも好ましい。
(Thermotropic liquid crystal polyester)
The thermotropic liquid crystal polymer according to the present invention is not particularly limited, but when used as a constituent material of an electric / electronic component to be surface-mounted in a solder reflow process or the like, the melting point is 320 ° C. or higher from the viewpoint of heat resistance. A wholly aromatic thermotropic liquid crystal polyester is preferred. In addition, a high melting point is inevitably high in terms of the melt-kneading temperature, and is preferable from the viewpoint of activating the interfacial interaction between the thermotropic liquid crystal polyester and the filler.
融点が320℃以上の全芳香族サーモトロピック液晶ポリエステルを得るには、原料モノマーとしてp−ヒドロキシ安息香酸を40モル%以上使用するとよい。これ以外は、公知の芳香族ヒドロキシカルボン酸、芳香族ジカルボン酸、芳香族ジオール、を任意に組み合わせて使用することができる。例えば、p−ヒドロキシ安息香酸や2−ヒドロキシ−6−ナフトエ酸などの芳香族ヒドロキシカルボン酸のみから得られるポリエステル、さらにこれらとテレフタル酸、イソフタル酸、2,6−ナフタレンジカルボン酸などの芳香族ジカルボン酸、および/またはハイドロキノン、レゾルシン、4,4’−ジヒドロキシジフェニル、2,6−ジヒドロキシナフタレンなどの芳香族ジヒドロキシ化合物とから得られる液晶性ポリエステルなどが好ましいものとして挙げられる。 In order to obtain a wholly aromatic thermotropic liquid crystal polyester having a melting point of 320 ° C. or higher, p-hydroxybenzoic acid may be used in an amount of 40 mol% or more as a raw material monomer. Other than this, known aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, and aromatic diols can be used in any combination. For example, polyesters obtained only from aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid. Preferable examples include acid and / or liquid crystalline polyester obtained from an aromatic dihydroxy compound such as hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, and 2,6-dihydroxynaphthalene.
特に好ましくは、p−ヒドロキシ安息香酸(I)、テレフタル酸(II)、4,4’−ジヒドロキシビフェニル(III)(これらの誘導体を含む。)を80〜100モル%(但し、(I)と(II)の合計を60モル%以上とする。)、および、(I)(II)(III)のいずれかと脱縮合反応可能な他の芳香族化合物0〜20モル%を重縮合して得られる全芳香族サーモトロピック液晶ポリエステルである。 Particularly preferably, p-hydroxybenzoic acid (I), terephthalic acid (II), 4,4′-dihydroxybiphenyl (III) (including these derivatives) is contained in an amount of 80 to 100 mol% (provided that (I) and (II) is 60 mol% or more), and (I) (II) (III) and any other aromatic compound capable of decondensation reaction is obtained by polycondensation in an amount of 0 to 20 mol%. A wholly aromatic thermotropic liquid crystal polyester.
全芳香族サーモトロピック液晶ポリエステルの製造に当たっては、溶融重縮合時間を短縮し工程中の熱履歴の影響を低減させ、揮発成分となる低分子量化合物の生成を抑制するために、上記のモノマーの水酸基を予めアセチル化した後に溶融重縮合を行うことが好ましい。さらに、工程を簡略化するためには、アセチル化は反応槽中のモノマーに無水酢酸を供給して行うのが好ましい。このアセチル化工程を溶融重縮合工程と同じ反応槽を用いて行うのが好ましい。すなわち、反応槽中で原料モノマーと無水酢酸でアセチル化反応を行い、反応終了後昇温して重縮合反応に移行するのが好ましい。 In the production of wholly aromatic thermotropic liquid crystalline polyesters, in order to shorten the melt polycondensation time, reduce the influence of thermal history during the process, and suppress the formation of low molecular weight compounds as volatile components, the hydroxyl groups of the above monomers It is preferable to carry out melt polycondensation after acetylation of the compound in advance. Furthermore, in order to simplify the process, acetylation is preferably performed by supplying acetic anhydride to the monomer in the reaction vessel. This acetylation step is preferably performed using the same reaction vessel as the melt polycondensation step. That is, it is preferable to carry out an acetylation reaction with a raw material monomer and acetic anhydride in a reaction vessel, and then proceed to a polycondensation reaction by raising the temperature after completion of the reaction.
アセチル化されたモノマーの脱酢酸反応を伴いながら溶融重縮合反応を行う。反応槽はモノマー供給手段、酢酸排出手段、溶融ポリエステル取り出し手段および攪拌手段を備えた反応槽を用いて行うのが好ましい。このような反応槽(重縮合装置)は公知のものから適宜選択することができる。重合温度は好ましくは150℃〜350℃である。アセチル化反応終了後、重合開始温度まで昇温して重縮合を開始し、0.1℃/分〜2℃/分の範囲で昇温して、最終温度として280〜350℃まで上昇させるのが好ましい。重縮合反応の触媒として、Ge,Sn,Ti、Sb、Co,Mn、Mg 等の化合物を使用することができる。重縮合の進行により生成重合体の溶融温度が上昇するのに対応して重縮合温度も上昇する。固相重縮合工程に供する溶融重縮合反応物は、低重合度の全芳香族サーモトロピック液晶ポリエステルであり、その流動点は、好ましくは200℃以上、さらに好ましくは220℃〜330℃である。 A melt polycondensation reaction is performed with a deacetic acid reaction of the acetylated monomer. The reaction vessel is preferably used using a reaction vessel equipped with monomer supply means, acetic acid discharge means, molten polyester take-out means and stirring means. Such a reaction vessel (polycondensation apparatus) can be appropriately selected from known ones. The polymerization temperature is preferably 150 ° C to 350 ° C. After completion of the acetylation reaction, the temperature is raised to the polymerization start temperature to start polycondensation, the temperature is raised in the range of 0.1 ° C./min to 2 ° C./min, and the final temperature is raised to 280 to 350 ° C. Is preferred. As the catalyst for the polycondensation reaction, compounds such as Ge, Sn, Ti, Sb, Co, Mn, and Mg can be used. The polycondensation temperature rises as the melting temperature of the produced polymer rises as the polycondensation proceeds. The melt polycondensation reaction product subjected to the solid phase polycondensation step is a wholly aromatic thermotropic liquid crystal polyester having a low polymerization degree, and its pour point is preferably 200 ° C. or higher, more preferably 220 ° C. to 330 ° C.
溶融重縮合において、その流動点が200℃以上、好ましくは220℃〜330℃に達したら、低重合度の全芳香族サーモトロピック液晶ポリエステルを溶融状態のまま重合槽から抜出し、スチールベルトやドラムクーラー等の冷却機へ供給し、冷却して固化させる。 In the melt polycondensation, when the pour point reaches 200 ° C. or higher, preferably 220 ° C. to 330 ° C., the fully aromatic thermotropic liquid crystalline polyester having a low polymerization degree is withdrawn from the polymerization tank in a molten state, and a steel belt or a drum cooler. Etc., cool and solidify.
ついで、固化した低重合度の全芳香族サーモトロピック液晶ポリエステルを、後続の固相重縮合に適した大きさに粉砕する。粉砕方法は特に限定されないが、例えば、ホソカワミクロン社製のフェザーミル、ビクトミル、コロプレックス、パルベラーザー、コントラプレックス、スクロールミル、ACMパルベラ-ザー等の衝撃式粉砕機、マツボー社製の架砕式粉砕機であるロールグラニュレーター等が挙げられる。特に好ましくは、ホソカワミクロン社製のフェザーミルである。本発明においては、粉砕物の粒径に特に制限はないが、工業フルイ(タイラーメッシュ)で4メッシュ通過〜2000メッシュ不通の範囲が好ましく、5メッシュ〜2000メッシュ(0.01〜4mm)にあればさらに好ましく、9メッシュ〜1450メッシュ(0.02〜2mm)にあれば最も好ましい。 Next, the solidified wholly aromatic thermotropic liquid crystal polyester having a low polymerization degree is pulverized to a size suitable for the subsequent solid phase polycondensation. The crushing method is not particularly limited. For example, impact mills such as feather mill, Victor mill, Coroplex, Pulverizer, Contraplex, scroll mill, ACM pulverizer, etc. manufactured by Hosokawa Micron Co., Ltd. A roll granulator or the like. Particularly preferred is a feather mill manufactured by Hosokawa Micron. In the present invention, the particle size of the pulverized material is not particularly limited, but it is preferably in the range of 4 mesh to 2000 mesh not passing through an industrial sieve (Tyler mesh), preferably 5 mesh to 2000 mesh (0.01 to 4 mm). More preferably, it is most preferably 9 mesh to 1450 mesh (0.02 to 2 mm).
ついで、粉砕工程で得られた粉砕物を固相重縮合工程に供して固相重縮合を行う。固相重縮合工程に使用する装置、運転条件には特に制限はなく、公知の装置および方法を用いることができる。 Next, the pulverized product obtained in the pulverization step is subjected to a solid phase polycondensation step to perform solid phase polycondensation. There is no restriction | limiting in particular in the apparatus used for a solid-phase polycondensation process, and operating conditions, A well-known apparatus and method can be used.
(金属酸化物微粒子)
サーモトロピック液晶ポリエステルに配合する金属酸化物微粒子は、平均粒径100nm以下を有するものである。100nmを超えると、表面処理の効率が低下するので好ましくない。好ましい平均粒径は5〜30nmである。好ましくは、溶液中でゾルを形成するような、ナノメータ単位のサイズを有する棒状、粒状、板状、羽毛状等の金属酸化物微粒子である。これらは、市場からゾルの状態で市場から入手できる。例示すれば、日産化学工業(株)が販売している、シリカゾル、アルミナゾル、酸化アンチモンゾル、に含有されるものである。
(Metal oxide fine particles)
The metal oxide fine particles blended in the thermotropic liquid crystal polyester has an average particle size of 100 nm or less. If it exceeds 100 nm, the efficiency of the surface treatment decreases, which is not preferable. A preferable average particle diameter is 5 to 30 nm. Preferred are metal oxide fine particles such as rods, granules, plates, feathers and the like having a size of a nanometer unit so as to form a sol in a solution. These are available from the market in sol form from the market. For example, it is contained in silica sol, alumina sol, and antimony oxide sol sold by Nissan Chemical Industries.
本発明の金属酸化物微粒子の添加によってサーモトロピック液晶ポリエステルから揮発性有機物がアウトガスとして放出されることを抑制する機構について、本発明者らは、サーモトロピック液晶ポリエステルの加工温度に耐える耐熱性のある金属酸化物が有している単位体積あたりの大きな表面積に基づく吸着機能であると考えている。 Regarding the mechanism for suppressing the release of volatile organic substances from the thermotropic liquid crystal polyester as outgas by the addition of the metal oxide fine particles of the present invention, the present inventors have heat resistance that can withstand the processing temperature of the thermotropic liquid crystal polyester. It is considered that the adsorption function is based on a large surface area per unit volume of the metal oxide.
特に、金属微粒子が酸化アルミニウムである場合、その両性(酸性およびアルカリ性)の特性により、モノマーのアセチル化誘導体を使用して溶融重縮合を実施する工程を含む場合、さらにモノマーのアセチル化とその結果得られるアセチル化誘導体を使用する溶融重縮合が同一反応槽で行われる場合等、酢酸系化合物が残存する可能性が高い場合にその効果がもっとも発揮される。 In particular, when the metal fine particle is aluminum oxide, due to its amphoteric (acidic and alkaline) characteristics, when it includes a step of performing melt polycondensation using an acetylated derivative of the monomer, the acetylation of the monomer and the result The effect is most exhibited when there is a high possibility that an acetic acid-based compound remains, such as when melt polycondensation using the obtained acetylated derivative is carried out in the same reaction vessel.
本発明においては、サーモトロピック液晶ポリエステル100質量部に対して溶液中でゾルを形成する金属酸化物微粒子0.1〜5質量部を添加する。金属酸化物微粒子が0.1質量部未満であると、吸着効果が十分に発揮できず、5質量部を超えると金属酸化物同士間の凝縮の問題が生じることがある。好ましい範囲は0.2〜2質量部の範囲である。 In the present invention, 0.1 to 5 parts by mass of metal oxide fine particles that form a sol in a solution is added to 100 parts by mass of thermotropic liquid crystal polyester. If the metal oxide fine particles are less than 0.1 parts by mass, the adsorption effect cannot be sufficiently exerted, and if it exceeds 5 parts by mass, a problem of condensation between the metal oxides may occur . Good preferable range is from 0.2 to 2 parts by weight.
本発明における溶融混練工程に使用する機器には特に制限はなく、単軸混練機、2軸混練機、バンバリーミキサー、加圧式ニーダー等が使用可能であるが、相互作用の向上の観点から効率的かつ均一な溶融混練が容易な2軸混練機が好ましい。 There are no particular limitations on the equipment used in the melt-kneading step in the present invention, and a single-screw kneader, a twin-screw kneader, a Banbury mixer, a pressure kneader, etc. can be used, but it is efficient from the viewpoint of improving the interaction. In addition, a twin-screw kneader that facilitates uniform melt-kneading is preferable.
本発明の樹脂組成物には、サーモトロピック液晶ポリエステルおよび金属酸化物微粒子に加えて、その他の公知の無機充填材、有機充填材を本発明の効果を損なわない範囲、好ましくは0〜150質量部、添加することができる。これらは、単独で使用しても2種類以上使用してもよい。 In the resin composition of the present invention, in addition to the thermotropic liquid crystal polyester and the metal oxide fine particles, other known inorganic fillers and organic fillers are within a range that does not impair the effects of the present invention, preferably 0 to 150 parts by mass. , Can be added. These may be used alone or in combination of two or more.
(サーモトロピック液晶ポリエステルの製造)
SUS316を材質とし、ダブルヘリカル攪拌翼を有する内容積が6Lの重合槽(日東高圧(株)製)を用い、重合槽の減圧−窒素注入を5回繰り返して窒素置換を行った後、上野製薬(株)製のp−ヒドロキシ安息香酸(HBA)1,330.10g(9.63モル)、エイジーインターナショナル社製のイソフタル酸(IPA)79.99g(0.4815モル)、三井石油化学工業(株)製のテレフタル酸(TPA)453.29g(2.7285モル)、本州化学工業(株)製のp,p’−ビフェノール(BP)597.73g(3.21モル)および触媒として東京化成社製の酢酸マグネシウム0.35gを仕込み、攪拌翼の回転数を50rpmとして重合槽内のモノマーを攪拌混合した。
次に、チッソ(株)製の無水酢酸1,769.22g(17.33モル)を添加し、攪拌翼の回転数を100rpmとして150℃まで1時間で昇温し、無水酢酸の還流状態で2時間アセチル化反応を行った。アセチル化終了後、酢酸を留出する状態にして速度0.5℃/分で昇温し、330℃において重合体2.1kgを重合槽下部の抜出し口から取り出した。取り出した重合体を冷却固化後に粉砕機により1mm以下に粉砕し、円筒型回転式リアクターを有する固相重合装置(旭硝工(株)製)により固相重合を行った。すなわち、リアクターに粉砕した重合体を投入し、窒素を1リットル/分の流量で流通させ、回転数20rpmで280℃まで2時間をかけて昇温した。280℃で1時間保持し、300℃まで30分で昇温して4時間保持した後、室温まで1時間で冷却して重合体を得た。得られた重合体の融点をDSCにより測定したところ、376℃であった。また、410℃における見掛け粘度は1,110ポイズであった。(以下、当該方法で得られたサーモトロピック液晶ポリエステルを「液晶ポリエステルA」という。)
(Manufacture of thermotropic liquid crystal polyester)
After using SUS316 as a material and a 6 L polymerization tank (manufactured by Nitto High Pressure Co., Ltd.) having a double helical stirring blade, the pressure in the polymerization tank was reduced and nitrogen injection was repeated 5 times, and then the Ueno Pharmaceutical was replaced. P-Hydroxybenzoic acid (HBA) 1,330.10 g (9.63 mol) manufactured by Co., Ltd., 79.99 g (0.4815 mol) of isophthalic acid (IPA) manufactured by AG International, Mitsui Petrochemical Industries ( 453.29 g (2.7285 mol) of terephthalic acid (TPA) manufactured by the same company, 59.73 g (3.21 mol) of p, p′-biphenol (BP) manufactured by Honshu Chemical Industry Co., Ltd., and Tokyo Chemical as a catalyst 0.35 g of magnesium acetate manufactured by the company was charged, and the monomer in the polymerization tank was stirred and mixed with the stirring blade rotating at 50 rpm.
Next, 1,769.22 g (17.33 mol) of acetic anhydride manufactured by Chisso Corporation was added, the temperature was increased to 150 ° C. over 1 hour with the rotation speed of the stirring blade being 100 rpm, and the acetic anhydride was refluxed. The acetylation reaction was performed for 2 hours. After completion of acetylation, acetic acid was distilled off and the temperature was raised at a rate of 0.5 ° C./min. The polymer taken out was cooled and solidified, and then pulverized to 1 mm or less with a pulverizer, and solid phase polymerization was performed with a solid phase polymerization apparatus (Asahi Glass Co., Ltd.) having a cylindrical rotary reactor. That is, the pulverized polymer was charged into the reactor, nitrogen was circulated at a flow rate of 1 liter / min, and the temperature was raised to 280 ° C. over 2 hours at a rotation speed of 20 rpm. It was kept at 280 ° C. for 1 hour, heated to 300 ° C. in 30 minutes and kept for 4 hours, and then cooled to room temperature in 1 hour to obtain a polymer. It was 376 degreeC when melting | fusing point of the obtained polymer was measured by DSC. The apparent viscosity at 410 ° C. was 1,110 poise. (Hereinafter, the thermotropic liquid crystal polyester obtained by the method is referred to as “liquid crystal polyester A”.)
(1)アルミナゾルとして、日産化学工業(株)製の商品名「520」(酸化アルミニウム濃度:20.9%、粒径:10〜20nm)を用いた。
(2)シリカヒドロゾルとして、日産化学工業(株)製の商品名「スノーテックスC」(酸化ケイ素濃度:20〜21%、粒径:10〜20nm)を用いた。
(3)ガラス繊維として、旭ファイバーグラス(株)製のチョップドガラス繊維、商品名「PX−1」(平均繊維長さ:3.5mm、平均繊維径:10μm、アスペクト比=350)を用いた。
(4)平均粒径80μmの酸化アルミニウムとして、日軽金(株)製の活性アルミナ、商品名「AA100−100」を用いた。
(5)平均粒径50μmの酸化ケイ素として、として、旭硝子エスアイテック(株)製のファインシリカ、商品名「M.S.GEL」を用いた。
(1) The product name “520” (aluminum oxide concentration: 20.9%, particle size: 10 to 20 nm) manufactured by Nissan Chemical Industries, Ltd. was used as the alumina sol.
(2) The product name “Snowtex C” (silicon oxide concentration: 20 to 21%, particle size: 10 to 20 nm) manufactured by Nissan Chemical Industries, Ltd. was used as the silica hydrosol.
(3) Chopped glass fiber manufactured by Asahi Fiber Glass Co., Ltd., trade name “PX-1” (average fiber length: 3.5 mm, average fiber diameter: 10 μm, aspect ratio = 350) was used as the glass fiber. .
(4) As aluminum oxide having an average particle size of 80 μm, activated alumina manufactured by Nichikin Kin Co., Ltd., trade name “AA100-100” was used.
(5) As silicon oxide having an average particle size of 50 μm, fine silica manufactured by Asahi Glass S-Tech Co., Ltd., trade name “MS GEL” was used.
(樹脂組成物の製造)
液晶ポリエステルA、アルミナゾル、シリカヒドロゾルおよびチョップドガラス繊維を用いて、次の方法で表1に示す組成の組成物(実施例1〜4および比較例1〜3)を得た。
(Manufacture of resin composition)
Using liquid crystal polyester A, alumina sol, silica hydrosol and chopped glass fiber, compositions (Examples 1 to 4 and Comparative Examples 1 to 3) having the compositions shown in Table 1 were obtained by the following method.
攪拌機、温度計、を備えた15リットルのセパラブルフラスコに「液晶ポリエステルA」1000gを入れ、「アルミナゾル」25gを加えて85℃で2攪拌混合を行った。その後、200℃で真空乾燥を20時間行い、室温まで冷却した後に、微細粒子酸化アルミニウム0.5質量部と液晶ポリマーA100質量部とからなる組成物(「組成物1」)を得た。 In a 15-liter separable flask equipped with a stirrer and a thermometer, 1000 g of “Liquid Crystal A” was added, 25 g of “Alumina Sol” was added, and the mixture was stirred and mixed at 85 ° C. for 2 times. Then, after vacuum-drying at 200 degreeC for 20 hours and cooling to room temperature, the composition ("Composition 1") which consists of 0.5 mass part of fine particle aluminum oxide and 100 mass parts of liquid crystal polymer A was obtained.
組成物1の「アルミナゾル」に代えて、「シリカヒドロゾル」を使用して、微細粒子酸化ケイ素0.5質量部と液晶ポリマーA100質量部とからなる組成物(「組成物2」)を得た。 Instead of “alumina sol” of composition 1, a “silica hydrosol” is used to obtain a composition (“composition 2”) comprising 0.5 parts by mass of fine-particle silicon oxide and 100 parts by mass of liquid crystal polymer A. It was.
100.5質量部の組成物1に、「ガラス繊維」を30質量部(実施例1)、60質量部(実施例2)および90質量部(実施例3)を、100.5質量部の組成物2に、「ガラス繊維」30質量部(実施例4)をそれぞれ混合し、30mmφの2軸押出機(池貝鉄鋼(株)製)によりシリンダーの最高温度430℃で溶融混練してペレットを得た。 In 100.5 parts by mass of Composition 1, 30 parts by mass (Example 1), 60 parts by mass (Example 2) and 90 parts by mass (Example 3) of “glass fiber” are 100.5 parts by mass. 30 parts by weight of “glass fiber” (Example 4) was mixed with composition 2, and melt-kneaded at a maximum temperature of 430 ° C. of the cylinder with a 30 mmφ twin-screw extruder (manufactured by Ikekai Steel Co., Ltd.). Obtained.
また、比較例1〜3として、「液晶ポリエステルA」100質量部に、「平均粒径80μmの酸化アルミニウム」、「平均粒径50μmの酸化ケイ素」、および「ガラス繊維」を表1に示す割合で配合して実施例と同様に溶融混練してペレットを得た。 Further, as Comparative Examples 1 to 3, the ratio of “Liquid Polyester A” in 100 parts by mass with “aluminum oxide having an average particle size of 80 μm”, “silicon oxide having an average particle size of 50 μm”, and “glass fiber” shown in Table 1. Then, the mixture was melt-kneaded in the same manner as in Example to obtain pellets.
(アウトガス量の測定)
得られたペレットを、1mmφメッシュの粉砕機により粉砕し、得られた粉砕物を20mlのバイアル瓶に入れて密封した後、150℃で24時間熱処理を行った。発生した酢酸およびフェノールのガスをヒューレットパッカード社製のヘッドスペースサンプラー(HP7694)を接続したガスクロマトグラフィー(HP6890)により定量した。カラムには化学品検査協会製のG−100(40m)を用い、その他の条件は、初期温度45℃、昇温速度20℃/分、最終温度280℃、ヘリウム圧8.3psiおよびスプリット比2.0として、FID検出器を用いて測定を行った。
結果を組成と対照して表1に示す。
(Measurement of outgas amount)
The obtained pellets were pulverized by a 1 mmφ mesh pulverizer, and the obtained pulverized product was sealed in a 20 ml vial, followed by heat treatment at 150 ° C. for 24 hours. The generated acetic acid and phenol gases were quantified by gas chromatography (HP6890) connected to a headspace sampler (HP7694) manufactured by Hewlett Packard. The column used was G-100 (40 m) manufactured by the Chemicals Inspection Association. Other conditions were an initial temperature of 45 ° C., a heating rate of 20 ° C./min, a final temperature of 280 ° C., a helium pressure of 8.3 psi, and a split ratio of 2 The measurement was performed using an FID detector as 0.0.
The results are shown in Table 1 in contrast to the composition.
表1に示すように、微粒子酸化アルミニウムまたは微粒子酸化ケイ素のような金属酸化物微粒子とサーモトロピック液晶ポリエステルとを含む本発明の樹脂組成物(実施例1〜4)は、金属酸化物微粒子を含まない樹脂組成物と比較して酢酸およびフェノールガスの発生量が極めて少ないことが判る。 As shown in Table 1, the resin compositions (Examples 1 to 4) of the present invention containing metal oxide fine particles such as fine particle aluminum oxide or fine particle silicon oxide and thermotropic liquid crystal polyester contain metal oxide fine particles. It can be seen that the amount of acetic acid and phenol gas generated is extremely small as compared with the resin composition without.
本発明に係る樹脂組成物は、腐食性ガスの発生量が極めて少なく、特に、電気電子部品の構成部材として使用するのに適している。 The resin composition according to the present invention generates very little corrosive gas, and is particularly suitable for use as a constituent member of electric and electronic parts.
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