JP6895032B1 - A connector containing a liquid crystal resin composition and a molded product of the liquid crystal resin composition. - Google Patents
A connector containing a liquid crystal resin composition and a molded product of the liquid crystal resin composition. Download PDFInfo
- Publication number
- JP6895032B1 JP6895032B1 JP2021503928A JP2021503928A JP6895032B1 JP 6895032 B1 JP6895032 B1 JP 6895032B1 JP 2021503928 A JP2021503928 A JP 2021503928A JP 2021503928 A JP2021503928 A JP 2021503928A JP 6895032 B1 JP6895032 B1 JP 6895032B1
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- crystal resin
- resin composition
- connector
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 103
- 239000011342 resin composition Substances 0.000 title claims abstract description 59
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 239000010445 mica Substances 0.000 claims abstract description 41
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 41
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 34
- 239000010456 wollastonite Substances 0.000 claims abstract description 34
- 125000003118 aryl group Chemical group 0.000 claims description 17
- 239000011295 pitch Substances 0.000 claims description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 12
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 11
- 239000000470 constituent Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000000034 method Methods 0.000 description 28
- -1 aromatic hydroxycarboxylic acids Chemical class 0.000 description 27
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 22
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 21
- 239000000203 mixture Substances 0.000 description 20
- 238000000465 moulding Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 238000011049 filling Methods 0.000 description 14
- 239000000155 melt Substances 0.000 description 14
- 239000000835 fiber Substances 0.000 description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 238000010298 pulverizing process Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000000945 filler Substances 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000004062 sedimentation Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 8
- 238000005452 bending Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 4
- 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 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
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000010438 heat treatment Methods 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
- 239000007788 liquid Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 235000011056 potassium acetate Nutrition 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000004984 aromatic diamines Chemical class 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052627 muscovite Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SYQQDAXGGKORQR-UHFFFAOYSA-N (4-hydroxyanilino) acetate Chemical compound CC(=O)ONC1=CC=C(O)C=C1 SYQQDAXGGKORQR-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 101150113959 Magix gene Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052626 biotite Inorganic materials 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical compound [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- PCILLCXFKWDRMK-UHFFFAOYSA-N naphthalene-1,4-diol Chemical compound C1=CC=C2C(O)=CC=C(O)C2=C1 PCILLCXFKWDRMK-UHFFFAOYSA-N 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
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachloro-phenol Natural products OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research 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
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- BPILDHPJSYVNAF-UHFFFAOYSA-M sodium;diiodomethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(I)I BPILDHPJSYVNAF-UHFFFAOYSA-M 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R12/00—Structural associations of a plurality of mutually-insulated electrical connecting elements, specially adapted for printed circuits, e.g. printed circuit boards [PCB], flat or ribbon cables, or like generally planar structures, e.g. terminal strips, terminal blocks; Coupling devices specially adapted for printed circuits, flat or ribbon cables, or like generally planar structures; Terminals specially adapted for contact with, or insertion into, printed circuits, flat or ribbon cables, or like generally planar structures
- H01R12/70—Coupling devices
- H01R12/71—Coupling devices for rigid printing circuits or like structures
- H01R12/72—Coupling devices for rigid printing circuits or like structures coupling with the edge of the rigid printed circuits or like structures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R12/00—Structural associations of a plurality of mutually-insulated electrical connecting elements, specially adapted for printed circuits, e.g. printed circuit boards [PCB], flat or ribbon cables, or like generally planar structures, e.g. terminal strips, terminal blocks; Coupling devices specially adapted for printed circuits, flat or ribbon cables, or like generally planar structures; Terminals specially adapted for contact with, or insertion into, printed circuits, flat or ribbon cables, or like generally planar structures
- H01R12/70—Coupling devices
- H01R12/77—Coupling devices for flexible printed circuits, flat or ribbon cables or like structures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/46—Bases; Cases
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Manufacturing Of Electrical Connectors (AREA)
- Connector Housings Or Holding Contact Members (AREA)
Abstract
耐熱性及び機械的性質に優れ、そり変形及びブリスター発生が抑制されたコネクターの製造を実現できる、流動性が良好な液晶性樹脂組成物、及び当該液晶性樹脂組成物の成形品を含むコネクターを提供する。本発明に係る液晶性樹脂組成物は、（Ａ）液晶性樹脂、（Ｂ）繊維状ウォラストナイト、及び（Ｃ）マイカを含有する液晶性樹脂組成物であって、前記繊維状ウォラストナイトにおいて、Ａｌ２Ｏ３の含有量は、０．０５〜０．６５質量％、Ｆｅ２Ｏ３の含有量は、０．０５〜１．０質量％であり、前記液晶性樹脂組成物全体に対して、前記（Ｂ）繊維状ウォラストナイトの含有量は、２．５〜１５質量％、前記（Ｃ）マイカの含有量は、１７．５〜２７．５質量％、前記（Ｂ）繊維状ウォラストナイトと前記（Ｃ）マイカとの合計の含有量は、２０〜３７．５質量％である。A liquid crystal resin composition having excellent fluidity, which is excellent in heat resistance and mechanical properties and can realize the manufacture of a connector in which warpage deformation and blister generation are suppressed, and a connector containing a molded product of the liquid crystal resin composition. provide. The liquid crystal resin composition according to the present invention is a liquid crystal resin composition containing (A) liquid crystal resin, (B) fibrous wollastonite, and (C) mica, and the fibrous wollastonite. The content of Al2O3 is 0.05 to 0.65% by mass and the content of Fe2O3 is 0.05 to 1.0% by mass. ) The content of the fibrous wollastonite is 2.5 to 15% by mass, the content of the (C) mica is 17.5 to 27.5% by mass, and the (B) fibrous wollastonite and the above. (C) The total content with mica is 20 to 37.5% by mass.
Description
本発明は、液晶性樹脂組成物、及び当該液晶性樹脂組成物の成形品を含むコネクターに関する。 The present invention relates to a liquid crystal resin composition and a connector containing a molded product of the liquid crystal resin composition.
液晶性樹脂は、寸法精度、流動性等に優れる熱可塑性樹脂である。このような特徴を有するため、液晶性樹脂は、従来より各種電子部品の材料として採用されてきた。 The liquid crystal resin is a thermoplastic resin having excellent dimensional accuracy, fluidity, and the like. Due to these characteristics, liquid crystal resins have been conventionally used as materials for various electronic components.
特に、近年のエレクトロニクス機器の小型化及び薄型化に伴い、エレクトロニクス機器を構成する電子部品（コネクター等）の低背化及び狭ピッチ化に対するニーズがある。例えば、特許文献１には、マイカ及びガラス繊維で強化された液晶性樹脂組成物から成形されたコネクターが開示されている。このようなコネクターは、耐熱性、そり変形の抑制、流動性、寸法安定性等が要求される、基板対基板コネクターや、フレキシブルプリント基板（ＦＰＣ）とフレキシブルフラットケーブル（ＦＦＣ）とを接続するために使用されるフレキシブルプリント基板用コネクター等として採用されている。 In particular, with the recent miniaturization and thinning of electronic devices, there is a need for lowering the height and narrowing the pitch of electronic components (connectors, etc.) constituting the electronic devices. For example, Patent Document 1 discloses a connector molded from a liquid crystal resin composition reinforced with mica and glass fiber. Such a connector is for connecting a board-to-board connector or a flexible printed circuit board (FPC) and a flexible flat cable (FFC), which are required to have heat resistance, suppression of warpage deformation, fluidity, dimensional stability, and the like. It is used as a connector for flexible printed circuit boards used in
しかし、従来の液晶性樹脂組成物から、コネクターを成形しようとすると、組成物の耐熱性、機械的性質の維持、そり変形の抑制、及び流動性が十分ではなく加工性に劣るため、低背化及び狭ピッチ化に対するニーズに対応した低背狭ピッチコネクターの製造が困難であった。 However, when an attempt is made to mold a connector from a conventional liquid crystal resin composition, the heat resistance of the composition, maintenance of mechanical properties, suppression of warpage deformation, and inferior fluidity and workability are therefore low. It has been difficult to manufacture a low-profile narrow-pitch connector that meets the needs for narrow pitching and narrowing.
また、液晶性樹脂組成物には、ブリスター発生の問題が生じ得る。即ち、液晶性ポリエステル、液晶性ポリエステルアミド等の液晶性樹脂は、高温熱安定性が良いため、高温での熱処理を要する材料に使用される場合が多い。しかし、成形品を高温の空気中及び液体中に長時間放置すると、表面にブリスターと呼ばれる細かい膨れが生じるという問題が起こる。 In addition, the liquid crystal resin composition may have a problem of blistering. That is, liquid crystal resins such as liquid crystal polyester and liquid crystal polyester amide are often used as materials that require heat treatment at high temperature because they have good high temperature thermal stability. However, if the molded product is left in high temperature air or liquid for a long time, there arises a problem that fine swelling called blister is generated on the surface.
この現象の一原因は、液晶性樹脂が溶融状態にある時に発生する分解ガス等が成形品内部に持ち込まれ、その後、高温の熱処理を行う際にそのガスが膨張し、加熱で軟化した成形品表面を押し上げ、押し上げられた部分がブリスターとして現れることである。ブリスターの発生は、材料の溶融押出し時にベント孔から充分脱気することや成形する際に成形機内に長く滞留させないこと等によって、少なくすることもできる。しかし、非常に条件範囲が狭く、ブリスターの発生を抑えた成形品、即ち、耐ブリスター性を有する成形品を得るには充分ではない。ブリスター発生の根本的な解決には、液晶性樹脂そのものの品質の向上を要し、公知の液晶性樹脂やそれを用いた方法では、ブリスター発生の問題を解決するには不充分である。 One cause of this phenomenon is that decomposition gas or the like generated when the liquid crystal resin is in a molten state is brought into the molded product, and then the gas expands when heat treatment is performed at a high temperature, and the molded product is softened by heating. The surface is pushed up, and the pushed up part appears as a blister. The generation of blisters can also be reduced by sufficiently degassing the vent holes during melt extrusion of the material and by not allowing the material to stay in the molding machine for a long time during molding. However, the condition range is very narrow, and it is not sufficient to obtain a molded product in which the generation of blisters is suppressed, that is, a molded product having blister resistance. A fundamental solution to the generation of blisters requires improvement in the quality of the liquid crystal resin itself, and known liquid crystal resins and methods using the same are insufficient to solve the problem of blistering.
本発明は、上記課題を解決するためになされたものであり、その目的は、耐熱性及び機械的性質に優れ、そり変形及びブリスター発生が抑制されたコネクターの製造を実現できる、流動性が良好な液晶性樹脂組成物、及び当該液晶性樹脂組成物の成形品を含むコネクターを提供することにある。 The present invention has been made to solve the above problems, and an object of the present invention is to realize the production of a connector having excellent heat resistance and mechanical properties and suppressing warpage deformation and blister generation, and having good fluidity. It is an object of the present invention to provide a liquid crystal resin composition and a connector containing a molded product of the liquid crystal resin composition.
本発明者らは、上記課題を解決するために鋭意研究を重ねた。その結果、液晶性樹脂と特定の組成を有する繊維状ウォラストナイトとマイカとを含有し、繊維状ウォラストナイト、マイカ、及びこれらの合計の各々の含有量が所定の範囲である液晶性樹脂組成物を用いることにより、上記課題を解決できることを見出し、本発明を完成するに至った。より具体的には本発明は以下のものを提供する。 The present inventors have conducted intensive studies to solve the above problems. As a result, a liquid crystal resin containing a liquid crystal resin, fibrous wollastonite having a specific composition, and mica, and the content of each of the fibrous wollastonite, mica, and the total of these is in a predetermined range. We have found that the above problems can be solved by using the composition, and have completed the present invention. More specifically, the present invention provides the following.
（１） （Ａ）液晶性樹脂、（Ｂ）繊維状ウォラストナイト、及び（Ｃ）マイカを含有する液晶性樹脂組成物であって、前記繊維状ウォラストナイトにおいて、Ａｌ２Ｏ３の含有量は、０．０５〜０．６５質量％、Ｆｅ２Ｏ３の含有量は、０．０５〜１．０質量％であり、前記液晶性樹脂組成物全体に対して、前記（Ｂ）繊維状ウォラストナイトの含有量は、２．５〜１５質量％、前記（Ｃ）マイカの含有量は、１７．５〜２７．５質量％、前記（Ｂ）繊維状ウォラストナイトと前記（Ｃ）マイカとの合計の含有量は、２０〜３７．５質量％である液晶性樹脂組成物。(1) A liquid crystal resin composition containing (A) a liquid crystal resin, (B) fibrous wollastonite, and (C) mica, which contains Al 2 O 3 in the fibrous wollastonite. The amount is 0.05 to 0.65% by mass, the content of Fe 2 O 3 is 0.05 to 1.0% by mass, and the fiber (B) is compared with the whole liquid resin composition. The content of the fibrous wollastonite is 2.5 to 15% by mass, the content of the (C) mica is 17.5 to 27.5% by mass, the fibrous wollastonite and the (C) fibrous wollastonite. ) A liquid crystal resin composition having a total content of 20 to 37.5% by mass with mica.
（２） 製品全長が３０ｍｍ未満であり、製品高さが５ｍｍ未満であるコネクター用である（１）に記載の液晶性樹脂組成物。 (2) The liquid crystal resin composition according to (1) for a connector having a product total length of less than 30 mm and a product height of less than 5 mm.
（３） （１）又は（２）に記載の液晶性樹脂組成物の成形品を含み、製品全長が３０ｍｍ未満であり、製品高さが５ｍｍ未満であるコネクター。 (3) A connector comprising the molded product of the liquid crystal resin composition according to (1) or (2), having a product total length of less than 30 mm and a product height of less than 5 mm.
（４） 低背狭ピッチコネクターである（３）に記載のコネクター。 (4) The connector according to (3), which is a low profile narrow pitch connector.
（５） ピッチ間距離が０．５ｍｍ以下であり、
製品全長が３．５ｍｍ以上３０ｍｍ未満であり、
製品高さが１．５ｍｍ以下であり、
基板対基板コネクター又はフレキシブルプリント基板用コネクターである低背狭ピッチコネクターである（３）又は（４）に記載のコネクター。(5) The distance between pitches is 0.5 mm or less,
The total length of the product is 3.5 mm or more and less than 30 mm.
The product height is 1.5 mm or less,
The connector according to (3) or (4), which is a low-profile narrow-pitch connector which is a board-to-board connector or a connector for a flexible printed circuit board.
本発明によれば、耐熱性及び機械的性質に優れ、そり変形及びブリスター発生が抑制されたコネクターの製造を実現できる、流動性が良好な液晶性樹脂組成物、及び当該液晶性樹脂組成物の成形品を含むコネクターを提供することができる。 According to the present invention, a liquid crystal resin composition having excellent heat resistance and mechanical properties, capable of producing a connector in which warpage deformation and blister generation are suppressed, and having good fluidity, and the liquid crystal resin composition. A connector including a molded product can be provided.
＜液晶性樹脂組成物＞
本発明に係る液晶性樹脂組成物は、（Ａ）液晶性樹脂、（Ｂ）繊維状ウォラストナイト、及び（Ｃ）マイカを含有する液晶性樹脂組成物であって、前記繊維状ウォラストナイトにおいて、Ａｌ２Ｏ３の含有量は、０．０５〜０．６５質量％、Ｆｅ２Ｏ３の含有量は、０．０５〜１．０質量％であり、前記液晶性樹脂組成物全体に対して、前記（Ｂ）繊維状ウォラストナイトの含有量は、２．５〜１５質量％、前記（Ｃ）マイカの含有量は、１７．５〜２７．５質量％、前記（Ｂ）繊維状ウォラストナイトと前記（Ｃ）マイカとの合計の含有量は、２０〜３７．５質量％である。<Liquid crystal resin composition>
The liquid crystal resin composition according to the present invention is a liquid crystal resin composition containing (A) liquid crystal resin, (B) fibrous wollastonite, and (C) mica, and the fibrous wollastonite. The content of Al 2 O 3 is 0.05 to 0.65% by mass, and the content of Fe 2 O 3 is 0.05 to 1.0% by mass. On the other hand, the content of the (B) fibrous wollastonite was 2.5 to 15% by mass, the content of the (C) mica was 17.5 to 27.5% by mass, and the content of the (B) fiber. The total content of the plastic wollastonite and the mica (C) is 20 to 37.5% by mass.
［（Ａ）液晶性樹脂］
本発明で使用する（Ａ）液晶性樹脂とは、光学異方性溶融相を形成し得る性質を有する溶融加工性ポリマーを指す。異方性溶融相の性質は、直交偏光子を利用した慣用の偏光検査法により確認することが出来る。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溶融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。本発明に適用できる液晶性樹脂は直交偏光子の間で検査したときに、たとえ溶融静止状態であっても偏光は通常透過し、光学的に異方性を示す。[(A) Liquid crystal resin]
The liquid crystal resin (A) used in the present invention refers to a melt-processable polymer having a property of forming an optically anisotropic melt phase. The properties of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizing element. More specifically, the confirmation of the anisotropic molten phase can be carried out by observing the molten sample placed on the Leitz hot stage at a magnification of 40 times in a nitrogen atmosphere using a Leitz polarizing microscope. When inspected between orthogonal polarizers, the liquid crystal resin applicable to the present invention normally transmits polarized light even in a molten and stationary state, and exhibits optical anisotropy.
上記のような（Ａ）液晶性樹脂の種類としては特に限定されず、芳香族ポリエステル及び／又は芳香族ポリエステルアミドであることが好ましい。（Ａ）液晶性樹脂は、全芳香族ポリエステル及び／又は全芳香族ポリエステルアミドでも、全芳香族ポリエステル及び／又は芳香族ポリエステルアミドを同一分子鎖中に部分的に含む液晶性樹脂でもよく、耐熱性等の観点から、全芳香族ポリエステル及び／又は全芳香族ポリエステルアミドが好ましい。（Ａ）液晶性樹脂としては、６０℃でペンタフルオロフェノールに濃度０．１質量％で溶解したときに、好ましくは少なくとも約２．０ｄｌ／ｇ、更に好ましくは２．０〜１０．０ｄｌ／ｇの対数粘度（Ｉ．Ｖ．）を有する、芳香族ポリエステル及び／又は芳香族ポリエステルアミド等の液晶性樹脂も好ましく使用される。 The type of the liquid crystal resin (A) as described above is not particularly limited, and is preferably an aromatic polyester and / or an aromatic polyester amide. The liquid crystal resin (A) may be a total aromatic polyester and / or a total aromatic polyester amide, or a liquid crystal resin partially containing a total aromatic polyester and / or an aromatic polyester amide in the same molecular chain, and is heat resistant. From the viewpoint of properties and the like, a total aromatic polyester and / or a total aromatic polyester amide is preferable. The liquid crystal resin (A) preferably at least about 2.0 dl / g, more preferably 2.0 to 10.0 dl / g when dissolved in pentafluorophenol at 60 ° C. at a concentration of 0.1% by mass. A liquid crystal resin such as aromatic polyester and / or aromatic polyesteramide having a logarithmic viscosity (IV) of is also preferably used.
本発明に適用できる（Ａ）液晶性樹脂としての芳香族ポリエステル又は芳香族ポリエステルアミドは、特に好ましくは、芳香族ヒドロキシカルボン酸、芳香族ヒドロキシアミン、及び芳香族ジアミンからなる群より選ばれる少なくとも１種の化合物に由来する繰り返し単位を構成成分として有する芳香族ポリエステル又は芳香族ポリエステルアミドである。 The aromatic polyester or aromatic polyesteramide as the (A) liquid crystal resin applicable to the present invention is particularly preferably at least one selected from the group consisting of aromatic hydroxycarboxylic acids, aromatic hydroxyamines, and aromatic diamines. It is an aromatic polyester or an aromatic polyester amide having a repeating unit derived from a species compound as a constituent.
より具体的には、
（１）主として芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上に由来する繰り返し単位からなるポリエステル；
（２）主として（ａ）芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上に由来する繰り返し単位と、（ｂ）芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の１種又は２種以上に由来する繰り返し単位とからなるポリエステル；
（３）主として（ａ）芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上に由来する繰り返し単位と、（ｂ）芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の１種又は２種以上に由来する繰り返し単位と、（ｃ）芳香族ジオール、脂環族ジオール、脂肪族ジオール、及びそれらの誘導体の少なくとも１種又は２種以上に由来する繰り返し単位、とからなるポリエステル；
（４）主として（ａ）芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上に由来する繰り返し単位と、（ｂ）芳香族ヒドロキシアミン、芳香族ジアミン、及びそれらの誘導体の１種又は２種以上に由来する繰り返し単位と、（ｃ）芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の１種又は２種以上に由来する繰り返し単位、とからなるポリエステルアミド；
（５）主として（ａ）芳香族ヒドロキシカルボン酸及びその誘導体の１種又は２種以上に由来する繰り返し単位と、（ｂ）芳香族ヒドロキシアミン、芳香族ジアミン、及びそれらの誘導体の１種又は２種以上に由来する繰り返し単位と、（ｃ）芳香族ジカルボン酸、脂環族ジカルボン酸、及びそれらの誘導体の１種又は２種以上に由来する繰り返し単位と、（ｄ）芳香族ジオール、脂環族ジオール、脂肪族ジオール、及びそれらの誘導体の少なくとも１種又は２種以上に由来する繰り返し単位、とからなるポリエステルアミド等が挙げられる。更に上記の構成成分に必要に応じ分子量調整剤を併用してもよい。More specifically
(1) Polyester composed of repeating units mainly derived from one or more kinds of aromatic hydroxycarboxylic acids and their derivatives;
(2) Repeating units mainly derived from (a) one or more aromatic hydroxycarboxylic acids and their derivatives, and (b) aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and one of their derivatives. Or polyester consisting of repeating units derived from two or more species;
(3) Repeating units mainly derived from (a) one or more kinds of aromatic hydroxycarboxylic acids and their derivatives, and (b) one kind of aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and their derivatives. Or a polyester consisting of a repeating unit derived from two or more kinds and (c) a repeating unit derived from at least one kind or two or more kinds of aromatic diols, alicyclic diols, aliphatic diols, and derivatives thereof;
(4) Repeating units mainly derived from (a) one or more of aromatic hydroxycarboxylic acids and their derivatives, and (b) one or two of aromatic hydroxyamines, aromatic diamines, and their derivatives. Polyester amides consisting of repeating units derived from species or higher and (c) aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and repeating units derived from one or more of their derivatives;
(5) Repetitive units mainly derived from (a) one or more aromatic hydroxycarboxylic acids and their derivatives, and (b) one or two aromatic hydroxyamines, aromatic diamines, and their derivatives. Repeating units derived from species or higher, (c) aromatic dicarboxylic acids, alicyclic dicarboxylic acids, and repeating units derived from one or more of their derivatives, and (d) aromatic diols, alicyclics. Examples thereof include polyesteramides composed of group diols, aliphatic diols, and repeating units derived from at least one or more of the derivatives thereof. Further, a molecular weight adjusting agent may be used in combination with the above-mentioned constituent components, if necessary.
本発明に適用できる（Ａ）液晶性樹脂を構成する具体的化合物の好ましい例としては、ｐ−ヒドロキシ安息香酸、６−ヒドロキシ−２−ナフトエ酸等の芳香族ヒドロキシカルボン酸；２，６−ジヒドロキシナフタレン、１，４−ジヒドロキシナフタレン、４，４’−ジヒドロキシビフェニル、ハイドロキノン、レゾルシン、下記一般式（Ｉ）で表される化合物、及び下記一般式（ＩＩ）で表される化合物等の芳香族ジオール；テレフタル酸、イソフタル酸、４，４’−ジフェニルジカルボン酸、２，６−ナフタレンジカルボン酸、及び下記一般式（ＩＩＩ）で表される化合物等の芳香族ジカルボン酸；ｐ−アミノフェノール、ｐ−フェニレンジアミン等の芳香族アミン類が挙げられる。
本発明に用いられる（Ａ）液晶性樹脂の調製は、上記のモノマー化合物（又はモノマーの混合物）から直接重合法やエステル交換法を用いて公知の方法で行うことができ、通常は溶融重合法、溶液重合法、スラリー重合法、固相重合法等、又はこれらの２種以上の組み合わせが用いられ、溶融重合法、又は溶融重合法と固相重合法との組み合わせが好ましく用いられる。エステル形成能を有する上記化合物類はそのままの形で重合に用いてもよく、また、重合の前段階でアシル化剤等を用いて前駆体から該エステル形成能を有する誘導体に変性されたものでもよい。アシル化剤としては、無水酢酸等の無水カルボン酸等を挙げることができる。 The liquid crystal resin (A) used in the present invention can be prepared from the above-mentioned monomer compound (or mixture of monomers) by a known method using a direct polymerization method or an ester exchange method, and is usually a melt polymerization method. , Solution polymerization method, slurry polymerization method, solid phase polymerization method, etc., or a combination of two or more of these is used, and a melt polymerization method or a combination of a melt polymerization method and a solid phase polymerization method is preferably used. The above compounds having an ester-forming ability may be used for polymerization as they are, or may be modified from a precursor to a derivative having the ester-forming ability by using an acylating agent or the like in the pre-polymerization step. Good. Examples of the acylating agent include carboxylic acid anhydride such as acetic anhydride.
重合に際しては、種々の触媒の使用が可能である。使用可能な触媒の代表的なものとしては、酢酸カリウム、酢酸マグネシウム、酢酸第一錫、テトラブチルチタネート、酢酸鉛、酢酸ナトリウム、三酸化アンチモン、トリス（２，４−ペンタンジオナト）コバルト（ＩＩＩ）等の金属塩系触媒、Ｎ−メチルイミダゾール、４−ジメチルアミノピリジン等の有機化合物系触媒を挙げることができる。触媒の使用量は、一般には、モノマーの全重量に対して、約０．００１〜１質量％であることが好ましく、約０．０１〜０．２質量％であることが特に好ましい。 Various catalysts can be used for the polymerization. Typical usable catalysts are potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, tris (2,4-pentandionato) cobalt (III). ) And other metal salt-based catalysts, and organic compound-based catalysts such as N-methylimidazole and 4-dimethylaminopyridine. Generally, the amount of the catalyst used is preferably about 0.001 to 1% by mass, particularly preferably about 0.01 to 0.2% by mass, based on the total weight of the monomer.
上記のような方法で得られた（Ａ）液晶性樹脂の溶融粘度は特に限定されない。一般には成形温度での溶融粘度が剪断速度１０００ｓｅｃ−１で１０Ｐａ・ｓ以上６００Ｐａ・ｓ以下のものが使用可能である。しかし、それ自体あまり高粘度のものは流動性が非常に悪化するため好ましくない。なお、上記（Ａ）液晶性樹脂は２種以上の液晶性樹脂の混合物であってもよい。The melt viscosity of the liquid crystal resin (A) obtained by the above method is not particularly limited. In general, those having a melt viscosity at a molding temperature of 1000 sec -1 and a shear rate of 10 Pa · s or more and 600 Pa · s or less can be used. However, the one having a very high viscosity by itself is not preferable because the fluidity is very deteriorated. The liquid crystal resin (A) may be a mixture of two or more kinds of liquid crystal resins.
（Ａ）液晶性樹脂の融点（以下、「Ｔｍ」ともいう。）及び結晶化温度（以下、「Ｔｃ」ともいう。）は特に限定されない。ＴｍとＴｃとの差Ｔｍ−Ｔｃは、ブリスター発生を抑制しやすく、機械的強度を維持しやすい点で、４５℃以下が好ましく、４２℃以下がより好ましく、４０℃以下が更により好ましい。Ｔｍ−Ｔｃの下限は、特に限定されず、０℃、１℃、５℃、１０℃、２０℃、３０℃、及び３７℃のいずれでもよい。 (A) The melting point (hereinafter, also referred to as “Tm”) and the crystallization temperature (hereinafter, also referred to as “Tc”) of the liquid crystal resin are not particularly limited. Difference between Tm and Tc Tm-Tc is preferably 45 ° C. or lower, more preferably 42 ° C. or lower, and even more preferably 40 ° C. or lower, in that blister generation is easily suppressed and mechanical strength is easily maintained. The lower limit of Tm-Tc is not particularly limited, and may be any of 0 ° C, 1 ° C, 5 ° C, 10 ° C, 20 ° C, 30 ° C, and 37 ° C.
本発明の液晶性樹脂組成物において、（Ａ）液晶性樹脂の好ましい含有量は、６２．５〜８０質量％である。（Ａ）成分の含有量が上記範囲内であると、組成物は、流動性を維持しつつ、ブリスター発生を抑制しやすい。（Ａ）成分の含有量は、より好ましくは６３．５〜７５質量％、更により好ましくは６５〜７０質量％である。 In the liquid crystal resin composition of the present invention, the preferable content of the liquid crystal resin (A) is 62.5 to 80% by mass. When the content of the component (A) is within the above range, the composition tends to suppress the generation of blisters while maintaining the fluidity. The content of the component (A) is more preferably 63.5 to 75% by mass, and even more preferably 65 to 70% by mass.
［（Ｂ）繊維状ウォラストナイト］
（Ｂ）成分は繊維状ウォラストナイトであり、（Ｂ）成分において、Ａｌ２Ｏ３の含有量は、０．０５〜０．６５質量％、Ｆｅ２Ｏ３の含有量は、０．０５〜１．０質量％である。即ち、（Ｂ）成分は、その主成分たるＳｉＯ２及びＣａＯの他に、Ａｌ２Ｏ３及びＦｅ２Ｏ３を上記範囲の量で含有するものである。（Ｂ）成分にＡｌ２Ｏ３及びＦｅ２Ｏ３が含まれることにより、組成物は、溶融粘度が低くなり、流動性を維持しやすくなるが、（Ｂ）成分におけるＡｌ２Ｏ３及びＦｅ２Ｏ３の各含有量が多すぎると、ブリスター発生の問題が生じ得る。（Ｂ）成分にＡｌ２Ｏ３及びＦｅ２Ｏ３が上記範囲の量で含まれることにより、組成物は、流動性を維持しつつ、ブリスター発生を抑制しやすい。なお、本明細書において、（Ｂ）成分におけるＡｌ２Ｏ３及びＦｅ２Ｏ３の各含有量としては、ＪＩＳ Ｋ ０１１９に準拠して分析した値を採用する。[(B) Fibrous wollastonite]
The component (B) is fibrous wollastonite, and in the component (B), the content of Al 2 O 3 is 0.05 to 0.65% by mass, and the content of Fe 2 O 3 is 0.05. ~ 1.0% by mass. That is, the component (B) contains Al 2 O 3 and Fe 2 O 3 in an amount in the above range in addition to SiO 2 and CaO, which are the main components thereof. By containing Al 2 O 3 and Fe 2 O 3 in the component (B), the composition has a low melt viscosity and is easy to maintain fluidity, but Al 2 O 3 and Fe in the component (B) If each content of 2 O 3 is too large, a problem of blister generation may occur. By containing Al 2 O 3 and Fe 2 O 3 in the amount in the above range as the component (B), the composition tends to suppress the generation of blisters while maintaining the fluidity. In this specification, the values analyzed in accordance with JIS K 0119 are adopted as the respective contents of Al 2 O 3 and Fe 2 O 3 in the component (B).
（Ｂ）成分において、Ａｌ２Ｏ３の含有量は、好ましくは０．０８〜０．４５質量％、より好ましくは０．１１〜０．３０質量％であり、Ｆｅ２Ｏ３の含有量は、好ましくは０．１〜０．５質量％、より好ましくは０．１８〜０．２３質量％である。Ａｌ２Ｏ３の含有量及びＦｅ２Ｏ３の含有量が上記範囲内であると、組成物は、ブリスター発生をより抑制しやすい。In the component (B), the content of Al 2 O 3 is preferably 0.08 to 0.45% by mass, more preferably 0.11 to 0.30% by mass, and the content of Fe 2 O 3 is , It is preferably 0.1 to 0.5% by mass, and more preferably 0.18 to 0.23% by mass. When the content of Al 2 O 3 and the content of Fe 2 O 3 are within the above ranges, the composition is more likely to suppress the generation of blisters.
（Ｂ）成分の平均繊維長は、好ましくは５０〜２００μｍであり、より好ましくは７０〜１８０μｍであり、更により好ましくは９０〜１６０μｍである。上記平均繊維長が上記範囲内であると、組成物は、ブリスター発生をより抑制しやすい。なお、本明細書において、平均繊維長としては、繊維状ウォラストナイトの実体顕微鏡画像１０枚をＣＣＤカメラからＰＣに取り込み、画像測定機によって画像処理手法により、実体顕微鏡画像１枚ごとに１００本の繊維状ウォラストナイト、即ち、合計１０００本の繊維状ウォラストナイトについて繊維長を測定した値の平均を採用する。なお、液晶性樹脂組成物中の（Ｂ）成分は、液晶性樹脂組成物を６００℃で２時間加熱して灰化することで得られる。 The average fiber length of the component (B) is preferably 50 to 200 μm, more preferably 70 to 180 μm, and even more preferably 90 to 160 μm. When the average fiber length is within the above range, the composition is more likely to suppress the generation of blisters. In the present specification, as the average fiber length, 10 stereomicroscopic images of fibrous wollastonite are captured from a CCD camera into a PC, and 100 stereomicroscopic images are taken for each stereomicroscopic image by an image processing method using an image measuring machine. The average of the measured fiber lengths of 1000 fibrous wollastonite, that is, a total of 1000 fibrous wollastonite, is adopted. The component (B) in the liquid crystal resin composition can be obtained by heating the liquid crystal resin composition at 600 ° C. for 2 hours to incinerate it.
（Ｂ）成分の好ましい平均繊維径は１〜２０μｍ以下であり、より好ましい平均繊維径は５〜１６μｍである。上記平均繊維径が上記範囲内であると、組成物は、ブリスター発生をより抑制しやすい。なお、本明細書において、平均繊維径としては、繊維状ウォラストナイトを走査型電子顕微鏡で観察し、１００本の繊維状ウォラストナイトについて繊維径を測定した値の平均を採用する。 The preferable average fiber diameter of the component (B) is 1 to 20 μm or less, and the more preferable average fiber diameter is 5 to 16 μm. When the average fiber diameter is within the above range, the composition is more likely to suppress the generation of blisters. In the present specification, as the average fiber diameter, the average of the values obtained by observing the fibrous wollastonite with a scanning electron microscope and measuring the fiber diameter of 100 fibrous wollastonite is adopted.
本発明の液晶性樹脂組成物において、（Ｂ）成分の含有量は、２．５〜１５質量％である。（Ｂ）成分の含有量が上記範囲内であると、組成物は、機械的性質を維持しつつ、流動性に優れるため、成形時の最小充填圧力が過度になりにくく、更に、ブリスター発生を抑制しやすい。（Ｂ）成分の含有量は、より好ましくは３．５〜１２．５質量％、更により好ましくは５〜１０質量％である。（Ｂ）成分は、１種単独で又は２種以上組み合わせて使用することができる。 In the liquid crystal resin composition of the present invention, the content of the component (B) is 2.5 to 15% by mass. When the content of the component (B) is within the above range, the composition is excellent in fluidity while maintaining mechanical properties, so that the minimum filling pressure at the time of molding is unlikely to become excessive, and further, blisters are generated. Easy to suppress. The content of the component (B) is more preferably 3.5 to 12.5% by mass, and even more preferably 5 to 10% by mass. The component (B) can be used alone or in combination of two or more.
［（Ｃ）マイカ］
（Ｃ）成分はマイカである。本発明に係る液晶性樹脂組成物に（Ｃ）成分が含まれることにより、そり変形が抑制された成形品を得やすい。（Ｃ）成分は、１種単独で又は２種以上組み合わせて使用することができる。[(C) Mica]
The component (C) is mica. Since the liquid crystal resin composition according to the present invention contains the component (C), it is easy to obtain a molded product in which warpage deformation is suppressed. The component (C) can be used alone or in combination of two or more.
本発明の液晶性樹脂組成物において、（Ｃ）成分の含有量は、１７．５〜２７．５質量％である。（Ｃ）成分の含有量が上記範囲内であると、組成物からは、そり変形が抑制された成形品をより得やすい。（Ｃ）成分の含有量は、より好ましくは１８．５〜２６．５質量％、更により好ましくは２０〜２５質量％である。 In the liquid crystal resin composition of the present invention, the content of the component (C) is 17.5 to 27.5% by mass. When the content of the component (C) is within the above range, it is easier to obtain a molded product in which warpage deformation is suppressed from the composition. The content of the component (C) is more preferably 18.5 to 26.5% by mass, and even more preferably 20 to 25% by mass.
〔マイカ〕
マイカとは、アルミニウム、カリウム、マグネシウム、ナトリウム、鉄等を含んだケイ酸塩鉱物の粉砕物である。本発明において使用できるマイカとしては、白雲母、金雲母、黒雲母、人造雲母等が挙げられるが、これらのうち色相が良好であり、低価格であるという点で白雲母が好ましい。[Mica]
Mica is a pulverized product of silicate minerals containing aluminum, potassium, magnesium, sodium, iron and the like. Examples of mica that can be used in the present invention include muscovite, phlogopite, biotite, and artificial mica. Of these, muscovite is preferable because it has a good hue and is inexpensive.
また、マイカの製造において、鉱物を粉砕する方法としては、湿式粉砕法及び乾式粉砕法が知られている。湿式粉砕法とは、マイカ原石を乾式粉砕機にて粗粉砕した後、水を加えてスラリー状態にて湿式粉砕で本粉砕し、その後、脱水、乾燥を行う方法である。湿式粉砕法と比較して、乾式粉砕法は低コストで一般的な方法であるが、湿式粉砕法を用いると、鉱物を薄く細かく粉砕することがより容易である。後述する好ましい平均粒子径及び厚みを有するマイカが得られるという理由で、本発明においては薄く細かい粉砕物を使用することが好ましい。したがって、本発明においては、湿式粉砕法により製造されたマイカを使用するのが好ましい。 Further, in the production of mica, a wet pulverization method and a dry pulverization method are known as methods for pulverizing minerals. The wet pulverization method is a method in which rough mica is roughly pulverized by a dry pulverizer, water is added, and the main pulverization is performed by wet pulverization in a slurry state, and then dehydration and drying are performed. Although the dry pulverization method is a low-cost and general method as compared with the wet pulverization method, it is easier to pulverize the mineral thinly and finely by using the wet pulverization method. In the present invention, it is preferable to use a thin and fine pulverized product because mica having a preferable average particle size and thickness described later can be obtained. Therefore, in the present invention, it is preferable to use mica produced by the wet pulverization method.
また、湿式粉砕法においては、被粉砕物を水に分散させる工程が必要であるため、被粉砕物の分散効率を高めるために、被粉砕物に凝集沈降剤及び／又は沈降助剤を加えることが一般的である。本発明において使用できる凝集沈降剤及び沈降助剤としては、ポリ塩化アルミニウム、硫酸アルミニウム、硫酸第一鉄、硫酸第二鉄、塩化コッパラス、ポリ硫酸鉄、ポリ塩化第二鉄、鉄−シリカ無機高分子凝集剤、塩化第二鉄−シリカ無機高分子凝集剤、消石灰（Ｃａ（ＯＨ）２）、苛性ソーダ（ＮａＯＨ）、ソーダ灰（Ｎａ２ＣＯ３）等が挙げられる。これらの凝集沈降剤及び沈降助剤は、ｐＨがアルカリ性又は酸性である。本発明で使用するマイカは、湿式粉砕する際に凝集沈降剤及び／又は沈降助剤を使用していないものが好ましい。凝集沈降剤及び／又は沈降助剤で処理されていないマイカを使用すると、液晶性樹脂組成物中のポリマーの分解が生じにくく、多量のガス発生やポリマーの分子量低下等が起きにくいため、コネクター等の成形品の性能をより良好に維持するのが容易である。Further, since the wet pulverization method requires a step of dispersing the object to be crushed in water, a coagulation sedimentation agent and / or a sedimentation aid is added to the object to be pulverized in order to improve the dispersion efficiency of the object to be pulverized. Is common. Examples of the coagulation sedimentation agent and sedimentation aid that can be used in the present invention include polyaluminum chloride, aluminum sulfate, ferrous sulfate, ferric sulfate, copper chloride, polyiron sulfate, ferric chloride, and iron-silica inorganic high. Examples thereof include a molecular flocculant, a ferric chloride-silica inorganic polymer flocculant, slaked lime (Ca (OH) 2 ), caustic soda (NaOH), and soda ash (Na 2 CO 3 ). These coagulation sedimentation agents and sedimentation aids have an alkaline or acidic pH. The mica used in the present invention is preferably one that does not use a coagulation sedimentation agent and / or a sedimentation aid during wet pulverization. When mica that has not been treated with a coagulation sedimentation agent and / or a sedimentation aid is used, decomposition of the polymer in the liquid crystal resin composition is unlikely to occur, and a large amount of gas is less likely to be generated or the molecular weight of the polymer is less likely to decrease. It is easy to maintain the performance of the molded product better.
本発明において使用できるマイカは、マイクロトラックレーザー回折法により測定した平均粒子径が１０〜１００μｍであるものが好ましく、平均粒子径が２０〜８０μｍであるものが特に好ましい。マイカの平均粒子径が１０μｍ以上であると、成形品の剛性に対する改良効果が十分となりやすいため好ましい。マイカの平均粒子径が１００μｍ以下であると、成形品の剛性の向上が十分となりやすく、ウェルド強度も十分となりやすいため好ましい。更に、マイカの平均粒子径が１００μｍ以下であると、本発明のコネクター等を成形するのに十分な流動性を確保しやすい。 The mica that can be used in the present invention preferably has an average particle size of 10 to 100 μm measured by a microtrack laser diffraction method, and particularly preferably an average particle size of 20 to 80 μm. When the average particle size of mica is 10 μm or more, the effect of improving the rigidity of the molded product tends to be sufficient, which is preferable. When the average particle size of mica is 100 μm or less, the rigidity of the molded product is likely to be sufficiently improved, and the weld strength is also likely to be sufficient, which is preferable. Further, when the average particle size of mica is 100 μm or less, it is easy to secure sufficient fluidity for molding the connector or the like of the present invention.
本発明において使用できるマイカの厚みは、電子顕微鏡の観察により実測した厚みが０．０１〜１μｍであることが好ましく、０．０３〜０．３μｍであることが特に好ましい。マイカの厚みが０．０１μｍ以上であると、液晶性樹脂組成物の溶融加工の際にマイカが割れにくくなるため、成形品の剛性が向上しやすい可能性があるため好ましい。マイカの厚みが１μｍ以下であると、成形品の剛性に対する改良効果が十分となりやすいため好ましい。 The thickness of mica that can be used in the present invention is preferably 0.01 to 1 μm, particularly preferably 0.03 to 0.3 μm, as measured by observation with an electron microscope. When the thickness of the mica is 0.01 μm or more, the mica is less likely to crack during the melt processing of the liquid crystal resin composition, and the rigidity of the molded product may be easily improved, which is preferable. When the thickness of mica is 1 μm or less, the effect of improving the rigidity of the molded product is likely to be sufficient, which is preferable.
本発明において使用できるマイカは、シランカップリング剤等で表面処理されていてもよく、かつ／又は、結合剤で造粒し顆粒状とされていてもよい。 The mica that can be used in the present invention may be surface-treated with a silane coupling agent or the like, and / or may be granulated with a binder to form granules.
更に、（Ｂ）成分と（Ｃ）成分との合計の含有量は、本発明の液晶性樹脂組成物において、２０〜３７．５質量％であり、好ましくは２５〜３６．５質量％であり、より好ましくは３０〜３５質量％である。上記合計の含有量が２０質量％以上であると、そり変形が抑制された成形品を得やすい。上記合計の含有量が３７．５質量％以下であると、組成物は、機械的性質を維持しつつ、流動性に優れるため、成形時の最小充填圧力が過度になりにくく、更に、ブリスター発生を抑制しやすい。 Further, the total content of the component (B) and the component (C) is 20 to 37.5% by mass, preferably 25 to 36.5% by mass in the liquid crystal resin composition of the present invention. , More preferably 30 to 35% by mass. When the total content is 20% by mass or more, it is easy to obtain a molded product in which warpage deformation is suppressed. When the total content is 37.5% by mass or less, the composition is excellent in fluidity while maintaining mechanical properties, so that the minimum filling pressure at the time of molding is unlikely to become excessive, and blisters are generated. Is easy to suppress.
［その他の成分］
本発明に係る液晶性樹脂組成物には、本発明の効果を害さない範囲で、その他の重合体、その他の充填剤、一般に合成樹脂に添加される公知の物質、即ち、酸化防止剤や紫外線吸収剤等の安定剤、帯電防止剤、難燃剤、染料や顔料等の着色剤、潤滑剤、離型剤、結晶化促進剤、結晶核剤等のその他の成分も要求性能に応じ適宜添加することができる。その他の成分は１種単独で用いても２種以上を組み合わせて用いてもよい。その他の充填剤とは、（Ｂ）繊維状ウォラストナイト及び（Ｃ）マイカ以外の充填剤をいい、例えば、（Ｃ）マイカ以外の板状充填剤；シリカ等の粒状充填剤が挙げられる。（Ｃ）マイカ以外の板状充填剤としては、例えば、タルク等が挙げられる。但し、成形品のそり変形の抑制等の観点から、本発明の液晶性樹脂組成物は、タルク等の、（Ｃ）マイカ以外の板状充填剤を含有しないことが好ましい。[Other ingredients]
The liquid crystal resin composition according to the present invention includes other polymers, other fillers, and known substances generally added to synthetic resins, that is, antioxidants and ultraviolet rays, as long as the effects of the present invention are not impaired. Stabilizers such as absorbents, antistatic agents, flame retardants, colorants such as dyes and pigments, lubricants, mold release agents, crystallization accelerators, crystal nucleating agents and other other components are also added as appropriate according to the required performance. be able to. Other components may be used alone or in combination of two or more. Examples of other fillers include (B) fibrous wollastonite and (C) fillers other than mica, and examples thereof include (C) plate-like fillers other than mica; and granular fillers such as silica. (C) Examples of the plate-like filler other than mica include talc and the like. However, from the viewpoint of suppressing warpage deformation of the molded product, the liquid crystal resin composition of the present invention preferably does not contain a plate-like filler other than (C) mica, such as talc.
［液晶性樹脂組成物の調製方法］
本発明の液晶性樹脂組成物の調製方法は特に限定されない。例えば、上記（Ａ）〜（Ｃ）成分、及び、任意に、その他の成分を配合して、これらを１軸又は２軸押出機を用いて溶融混練処理することで、液晶性樹脂組成物の調製が行われる。[Method for preparing liquid crystal resin composition]
The method for preparing the liquid crystal resin composition of the present invention is not particularly limited. For example, the liquid crystal resin composition can be obtained by blending the above components (A) to (C) and optionally other components and melt-kneading them using a single-screw or twin-screw extruder. Preparation is done.
本発明に係る液晶性樹脂組成物は流動性に優れるため、成形時の最小充填圧力が過度になりにくく、コネクター、特に、低背狭ピッチコネクター等のような小型で複雑な形状を有する部品等を好ましく成形できる。流動性の程度は、コネクターの最小充填圧力により判断する。即ち、図１に示すＦＰＣコネクターを射出成形する際に良好な成形体を得られる最小の射出充填圧力を最小充填圧力として特定する。最小充填圧力が低いほど、流動性が優れていると評価される。 Since the liquid crystal resin composition according to the present invention has excellent fluidity, the minimum filling pressure during molding is unlikely to be excessive, and connectors, particularly parts having a small and complicated shape such as low-profile narrow pitch connectors and the like, etc. Can be preferably molded. The degree of fluidity is determined by the minimum filling pressure of the connector. That is, the minimum injection filling pressure at which a good molded body can be obtained when the FPC connector shown in FIG. 1 is injection molded is specified as the minimum filling pressure. The lower the minimum filling pressure, the better the fluidity is evaluated.
液晶性樹脂の融点より１０〜３０℃高い温度で、剪断速度１０００／秒で、ＩＳＯ１１４４３に準拠して測定した液晶性樹脂組成物の溶融粘度は、好ましくは１×１０５Ｐａ・ｓ以下、より好ましくは５Ｐａ・ｓ以上１×１０２Ｐａ・ｓ以下である。上記溶融粘度が１×１０５Ｐａ・ｓ以下であると、コネクター、特に、低背狭ピッチコネクターの成形時において、液晶性樹脂組成物の流動性を確保しやすく、充填圧力が過度になりにくい。At 10 to 30 ° C. above the melting point of the liquid resin, at a shear rate of 1000 / sec, the melt viscosity of the liquid resin composition was measured according to ISO11443, the following preferably 1 × 10 5 Pa · s, more It is preferably 5 Pa · s or more and 1 × 10 2 Pa · s or less. When the melt viscosity is 1 × 10 5 Pa · s or less, it is easy to secure the fluidity of the liquid crystal resin composition when molding the connector, especially the low-profile narrow pitch connector, and the filling pressure is unlikely to become excessive. ..
＜コネクター＞
本発明に係る液晶性樹脂組成物を成形することにより、本発明のコネクターを得ることができる。本発明のコネクターとしては、特に限定されず、例えば、製品全長が３０ｍｍ未満、製品高さが５ｍｍ未満であるコネクターが挙げられる。製品全長が３０ｍｍ未満、製品高さが５ｍｍ未満であるコネクターとしては、特に限定されず、例えば、低背狭ピッチコネクター、同軸コネクター、マイクロＳＩＭコネクター、マイクロＳＤコネクター等が挙げられる。中でも、低背狭ピッチコネクターが好適である。低背狭ピッチコネクターとしては、特に限定されず、例えば、基板対基板コネクター（「ＢｔｏＢコネクター」としても知られる）、フレキシブルプリント基板用コネクター（フレキシブルプリント基板（ＦＰＣ）とフレキシブルフラットケーブル（ＦＦＣ）とを接続するために使用され、「ＦＰＣコネクター」としても知られる）等が挙げられる。中でも、ピッチ間距離が０．５ｍｍ以下、製品全長が３．５ｍｍ以上３０ｍｍ未満、製品高さが１．５ｍｍ以下であり、基板対基板コネクター又はフレキシブルプリント基板用コネクターである低背狭ピッチコネクターが好適である。<Connector>
The connector of the present invention can be obtained by molding the liquid crystal resin composition according to the present invention. The connector of the present invention is not particularly limited, and examples thereof include a connector having a product total length of less than 30 mm and a product height of less than 5 mm. The connector having a product total length of less than 30 mm and a product height of less than 5 mm is not particularly limited, and examples thereof include a low profile narrow pitch connector, a coaxial connector, a micro SIM connector, and a micro SD connector. Of these, a low profile narrow pitch connector is preferable. The low profile narrow pitch connector is not particularly limited, and includes, for example, a board-to-board connector (also known as a "BtoB connector"), a flexible printed circuit board connector (flexible printed circuit board (FPC), and a flexible flat cable (FFC). (Also known as an "FPC connector"), etc. Among them, the low-profile narrow-pitch connector, which has a distance between pitches of 0.5 mm or less, a product overall length of 3.5 mm or more and less than 30 mm, a product height of 1.5 mm or less, and a board-to-board connector or a connector for a flexible printed circuit board. Suitable.
本発明のコネクターを得る成形方法としては特に限定されず、コネクターの変形等を防ぐために、残留内部応力のない成形条件を選ぶことが好ましい。充填圧力を低くし、コネクターの残留内部応力を低下させるために、成形機のシリンダー温度は、液晶性樹脂の融点以上の温度が好ましい。 The molding method for obtaining the connector of the present invention is not particularly limited, and it is preferable to select molding conditions without residual internal stress in order to prevent deformation of the connector. In order to lower the filling pressure and reduce the residual internal stress of the connector, the cylinder temperature of the molding machine is preferably a temperature equal to or higher than the melting point of the liquid crystal resin.
また、金型温度は７０〜１００℃が好ましい。金型温度が低いと、金型に充填された液晶性樹脂組成物が流動不良を起こす可能性があるため好ましくない。金型温度が高いと、バリ発生等の問題が生じる可能性があるため好ましくない。射出速度については、１５０ｍｍ／秒以上で成形することが好ましい。射出速度が低いと、未充填成形体しか得られない可能性があり、完全に充填した成形体が得られたとしても、充填圧力が高く残留内部応力の大きい成形体となり、平面度が劣るコネクターしか得られない可能性がある。 The mold temperature is preferably 70 to 100 ° C. If the mold temperature is low, the liquid crystal resin composition filled in the mold may cause poor flow, which is not preferable. If the mold temperature is high, problems such as burrs may occur, which is not preferable. The injection speed is preferably 150 mm / sec or more. If the injection rate is low, only an unfilled molded product may be obtained, and even if a completely filled molded product is obtained, the molded product has a high filling pressure and a large residual internal stress, resulting in poor flatness. May only be obtained.
本発明のコネクターは、そり変形が抑制されている。コネクターのそりの程度は、以下の通りにして判断する。即ち、図１に示すＦＰＣコネクターにて、図２において黒丸で示す複数の位置で高さを測定し、最小二乗平面からの最大高さと最小高さとの差をそりとする。本発明のコネクターは、ＩＲリフローを行う前後において、そりの変化が抑制されている。 The connector of the present invention is suppressed from warpage deformation. The degree of warpage of the connector is determined as follows. That is, with the FPC connector shown in FIG. 1, the height is measured at a plurality of positions indicated by black circles in FIG. 2, and the difference between the maximum height and the minimum height from the least squares plane is used as a sled. In the connector of the present invention, the change in warpage is suppressed before and after performing IR reflow.
また、本発明のコネクターは、ブリスター発生が抑制されている。ブリスター発生の程度は、ブリスター温度により判断する。即ち、所定温度のシリコーンオイルに浸漬した成形品の表面におけるブリスター発生の有無を目視にて観察し、成形品３０個中、ブリスターの発生個数がゼロとなる最高温度をブリスター温度とする。ブリスター温度が高いほど、ブリスター発生が抑制されていると評価される。 Further, the connector of the present invention suppresses the generation of blisters. The degree of blister generation is determined by the blister temperature. That is, the presence or absence of blister generation on the surface of the molded product immersed in silicone oil at a predetermined temperature is visually observed, and the maximum temperature at which the number of blister generation is zero among the 30 molded products is defined as the blister temperature. It is evaluated that the higher the blister temperature, the more the blister generation is suppressed.
また、本発明のコネクターは、耐熱性、例えば、高温剛性により評価されるような耐熱性に優れる。高温剛性は、ＩＳＯ７５−１，２に準拠して荷重たわみ温度を測定することで評価する。 Further, the connector of the present invention is excellent in heat resistance, for example, heat resistance as evaluated by high temperature rigidity. High temperature rigidity is evaluated by measuring the deflection temperature under load in accordance with ISO75-1 and ISO75-1.
本発明のコネクターは、機械的強度に優れる。機械的強度は、ＡＳＴＭ Ｄ７９０に準拠した曲げ試験により、曲げ強度、破断歪、及び曲げ弾性率を測定することで評価する。 The connector of the present invention has excellent mechanical strength. Mechanical strength is evaluated by measuring bending strength, breaking strain, and flexural modulus by a bending test according to ASTM D790.
以下、実施例により本発明を更に詳しく説明するが、本発明は以下の実施例に限定されない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
（Ａ）液晶性樹脂
（液晶性樹脂１の製造方法）
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧／流出ラインを備えた重合容器に、以下の原料モノマー、脂肪酸金属塩触媒、アシル化剤を仕込み、窒素置換を開始した。
（Ｉ）４−ヒドロキシ安息香酸１３８５ｇ（６０モル％）（ＨＢＡ）
（ＩＩ）６−ヒドロキシ−２−ナフトエ酸８８ｇ（２．８モル％）（ＨＮＡ）
（ＩＩＩ）テレフタル酸５０４ｇ（１８．１５モル％）（ＴＡ）
（ＩＶ）イソフタル酸１９ｇ（０．７モル％）（ＩＡ）
（Ｖ）４，４’−ジヒドロキシビフェニル４１５ｇ（１３．３５モル％）（ＢＰ）
（ＶＩ）Ｎ−アセチル−ｐ−アミノフェノール１２６ｇ（５モル％）（ＡＰＡＰ）
酢酸カリウム触媒１２０ｍｇ
無水酢酸１６６２ｇ
重合容器に原料を仕込んだ後、反応系の温度を１４０℃に上げ、１４０℃で１時間反応させた。その後、更に３６０℃まで５．５時間かけて昇温し、そこから２０分かけて１０Ｔｏｒｒ（即ち１３３０Ｐａ）まで減圧にして、酢酸、過剰の無水酢酸、その他の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して減圧状態から常圧を経て加圧状態にして、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレット化した。得られたペレットの融点は３４５℃、融点と結晶化温度との差Ｔｍ−Ｔｃは３７℃、溶融粘度は１０Ｐａ・ｓであった。(A) Liquid crystal resin (Manufacturing method of liquid crystal resin 1)
The following raw material monomers, fatty acid metal salt catalysts, and acylating agents were charged into a polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a depressurization / outflow line, and nitrogen substitution was started.
(I) 4-Hydroxybenzoic acid 1385 g (60 mol%) (HBA)
(II) 6-Hydroxy-2-naphthoic acid 88 g (2.8 mol%) (HNA)
(III) 504 g (18.15 mol%) of terephthalic acid (TA)
(IV) Isophthalic acid 19 g (0.7 mol%) (IA)
(V) 415 g (13.35 mol%) (BP) of 4,4'-dihydroxybiphenyl
(VI) 126 g (5 mol%) of N-acetyl-p-aminophenol (APAP)
Potassium acetate catalyst 120 mg
1662 g of acetic anhydride
After charging the raw materials into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 1 hour. Then, the temperature is further raised to 360 ° C. over 5.5 hours, and then the pressure is reduced to 10 Torr (that is, 1330 Pa) over 20 minutes to melt acetic acid, excess acetic anhydride, and other low boiling components while distilling. Polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to bring the mixture from a reduced pressure state to a pressurized state through normal pressure, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized and pelletized. The melting point of the obtained pellet was 345 ° C., the difference Tm-Tc between the melting point and the crystallization temperature was 37 ° C., and the melt viscosity was 10 Pa · s.
（液晶性樹脂２の製造方法）
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧／流出ラインを備えた重合容器に、以下の原料モノマー、金属触媒、アシル化剤を仕込み、窒素置換を開始した。
（Ｉ）４−ヒドロキシ安息香酸：１３８０ｇ（６０モル％）（ＨＢＡ）
（ＩＩ）６−ヒドロキシ−２−ナフトエ酸：１５７ｇ（５モル％）（ＨＮＡ）
（ＩＩＩ）テレフタル酸：４８４ｇ（１７．５モル％）（ＴＡ）
（ＩＶ）４，４’−ジヒドロキシビフェニル：３８８ｇ（１２．５モル％）（ＢＰ）
（Ｖ）４−アセトキシアミノフェノール：１７．２ｇ（５モル％）（ＡＰＡＰ）
酢酸カリウム触媒：１１０ｍｇ
無水酢酸：１６５９ｇ(Manufacturing method of liquid crystal resin 2)
The following raw material monomers, metal catalysts, and acylating agents were charged into a polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a depressurization / outflow line, and nitrogen substitution was started.
(I) 4-Hydroxybenzoic acid: 1380 g (60 mol%) (HBA)
(II) 6-Hydroxy-2-naphthoic acid: 157 g (5 mol%) (HNA)
(III) Terephthalic acid: 484 g (17.5 mol%) (TA)
(IV) 4,4'-dihydroxybiphenyl: 388 g (12.5 mol%) (BP)
(V) 4-acetoxyaminophenol: 17.2 g (5 mol%) (APAP)
Potassium acetate catalyst: 110 mg
Acetic anhydride: 1659 g
重合容器に原料を仕込んだ後、反応系の温度を１４０℃に上げ、１４０℃で１時間反応させた。その後、更に３４０℃まで４．５時間かけて昇温し、そこから１５分かけて１０Ｔｏｒｒ（即ち、１３３０Ｐａ）まで減圧して、酢酸、過剰の無水酢酸、その他の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して減圧状態から常圧を経て加圧状態にして、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレット化した。得られたペレットの融点は３３６℃、Ｔｍ−Ｔｃは４０℃、溶融粘度は２０Ｐａ・ｓであった。 After charging the raw materials into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 1 hour. Then, the temperature is further raised to 340 ° C. over 4.5 hours, and then the pressure is reduced to 10 Torr (that is, 1330 Pa) over 15 minutes while distilling acetic acid, excess acetic anhydride, and other low boiling points. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to bring the mixture from a reduced pressure state to a pressurized state through normal pressure, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized and pelletized. The obtained pellet had a melting point of 336 ° C, a Tm-Tc of 40 ° C, and a melt viscosity of 20 Pa · s.
（液晶性樹脂３の製造方法）
撹拌機、還流カラム、モノマー投入口、窒素導入口、減圧／流出ラインを備えた重合容器に、以下の原料モノマー、金属触媒、アシル化剤を仕込み、窒素置換を開始した。
（Ｉ）２−ヒドロキシ−６−ナフトエ酸１６６ｇ（４８モル％）（ＨＮＡ）
（ＩＩ）テレフタル酸７６ｇ（２５モル％）（ＴＡ）
（ＩＩＩ）４，４’−ジヒドロキシビフェニル８６ｇ（２５モル％）（ＢＰ）
（ＩＶ）４−ヒドロキシ安息香酸５ｇ（２モル％）（ＨＢＡ）
酢酸カリウム触媒２２．５ｍｇ
無水酢酸１９１ｇ
重合容器に原料を仕込んだ後、反応系の温度を１４０℃に上げ、１４０℃で１時間反応させた。その後、更に３６０℃まで５．５時間かけて昇温し、そこから３０分かけて５Ｔｏｒｒ（即ち、６６７Ｐａ）まで減圧して、酢酸、過剰の無水酢酸、その他の低沸分を留出させながら溶融重合を行った。撹拌トルクが所定の値に達した後、窒素を導入して減圧状態から常圧を経て加圧状態にして、重合容器の下部からポリマーを排出し、ストランドをペレタイズしてペレット化した。得られたペレットについて、窒素気流下、３００℃で８時間の熱処理を行った。ペレットの融点は３５２℃、Ｔｍ−Ｔｃは２５℃、溶融粘度は２３Ｐａ・ｓであった。
なお、液晶性樹脂１〜３の溶融粘度は、後述する液晶性樹脂組成物の溶融粘度の測定方法と同様にして測定した。(Manufacturing method of liquid crystal resin 3)
The following raw material monomers, metal catalysts, and acylating agents were charged into a polymerization vessel equipped with a stirrer, a reflux column, a monomer inlet, a nitrogen inlet, and a depressurization / outflow line, and nitrogen substitution was started.
(I) 2-Hydroxy-6-naphthoic acid 166 g (48 mol%) (HNA)
(II) 76 g (25 mol%) of terephthalic acid (TA)
(III) 4,4'-Dihydroxybiphenyl 86 g (25 mol%) (BP)
(IV) 4-Hydroxybenzoic acid 5 g (2 mol%) (HBA)
Potassium acetate catalyst 22.5 mg
Acetic anhydride 191g
After charging the raw materials into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C., and the reaction was carried out at 140 ° C. for 1 hour. Then, the temperature is further raised to 360 ° C. over 5.5 hours, and then the pressure is reduced to 5 Torr (that is, 667 Pa) over 30 minutes while distilling acetic acid, excess acetic anhydride, and other low boiling points. Melt polymerization was performed. After the stirring torque reached a predetermined value, nitrogen was introduced to bring the mixture from a reduced pressure state to a pressurized state through normal pressure, the polymer was discharged from the lower part of the polymerization vessel, and the strands were pelletized and pelletized. The obtained pellets were heat-treated at 300 ° C. for 8 hours under a nitrogen stream. The melting point of the pellet was 352 ° C, the Tm-Tc was 25 ° C, and the melt viscosity was 23 Pa · s.
The melt viscosities of the liquid crystal resins 1 to 3 were measured in the same manner as the method for measuring the melt viscosities of the liquid crystal resin compositions described later.
（充填剤）
（Ｂ）繊維状ウォラストナイト
繊維状ウォラストナイト１：キンセイマテック（株）製ＳＨ−１２５０ＢＪ
繊維状ウォラストナイト２：ＮＹＣＯ Ｍａｔｅｒｉａｌｓ社製ＮＹＧＬＯＳ ８
繊維状ウォラストナイト３：キンセイマテック（株）製ＦＰＷ＃１５０
繊維状ウォラストナイト４：キンセイマテック（株）製ＳＨ−８００
繊維状ウォラストナイト１〜４の組成、平均繊維長、及び平均繊維径は、表１に示す通りである。なお、繊維状ウォラストナイトにおけるＳｉＯ２、ＣａＯ、Ａｌ２Ｏ３、及びＦｅ２Ｏ３の各含有量は、繊維状ウォラストナイト約３ｇとセルロースパウダー（ＧＥヘルスケア バイオサイエンス（株）製、Ｗｈａｔｍａｎ ＣＣ３１）約３ｇとを混合し、プレスして得たタブレット状試料について、全自動蛍光Ｘ線分析装置（スペクトリス（株）製、ＭａｇｉＸ Ｐｒｏ Ｐｗ２５４０／００）を用いて、ＪＩＳ Ｋ ０１１９に準拠して、ファンダメンタルパラメーター（ＦＰ）法にて定量分析を行い、算出した。(filler)
(B) Fibrous Wollastonite Fibrous Wollastonite 1: SH-1250BJ manufactured by Kinsei Matek Co., Ltd.
Fibrous Wollastonite 2: NYGLOS 8 manufactured by NYCO Materials
Fibrous Wollastonite 3: FPW # 150 manufactured by Kinsei Matek Co., Ltd.
Fibrous Wollastonite 4: SH-800 manufactured by Kinsei Matek Co., Ltd.
The composition, average fiber length, and average fiber diameter of the fibrous wollastonites 1 to 4 are as shown in Table 1. The contents of SiO 2 , CaO, Al 2 O 3 , and Fe 2 O 3 in the fibrous wollastonite are about 3 g of the fibrous wollastonite and cellulose powder (manufactured by GE Healthcare Bioscience Co., Ltd.). About 3 g of Whatman CC31) was mixed and pressed, and the tablet-shaped sample was obtained in accordance with JIS K 0119 using a fully automatic fluorescent X-ray analyzer (MagiX Pro Pw2540/00, manufactured by Spectris Co., Ltd.). Then, quantitative analysis was performed by the fundamental parameter (FP) method, and the calculation was performed.
（Ｃ）板状充填剤
マイカ：（株）ヤマグチマイカ製ＡＢ−２５Ｓ、平均粒子径２５．０μｍ
タルク：松村産業（株）製クラウンタルクＰＰ、平均粒子径１２．８μｍ(C) Plate-shaped filler Mica: AB-25S manufactured by Yamaguchi Mica Co., Ltd., average particle size 25.0 μm
Talc: Crown Talc PP manufactured by Matsumura Sangyo Co., Ltd., average particle size 12.8 μm
［液晶性樹脂組成物の製造］
上記成分を、表２又は表３に示す割合（単位：質量％）で二軸押出機（（株）日本製鋼所製ＴＥＸ３０α型）を用いて、下記シリンダー温度にて溶融混練し、液晶性樹脂組成物ペレットを得た。その際、上記押出機のメインフィード口から液晶性樹脂を供給し、上記メインフィード口より押出方向後方に設けられたサイドフィード口から充填剤を供給した。
シリンダー温度：
３６０℃（実施例１〜４、７、及び８、比較例１〜７）
３５０℃（実施例５）
３７０℃（実施例６）[Manufacturing of liquid crystal resin composition]
The above components are melt-kneaded at the following cylinder temperature using a twin-screw extruder (TEX30α type manufactured by Japan Steel Works, Ltd.) at the ratio (unit: mass%) shown in Table 2 or Table 3, and are liquid crystal resins. Composition pellets were obtained. At that time, the liquid crystal resin was supplied from the main feed port of the extruder, and the filler was supplied from the side feed port provided behind the main feed port in the extrusion direction.
Cylinder temperature:
360 ° C. (Examples 1 to 4, 7, and 8, Comparative Examples 1 to 7)
350 ° C (Example 5)
370 ° C (Example 6)
［融点の測定］
ＴＡインスツルメント社製ＤＳＣにて、液晶性樹脂を室温から２０℃／分の昇温条件で測定した際に観測される吸熱ピーク温度（Ｔｍ１）の観測後、（Ｔｍ１＋４０）℃の温度で２分間保持した後、２０℃／分の降温条件で室温まで一旦冷却した後、再度、２０℃／分の昇温条件で測定した際に観測される吸熱ピークの温度を測定した。[Measurement of melting point]
After observing the heat absorption peak temperature (Tm1) observed when the liquid crystal resin was measured at a temperature rising condition of 20 ° C./min from room temperature with a DSC manufactured by TA Instruments, 2 at a temperature of (Tm1 + 40) ° C. After holding for 1 minute, the temperature was once cooled to room temperature under a temperature lowering condition of 20 ° C./min, and then the temperature of the heat absorption peak observed when measured again under a temperature rising condition of 20 ° C./min was measured.
［結晶化温度の測定］
ＴＡインスツルメント社製ＤＳＣにて、液晶性樹脂を室温から２０℃／分の昇温条件で測定した際に観測される吸熱ピーク温度（Ｔｍ１）の観測後、（Ｔｍ１＋４０）℃の温度で２分間保持した後、２０℃／分の降温条件で測定した際に観測される発熱ピーク温度を測定した。[Measurement of crystallization temperature]
After observing the heat absorption peak temperature (Tm1) observed when the liquid crystal resin was measured at a temperature rising condition of 20 ° C./min from room temperature with a DSC manufactured by TA Instruments, 2 at a temperature of (Tm1 + 40) ° C. After holding for 1 minute, the exothermic peak temperature observed when measured under the temperature lowering condition of 20 ° C./min was measured.
［液晶性樹脂組成物の溶融粘度の測定］
（株）東洋精機製作所製キャピログラフ１Ｂ型を使用し、液晶性樹脂の融点よりも１０〜３０℃高い温度で、内径１ｍｍ、長さ２０ｍｍのオリフィスを用いて、剪断速度１０００／秒で、ＩＳＯ１１４４３に準拠して、液晶性樹脂組成物の溶融粘度を測定した。なお、測定温度は、液晶性樹脂１を使用した液晶性樹脂組成物については３５０℃、液晶性樹脂２を使用した液晶性樹脂組成物については３６０℃、液晶性樹脂３を使用した液晶性樹脂組成物については３８０℃であった。結果を表２及び３に示す。[Measurement of melt viscosity of liquid crystal resin composition]
Using Capillograph 1B type manufactured by Toyo Seiki Seisakusho Co., Ltd., using an orifice with an inner diameter of 1 mm and a length of 20 mm at a temperature 10 to 30 ° C higher than the melting point of the liquid crystal resin, to ISO11443 at a shear rate of 1000 / sec. According to this, the melt viscosity of the liquid crystal resin composition was measured. The measurement temperature was 350 ° C. for the liquid crystal resin composition using the liquid crystal resin 1, 360 ° C for the liquid crystal resin composition using the liquid crystal resin 2, and the liquid crystal resin using the liquid crystal resin 3. The temperature of the composition was 380 ° C. The results are shown in Tables 2 and 3.
［曲げ試験］
下記成形条件で、液晶性樹脂組成物を射出成形して０．８ｍｍ厚の成形品を得、ＡＳＴＭ Ｄ７９０に準拠し、曲げ強度、破断歪、及び曲げ弾性率を測定した。結果を表２及び３に示す。[Bending test]
The liquid crystal resin composition was injection-molded under the following molding conditions to obtain a molded product having a thickness of 0.8 mm, and the bending strength, breaking strain, and flexural modulus were measured in accordance with ASTM D790. The results are shown in Tables 2 and 3.
［荷重たわみ温度］
下記成形条件で、液晶性樹脂組成物を射出成形して成形品を得、ＩＳＯ７５−１，２に準拠して荷重たわみ温度を測定した。なお、曲げ応力としては、１．８ＭＰａを用いた。結果を表２及び３に示す。[Deflection temperature under load]
Under the following molding conditions, the liquid crystal resin composition was injection-molded to obtain a molded product, and the deflection temperature under load was measured in accordance with ISO75-1 and ISO75-1. As the bending stress, 1.8 MPa was used. The results are shown in Tables 2 and 3.
［ＦＰＣコネクターそり］
下記成形条件で、液晶性樹脂組成物を射出成形し（ゲート：トンネルゲート、ゲートサイズ：φ０．４ｍｍ）、図１に示すような、全体の大きさ１７．６ｍｍ×４．００ｍｍ×１．１６ｍｍ、ピッチ間距離０．５ｍｍ、ピン孔数３０×２ピン、最小肉厚：０．１２ｍｍのＦＰＣコネクターを得た。[FPC connector sled]
The liquid crystal resin composition is injection-molded under the following molding conditions (gate: tunnel gate, gate size: φ0.4 mm), and the overall size is 17.6 mm × 4.00 mm × 1.16 mm as shown in FIG. An FPC connector having a distance between pitches of 0.5 mm, a number of pin holes of 30 × 2 pins, and a minimum wall thickness of 0.12 mm was obtained.
得られたコネクターを水平な机の上に静置し、コネクターの高さをミツトヨ製クイックビジョン４０４ＰＲＯＣＮＣ画像測定機により測定した。その際、図２において黒丸で示す複数の位置で高さを測定し、最小二乗平面からの最大高さと最小高さとの差をＦＰＣコネクターのそりとした。なお、そりは、下記条件で行ったＩＲリフローの前後で測定した。結果を表２及び３に示す。
（ＩＲリフロー条件）
測定機：日本パルス技術研究所製大型卓上リフローハンダ付け装置ＲＦ−３００（遠赤外線ヒーター使用）
試料送り速度：１４０ｍｍ／ｓｅｃ
リフロー炉通過時間：５分
プレヒートゾーンの温度条件：１５０℃
リフローゾーンの温度条件：１９０℃
ピーク温度：２５１℃The obtained connector was allowed to stand on a horizontal desk, and the height of the connector was measured by a Mitutoyo Quick Vision 404PROCNC image measuring machine. At that time, the heights were measured at a plurality of positions indicated by black circles in FIG. 2, and the difference between the maximum height and the minimum height from the least squares plane was defined as the warp of the FPC connector. The warp was measured before and after the IR reflow performed under the following conditions. The results are shown in Tables 2 and 3.
(IR reflow condition)
Measuring machine: Large desktop reflow soldering device RF-300 (using far-infrared heater) manufactured by Japan Pulse Technology Research Institute
Sample feed rate: 140 mm / sec
Reflow furnace transit time: 5 minutes Preheat zone temperature condition: 150 ° C
Reflow zone temperature conditions: 190 ° C
Peak temperature: 251 ° C
［ＦＰＣコネクター最小充填圧力］
図１のＦＰＣコネクターを射出成形する際に良好な成形品を得られる最小の射出充填圧力を最小充填圧力として測定した。結果を表２及び３に示す。[Minimum filling pressure of FPC connector]
When the FPC connector of FIG. 1 was injection-molded, the minimum injection-filling pressure at which a good molded product could be obtained was measured as the minimum filling pressure. The results are shown in Tables 2 and 3.
［ブリスター温度］
下記成形条件で、液晶性樹脂組成物を射出成形して１２．５ｍｍ×１２０ｍｍ×０．８ｍｍの成形品を得、この成形品３０個を所定温度のシリコーンオイルに浸漬して、洗剤で洗浄後、自然乾燥し、目視にて表面にブリスターが発生しているかどうかを調べた。ブリスター温度は、成形品３０個中、ブリスターの発生個数がゼロとなる最高温度とし、以下の基準に従って評価した。結果を表２及び３に示す。
○（良好）：上記ブリスター温度が２６０℃以上であった。
×（不良）：上記ブリスター温度が２６０℃未満であった。[Blister temperature]
Under the following molding conditions, the liquid crystal resin composition is injection-molded to obtain a molded product having a size of 12.5 mm × 120 mm × 0.8 mm, and 30 of these molded products are immersed in silicone oil at a predetermined temperature and washed with a detergent. After drying naturally, it was visually examined whether or not blisters were generated on the surface. The blister temperature was set to the maximum temperature at which the number of blisters generated was zero among the 30 molded products, and was evaluated according to the following criteria. The results are shown in Tables 2 and 3.
◯ (Good): The blister temperature was 260 ° C. or higher.
X (defective): The blister temperature was less than 260 ° C.
［成形条件］
成形機：
住友重機械工業（株）製ＳＥ１００ＤＵ（曲げ試験、荷重たわみ温度、ブリスター温度の場合）
住友重機械工業（株）製ＳＥ３０ＤＵＺ（ＦＰＣコネクターそりの場合）
シリンダー温度：
３６０℃（実施例１〜４、７、及び８、比較例１〜７）
３５０℃（実施例５）
３７０℃（実施例６）
金型温度：９０℃
射出速度：３３ｍｍ／ｓｅｃ[Molding condition]
Molding machine:
SE100DU manufactured by Sumitomo Heavy Industries, Ltd. (for bending test, deflection temperature under load, blister temperature)
SE30DUZ manufactured by Sumitomo Heavy Industries, Ltd. (for FPC connector sled)
Cylinder temperature:
360 ° C. (Examples 1 to 4, 7, and 8, Comparative Examples 1 to 7)
350 ° C (Example 5)
370 ° C (Example 6)
Mold temperature: 90 ° C
Injection speed: 33 mm / sec
表２及び表３から分かる通り、実施例において、溶融粘度は３５Ｐａ・ｓ以下、曲げ強度は１４０ＭＰａ以上、曲げ弾性率は１００００ＭＰａ超、破断歪は２．０％超、荷重たわみ温度は２３０℃以上、リフロー前のＦＰＣコネクターそりは０．０３０ｍｍ未満、リフロー後のＦＰＣコネクターそりは０．０９０ｍｍ未満、ＦＰＣコネクター最小充填圧力は７５ＭＰａ未満であり、ブリスター温度の評価は良好であった。よって、本発明に係る液晶性樹脂組成物は、流動性に優れ、この液晶性樹脂組成物の成形品を含むコネクターは、耐熱性及び機械的性質に優れ、そり変形及びブリスター発生が抑制されていることが確認された。 As can be seen from Tables 2 and 3, in the examples, the melt viscosity is 35 Pa · s or less, the bending strength is 140 MPa or more, the flexural modulus is more than 10,000 MPa, the fracture strain is more than 2.0%, and the deflection temperature under load is 230 ° C. or more. The FPC connector warp before reflow was less than 0.030 mm, the FPC connector warp after reflow was less than 0.090 mm, and the minimum filling pressure of the FPC connector was less than 75 MPa, and the evaluation of the blister temperature was good. Therefore, the liquid crystal resin composition according to the present invention has excellent fluidity, and the connector containing the molded product of this liquid crystal resin composition has excellent heat resistance and mechanical properties, and warpage deformation and blister generation are suppressed. It was confirmed that there was.
Claims (5)
（Ｂ）繊維状ウォラストナイト、及び
（Ｃ）マイカ
を含有する液晶性樹脂組成物であって、
前記（Ａ）液晶性樹脂は、芳香族ヒドロキシカルボン酸に由来する繰り返し単位を構成成分として有する芳香族ポリエステル又は芳香族ポリエステルアミドであり、
前記繊維状ウォラストナイトにおいて、Ａｌ２Ｏ３の含有量は、０．０５〜０．６５質量％、Ｆｅ２Ｏ３の含有量は、０．０５〜１．０質量％であり、
前記液晶性樹脂組成物全体に対して、
前記（Ｂ）繊維状ウォラストナイトの含有量は、２．５〜１５質量％、
前記（Ｃ）マイカの含有量は、１７．５〜２７．５質量％、
前記（Ｂ）繊維状ウォラストナイトと前記（Ｃ）マイカとの合計の含有量は、２０〜３７．５質量％
である液晶性樹脂組成物。 (A) Liquid crystal resin,
A liquid crystal resin composition containing (B) fibrous wollastonite and (C) mica.
The liquid crystal resin (A) is an aromatic polyester or an aromatic polyester amide having a repeating unit derived from an aromatic hydroxycarboxylic acid as a constituent component.
In the fibrous wollastonite, the content of Al 2 O 3 is 0.05 to 0.65% by mass, and the content of Fe 2 O 3 is 0.05 to 1.0% by mass.
For the entire liquid crystal resin composition
The content of the fibrous wollastonite (B) is 2.5 to 15% by mass.
The content of (C) mica was 17.5 to 27.5% by mass.
The total content of the (B) fibrous wollastonite and the (C) mica is 20 to 37.5% by mass.
Is a liquid crystal resin composition.
製品全長が３．５ｍｍ以上３０ｍｍ未満であり、
製品高さが１．５ｍｍ以下であり、
基板対基板コネクター又はフレキシブルプリント基板用コネクターである低背狭ピッチコネクターである請求項３又は４に記載のコネクター。 The distance between pitches is 0.5 mm or less,
The total length of the product is 3.5 mm or more and less than 30 mm.
The product height is 1.5 mm or less,
The connector according to claim 3 or 4, which is a low-profile narrow-pitch connector that is a board-to-board connector or a connector for a flexible printed circuit board.
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| PCT/JP2020/034341 WO2021084932A1 (en) | 2019-10-28 | 2020-09-10 | Liquid crystalline resin composition and connector including molded article of said liquid crystalline resin composition |
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| JPH1060251A (en) * | 1996-08-13 | 1998-03-03 | Teijin Chem Ltd | Aromatic polycarbonate resin composition excellent in blow moldability and its molded product |
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| WO2017038421A1 (en) * | 2015-09-01 | 2017-03-09 | ポリプラスチックス株式会社 | Liquid crystalline resin composition for camera module and camera module using same |
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| Publication number | Publication date |
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| WO2021084932A1 (en) | 2021-05-06 |
| JPWO2021084932A1 (en) | 2021-11-25 |
| CN114667322A (en) | 2022-06-24 |
| CN114667322B (en) | 2023-02-28 |
| TW202124679A (en) | 2021-07-01 |
| KR20220066182A (en) | 2022-05-23 |
| KR102416379B1 (en) | 2022-07-05 |
| TWI824180B (en) | 2023-12-01 |
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