JP4866009B2 - Compound and composition containing the same - Google Patents
Compound and composition containing the same Download PDFInfo
- Publication number
- JP4866009B2 JP4866009B2 JP2005069771A JP2005069771A JP4866009B2 JP 4866009 B2 JP4866009 B2 JP 4866009B2 JP 2005069771 A JP2005069771 A JP 2005069771A JP 2005069771 A JP2005069771 A JP 2005069771A JP 4866009 B2 JP4866009 B2 JP 4866009B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- compound
- weight
- group
- resorcin
- 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.)
- Active
Links
- 150000001875 compounds Chemical class 0.000 title claims description 75
- 239000000203 mixture Substances 0.000 title claims description 51
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 44
- 229960001755 resorcinol Drugs 0.000 description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 239000000843 powder Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- -1 2-ethylhexylene group Chemical group 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000012779 reinforcing material Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- AWNCOSZGPLLXNC-UHFFFAOYSA-N bis(3-hydroxyphenyl) hexanedioate Chemical compound OC1=CC=CC(OC(=O)CCCCC(=O)OC=2C=C(O)C=CC=2)=C1 AWNCOSZGPLLXNC-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- PWAXUOGZOSVGBO-UHFFFAOYSA-N adipoyl chloride Chemical compound ClC(=O)CCCCC(Cl)=O PWAXUOGZOSVGBO-UHFFFAOYSA-N 0.000 description 4
- RNZMAGAKJWUTEF-UHFFFAOYSA-N bis(3-hydroxyphenyl) butanedioate Chemical compound OC1=CC=CC(OC(=O)CCC(=O)OC=2C=C(O)C=CC=2)=C1 RNZMAGAKJWUTEF-UHFFFAOYSA-N 0.000 description 4
- PTZHISGNBGKPGG-UHFFFAOYSA-N bis(3-hydroxyphenyl) decanedioate Chemical compound OC1=CC=CC(OC(=O)CCCCCCCCC(=O)OC=2C=C(O)C=CC=2)=C1 PTZHISGNBGKPGG-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000004450 alkenylene group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- IRXBNHGNHKNOJI-UHFFFAOYSA-N butanedioyl dichloride Chemical compound ClC(=O)CCC(Cl)=O IRXBNHGNHKNOJI-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- WMPOZLHMGVKUEJ-UHFFFAOYSA-N decanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCC(Cl)=O WMPOZLHMGVKUEJ-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 150000007530 organic bases Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- YVXPOZFNECJRIC-UHFFFAOYSA-N butanedioyl dibromide Chemical compound BrC(=O)CCC(Br)=O YVXPOZFNECJRIC-UHFFFAOYSA-N 0.000 description 2
- YQAGVUODRGLPSR-UHFFFAOYSA-N decanedioyl dibromide Chemical group BrC(=O)CCCCCCCCC(Br)=O YQAGVUODRGLPSR-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- HCIQVHYVJXUCPJ-UHFFFAOYSA-N nonanedioyl dibromide Chemical group BrC(=O)CCCCCCCC(Br)=O HCIQVHYVJXUCPJ-UHFFFAOYSA-N 0.000 description 2
- HGEVGSTXQGZPCL-UHFFFAOYSA-N nonanedioyl dichloride Chemical compound ClC(=O)CCCCCCCC(Cl)=O HGEVGSTXQGZPCL-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- GKIVTXLMSMDQJI-UHFFFAOYSA-N propanedioyl dibromide Chemical compound BrC(=O)CC(Br)=O GKIVTXLMSMDQJI-UHFFFAOYSA-N 0.000 description 2
- SXYFKXOFMCIXQW-UHFFFAOYSA-N propanedioyl dichloride Chemical compound ClC(=O)CC(Cl)=O SXYFKXOFMCIXQW-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- XGSSMJZGYVOGEM-OWOJBTEDSA-N (e)-but-2-enedioyl dibromide Chemical compound BrC(=O)\C=C\C(Br)=O XGSSMJZGYVOGEM-OWOJBTEDSA-N 0.000 description 1
- ZLYYJUJDFKGVKB-OWOJBTEDSA-N (e)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C\C(Cl)=O ZLYYJUJDFKGVKB-OWOJBTEDSA-N 0.000 description 1
- XGSSMJZGYVOGEM-UPHRSURJSA-N (z)-but-2-enedioyl dibromide Chemical compound BrC(=O)\C=C/C(Br)=O XGSSMJZGYVOGEM-UPHRSURJSA-N 0.000 description 1
- ZLYYJUJDFKGVKB-UPHRSURJSA-N (z)-but-2-enedioyl dichloride Chemical compound ClC(=O)\C=C/C(Cl)=O ZLYYJUJDFKGVKB-UPHRSURJSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- 125000004208 3-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C([H])C(*)=C1[H] 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 0 Oc1cc(*C(*C(Oc2cc(O)ccc2)=O)=O)ccc1 Chemical compound Oc1cc(*C(*C(Oc2cc(O)ccc2)=O)=O)ccc1 0.000 description 1
- 244000171726 Scotch broom Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- KVBYPTUGEKVEIJ-UHFFFAOYSA-N benzene-1,3-diol;formaldehyde Chemical compound O=C.OC1=CC=CC(O)=C1 KVBYPTUGEKVEIJ-UHFFFAOYSA-N 0.000 description 1
- VYXZOVLCVHPKPH-BQYQJAHWSA-N bis(3-hydroxyphenyl) (e)-but-2-enedioate Chemical compound OC1=CC=CC(OC(=O)\C=C\C(=O)OC=2C=C(O)C=CC=2)=C1 VYXZOVLCVHPKPH-BQYQJAHWSA-N 0.000 description 1
- OJUVMPCXMHEPAO-FLIBITNWSA-N bis(3-hydroxyphenyl) (z)-2-methylbut-2-enedioate Chemical compound C=1C=CC(O)=CC=1OC(=O)C(/C)=C\C(=O)OC1=CC=CC(O)=C1 OJUVMPCXMHEPAO-FLIBITNWSA-N 0.000 description 1
- VYXZOVLCVHPKPH-FPLPWBNLSA-N bis(3-hydroxyphenyl) (z)-but-2-enedioate Chemical compound OC1=CC=CC(OC(=O)\C=C/C(=O)OC=2C=C(O)C=CC=2)=C1 VYXZOVLCVHPKPH-FPLPWBNLSA-N 0.000 description 1
- PARDGMZERLVHBY-UHFFFAOYSA-N bis(3-hydroxyphenyl) 2,3-dihydroxybutanedioate Chemical compound C=1C=CC(O)=CC=1OC(=O)C(O)C(O)C(=O)OC1=CC=CC(O)=C1 PARDGMZERLVHBY-UHFFFAOYSA-N 0.000 description 1
- ZBXMZDHSINDMAF-UHFFFAOYSA-N bis(3-hydroxyphenyl) 2-methylidenebutanedioate Chemical compound OC1=CC=CC(OC(=O)CC(=C)C(=O)OC=2C=C(O)C=CC=2)=C1 ZBXMZDHSINDMAF-UHFFFAOYSA-N 0.000 description 1
- WECOISGMNJGLPF-UHFFFAOYSA-N bis(3-hydroxyphenyl) cyclohexane-1,1-dicarboxylate Chemical compound OC1=CC=CC(OC(=O)C2(CCCCC2)C(=O)OC=2C=C(O)C=CC=2)=C1 WECOISGMNJGLPF-UHFFFAOYSA-N 0.000 description 1
- DDPHMTWWRIJAQB-UHFFFAOYSA-N bis(3-hydroxyphenyl) nonanedioate Chemical compound OC1=CC=CC(OC(=O)CCCCCCCC(=O)OC=2C=C(O)C=CC=2)=C1 DDPHMTWWRIJAQB-UHFFFAOYSA-N 0.000 description 1
- PBTOGQAXCLGAJA-UHFFFAOYSA-N bis(3-hydroxyphenyl) propanedioate Chemical compound OC1=CC=CC(OC(=O)CC(=O)OC=2C=C(O)C=CC=2)=C1 PBTOGQAXCLGAJA-UHFFFAOYSA-N 0.000 description 1
- 125000005569 butenylene group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000010073 coating (rubber) Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- BXLBOLOUCITZFA-UHFFFAOYSA-N cyclohex-2-ene-1,1-dicarbonyl bromide Chemical compound BrC(=O)C1(C(Br)=O)CCCC=C1 BXLBOLOUCITZFA-UHFFFAOYSA-N 0.000 description 1
- OANFVMFCLUSQJY-UHFFFAOYSA-N cyclohex-2-ene-1,1-dicarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCCC=C1 OANFVMFCLUSQJY-UHFFFAOYSA-N 0.000 description 1
- BTLPDWRKFKDZIH-UHFFFAOYSA-N cyclohexane-1,1-dicarbonyl bromide Chemical compound BrC(=O)C1(C(Br)=O)CCCCC1 BTLPDWRKFKDZIH-UHFFFAOYSA-N 0.000 description 1
- MLCGVCXKDYTMRG-UHFFFAOYSA-N cyclohexane-1,1-dicarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCCCC1 MLCGVCXKDYTMRG-UHFFFAOYSA-N 0.000 description 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000002228 disulfide group Chemical group 0.000 description 1
- SFRNMPHYXBZOEE-UHFFFAOYSA-N dodecanedioyl dibromide Chemical group BrC(=O)CCCCCCCCCCC(Br)=O SFRNMPHYXBZOEE-UHFFFAOYSA-N 0.000 description 1
- CNXXEPWXNDFGIG-UHFFFAOYSA-N dodecanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCCCC(Cl)=O CNXXEPWXNDFGIG-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960004279 formaldehyde Drugs 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- UJGPNLWJDSIACI-UHFFFAOYSA-N hexanedioyl dibromide Chemical compound BrC(=O)CCCCC(Br)=O UJGPNLWJDSIACI-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- PTKUJIQGGSQZMK-UHFFFAOYSA-N octadecanedioyl dibromide Chemical group BrC(=O)CCCCCCCCCCCCCCCCC(Br)=O PTKUJIQGGSQZMK-UHFFFAOYSA-N 0.000 description 1
- CQUZBCLCWSTQMV-UHFFFAOYSA-N octadecanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCCCCCCCCCC(Cl)=O CQUZBCLCWSTQMV-UHFFFAOYSA-N 0.000 description 1
- FVENDMFTYXWGLT-UHFFFAOYSA-N octanedioyl dibromide Chemical group BrC(=O)CCCCCCC(Br)=O FVENDMFTYXWGLT-UHFFFAOYSA-N 0.000 description 1
- PUIBKAHUQOOLSW-UHFFFAOYSA-N octanedioyl dichloride Chemical compound ClC(=O)CCCCCCC(Cl)=O PUIBKAHUQOOLSW-UHFFFAOYSA-N 0.000 description 1
- PHLZDCSVSDSPPH-UHFFFAOYSA-N pentanedioyl dibromide Chemical compound BrC(=O)CCCC(Br)=O PHLZDCSVSDSPPH-UHFFFAOYSA-N 0.000 description 1
- YVOFTMXWTWHRBH-UHFFFAOYSA-N pentanedioyl dichloride Chemical compound ClC(=O)CCCC(Cl)=O YVOFTMXWTWHRBH-UHFFFAOYSA-N 0.000 description 1
- 238000002953 preparative HPLC Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- ZZPKZRHERLGEKA-UHFFFAOYSA-N resorcinol monoacetate Chemical compound CC(=O)OC1=CC=CC(O)=C1 ZZPKZRHERLGEKA-UHFFFAOYSA-N 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- UWQVBYLPQVGHME-UHFFFAOYSA-N tetradecanedioyl dibromide Chemical group BrC(=O)CCCCCCCCCCCCC(Br)=O UWQVBYLPQVGHME-UHFFFAOYSA-N 0.000 description 1
- DBZWFSYEKKZLNS-UHFFFAOYSA-N tetradecanedioyl dichloride Chemical compound ClC(=O)CCCCCCCCCCCCC(Cl)=O DBZWFSYEKKZLNS-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、空気入りタイヤや工業用ベルト等のゴム物品に用いられるスチールコード等の金属補強材との接着耐久性を向上させる新規な組成物または化合物に関し、更に詳しくは、ゴムと配合した際のゴム組成物の加工性が良好であり、且つ該ゴム組成物の貯蔵期間に係らず金属補強材に対し安定して初期接着性及び耐湿熱接着性を発現させることができる、特定構造を有する化合物および該化合物を主成分とする組成物に関するものである。 The present invention relates to a novel composition or compound that improves adhesion durability with a metal reinforcing material such as a steel cord used in rubber articles such as pneumatic tires and industrial belts, and more particularly, when blended with rubber. The rubber composition has a specific structure that has good processability and can stably exhibit initial adhesiveness and heat-and-moisture resistance to metal reinforcing materials regardless of the storage period of the rubber composition. The present invention relates to a compound and a composition containing the compound as a main component.
自動車用タイヤ、コンベアベルト、ホース等、特に強度が要求されるゴム製品には、ゴムを補強し強度、耐久性を向上させる目的で、スチールコード等の金属補強材をゴム組成物で被覆した複合材料が用いられている。該ゴム−金属複合材料が高い補強効果を発揮し信頼性を得るためにはゴム−金属補強材間に混合、配合、貯蔵等の条件に左右されない安定した接着が必要である。かかる複合体を得るには、亜鉛、黄銅、真鍮等でメッキされたスチールコード等の金属補強材を、硫黄を配合したゴム組成物に埋設し加熱加硫時に、ゴムの加硫と同時に接着させるいわゆる直接加硫接着が広く用いられており、これまで該直接加硫接着におけるゴム−金属補強材間の接着性、特に耐湿熱接着性向上のため様々な検討が行われている。 For rubber products that require particularly high strength, such as automobile tires, conveyor belts, hoses, etc., composites in which a metal reinforcing material such as a steel cord is coated with a rubber composition to reinforce the rubber and improve its strength and durability. Material is used. In order for the rubber-metal composite material to exhibit a high reinforcing effect and to obtain reliability, stable adhesion that is not affected by the conditions of mixing, blending, storage and the like is necessary between the rubber-metal reinforcing material. In order to obtain such a composite, a metal reinforcing material such as a steel cord plated with zinc, brass, brass or the like is embedded in a rubber composition containing sulfur, and is adhered at the same time as rubber vulcanization at the time of heat vulcanization. So-called direct vulcanization bonding has been widely used, and various studies have been made so far in order to improve the adhesion between the rubber and the metal reinforcing material in the direct vulcanization bonding, particularly the wet heat resistance.
例えば、レゾルシン又は、レゾルシンとホルマリンを縮合して得られる、レゾルシン−ホルムアルデヒド樹脂（以下、「ＲＦ樹脂」と略記する。）を耐湿熱接着性向上の目的で配合したゴム組成物が報告されている（特開２００１−２３４１４０号公報）。ＲＦ樹脂を配合することでスチールコードとゴムの耐湿熱接着性は確かに飛躍的に向上する。 For example, there has been reported a rubber composition containing resorcin or a resorcin-formaldehyde resin (hereinafter abbreviated as “RF resin”) obtained by condensing resorcin or resorcin and formalin for the purpose of improving moisture and heat resistance. (Japanese Patent Laid-Open No. 2001-234140). By blending the RF resin, the moisture and heat resistance of the steel cord and rubber will certainly improve dramatically.
しかしながら、レゾルシンやＲＦ樹脂は極性が非常に高いためゴムとの相溶性に乏しく、混合、配合、貯蔵等の条件によって、レゾルシンやＲＦ樹脂が析出するいわゆるブルームが発生するため、ゴム物品の外観を損ねる恐れがある。また、ブルーム発生により、該ゴム組成物を配合してから加硫接着まで長期間貯蔵すると接着性が低下するといった問題が生じるため、レゾルシンやＲＦ樹脂を配合したゴム組成物は速やかに加硫接着させる必要があり、ゴム物品の生産性を損ねかねない。 However, resorcin and RF resins are very polar and have poor compatibility with rubber, and so-called blooms that precipitate resorcin and RF resins are generated depending on the conditions of mixing, blending, storage, etc. There is a risk of damage. In addition, due to the occurrence of bloom, there is a problem that the adhesiveness decreases when the rubber composition is compounded and then stored for a long time from vulcanization adhesion. Therefore, the rubber composition formulated with resorcin or RF resin is vulcanized and bonded quickly. This may impair the productivity of rubber articles.
また、重量平均分子量が３０００〜４５０００のレゾルシン骨格を有する混合ポリエステルからなる、接着材料が報告されている（特開平７−１１８６２１号公報）。しかしながら、分子量が大きな混合ポリエステルはＲＦ樹脂と比較してゴムとの相溶性は改善されるものの、完全に満足できるものとはなっていない。さらに、高分子量の混合ポリエステルをゴムに配合すると、配合ゴムの粘度が上昇し、加工性が低下するといった問題があり、耐湿熱接着性も十分なものとはなっていない。
本発明は、ゴムに配合した際のゴム組成物が加工性と高い耐湿熱接着性を維持しながら、レゾルシンやＲＦ樹脂を配合した時に見られるブルームを極力抑制し、該ゴム組成物の貯蔵中の接着性低下を少なくでき、優れた接着安定性を発現させることができる、特定構造を有する化合物および該化合物を主成分とする組成物を提供することを目的とする。 The present invention suppresses bloom as seen when compounding resorcinol and RF resin as much as possible while maintaining the processability and high heat-and-moisture resistance adhesion when the rubber composition is compounded with rubber. It is an object of the present invention to provide a compound having a specific structure and a composition containing the compound as a main component, which can reduce a decrease in adhesiveness and can exhibit excellent adhesion stability.
本発明者らは、前記課題を達成するため鋭意検討した結果、特定構造の化合物または該化合物を主成分とする組成物をゴムに配合することで、レゾルシンやＲＦ樹脂と同等以上の耐湿熱接着性を維持しつつ、レゾルシンやＲＦ樹脂の問題点であるゴムと配合して得られるゴム組成物の加工性を保持するとともに、ブルーム発生を抑制し、配合、貯蔵等の条件によらず優れた接着安定性を示すことを見出し、本発明を完成させるに至った。 As a result of diligent studies to achieve the above-mentioned problems, the present inventors have formulated a compound having a specific structure or a composition containing the compound as a main component into a rubber so that the heat- and heat-resistant adhesion equivalent to or better than that of resorcinol or RF resin can be obtained. While maintaining the properties, while maintaining the workability of the rubber composition obtained by blending with the rubber which is a problem of resorcinol and RF resin, it suppresses the occurrence of bloom and is excellent regardless of the conditions of blending, storage, etc. The present inventors have found that it exhibits adhesion stability and have completed the present invention.
即ち、本発明は、
（Ｉ）下記一般式（２）で表される化合物；
（式中、Ｒは炭素数１〜１６の２価の脂肪族基を表す。）
並びに
（ＩＩ）上記一般式（２）で表される化合物が６０〜１００重量％、下記一般式（３）で表され且つｎ＝２の化合物が０〜２０重量％、下記一般式（３）で表され且つｎ＝３の化合物が０〜１０重量％及び下記一般式（３）で表され且つｎ＝４〜６の化合物が合計で０〜１０重量％からなる組成物（但し、該組成物は、上記一般式（２）で表される化合物が１００重量％である純物質を包含しない）
（式中、Ｒは炭素数１〜１６の２価の脂肪族基を表し、ｎは２〜６の整数を示す。）
に関するものである。
That is, the present invention
(I) a compound represented by the following general formula (2) ;
(In the formula, R represents a divalent aliphatic group having 1 to 16 carbon atoms.)
And
(II) The compound represented by the general formula (2) is 60 to 100% by weight, the compound represented by the following general formula (3) and n = 2 is 0 to 20% by weight, and the following general formula (3) And a compound represented by the following general formula (3), wherein n = 3 is 0 to 10% by weight, and n = 4 to 6 is a composition comprising 0 to 10% by weight in total (provided that the composition Does not include a pure substance in which the compound represented by the general formula (2) is 100% by weight)
(In the formula, R represents a divalent aliphatic group having 1 to 16 carbon atoms, and n represents an integer of 2 to 6.)
It is about.
本発明によれば、ゴムと配合して得られるゴム組成物が加工性と高い耐湿熱接着性を維持しながら、レゾルシンやＲＦ樹脂を配合した時に見られるブルームを極力抑制し、該ゴム組成物の貯蔵中の接着性低下が少なく安定した接着性を発現させる事ができる、化合物および該化合物を主成分とする組成物を提供することができる。 According to the present invention, the rubber composition obtained by blending with rubber maintains the workability and high moisture and heat resistance adhesion, while suppressing the bloom seen when blending resorcinol and RF resin as much as possible, and the rubber composition It is possible to provide a compound and a composition containing the compound as a main component, which can exhibit stable adhesiveness with little decrease in adhesiveness during storage.
以下に、本発明を詳細に説明する。本発明の化合物は、上記一般式（２）で表されることを特徴とする。一般式（２）中のＲは、炭素数１〜１６の２価の脂肪族基を表す。 The present invention is described in detail below. The compound of the present invention is represented by the general formula (2) . R in General formula (2) represents a C1-C16 bivalent aliphatic group .
ここで、炭素数１〜１６の２価の脂肪族基としては、例えば、メチレン基、エチレン基、ブチレン基、イソブチレン基、オクチレン基、２−エチルヘキシレン基等の直鎖または分岐鎖のアルキレン基、ビニレン基（エテニレン基）、ブテニレン基、オクテニレン基等の直鎖または分岐鎖のアルケニレン基、これらのアルキレン基又はアルケニレン基の水素原子がヒドロキシル基又はアミノ基等で置換されたアルキレン基またはアルケニレン基、シクロヘキシレン基等の脂環式基が挙げられる。これらの中でも入手の容易さ等を考慮すれば、炭素数２〜１０のアルキレン基が望ましく、特にエチレン基、ブチレン基又はオクチレン基が好ましい。 Here, examples of the divalent aliphatic group having 1 to 16 carbon atoms include linear or branched alkylene such as methylene group, ethylene group, butylene group, isobutylene group, octylene group, and 2-ethylhexylene group. Group, vinylene group (ethenylene group), butenylene group, octenylene group or other linear or branched alkenylene group, alkylene group or alkylene group or alkenylene in which the hydrogen atom of alkenylene group is substituted with hydroxyl group or amino group And alicyclic groups such as a cyclohexylene group. Among these, in view of availability, an alkylene group having 2 to 10 carbon atoms is preferable, and an ethylene group, a butylene group, or an octylene group is particularly preferable.
一般式（２）で表される化合物の具体例としては、マロン酸ビス（３−ヒドロキシフェニル）エステル、コハク酸ビス（３−ヒドロキシフェニル）エステル、フマル酸ビス（３−ヒドロキシフェニル）エステル、マレイン酸ビス（３−ヒドロキシフェニル）エステル、リンゴ酸ビス（３−ヒドロキシフェニル）エステル、イタコン酸ビス（３−ヒドロキシフェニル）エステル、シトラコン酸ビス（３−ヒドロキシフェニル）エステル、アジピン酸ビス（３−ヒドロキシフェニル）エステル、酒石酸ビス（３−ヒドロキシフェニル）エステル、アゼライン酸ビス（３−ヒドロキシフェニル）エステル、セバシン酸ビス（３−ヒドロキシフェニル）エステル、シクロヘキサンジカルボン酸ビス（３−ヒドロキシフェニル）エステル等が挙げられる。 Specific examples of the compound represented by the general formula (2), malonic acid bis (3-hydroxyphenyl) ester, succinic acid bis (3-hydroxyphenyl) ester, fumaric acid bis (3-hydroxyphenyl) ester, maleic Acid bis (3-hydroxyphenyl) ester, malic acid bis (3-hydroxyphenyl) ester, itaconic acid bis (3-hydroxyphenyl) ester, citraconic acid bis (3-hydroxyphenyl) ester, adipic acid bis (3-hydroxy Phenyl) ester, tartrate bis (3-hydroxyphenyl) ester, azelaic acid bis (3-hydroxyphenyl) ester, sebacic acid bis (3-hydroxyphenyl) ester, cyclohexanedicarboxylic acid bis (3-hydroxyphenyl) ester, etc. Be
これらの中でも、コハク酸ビス（３−ヒドロキシフェニル）エステル、アジピン酸ビス（３−ヒドロキシフェニル）エステル、セバシン酸ビス（３−ヒドロキシフェニル）エステルが好ましい。 Among these , succinic acid bis (3-hydroxyphenyl) ester, adipic acid bis (3-hydroxyphenyl) ester, and sebacic acid bis (3-hydroxyphenyl) ester are preferable.
一般式（２）で表される化合物の製造法は特に限定されないが、例えば、下記一般式（４）で表されるジカルボン酸ハライドと、
（式中、Ｒは炭素数１〜１６の２価の脂肪族基を表し、Ｘはハロゲン原子を表す。）
レゾルシンと
を塩基の存在下または非存在下で反応させて製造される。
Although the manufacturing method of the compound represented by General formula (2) is not specifically limited, For example, the dicarboxylic acid halide represented by following General formula (4),
(In the formula, R represents a divalent aliphatic group having 1 to 16 carbon atoms, and X represents a halogen atom.)
It is produced by reacting resorcin with or without a base.
一般式（４）中のＲは、前記一般式（２）中のＲと同義であり、Ｘはハロゲン原子を表す。ハロゲン原子としては、塩素原子又は臭素原子が好ましい。 R in the general formula (4) has the same meaning as R in the general formula (2) , and X represents a halogen atom. As a halogen atom, a chlorine atom or a bromine atom is preferable.
一般式（４）で表される化合物としては、マロン酸ジクロライド、コハク酸ジクロライド、フマル酸ジクロライド、マレイン酸ジクイロライド、グルタル酸ジクロライド、アジピン酸ジクロライド、スベリン酸ジクロライド、アゼライン酸ジクロライド、セバシン酸ジクロライド、１，１０−デカンジカルボン酸ジクロライド、１，１２−ドデカンジカルボン酸ジクロライド、１，１６−ヘキサデカンジカルボン酸ジクロライド等の脂肪族ジカルボン酸ジクロライド、シクロヘキサンジカルボン酸ジクロライド、シクロヘキセンジカルボン酸ジクロライド等の脂環式ジカルボン酸ジクロライド、マロン酸ジブロマイド、コハク酸ジブロマイド、フマル酸ジブロマイド、マレイン酸ジブロマイド、グルタル酸ジブロマイド、アジピン酸ジブロマイド、スベリン酸ジブロマイド、アゼライン酸ジブロマイド、セバシン酸ジブロマイド、１，１０−デカンジカルボン酸ジブロマイド、１，１２−ドデカンジカルボン酸ジブロマイド、１，１６−ヘキサデカンジカルボン酸ジブロマイド等の脂肪族ジカルボン酸ジブロマイド、シクロヘキサンジカルボン酸ジブロマイド、シクロヘキセンジカルボン酸ジブロマイド等の脂環式ジカルボン酸ジブロマイドが挙げられる。これらの中でも、マロン酸ジクロライド、コハク酸ジクロライド、アジピン酸ジクロライド、アゼライン酸ジクロライド、セバシン酸ジクロライド、マロン酸ジブロマイド、コハク酸ジブロマイド、アジピン酸ジブロマイド、アゼライン酸ジブロマイド、セバシン酸ジブロマイド等が好ましい。 The compound represented by the general formula (4) includes malonic acid dichloride, succinic acid dichloride, fumaric acid dichloride, maleic acid dichloride, glutaric acid dichloride, adipic acid dichloride, suberic acid dichloride, azelaic acid dichloride, sebacic acid dichloride, 1 , 10-decane dicarboxylic acid dichloride, 1,12-dodecane dicarboxylic acid dichloride, aliphatic dicarboxylic acid dichloride such as 1,16-hexadecane dicarboxylic acid dichloride, cyclohexane dicarboxylic acid dichloride, alicyclic dicarboxylic acid dichloride such as cyclohexene dicarboxylic acid dichloride , Malonic acid dibromide, succinic acid dibromide, fumaric acid dibromide, maleic acid dibromide, glutaric acid dibromide, adipic acid dibromide Aliphatic groups such as disulfide, suberic acid dibromide, azelaic acid dibromide, sebacic acid dibromide, 1,10-decanedicarboxylic acid dibromide, 1,12-dodecanedicarboxylic acid dibromide, 1,16-hexadecanedicarboxylic acid dibromide Examples thereof include alicyclic dicarboxylic acid dibromides such as dicarboxylic acid dibromide, cyclohexane dicarboxylic acid dibromide, and cyclohexene dicarboxylic acid dibromide. Among these, malonic acid dichloride, succinic acid dichloride, adipic acid dichloride, azelaic acid dichloride, sebacic acid dichloride, malonic acid dibromide, succinic acid dibromide, adipic acid dibromide, azelaic acid dibromide, sebacic acid dibromide, etc. preferable.
一般式（４）で表される化合物とレゾルシンとを反応させる際に使用する塩基としては、通常、ピリジン、β−ピコリン、Ｎ−メチルモルホリン、ジメチルアニリン、ジエチルアニリン、トリメチルアミン、トリエチルアミン、トリブチルアミン等の有機塩基が用いられる。 As the base used for reacting the compound represented by the general formula (4) with resorcin , usually, pyridine, β-picoline, N-methylmorpholine, dimethylaniline, diethylaniline, trimethylamine, triethylamine, tributylamine, etc. The organic base is used.
一般式（４）で表される化合物とレゾルシンとを反応させる際は、通常、一般式（４）で表される化合物とレゾルシンとが１：４〜１：３０のモル比となるように反応させる。 When the compound represented by the general formula (4) and resorcin are reacted, the reaction is usually performed so that the compound represented by the general formula (4) and resorcin have a molar ratio of 1: 4 to 1:30. Let
一般式（４）で表される化合物とレゾルシンとを反応させる際、原料を溶解させること等を目的として溶媒を用いる事ができる。溶媒としては、上述の有機塩基をそのまま溶媒として使用しても良いし、反応を阻害しない他の有機溶媒を用いても構わない。このような溶媒としては、例えば、ジメチルエーテル、ジオキサン等のエーテル系溶媒が挙げられる。 When the compound represented by the general formula (4) is reacted with resorcin , a solvent can be used for the purpose of dissolving the raw materials. As the solvent, the above-described organic base may be used as it is, or another organic solvent that does not inhibit the reaction may be used. Examples of such a solvent include ether solvents such as dimethyl ether and dioxane.
一般式（４）で表される化合物とレゾルシンとを反応させる際の反応温度は、通常、−２０℃〜１００℃で行なわれる。 The reaction temperature for reacting the compound represented by the general formula (4) with resorcin is usually -20 ° C to 100 ° C.
前記の反応により得られる一般式（２）で表される化合物は、公知の方法により反応混合物から単離することができる。即ち、減圧蒸留等の操作により、反応に用いた有機塩基およびレゾルシン、反応に有機溶媒を使用した場合にはこの有機溶媒を留去し乾固させる方法、反応混合物に一般式（２）で表される化合物の貧溶媒を添加して再沈殿させる方法、反応混合液に水および水と混和しない有機溶媒を添加して有機層に抽出する方法等が挙げられる。また、場合によっては再結晶により精製しても良い。 The compound represented by the general formula (2) obtained by the above reaction can be isolated from the reaction mixture by a known method. That is, the organic base and resorcin used in the reaction by an operation such as distillation under reduced pressure, and when an organic solvent is used in the reaction, the organic solvent is distilled off to dryness, and the reaction mixture is represented by the general formula (2) . And a method of reprecipitation by adding a poor solvent of the compound to be added, a method of adding water and an organic solvent immiscible with water to the reaction mixture, and extracting to the organic layer. Moreover, you may refine | purify by recrystallization depending on the case.
前記一般式（２）で表される化合物の貧溶媒としては、通常、水が用いられる。また、上記水と混和しない有機溶媒としては、酢酸エチル、酢酸ブチル等のエステル類、メチルイソブチルケトン、ジイソブチルケトン等のケトン類が用いられる。 As a poor solvent for the compound represented by the general formula (2) , water is usually used. Examples of the organic solvent immiscible with water include esters such as ethyl acetate and butyl acetate, and ketones such as methyl isobutyl ketone and diisobutyl ketone.
レゾルシンを用いることで、一般式（２）で表される化合物を主成分とする、一般式（２）で表される化合物と一般式（３）で表される化合物とからなる組成物が得られる。 In Rukoto using resorcin, as a main component a compound represented by the general formula (2), a composition comprising a compound represented by the compound represented by the general formula (2) and the general formula (3) is can get.
一般式（３）中のＲは、一般式（２）中のＲと同義であり、ｎは２〜６の整数を示す。 R in General formula (3) is synonymous with R in General formula (2) , and n shows the integer of 2-6.
例えば、前記の反応にレゾルシンを用いることで得られる一般式（２）で表される化合物と一般式（３）で表される化合物とからなる組成物中には、通常、一般式（２）で表される化合物が６０〜１００重量％、一般式（３）におけるｎ＝２の化合物が０〜２０重量％、一般式（３）におけるｎ＝３の化合物が０〜１０重量％、一般式（３）におけるｎ＝４〜６の化合物が合計で１０重量％程度含まれる。これらの比率は、一般式（４）で表される化合物とレゾルシンのモル比を変化させる事でコントロール可能である。 For example, the the composition which is composed of a compound represented by the general formula obtained in Rukoto using resorcinol compound represented by (2) and the general formula (3) in the reaction, usually, the general formula (2 ) Is 60 to 100% by weight, the compound of n = 2 in the general formula (3) is 0 to 20% by weight, the compound of n = 3 in the general formula (3) is 0 to 10% by weight, The compound of n = 4-6 in Formula (3) is contained about 10 weight% in total. These ratios can be controlled by changing the molar ratio of the compound represented by the general formula (4) and resorcin.
前記一般式（２）で表される化合物と一般式（３）で表される化合物とからなる組成物も前記一般式（２）で表される化合物の単離方法と同様の方法により、これらを含む反応混合物から単離することができる。 A composition comprising the compound represented by the general formula (2) and the compound represented by the general formula (3) can be obtained by the same method as the method for isolating the compound represented by the general formula (2). Can be isolated from a reaction mixture comprising
一般式（２）で表される化合物が６０重量％以上である組成物の場合、ゴムと配合して接着した際の湿熱接着性が向上する。湿熱接着性向上の観点から判断すれば、より好ましくは一般式（２）で表される化合物の含有量が７０〜１００重量％であり、更に好ましくは８０〜１００重量％である。 In the case of a composition in which the compound represented by the general formula (2) is 60% by weight or more, the wet heat adhesiveness is improved when blended with rubber and bonded. Judging from the viewpoint of improving wet heat adhesion, the content of the compound represented by the general formula (2) is more preferably 70 to 100% by weight, still more preferably 80 to 100% by weight.
本発明の化合物および該化合物を主成分とする組成物は、レゾルシンやＲＦ樹脂に比べ、ゴム成分と混ざりやすいという特徴がある。そのため、本発明の化合物又は該化合物を主成分とする組成物を配合したゴム組成物は、レゾルシンやＲＦ樹脂を配合したゴム組成物よりもブルームしにくい傾向がある。これは、本発明の化合物および該化合物を主成分とする組成物がレゾルシンやＲＦ樹脂に比べて極性が低いためと推定される。また、本発明の化合物および該化合物を主成分とする組成物を配合したゴム組成物は、貯蔵期間に関わらず接着安定性に優れている。そのため、本発明の化合物および該化合物を主成分とする組成物は接着向上剤として有用である。 The compound of the present invention and the composition containing the compound as a main component are characterized by being easily mixed with a rubber component as compared with resorcin and RF resin. Therefore, a rubber composition containing the compound of the present invention or a composition containing the compound as a main component tends to be less likely to bloom than a rubber composition containing resorcin or RF resin. This is presumably because the compound of the present invention and the composition containing the compound as a main component have a lower polarity than resorcin or RF resin. Moreover, the rubber composition containing the compound of the present invention and the composition containing the compound as a main component is excellent in adhesion stability regardless of the storage period. Therefore, the compound of the present invention and the composition containing the compound as a main component are useful as an adhesion improver.
以下に、実施例、参考例、比較例を上げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, Reference Examples, and Comparative Examples, but the present invention is not limited to the following Examples.
（実施例１）
レゾルシン３３０．６ｇ（3.0mol）をピリジン６００．０ｇに溶解した溶液を氷浴上で１５℃以下に保ちながら、これに塩化アジポイル５４．９ｇ（0.30mol）を徐々に滴下した。滴下終了後、得られた反応混合物を室温まで昇温し、１昼夜放置し反応を完結させた。反応混合物から、ピリジンを減圧下に留去し、残留物に水１２００ｇを加えて氷冷すると沈殿が析出した。析出した沈殿をろ過、水洗し、得られた湿体を減圧乾燥して、白色〜淡黄色の粉体８４gを得た。この粉体を分取用装置を備えた液体クロマトグラフィーで下記の条件で処理し、主たる成分を含む溶離液を分取した。この溶離液を濃縮し、析出した結晶をろ過して回収し、減圧乾燥して融点１４０〜１４３℃の結晶を得た。ＨＰＬＣ分析の結果、この結晶は純度９８％のアジピン酸ビス（３−ヒドロキシフェニル）エステルであった。
Example 1
While a solution of 330.6 g (3.0 mol) of resorcin in 600.0 g of pyridine was kept at 15 ° C. or lower on an ice bath, 54.9 g (0.30 mol) of adipoyl chloride was gradually added dropwise thereto. After completion of the dropping, the resulting reaction mixture was warmed to room temperature and allowed to stand for one day to complete the reaction. From the reaction mixture, pyridine was distilled off under reduced pressure, and 1200 g of water was added to the residue and ice-cooled to precipitate. The deposited precipitate was filtered and washed with water, and the obtained wet body was dried under reduced pressure to obtain 84 g of white to light yellow powder. This powder was processed under the following conditions by liquid chromatography equipped with a fractionation device, and an eluent containing main components was fractionated. The eluent was concentrated, and the precipitated crystals were collected by filtration and dried under reduced pressure to obtain crystals having a melting point of 140 to 143 ° C. As a result of HPLC analysis, the crystals were 98% pure adipic acid bis (3-hydroxyphenyl) ester.
分取用のＨＰＬＣ条件は下記の通りである。
カラム ：Shim-pack ＰＲＥＰ−ＯＤＳ（島津製作所製）
カラム温度 ：２５℃
溶離液 ：メタノール／水混合溶剤（８５／１５（w/w％））
溶離液の流速：流量３ml／分
検出器 ：ＵＶ検出器（254nm）
Preparative HPLC conditions are as follows.
Column: Shim-pack PREP-ODS (manufactured by Shimadzu Corporation)
Column temperature: 25 ° C
Eluent: Methanol / water mixed solvent (85/15 (w / w%))
Eluent flow rate: Flow rate 3ml / min Detector: UV detector (254nm)
尚、アジピン酸ビス（３−ヒドロキシフェニル）エステルの同定データは下記の通りである。
ＭＳスペクトルデータ
ＥＩ(Pos.) ｍ／ｚ＝３３０
ＩＲスペクトルデータ
３４３６ｃｍ−１ ： 水酸基
２９３６ｃｍ−１ ： アルキル
１７３９ｃｍ−１ ： エステル
ＮＭＲスペクトルデータを表１−１および表１−２に示した。
In addition, the identification data of adipic acid bis (3-hydroxyphenyl) ester are as follows.
MS spectrum data EI (Pos.) M / z = 330
IR spectrum data 3436 cm −1: hydroxyl group 2936 cm −1: alkyl 1739 cm −1: ester NMR spectrum data are shown in Table 1-1 and Table 1-2.
（実施例２）
実施例１と同様に反応を行い得られた粉体８４ｇをＨＰＬＣにて分析した結果、この粉体中のアジピン酸ビス（３−ヒドロキシフェニル）エステルは８９重量％であった。粉体中には、他に下記式（６）で表される化合物（以下、オリゴマーということもある。）中のｎ＝２の化合物が７重量％、下記式（６）で表される化合物中のｎ＝３の化合物が２重量％、原料レゾルシンが２重量％含まれていた。尚、下記式（６）で表される化合物の同定はＬＣ−ＭＳにて行った。
(Example 2)
As a result of HPLC analysis of 84 g of the powder obtained by carrying out the reaction in the same manner as in Example 1, 89% by weight of bis (3-hydroxyphenyl) adipic acid ester in this powder was obtained. In the powder, the compound represented by the following formula (6) is 7% by weight of the compound of n = 2 in the compound represented by the following formula (6) (hereinafter sometimes referred to as oligomer). Among them, the compound of n = 3 contained 2% by weight and the raw material resorcin was contained by 2% by weight. The compound represented by the following formula (6) was identified by LC-MS.
ＭＳスペクトルの測定条件は下記の通りである。
質量範囲 ： ２００〜２０００ａｍｕ（１．９８＋０．０２ｓｅｃ）
イオン化法 ： ＥＳＩ（エレクトロスプレー）
モード ： 正
Capilary ： ３．１５ｋＶ
Cone ： ３５Ｖ
S.B.Tmp. ： １５０℃
Deslv.tmp ： ４００℃
Multi ： ６５０Ｖ
N2 ： ７５０Ｌ／ｈｒ
ｎ＝２ ： ５５１．１[M+H]+ 、 ５６８．２[M+NH4]+
ｎ＝３ ： ７７１．２[M+H]+ 、 ７８８．２[M+NH4]+
ｎ＝４ ： １００８．３[M+NH4]+
ｎ＝５ ： １２２８．３[M+NH4]+
The measurement conditions for the MS spectrum are as follows.
Mass range: 200 to 2000 amu (1.98 + 0.02 sec)
Ionization method: ESI (electrospray)
Mode: Positive
Capilary: 3.15kV
Cone: 35V
SBTmp .: 150 ° C
Deslv.tmp: 400 ° C
Multi: 650V
N2: 750 L / hr
n = 2: 551.1 [M + H] +, 568.2 [M + NH4] +
n = 3: 771.2 [M + H] +, 788.2 [M + NH4] +
n = 4: 1008.3 [M + NH4] +
n = 5: 1228.3 [M + NH4] +
また、ＨＰＬＣの分析条件は下記の通りである。
１．アジピン酸ビス（３−ヒドロキシフェニル）エステル、レゾルシンの分析
カラム ： ＹＭＣ社 Ａ−３１２ ＯＤＳ
カラム温度： ４０℃
溶離液 ： メタノール／水＝７／３（リン酸でｐＨ＝３に調整）
検出 ： ＵＶ（２５４ｎｍ）
The HPLC analysis conditions are as follows.
1. Analysis of bis (3-hydroxyphenyl) adipate and resorcin Column: YMC A-312 ODS
Column temperature: 40 ° C
Eluent: Methanol / water = 7/3 (adjusted to pH = 3 with phosphoric acid)
Detection: UV (254 nm)
２．オリゴマーの分析
カラム ： ＹＭＣ社 Ａ−３１２ ＯＤＳ
カラム温度： ４０℃
溶離液 ： アセトニトリル／水＝８／２（酢酸でｐＨ＝３．５に調整）
検出 ： ＵＶ（２５４ｎｍ）
2. Analysis of oligomer Column: YMC A-312 ODS
Column temperature: 40 ° C
Eluent: acetonitrile / water = 8/2 (adjusted to pH = 3.5 with acetic acid)
Detection: UV (254 nm)
（実施例３）
レゾルシンを１７６．２ｇ（1.6mol）、ピリジンを４００ｇ、塩化アジポイルを７３．２ｇ（0.40mol）に変えた以外は実施例１と同様の操作を行い、１１８．６ｇの粉体を得た。ＨＰＬＣ分析の結果、粉体中には、アジピン酸ビス（３−ヒドロキシフェニル）エステルが７３．４重量％、前記式（６）中のｎ＝２の化合物が１３．９重量％、前記式（６）中のｎ＝３の化合物が３．０重量％、前記式（６）中のｎ＝４の化合物が０．８重量％、前記式（６）中のｎ＝５の化合物が０．２重量％、原料レゾルシンが２．９重量％含まれていた。
(Example 3)
The same operation as in Example 1 was carried out except that 176.2 g (1.6 mol) of resorcin, 400 g of pyridine and 73.2 g (0.40 mol) of adipoyl chloride were changed to obtain 118.6 g of powder. As a result of HPLC analysis, in the powder, 73.4% by weight of bis (3-hydroxyphenyl) adipic acid ester, 13.9% by weight of the compound of n = 2 in the formula (6), The compound of n = 3 in 6) is 3.0% by weight, the compound of n = 4 in the formula (6) is 0.8% by weight, and the compound of n = 5 in the formula (6) is 0.8%. It contained 2% by weight and 2.9% by weight of the raw material resorcin.
（実施例４）
レゾルシン４４０．４ｇ（4.0mol）をピリジン４０５．０ｇに溶解した溶液を氷浴上で１５℃以下に保ちながら、これにコハク酸ジクロライド６２．０ｇ（0.4mol）を徐々に滴下した。滴下終了後、得られた反応混合物を室温まで昇温し、１昼夜放置し反応を完結させた。反応混合物から、ピリジンを減圧下に留去し、残留物に水１８００ｇを加えて氷冷すると液全体が白濁し二層に分離した。オイル層に水２００ｇおよび酢酸エチル６００ｇを添加し抽出操作を行った。得られた有機層を冷水で５回洗浄した後に硫酸マグネシウムで乾燥した。その後酢酸エチルを留去し得られた粘ちょう物にトルエン５００ｇを添加して結晶化させ、濾過、トルエン洗浄した後、水１Ｌでのスラッジングを２回行った。得られた湿体を１００ｇのメタノールに溶解した後、水１Ｌを装入して再沈殿させ、濾過、洗浄、乾燥して８２．３ｇの淡黄色粉体を得た。ＨＰＬＣ分析の結果、粉体の主成分は９１．０面積％に相当する成分であることがわかった。また、この粉体中にはレゾルシンが０．７重量％含まれていた。構造解析の結果、粉体中の主成分はコハク酸ビス（３−ヒドロキシフェニル）エステルである事が判った。
Example 4
While keeping a solution of 440.4 g (4.0 mol) of resorcin in 405.0 g of pyridine at 15 ° C. or lower on an ice bath, 62.0 g (0.4 mol) of succinic dichloride was gradually added dropwise thereto. After completion of the dropping, the resulting reaction mixture was warmed to room temperature and allowed to stand for one day to complete the reaction. From the reaction mixture, pyridine was distilled off under reduced pressure. When 1800 g of water was added to the residue and cooled on ice, the whole solution became cloudy and separated into two layers. Extraction operation was performed by adding 200 g of water and 600 g of ethyl acetate to the oil layer. The obtained organic layer was washed 5 times with cold water and then dried over magnesium sulfate. Thereafter, 500 g of toluene was added to the viscous product obtained by distilling off ethyl acetate, and the mixture was crystallized, filtered, washed with toluene, and then sludged with 1 L of water twice. The obtained wet substance was dissolved in 100 g of methanol, and then 1 L of water was charged to cause reprecipitation, followed by filtration, washing and drying to obtain 82.3 g of a pale yellow powder. As a result of HPLC analysis, it was found that the main component of the powder was a component corresponding to 91.0 area%. The powder contained 0.7% by weight of resorcin. As a result of structural analysis, it was found that the main component in the powder was bis (3-hydroxyphenyl) succinate.
尚、コハク酸ビス（３−ヒドロキシフェニル）エステルの同定データは下記の通りである。
ＭＳスペクトルデータ
ＥＩ(Pos.) ｍ／ｚ＝３０２
ＩＲスペクトルデータ
３３６１ｃｍ−１ ： 水酸基
２９８４ｃｍ−１ ： アルキル
１７３２ｃｍ−１ ： エステル
ＮＭＲスペクトルデータを表２−１及び表２−２に示した。
The identification data of succinic acid bis (3-hydroxyphenyl) ester is as follows.
MS spectrum data EI (Pos.) M / z = 302
IR spectrum data 3361 cm −1: hydroxyl group 2984 cm −1: alkyl 1732 cm −1: ester NMR spectrum data are shown in Table 2-1 and Table 2-2.
（実施例５）
レゾルシン３３０．３ｇ（3.0mol）をピリジン３０３．７ｇに溶解した溶液を氷浴上で１５℃以下に保ちながら、これにセバシン酸ジクロライド７１．７ｇ（0.3mol）を徐々に滴下した。滴下終了後、得られた反応混合物を室温まで昇温し、１昼夜放置し反応を完結させた。反応混合物から、ピリジンを減圧下に留去し、残留物に水２５０ｇを加えて氷冷すると沈殿が析出した。析出した沈殿をろ過、水洗し、得られた湿体を減圧乾燥して、白色〜淡黄色の粉体１０２．８ｇを得た。ＨＰＬＣ分析の結果、粉体の主成分は９８．７面積％に相当する成分であることがわかった。また、この粉体中にはレゾルシンが０．２重量％含まれていた。構造解析の結果、粉体中の主成分はセバシン酸ビス（３−ヒドロキシフェニル）エステルである事が判った。
(Example 5)
While maintaining a solution obtained by dissolving 330.3 g (3.0 mol) of resorcin in 303.7 g of pyridine on an ice bath at 15 ° C. or lower, 71.7 g (0.3 mol) of sebacic acid dichloride was gradually added dropwise thereto. After completion of the dropping, the resulting reaction mixture was warmed to room temperature and allowed to stand for one day to complete the reaction. From the reaction mixture, pyridine was distilled off under reduced pressure, 250 g of water was added to the residue, and the mixture was cooled with ice to precipitate. The deposited precipitate was filtered and washed with water, and the obtained wet body was dried under reduced pressure to obtain 102.8 g of a white to pale yellow powder. As a result of HPLC analysis, it was found that the main component of the powder was a component corresponding to 98.7 area%. The powder contained 0.2% by weight of resorcin. As a result of structural analysis, it was found that the main component in the powder was sebacic acid bis (3-hydroxyphenyl) ester.
尚、セバシン酸ビス（３−ヒドロキシフェニル）エステルの同定データは下記の通りである。
ＭＳスペクトルデータ
ＥＩ(Pos.) ｍ／ｚ＝３８６
ＩＲスペクトルデータ
３３８０ｃｍ−１ ： 水酸基
３０００〜２８００ｃｍ−１ ： 長鎖アルキル
１７３２、１７４９ｃｍ−１ ： エステル
ＮＭＲスペクトルデータを表３−１および表３−２に示した。
The identification data of sebacic acid bis (3-hydroxyphenyl) ester is as follows.
MS spectrum data EI (Pos.) M / z = 386
IR spectrum data 3380 cm-1: hydroxyl group 3000-2800 cm-1: long chain alkyl 1732, 1749 cm-1: ester NMR spectrum data are shown in Table 3-1 and Table 3-2.
（参考例１〜５）
実施例１〜５で製造した組成物を供試化合物として２２００ｍＬのバンバリーミキサーを使用して、表４に示すゴム配合処方で混練り混合して、未加硫のゴム組成物を調製し、以下の方法で耐ブルーム性、ムーニー粘度、配合直後の接着性及び、配合ゴム放置後の接着性を測定、評価した。結果を表４に示す。
(Reference Examples 1-5)
Using a 2200 mL Banbury mixer with the compositions produced in Examples 1 to 5 as test compounds, kneading and mixing with the rubber compounding formulation shown in Table 4 to prepare an unvulcanized rubber composition, In this way, bloom resistance, Mooney viscosity, adhesiveness immediately after compounding, and adhesiveness after leaving the compounded rubber were measured and evaluated. The results are shown in Table 4.
（耐ブルーム性）
未加硫のゴム組成物を４０℃で７日間貯蔵した後、配合剤がゴム表面に析出したか否かを目視で確認し、○、△、×で判定した。
○：表面に配合剤が析出していない
△：一部に析出
×：全面に配合剤が析出
(Broom resistance)
After storing the unvulcanized rubber composition at 40 ° C. for 7 days, whether or not the compounding agent was deposited on the rubber surface was visually confirmed, and judged by ○, Δ, and ×.
○: No compounding agent is deposited on the surface Δ: Partly deposited ×: The compounding agent is deposited on the entire surface
（ムーニー粘度）
未加硫のゴム組成物をＪＩＳ Ｋ６３００−２００１に準拠して、ML(1＋4)130℃を測定した。結果は数値が低い程良好であることを示す。
(Mooney viscosity)
The unvulcanized rubber composition was measured for ML (1 + 4) 130 ° C. according to JIS K6300-2001. A result shows that it is so favorable that a numerical value is low.
（接着試験）
黄銅（Ｃｕ；６３質量％、Ｚｎ；３７質量％）メッキしたスチールコード(１×５構造、素線径０．２５mm)を１２．５mm間隔で平行に並べ、このスチールコードを上下両側から各ゴム組成物でコーティングして、これを直ちに１６０℃×１５分の条件で加硫し、幅１２．５mmのサンプルを作製した。下記の各接着性に対してＡＳＴＭ−Ｄ−２２２９に準拠して、各サンプルに対してスチールコードを引き抜き、ゴムの被覆状態を目視で観察して、０〜１００％で表示し、各接着性の指標とした。数値が大きい程良好であることを示す。初期接着性は前記加硫の直後に測定した。湿熱接着性は前記加硫後、７０℃、湿度１００％ＲＨ、４日の湿熱条件下で老化させた後に測定した。
(Adhesion test)
Steel cords (1x5 structure, strand diameter 0.25mm) plated with brass (Cu; 63% by mass, Zn: 37% by mass) are arranged in parallel at 12.5mm intervals. After coating with the composition, this was immediately vulcanized under conditions of 160 ° C. × 15 minutes to prepare a sample having a width of 12.5 mm. In accordance with ASTM-D-2229 for each of the following adhesive properties, a steel cord is pulled out from each sample, and the state of rubber coating is visually observed and displayed at 0 to 100%. It was used as an index. It shows that it is so favorable that a numerical value is large. Initial adhesion was measured immediately after the vulcanization. The wet heat adhesiveness was measured after aging, after aging at 70 ° C., 100% RH, 4 days of wet heat conditions.
（接着安定性試験）
前記スチールコードを上下両側から各ゴム組成物でコーティングした未加硫状態のスチールコード−ゴム複合体を、４０℃×８０ＲＨ％の恒温恒湿槽に７日間放置後、１６０℃×１５分間加硫して、初期接着性を測定し、接着安定性の指標とした。
(Adhesion stability test)
The steel cord-rubber composite in an unvulcanized state in which the steel cord is coated with each rubber composition from the upper and lower sides is left in a constant temperature and humidity bath of 40 ° C. × 80 RH% for 7 days, and then vulcanized at 160 ° C. for 15 minutes. Then, initial adhesiveness was measured and used as an index of adhesive stability.
（比較例１）
供試化合物として本発明の組成物を使用しない以外は参考例と同様に配合してゴム組成物を調製し、評価した。結果を表４に示す。
(Comparative Example 1)
A rubber composition was prepared and evaluated in the same manner as in the Reference Example except that the composition of the present invention was not used as a test compound. The results are shown in Table 4.
（比較例２）
供試化合物としてレゾルシンをゴム基本配合に２質量部配合する以外は参考例と同様に配合してゴム組成物を調製し、評価した。結果を表４に示す。
(Comparative Example 2)
A rubber composition was prepared and evaluated in the same manner as in the Reference Example except that resorcin as a test compound was mixed in 2 parts by mass in the basic rubber compound. The results are shown in Table 4.
（比較例３）
供試化合物としてＲＦ樹脂をゴム基本配合に２質量部配合する以外は参考例と同様に配合してゴム組成物を調製し、評価した。結果を表４に示す。なお、ＲＦ樹脂は下記の方法で製造した。
(Comparative Example 3)
A rubber composition was prepared and evaluated in the same manner as in the Reference Example except that 2 parts by mass of RF resin was added to the basic rubber compound as a test compound. The results are shown in Table 4. In addition, RF resin was manufactured with the following method.
まず、水１１００ｇ、レゾルシン１１００ｇ（１０ｍｏｌ）、ｐ−トルエンスルホン酸１．７２ｇ（１０ｍｍｏｌ）を冷却管、攪拌装置、温度計、滴下ロート、窒素導入管を備えた４つ口フラスコに仕込み、７０℃まで昇温した。３７％ホルマリン溶液を４７７ｇ（５．９ｍｏｌ）を２時間かけて滴下し、そのままの温度で５時間保持し、反応を完結させた。反応終了後、１０％水酸化ナトリウム水溶液を４ｇ加え中和した後、冷却器をディーンスターク型還流器に変え、水を留去しながら１５０℃まで昇温し、更に２０ｍｍＨｇの減圧下で１時間かけて水を除去し、ＲＦ樹脂を得た。得られたＲＦ樹脂の軟化点は１２４℃、残存レゾルシン量は１７％であった。 First, 1100 g of water, 1100 g (10 mol) of resorcin, and 1.72 g (10 mmol) of p-toluenesulfonic acid were charged into a four-necked flask equipped with a cooling tube, a stirrer, a thermometer, a dropping funnel, and a nitrogen introducing tube, and 70 ° C. The temperature was raised to. 477 g (5.9 mol) of 37% formalin solution was added dropwise over 2 hours, and kept at the same temperature for 5 hours to complete the reaction. After the completion of the reaction, 4 g of 10% aqueous sodium hydroxide solution was added to neutralize, and then the condenser was changed to a Dean-Stark type refluxing device. The temperature was raised to 150 ° C. while distilling off water, and further under reduced pressure of 20 mmHg for 1 hour. Water was removed to obtain an RF resin. The obtained RF resin had a softening point of 124 ° C. and a residual resorcin content of 17%.
（比較例４）
供試化合物として特開平７−１１８６２１号公報記載の混合ポリエステルをゴム基本配合に２質量部配合する以外は実施例と同様に配合してゴム組成物を調製し、評価した。結果を表４に示す。尚、混合ポリエステルは上記特許記載の実施例１に準じて合成した。
(Comparative Example 4)
A rubber composition was prepared and evaluated in the same manner as in the examples except that 2 parts by mass of the mixed polyester described in JP-A-7-118621 as a test compound was mixed in the basic rubber compound. The results are shown in Table 4. The mixed polyester was synthesized according to Example 1 described in the above patent.
還流冷却器および温度計を備えた３００ｍｌの４つ口フラスコに、レゾルシン１０８．９ｇ(0.99mol)、アジピン酸１３１．４ｇ（0.90mol）、無水酢酸２２２．０ｇ（2.175mol）およびピリジン０．５４ｇ（レゾルシンに対して０．５重量％）を仕込み、窒素置換後、室温で１５分攪拌し、その後１００℃に昇温して同温度で２ｈｒアセチル化を行なった。その後、副生する酢酸を系外に留去しながら昇温し１４０℃で１ｈｒ、さらに昇温し２４０℃で２ｈｒ熟成した。次いで、減圧下（５０ｍｍＨｇ）２４０℃で熟成を続けた。反応混合物を磁性皿に排出し、黄土色のあめ状物１９５．６ｇを得た。ガラス棒で練る事で徐々に結晶化した。分析の結果、レゾルシンを０．１重量％、レゾルシンモノアセテートを０．５重量％、レゾルシンジアセテートを０．８重量％含んでいた。また、ＧＰＣにて分子量を測定した結果、重量平均分子量は約３００００（ＰＳ換算）であった。 A 300 ml four-necked flask equipped with a reflux condenser and a thermometer was charged with 108.9 g (0.99 mol) of resorcin, 131.4 g (0.90 mol) of adipic acid, 222.0 g (2.175 mol) of acetic anhydride and 0.54 g of pyridine. (0.5% by weight based on resorcin) was charged, and after substitution with nitrogen, the mixture was stirred at room temperature for 15 minutes, then heated to 100 ° C. and subjected to 2 hr acetylation at the same temperature. Thereafter, the temperature was raised while distilling acetic acid produced as a by-product out of the system, and the mixture was further aged at 140 ° C. for 1 hr and further at 240 ° C. for 2 hr. Next, aging was continued at 240 ° C. under reduced pressure (50 mmHg). The reaction mixture was discharged into a magnetic dish to obtain 195.6 g of an ocher candy. It gradually crystallized by kneading with a glass rod. As a result of the analysis, it contained 0.1% by weight of resorcin, 0.5% by weight of resorcin monoacetate, and 0.8% by weight of resorcin diacetate. Moreover, as a result of measuring molecular weight by GPC, the weight average molecular weight was about 30000 (PS conversion).
Claims (6)
（式中、Ｒは炭素数１〜１６の２価の脂肪族基を表す。） A compound represented by the following general formula (2) .
(In the formula, R represents a divalent aliphatic group having 1 to 16 carbon atoms.)
The compound represented by the general formula (2) is represented by 60 to 100% by weight, represented by the following general formula (3), and the compound of n = 2 is represented by 0 to 20% by weight, represented by the following general formula (3) and A composition in which 0 to 10% by weight of a compound of n = 3 and the following general formula (3) and a total of 0 to 10% by weight of compounds of n = 4 to 6 (provided that the composition is It does not include a pure substance in which the compound represented by the general formula (2) is 100% by weight) .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005069771A JP4866009B2 (en) | 2004-03-12 | 2005-03-11 | Compound and composition containing the same |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004070791 | 2004-03-12 | ||
| JP2004070791 | 2004-03-12 | ||
| WOPCT/JP2005/003899 | 2005-03-07 | ||
| PCT/JP2005/003899 WO2005087704A1 (en) | 2004-03-12 | 2005-03-07 | Compound and composition containing the same |
| JP2005069771A JP4866009B2 (en) | 2004-03-12 | 2005-03-11 | Compound and composition containing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005289989A JP2005289989A (en) | 2005-10-20 |
| JP4866009B2 true JP4866009B2 (en) | 2012-02-01 |
Family
ID=35323326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005069771A Active JP4866009B2 (en) | 2004-03-12 | 2005-03-11 | Compound and composition containing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4866009B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5037907B2 (en) * | 2006-11-16 | 2012-10-03 | 三井化学株式会社 | Method for producing resorcin diester compound |
| JP5000986B2 (en) * | 2006-11-16 | 2012-08-15 | 三井化学株式会社 | Method for producing dihydroxybenzene derivative |
| JP5037984B2 (en) * | 2007-03-27 | 2012-10-03 | 三井化学株式会社 | Method for producing resorcin diester compound |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5290307A (en) * | 1976-01-26 | 1977-07-29 | Canon Kk | Thermoodeveloping photoosensitive material for electrostatic printing master |
| US4446216A (en) * | 1981-12-10 | 1984-05-01 | Smith Norman A | Photographic material |
| JPH0676583B2 (en) * | 1987-05-18 | 1994-09-28 | キヤノン株式会社 | Liquid crystal composition and liquid crystal element |
| JPH07118621A (en) * | 1993-10-19 | 1995-05-09 | Sumitomo Chem Co Ltd | Adhesive and its application to rubber |
| JP4571263B2 (en) * | 2000-02-25 | 2010-10-27 | 株式会社ブリヂストン | Adhesive rubber composition |
| JP4833436B2 (en) * | 2001-05-17 | 2011-12-07 | 東洋ゴム工業株式会社 | Rubber composition for covering tire cord |
| JP4863629B2 (en) * | 2004-03-12 | 2012-01-25 | 株式会社ブリヂストン | Rubber composition and pneumatic tire using the same |
-
2005
- 2005-03-11 JP JP2005069771A patent/JP4866009B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005289989A (en) | 2005-10-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4842145B2 (en) | Pneumatic tire | |
| JP4863629B2 (en) | Rubber composition and pneumatic tire using the same | |
| US9464183B2 (en) | Rubber composition and pneumatic tire using the same | |
| FR3067713A1 (en) | BENZOXAZINE SULFURIZED FOR USE IN THE SYNTHESIS OF A POLYBENZOXAZINE | |
| JP4866009B2 (en) | Compound and composition containing the same | |
| FR3067714A1 (en) | SULFURIZED POLYBENZOXAZINE FOR METAL COATING AND RUBBER COLLAGE | |
| EP1724252B1 (en) | Compound and composition containing the same | |
| JP5252799B2 (en) | Hydroxybenzene derivative and method for producing the same | |
| JP5553545B2 (en) | Rubber composition | |
| JP5200908B2 (en) | Method for producing polyester resin composition | |
| JP5265108B2 (en) | Rubber composition | |
| JP2007084706A (en) | Rubber composition | |
| JP5094003B2 (en) | Rubber composition for metal reinforcement and adhesion improver between rubber and metal reinforcement | |
| JP5000986B2 (en) | Method for producing dihydroxybenzene derivative | |
| JP5037907B2 (en) | Method for producing resorcin diester compound | |
| US8222446B2 (en) | Method for producing dihydroxybenzene derivative | |
| JP2011012164A (en) | Pneumatic tire | |
| JP5239684B2 (en) | Method for producing polyester resin composition | |
| JP6316455B2 (en) | Polyurethane resin composition and polyurethane resin molded article | |
| JP5203619B2 (en) | Method for producing resorcin-based diester compound | |
| EP0426144B1 (en) | Organic sulfide antioxidants | |
| JP2008138117A (en) | Pneumatic tire | |
| CN100480316C (en) | Rubber composition and pneumatic tire using the same | |
| JP2007084712A (en) | Pneumatic tire | |
| KR101643802B1 (en) | Sucrose aromatic monocarboxylic acid ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20060609 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070711 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20070711 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070720 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20070720 |
|
| RD04 | Notification of resignation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7424 Effective date: 20100312 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100720 |
|
| A256 | Written notification of co-pending application filed on the same date by different applicants |
Free format text: JAPANESE INTERMEDIATE CODE: A2516 Effective date: 20100720 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100917 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20110802 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110916 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20111108 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20111111 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20141118 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4866009 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |