JP5705685B2 - Liquid air freshener composition for spraying - Google Patents
Liquid air freshener composition for spraying Download PDFInfo
- Publication number
- JP5705685B2 JP5705685B2 JP2011184638A JP2011184638A JP5705685B2 JP 5705685 B2 JP5705685 B2 JP 5705685B2 JP 2011184638 A JP2011184638 A JP 2011184638A JP 2011184638 A JP2011184638 A JP 2011184638A JP 5705685 B2 JP5705685 B2 JP 5705685B2
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- carbon atoms
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- spraying
- composition
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- 239000000203 mixture Substances 0.000 title claims description 87
- 239000007788 liquid Substances 0.000 title claims description 58
- 238000005507 spraying Methods 0.000 title claims description 57
- 239000002386 air freshener Substances 0.000 title claims description 4
- 239000003205 fragrance Substances 0.000 claims description 101
- 125000004432 carbon atom Chemical group C* 0.000 claims description 64
- -1 Silicate ester Chemical class 0.000 claims description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000007921 spray Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 239000002304 perfume Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 5
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000010494 dissociation reaction Methods 0.000 claims description 4
- 230000005593 dissociations Effects 0.000 claims description 4
- 239000000796 flavoring agent Substances 0.000 claims description 4
- 235000019634 flavors Nutrition 0.000 claims description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 239000004744 fabric Substances 0.000 description 30
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000012086 standard solution Substances 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 230000002085 persistent effect Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229920000742 Cotton Polymers 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000004753 textile Substances 0.000 description 11
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 238000003860 storage Methods 0.000 description 8
- 239000005792 Geraniol Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229940113087 geraniol Drugs 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 235000000484 citronellol Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 238000001139 pH measurement Methods 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 230000002688 persistence Effects 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OIYVLSMPJCJTEX-UHFFFAOYSA-N tetrakis(2-phenylethyl) silicate Chemical compound C=1C=CC=CC=1CCO[Si](OCCC=1C=CC=CC=1)(OCCC=1C=CC=CC=1)OCCC1=CC=CC=C1 OIYVLSMPJCJTEX-UHFFFAOYSA-N 0.000 description 3
- UXPNNKCIEHKAAV-NISPWTRESA-N tetrakis[(2e)-3,7-dimethylocta-2,6-dienyl] silicate Chemical compound CC(C)=CCC\C(C)=C\CO[Si](OC\C=C(/C)CCC=C(C)C)(OC\C=C(/C)CCC=C(C)C)OC\C=C(/C)CCC=C(C)C UXPNNKCIEHKAAV-NISPWTRESA-N 0.000 description 3
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- PRNCMAKCNVRZFX-UHFFFAOYSA-N 3,7-dimethyloctan-1-ol Chemical compound CC(C)CCCC(C)CCO PRNCMAKCNVRZFX-UHFFFAOYSA-N 0.000 description 2
- KQROHCSYOGBQGJ-UHFFFAOYSA-N 5-Hydroxytryptophol Chemical compound C1=C(O)C=C2C(CCO)=CNC2=C1 KQROHCSYOGBQGJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000002781 deodorant agent Substances 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229940067107 phenylethyl alcohol Drugs 0.000 description 2
- 229920006298 saran Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- NOOLISFMXDJSKH-KXUCPTDWSA-N (-)-Menthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1O NOOLISFMXDJSKH-KXUCPTDWSA-N 0.000 description 1
- KHWTYGFHPHRQMP-UHFFFAOYSA-N (4-propan-2-ylcyclohexyl)methanol Chemical compound CC(C)C1CCC(CO)CC1 KHWTYGFHPHRQMP-UHFFFAOYSA-N 0.000 description 1
- QLRNLHNEZFMRSR-SOFGYWHQSA-N (4e)-3,7-dimethylocta-4,6-dien-3-ol Chemical compound CCC(C)(O)\C=C\C=C(C)C QLRNLHNEZFMRSR-SOFGYWHQSA-N 0.000 description 1
- KHQDWCKZXLWDNM-KPKJPENVSA-N (e)-2-ethyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)but-2-en-1-ol Chemical compound CC\C(CO)=C/CC1CC=C(C)C1(C)C KHQDWCKZXLWDNM-KPKJPENVSA-N 0.000 description 1
- MTVBNJVZZAQKRV-BJMVGYQFSA-N (e)-2-methyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)but-2-en-1-ol Chemical compound OCC(/C)=C/CC1CC=C(C)C1(C)C MTVBNJVZZAQKRV-BJMVGYQFSA-N 0.000 description 1
- WSTQLNQRVZNEDV-CSKARUKUSA-N (e)-4-methyldec-3-en-5-ol Chemical compound CCCCCC(O)C(\C)=C\CC WSTQLNQRVZNEDV-CSKARUKUSA-N 0.000 description 1
- NEHPIUGJDUWSRR-UHFFFAOYSA-N 1-(4-propan-2-ylcyclohexyl)ethanol Chemical compound CC(C)C1CCC(C(C)O)CC1 NEHPIUGJDUWSRR-UHFFFAOYSA-N 0.000 description 1
- YIJOZSCZCHDKAT-UHFFFAOYSA-N 1-aminopentane-1,3,5-triol Chemical compound NC(O)CC(O)CCO YIJOZSCZCHDKAT-UHFFFAOYSA-N 0.000 description 1
- GIEMHYCMBGELGY-UHFFFAOYSA-N 10-undecen-1-ol Chemical compound OCCCCCCCCCC=C GIEMHYCMBGELGY-UHFFFAOYSA-N 0.000 description 1
- XSNQECSCDATQEL-SECBINFHSA-N 2,6-dimethyl-7-octen-2-ol Chemical compound C=C[C@@H](C)CCCC(C)(C)O XSNQECSCDATQEL-SECBINFHSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- IOAOAKDONABGPZ-UHFFFAOYSA-N 2-amino-2-ethylpropane-1,3-diol Chemical compound CCC(N)(CO)CO IOAOAKDONABGPZ-UHFFFAOYSA-N 0.000 description 1
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- KJJPLEZQSCZCKE-UHFFFAOYSA-N 2-aminopropane-1,3-diol Chemical compound OCC(N)CO KJJPLEZQSCZCKE-UHFFFAOYSA-N 0.000 description 1
- RADIRXJQODWKGQ-UHFFFAOYSA-N 2-ethoxy-5-prop-1-enylphenol Chemical compound CCOC1=CC=C(C=CC)C=C1O RADIRXJQODWKGQ-UHFFFAOYSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- CYVGAJHMMVDTDZ-UHFFFAOYSA-N 2-methyl-4-(2,2,3-trimethylcyclopent-3-en-1-yl)butan-1-ol Chemical compound OCC(C)CCC1CC=C(C)C1(C)C CYVGAJHMMVDTDZ-UHFFFAOYSA-N 0.000 description 1
- DLHQZZUEERVIGQ-UHFFFAOYSA-N 3,7-dimethyl-3-octanol Chemical compound CCC(C)(O)CCCC(C)C DLHQZZUEERVIGQ-UHFFFAOYSA-N 0.000 description 1
- AEJRTNBCFUOSEM-UHFFFAOYSA-N 3-Methyl-1-phenyl-3-pentanol Chemical compound CCC(C)(O)CCC1=CC=CC=C1 AEJRTNBCFUOSEM-UHFFFAOYSA-N 0.000 description 1
- NGYMOTOXXHCHOC-UHFFFAOYSA-N 3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)pentan-2-ol Chemical compound CC(O)C(C)CCC1CC=C(C)C1(C)C NGYMOTOXXHCHOC-UHFFFAOYSA-N 0.000 description 1
- OXYRENDGHPGWKV-UHFFFAOYSA-N 3-methyl-5-phenylpentan-1-ol Chemical compound OCCC(C)CCC1=CC=CC=C1 OXYRENDGHPGWKV-UHFFFAOYSA-N 0.000 description 1
- HACQKMWYOKGLET-UHFFFAOYSA-N 4-amino-4-(3-hydroxypropyl)heptane-1,7-diol Chemical compound OCCCC(N)(CCCO)CCCO HACQKMWYOKGLET-UHFFFAOYSA-N 0.000 description 1
- YXVSKJDFNJFXAJ-UHFFFAOYSA-N 4-cyclohexyl-2-methylbutan-2-ol Chemical compound CC(C)(O)CCC1=CC=CC=C1 YXVSKJDFNJFXAJ-UHFFFAOYSA-N 0.000 description 1
- WRYLYDPHFGVWKC-UHFFFAOYSA-N 4-terpineol Chemical compound CC(C)C1(O)CCC(C)=CC1 WRYLYDPHFGVWKC-UHFFFAOYSA-N 0.000 description 1
- NGSJNQJPYFYNJV-UHFFFAOYSA-N 5-methyl-2-propylphenol Chemical compound CCCC1=CC=C(C)C=C1O NGSJNQJPYFYNJV-UHFFFAOYSA-N 0.000 description 1
- QGFSQVPRCWJZQK-UHFFFAOYSA-N 9-Decen-1-ol Chemical compound OCCCCCCCCC=C QGFSQVPRCWJZQK-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-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
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- RECUKUPTGUEGMW-UHFFFAOYSA-N carvacrol Chemical compound CC(C)C1=CC=C(C)C(O)=C1 RECUKUPTGUEGMW-UHFFFAOYSA-N 0.000 description 1
- HHTWOMMSBMNRKP-UHFFFAOYSA-N carvacrol Natural products CC(=C)C1=CC=C(C)C(O)=C1 HHTWOMMSBMNRKP-UHFFFAOYSA-N 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- CZVXBFUKBZRMKR-UHFFFAOYSA-N lavandulol Chemical compound CC(C)=CCC(CO)C(C)=C CZVXBFUKBZRMKR-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 210000004914 menses Anatomy 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 229930007501 p-menthan-3-ol Natural products 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 235000019629 palatability Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000012487 rinsing solution Substances 0.000 description 1
- 229930004725 sesquiterpene Natural products 0.000 description 1
- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- BJIOGJUNALELMI-ONEGZZNKSA-N trans-isoeugenol Chemical compound COC1=CC(\C=C\C)=CC=C1O BJIOGJUNALELMI-ONEGZZNKSA-N 0.000 description 1
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Description
本発明は、噴霧用液体芳香剤組成物、及びスプレー式芳香剤物品に関する。 The present invention relates to a liquid fragrance composition for spraying and a spray fragrance article.
従来から、自分の香りを周りにアピールする為に、身体に適用する香水が用いられてきた。近年、身体に適用する香水のみならず、着用したり使用する衣類から、自分が気に入った香りを香らせ、自らを周囲にアピールする行動が増えてきている。それに伴い、トイレタリーメーカー各社から、衣類に種々の香りを付与し、香りの持続性に優れる柔軟剤組成物が販売されている。また、居住空間にも香りを香らせる置型の芳香剤や、スプレーで噴霧する芳香剤の市場も大きくなってきている。 Traditionally, perfumes applied to the body have been used to appeal their fragrance to others. In recent years, not only the perfume applied to the body but also the clothes that are worn and used have been scented by the scents that they like and appealed to the surroundings. Along with this, softener compositions that give various scents to clothing and have excellent scent sustainability are sold by toiletry manufacturers. In addition, the market for stationary fragrances that give scents to living spaces and fragrances that are sprayed with sprays is also increasing.
特許文献１及び２には、加水分解により香料アルコールを放出するケイ酸エステルを、繊維製品に付着させることで、衣類からの香りの持続性を向上させる技術が開示されている。特許文献３には、特定の構造を有するヒドロキシアミンを含有する組成物を、臭いを発する衣類に付着させることで、優れた消臭効果を有する消臭剤組成物が開示されている。 Patent Documents 1 and 2 disclose a technique for improving the sustainability of a scent from clothing by attaching a silicate ester that releases perfume alcohol by hydrolysis to a textile product. Patent Document 3 discloses a deodorant composition having an excellent deodorizing effect by attaching a composition containing a hydroxyamine having a specific structure to a garment that emits a smell.
特許文献１又は２に記載のケイ酸エステルを含む組成物を、衣類に付着させることで、衣類から香るほのかな香りが長期間持続することが知られている。しかし、乾燥後の衣類から香る香りの強さを、より持続的に発現させる事が望まれている。これらの組成物では、乾燥後の衣類から香る香りを持続的に強くするために、衣類に付着させるケイ酸エステルを増加させると、衣類に付着させた後、乾燥途中の湿潤した衣類から香る香りが強くなりすぎてしまい、消費者によっては好まれない場合がある。本発明者らの検討の結果、特許文献１や２の組成物よりも、乾燥途中の湿潤した衣類から香る香りを強すぎない程度に抑え、且つ特に乾燥後の衣類から、持続的に強い香りを発生させることが出来る液体芳香剤組成物を消費者に提案することで、消費者の嗜好性がより高まることを見出した。また、特許文献３は消臭剤組成物に関するものであり、比較的強い香りを持続的に発現させるという、芳香剤としての課題については言及していない。 It is known that a faint fragrance scented from clothing persists for a long period of time by attaching the composition containing the silicate ester described in Patent Document 1 or 2 to the clothing. However, it is desired that the intensity of the fragrance scented from the dried clothes is expressed more continuously. In these compositions, in order to continually strengthen the fragrance from the dried clothing, increasing the amount of silicate ester attached to the clothing will cause the fragrance from the wet clothing during drying to adhere to the clothing. May become too strong and may not be preferred by some consumers. As a result of the study by the present inventors, the fragrance from the wet clothing in the middle of drying is suppressed to a level that is not too strong as compared with the compositions of Patent Documents 1 and 2, and the strong fragrance is particularly strong from the dried clothing. It has been found that the consumer's palatability is further improved by proposing to consumers a liquid fragrance composition that can generate odor. Moreover, patent document 3 is related with a deodorant composition, and does not mention the subject as a fragrance | flavor of expressing a comparatively strong fragrance continuously.
本発明の課題は、衣類等の対象物に液体芳香剤組成物を噴霧により付着させた後、乾燥途中の湿潤状態の衣類等の対象物から香る香りの強さが抑制され、乾燥後の衣類等の対象物に持続的な強い香りを付与できる噴霧用液体芳香剤組成物及びこれを用いたスプレー式芳香剤物品を提供することにある。 An object of the present invention is to apply a liquid fragrance composition to an object such as clothing by spraying, and then to suppress the intensity of a fragrance from the object such as wet clothing in the middle of drying, so that the clothing after drying It is an object to provide a liquid fragrance composition for spraying that can impart a persistent strong scent to an object such as the above, and a spray-type fragrance article using the same.
本発明は、下記（ａ）成分、（ｂ）成分及び水を含有し、２５℃におけるｐＨが６．５〜８．５である噴霧用液体芳香剤組成物に関する。
（ａ）成分：下記一般式（ａ１）で表されるケイ酸エステル
The present invention relates to a liquid fragrance composition for spraying containing the following component (a), component (b), and water, and having a pH of 6.5 to 8.5 at 25 ° C.
(A) Component: Silicate ester represented by the following general formula (a1)
〔式中、Ｘは−ＯＨ、−Ｒ1a、−ＯＲ2a又は−ＯＲ3aであり、ＹはＸ又は−ＯＳｉ（Ｘ）3であり、Ｒ1aは炭素数１〜２２の炭化水素基、Ｒ2aは分子内に炭素数６〜２２の炭素原子を有する香料アルコールからヒドロキシ基を１つ除いた残基、Ｒ3aは炭素数１〜５の炭化水素基又はベンジル基、ｎは０〜５の数である。複数個のＸ及びＹはそれぞれ同一でも異なっていても良いが、一分子中に−ＯＲ2aを少なくとも１つ有する。〕
（ｂ）成分：下記一般式（ｂ１）で表される化合物、ジエタノールアミン及びトリエタノールアミンから選ばれる、少なくとも１種のｐＫａが７．０〜９．０のヒドロキシアミン化合物並びに該ヒドロキシアミン化合物の塩から選ばれる化合物
[Wherein, X is —OH, —R 1a , —OR 2a or —OR 3a , Y is X or —OSi (X) 3 , R 1a is a hydrocarbon group having 1 to 22 carbon atoms, R 2a is a residue obtained by removing one hydroxy group from a perfume alcohol having 6 to 22 carbon atoms in the molecule, R 3a is a hydrocarbon group or benzyl group having 1 to 5 carbon atoms, and n is 0 to 5 Is a number. The plurality of X and Y may be the same or different, but have at least one —OR 2a in one molecule. ]
(B) Component: a compound represented by the following general formula (b1), at least one hydroxyamine compound selected from diethanolamine and triethanolamine and having a pKa of 7.0 to 9.0, and a salt of the hydroxyamine compound Compound selected from
〔式中、Ｒ1bは、水素原子、炭素数１〜５のアルキル基、又は炭素数１〜５のヒドロキシアルキル基であり、Ｒ2bは、水素原子、炭素数１〜６のアルキル基、又は炭素数１〜５のヒドロキシアルキル基であり、Ｒ3b及びＲ4bは、炭素数１〜５のアルカンジイル基である。Ｒ3b及びＲ4bは、同一でも異なっていてもよい。上記Ｒ1b〜Ｒ4bの基の種類は、一般式（ｂ１）で表される化合物のｐＫａ（２５℃）が７．０〜９．０になるように選択される。〕 [Wherein, R 1b is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms, and R 2b is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or It is a C1-C5 hydroxyalkyl group, R <3b> and R <4b> are C1-C5 alkanediyl groups. R 3b and R 4b may be the same or different. The type of group R 1b to R 4b are, pKa of the compound represented by the general formula (b1) (25 ℃) is selected to be 7.0 to 9.0. ]
また、本発明は、上記本発明の噴霧用液体芳香剤組成物を、スプレー容器に充填してなる、スプレー式芳香剤物品に関する。 Moreover, this invention relates to the spray-type fragrance | flavor article | item formed by filling the spraying liquid fragrance composition of the said invention into the spray container.
本発明によれば、衣類等の対象物に持続的な強い香りを付与できる噴霧用液体芳香剤組成物及びこれを用いたスプレー式芳香剤物品が提供される。本発明の噴霧用液体芳香剤組成物が適用された衣類等の対象物は、噴霧用液体芳香剤組成物が噴霧に適用された後の湿潤状態での衣類等の対象物から香る香りが抑制される一方、乾燥後の衣類等の対象物から香る初期の香り立ちがよく、しかも、保管中ないし保管後も香りが持続する。 ADVANTAGE OF THE INVENTION According to this invention, the liquid fragrance composition for spraying which can provide persistent strong fragrance to objects, such as clothing, and the spray-type fragrance | flavor article using the same are provided. An object such as clothing to which the liquid fragrance composition for spraying of the present invention is applied is suppressed in a fragrance from the object such as clothing in a wet state after the liquid fragrance composition for spraying is applied to spraying. On the other hand, the initial fragrance from the object such as clothes after drying is good, and the fragrance persists during or after storage.
本発明の効果が発現する作用機構は必ずしも明らかではないが、本発明者らは次のように考えている。特定のｐＫａを有するヒドロキシアミン化合物及び該ヒドロキシアミン化合物の塩から選ばれる化合物、ケイ酸エステル及び水を含有し、特定のｐＨを有する本発明の噴霧用液体芳香剤組成物が、衣類等の対象物に噴霧され付着した後、噴霧用液体芳香剤組成物中の水が揮発し乾燥する。その際、前記の特定のｐＫａを有するヒドロキシアミン化合物及び該ヒドロキシアミン化合物の塩から選ばれる化合物が、湿潤状態から乾燥状態に移行する過程でのケイ酸エステルの加水分解を抑制しているものと考えている。 The mechanism of action by which the effects of the present invention are manifested is not necessarily clear, but the present inventors consider as follows. The liquid fragrance composition for spraying of the present invention containing a hydroxyamine compound having a specific pKa and a salt selected from the hydroxyamine compound, a silicate ester, and water and having a specific pH is suitable for clothing and the like. After spraying and adhering to the product, the water in the liquid fragrance composition for spraying volatilizes and dries. At that time, the compound selected from the hydroxyamine compound having the specific pKa and the salt of the hydroxyamine compound suppresses hydrolysis of the silicate ester in the process of shifting from the wet state to the dry state. thinking.
本発明者らが考える作用機構によれば、本発明の液体芳香剤組成物が噴霧用であることに意味を有する。即ち、本発明の噴霧用液体芳香剤組成物が、衣類等の対象物に噴霧より付着された後、ケイ酸エステル並びに該ヒドロキシアミン化合物及び該ヒドロキシアミン化合物の塩から選ばれる化合物が共に水中で共存した状態で、水が揮発する過程で本発明の作用機構が発現すると考えられる。よって、例えば、衣類等の対象物の質量に対して通常５倍以上の水が存在する、洗濯工程の洗浄液中や濯ぎ液中に、本発明の噴霧用液体芳香剤組成物を適用しても、比較的疎水性が高いと考えられるケイ酸エステルは衣類等の対象物に付着するが、比較的親水性が高いと考えられる該ヒドロキシアミン化合物は、洗浄液中や濯ぎ液中に多く残り、脱水後の乾燥工程において、ケイ酸エステル並びに該ヒドロキシアミン化合物及び該ヒドロキシアミン化合物の塩から選ばれる化合物が共存しない状態で乾燥されるため、本発明の効果は得られにくいと考えられる。 According to the mechanism of action considered by the present inventors, it is meaningful that the liquid fragrance composition of the present invention is for spraying. That is, after the liquid fragrance composition for spraying of the present invention is attached to an object such as clothing by spraying, both the silicate ester and the compound selected from the hydroxyamine compound and the salt of the hydroxyamine compound are both in water. In the coexisting state, it is considered that the action mechanism of the present invention is expressed in the process of volatilization of water. Therefore, for example, even when the liquid air freshener composition for spraying of the present invention is applied to a washing liquid or a rinsing liquid in a washing process in which there is usually 5 times or more water relative to the mass of an object such as clothing. Silicate esters that are considered to be relatively hydrophobic adhere to objects such as clothes, but a large amount of the hydroxyamine compound, which is considered to be relatively hydrophilic, remains in the washing solution and the rinsing solution. In the subsequent drying step, the effect of the present invention is considered difficult to obtain because the silicate ester and the hydroxyamine compound and the compound selected from the salt of the hydroxyamine compound are dried in the absence of coexistence.
［（ａ）成分］
本発明の（ａ）成分は、下記一般式（ａ１）で表されるケイ酸エステルである。一般式（ａ１）で表されるケイ酸エステルは、１種又は２種以上が用いられる。
[(A) component]
The component (a) of the present invention is a silicate ester represented by the following general formula (a1). 1 type (s) or 2 or more types are used for the silicate ester represented by general formula (a1).
〔式中、Ｘは−ＯＨ、−Ｒ1a、−ＯＲ2a又は−ＯＲ3aであり、ＹはＸ又は−ＯＳｉ（Ｘ）3であり、Ｒ1aは炭素数１〜２２の炭化水素基、Ｒ2aは分子内に炭素数６〜２２の炭素原子を有する香料アルコールからヒドロキシ基を１つ除いた残基、Ｒ3aは炭素数１〜５の炭化水素基又はベンジル基、ｎは０〜５の数である。複数個のＸ及びＹはそれぞれ同一でも異なっていても良いが、一分子中に−ＯＲ2aを少なくとも１つ有する。〕 [Wherein, X is —OH, —R 1a , —OR 2a or —OR 3a , Y is X or —OSi (X) 3 , R 1a is a hydrocarbon group having 1 to 22 carbon atoms, R 2a is a residue obtained by removing one hydroxy group from a perfume alcohol having 6 to 22 carbon atoms in the molecule, R 3a is a hydrocarbon group or benzyl group having 1 to 5 carbon atoms, and n is 0 to 5 Is a number. The plurality of X and Y may be the same or different, but have at least one —OR 2a in one molecule. ]
Ｒ1aは置換基として炭素数１〜２２の脂肪族炭化水素基を示すが、製造の容易性の観点から、炭素数１〜２２の直鎖又は分岐鎖のアルキル基又はアルケニル基が好ましく、炭素数１〜１８の直鎖又は分岐鎖のアルキル基がより好ましい。ｎが０の場合には、組成物への配合の容易性の観点から、炭素数１〜８の炭化水素基がより好ましく、炭素数１〜３のアルキル基又はベンジル基が更に好ましい。また、ｎが１〜５の場合には、組成物への配合の容易性の観点から、メチル基又はベンジル基がより好ましく、メチル基が更に好ましい。 R 1a represents an aliphatic hydrocarbon group having 1 to 22 carbon atoms as a substituent, but from the viewpoint of ease of production, a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms is preferable, and carbon A linear or branched alkyl group having 1 to 18 is more preferable. When n is 0, a hydrocarbon group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 3 carbon atoms or a benzyl group is more preferable from the viewpoint of easy blending into the composition. Moreover, when n is 1-5, a methyl group or a benzyl group is more preferable from a viewpoint of the ease of the mixing | blending to a composition, and a methyl group is still more preferable.
Ｒ2aは、分子内に炭素数６〜２２の炭素原子を有する香料アルコールからヒドロキシ基を１つ除いた残基である。本明細書において香料アルコールとは、香料として用いられるアルコールを意味する。具体的な香料アルコールとしては、「香料と調香の基礎知識」（産業図書株式会社、中島基貴編著、２００５年４月２０日第４刷）に記載される、脂肪族アルコール、テルペン又はセスキテルペンアルコール、脂環式アルコール、芳香族アルコール及び合成サンダル（サンダルウッド様の香りを有する合成された香料アルコール）から選ばれる１種以上の化合物が挙げられる。 R 2a is a residue obtained by removing one hydroxy group from a perfume alcohol having 6 to 22 carbon atoms in the molecule. In this specification, the fragrance alcohol means an alcohol used as a fragrance. Specific examples of perfume alcohols include aliphatic alcohols, terpenes, and sesquiterpenes described in “Fundamental knowledge of perfumes and fragrances” (Sangyo Tosho Co., Ltd., edited by Motoki Nakajima, 4th edition, April 20, 2005). One or more compounds selected from alcohols, alicyclic alcohols, aromatic alcohols, and synthetic sandals (synthesized perfume alcohol having a sandalwood-like scent) can be used.
本発明における香りの強さとは、一般式（ａ１）の化合物が加水分解することで生成する、香料アルコール（Ｒ2aＯＨ）由来の香りの強さを意味する。 The strength of the scent in the present invention means the strength of the scent derived from the fragrance alcohol (R 2a OH) produced by hydrolysis of the compound of the general formula (a1).
本発明において、Ｒ2aは、分子内に炭素数６〜２２の炭素原子を有する香料アルコールからヒドロキシ基を１つ除いた残基である。衣類を保管した後の香りの強さを高める等、持続的な強い香りを発現させる観点から、Ｒ2aの由来となる、分子内に炭素数６〜２２の炭素原子を有する香料アルコール（Ｒ2aＯＨ）は、炭素数１０〜１４の香料アルコールが好ましく、より好ましくは炭素数１０〜１２の香料アルコールである。具体的には、炭素数１０〜１１の脂肪族アルコール、炭素数１０のテルペン系アルコール、炭素数１０の脂環式アルコール、炭素数１０〜１２の芳香族アルコール及び炭素数１３〜１４の合成サンダルから選ばれる香料アルコールが好ましい。 In the present invention, R 2a is a residue obtained by removing one hydroxy group from a perfume alcohol having 6 to 22 carbon atoms in the molecule. Like increasing the strength of the fragrance after storage clothing, from the viewpoint of expressing a sustained strong smell, the origin of R 2a, perfume alcohol (R 2a having carbon atoms of 6 to 22 carbon atoms in the molecule OH) is preferably a fragrance alcohol having 10 to 14 carbon atoms, and more preferably a fragrance alcohol having 10 to 12 carbon atoms. Specifically, an aliphatic alcohol having 10 to 11 carbon atoms, a terpene alcohol having 10 carbon atoms, an alicyclic alcohol having 10 carbon atoms, an aromatic alcohol having 10 to 12 carbon atoms, and a synthetic sandal having 13 to 14 carbon atoms A perfume alcohol selected from is preferred.
炭素数１０〜１１の脂肪族アルコールとしては、９−デセノール、４−メチル−３−デセン−５−オール又は１０−ウンデセノールが挙げられる。 Examples of the aliphatic alcohol having 10 to 11 carbon atoms include 9-decenol, 4-methyl-3-decen-5-ol, and 10-undecenol.
炭素数１０のテルペン系アルコールとしては、３，７−ジメチル−１，６−オクタジエン−３−オール、３，７−ジメチル−トランス−２，６−オクタジエン−１−オール、３，７−ジメチル−シス−２，６−オクタジエン−１−オール、３，７−ジメチル−６−オクテン−１−オール、２−メチル−６−メチレン−７−オクテン−２−オール、２−イソプロペニル−５−メチル−４−ヘキセン−１−オール、３，７−ジメチルオクタノール、３，７−ジメチルオクタン−３−オール、２，６−ジメチル−７−オクテン−２−オール、３，７−ジメチル−４，６−オクタジエン−３−オール、ｐ−メンタン−８−オール、１−ｐ−メンテン−４−オール、ｐ−メンタン−３−オール、１，７，７−トリメチル−ビシクロ［１，２，２−］ヘプタン−２−オール又はｐ−メンス−８−エン−３−オールが挙げられる。 Examples of the terpene alcohol having 10 carbon atoms include 3,7-dimethyl-1,6-octadien-3-ol, 3,7-dimethyl-trans-2,6-octadien-1-ol, and 3,7-dimethyl- Cis-2,6-octadien-1-ol, 3,7-dimethyl-6-octen-1-ol, 2-methyl-6-methylene-7-octen-2-ol, 2-isopropenyl-5-methyl -4-hexen-1-ol, 3,7-dimethyloctanol, 3,7-dimethyloctane-3-ol, 2,6-dimethyl-7-octen-2-ol, 3,7-dimethyl-4,6 -Octadien-3-ol, p-menthan-8-ol, 1-p-menthen-4-ol, p-menthan-3-ol, 1,7,7-trimethyl-bicyclo [1,2,2-] Hep Down 2-ol or p- menses 8-en-3-ol.
炭素数１０〜１２の脂環式アルコールとしては、４−イソプロピルシクロヘキサンメタノール、１−（４−イソプロピルシクロヘキシル）エタノール、ｐ−ｔ−ブチルシクロヘキサノール又はｏ−ｔ−ブチルシクロヘキサノールが挙げられる。 Examples of the alicyclic alcohol having 10 to 12 carbon atoms include 4-isopropylcyclohexanemethanol, 1- (4-isopropylcyclohexyl) ethanol, pt-butylcyclohexanol, and ot-butylcyclohexanol.
炭素数１０〜１２の芳香族アルコールとしては、１−フェニル−２−メチル−２−プロパノール、２−プロピル−５−メチルフェノール、２−メチル−５−イソプロピルフェノール、２−メトキシ−４−アリールフェノール、２−メトキシ−４−（１−プロペニル）−フェノール、４−フェニル−２−メチル−２−ブタノール、５−プロペニル−２−エトキシフェノール、１−フェニル−３−メチル−３−ペンタノール又は３−メチル−５−フェニル−１−ペンタノールが挙げられる。 Examples of the aromatic alcohol having 10 to 12 carbon atoms include 1-phenyl-2-methyl-2-propanol, 2-propyl-5-methylphenol, 2-methyl-5-isopropylphenol, and 2-methoxy-4-arylphenol. 2-methoxy-4- (1-propenyl) -phenol, 4-phenyl-2-methyl-2-butanol, 5-propenyl-2-ethoxyphenol, 1-phenyl-3-methyl-3-pentanol or 3 -Methyl-5-phenyl-1-pentanol.
炭素数１３〜１４の合成サンダルとしては、２−メチル−４−（２，２，３−トリメチル−３−シクロペンテン−１−イル）−２−ブテン−１−オール、２−メチル−４−（２，２，３−トリメチル−３−シクロペンテン−１−イル）−ブタン−１−オール、３−メチル−５−（２，２，３−トリメチル−３−シクロペンテン−１−イル）−ペンタン−２−オール又は２−エチル−４−（２，２，３−トリメチル−３−シクロペンテン−１−イル）−２−ブテン−１−オールが挙げられる。 Synthetic sandals having 13 to 14 carbon atoms include 2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol, 2-methyl-4- ( 2,2,3-trimethyl-3-cyclopenten-1-yl) -butan-1-ol, 3-methyl-5- (2,2,3-trimethyl-3-cyclopenten-1-yl) -pentane-2 -Ol or 2-ethyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol.
本発明において、持続的な強い香りを発現させる観点から、分子内に炭素数６〜２２の炭素原子を有する香料アルコールは、炭素数１０のテルペン系アルコール、炭素数１０〜１２の芳香族アルコール並びに炭素数１３〜１４の合成サンダルから選ばれる香料アルコールが好ましい。更に、炭素数１０のテルペン系アルコールが好ましい。 In the present invention, from the viewpoint of expressing a persistent strong fragrance, the fragrance alcohol having 6 to 22 carbon atoms in the molecule is a terpene alcohol having 10 carbon atoms, an aromatic alcohol having 10 to 12 carbon atoms, and A perfume alcohol selected from synthetic sandals having 13 to 14 carbon atoms is preferred. Furthermore, C10 terpene alcohol is preferable.
Ｒ3aは、ケイ酸エステルの製造の容易性の観点から、メチル基、エチル基又はベンジル基が好ましい。分子内にＲ3aが複数存在する場合には、各々のＲ3aは同一であっても異なっていても良い。 R 3a is preferably a methyl group, an ethyl group or a benzyl group from the viewpoint of ease of production of the silicate ester. When a plurality of R 3a are present in the molecule, each R 3a may be the same or different.
一般式（ａ１）において、ｎは０〜５の数であり、持続的な強い香りを発現させる観点から、０〜３の数が好ましく、０の数がより好ましい。 In the general formula (a1), n is a number from 0 to 5, and from the viewpoint of developing a persistent strong fragrance, a number from 0 to 3 is preferable, and a number of 0 is more preferable.
一般式（ａ１）において、ｎが０のケイ酸エステル〔以下、（ａ１１）成分という〕の場合には、持続的な強い香りを発現させる観点から、４個のＸのうち２〜４個、好ましくは３又は４個が−ＯＲ2aであり、残りが−ＯＲ2aである化合物が好適である。 In the general formula (a1), when n is 0 silicate ester (hereinafter referred to as the component (a11)), 2 to 4 of 4 Xs from the viewpoint of developing a strong strong scent, A compound in which 3 or 4 are —OR 2a and the rest is —OR 2a is preferred.
ｎが０の場合の好ましい化合物〔（ａ１１）成分〕としては、下記式（ａ１１−１）又は（ａ１１−２）で表される化合物が挙げられる。 Preferred compounds when n is 0 [(a11) component] include compounds represented by the following formula (a11-1) or (a11-2).
〔式中、Ｒ2a及びＲ3aは前記と同じ意味を示す。〕 [Wherein, R 2a and R 3a have the same meaning as described above. ]
一般式（ａ１）において、ｎが１〜５のケイ酸エステル〔以下、（ａ１２）成分という〕の場合には、持続的な強い香りを発現させる観点から、噴霧用液体芳香剤組成物中に含まれる全ての（ａ）成分中のＸ及びＹの合計の数に対して、１／５以上、好ましくは１／２以上が−ＯＲ2aであり、残りが−ＯＲ3aである化合物が好適であり、全てのＸ及びＹが−ＯＲ2aである化合物がより好ましい。 In the general formula (a1), when n is a silicate ester of 1 to 5 (hereinafter referred to as the component (a12)), from the viewpoint of expressing a persistent strong scent, in the liquid fragrance composition for spraying A compound in which 1/5 or more, preferably 1/2 or more is —OR 2a and the rest is —OR 3a with respect to the total number of X and Y in all the components (a) contained is suitable. More preferred are compounds in which all X and Y are —OR 2a .
ｎが１〜５の場合の好ましい化合物〔（ａ１２）成分〕としては、下記式（ａ１２−１）又は（ａ１２−２）で表される化合物が挙げられる。 Preferred compounds when n is 1 to 5 [component (a12)] include compounds represented by the following formula (a12-1) or (a12-2).
〔式中、Ｒ2a及びＲ3aは前記と同じ意味を示す。ｍは１〜５の数を示し、Ｔは、−ＯＲ2a又は−ＯＲ3aを示す。〕 [Wherein, R 2a and R 3a have the same meaning as described above. m represents a number of 1 to 5, T indicates the -OR 2a or -OR 3a. ]
香りの持続性の観点から、ｍとしては、１〜４が好ましく、１〜２がより好ましく、持続的な強い香りを発現させる観点から、ｍは１が更に好ましい。 From the viewpoint of scent sustainability, m is preferably 1 to 4, more preferably 1 to 2, and m is more preferably 1 from the viewpoint of expressing a strong persistent scent.
一般式（ａ１）で表される化合物は、特許文献２の段落００２９〜００４１などに記載されている方法で入手することができる。 The compound represented by the general formula (a1) can be obtained by the method described in paragraphs 0029 to 0041 of Patent Document 2.
上記一般式（ａ１）において、ｎが０のケイ酸エステル〔（ａ１１）成分〕とｎが１〜５のケイ酸エステル〔（ａ１２）成分〕を併用して用いることもできる。噴霧用液体芳香剤組成物中の（ａ１１）成分と（ａ１２）成分の割合は、質量比で（ａ１１）成分／（ａ１２）成分＝１〜２００が好ましく、２〜１１０がより好ましく、３〜１００が更に好ましい。 In the general formula (a1), a silicate ester (component (a11)) in which n is 0 and a silicate ester (component (a12)) in which n is 1 to 5 can be used in combination. The ratio of the (a11) component and the (a12) component in the liquid air freshener composition for spraying is preferably (a11) component / (a12) component = 1 to 200, more preferably 2 to 110, in terms of mass ratio. 100 is more preferable.
［（ｂ）成分］
本発明の（ａ）成分は、（ｂ）成分である、２５℃における酸解離定数（ｐＫａ）（以後、「ｐＫａ（２５℃）」という）が７．０〜９．０である、特定のヒドロキシアミン化合物及びその塩から選ばれる化合物と共存することにより、湿潤状態で適用された後から乾燥するまでの過程では香りが抑制され、乾燥後には持続的な強い香りを発現させることができる。
[Component (b)]
The component (a) of the present invention has a specific acid dissociation constant (pKa) at 25 ° C. (hereinafter referred to as “pKa (25 ° C.)”) of 7.0 to 9.0, which is the component (b). By coexisting with a compound selected from a hydroxyamine compound and a salt thereof, the scent is suppressed in the process from application in a wet state to drying, and a persistent strong scent can be expressed after drying.
本発明の（ｂ）成分の特定のヒドロキシアミン化合物のｐＫａ（２５℃）は、持続的な強い香りを発現させる観点から、７．３〜８．８が好ましく、７．５〜８．８がより好ましく、７．９〜８．８がより好ましく、７．９〜８．６が特に好ましい。 The pKa (25 ° C.) of the specific hydroxyamine compound of the component (b) of the present invention is preferably 7.3 to 8.8, and preferably 7.5 to 8.8 from the viewpoint of expressing a persistent strong scent. More preferably, 7.9 to 8.8 is more preferable, and 7.9 to 8.6 is particularly preferable.
本発明の（ｂ）成分の特定のヒドロキシアミン化合物のｐＫａ（２５℃）は、水を溶媒とした時に、（ｂ）成分の特定のヒドロキシアミン化合物の０．１ｍｏｌ／Ｌの濃度におけるｐＫａ（２５℃）を示す。 The pKa (25 ° C.) of the specific hydroxyamine compound of component (b) of the present invention is pKa (25 at a concentration of 0.1 mol / L of the specific hydroxyamine compound of component (b) when water is used as the solvent. ° C).
酸解離定数（ｐＫａ）は、「日本化学会編 化学便覧 基礎編 改訂５版」（平成１６年２月２０日、丸善株式会社発行、II−３３４〜II−３４３頁）に記載されている２５℃におけるｐＫａを用いることができる。化学便覧に記載されていない場合は、各アミンの０．１ｍｏｌ／Ｌ水溶液のｐＨを測定し、ｐＫａ＝〔２×（ｐＨの測定値）〕−１４−〔（１／２）×ｌｏｇ（０．１）〕から計算する事が出来る。ｐＨは次に示す方法で測定する。 The acid dissociation constant (pKa) is described in “The Chemical Society of Japan, Chemistry Handbook, Basic, 5th revised edition” (February 20, 2004, published by Maruzen Co., Ltd., pages II-334 to II-343) 25 PKa at ° C can be used. When it is not described in the chemical handbook, the pH of 0.1 mol / L aqueous solution of each amine is measured, and pKa = [2 × (measured value of pH)]-14-[(1/2) × log (0 .1)]. The pH is measured by the following method.
＜ｐＨの測定方法＞
ｐＨ測定装置は測定の１時間前に電源を入れる。未使用のｐＨ電極を用い、電極を予め２５℃±０．２℃のイオン交換水に２４時間浸しておいたものを使用する。ゼロ校正とスパン校正は、以下に記載のｐＨ標準液を用いて、２５℃におけるｐＨの指示値が、標準ｐＨ±０．０２になるまで繰り返し校正を行う。校正後にｐＨ電極に２５℃のイオン交換水２００ｍＬをかけて洗浄後、各測定サンプル（ヒドロキシアミン化合物）の水溶液（濃度０．１ｍｏｌ／Ｌ）を３回繰り返し測定する。尚、１回測定を終える度に、ゼロ校正とスパン校正を行う。得られた３回の測定値の平均値をｐＨ測定値とする。
<Measurement method of pH>
The pH measuring device is turned on 1 hour before the measurement. An unused pH electrode is used, and the electrode is previously immersed in ion exchange water at 25 ° C. ± 0.2 ° C. for 24 hours. Zero calibration and span calibration are repeatedly performed using the pH standard solution described below until the indicated value of pH at 25 ° C. becomes standard pH ± 0.02. After calibration, 200 mL of ion exchange water at 25 ° C. is applied to the pH electrode and washed, and then an aqueous solution (concentration 0.1 mol / L) of each measurement sample (hydroxyamine compound) is repeatedly measured. In addition, zero calibration and span calibration are performed every time one measurement is completed. The average value of the three measurement values obtained is taken as the pH measurement value.
＜測定サンプルの水溶液の調製＞
測定サンプルの水溶液（濃度０．１ｍｏｌ／Ｌ）２００ｍＬを、２００ｍＬ容積のガラス製のトールビーカーに入れる。水が蒸散しないように、ビーカーの口を食品包装用ラップフィルム〔例えば、サランラップ（登録商標）〕で封をし、ウォーターバス中で、液温が２５±０．２℃になるように調整する。
<Preparation of aqueous solution of measurement sample>
200 mL of the measurement sample aqueous solution (concentration: 0.1 mol / L) is put into a 200 mL glass tall beaker. Seal the beaker mouth with a food packaging wrap film (eg Saran Wrap (registered trademark)) and adjust the temperature of the beaker to 25 ± 0.2 ° C in a water bath so that water does not evaporate. .
〔ｐＨ標準液〕
堀場製作所株式会社製ｐＨ標準液を用いる。
・ｐＨ標準液１００−７（中性りん酸塩標準液、精度；±０．０２ｐＨ）
・ｐＨ標準液１００−９（ホウ酸塩標準液、精度；±０．０２ｐＨ）
〔ｐＨ測定装置〕
・株式会社堀場製作所製のｐＨメータ「Ｄ−５２Ｓ」
・ｐＨ電極：６３６７−１０Ｄ
[PH standard solution]
A pH standard solution manufactured by HORIBA, Ltd. is used.
・ PH standard solution 100-7 (neutral phosphate standard solution, accuracy; ± 0.02 pH)
・ PH standard solution 100-9 (borate standard solution, accuracy; ± 0.02 pH)
[PH measuring device]
・ PH meter “D-52S” manufactured by HORIBA, Ltd.
-PH electrode: 6367-10D
本発明の（ｂ）成分は、下記一般式（ｂ１）で表される化合物、ジエタノールアミン及びトリエタノールアミンから選ばれる、少なくとも１種のｐＫａが７．０〜９．０のヒドロキシアミン化合物並びに該ヒドロキシアミン化合物の塩から選ばれる化合物である。 The component (b) of the present invention is a compound represented by the following general formula (b1), at least one hydroxyamine compound selected from diethanolamine and triethanolamine, having a pKa of 7.0 to 9.0, and the hydroxy It is a compound selected from salts of amine compounds.
〔式中、Ｒ1bは、水素原子、炭素数１〜５のアルキル基、又は炭素数１〜５のヒドロキシアルキル基であり、Ｒ2bは、水素原子、炭素数１〜６のアルキル基、又は炭素数１〜５のヒドロキシアルキル基であり、Ｒ3b及びＲ4bは、炭素数１〜５のアルカンジイル基である。Ｒ3b及びＲ4bは、同一でも異なっていてもよい。上記Ｒ1b〜Ｒ4bの基の種類は、一般式（ｂ１）で表される化合物のｐＫａ（２５℃）が７．０〜９．０になるように適宜選択される。〕 [Wherein, R 1b is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms, and R 2b is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or It is a C1-C5 hydroxyalkyl group, R <3b> and R <4b> are C1-C5 alkanediyl groups. R 3b and R 4b may be the same or different. The type of group R 1b to R 4b are, pKa of the compound represented by the general formula (b1) (25 ℃) is appropriately selected to be 7.0 to 9.0. ]
一般式（ｂ１）において、Ｒ1bは、水素原子、炭素数１〜５のアルキル基、又は炭素数１〜５のヒドロキシアルキル基である。炭素数１〜５のアルキル基は、直鎖又は分岐鎖のいずれであってもよく、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、各種ブチル基、各種ペンチル基が挙げられる。また、炭素数１〜５のヒドロキシアルキル基としては、ヒドロキシメチル基、２−ヒドロキシエチル基、２−ヒドロキシプロピル基、３−ヒドロキシプロピル基、２−ヒドロキシブチル基、３−ヒドロキシブチル基、４−ヒドロキシブチル基等が挙げられる。Ｒ1bは、香りの持続性及び入手性の観点から、上記の中では水素原子、メチル基、エチル基、ヒドロキシメチル基、２−ヒドロキシエチル基が好ましく、水素原子、メチル基、ヒドロキシメチル基、２−ヒドロキシエチル基がより好ましく、メチル基、ヒドロキシメチル基が最も好ましい。 In General Formula (b1), R 1b is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, and various pentyl groups. Examples of the hydroxyalkyl group having 1 to 5 carbon atoms include hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4- Examples thereof include a hydroxybutyl group. R 1b is preferably a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group or a 2-hydroxyethyl group from the viewpoints of scent persistence and availability, and a hydrogen atom, a methyl group, a hydroxymethyl group, A 2-hydroxyethyl group is more preferable, and a methyl group and a hydroxymethyl group are most preferable.
Ｒ2bは、水素原子、炭素数１〜６のアルキル基、又は炭素数１〜５のヒドロキシアルキル基を表す。炭素数１〜６のアルキル基は、直鎖状、分岐鎖状、環状のいずれであってもよい。アルキル基の具体例としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、各種ブチル基、各種ペンチル基、各種ヘキシル基、シクロペンチル基、シクロヘキシル基等が挙げられる。炭素数１〜５のヒドロキシアルキル基としては、Ｒ1bと同じものが挙げられる。Ｒ2bは、香りの持続性及び入手性の観点から、上記の中では水素原子、炭素数１〜３のアルキル基、ヒドロキシエチル基が好ましく、水素原子がより好ましい。 R 2b represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, cyclopentyl groups, and cyclohexyl groups. As a C1-C5 hydroxyalkyl group, the same thing as R <1b> is mentioned. R 2b is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyethyl group, and more preferably a hydrogen atom, from the viewpoints of scent sustainability and availability.
Ｒ3b及びＲ4bは、炭素数１〜５のアルカンジイル基である。Ｒ3b及びＲ4bは、同一でも異なっていてもよい。炭素数１〜５のアルカンジイル基としては、メチレン基、エチレン基、トリメチレン基、プロパン−１，２−ジイル基、テトラメチレン基等が好ましく、メチレン基がより好ましい。 R 3b and R 4b are alkanediyl groups having 1 to 5 carbon atoms. R 3b and R 4b may be the same or different. The alkanediyl group having 1 to 5 carbon atoms is preferably a methylene group, an ethylene group, a trimethylene group, a propane-1,2-diyl group or a tetramethylene group, and more preferably a methylene group.
上記Ｒ１b〜Ｒ4bの基の種類は、一般式（ｂ１）で表される化合物のｐＫａ（２５℃）が７．０〜９．０になるように適宜選択される。 The type of R1 b to R 4b groups, pKa of the compound represented by the general formula (b1) (25 ℃) is appropriately selected to be 7.0 to 9.0.
一般式（ｂ１）で表される化合物を塩として用いる場合の酸としては、無機酸（例えば、塩酸、硫酸、硝酸、リン酸）、又は有機酸（例えば、グリコール酸、乳酸、クエン酸、炭酸等の炭素数１〜６の炭素原子を有する有機酸）を用いることが出来る。 As an acid when the compound represented by the general formula (b1) is used as a salt, an inorganic acid (for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid) or an organic acid (for example, glycolic acid, lactic acid, citric acid, carbonic acid) Organic acids having 1 to 6 carbon atoms, such as
（ｂ）成分の具体例としては、例えば、２−アミノ−１，３−プロパンジオール、２−アミノ−２−メチル−１，３−プロパンジオール（ｐＫａ（２５℃）＝８．８）、２−アミノ−２−エチル−１，３−プロパンジオール、２−アミノ−２−ヒドロキシメチル−１，３−プロパンジオール（ｐＫａ（２５℃）＝８．２）、２−アミノ−２−ヒドロキシエチル−１，３−プロパンジオール、４−アミノ−４−ヒドロキシプロピル−１，７−ヘプタンジオール、２−（Ｎ−エチル）アミノ−１，３−プロパンジオール、２−（Ｎ−エチル）アミノ−２−ヒドロキシメチル−１，３−プロパンジオール、２−（Ｎ−デシル）アミノ−１，３−プロパンジオール、２−（Ｎ−デシル）アミノ−２−ヒドロキシメチル−１，３−プロパンジオール、ジエタノールアミン(ｐＫａ（２５℃）=８．９)、トリエタノールアミン（ｐＫａ（２５℃）＝７．８）等、及びそれらと塩酸、硫酸、硝酸、リン酸、炭酸等との塩が挙げられる。 Specific examples of the component (b) include, for example, 2-amino-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol (pKa (25 ° C.) = 8.8), 2 -Amino-2-ethyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol (pKa (25 ° C.) = 8.2), 2-amino-2-hydroxyethyl- 1,3-propanediol, 4-amino-4-hydroxypropyl-1,7-heptanediol, 2- (N-ethyl) amino-1,3-propanediol, 2- (N-ethyl) amino-2- Hydroxymethyl-1,3-propanediol, 2- (N-decyl) amino-1,3-propanediol, 2- (N-decyl) amino-2-hydroxymethyl-1,3-propanediol, di Examples include tanolamine (pKa (25 ° C.) = 8.9), triethanolamine (pKa (25 ° C.) = 7.8), and salts thereof with hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, and the like. .
これらの中では、香りの持続性の観点から、２−アミノ−２−メチル−１，３−プロパンジオール（ｐＫａ（２５℃）＝８．８）、２−アミノ−２−ヒドロキシメチル−１，３−プロパンジオール（ｐＫａ（２５℃）＝８．２）、ジエタノールアミン（ｐＫａ（２５℃）＝８．９）、トリエタノールアミン（ｐＫａ（２５℃）＝７．８）及びそれらと塩酸等の酸との塩から選ばれる１種以上が好ましい。 Among these, from the viewpoint of sustaining fragrance, 2-amino-2-methyl-1,3-propanediol (pKa (25 ° C.) = 8.8), 2-amino-2-hydroxymethyl-1, 3-propanediol (pKa (25 ° C.) = 8.2), diethanolamine (pKa (25 ° C.) = 8.9), triethanolamine (pKa (25 ° C.) = 7.8) and acids such as hydrochloric acid 1 or more types selected from the salt with are preferable.
ヒドロキシアミン化合物を塩酸等の塩として用いる場合は、塩基や酸を添加することにより、本発明の噴霧用液体芳香剤組成物のｐＨを調整することができる。用いることができる塩基としては、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム等が挙げられる。これらの中では、水酸化ナトリウム、水酸化カリウムが好ましい。酸としては、塩酸、硫酸、硝酸、リン酸等の無機酸を用いることが出来る。また、グリコール酸、乳酸、クエン酸、炭酸等の炭素数１〜６の炭素原子を有する有機酸を用いることも出来る。 When the hydroxyamine compound is used as a salt such as hydrochloric acid, the pH of the sprayed liquid fragrance composition of the present invention can be adjusted by adding a base or an acid. Examples of the base that can be used include sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and the like. Among these, sodium hydroxide and potassium hydroxide are preferable. As the acid, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid can be used. Moreover, organic acids having 1 to 6 carbon atoms such as glycolic acid, lactic acid, citric acid, and carbonic acid can also be used.
上記のヒドロキシアミン化合物類（ａ）は、単独で又は２種以上を混合して用いることができる。 Said hydroxyamine compound (a) can be used individually or in mixture of 2 or more types.
［噴霧用液体芳香剤組成物及びスプレー式芳香剤物品］
本発明の噴霧用液体芳香剤組成物中の（ａ）成分、（ｂ）成分の含有量は、使用形態、繊維製品の種類、香らせる香りの強さの程度などによって適宜調整することができる。
[Liquid fragrance composition for spray and spray fragrance article]
The content of the component (a) and the component (b) in the liquid fragrance composition for spraying of the present invention can be appropriately adjusted depending on the use form, the type of the textile product, the intensity of the fragrance to be scented, and the like. it can.
（ａ）成分の組成物中の含有量は、香りの持続性の点で、０．０００１質量％以上が好ましく、また、衣類等に適用した場合に乾燥途中で香る香りが強すぎない点で０．１質量％以下が好ましい。従って、（ａ）成分の組成物中の含有量は、０．０００１〜０．１質量％が好ましく、０．０００３〜０．０３質量％がより好ましく、０．０００５〜０．０１質量％が更に好ましい。 The content of the component (a) in the composition is preferably 0.0001% by mass or more from the viewpoint of fragrance sustainability, and the fragrance fragrant during drying when applied to clothing or the like is not too strong. 0.1 mass% or less is preferable. Accordingly, the content of the component (a) in the composition is preferably 0.0001 to 0.1% by mass, more preferably 0.0003 to 0.03% by mass, and 0.0005 to 0.01% by mass. Further preferred.
（ｂ）成分の組成物中の含有量は、持続的な強い香りを発現させる点で、０．０１質量％以上が好ましく、また、経済的な点で１質量％以下が好ましい。０．０１〜１質量％がより好ましく、０．０２〜０．９質量％が更に好ましく、０．０２〜０．８質量％がより更に好ましい。尚、本明細書において、（ｂ）成分の含有量とは、（ｂ）成分がアミンの状態で存在すると仮定した時の含有量を示す。 The content of the component (b) in the composition is preferably 0.01% by mass or more, and preferably 1% by mass or less from the viewpoint of developing a strong persistent fragrance. 0.01-1 mass% is more preferable, 0.02-0.9 mass% is still more preferable, and 0.02-0.8 mass% is still more preferable. In addition, in this specification, content of (b) component shows content when it assumes that (b) component exists in the state of an amine.
本発明の噴霧用液体芳香剤組成物において、（ｂ）成分は、（ａ）成分と併用することで、適用後、乾燥する途中での香りを抑制しつつ、衣類を保管した後の香りの強さを高める等、持続的な強い香りを発現させることが出来る。持続的な強い香りを発現させる観点から、（ａ）成分及び（ｂ）成分の質量比は、（ａ）成分／（ｂ）成分＝０．００１〜１が好ましく、より好ましくは０．００５〜０．５、更に好ましくは０．００２〜０．２、特に好ましくは０．０１〜０．１である。 In the liquid fragrance composition for spraying of the present invention, the component (b) is used in combination with the component (a), so that the scent of the scent after storing the clothing is suppressed while being applied and the scent during drying is suppressed. Sustained strong aroma such as increasing strength can be expressed. From the viewpoint of expressing a strong and persistent scent, the mass ratio of the component (a) and the component (b) is preferably (a) component / (b) component = 0.001 to 1, more preferably 0.005. 0.5, more preferably 0.002 to 0.2, and particularly preferably 0.01 to 0.1.
本発明の噴霧用液体芳香剤組成物において、（ａ）成分及び（ｂ）成分以外の残部は水とすることができる。使用する水は、蒸留水やイオン交換水等からイオン成分を除去したものが好ましい。組成物中の水の含有量は、噴霧用液体芳香剤組成物の調製のし易さの点から、７５〜９９．９質量％が好ましく、８０〜９９．８質量％が更に好ましい。 In the liquid fragrance composition for spraying of the present invention, the remainder other than the components (a) and (b) can be water. The water to be used is preferably one obtained by removing ionic components from distilled water, ion-exchanged water or the like. The content of water in the composition is preferably 75 to 99.9% by mass, more preferably 80 to 99.8% by mass, from the viewpoint of easy preparation of the liquid fragrance composition for spraying.
また必要に応じて、本発明の効果を損なわない範囲で、更に、界面活性剤、溶剤、硫酸ナトリウム等の塩、ｐＨ調整剤、酸化防止剤、防腐剤、香料、染料、顔料、紫外線吸収剤等の他の成分を添加することができる。 Further, if necessary, the surfactant, solvent, salt such as sodium sulfate, pH adjuster, antioxidant, preservative, perfume, dye, pigment, UV absorber, as long as the effects of the present invention are not impaired. Other ingredients such as can be added.
溶剤〔以下、（ｃ）成分という〕としては、炭素数２〜４の１価アルコール（例えば、エタノール等）、２〜６価で１分子の総炭素数が２〜１２の多価アルコール（例えば、エチレングリコール、プロピレングリコール、グリセリン、ソルビトール等）、又は前記アルコールのアルキル（炭素数１〜６）のエーテル誘導体が挙げられる。これらの中では、保存安定性の点から、エタノール、ジエチレングリコール、ジプロピレングリコールが好ましい。（ｃ）成分の組成物中の含有量は０．０５〜１０質量％、エタノールを含有する場合には、３〜９質量％が好ましく、４〜８質量％がより好ましい。ジエチレングリコール、ジプロピレングリコールを含有する場合には、０．１〜２質量％が好ましく、０．２〜１質量％がより好ましい。とすることができる。 Examples of the solvent [hereinafter referred to as component (c)] include monohydric alcohols having 2 to 4 carbon atoms (for example, ethanol), polyhydric alcohols having 2 to 6 valences and 2 to 12 total carbon atoms in one molecule (for example, , Ethylene glycol, propylene glycol, glycerin, sorbitol, etc.), or alkyl (carbon number 1 to 6) ether derivatives of the alcohols. Among these, ethanol, diethylene glycol, and dipropylene glycol are preferable from the viewpoint of storage stability. The content of the component (c) in the composition is 0.05 to 10% by mass, and when ethanol is contained, 3 to 9% by mass is preferable, and 4 to 8% by mass is more preferable. When diethylene glycol and dipropylene glycol are contained, 0.1 to 2% by mass is preferable, and 0.2 to 1% by mass is more preferable. It can be.
界面活性剤〔以下、（ｄ）成分という〕としては、特に制限はなく、非イオン性界面活性剤、陽イオン性界面活性剤、陰イオン性界面活性剤、及び両性界面活性剤の中から選ばれる１種以上が挙げられる。これらの中では、噴霧用液体芳香剤組成物の安定性を高める観点や持続的な強い香りを発現させる観点から、非イオン性界面活性剤が好ましく、下記一般式（ｄ１）で表される化合物がより好ましい。
Ｒ1d−Ｚ−［（ＥＯ）s／（ＰＯ）t］−Ｒ2d （ｄ１）
〔式（ｄ１）中、Ｒ1dは、炭素数１０〜２２の脂肪族炭化水素基、好ましくは炭素数１２〜１６の炭化水素基、より好ましくは炭素数１２〜１６のアルキル基又はアルケニル基であり、Ｒ2dは、水素原子、又は炭素数１〜３のアルキル基であり、Ｚは−Ｏ−又は−ＣＯＯ−のいずれかであり、ＥＯは、オキシエチレン基であり、ＰＯはオキシプロピレン基であり、（ＥＯ）と（ＰＯ）はランダム付加でもブロック付加でもいずれでもよく、（ＥＯ）と（ＰＯ）の付加順序は問わない。ｓ及びｔは平均付加モル数であり、ｓは４〜４０の数、好ましくは５〜２５の数、ｔは２以下の数、好ましくは０の数である。持続的な強い香りを発現させる観点からｓ＋ｔの合計は５〜２０の数が好ましく、５〜１５の数が好ましい。〕
The surfactant (hereinafter referred to as “component (d)”) is not particularly limited, and is selected from nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants. 1 type or more to be mentioned. Among these, nonionic surfactants are preferable from the viewpoint of enhancing the stability of the liquid fragrance composition for spraying and developing a persistent strong fragrance, and are compounds represented by the following general formula (d1) Is more preferable.
R1d- Z-[(EO) s / (PO) t ] -R2d (d1)
[In the formula (d1), R 1d is an aliphatic hydrocarbon group having 10 to 22 carbon atoms, preferably a hydrocarbon group having 12 to 16 carbon atoms, more preferably an alkyl group or alkenyl group having 12 to 16 carbon atoms. R 2d is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Z is either —O— or —COO—, EO is an oxyethylene group, and PO is an oxypropylene group (EO) and (PO) may be either random addition or block addition, and the addition order of (EO) and (PO) does not matter. s and t are average added mole numbers, s is a number of 4 to 40, preferably 5 to 25, and t is a number of 2 or less, preferably 0. The number of 5 to 20 is preferable, and the number of 5 to 15 is preferable from the viewpoint of expressing a persistent strong scent. ]
組成物の配合性の観点から、一般式（ｄ１）で表される化合物のＲ1dは、好ましくは炭素数１０〜１６、更に好ましくは炭素数１０〜１４のアルキル基又はアルケニル基であり、Ｒ2dは、好ましくは水素原子、又は炭素数１〜２のアルキル基、より好ましくは水素原子又はメチル基、更に好ましくは水素原子である。 From the viewpoint of the composition of the composition, R 1d of the compound represented by the general formula (d1) is preferably an alkyl group or an alkenyl group having 10 to 16 carbon atoms, more preferably 10 to 14 carbon atoms, and R 2d is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.
一般式（ｄ１）で表される化合物としては、ポリオキシエチレン（ｓ＝６〜１２）−１−ドデシルエーテル、ポリオキシエチレン（ｓ＝５〜１２）モノアルキル（炭素数１２〜１４の２級の炭化水素基）エーテル、ラウリン酸ポリオキシチレン（ｓ＝６〜１３）メチルエーテルから選ばれる１種以上が好ましい。 Examples of the compound represented by the general formula (d1) include polyoxyethylene (s = 6 to 12) -1-dodecyl ether, polyoxyethylene (s = 5 to 12) monoalkyl (secondary having 12 to 14 carbon atoms) And at least one selected from the group consisting of ether and lauric acid polyoxyethylene (s = 6 to 13) methyl ether.
（ｄ）成分の組成物中の含有量は、ケイ酸エステル〔（ａ）成分〕の配合性の観点から、好ましくは０．００１〜１０質量％、より好ましくは０．０１〜１質量％である。 The content of the component (d) in the composition is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass, from the viewpoint of compoundability of the silicate ester (component (a)). is there.
本発明の噴霧用液体芳香剤組成物において、持続的な強い香りを発現させる観点から、（ａ）成分及び（ｄ）成分の質量比は、（ａ）成分／（ｄ）成分＝０．００１〜０．５が好ましく、より好ましくは０．００２〜０．１、更に好ましくは０．００３〜０．０３である。 In the sprayed liquid fragrance composition of the present invention, from the viewpoint of expressing a persistent strong scent, the mass ratio of the component (a) and the component (d) is (a) component / (d) component = 0.001. -0.5 is preferable, More preferably, it is 0.002-0.1, More preferably, it is 0.003-0.03.
本発明の噴霧用液体芳香剤組成物の２５℃におけるｐＨは、持続的な強い香りを発現させる観点から、６．５〜８．５であり、６．８〜８．５が好ましく、７．０〜８．３がより好ましく、７．０〜８．０が更に好ましく、７．０〜７．７が最も好ましい。本発明の噴霧用液体芳香剤組成物のｐＨは、塩酸等の酸、又は水酸化ナトリウム等のアルカリを添加することにより調整することができる。噴霧用液体芳香剤組成物のｐＨは実施例に記載の方法で測定した値である。 The pH at 25 ° C. of the liquid fragrance composition for spraying of the present invention is 6.5 to 8.5, preferably 6.8 to 8.5, from the viewpoint of developing a persistent strong scent. 0-8.3 are more preferable, 7.0-8.0 are still more preferable, and 7.0-7.7 are the most preferable. The pH of the liquid fragrance composition for spraying of the present invention can be adjusted by adding an acid such as hydrochloric acid or an alkali such as sodium hydroxide. The pH of the liquid fragrance composition for spraying is a value measured by the method described in Examples.
本発明の噴霧用液体芳香剤組成物の２５℃における粘度は、スプレー容器での噴霧適性の観点から、１５ｍＰａ・ｓ以下が好ましく、より好ましくは１〜１０ｍＰａ・ｓ、更に好ましくは１〜５ｍＰａ・ｓである。本発明の噴霧用液体芳香剤組成物において、２５℃における粘度が１５ｍＰａ・ｓ以下であると噴霧パターンが適正となる。粘度は、東京計器株式会社製、Ｂ型粘度計（モデル形式ＢＭ）に、Ｎｏ．１のローターを取り付け、噴霧用液体芳香剤組成物を２００ｍＬ容量のガラス製トールビーカーに充填し、ウォーターバスにて２５±０．３℃に調製し、ローターの回転数を６０ｒ／ｍｉｎに設定し、測定を始めてから６０秒後の指示値である。 The viscosity at 25 ° C. of the liquid fragrance composition for spraying of the present invention is preferably 15 mPa · s or less, more preferably 1 to 10 mPa · s, still more preferably 1 to 5 mPa · s, from the viewpoint of sprayability in a spray container. s. In the liquid fragrance composition for spraying of the present invention, the spray pattern is appropriate when the viscosity at 25 ° C. is 15 mPa · s or less. Viscosity is the same as that of Tokyo Keiki Co., Ltd., B type viscometer (model type BM). No. 1 rotor is attached, and the liquid fragrance composition for spraying is filled into a 200 mL glass tall beaker, adjusted to 25 ± 0.3 ° C. in a water bath, and the rotational speed of the rotor is set to 60 r / min. The indicated value is 60 seconds after the start of measurement.
本発明の噴霧用液体芳香剤組成物をスプレー容器に充填してスプレー式芳香剤物品を得ることができる。本発明のスプレー式芳香剤物品は、本発明の噴霧用液体芳香剤組成物と、スプレー容器とを含んで構成される物品である。本発明の噴霧用液体芳香剤組成物は水を含有するミストタイプであり、これをスプレー容器に充填し、一回の噴霧量を０．１〜３ｍｌに調整したものが好ましい。使用するスプレー容器としては、トリガースプレー容器（直圧あるいは蓄圧型）やディスペンサータイプのポンプスプレー容器、耐圧容器を具備したエアゾールスプレー容器等が挙げられる。性能を効果的に発現するために、トリガー式スプレーヤーあるいはエアゾールスプレーヤーを具備するスプレー容器が好ましく、本発明においては、耐久性や布付着性の点から、トリガー式スプレーヤーを具備するスプレー容器がより好ましい。 A spray-type fragrance article can be obtained by filling a spray container with the sprayed liquid fragrance composition of the present invention. The spray-type fragrance article of the present invention is an article comprising the sprayed liquid fragrance composition of the present invention and a spray container. The liquid fragrance composition for spraying of the present invention is a mist type containing water, and it is preferable to fill this in a spray container and adjust the spray amount at one time to 0.1 to 3 ml. Examples of the spray container to be used include a trigger spray container (direct pressure or pressure accumulation type), a dispenser type pump spray container, an aerosol spray container equipped with a pressure resistant container, and the like. In order to effectively exhibit the performance, a spray container equipped with a trigger sprayer or an aerosol sprayer is preferable. In the present invention, a spray container equipped with a trigger sprayer from the viewpoint of durability and cloth adhesion. Is more preferable.
スプレー容器としては、噴射口から噴射方向に１０ｃｍ離れた地点における噴霧液滴の平均粒径が１０〜２００μｍとなり、噴射口から噴射方向に１５ｃｍ離れた地点における粒径２００μｍを超える液滴の数が噴霧液滴の総数の１％以下となり、噴射口から噴射方向に１０ｃｍ離れた地点における粒径１０μｍ未満の液滴の数が噴霧液滴の総数の１％以下となる噴霧手段を備えたものが好ましい。噴霧液滴の粒子径分布は体積平均粒子径であり、例えば、レーザー回折式粒度分布計（日本電子株式会社製）により測定することができる。 As a spray container, the average particle size of spray droplets at a point 10 cm away from the injection port in the injection direction is 10 to 200 μm, and the number of droplets exceeding the particle size 200 μm at a point 15 cm away from the injection port in the injection direction. What is provided with a spraying means in which the number of droplets having a particle size of less than 10 μm at a point 10 cm away from the spray port in the ejection direction is 1% or less of the total number of sprayed droplets. preferable. The particle size distribution of the spray droplets is a volume average particle size, and can be measured by, for example, a laser diffraction particle size distribution meter (manufactured by JEOL Ltd.).
本発明の噴霧用液体芳香剤組成物及びスプレー式芳香剤物品は、繊維製品用として好適であり、かかる噴霧用液体芳香剤組成物は、噴霧により繊維製品に付着させて、対象物に香りを付与することが出来る。前記スプレー式芳香剤物品はこの方法に好適に用いられる。繊維製品としては、スーツ、セーター等の衣類、カーテン、ソファー等が挙げられる。 The liquid fragrance composition for spraying and the spray type fragrance article of the present invention are suitable for textile products, and the liquid fragrance composition for spraying is attached to the textile product by spraying to give a scent to the object. Can be granted. The spray fragrance article is preferably used in this method. Examples of the textile products include suits, sweaters and other clothing, curtains, sofas and the like.
本発明の噴霧用液体芳香剤組成物を、噴霧より繊維製品に対象物に付着させる方法が本発明の効果を享受出来る点で好ましい。付着させる量は、対象物が繊維製品である場合には、噴霧された繊維製品の乾燥時間を短くする点で、噴霧用液体芳香剤組成物が付着した範囲の繊維製品の質量に対して、１００質量％以下が好ましく、７０質量％以下がより好ましい。繊維製品に対して均一に付着させる点で、噴霧用液体芳香剤組成物が付着した範囲の繊維製品の質量に対して５質量％以上が好ましく、１０質量％以上がより好ましい。対象物の質量が容易に測定できない場合（例えば、大型家具などの布張部分、建物等に固定されている繊維製品等）には、対象物の１０ｃｍ2の面積に対して０．１〜３ｇ、好ましくは０．３〜２．５ｇ、より好ましくは０．５〜２．０ｇとなる量の噴霧用液体芳香剤組成物を付着させることが、本発明の効果が得られる点で好ましい。 The method of adhering the liquid fragrance composition for spraying of the present invention to an object to a textile product by spraying is preferable in that the effect of the present invention can be enjoyed. When the object is a textile product, the amount to be adhered is that the drying time of the sprayed textile product is shortened, and the mass of the textile product in the range where the liquid fragrance composition for spraying is adhered, 100 mass% or less is preferable and 70 mass% or less is more preferable. 5 mass% or more is preferable with respect to the mass of the fiber product of the range to which the liquid fragrance composition for spraying adhered, and 10 mass% or more is more preferable at the point made to adhere uniformly with respect to textiles. When the mass of the object cannot be easily measured (for example, a fabric tension part such as large furniture, a textile product fixed to a building, etc.), 0.1 to 3 g with respect to an area of 10 cm 2 of the object. In order to obtain the effects of the present invention, it is preferable to attach an amount of the liquid fragrance composition for spraying that is preferably 0.3 to 2.5 g, more preferably 0.5 to 2.0 g.
実施例及び比較例で用いた各配合成分をまとめて以下に示す。なお、（ｂ）成分及び（ｂ’）成分の酸解離定数（ｐＫａ）は、「日本化学会編 化学便覧 基礎編 改訂５版」（平成１６年２月２０日、丸善株式会社発行、II−３３４〜II−３４３頁）に記載されている２５℃におけるｐＫａを用いた。 Each compounding component used in Examples and Comparative Examples is shown below. In addition, the acid dissociation constant (pKa) of the component (b) and the component (b ′) is “Chemical Handbook Basic Edition Revised 5th Edition” (February 20, 2004, issued by Maruzen Co., Ltd., II- Pp. 334 to II-343) was used at 25 ° C.
（ａ）成分
・ａ−１：下記合成例１で得られたポリ（ゲラニルオキシ）シロキサン
・ａ−２：下記合成例２で得られたテトラキス（ゲラニルオキシ）シラン
・ａ−３：下記合成例３で得られたテトラキス（シトロネルオキシ）シラン
・ａ−４：下記合成例４で得られたテトラキス（フェニルエチルオキシ）シラン
（ａ’）成分：（ａ）成分の比較化合物
・ａ’−１：ゲラニオール
（ｂ）成分
・ｂ−１：トリス（ヒドロキシメチル）アミノメタン（ｐＫａ（２５℃）＝８．２）
・ｂ−２：２−アミノ−２−メチル−１，３−プロパンジオール（ｐＫａ（２５℃）＝８．８）
・ｂ−３：ジエタノールアミン（ｐＫａ（２５℃）＝８．９）
・ｂ−４：トリエタノールアミン（ｐＫａ（２５℃）＝７．８）
（ｂ’）成分〔（ｂ）成分の比較化合物〕
・ｂ’−１：２−アミノ−２−メチル−１−プロパノール（ｐＫａ（２５℃）＝９．８）
・ｂ’−２：モノエタノールアミン（ｐＫａ（２５℃）＝９．６）
その他成分
・ｃ−１：エタノール
・ｄ−１：ポリオキシエチレン（平均付加モル数＝８）−１−ドデシルエーテル
・ｄ−２：ポリオキシエチレン（平均付加モル数＝２０）−１−ドデシルエーテル
・抗菌剤：プロキセルＢＤＮ（アビシア株式会社製、１０％水溶液）
(A) Component a-1: Poly (geranyloxy) siloxane obtained in Synthesis Example 1 below a-2: Tetrakis (geranyloxy) silane obtained in Synthesis Example 2 below a-3: Synthesis Example below Tetrakis (citroneloxy) silane obtained in Step 3: a-4: Tetrakis (phenylethyloxy) silane obtained in Synthesis Example 4 below (a ′) Component: Component (a) Comparative Compound a′-1: Geraniol (b) component b-1: Tris (hydroxymethyl) aminomethane (pKa (25 ° C.) = 8.2)
B-2: 2-amino-2-methyl-1,3-propanediol (pKa (25 ° C.) = 8.8)
B-3: Diethanolamine (pKa (25 ° C.) = 8.9)
B-4: Triethanolamine (pKa (25 ° C.) = 7.8)
Component (b ′) [Comparative compound of component (b)]
B′-1: 2-amino-2-methyl-1-propanol (pKa (25 ° C.) = 9.8)
B′-2: monoethanolamine (pKa (25 ° C.) = 9.6)
Other components: c-1: ethanol d-1: polyoxyethylene (average number of moles added = 8) -1-dodecyl ether d-2: polyoxyethylene (average number of moles added = 20) -1-dodecyl ether Antibacterial agent: Proxel BDN (manufactured by Avicia Co., Ltd., 10% aqueous solution)
〔（ａ）成分の合成〕
合成例１（ポリ（ゲラニルオキシ）シロキサンの合成）
２００ｍＬの四つ口フラスコにテトラエトキシシラン１４５．９２ｇと水酸化カリウム０．４８ｇ、イオン交換水０．８ｍＬを入れ、窒素気流下１２０〜１２５℃、３３ｋＰａ〜１０１ｋＰａ（常圧）で約３７時間反応を行った。この間イオン交換水を０．８ｍＬ追加した。反応後、３３ｋＰａで更に２時間反応させた後、冷却、濾過を行い、１３４．５８ｇのエトキシシランの縮合物を淡黄色液体として得た。
[Synthesis of component (a)]
Synthesis Example 1 (Synthesis of poly (geranyloxy) siloxane)
In a 200 mL four-necked flask, add 145.92 g of tetraethoxysilane, 0.48 g of potassium hydroxide, and 0.8 mL of ion exchange water, and react for about 37 hours at 120 to 125 ° C. and 33 kPa to 101 kPa (normal pressure) under a nitrogen stream. Went. During this time, 0.8 mL of ion-exchanged water was added. After the reaction, the reaction was further continued at 33 kPa for 2 hours, followed by cooling and filtration to obtain 134.58 g of an ethoxysilane condensate as a pale yellow liquid.
続いて、１００ｍＬの四つ口フラスコに先のテトラエトキシシラン縮合物２５．００ｇとゲラニオール（沸点２３０℃、ｌｏｇＰ値２．７７）６２．９３ｇ（０．４１ｍｏｌ）、４．８％水酸化ナトリウム水溶液０．１７ｇを入れ、エタノールを留出させながら９５〜１１９℃でさらに２時間攪拌した。２時間後、槽内の圧力を徐々に８ｋＰａまで下げ、エタノールを留出させながら１１６〜１１９℃でさらに３時間攪拌した。３時間後、冷却、減圧を解除した後、濾過を行い、ポリ（ゲラニルオキシ）シロキサン（式（ａ１）において、Ｘ＝Ｙ＝−ＯＲ2aで、Ｒ2aがゲラニオールから水酸基を除いた残基、ｎが平均４の化合物である）を含む６５．３９ｇの淡黄色油状物を得た。 Subsequently, 25.00 g of the above tetraethoxysilane condensate and 62.93 g (0.41 mol) of geraniol (boiling point 230 ° C., log P value 2.77) were added to a 100 mL four-necked flask and a 4.8% aqueous sodium hydroxide solution. 0.17 g was added, and the mixture was further stirred at 95 to 119 ° C. while distilling ethanol. After 2 hours, the pressure in the tank was gradually lowered to 8 kPa, and the mixture was further stirred at 116 to 119 ° C. for 3 hours while distilling ethanol. After 3 hours, cooling and releasing the reduced pressure, followed by filtration, poly (geranyloxy) siloxane (in formula (a1), X = Y = -OR 2a , R 2a is a residue obtained by removing the hydroxyl group from geraniol, 65.39 g of a pale yellow oil containing n is an average of 4 compounds).
合成例２（テトラキス（ゲラニルオキシ）シランの合成）
２００ｍＬの四つ口フラスコにテトラエトキシシラン３５．４５ｇ（０．１７ｍｏｌ）、ゲラニオール１００．２６ｇ（０．６５ｍｏｌ）、２．８％ナトリウムメトキシドメタノール溶液１．３４ｍＬを入れ、窒素気流下エタノールを留出させながら１１８〜１２０℃で約２時間攪拌した。２時間後、槽内の圧力を徐々に８ｋＰａまで下げ、エタノールを留出させながら１１２〜１１９℃でさらに３時間攪拌した。３時間後、冷却、減圧を解除した後、濾過を行い、テトラキス（ゲラニルオキシ）シラン（式（ａ１）において、Ｘ＝−ＯＲ2aで、Ｒ2aがゲラニオールから水酸基を除いた残基、ｎが０の化合物である）を含む薄茶色油状物を得た。
Synthesis Example 2 (Synthesis of tetrakis (geranyloxy) silane)
In a 200 mL four-necked flask, put 35.45 g (0.17 mol) of tetraethoxysilane, 100.26 g (0.65 mol) of geraniol, and 1.34 mL of 2.8% sodium methoxide methanol solution. The mixture was stirred at 118 to 120 ° C. for about 2 hours. After 2 hours, the pressure in the tank was gradually lowered to 8 kPa, and the mixture was further stirred at 112 to 119 ° C. for 3 hours while distilling ethanol. Three hours later, after cooling and releasing the reduced pressure, filtration was performed, and tetrakis (geranyloxy) silane (in formula (a1), X = —OR 2a , R 2a is a residue obtained by removing a hydroxyl group from geraniol, and n is A light brown oil containing 0) was obtained.
合成例３（テトラキス（シトロネルオキシ）シランの合成）
ゲラニオールの代わりにシトロネロール（沸点２２５℃、ｌｏｇＰ値３．２６）を１０１．５７ｇ（０．６５ｍｏｌ）用いる以外は合成例２と同様にして、テトラキス（シトロネルオキシ）シラン（式（ａ１）において、Ｘ＝−ＯＲ2aで、Ｒ2aがシトロネロールから水酸基を除いた残基、ｎが０の化合物である）を含む薄茶色油状物を得た。
Synthesis Example 3 (Synthesis of tetrakis (citroneloxy) silane)
Tetrakis (citroneloxy) silane (in formula (a1), X is the same as in Synthesis Example 2 except that 101.57 g (0.65 mol) of citronellol (boiling point 225 ° C., log P value 3.26) is used instead of geraniol. = -OR 2a , R 2a is a residue obtained by removing the hydroxyl group from citronellol, and n is a compound having n of 0).
合成例４（テトラキス（フェニルエチルオキシ）シランの合成）
ゲラニオールの代わりにフェニルエチルアルコールを７９．４１ｇ（０．６５ｍｏｌ）用いる以外は合成例２と同様にして、テトラキス（フェニルエチルオキシ）シラン（式（ａ１）において、Ｘ＝−ＯＲ2aで、Ｒ2aがフェニルエチルアルコールから水酸基を除いた残基、ｎが０の化合物である）を含む薄茶色油状物を得た。
Synthesis Example 4 (Synthesis of tetrakis (phenylethyloxy) silane)
Tetrakis (phenylethyloxy) silane (in formula (a1), X = —OR 2a , R 2a except that 79.41 g (0.65 mol) of phenylethyl alcohol is used instead of geraniol. Is a residue obtained by removing a hydroxyl group from phenylethyl alcohol, and n is a compound of 0).
実施例１〜１４及び比較例１〜５
＜噴霧用液体芳香剤組成物の調製＞
表１に示す配合成分を用い、表１に示す組成の噴霧用液体芳香剤組成物を調製した。得られた組成物は、１規定の塩酸で表１に示すｐＨ（２５℃）に調整した。また、表１において、（ｂ）成分又は（ｂ’）成分を含有しない（その分を水に置き換える）基準組成物を調製した。基準組成物のｐＨはそれぞれの表１記載の噴霧用液体芳香剤組成物と同じｐＨ（２５℃）になるように、１規定の塩酸で調製した。得られた組成物について、下記方法で香りの強さを評価した。噴霧用液体芳香剤組成物のｐＨの測定は以下の測定方法で行った。
Examples 1-14 and Comparative Examples 1-5
<Preparation of liquid fragrance composition for spraying>
Using the formulation components shown in Table 1, a spray liquid fragrance composition having the composition shown in Table 1 was prepared. The obtained composition was adjusted to pH (25 ° C.) shown in Table 1 with 1N hydrochloric acid. Moreover, in Table 1, the reference composition which does not contain (b) component or (b ') component (it replaces that with water) was prepared. The pH of the reference composition was adjusted with 1 N hydrochloric acid so that the pH was the same as that of the liquid fragrance composition for spraying shown in Table 1 (25 ° C.). About the obtained composition, the intensity | strength of the fragrance was evaluated by the following method. The pH of the liquid fragrance composition for spraying was measured by the following measuring method.
＜ｐＨの測定方法＞
ｐＨの測定で使用したｐＨ測定装置及びｐＨ標準液を下記に示す。
〔ｐＨ標準液〕
堀場製作所（株）製ｐＨ標準液を用いた。
・ｐＨ標準液１００−７（中性りん酸塩標準液、精度；±０．０２ｐＨ）
・ｐＨ標準液１００−９（ホウ酸塩標準液、精度；±０．０２ｐＨ）
〔ｐＨ測定装置〕
・株式会社堀場製作所製のｐＨメータ「Ｄ−５２Ｓ」
・ｐＨ電極：６３６７−１０Ｄ
<Measurement method of pH>
The pH measuring apparatus and pH standard solution used in the measurement of pH are shown below.
[PH standard solution]
A pH standard solution manufactured by HORIBA, Ltd. was used.
・ PH standard solution 100-7 (neutral phosphate standard solution, accuracy; ± 0.02 pH)
・ PH standard solution 100-9 (borate standard solution, accuracy; ± 0.02 pH)
[PH measuring device]
・ PH meter “D-52S” manufactured by HORIBA, Ltd.
-PH electrode: 6367-10D
ｐＨ測定装置は測定の１時間前に電源を入れた。未使用のｐＨ電極を用い、電極を予め２５℃±０．２℃のイオン交換水に２４時間浸しておいたものを使用した。ゼロ校正とスパン校正は、以下に記載のｐＨ標準液を用いて、２５℃におけるｐＨの指示値が、標準ｐＨ±０．０２になるまで繰り返し校正を行った。 The pH measuring device was turned on 1 hour before the measurement. An unused pH electrode was used, and the electrode was previously immersed in 25 ° C. ± 0.2 ° C. ion exchange water for 24 hours. Zero calibration and span calibration were repeatedly performed using the pH standard solution described below until the indicated value of pH at 25 ° C. became standard pH ± 0.02.
噴霧用液体芳香剤組成物２００ｇを２００ｍＬ容量のガラス製トールビーカーに入れ、サランラップ（登録商標）で封をし、ウォーターバス中で、噴霧用液体芳香剤組成物の温度が２５±０．２℃になるように調整した。 200 g of the sprayed liquid fragrance composition is placed in a 200 mL glass tall beaker, sealed with Saran Wrap (registered trademark), and the temperature of the sprayed liquid fragrance composition is 25 ± 0.2 ° C. in a water bath. It was adjusted to become.
校正後にｐＨ電極に２５℃のイオン交換水２００ｍＬをかけて洗浄後、各噴霧用液体芳香剤組成物を３回繰り返し測定した。得られた３回の測定値の平均値をｐＨ測定値とした。 After calibration, 200 mL of 25 ° C. ion-exchanged water was washed on the pH electrode, and each liquid fragrance composition for spraying was repeatedly measured three times. The average value of the three measurement values obtained was taken as the pH measurement value.
＜香りの強さの評価＞
（１）評価用布の調製
綿メリヤスニット布（（株）谷頭商店製、染色試材、綿ニット未シル）２ｋｇを市販の弱アルカリ性洗剤（花王（株）製、アタック高活性バイオＥＸ（登録商標）、２００９年発売品）を用いて全自動洗濯機（日立ＮＷ−７ＦＴ）で洗濯した（洗剤濃度０．０６６７質量％、水道水（２０℃）４０Ｌ使用、標準コース、洗濯９分−すすぎ２回−脱水６分）。洗濯終了後の綿メリヤスニット布を、２５℃、５０％ＲＨの恒温室に干し、１２時間乾燥させた。綿メリヤスニット布を裁断（１０ｃｍ×１０ｃｍ）し評価用布とした。
<Evaluation of fragrance strength>
(1) Preparation of evaluation cloth 2 kg of cotton knitted fabric (manufactured by Tanigami Shoten Co., Ltd., dyeing test material, cotton knit unsill), commercially available weak alkaline detergent (manufactured by Kao Corporation, Attack High Activity Bio EX (registered) (Trademark), product released in 2009) using a fully automatic washing machine (Hitachi NW-7FT) (detergent concentration 0.0667% by mass, tap water (20 ° C) 40L used, standard course, washing 9 minutes-rinse) 2 times-6 minutes dehydration). The cotton knit fabric after washing was dried in a constant temperature room at 25 ° C. and 50% RH and dried for 12 hours. A cotton knit fabric was cut (10 cm × 10 cm) to obtain an evaluation fabric.
（２）木綿タオルの調製
木綿タオル（武井タオル（株）製、ＴＷ−２２０、白色、綿１００％）２４枚を市販の弱アルカリ性洗剤（花王（株）アタック高活性バイオＥＸ（登録商標）、２００９年発売品）を用いて全自動洗濯機（日立ＮＷ−７ＦＴ）で洗濯した（洗剤濃度０．０６６７質量％、水道水（２０℃）４０Ｌ使用、標準コース、洗濯９分−すすぎ２回−脱水６分）。洗濯終了後の木綿タオルを、２５℃、５０％ＲＨの恒温室に干し、１２時間乾燥させた。
(2) Preparation of cotton towels 24 sheets of cotton towels (manufactured by Takei Towel Co., Ltd., TW-220, white, 100% cotton) are commercially available weak alkaline detergent (Kao Co., Ltd. Attack High Activity Bio EX (registered trademark)) (Product released in 2009) was washed with a fully automatic washing machine (Hitachi NW-7FT) (detergent concentration 0.0667% by weight, tap water (20 ° C.) 40 L used, standard course, washing 9 minutes-two rinses- Dehydration 6 minutes). The cotton towel after washing was dried in a constant temperature room at 25 ° C. and 50% RH and dried for 12 hours.
（３）香りの強さの評価方法
（３−１）試験布の調製
前記評価用布１枚を用い、２００メッシュのステンレス製金網の上に平らに置いた。評価用布の乾燥時質量（前記（１）評価用布の調製において、洗濯終了後に２５℃、５０％ＲＨで１２時間乾燥した直後の質量）に対して、表１に示す組成物を５０質量％噴霧した後、２５℃／５０％ＲＨの恒温室にて２４時間自然乾燥させて試験布を得た。また、噴霧直後から２５℃／５０％ＲＨの恒温室にて２時間経過後の湿潤状態にある評価用試験布も用意した。スプレー容器は、キャニオン製Ｔ−７５００を用いた。試験布は、各条件ごとに、１組成当たり５枚調製した。長辺を４つ折りにした木綿タオル（武井タオル（株）製、ＴＷ−２２０、白色、綿１００％）６枚を重ね、重ねた６枚の木綿タオルで、２４時間自然乾燥後の試験布５枚を交互に挟み、内容積約６０Ｌのプラスチック製収納ボックス（容器の内寸は横６４ｃｍ×縦４０ｃｍ×高さ２３ｃｍ、ヨシカワ製、ネオテナーミドルＭ２３）に入れ、２５℃／５０％ＲＨで７日間保管した。噴霧直後から２時間後の湿潤状態にある評価用布、２４時間自然乾燥させた後の評価用布及び７日間保管後の評価用布を、試験布として用いた。
(3) Evaluation method of fragrance strength (3-1) Preparation of test cloth One sheet of the evaluation cloth was used and placed flat on a 200 mesh stainless steel wire mesh. 50 masses of the composition shown in Table 1 with respect to the dry mass of the evaluation fabric (the mass immediately after drying for 12 hours at 25 ° C. and 50% RH in the preparation of the evaluation fabric in (1) above). % Spraying was followed by air drying in a constant temperature room at 25 ° C./50% RH for 24 hours to obtain a test cloth. In addition, an evaluation test cloth in a wet state after 2 hours in a constant temperature room at 25 ° C./50% RH immediately after spraying was also prepared. The spray container used was T-7500 made by Canyon. Five test cloths were prepared per composition for each condition. Test cloth 5 which was naturally dried for 24 hours with 6 cotton towels, 6 layers of cotton towels (Tui-220, white, 100% cotton) with long sides folded in 4 (made by Takei Towel Co., Ltd.) Put the sheets alternately and place them in a plastic storage box with an internal volume of about 60L (the inner dimensions of the container are 64cm wide x 40cm long x 23cm high, manufactured by Yoshikawa, Neo Tenor Middle M23), 7 at 25 ° C / 50% RH. Stored for days. An evaluation cloth in a wet state 2 hours after immediately after spraying, an evaluation cloth after being naturally dried for 24 hours, and an evaluation cloth after storage for 7 days were used as test cloths.
（３−２）基準試験布の調製
表１記載の噴霧用液体芳香剤組成物において（ｂ）成分又は（ｂ’）成分を含まない基準組成物を用いた以外は、前記「（３−１）試験布の調製」と同じ方法で、各条件に対応する基準試験布を調製した。
(3-2) Preparation of Reference Test Cloth The above-described “(3-1)” except that the reference composition containing no component (b) or (b ′) in the liquid fragrance composition for spraying described in Table 1 was used. The reference test cloth corresponding to each condition was prepared in the same manner as “) Preparation of test cloth”.
（４）香りの強さの評価
各条件ごとに１組成当たり５枚の試験布を用い、５枚の試験布を重ねて、３０歳代の男性５人及び女性５人の計１０人のパネラーで経時的な香りの強さを評価した。２５℃、５０％ＲＨで２時間経過後の湿潤状態にある試験布、２５℃、５０％ＲＨで２４時間乾燥後の試験布、及び７日間保管後の試験布の香りの強さを評価した。評価は、各条件に対応する５枚の基準試験布を重ねて用いて下記の基準で比較評価し、その平均値を求め、表１に示した。２４時間乾燥後及び７日保管後の香りの強さとしては、香りの持続性の点で、いずれの香りの強さも平均点３未満であることが好ましい。一方で、噴霧直後から２時間後の湿潤状態の試験布の香りの強さとしては、湿潤状態での香り抑制の点で、平均点が３．６以上が好ましい。
０：基準試験布よりも明らかに香りが強い
１：基準試験布よりも香りが強い
２：基準試験布よりもやや香りが強い
３：基準試験布よりも僅かに香りが強い
４：基準試験布よりやや香りが弱い
５：基準試験布よりも香りが弱い
(4) Evaluation of the intensity of fragrance Five test cloths were used per composition for each condition, and five test cloths were stacked to make a total of 10 panelists, 5 males and 5 females in their 30s. The strength of the scent over time was evaluated. The strength of the scent of the test cloth in a wet state after 2 hours at 25 ° C. and 50% RH, the test cloth dried for 24 hours at 25 ° C. and 50% RH, and the test cloth after storage for 7 days was evaluated. . Evaluation was carried out by comparing and evaluating the five criteria test cloths corresponding to each condition according to the following criteria, and the average value was obtained and shown in Table 1. The strength of the scent after drying for 24 hours and after storage for 7 days is preferably less than the average score of 3 in terms of scent persistence. On the other hand, as the strength of the scent of the wet test cloth 2 hours after the spraying, an average score of 3.6 or more is preferable from the viewpoint of suppressing the scent in the wet state.
0: Clearly stronger fragrance than the standard test cloth 1: Stronger fragrance than the standard test cloth 2: Slightly stronger fragrance than the standard test cloth 3: Slightly stronger fragrance than the standard test cloth 4: Reference test cloth Slightly weaker fragrance 5: Scent is weaker than standard test cloth
表１から、比較例１〜５の噴霧用液体芳香剤組成物は、香りの持続性が乏しいのに対し、実施例１〜１４の噴霧用液体芳香剤組成物は、噴霧後の湿潤状態では香りが抑制され、衣類保管時の乾燥状態では香りの持続性が優れていることがわかる。 From Table 1, the liquid fragrance compositions for spraying of Comparative Examples 1 to 5 have poor fragrance persistence, whereas the liquid fragrance compositions for spraying of Examples 1 to 14 are in a wet state after spraying. It can be seen that the scent is suppressed, and that the scent is excellent in the dry state during storage of clothes.
Claims (5)
（ａ）成分：下記一般式（ａ１）で表されるケイ酸エステル
〔式中、Ｘは−ＯＨ、−Ｒ1a、−ＯＲ2a又は−ＯＲ3aであり、ＹはＸ又は−ＯＳｉ（Ｘ）3であり、Ｒ1aは炭素数１〜２２の炭化水素基、Ｒ2aは分子内に炭素数６〜２２の炭素原子を有する香料アルコールからヒドロキシ基を１つ除いた残基、Ｒ3aは炭素数１〜５の炭化水素基又はベンジル基、ｎは０〜５の数である。複数個のＸ及びＹはそれぞれ同一でも異なっていても良いが、一分子中に−ＯＲ2aを少なくとも１つ有する。〕
（ｂ）成分：下記一般式（ｂ１）で表される化合物、ジエタノールアミン及びトリエタノールアミンから選ばれる、少なくとも１種のｐＫａが７．０〜９．０のヒドロキシアミン化合物並びに該ヒドロキシアミン化合物の塩から選ばれる化合物
〔式中、Ｒ1bは、水素原子、炭素数１〜５のアルキル基、又は炭素数１〜５のヒドロキシアルキル基であり、Ｒ2bは、水素原子、炭素数１〜６のアルキル基、又は炭素数１〜５のヒドロキシアルキル基であり、Ｒ3b及びＲ4bは、炭素数１〜５のアルカンジイル基である。Ｒ3b及びＲ4bは、同一でも異なっていてもよい。上記Ｒ1b〜Ｒ4bの基の種類は、一般式（ｂ１）で表されるヒドロキシアミン化合物のｐＫａ（２５℃）が７．０〜９．０になるように選択される。〕 The liquid aromatic agent composition for spraying which contains the following (a) component, (b) component, and water and whose pH in 25 degreeC is 6.5-8.5.
(A) Component: Silicate ester represented by the following general formula (a1)
[Wherein, X is —OH, —R 1a , —OR 2a or —OR 3a , Y is X or —OSi (X) 3 , R 1a is a hydrocarbon group having 1 to 22 carbon atoms, R 2a is a residue obtained by removing one hydroxy group from a perfume alcohol having 6 to 22 carbon atoms in the molecule, R 3a is a hydrocarbon group or benzyl group having 1 to 5 carbon atoms, and n is 0 to 5 Is a number. The plurality of X and Y may be the same or different, but have at least one —OR 2a in one molecule. ]
(B) Component: a compound represented by the following general formula (b1), at least one hydroxyamine compound selected from diethanolamine and triethanolamine and having a pKa of 7.0 to 9.0, and a salt of the hydroxyamine compound Compound selected from
[Wherein, R 1b is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms, and R 2b is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or It is a C1-C5 hydroxyalkyl group, R <3b> and R <4b> are C1-C5 alkanediyl groups. R 3b and R 4b may be the same or different. The type of group R 1b to R 4b are, pKa of the general formula hydroxy amine compound represented by (b1) (25 ℃) is selected to be 7.0 to 9.0. ]
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