CN100341584C - 消臭性组合物 - Google Patents
消臭性组合物 Download PDFInfo
- Publication number
- CN100341584C CN100341584C CNB2005100042664A CN200510004266A CN100341584C CN 100341584 C CN100341584 C CN 100341584C CN B2005100042664 A CNB2005100042664 A CN B2005100042664A CN 200510004266 A CN200510004266 A CN 200510004266A CN 100341584 C CN100341584 C CN 100341584C
- Authority
- CN
- China
- Prior art keywords
- acid
- composition
- present
- ammonium
- formulation example
- 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.)
- Expired - Lifetime
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- 239000002131 composite material Substances 0.000 title description 13
- 238000004332 deodorization Methods 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 144
- 239000002781 deodorant agent Substances 0.000 claims abstract description 47
- 150000003868 ammonium compounds Chemical class 0.000 claims abstract description 9
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 22
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 19
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 10
- 239000004615 ingredient Substances 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 6
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 6
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 6
- 239000001393 triammonium citrate Substances 0.000 claims description 6
- 235000011046 triammonium citrate Nutrition 0.000 claims description 6
- 206010008190 Cerebrovascular accident Diseases 0.000 claims description 5
- 208000006011 Stroke Diseases 0.000 claims description 5
- 239000002253 acid Substances 0.000 abstract description 18
- 150000003839 salts Chemical class 0.000 abstract description 16
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 abstract description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 abstract 2
- 150000003851 azoles Chemical class 0.000 abstract 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 abstract 1
- OZQGLZFAWYKKLQ-UHFFFAOYSA-N oxazinane Chemical compound C1CCONC1 OZQGLZFAWYKKLQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000009472 formulation Methods 0.000 description 66
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 58
- -1 inorganic acid ammonium salt Chemical class 0.000 description 38
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 37
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- 239000012153 distilled water Substances 0.000 description 15
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 13
- 239000001632 sodium acetate Substances 0.000 description 13
- 235000017281 sodium acetate Nutrition 0.000 description 13
- 239000004567 concrete Substances 0.000 description 12
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- 239000000843 powder Substances 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
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- 239000000835 fiber Substances 0.000 description 9
- 239000004088 foaming agent Substances 0.000 description 9
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
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- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
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- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 4
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000001118 alkylidene group Chemical group 0.000 description 4
- 239000007767 bonding agent Substances 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000012488 sample solution Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- 150000003852 triazoles Chemical class 0.000 description 4
- 229920006305 unsaturated polyester Polymers 0.000 description 4
- 229940005605 valeric acid Drugs 0.000 description 4
- 229940117958 vinyl acetate Drugs 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- XKVUYEYANWFIJX-UHFFFAOYSA-N 5-methyl-1h-pyrazole Chemical compound CC1=CC=NN1 XKVUYEYANWFIJX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
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- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical class C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000004378 air conditioning Methods 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
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- 150000002576 ketones Chemical class 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- 229910052783 alkali metal Inorganic materials 0.000 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
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Abstract
本发明的目的是提供可以有效地除去恶臭成分的乙醛、甲醛等醛类的消臭性组合物。本发明涉及的消臭性组合物特征为以(A)选自酰肼类、唑类和嗪类中至少一种和选自(B)弱酸金属盐以及(C)铵化合物中的1种作为有效成分。
Description
技术领域
本发明涉及消臭性组合物,更详细地说,涉及可以有效地除去恶臭成分乙醛、甲醛等醛类的消臭性组合物。
技术背景
近几年生活水平的提高,要求更加舒适的生活环境和工作环境,随之出现了各种问题。例如戒烟运动兴起的原因之一,是香烟中含有的乙醛、氨、三甲胺、硫醇、硫化氢等多种恶臭成分附着在毛发、衣服、室内墙壁、家居、地毯以及汽车、电车等交通工具室内等,形成恶臭残存物。另外在最近新住宅中大量使用含浸或涂附有甲醛等化学物质的新建筑材料,该化学物质大量地气化扩散,形成恶臭,恶化生活环境,而且也有损于居住者的身体健康,存在有很大问题。
本发明者为了解决所述问题,提出有效地除去在香烟恶臭成分中占有大比例的乙醛以及从新建筑材料扩散气化的甲醛等醛类的消臭剂为酰肼类、唑类和嗪类(日本专利申请公开10-36681号、10-111745号)。
发明的公开
酰肼类、唑类和嗪类由于本身具有优良的消臭性能,本发明者为了进一步提高这些化合物的消臭效率和降低添加量,快速显示效果,考察了使用各种助剂。
结果发现通过合用各种助剂,可以显著提高消臭效率,相应的减小添加量,实现快速显示效果。从而完成了本发明。
也就是本发明涉及以(A)选自酰肼类、唑类和嗪类中至少一种、(B)弱酸金属盐以及(C)选自铵化合物中的1种作为有效成分的消臭性组合物。
所述构成组成的本发明的消臭性组合物可以显著提高消臭效率。
另外使用铵化合物作为助剂的消臭性化合物助剂,不仅消臭效率显著,而且也不会使被处理体着色。
而且,本发明涉及以(A)选自酰肼类、唑类和嗪类中至少一种、(B)选自弱酸金属盐的1种作为有效成分的消臭性组合物。
另外,本发明涉及以(A)选自酰肼类、唑类和嗪类中至少一种、(C)选自铵化合物中的1种作为有效成分的消臭性组合物。
另外,所谓的弱酸金属盐为电离常数为-0.01以下的酸的金属盐,例如下述的羧酸、硼酸、磷酸、碳酸等的金属盐。
另外,所述铵化合物为具有铵离子(-NH4)的化合物,例如下述无机酸铵盐及有机酸铵盐等。
本发明的最佳实施方案
本发明的消臭性组合物中,以(A)选自酰肼类、唑类和嗪类中至少一种(本发明说明书中有时称为(A)成分)作为有效成分使用。
作为酰肼类例如有在分子中具有1个酰肼基的单酰肼化合物、在分子中具有2个酰肼基的二酰肼化合物、在分子中具有3个以上酰肼基的多酰肼化合物等。
作为单酰肼化合物的具体例,例如有通式
R-CO-NHNH2 (1)
[式中R表示氢原子、烷基、或可具有取代基的芳基。]
表示的单酰肼化合物。
所述通式(1)中,R表示的烷基例如有甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基、正壬基、正癸基、正十一烷基等碳数1~12的直链烷基。芳基例如有苯基、联苯基、萘基等。
其中优选苯基。
另外作为芳基取代基例如有羟基,氟、氯、溴等卤原子,甲基、乙基、正丙基、异丙基、正丁基、叔丁基、异丁基等碳1~4的直链或支链状烷基等。
所述通式(1)的酰肼化合物具体有:月桂酰肼、水杨酰肼、甲酰肼、乙酰肼、丙酰肼、对羟基苯甲酰肼、萘甲酰肼、3-羟基-2-萘甲酰肼等。
二酰肼化合物的具体例例如有通式
H2NHN-X-NHNH2 (2)
[式中X表示基团-CO-或-CO-A-CO-,A表示亚烷基或亚芳基]
表示的二酰肼化合物。
所述通式(2)中,A表示的亚烷基例如有亚甲基、亚乙基、三亚甲基、四亚甲基、五亚甲基、六亚甲基、七亚甲基、八亚甲基、九亚甲基、十亚甲基、十一亚甲基等碳1~12的直链状亚烷基。亚烷基的取代基例如有羟基等。亚芳基例如有:亚苯基、亚联苯基、亚萘基、亚蒽基、亚菲基等,其中优选亚苯基、亚萘基等。亚芳基取代基例如有与所述芳基的取代基相同的基团。
所述通式(2)的二酰肼化合物具体例如有草酸二酰肼、丙二酸二酰肼、琥珀酸二酰肼、己二酸二酰肼、壬二酸二酰肼、癸二酸二酰肼、十二烷-2酸二酰肼、马来酸二酰肼、富马酸二酰肼、二乙二醇酸二酰肼、酒石酸二酰肼、苹果酸二酰肼、间苯二甲酸二酰肼、对苯二甲酸二酰肼、二聚酸二酰肼、2,6-萘二甲酸二酰肼等二元酸二酰肼等。
而且,在日本专利公告平2-4607号公报中所述的各种二元酸二酰肼化合物、2,4-二肼基-6-甲基氨基-均-三嗪等也可以用作本发明的二酰肼。
多酰肼化合物具体例如有聚丙烯酰肼等。
上述化合物中,优选二酰肼化合物,特别优选二元酸二酰肼,更优选己二酸二酰肼。
所述酰肼化合物可以单独使用也可以2种以上混合使用。
唑类以及嗪类可以广泛使用作为杂原子具有2个或3个氮原子的,已知的5元至六元杂环化合物。这些杂环化合物中可以取代1个或2个以上的碳1~4左右的直链或支链烷基、可具有1或2个以上取代基的芳基、羟基、氨基、烷基氨基、二烷基氨基、芳基氨基、二芳基氨基、巯基、酯基、羧基、苯并三唑基、1-羟基苯并三唑基等取代基。
这里碳1~4左右的直链或支链烷基例如有甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基等。另外,芳基例如有苯基、联苯基、萘基。这些基团中也可以取代1或2个羟基、卤原子、磺酸基、碳1-4的直链或支链的烷基等取代基。另外取代基具有羧基的场合,其酯也包括在本发明的有效成分中。
唑类例如有二唑类、三唑类、噻二唑类等,优选使用二唑类、三唑类、
二唑类的具体例例如有:3-甲基吡唑啉-5-酮、1,3-二甲基吡唑啉-5-酮、3-甲基-1-苯基吡唑啉-5-酮、3-苯基吡唑啉-6-酮、3-甲基-1-(3-磺基苯基)吡唑啉-5-酮等吡唑啉-5-酮类、吡唑、3-甲基吡唑、1,4-二甲基吡唑、3,5-二甲基吡唑、3,5-二甲基-1-苯基吡唑、3-氨基吡唑、5-氨基-3-甲基吡唑、3-甲基吡唑-5-羧酸、3-甲基吡唑-5羧酸甲基酯、3-甲基吡唑-5羧酸乙基酯、3,5-甲基吡唑二羧酸类等吡唑类等。
三唑类具体例如有:1,2,3-三唑、1,2,4-三唑、3-正丁基-1,2,4-三唑、3,5-二甲基-1,2,4-三唑、3,5-二丁基-1,2,4-三唑、3-巯基-1,2,4-三唑、3-氨基-1,2,4-三唑、4-氨基-1,2,4-三唑、3,5-二氨基-1,2,4-三唑、5-氨基-3-巯基-1,2,4-三唑、3-氨基-5-苯基-1,2,4-三唑、3,5-二苯基-1,2,4-三唑、1,2,4-三唑-3-酮、尿唑(3,5-二羟基-1,2,4-三唑)、1,2,4-三唑-3-羧酸、1-羟基苯并三唑、5-羟基-7-甲基-1,3,8-二氮杂中氮茚、1H-苯并三唑、4-甲基-1H-苯并三唑、5-甲基-1H-苯并三唑等。
嗪类例如有二嗪类、三嗪类、哒嗪类等。其中优选使用哒嗪类。
哒嗪类的具体例例如有6-甲基-8-羟基三唑并哒嗪、4,5-二氯-3-哒嗪、马来酰肼、6-甲基-3-哒酮等。
上述之中,优选唑类,特别优选1,2,4-三唑、1,2,3-三唑等三唑类、3,5-二甲基吡唑等吡唑类以及3-甲基-吡唑啉-5酮等吡唑啉-5酮。
本发明所述唑类以及嗪类可以单独使用也可以2种以上混合使用。
(B)选自弱酸金属盐中的至少1种(本说明书中(有时称为(B)成分)例如有选自羧酸金属盐、硼酸金属盐、羧酸氢金属盐、磷酸金属盐以及碳酸金属盐等中的至少一种。
羧酸金属盐例如有:甲酸、乙酸、丙酸、丁酸、异丁酸、戊酸、异戊酸、戊酸、己酸、庚酸、辛酸、癸酸、十二酸、硬脂酸等饱和单羧酸类、丙烯酸、甲基丙烯酸、丙炔酸、丁烯酸、异丁烯酸、油酸、马来酸、富马酸等不饱和脂肪酸类,草酸、丙二酸、琥珀酸、戊二酸、己二酸、辛二酸、癸二酸等饱和二羧酸类,苯甲酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、1-萘甲酸、苯乙酸、阿托酸、肉桂酸等芳香族羧酸类,烟酸、异烟酸、呋喃甲酸、噻吩甲酸等杂环羧酸类等羧酸类的钠盐、钾盐、锂盐等碱金属盐、钡盐、锶盐、钙盐、镁盐等碱土金属盐以及铬盐、锰盐、铝盐、锡盐、锌盐、铜盐、铁盐、钴盐、镍盐。其中优选碱金属盐、碱土金属盐。
另外作为硼酸盐例如有硼酸碱金属盐、四硼酸碱金属盐。这些羧酸金属盐以及硼酸金属盐可以单独使用也可以两种以上混合使用。
可以用在这些(B)成分中的化合物优选的具体例有:醋酸钠、丙酸钠、苯甲酸钠、邻苯二甲酸氢钾、四硼酸钠、磷酸二氢钾等。
本发明中相对于(A)成分(B)成分的使用比例为:(A)成分∶(B)成分=1∶5~100∶1(重量比)的范围。
(C)选自铵化合物中的至少一种(本说明书中有时称为(C)成分)只要是选自具有铵(-NH4)离子的化合物中的至少一种,没有特别限定。例如可以是无机酸的铵盐或有机酸的铵盐等。
无机酸的铵盐例如有:氯化铵、硫酸铵、亚硫酸铵、硝酸铵、溴化铵、氟化铵、硫化铵、磷酸铵、三聚磷酸铵、碳酸铵等。
另外,作为有机酸铵盐,羧酸铵盐具体有:甲酸、乙酸、丙酸、丁酸、异丁酸、戊酸、异戊酸、戊酸、己酸、庚酸、辛酸、癸酸、十二酸、硬脂酸等饱和单羧酸类,或者草酸、丙二酸、琥泊酸、戊二酸、己二酸、辛二酸、癸二酸等饱和二羧酸类,或柠檬酸等饱和三羧酸类,或者丙烯酸、甲基丙烯酸、丙炔酸、丁烯酸、异丁烯酸、油酸、马来酸、富马酸等不饱和脂肪酸类、或者苯甲酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、1-萘甲酸、苯乙酸、阿托酸、肉桂酸等芳香族羧酸类,或者烟酸、异烟酸、呋喃甲酸、噻吩甲酸等杂环羧酸类等各种羧酸类的铵盐。
这些无机酸铵盐以及有机酸铵盐等可以单独使用也可以两种以上混合使用。
本发明的消臭性组合物的(C)成分可以使用的化合物优选具体物质如:氯化铵、硫酸铵、柠檬酸三铵等,其中特别优选氯化铵、柠檬酸三铵。
本发明中相对于(A)成分,(C)成分的使用比例为:(A)成分∶(C)成分=1∶5~100∶1(重量比)的范围。
另外,将选自所述(B)成分的至少一种或选自所述(C)成分的至少一种任何一种添加到(A)成分中,也可以配制本发明的消臭性组合物;另外,也可以将选自所述(B)成分的至少一种以及选自所述(C)成分的至少一种添加到(A)成分中,配制本发明的消臭性组合物。
在本发明的消臭性组合物中在不影响其效果的范围内可以添加公知的消臭剂(例如珍珠岩、沸石、硅胶、活性炭、尿素、硫酸亚铁和L-抗坏血酸的结合体等)。
本发明的消臭性组合物通常以粉末、溶液、或乳化物的形态使用。
本发明的组合物的粉末可以和一般的粉末同样使用,例如可以直接作为消臭剂混合添加到被处理材料中使用。
另外本发明的组合物的粉末将其溶解于适当的有机溶剂、水等溶剂中,之后涂附、含浸或混合在被处理材料中使用。这里有机溶剂可以使用公知的物质,例如1~8左右的碳数的直链或支链状脂肪族饱和醇类、环戊醇、环己醇等脂环式醇类、乙二醇等多元醇类、碳1~8左右的直链或支链或环状脂肪族烃类、烷基部分碳1~8左右的直链或支链状二烷基醚类、二芳基醚类、四氢呋喃、二氧六环等环状醚类、酮类、酯类、乙腈等腈类、二甲基甲酰胺、二甲基亚砜等极性溶剂、磷酸酯类、这些2种以上的混合溶剂等。另外也可以使有关的有机溶剂中含有适量的水。有机溶剂溶液的形态中配制时的有效成分浓度没有特别限制,可根据得到的溶液的用途进行广泛地选择。例如(A)成分、(B)成分和/或(C)成分的总量通常可以为溶液总量的0.1~80重量%程度,优选0.5~60重量%程度。
另外,本发明的消臭性组合物的乳化物也可以利用公知的方法例如适量逐步混合本发明的组合物的粉末、水以及表面活性剂进行制造。再通过将该乳化物和合成树脂乳液混合,也可以制造成乳液的形态进行使用。这里作为合成树脂乳液例如有:利用醋酸乙烯酯聚合物乳液、乙烯-醋酸乙烯酯共聚物乳液、醋酸乙烯酯Bersatate共聚物乳液、乙烯-醋酸乙烯酯-氯乙烯共聚物乳液、乙烯-醋酸乙烯酯-丙烯酸酯共聚物乳液、丙烯酸酯共聚物乳液、丙烯酸酯-苯乙烯共聚物乳液、氯乙烯共聚物乳液、氨基甲酸酯聚合物乳液、硅氧烷聚合物乳液,环氧聚合物乳液等乳液聚合、溶液聚合等制造得到的合成树脂乳液或淀粉水溶液等。制造乳化物时的有效成分的使用量没有特别限制,可以宽范围适当选择。例如通常合成树脂乳液的固体成分100重量份适当配制成(A)成分、(B)和/或(C)成分的总量为0.1~30重量份左右、优选0.5~20重量份左右。
另外也可以将本发明的组合物的粉末或该粉末的溶液或配制成分散液的形态的本发明的组合物和适当的合成树脂混合,制成消臭性树脂组合物。合成树脂没有特别限定。只要是公知的就可以,例如有:聚氯乙烯、聚烯烃(聚乙烯、聚丙烯等)、甲基丙烯酸树脂、聚乙烯醇、乙酰乙酰化聚乙烯醇、ABS树脂、偏氯乙烯树脂、醋酸乙烯酯树脂、聚酰胺、聚缩醛、聚碳酸酯、改性聚苯醚聚砜、聚苯硫醚等热塑性树脂、环氧树脂、二甲苯树脂、胍胺树脂、邻苯二甲酸二烯丙基酯树脂、乙烯酯树脂、酚醛树脂、不饱和聚酯、呋喃树脂、聚酰亚胺、聚氨酯、马来酸树脂、三聚氰胺树脂、脲醛树脂、尿素树脂等热固性树脂等。其中热塑性树脂优选聚氯乙烯、聚烯烃(聚乙烯、聚丙烯等)、甲基丙烯酸树脂、聚乙烯醇、乙酰乙酰化聚乙烯醇、ABS树脂等,特别优选聚氯乙烯、聚烯烃等。另外热固性树脂例如有酚醛树脂、脲醛树脂、尿素树脂、三聚氰胺树脂、不饱和聚酯、环氧树脂、硅树脂、聚氨酯等,特别优选环氧树脂、聚氨酯等。本发明的消臭性树脂组合物中对有效成分的配合量没有特别限定,可以在广泛的范围选择。例如相对通常合成树脂100重量份适当配制成(A)成分、(B)以及/或(C)成分的总量为0.1~30重量份左右、优选0.5~20重量份左右。
本发明的消臭性树脂组合物中也可以添加发泡剂。通过将得到的组合物加热使其发泡,微小的气泡均一地分散于发泡后的涂附膜、成型品等中,和空气接触的表面积显著增大,进一步提高消臭效果。发泡剂没有特别限制。根据使用的合成树脂的种类和得到的消臭性发泡体的使用目的以及使用场所等可以从公知的有机系发泡剂以及无机系发泡剂中适当地选择使用。有机系发泡剂例如有:偶氮二甲酰胺、偶氮二异丁腈、偶氮六氢苄腈等偶氮化合物、苯磺酰肼、p,p’-羟基双(苯磺酰肼)、对甲苯磺酰肼、二苯砜-3,3-二苯磺酰肼、二苯醚-4,4’-二苯磺酰肼、等苯磺酰肼化合物、N,N’-二亚硝基五甲撑四胺、N,N’-二亚硝基-N,N’-二甲基对苯二甲酰胺等亚硝基化合物、对苯二甲酰迭氮、对叔丁基苯甲酰迭氮等迭氮系化合物等。其中优选偶氮化合物,更优选偶氮二甲酰胺。无机系发泡剂例如有碳酸氢钠、碳酸铵等。另外也可以使用二氧化碳、氯氟烃类、二氯甲烷、戊烷、空气等气体。例如在使聚氨酯发泡时,聚氨酯中添加适量的水,作为聚氨酯一种成分的异氰酸酯和水反应生成二氧化碳,由此形成发泡体。发泡剂的配合量相对合成树脂100重量份通常配制为0.1~30重量份左右、优选0.5~20重量份左右。不足0.1重量份时,由于发泡剂分解释放的气体的量少,发泡时必要的气体状物的量或反应生成的气体的量少,有得不到希望的发泡体之虞。另外,超过30重量份,存在的缺点是由于发泡剂分解释放的气体的量多,而且气压增高,树脂组合物不能承受此气体量和气压,要么因膨胀气泡破坏,或者更加污染环境,安全上也存在问题。
考虑其消臭效果以及其持续性,得到的发泡体的发泡倍率优选1.2~60倍,更优选1.5~50倍。
在本发明的消臭性树脂组合物中也可以添加例如抗氧化剂、紫外线吸收剂、抗静电剂、阻燃剂、着色剂、防霉剂、强化剂、填充剂等公知的塑料添加剂。这里强化材料以及填充剂例如有:熔融二氧化硅、结晶二氧化硅、氢氧化铝、氧化铝、白碳黑、碳黑等公知的无机填充剂、钛酸钾晶须、硅酸钙晶须、硼酸铝晶须、硼酸镁晶须、硅酸锌晶须等无机晶须等。
本发明的组合物为粉末形态场合,例如将其作为合成树脂添加剂使用,也可以将其做成薄膜、片等适当的形状的成型品。而且,也可以在建材等表面处理用涂料中添加本发明的组合物粉末。
以溶液形态使用的本发明组合物的具体用途例如有:木材(主要是复合板和纤维板或装饰板等建筑材料)、纸、纤维、纤维制品、树脂成型品等的处理剂。对纸、纤维、纤维制品(例如膜或片)等处理时,可以涂附或含浸本发明组合物的粉末溶液或分散液。例如对无纺布进行处理,可以用作空调或空气清洁机的空气过滤物。
乳化物形态使用的本发明的组合物的具体的用途例如有:向粘接剂、纸类(纸、壁纸等)、纤维、木材(主要是复合板和纤维板或装饰板等建筑材料)、树脂成型品(主要是薄膜或片)的表面处理剂、合成树脂中添加的添加剂。粘接剂可以通过向树脂乳液(特别优选醋酸乙烯树脂系乳液、丙烯酸树脂系乳液、苯乙烯-丁二烯共聚物乳液等)或淀粉水溶液中添加混合本发明的组合物的乳化物、优选乳液进行制造。对纸、纤维、木材、树脂成型品等进行处理的,可以涂附或含浸本发明组合物的乳化物。
更具体地说,如果在壁纸上使用时,以合成树脂片材(例如氯乙烯树脂片材)和不燃烧纸组成的物质为例进行说明,可以将本发明的组合物或者与合成树脂混合成形、片材化,或者涂附在合成树脂片材的表面上,或者可以含浸或涂附在不燃烧纸上。另外含有本发明的组合物的乳液也可以作为层合氯乙烯树脂片材和阻燃烧纸时的粘接剂使用。另外,将本发明的组合物的乳化物涂附或含浸在无纺布上,可以用作空调或空气清洁机的空气过滤物。
以树脂组合物的形态使用的本发明的组合物可以做成希望形状的成型物。该成型物的具体例例如有空调或空气清洁机用的空气过滤物、薄膜、片材等。这时优选的合成树脂例如有聚丙烯、聚乙烯等聚烯烃类等。另外树脂组合物形态的本发明的组合物也可以用作粘接剂。这时优选的合成树脂例如有:尿素树脂、酚醛树脂、呋喃树脂等热固性树脂等。
本发明的消臭性组合物也可以用作涂料特别是室内用涂料等。
实施例
下面利用实施例、比较例以及试验例,更详细地说明本发明。
制剂例1
将己二酸二酰肼(ADH)以及醋酸钠(AcONa)溶解于蒸馏水中,配制成本发明的消臭剂。另外己二酸二酰肼(ADH)以及醋酸钠(AcONa)的浓度共为8重量%。
制剂例2~6
用表1所示的比例使己二酸二酰肼以及醋酸钠溶解于蒸馏水中,配制成本发明的消臭剂。
制剂例7~11
用表2所示的比例使己二酸二酰肼以及各种化合物溶解于蒸馏水中,配制成本发明的消臭剂。
比较制剂例1
将己二酸二酰肼单独溶解于蒸馏水中,配制浓度8重量%,做成比较制剂例1的消臭剂。
比较制剂例2
将用醋酸钠单独溶解于蒸馏水中,配制浓度8重量%,做成比较制剂例2的消臭剂。
试验例1
对实施例以及比较例得到的各种消臭剂根据[JIS 5905纤维板甲醛挥发量]测定法,按照下述方法评价该消臭性能。
MDF复合板使用市售的不同批量5种(MDF复合板A~E)。
样品片的配制1
MDF复合板A~E(各40cm×40cm×0.3cm)上使用喷雾器以38.1g/m2的比例均一地喷撒制剂例或比较制剂例得到的各种消臭剂。将试样在室温干燥,将各试样分别放入乙烯基袋中,放置一周。放置结束后将各试样分别截断成11片15cm×5cm×0.3cm的长方形样品片。
测定方法1
将盛有300ml蒸馏水的结晶皿(直径120mm、高度60mm)放置在干燥器(JIS R3503规定的大小的240mm的容积为10升者)底部,在其上放置贴有磁片的样品(15cm×5cm×0.3cm)11片,在20~25℃下放置24小时,使蒸馏水吸收释放的甲醛,为样品溶液。
试样溶液中的甲醛浓度利用乙酰丙酮法使用光电比色计进行比色定量。
结果示于表1以及表2中。表中MDF复合板一栏的数值显示甲醛释放量,括号内的数值显示对应的未处理的MDF复合板的甲醛释放量中释放量减少率,用百分率表示。
表1
添加量(重量%) | MDF复合板 | ||||
ADH | AcONa | A | B | C | |
制剂例1 | 8 | 8 | 0.26(90) | ||
制剂例2 | 8 | 4 | 0.29(88) | ||
制剂例3 | 8 | 2 | 0.38(85) | ||
制剂例4 | 8 | 0.5 | 0.46(74) | ||
制剂例5 | 4 | 8 | 0.24(86) | ||
制剂例6 | 2 | 8 | 0.61(65) | ||
比较制剂例1 | 8 | 0 | 1.80(30) | ||
比较制剂例1 | 8 | 0 | 1.69(27) | ||
比较制剂例2 | 0 | 8 | 2.12(-21) | ||
未处理A | - | - | 2.57 | ||
未处理B | - | - | 2.33 | ||
未处理C | - | - | 1.75 |
表2
配合成分和添加量(重量%) | MDF复合板 | |||||
配合成分 | 添加量 | 配合成分 | 添加量 | D | E | |
制剂例7 | ADH | 8 | (AcO)2Mg | 8 | 0.24(76) | |
制剂例8 | ADH | 8 | 丙酸钠 | 8 | 0.18(82) | |
制剂例9 | ADH | 8 | 苯甲酸钠 | 8 | 0.15(86) | |
制剂例10 | ADH | 8 | 邻苯二甲酸氢钾 | 8 | 0.23(79) | |
制剂例11 | ADH | 8 | 四硼酸钠 | 4 | 0.27(75) | |
制剂例1 | ADH | 8 | 醋酸钠 | 8 | 0.09(91) | 0.11(90) |
比较制剂例1 | ADH | 8 | - | - | 0.67(32) | |
未处理D | - | - | - | 0.98 | ||
未处理E | - | - | - | 1.07 |
从制剂例1~6和制剂比较例1的试验结果可知,己二酸二酰肼和醋酸钠合用的制剂例消臭剂与单独使用二酰肼的比较例消臭剂比较具有优良的除去甲醛的能力。
另外从制剂比较例2的试验结果可知,不仅醋酸钠单独使用不仅没有除去甲醛的性能,相反可以加速甲醛的释放。
从制剂例7~11的试验结果可知,取代醋酸钠使用各种羧酸金属盐或硼酸金属盐的消臭剂也具有良好的消臭性能。
另外从表2的结果可知,使用醋酸钠的消臭剂具有特别好的消臭性能。
制剂例12及13
蒸馏水中溶解表3所示比例(重量%)的己二酸二酰肼(ADH)和醋酸钠,配制本发明的消臭剂。
制剂例14和15
蒸馏水中溶解表3所示比例(重量%)的己二酸二酰肼(ADH)和氯化铵,配制本发明的消臭剂。
制剂例16和17
蒸馏水中溶解表3所示比例(重量%)的己二酸二酰肼(ADH)和硫酸铵,配制本发明的消臭剂。
制剂例18和19
蒸馏水中溶解表3所示比例(重量%)的己二酸二酰肼(ADH)柠檬酸三铵,配制本发明的消臭剂。
比较制剂例3
只使用蒸馏水。
比较制剂例4
蒸馏水中溶解5重量%的己二酸二酰肼(ADH),配制本发明的比较制剂例4消臭剂。
试验例2
表3
消臭剂成分 | 添加量 | 助剂 | 添加量 | |
制剂例12 | ADH | 5 | 醋酸钠 | 1 |
制剂例13 | ADH | 5 | 醋酸钠 | 4 |
制剂例14 | ADH | 5 | 氯化铵 | 1 |
制剂例15 | ADH | 5 | 氯化铵 | 4 |
制剂例16 | ADH | 5 | 硫酸铵 | 1 |
制剂例17 | ADH | 5 | 硫酸铵 | 4 |
制剂例18 | ADH | 5 | 柠檬酸三铵 | 1 |
制剂例19 | ADH | 5 | 柠檬酸三铵 | 4 |
比较制剂例3 | - | - | - | - |
比较制剂例4 | ADH | 5 | - | - |
对于制剂例和比较制剂得到的各消臭剂例,按照[JIS普通复合板甲醛挥发量]测定法,根据下述方法评价该消臭性能。
样品片的配制2
5.5mm的市售F2复合板(各30cm×30cm×0.55cm)上在两面均一地涂附2g/尺2(22.2g/m2)。在室温干燥试样,培养一夜。培养结束之后,从各样品分别剪切10片15cm×5cm×0.55cm的长方形的样品片。
测定方法
将盛有300ml蒸馏水的结晶皿(直径120mm、高度60mm)放置在干燥器(JIS R3503规定大小240mm的容积约为10升的容器)底部,在其上涂附磁制涂附金属,放置所述贴有磁片的样品10片,在20~25℃下放置24小时,使蒸馏水吸收释放的甲醛,做成样品溶液。
样品溶液中的甲醛浓度利用乙酰丙酮法使用光电比色计进行比色定量。
结果示于表4中。表中的添加量通过水溶液得到的消臭剂总量对应的重量%换算表示。另外表中的释放量表示甲醛释放量(mg/l)。而且表中的除去率是百分率(%)表示释放量减少率(除去量除以比较制剂例3甲醛释放量(未处理MDF复合板产生的甲醛释放量))
表4
释放量 | 除去率 | 着色* | |
制剂例12 | 0.49 | 91 | × |
制剂例13 | 0.37 | 93 | × |
制剂例14 | 0.42 | 92 | ○ |
制剂例15 | 0.25 | 95 | ○ |
制剂例16 | 0.48 | 91 | ○ |
制剂例17 | 0.32 | 94 | ○ |
制剂例18 | 0.43 | 92 | ○ |
制剂例19 | 0.26 | 95 | ○ |
比较制剂例3 | 5.19 | 0 | - |
比较制剂例4 | 1.02 | 80 | ○ |
*○:无着色。×:显著着色。
制剂例14~19消臭剂具有和制剂例12和13消臭剂相同或以上的除去甲醛能力,其中制剂例15、17和19消臭剂除去甲醛能力强。
另外制剂例15,17和19与制剂例14,16和18相比除去甲醛能力强。由此可知只要添加量比较多,不太受铵化合物种类的影响,具有优良的除去甲醛的能力。
观察制剂例12~19以及比较例3~4样品片的表面,可见如表4所示制剂例12和13上着色。由此可知,制剂例14~19消臭剂不使被处理体着色,具有足够的消臭性能。
如上所述,本发明所述的消臭性组合物明显提高消臭效率。
另外作为助剂使用铵化合物的消臭性组合物不仅消臭效率高,而且也不使被处理体着色。
Claims (2)
1.一种消臭性组合物,以(A)选自酰肼类、唑类和嗪类中的至少一种和(C)选自氯化铵、硫酸铵、柠檬酸三铵中的至少一种铵化合物作为有效成分,(A)成分和(C)成分的使用重量比例为(A)成分:(C)成分=1∶5~100∶1。
2.根据权利要求1所述的消臭性组合物,其中上述(A)成分为为选自酰肼类的至少一种。
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Citations (3)
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JPH09173774A (ja) * | 1995-12-21 | 1997-07-08 | Nippon Steel Corp | 室内で発生するフォルムアルデヒドの除去方法 |
JPH114879A (ja) * | 1997-04-25 | 1999-01-12 | Otsuka Chem Co Ltd | 消臭剤 |
JP2000037447A (ja) * | 1997-04-25 | 2000-02-08 | Otsuka Chem Co Ltd | 消臭剤 |
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JPH09173774A (ja) * | 1995-12-21 | 1997-07-08 | Nippon Steel Corp | 室内で発生するフォルムアルデヒドの除去方法 |
JPH114879A (ja) * | 1997-04-25 | 1999-01-12 | Otsuka Chem Co Ltd | 消臭剤 |
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