CN1036882A - 协同杀菌组合物 - Google Patents

协同杀菌组合物 Download PDF

Info

Publication number
CN1036882A
CN1036882A CN89100616A CN89100616A CN1036882A CN 1036882 A CN1036882 A CN 1036882A CN 89100616 A CN89100616 A CN 89100616A CN 89100616 A CN89100616 A CN 89100616A CN 1036882 A CN1036882 A CN 1036882A
Authority
CN
China
Prior art keywords
composition
preservative
individual
microorganism
washing article
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.)
Granted
Application number
CN89100616A
Other languages
English (en)
Other versions
CN1041989C (zh
Inventor
马文·罗森
肯尼斯·J·伊安多里
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lonza AG
Lonza LLC
Original Assignee
Lonza AG
Lonza LLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Lonza AG, Lonza LLC filed Critical Lonza AG
Publication of CN1036882A publication Critical patent/CN1036882A/zh
Application granted granted Critical
Publication of CN1041989C publication Critical patent/CN1041989C/zh
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/44—Aminocarboxylic acids or derivatives thereof, e.g. aminocarboxylic acids containing sulfur; Salts; Esters or N-acylated derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4946—Imidazoles or their condensed derivatives, e.g. benzimidazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/494—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with more than one nitrogen as the only hetero atom
    • A61K8/4966—Triazines or their condensed derivatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/52—Stabilizers
    • A61K2800/524—Preservatives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/59—Mixtures

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • Animal Behavior & Ethology (AREA)
  • Dentistry (AREA)
  • Environmental Sciences (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Epidemiology (AREA)
  • Birds (AREA)
  • Chemical & Material Sciences (AREA)
  • Dermatology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Cosmetics (AREA)
  • Detergent Compositions (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

本发明介绍了一种广谱防腐剂组合物，它包括 (a)甲醛给予体和(b)卤代炔丙化合物；包括这些组 合物(特别是个人护洗用品和家庭用品)的处方；抑制 微生物生长的方法，它包括将所说的微生物与防腐剂 组合物接触。

Description

对于有效的、经济的防腐组合物的需求是众所周知的。在众多的应用中都需要抑制微生物的生长，诸如个人护洗用品（Personal    care    products）中的香波、乳剂、洗洁剂、化妆品、肥皂以及家庭用品（household    products）中的洗涤剂、去污粉（hard    surface    cleaners）织物软化剂。这些产品的货架寿命取决于它们对微生物腐败的抵抗力。
此外，许多工业也广为使用抑菌剂，如油漆、木材、纺织、胶粘剂、密封剂、皮毛、绳缆、纸浆、塑料、燃料、石油和橡胶以及金属加工润滑剂。在纸浆厂、造纸厂和冷却塔中控制产生粘液的细菌及真菌具有现实的商业价值。
有些化合物早已为人所知作防腐剂用。如美国专利3，987，184表明，1，3-二羟甲基-5，5-二甲基乙内酰脲（DMDMH）是一个有效的甲醛给予体、用于个人护洗用品、化妆品，家庭用品以及工业产品的防腐。虽然它杀伤各种不同的细菌是经济而有效的，但在抑制霉菌和酵母时它的杀伤速度很慢。
另一方面，卤代炔丙基氨基甲酸酯类化合物被认为有杀真菌活性。然而它非常昂贵，仅在可以承受昂贵费用的特殊领域中使用。
其它已知商品防腐剂有季盐-15（Dowicil200，Dow化学公司的商品名）。这个化合物有一个缺点，即它是一个固体物质，必须先在水中增溶再用于最终产品。在水溶液中它显现pH值漂移，并产生构成变化问题，特别是粘性和颜色的改变。
咪唑烷基脲（Germall115，Sutton公司的商品名）本来并没有杀真菌活性，但该产品制造者介绍它与对羟苯甲酸酯类一起使用具有杀真菌的作用。
福尔马林中的游离态甲醛作用时间比较短，同时它被蛋白质失活。
甲氯异噻唑啉酮和甲基异噻唑啉酮的混和物（KathonCG，Rohm    &    Haas公司的商品名）在有机硫化物存在时是不稳定的，其成分通常用于个人护洗用品中。它们还和原料中存在的一些过氧化物杂质如氧化胺反应。
2-溴-2硝丙基-1，3-二醇（Lexgard    Bronopol，Inolex公司的商品名）的杀真菌活性有限，必须与对羟苯甲酸酯类合用才能对微生物产生活性。
对羟苯甲酸烷基酯类（如甲基，乙基，丙基）有一定的杀菌作用。因为其水溶性较差，通常须溶于油中，它们常被一些日用品如明胶、甲基纤维素和聚乙二醇所失活。
很久以来，人们一直希望开发一种廉价、广谱、有效的协同组合物。例如美国专利4，454，146的防腐组合物含有两个成分（第一种是苯甲酸、甲醛或由异噻唑啉酮组成的混合物，第二种是含有稠合芳环的化合物）。此外，美国专利3，699，231记载，二甲基二硫氨基甲酸钠和甲醛的协同混合物用于杀伤钻机润滑油中的细菌;美国专利3，929，561记载，异噻唑啉酮和双（三氯甲基）砜的混合物在工业生产中具有抑制粘液细菌生长的作用;美国专利4，655，815记载了2-溴-2-溴羟甲基戊二腈与甲醛给予体组成的协同剂，这些甲醛给予体的例子有二羟甲基二甲基乙内酰脲、羟基氨基丙醇、羟乙基硝基丙二醇、羟甲基氮杂二氧杂二环辛烷和羟甲基氨基乙醇的混合物，氯代烯丙基迭氮金钢烷氯化物，氯代烯丙基己亚胺鎓（heximinium）氯化物和六亚甲四胺卤代烃季盐。
遗憾的是，上述组合物由于具有不良毒性，特别是针对皮肤和眼睛的刺激以及与常用成分的不相容性，不适宜用于个人护洗用品和家庭用品中。
根据本发明，现已找到了一种由选择的甲醛给予体和碘炔丙化合物组成的协同组合物。它具有广谱杀细菌和真菌的活性，适用于个人护洗用品和家庭用品的防腐。本发明的特别惊人之处在于，极少量的昂贵的卤炔丙氨基甲酸酯与甲醛给予体组合后，得到一种组合物，它具有突出的杀真菌活性。这种活性是无法由已知的单一成分的杀菌作用预测出来的。
两种成分相对的比例可在很大范围里变化，并且最佳比例与所选的化合物的不同及期望用途的不同有关。已经发现，在总组合物中仅含少至1/50的昂贵的碘炔丙化合物所具有的杀真菌活性，超过相同总重量的卤炔丙氨基甲酸酯单独使用的作用。特别令人惊奇的是这种作用的增加是由无杀真菌活性的甲醛给予体实现的。
本发明的协同组合物的第一种成分选自已知的甲醛给予体，它们的理化特性与其在个人护肤洗用品中的用途相一致。当然，这些产品在用于皮肤时必须无气味、无刺激、无毒性。这些化合物包括：二羟甲基二甲基乙内酰脲，N，N″-亚甲基双〔N′-〔1-（羟甲基）-2，5-二氧-4-咪唑烷基〕脲〕和N-（羟甲基）-N-（1，3-二羟甲基-2，5-二氧-4-咪唑烷基）-N′-（羟甲基）脲;1-（3-氯烯丙基）-3，5，7-三氮杂-1-氮鎓金钢烷氯化物的顺式异构体。
本发明中可能用作第二种成分的化合物的例子是有杀真菌活性的碘炔丙化合物的衍生物。它们包括炔丙基或碘炔丙基醇的衍生物，如酯、醚、缩醛、氨基甲酸酯及碳酸酯，还可以是其它化合物的碘炔丙基的衍生物，如嘧啶，三唑啉酮、四唑、三叠氮酮、磺胺、苯并噻唑、胺盐、羧酰胺、羟氨酸酯、和脲的碘炔丙基衍生物。其中较好的是3-碘-2-炔丙基丁基氨基甲酸酯（IPBC）。这个化合物属于一类有广泛用途的化合物，其通式为：
Figure 891006168_IMG1
其中R可选自取代的和不取代的烷基、芳基和烷基取代芳基，所含碳原子数目从1到20，m和n是从1到3独立的整数。
如上所述，两种成分的比例变化取决于用途和所选择的特定成分。一般说来，第一种成分与可能使用的第二种成分的重量比通常从50∶1到1∶1，较好的是从30∶1到2∶1，最好的是20∶1到10∶1。
本发明的组合物已被证明可以有效抑制细菌，霉菌和酵母的生长。被抑制的霉菌和酵母包括：黑曲霉、白色念珠菌、洁酶香茹、密粘褶菌、采绒革盖菌、绿色木霉、互生子菌、斜卧青霉、灰质葡萄孢霉、咖啡刺盘孢、大丽花轮枝孢、和须发癣菌。细菌包括猪霍乱沙门氏菌、粘质沙雷氏菌、肺炎杆菌、肠产气菌、产气气杆菌、枯草杆菌、普通变形杆菌、粪链球菌、绿脓杆菌、大肠杆菌和金黄色葡萄球菌。
将本发明的组合物应用于个人护洗用品和家庭用品是按照标准做法进行的。
除在实施例中所叙述的以外，典型的个人护洗用品组合物按下列表格所述：
个人护洗用品
传统的全能香波
成分    百分比（重量）    功效
月桂基硫酸钠    35.00    表面活性剂
椰子酰二乙醇胺    4.00    粘滞剂
（Cocodiethanolamide）
氯化钠    0.80
柠檬酸    0.17
防腐剂    足够量
去离子水    60.03
制做香波时，为确保均匀性，需在搅拌下将柠檬酸、氯化钠、月桂基硫酸钠和防腐剂溶于水中，然后加入椰子酰二乙醇胺。
个人护洗用品
香波
成分    百分比（重量）    功效
月桂基醚（2）硫酸钠    35.0    表面活性剂
月桂基硫酸四乙胺    25.0    表面活性剂
椰子酰二乙醇胺    3.0    泡沫促进剂
水解动物蛋白    1.0    调节剂
防腐剂    足够量
去离子水    36.0
在配制香波时，除防腐剂对，所有成分都加入水中并加热到65℃。在搅拌下放冷至室温，加入防腐剂得到一澄清溶液。如果需要，可用50%柠檬酸和三乙醇胺调节pH值至7.0。
个人护洗用品
婴儿香波
成分    百分比（重量）    功效
椰子酸两性羧基甘氨酸盐    20.0    两性表面活性
（Cocoamphocarboxyglycinate），    剂、浓缩剂
月桂基硫酸钠和乙氧化月桂基硫酸钠
椰子酸两性羧基甘氨酸盐    10.0    两性表面活性
剂
脱水山梨醇月桂酸单酯    5.0    眼刺激缓和剂
（20）聚氧化乙烯
聚乙二醇6000    1.3    粘滞剂
二硬脂酸酯
柠檬酸    0.3
防腐剂    足够量
去离子水    63.36
在制作这种香波时，应将柠檬酸溶于水中，加热后，按所列顺序加入各成分。聚乙二醇6000二硬脂酸酯要在75℃溶解。混合物在搅拌下冷却至室温，在室温下加入防腐剂。
个人护洗用品
阳离子护发调节剂
成分    百分（重量）    功效
十八烷基二甲基苄铵    8.0    调节剂
氯化物
氢化淀粉水解物    3.0    润湿剂
甘油单硬酯酸酯，S.e.    1.0    乳化剂，遮光剂
脱水山梨醇三硬脂酸酯    0.5    乳化剂
20（聚氧化乙烯）
氯化钾    0.4
防腐剂    足够量
去离子水    87.1
该处方中，将一半水加热到70℃，在搅拌下加入甘油硬脂酸单酯和聚氧乙烯-20脱水山梨醇三硬脂酸酯。然后，把事先加热到70℃的季盐和氢化淀粉水解物一齐加入，继续搅拌15-30分钟，在另一个萜髦校崖然睾腿苡诹硪话胨校尤鹊?5℃，并加入到前述溶液中。该乳剂在搅动下慢慢冷却到40℃。
个人护洗用品
护发膏
成分    百分比（重量）    功效
乙酰胺羟乙醇胺（MEA）    5.0    润滑剂
十八烷基鎓氯化物    4.5    调节剂
月桂基硫酸钠    3.5    乳化剂
氢化淀粉水解物    5.0    湿润剂
聚季碱-11    4.0    支持剂
聚季碱-10    0.7    支持剂
月桂醇（23）乙氧化物    0.5    增溶剂
防腐剂    足够量
去离子水    76.5
温和搅动下，将季碱-10分散到水中，加热到70℃，然后将十八烷基鎓氯化物，月桂基硫酸钠，氢化淀粉水解物，季碱-11和月桂基醇乙氧化物一齐加入，充分混合，在温和搅拌下将其冷却并加入防腐剂。
个人护洗用品
斥水防晒霜
成分    百分比（重量）    功效
A相
肉豆蔻基丙酸酯    2.0    软化剂
硅油    10.0    斥水剂
辛基二甲基对氨苯甲酸    5.0    防晒剂
硬脂酸甘油酯    1.5    乳化剂
遮光剂
三压硬酯酸    3.5    肥皂乳化剂
貂油    5.0    皮肤调节剂
B相
氢化淀粉水解物    5.0    湿润剂
三乙醇胺    1.0    肥皂乳化剂
防腐剂    足够量
去离子水    66.7
A相成分和B相成分均不加防腐剂，在不同容器中混合，各相在75℃溶化，然后将B相在搅拌下慢慢加到A相中，混合物不断搅拌冷却至室温。防腐剂在冷却条件下加入。
下列是家庭用品的例子。
家庭用品
软性液体洗涤剂
成分    百分比（重量）    功效
月桂基醚硫酸钠（60%）    14.50    表面活性剂
直链烷基磺酸钠（60%）    28.50    表面活性剂
椰子酰二乙醇胺    4.50    粘滞剂
柠檬酸（50%）    0.15
防腐剂    足够量
去离子水    52.35
这些成分按表中列出的顺序用水混合，当每种成分加入后搅拌直至溶液澄清。
家庭用品
精细织物洗涤剂
成分    百分比（重量）    功效
肉豆蔻胺氧化物    5.00    泡沫促进剂
椰子酰二乙醇胺    2.00    粘滞剂，泡
沫促进剂
直链烷基磺酸钠（60%）    15.00    表面活性剂
α-链烯磺酸钠（40%）    25.00    表面活性剂
无水柠檬酸    0.25
防腐剂    足够量
水    52.75
先将柠檬酸溶解在水中，在搅拌下将剩余成分按所列顺序先后加入，直至混合均匀。
家庭用品
织物软化剂
成分    百分比（重量）    功效
二（动物）脂二酰胺甲基硫酸酯或    4.0    软化剂
二（动物）脂二甲铵氯化物    4.0
聚乙二醇硬脂酸酯400    1.5    乳化剂，遮
光剂
防腐剂    足够量
水    96.0
将季盐、防腐剂和水混合直至均匀。
家庭用品
固体凝胶室内除臭剂
成分    百分比（重量）    功效
西黄蓍树胶    15.0    增稠剂
或洋槐豆树胶
防腐剂    足够量
水    85.0
制作这个产品时，首先将防腐剂加入水中，然后逐渐加入增稠剂，同时用奥氏（oster）掺和器以低速搅拌。速度逐渐增高直至制备物呈现石油胶状。加热到55℃后，转移到适当容器中。
按上述个人护洗用品和家庭用品的例子，将协同组合物掺入。一般防腐剂按重量计是0.01～1.0%，最好是0.01～0.4%。
当然，在该组合物的调制中，协同组合物的量必须足以有效地对抗应该受抑制的微生物。这个最小抑菌浓度可用标准化的实验技术，依靠简单实验室实验就可确定。
为了更完整地阐明本发明，请注意下面实施例。
实施例
为证明协同组合物产生的抑制微生物的效应，制备了乳剂和洗洁剂的处方。二羟甲基二甲基乙内酰脲（DMDMH）和3-碘-2-炔丙基-丁基氨基甲酸酯（IPBC）以各种使用水平加入，并进微生物免疫实验。
乳剂有如下配方：
成分    重量百分比
聚乙二醇-20甘油硬脂酸酯    4.0
单硬脂酸甘油酯    6.0
鲸蜡烯芳基醇（TA    16185）    1.5
肉豆蔻基丙酸酯    8.0
甘油，99%    5.0
去离子水    75.5
制备乳剂时，首先将油相在60-65℃溶解。将水相（甘油和水）加热到相同温度，并加入到油相中混合。温度保持在48-52℃，并加入防腐剂。产品在搅拌下冷却至室温。
洗洁剂有如下配方：
成分    百分比（重量）    功效
A相
硬脂酸（美国药典/国家处方集）    3.0    乳化剂
肉豆蔻基丙酸酯    2.0    润滑剂
甘油单硬脂酸酯    1.5    乳化剂
鲸蜡醇    1.0    二级乳化剂
乙氧基（5）羊毛脂醇    0.5    润滑剂
乙氧基（25）羊毛脂醇    0.3    乳化剂
B相
氢化淀粉水解物    5.0    湿润剂
三乙醇胺，（99%）    0.4    乳化剂
防腐剂    足够量
去离子水    85.3
C相
水解动物蛋白    1.0    吸湿剂
为制备这种洗洁剂（即三乙醇胺硬酯酸洗洁剂），A相和B相分别加热到65℃，将C相加入到A相中混合，将混合物在60℃条件下加到B相中。然后，在该温度下加入防腐剂。如果必要，用50%乙酸将混合物pH值调到7。搅拌下冷却至室温，以完成该处方。
微生物抗原剂量实验进行如下。首先，将白色念珠菌（ATCCNO.10231）和黑曲霉（ATCC    NO.16404）接种到含有不同量防腐剂的40克处方中，其浓度为每克处方中含大约5×106个微生物。样品的温度保持在48～52℃，样品的粘度应足够低，以保证接种微生物均匀分布。样品在18～22℃培养整整7天，在培养0、1、2、3和7天时，从每一试样中各取1ml，再将浓度分步稀释106倍，每个稀释样品放在喜菌琼脂介质中，并在20～25℃培养3至7天。经过培养后，从0～7天的试样中得到每毫升菌落数（cfu/ml），数据列在表1～3中。
Figure 891006168_IMG3
Figure 891006168_IMG5
Figure 891006168_IMG6
Figure 891006168_IMG7
从上面表中可以看出，对于所试微生物，本发明的协同组合物比任何单一成分的作用要好得多。

Claims (11)

1、防腐剂组合物，它由(a)无毒的，无气味的甲醛给予体和(b)卤炔丙化合物的混合物组成。
2、权利要求1所述的组合物，其中混合物含有二羟甲基二甲基乙内酰脲和3-碘-2-炔丙基丁基氨基甲酸酯。
3、权利要求1所述的组合物，其中成分（a）是咪唑啉脲，咪唑啉脲Ⅱ或季盐15。
4、权利要求1所述的组合物，其中成分（b）是3-碘-2-炔丙基丁基氨基甲酸酯。
5、权利要求1所述的组合物，其中成分（a）对成分（b）的重量比从50∶1到1∶1。
6、权利要求1所述的组合物，其中成分（a）对成分（b）的重量比是从20∶1到10∶1。
7、个人护洗用品组合物，它由含有有效量的权利要求1的组合物的表面活性剂组成。
8、权利要求7所述的个人护洗用品，其中组合物是皮肤乳剂，洗洁剂，香波或肥皂。
9、家庭用品组合物，它由含有有效量的权利要求1组合物的表面活化剂组成。
10、权利要求9所述的家庭用品组合物，其中组合物是洗涤剂、去污粉（hard  surface  cleaners），织物软化剂或房间除臭剂。
11、抑制微生物生长的方法，它包括将所说的微生物与权利要求1的组合物接触。
CN89100616A 1988-02-03 1989-02-02 协同杀菌组合物 Expired - Lifetime CN1041989C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/151,702 US4844891A (en) 1988-02-03 1988-02-03 Admixtures of iodopropargyl compounds and a formaldehyde donor
US151,702 1988-02-03

Publications (2)

Publication Number Publication Date
CN1036882A true CN1036882A (zh) 1989-11-08
CN1041989C CN1041989C (zh) 1999-02-10

Family

ID=22539907

Family Applications (1)

Application Number Title Priority Date Filing Date
CN89100616A Expired - Lifetime CN1041989C (zh) 1988-02-03 1989-02-02 协同杀菌组合物

Country Status (15)

Country Link
US (1) US4844891A (zh)
EP (1) EP0327220B1 (zh)
JP (1) JPH0667808B2 (zh)
KR (1) KR950006926B1 (zh)
CN (1) CN1041989C (zh)
AT (1) ATE93681T1 (zh)
AU (1) AU606260B2 (zh)
BR (1) BR8900229A (zh)
CA (1) CA1331141C (zh)
DE (1) DE68908730T2 (zh)
DK (1) DK175698B1 (zh)
ES (1) ES2059715T3 (zh)
IL (1) IL88902A (zh)
MX (1) MX163599B (zh)
ZA (1) ZA89234B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100456932C (zh) * 2002-08-20 2009-02-04 隆萨股份有限公司 游离甲醛低的稳定的醛供体和脱氢乙酸的增效抗菌组合物

Families Citing this family (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5190944A (en) * 1988-12-22 1993-03-02 Rohm And Haas Company Synergistic microbicidal combinations containing 3-isothiazoline and commercial biocides
DE3930725A1 (de) * 1989-09-14 1991-03-21 Benckiser Gmbh Joh A Extra-milde duschgel- und haarshampoo-formulierung mit niedriger tensidkonzentration
US5037843A (en) * 1990-03-05 1991-08-06 The Mcintyre Group, Ltd. Antimicrobial preservative system and method comprising a formaldehyde substituted hydantoin
ZA918514B (en) * 1990-10-31 1992-11-25 Buckman Labor Inc Synergistic combinations of idopropargyl compounds with hexahydro-1,3,5-tris(2-hydroxyethyl)-s-triazine in controlling fungal and bacterial growth in metalworking fluids
CA2054533C (en) * 1990-11-27 2002-04-16 Samuel Eugene Sherba Antimicrobial compositions comprising iodopropargyl butylcarbamate and 2-mercaptopyridine n-oxide and methods of controlling microbes
US5209930A (en) * 1990-12-10 1993-05-11 Rohm And Haas Company Preparation and use of n-iodopropargyl oxycarbonyl amino acid esters and derivatives as antimicrobial agents
US5156665A (en) * 1991-01-03 1992-10-20 Rohm And Haas Company Antimicrobial compositions comprising iodopropargyl compounds and isothiazolones and methods of controlling microbes
US5459073A (en) * 1991-05-08 1995-10-17 Streck Laboratories, Inc. Method and composition for preserving antigens and process for utilizing cytological material produced by same
US5849517A (en) * 1991-05-08 1998-12-15 Streck Laboratories, Inc. Method and composition for preserving antigens and nucleic acids and process for utilizing cytological material produced by same
US5460797A (en) * 1991-05-08 1995-10-24 Streck Laboratories, Inc. Method for fixing tissues and cells for analysis using oxazolidine compounds
US5464850A (en) * 1991-10-04 1995-11-07 Ciba Corning Diagnostics Corp. Synergistic preservative systems for chemistry reagents
US5648348A (en) * 1991-10-28 1997-07-15 Mona Industries, Inc. Phospholipid antimicrobial compositions
US5215976A (en) * 1991-10-28 1993-06-01 Mona Industries, Inc. Phospholipids useful as spermicidal agents
US5286719A (en) * 1991-10-28 1994-02-15 Mona Industries, Inc. Phospholipid virucidal compositions
DE4141953A1 (de) * 1991-12-19 1993-06-24 Bayer Ag Mikrobizide mittel
US5252246A (en) * 1992-01-10 1993-10-12 Allergan, Inc. Nonirritating nonionic surfactant compositions
DE4217523A1 (de) * 1992-05-27 1993-12-02 Bayer Ag Mittel zum Schutz von Schnittholz
EP0639985B1 (en) * 1992-09-10 2004-08-11 Streck Laboratories, Inc. Method and composition for preserving antigens and process for utilizing cytological material produced by same
JP2886446B2 (ja) * 1994-03-03 1999-04-26 関西ペイント株式会社 塗膜保護用シート
US5552425A (en) * 1994-04-28 1996-09-03 Isp Chemicals Inc. Synergistic water soluble preservative compositions of biocidal mixtures
US5428050A (en) * 1994-04-28 1995-06-27 Isp Chemicals Inc. Synergistic water soluble preservative compositions of biocidal mixtures
US6335374B1 (en) 1994-10-07 2002-01-01 Troy Technology Corporation, Inc. Penetrating protectant
US5648083A (en) * 1995-02-10 1997-07-15 The Procter & Gamble Company Personal care compositions and wipe products containing the compositions
US6080707A (en) * 1995-02-15 2000-06-27 The Procter & Gamble Company Crystalline hydroxy waxes as oil in water stabilizers for skin cleansing liquid composition
WO1996025144A1 (en) * 1995-02-15 1996-08-22 The Procter & Gamble Company Crystalline hydroxy waxes as oil in water stabilizers for skin cleansing liquid composition
US6080708A (en) * 1995-02-15 2000-06-27 The Procter & Gamble Company Crystalline hydroxy waxes as oil in water stabilizers for skin cleansing liquid composition
US5733362A (en) * 1995-12-08 1998-03-31 Troy Corporation Synergistic bactericide
US5661149A (en) * 1995-12-29 1997-08-26 Buckman Laboratories International, Inc. Synergistic antimicrobial compositions containing 1-hydroxymethylpyrazole and a preservative
US6241783B1 (en) 1996-09-13 2001-06-05 The Regents Of The University Of California Formaldehyde scavenging in microbiocidal articles
US5882357A (en) * 1996-09-13 1999-03-16 The Regents Of The University Of California Durable and regenerable microbiocidal textiles
US5871762A (en) * 1996-10-07 1999-02-16 The Procter & Gamble Company Cosmetic applicators which contain stable oil-in-water emulsions
US5886031A (en) * 1997-01-27 1999-03-23 Pacific Corporation Hair-care cosmetic compositions having dandruff formation-suppressing effect
USH2043H1 (en) 1997-05-23 2002-08-06 The Procter & Gamble Company Skin care compositions
DE19722858B4 (de) * 1997-05-23 2004-01-29 Schülke & Mayr GmbH Zusammensetzungen auf der Basis von Iodpropinyl- und Formaldehyd-Depot-Verbindungen und deren Verwendung als Konservierungsmittel
US5968528A (en) * 1997-05-23 1999-10-19 The Procter & Gamble Company Skin care compositions
USH2013H1 (en) 1997-05-23 2002-02-05 The Procter & Gamble Company Skin care compositions
DE19753982A1 (de) * 1997-12-05 1999-06-10 Henkel Kgaa Geschirrspülmittel mit antibakterieller Wirkung
US5965594A (en) * 1998-03-30 1999-10-12 Mcintyre Group, Ltd. Antimicrobial liquid preservative solutions and process for preparation
US6143204A (en) * 1998-06-19 2000-11-07 Lonza Inc. Stabilization of iodopropynl compounds
DE19829475A1 (de) * 1998-07-01 2000-01-05 Troy Chemie Gmbh Umsetzungsprodukte aus Formaldehyd und Kohlenhydraten bzw. Kohlenhydratderivaten sowie deren Verwendung als Konservierungsmittel
US5935556A (en) * 1998-07-30 1999-08-10 The Procter & Gamble Company Sunscreen compositions
US6010996A (en) * 1998-10-01 2000-01-04 Albemarle Corporation Biocidal surfactant compositions and their use
US6133300A (en) * 1999-10-15 2000-10-17 Troy Technology Corporation, Inc. Antimicrobial mixtures of 1,3-bis(hydroxymethyl)-5,5-dimethylhydantoin and 1,2-benzisothiazolin-3-one
US6290945B1 (en) 1999-10-28 2001-09-18 Bbj Environmental Solutions, Inc. Aqueous deodorizer compositions with controlled release
US20030166483A1 (en) * 2000-04-04 2003-09-04 Michael Heinzel Use of 3-iodine-2-propinyl-carbamates as antimicrobial active agent
DE10016371A1 (de) * 2000-04-04 2001-10-18 Henkel Kgaa Verwendung von 3-Iod-2-propinyl-carbamaten als antimikrobieller Wirkstoff
US6432433B1 (en) 2000-06-05 2002-08-13 Isp Investments Inc. Liquid biocidal composition of a formaldehyde adduct and an isothiazolone and method of use
CA2412444C (en) * 2000-06-08 2011-01-04 Lonza Inc. Aldehyde donors for stabilizing peroxides in papermaking applications
US6770287B1 (en) * 2000-06-19 2004-08-03 The Regents Of The University Of California Biocidal cellulosic material
WO2002067685A1 (en) * 2001-02-26 2002-09-06 Lonza Inc. Stable preservative formulations comprising halopropynyl compounds and butoxydiglycol solvent
TW201002201A (en) 2001-03-01 2010-01-16 Lonza Ag Preservative blends containing quaternary ammonium compounds
CN1315382C (zh) 2001-03-01 2007-05-16 隆萨公司 碘代丙炔基衍生物与酮酸或其盐和/或与芳香羧酸或其盐的组合
DE10244442A1 (de) 2002-09-24 2004-04-01 Schülke & Mayr GmbH Emissionsarme Formaldehyd-Depot-Zubereitungen und deren Verwendung
US8377459B2 (en) * 2003-07-09 2013-02-19 The Procter & Gamble Company Composition for wet wipes that enhances the efficacy of cleansing while being gentle to the skin
DE10340830B4 (de) 2003-09-04 2006-04-13 Schülke & Mayr GmbH Verbesserte mikrobizide Zusammensetzung auf Basis von Formaldehyd-Depotverbindungen und Antioxidantien
EP1704216A2 (en) * 2004-01-16 2006-09-27 The Procter and Gamble Company Aqueous laundry detergent compositions having improved softening properties and improved aesthetics
DE102004014447A1 (de) * 2004-03-24 2005-10-20 Schuelke & Mayr Gmbh Emissionsarme Formaldehyd-Depot-Zubereitungen
US20080145443A1 (en) * 2006-12-15 2008-06-19 Kimberly-Clark Worldwide, Inc. Diaper rash composition and method
JP5229734B2 (ja) * 2008-11-26 2013-07-03 住化エンビロサイエンス株式会社 木材保存組成物
JP2015196745A (ja) * 2014-03-31 2015-11-09 シヤチハタ株式会社 水性インキ

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB960732A (en) * 1962-01-16 1964-06-17 Dow Chemical Co Method for preventing the growth of micro organisms in aqueous media
US3228829A (en) * 1963-11-04 1966-01-11 Dow Chemical Co Preservation of aqueous dispersions
US3830913A (en) * 1971-04-29 1974-08-20 Rush Hampton Antifungal and antibacterial grapefruit derivative
US3923870A (en) * 1973-07-11 1975-12-02 Troy Chemical Corp Urethanes of 1-halogen substituted alkynes
US4202882A (en) * 1973-12-03 1980-05-13 Herbert Schwartz Novel deodorizing method
US3987184A (en) * 1974-06-07 1976-10-19 Glyco Chemicals, Inc. Dimethylol dimethylhydantoin solution
US4172140A (en) * 1977-08-19 1979-10-23 Glyco Chemicals, Inc. Antimicrobial hydantoin derivative compositions and method of use
US4323602A (en) * 1980-05-14 1982-04-06 Roberts Consolidated Industries, Inc. Water repellent and preservative for wood products
US4496576A (en) * 1980-10-23 1985-01-29 Mallinckrodt, Inc. Compositions of p-hydroxybenzoic acid esters and methods of preparation and use
EP0091740A3 (en) * 1982-03-19 1984-04-18 Syntex (U.S.A.) Inc. A composition and process for treating hair
DE3377615D1 (en) * 1982-11-23 1988-09-15 Sutton Lab Inc Composition of matter containing imidazolidinyl urea and pyrithione and its derivatives
US4655815A (en) * 1985-03-27 1987-04-07 Calgon Corporation Admixtures of 2-bromo-2-bromomethylglutaronitrile and a formaldehyde donor
DE3508928A1 (de) * 1985-03-13 1986-09-18 Giulini Chemie Gmbh, 6700 Ludwigshafen Kombination zur antimikrobiellen und antioxidativen stabilisierung von externa und koerperpflegemitteln

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100456932C (zh) * 2002-08-20 2009-02-04 隆萨股份有限公司 游离甲醛低的稳定的醛供体和脱氢乙酸的增效抗菌组合物

Also Published As

Publication number Publication date
CA1331141C (en) 1994-08-02
DE68908730T2 (de) 1994-01-27
MX163599B (es) 1992-06-03
EP0327220A1 (en) 1989-08-09
IL88902A (en) 1992-11-15
ES2059715T3 (es) 1994-11-16
EP0327220B1 (en) 1993-09-01
BR8900229A (pt) 1989-09-12
DK47189A (da) 1989-08-04
KR950006926B1 (ko) 1995-06-26
AU2958089A (en) 1989-08-03
US4844891A (en) 1989-07-04
DE68908730D1 (de) 1993-10-07
IL88902A0 (en) 1989-08-15
DK47189D0 (da) 1989-02-02
KR890012543A (ko) 1989-09-18
DK175698B1 (da) 2005-01-24
JPH02191204A (ja) 1990-07-27
ATE93681T1 (de) 1993-09-15
JPH0667808B2 (ja) 1994-08-31
ZA89234B (en) 1990-06-27
AU606260B2 (en) 1991-01-31
CN1041989C (zh) 1999-02-10

Similar Documents

Publication Publication Date Title
CN1036882A (zh) 协同杀菌组合物
CN1241538C (zh) 含有过渡金属螯合剂盐的抗微生物组合物
CN1174733C (zh) 洗涤剂组合物
CN1736198A (zh) 抗微生物组合物
CN1281129C (zh) 含季铵化合物的防腐剂混合物
CN1231124C (zh) 抗微生物组合物
CN1066170A (zh) 用作生物杀伤剂和防腐剂的二羟甲基2，5-哌嗪二酮
CN1401240A (zh) 杀菌剂、其组合物、应用和杀菌方法
CN101076315A (zh) 杀菌配制剂
CN1106251A (zh) 香波调理剂组合物
JP2007262092A (ja) 改良された有効性を有するトリクロサンスキンウォッシュ
CN1265561A (zh) 含有卤素过氧化物酶、过氧化氢源、卤化物源和铵源的抗微生物组合物
CN87105156A (zh) 杀真菌混合物
CN1494380A (zh) 碘代丙炔基衍生物与酮酸或其盐和/或与芳香羧酸或其盐的组合
CN1137220A (zh) 含有季铵盐的低毒性的杀菌剂
CN1215765C (zh) 用作杀微生物活性物质的羟基茋化合物
CN1308067A (zh) 制备低游离甲醛的羟甲基乙内酰脲组合物的方法
CN1325270A (zh) 包含氧化还原酶和n－羟基－n－酰基苯胺型增强剂的抗微生物组合物
CN1684662A (zh) 抗真菌剂及配合了抗细菌剂的洗涤用组合物
CN1045362C (zh) 含有碘化物的杀菌组合物
CN1106651A (zh) 化妆品制剂
CN1344709A (zh) 新的二季铵盐化合物
CN1136272A (zh) 超温和个人用泡沫清洁组合物
CN1895672A (zh) 多元体协同增效多功能广谱消毒止痛剂及其应用
JP5390090B2 (ja) 固形石鹸組成物

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C15 Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993)
OR01 Other related matters
C17 Cessation of patent right
CX01 Expiry of patent term