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CN1060513C - 块皂 - Google Patents

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CN1060513C
CN1060513C CN94193933A CN94193933A CN1060513C CN 1060513 C CN1060513 C CN 1060513C CN 94193933 A CN94193933 A CN 94193933A CN 94193933 A CN94193933 A CN 94193933A CN 1060513 C CN1060513 C CN 1060513C
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formula
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CN1133613A (zh
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马林·霍梅斯
沃纳·施奈德
沃尔夫哈德·肖尔茨
尤多·亨内恩
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Henkel AG and Co KGaA
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    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
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    • C11D3/2079—Monocarboxylic acids-salts thereof
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    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives

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Abstract

提出了新的块皂，它含有a)70至85%(重量)脂肪酸盐，b)0.5至10%(重量)脂肪酸，c)1至10%(重量)烷基醚硫酸盐，d)0.1至1%(重量)烷基和/或链烯基低聚糖苷以及任选的其它的助剂和添加物。新块皂泡沫丰富、细腻，钙皂分散能力强，护肤性和机械性能优异。此外，还改进了块皂生产过程中尤其是加温加压时的颜色稳定性。

Description

块皂
本发明涉及含有脂肪酸盐、脂肪酸、烷基醚硫酸盐、烷基和／或链烯基低聚糖苷及任选的其它的助剂和添加物的块皂。
现代的块皂尤其是香皂或细皂通常以约8∶2的牛脂与椰子油的混合物为原料制得。通过添加氢氧化钠使这种油脂原料水解成基皂，再向该基皂加入其它添加物，例如保湿剂、填料和粘合剂、富脂剂、色素和香料等等。常见的细皂含有约80％脂肪酸盐、10％水和补足至100％的助剂和添加物。现在提供给消费者的许多产品反映了活跃的市场需求，由此可以清楚地看出，消费者一直在寻求进一步改进的产品，特别是改进的皮肤病学的相容性、更强的发泡剂、较高的乳化性、回脂性(Ruckfettung)、去污力及肤感等。而肥皂生产厂家则寻求例如可生产耐裂性能好并可顺利地掺入特定表面活性剂如烷基硫酸盐的脂皂配方。对这一主题的概述例如可在J．Am．Oil．Chem．Soc．59，442(1982)上找到。
关于块皂的制造，现有技术中已有为数众多的方法。这里必须基本上区分合成的“无皂”肥皂即所称的合成洗涤剂，特别是脂肪酸盐与合成表面活性剂的组合物(“组合条”)。例如，为了制造组合条，EP-A-0176330(Unilever)建议将脂肪酸皂与羟乙基磺酸盐组合。EP-A-0189332、EP-A-0472320和EP-A-0508006(Unilev-er)公开了将脂肪酸羟乙基磺酸盐作为组合条合成组分的应用。
过去，人们也曾用烷基葡糖苷作为一类非离子性柔性的表面活性剂以制造香皂。例如，罗姆·哈斯公司出版的“Triton CG-110”的技术手册中就提出向基皂添加入2％(重量)的这种C8-C10-烷基低聚葡糖苷。由德国展示说明书DE-AS-593422(Th·Boehme)已知，向基皂混合物添加10至15％(重量)的鲸蜡基麦芽糖苷可以改进洗涤能力。
US 4，536，318和US 5，599，188(Procter ＆ Gamble)专利说明书公开了烷基葡糖苷脂和皂的发泡混合物，它基本上适用于制造块皂。欧洲专利申请EP-A 0227321、EP-A 0308189和EP-A 308190(Procter & Gamble)还公开了除皂和烷基葡糖苷之外还含有阳离子聚合物的香皂。
根据US 5，043，091(Colgate)的学说，向含有烷基苯磺酸盐和烷基硫酸盐的皂中添加烷基葡糖苷可以改进制造时的机械性能。
欧洲专利申请EP-A 0463912(Colgate)公开的香皂含有45至95％(重量)C8-C24-脂肪酸皂、1至20％(重量)烷基葡糖苷、保湿剂和任选的阴离子表面活性剂和／或脂肪酸。该文献明确提出，加入的烷基葡糖苷的量要明显高于1．5％(重量)。作为可用的阴离子的助表面活性剂虽然提到烷基醚硫酸盐，但实施例中却只公开了脂肪酸、皂和烷基葡糖苷的组合物。
尽管现有技术相当广泛，但所有已知方案均不完全令人满意。尤其是块皂的加工性能(光洁度，加温时的颜色稳定性)、泡沫的乳化性和硬水容许值仍然不尽人意。
因此，本发明的任务是提供没有所述缺点的、而具有综合特性的新型的块皂配方。
本发明的主题为块皂，它含有：
a)70至85％(重量)脂肪酸盐，
b)0．5至10％(重量)脂肪酸，
c)1至10％(重量)烷基醚硫酸盐，
d)0．1至1％(重量)烷基和／或链烯基低聚糖苷以及任选的其它的助剂和添加物。
作为本发明一种优选实施方式的块皂含有：
a)73至80％(重量)脂肪酸盐，
b)2至6％(重量)脂肪酸，
c)2至4％(重量)烷基醚硫酸盐，
d)0．5至1％(重量)烷基和／或链烯基低聚糖苷以及任选的其它的助剂和添加物。
出人意料地发现，加入规定量0．1至1％(重量)烷基和／或链烯基低聚糖苷可使基于皂和烷基醚硫酸盐的市售组合块皂的乳化性和硬水容许值以及钙质皂(Kalseifen)分散能力得到明显改进。因此，本发明的块皂在制造时改进了色稳定性且机械成型后表明表面特别光滑。本发明还进一步认识到，加入的烷基和／或链烯基低聚糖苷大于1％(重量)会导致综合性能状况的跳跃性恶化。观察到的积极效果与所加入的烷基醚硫酸盐密切相关，因而不易于使用于其它阴离子基表面活性剂例如烷基硫酸盐或酯磺酸盐。
脂肪酸盐和脂肪酸
涉及皂的脂肪酸盐是R1CO-ONa    (Ⅰ)式中R1CO表示有6至22个碳原子的脂族酰基。典型的实例是己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、棕榈油酸(Palmoleyls-aure)、硬脂酸、异硬脂酸、油酸、反油酸、石芹酸、亚油酸、亚麻酸、桐酸、花生酸、廿碳烯酸、山萮酸和芥酸的钠盐及其工业混合物，例如在天然脂肪和油加压裂解时所形成的混合物。特别优选的是基于C12-C18-、C12-C14-椰子油脂肪酸和／或C16-C18-牛脂酸的工业混合皂。
作为脂肪酸可以考虑式(Ⅱ)的羧酸，R2CO-OH    (Ⅱ)式中R2CO表示含6至22个碳原子的脂族酰基。典型的实例是己酸、辛酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、棕榈油酸、硬脂酸、异硬脂酸、油酸、反油酸、石芥酸、亚油酸、亚麻酸、桐酸、花生酸、廿碳烯酸、山萮酸和芥酸以及其工业混合物，例如天然脂肪和油加压裂解时所形成的混合物。特别优选的是基于C12-C18-、C12-C14-椰子油脂肪酸和／或C16-C18-牛脂酸的工业混合皂。
烷基醚硫酸盐
本发明的烷基醚硫酸盐的起始原料为式(Ⅲ)的乙氧基化的醇，R3O-(CH2CH2O)nH    (Ⅲ)式中R3为含6至22个碳原子的直链或支链烷基和／或链烯基，n为1至10的数值。这里指环氧乙烷与脂肪醇及羰基合成醇的已知加成产物，它们具有常规或较窄的同等物分布。典型的实例是1至5摩尔环氧乙烷与1摩尔C12／14及C12／18椰子油脂肪醇的加成产物。
烷基和／或链烯基低聚糖苷
烷基和链烯基低聚糖苷是已知物质，它可用有机化学的有关制备方法得到，且具有式(Ⅳ)R4O-[G]p    (Ⅳ)式中R4为6至22个碳原子的直链或支链烷基和／或链烯基，G为5或6个碳原子的糖基，P为1至10的数值。
这里作为众多文献的代表可参考EP-A1-0301298和WO 90／3977。该烷基和／或链烯基低聚糖苷可以是由5或6个碳原子的醛糖或酮糖优选的是由葡糖衍生的。因此，优选的烷基和／或链烯基低聚糖是烷基和／或链烯基葡糖基。
通式(Ⅳ)中的指数P表示低聚度(DP度)，也就是说单体和低聚糖苷的分布，其数值为1至10。在给定化合物中P值必须是整数，首先是P=1至6，而对于特定的烷基低聚糖苷来说，P值是由分析测得的计算值，该值通常是一个分数。优先采用的烷基和／或链烯基低聚糖苷的平均低聚度P为1．1至3．0。从应用技术观点，优选的烷基和／或链烯基低聚糖苷的低聚度小于1．7，尤其是1．2至1．4。
烷基或链烯基R4可由含6至11，优选8至10个碳原子的伯醇衍生。典型的实例是己醇、辛醇、癸醇和十一醇及其工业混合物，例如在工业用脂肪酸甲酯加氢时或在Roelen法的羰基合成所得醛的加氢过程中所生成的混合醇。优选的是链长为C8-C10(DP=1至3)的烷基低聚葡糖苷以及基于工业C9／11-羰基合成醇(DP=1至3)的烷基低聚葡糖苷，前者是工业C8-C18-椰子油脂肪醇蒸馏分离时得到的初馏份且可掺杂有低于6％(重量)的C12-醇。
烷基或链烯基R4还可以由含12至22，优选12至14个碳原子的伯醇衍生得到。典型的实例是月桂醇、肉豆蔻醇、鲸蜡醇、棕榈油醇、硬脂醇、异硬脂醇、油醇、反油醇、石芹醇、花生醇、廿碳烯醇、山萮醇和芥醇以及如上所述可以得到的它们的工业混合物。优选DP=1至3的基于氢化C12／14-椰子油脂肪醇的烷基低聚葡糖苷。助剂和添加物
本发明的块皂可以含有例如助洗剂作为添加物。对此可以考虑细粒水不溶性碱金属铝硅酸盐等，其中优选使用合成的含结晶水的晶体铝硅酸钠，特别是沸石A；同时也可使用沸石NaX及其与沸石NaA的混合物。合适的沸石的钙结合能力为100至200mg CaO／g。优选应用一种商品名为WESSALITH(R)P (Degussa)的沸石NaA，其结晶水含量约为20％(重量)，用量为8至15％(重量)。
作为增塑剂或粘合剂可以应用甘油、含12至22个碳原子的脂肪醇、C12-C22-脂肪酸的脂肪酸甘油酯或相应的蜡酯。
配方中的其它组份也可以是非离子表面活性剂，例如HLB值为12至18的聚乙二醇醚和／或蛋白脂肪酸的缩聚产物。后者例如为长期以来的市售商品LAMEPON(R)或MAYPON(R)。加入选自季戊四醇二脂肪酸酯和柠檬酸二脂肪酸酯的水／油乳化剂表明特别有利。配方还可以含有白色素(例如BAYERTITAN(R))、颜料、香料和防腐剂(例如IRGASAN(R) DP 300、FARNESOL(R)、GRILLOCIN(R) cW 90)。最后，本发明的块皂还可含少量水。
按块皂的重量计，所含助剂和添加物的总量为1至5％，优选2至3％(重量)。
块皂的制造
本发明块皂的制备可按这种产品的常规方法进行。其中，特别是通过本发明方法使皂与烷基醚硫酸盐和烷基低聚葡糖苷相组合而形成一种特别易于成形、并加热变软且冷却后变硬的物料，而且成形后的产品具有光滑的表面。常规的混合、均化、捏合、必要时的磨碎、压条、需要时的造球、挤压、切割和压块的方法都是专业人员熟悉的，均可用以制备本发明的块皂。制备优选是在60至90℃温度下进行，其中预先将可熔化的原料放在一个可加热的捏合机或混合机中，并搅入不熔化的成分。为了均质，使所得混合物接着过筛，然后再成型。
本发明的块皂表面光滑，发泡性好，泡沫持久，乳化性好，优良的钙皂分散性，护肤性能突出。该块皂已证明在制造过程中具有分外的色稳定性。
实施例
Ⅰ．配方：表1皂配方
组份 配方1(％) 配方2(％) 配方3(％) 配方4(％) 配方5(％) 配方6(％)
基    皂   94．0   94．5   94．0   94．0   94．0   94．0
醚硫酸盐   3．5   3．5   3．5   3．5   －   －
烷基硫酸盐   －   －   －   －  3．5   －
酯磺酸盐   －   －   －   －   －   3．5
烷基葡糖苷   0．5   1．0   1．5   2．0   1．0   1．0
a)基皂：47％(重量)C16／18-牛脂酸钠盐，31％(重量)C12／18-椰子油脂肪酸钠盐，5％(重量)C12／18-椰子油脂肪酸，1％(重量)甘油，补足至100％(重量)的常用添加物和水；b)醚硫酸盐：C12／14-椰子油脂肪醇-3．6 EO-硫酸钠盐[Texapon(R)K14S(70％(重量)的)，Henkel KGaA，杜塞尔多夫／联邦德国]；c)烷基硫酸盐：月桂硫酸钠盐；d)酯磺酸盐：α-磺化的椰子油脂肪酸甲酯钠盐；e)烷基葡糖苷：C8／16-椰子油烷基低聚葡糖苷，DP=1．4[Plantar-en(R) APG 2000 CS-UP，Henkel KGaA杜塞尔多夫／联邦德国]。
配方1和2是本发明，配方3至6是用作比较。助剂(香料油、颜料和防腐剂)补足至100％。所有百分含量都是重量％。
Ⅱ．配方的评价：
a)块皂的表面光滑程度
Ⅰ=非常光滑
Ⅱ=不太光滑
b)块皂挤压时的褪色程度
0=不褪色
Ⅰ=轻微褪色
Ⅱ=明显褪色
c)泡沫的乳化性
Ⅰ=乳化性泡沫
Ⅱ=大孔性泡沫
d)钙皂分散能力
Ⅰ=良好
Ⅱ=不太好
结果汇总在表2中：
表2 应用技术的效果
配方 光滑度 褪色性 乳化性 钙皂分散能力
配方1 Ⅰ 0 Ⅰ Ⅰ
配方2 Ⅰ 0 Ⅰ Ⅰ
配方3 Ⅰ Ⅰ Ⅱ Ⅱ
配方4 Ⅱ Ⅰ Ⅱ Ⅱ
配方5 Ⅱ Ⅰ Ⅱ Ⅱ
配方6 Ⅱ Ⅱ Ⅱ Ⅱ
本发明实施例(配方1和2)和对比例(配方3至6)表明：一仅在本发明配方范围内达到了复合的要求即表面光滑，加工不褪色，泡沫的乳化性和高的钙皂分散能力：一烷基葡糖苷超过1％(重量)量导致性能状况的跳跃性恶化；一块皂性能改进与阴离子基表面活性剂性质有关。

Claims (5)

1、块皂，它含有：
a)70-85％重量脂肪酸盐，
b)0．5-10％重量脂肪酸，
c)1-10％重量烷基醚硫酸盐，
d)0．1-1％重量烷基和／或链烯基低聚糖苷，
e)1-5％重量的其它助剂和添加剂，
其余为水，补足至100％重量。
2、按权利要求1所述的块皂，其特征是，它含有式(Ⅰ)的脂肪酸盐，R1CO-ONa  (Ⅰ)
式中R1CO为6至22个碳原子的脂族酰基。
3、按权利要求1或2所述的块皂，其特征是，它含有式(Ⅱ)的脂肪酸，R2CO-OH  (Ⅱ)
式中R2CO为6至22个碳原子的脂族酰基。
4、按权利要求1或2所述的块皂，其特征是，它含有式(Ⅲ)的乙氧基化的醇的烷基醚硫酸盐，R3O-(CH2CH2O)nH  (Ⅲ)
式中R3为6至22个碳原子的直链或支链烷基和／或链烯基，n为1至10的数值。
5、按权利要求1或2所述的块皂，其特征是，它含有式(Ⅳ)的烷基和／或链烯基低聚糖苷，R4O-[G]p  (Ⅳ)
式中R4为6至22个碳原子的直链或支链烷基和／或链烯基，G为5或6个碳原子的糖基，p为1至10的数值。
CN94193933A 1993-10-29 1994-10-20 块皂 Expired - Fee Related CN1060513C (zh)

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ES2102889T3 (es) 1997-08-01
CA2175188A1 (en) 1995-05-04
DE4337031A1 (de) 1995-05-04
DE4337031C2 (de) 1995-11-30
ATE154633T1 (de) 1997-07-15
US5705462A (en) 1998-01-06
JPH09504316A (ja) 1997-04-28
PL177258B1 (pl) 1999-10-29
EP0724626B1 (de) 1997-06-18
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