CN101712911A - 用于向基质送递有益添加剂的含油的淀粉颗粒 - Google Patents
用于向基质送递有益添加剂的含油的淀粉颗粒 Download PDFInfo
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- CN101712911A CN101712911A CN200910246170A CN200910246170A CN101712911A CN 101712911 A CN101712911 A CN 101712911A CN 200910246170 A CN200910246170 A CN 200910246170A CN 200910246170 A CN200910246170 A CN 200910246170A CN 101712911 A CN101712911 A CN 101712911A
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- Prior art keywords
- starch
- alkyl
- oil
- replaced
- butyraceous
- Prior art date
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- 239000008107 starch Substances 0.000 title claims abstract description 72
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 11
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000013508 migration Methods 0.000 claims abstract description 6
- 230000005012 migration Effects 0.000 claims abstract description 6
- 238000005192 partition Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 48
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- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical group 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
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- 239000013543 active substance Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 125000005466 alkylenyl group Chemical group 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
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- 239000000243 solution Substances 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
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- 239000002253 acid Substances 0.000 description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 16
- 239000010457 zeolite Substances 0.000 description 16
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- -1 aliphatic ester Chemical class 0.000 description 11
- 238000002470 solid-phase micro-extraction Methods 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
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- 239000000047 product Substances 0.000 description 7
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
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- 239000011591 potassium Substances 0.000 description 4
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- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 3
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
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- 239000004094 surface-active agent Substances 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- 241000196324 Embryophyta Species 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
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- 239000002671 adjuvant Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
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- 125000004429 atom Chemical group 0.000 description 2
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- 150000001768 cations Chemical class 0.000 description 2
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- 238000005202 decontamination Methods 0.000 description 2
- 230000003588 decontaminative effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 238000007046 ethoxylation reaction Methods 0.000 description 2
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- 150000002191 fatty alcohols Chemical class 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- LUZDYPLAQQGJEA-UHFFFAOYSA-N 2-Methoxynaphthalene Chemical compound C1=CC=CC2=CC(OC)=CC=C21 LUZDYPLAQQGJEA-UHFFFAOYSA-N 0.000 description 1
- GUOCOOQWZHQBJI-UHFFFAOYSA-N 4-oct-7-enoxy-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OCCCCCCC=C GUOCOOQWZHQBJI-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OKTJSMMVPCPJKN-IGMARMGPSA-N Carbon-12 Chemical compound [12C] OKTJSMMVPCPJKN-IGMARMGPSA-N 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- MSCCTZZBYHQMQJ-AZAGJHQNSA-N Tocopheryl nicotinate Chemical compound C([C@@](OC1=C(C)C=2C)(C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)CC1=C(C)C=2OC(=O)C1=CC=CN=C1 MSCCTZZBYHQMQJ-AZAGJHQNSA-N 0.000 description 1
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- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
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- 235000020679 tap water Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- REZQBEBOWJAQKS-UHFFFAOYSA-N triacontyl alcohol Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCO REZQBEBOWJAQKS-UHFFFAOYSA-N 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
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- C11D1/38—Cationic compounds
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Abstract
提供了含油的淀粉颗粒,它包括:(a)形成所述颗粒的有效基质的淀粉;(b)芳香油,其所含成分的计算的Clog P至少为3,所述Clog P是计算的辛醇与水分配系数,所述芳香油在与基质接触后,能够为基质提供有益添加剂,所述基质选自:织物、硬表面、毛发和皮肤;和(c)有效量的特定的有机化合物,用于抑制所述油向所述淀粉颗粒表面的迁移。
Description
本申请是申请日为2005年3月17日,申请号为200580008458.0的、发明名称和本发明相同的发明专利申请的分案申请。
本发明涉及含油的淀粉颗粒,它包括能形成所述颗粒的基质的淀粉,芳香油和用于抑制所述油向淀粉颗粒表面的迁移的具有特定结构的化合物。更具体地讲,本发明涉及含油的淀粉颗粒,它包含特定的芳香油,它能够在所述淀粉颗粒与所述基质接触后向诸如织物、硬表面、毛发和皮肤的基质送递有益添加剂。
发明背景
在液体去污剂组合物中添加香料,以使这种去污剂组合物具有怡人的芳香或香味在本领域中是众所周知的。香料的存在,在使用所述去污剂组合物后为消费者提供了美学利益,并且通常被用作洗涤过的织物的清新和洁净的信号,所述织物含有怡人的香味。不过,尽管去污剂组合物本身具有较强的芳香,但只有相对少的香料香味在洗涤期间赋予织物。这主要是因为液体组合物中的香料成分在洗涤期间会很快分散和稀释在水性洗涤和漂洗用水中。因此,在洗涤过程中只有相对有限量的香料能够接触织物,大部分的香料随着洗涤溶液一起从洗衣机中排出。因此,本领域仍然需要改进将香料从去污剂组合物送递到洗涤过的织物的效力,并且增强所述香味在织物上的寿命。
类似地,本领域需要将除了香料之外的油作为有益添加剂有效送递到诸如硬表面、毛发和皮肤的基质上,从而所述油在所述基质上的寿命相对于向基质提供这种有益添加剂的常规方法而言得到显著增加。
发明概述
本发明提供了含油的淀粉颗粒,它包括
(a)淀粉,所述淀粉以形成所述颗粒的有效基质的量存在;
(b)芳香油,其所含成分的计算的ClogP至少为3,所述ClogP是计算的辛醇与水分配系数,所述芳香油在与基质接触后,能够为基质提供有益添加剂,所述基质选自:织物、硬表面、毛发和皮肤;和
(c)有效量的有机化合物,用于抑制所述油向所述淀粉颗粒表面的迁移,所述化合物通过以下结构表示:
其中,R1和R2各自独立地是H或:
(a)C1-C22亚烷基羧基部分,其具有式-(CH2)eR3,其中,R3是-NHCOR4;或-OCOR4;或-NR5COR4;且其中,R4和R5各自独立地是C1-C22烷基或链烯基;且e是1-22的整数;或
(b)C1-C22线性或分支的烷基;或
(c)C1-C22线性或分支的链烯基;或
(d)C2-C22取代过的或未取代过的亚烷氧基(alkylenoxy);或
(e)C3-C22取代过的或未取代过的亚烷氧基烷基;或
(f)C6-C22取代过的或未取代过的芳氧基;或
(g)C7-C22取代过的或未取代过的亚烷基芳基;或
(h)C7-C22取代过的或未取代过的亚烷氧基芳基(alkyleneoxyaryl);或
(i)C7-C22氧化亚烷基芳基;或
(j)阴离子单位,其具有式:
-(CH2)yR6
其中,R6是-SO3M、-OSO3M、-PO3M、-OPO3M、Cl或其混合物,其中,M是氢,或一个或多个足以满足电荷平衡的形成盐的阳离子,或其混合物;
y是1-大约22的整数;或
(k)包括(a)-(j)中的至少两种的混合物;和
q是0-大约22的整数;m是0-大约22的整数;Q是(CH2)m或(CH2CHR7O);R7独立地是氢、甲基、乙基、丙基或苄基;B是H或OH;且Y是CR1或N。
在本发明的其他实施方案中,所述用于抑制所述油向淀粉颗粒表面迁移的化合物通过相当于下面的式(2)的二脂肪酰胺基胺化合物或相当于
下面式(3)的季铵化合物表示:
其中,R1和R2独立地表示C12-C30脂族烃基,R3表示(CH2CH2O)pH、CH3或H;T表示NH;n是1-5的整数;m是1-5的整数,且p是1-10的整数。
其中,R1和R2各自独立地是H或:
(a)C1-C22亚烷基羧基部分,其具有式:
-(CH2)eR3,其中,R3是-NHCOR4;或-OCOR4;或-NR5COR4;且其中,R4和R5各自独立地是C1-C22烷基或链烯基;且e是1-22的整数;或
(b)C1-C22线性或分支的烷基;或
(c)C1-C22线性或分支的链烯基;或
(d)C2-C22取代过的或未取代过的亚烷氧基;或
(e)C3-C22取代过的或未取代过的亚烷氧基烷基;或
(f)C6-C22取代过的或未取代过的芳氧基;或
(g)C7-C22取代过的或未取代过的亚烷基芳基;或
(h)C7-C22取代过的或未取代过的亚烷氧基芳基;或
(i)C7-C22氧化亚烷基芳基;或
(j)阴离子单位,其具有式:
-(CH2)yR6
其中,R6是-SO3M、-OSO3M、-PO3M、-OPO3M、Cl或其混合物,其中,M是氢,或一个或多个足以满足电荷平衡的形成盐的阳离子,或其混合物;R6还可以是氯化物;y是1-大约22的整数;和
(k)包括(a)-(j)中的至少两种的混合物;和
q是0-大约22的整数;m是0-大约22的整数;Q是(CH2)m或(CH2CHR7O);R7独立地是氢、甲基、乙基、丙基或苄基;及其混合物;B是H或OH;Y是N;R8是H或C1-C4烷基;Z-是抗衡阴离子,并且优选是氯化物,或硫酸二甲酯。
根据本发明的方法方面,提供了洗涤织物的方法,该方法包括让所述织物与含有有效量的本发明的含油的淀粉颗粒的水溶液接触的步骤。
还提供了制备含油的淀粉颗粒的方法,其包括以下步骤
(a)提供淀粉在水中的分散体,以形成淀粉浆;
(b)熔化有效量的有机化合物,如包括二(烷基酰胺乙基(amidoethyl))-2-聚乙氧基胺的酰胺-胺,以形成酰胺-胺熔化物;
(c)向步骤(b)的有机化合物熔化物或酰胺-胺熔化物中添加芳香油,以形成有机化合物或酰胺-胺在芳香油中的溶液;所述芳香油所含成分的计算的ClogP至少为3,所述ClogP是计算的辛醇与水分配系数;
(d)将步骤(c)的溶液添加到步骤(a)的淀粉浆;
(e)通过混合对所得到的浆进行匀浆,以形成均匀的均相混合物;和
(f)对所述均相混合物进行喷雾干燥,以形成含油的淀粉颗粒。
可用于本发明的油可以是任何油类,它在大约10℃-90℃下是液体,并且能够向织物、硬表面、毛发或皮肤提供有益添加剂。对于洗衣用途来说,优选的油类是香料,术语“香料”在本文中用于表示能散发气味的材料,它能够为织物提供怡人的香味,并且包括常用于去污剂组合物中以抵消所述组合物中的恶臭和/或为该组合物提供怡人的香味的常规材料。所述香料在环境温度下优选是液体状态的,尽管还可以使用固体香料。
本发明的芳香油包括的成分的ClogP至少为3,其中,ClogP是计算的辛醇与水分配系数。ClogP是表示香料的水溶解度或疏水性的参数。Clog P的值越高,香料的疏水性越高。分配系数的提高,提供了更高的直接性(持久的气味,缓慢地从洗涤过的织物中发出;Sina D.Escher和Esther Oliveros;A Quantitative Study of Factors That Influence theSubstantivity of Fragrance Chemicals on Laundered and Dried Fabrics;Journal of American Oil Chemist′s Society Volume 71,No.1,pages 31-40,1994)。ClogP值为3或以上的香料比ClogP值低于3的香料更有效地沉积在织物表面上(从洗衣产品中沉积)。因此,本发明的香料成分的ClogP大约为3或更高,优选超过大约3.2,且甚至更优选超过大约3.3。
业已报导了很多香料成分的ClogP,例如,可以从Daylight ChemicalInformation Systems,Inc.(Daylight CIS)Irvine,California获得的Ponoma92数据库。所述值最常见的是使用ClogP程序计算的,该程序同样可以从Daylight CIS获得。该程序还列举了通过实验确定的log P值,它是可以从Pomona数据库获得的。计算的logP(ClogP)通常是通过Hansch和Leo的分段方法确定的(A.Leo,in ComprehensiveMedicinal Chemistry,Vol.4,C.Hansch,P.G.Sammens,J.B.Taylor和C.A.Ransden,Editors,p.295 Pergamon Press,1990)。该方法基于香料成分的化学结构,并且考虑了原子的数目和类型、原子连通性和化学成键。最可靠的并且被广泛用于估计这一生理化学特性的ClogP值可用于代替在本发明中使用的实验的LogP值。有关ClogP和logP值的其他信息可以参见美国专利5,500,138。
在本发明预期使用的香料中包含诸如醛、酮、酯等的材料,它们通常被用于赋予液体和颗粒状去污剂组合物怡人的香味。天然存在的植物和动物油通常还被用作香料的成分。因此,可用于本发明的香料可以具有相对简单的组成或可以包括天然和合成化学成分的复杂混合物,它们都被预期在用于织物时提供怡人的气味或香味。用于去污剂组合物中的香料通常要进行选择,以满足气味、稳定性、价格和工业可用性的正常要求。术语“香料”在这里通常被用于表示香料本身,而不是由所述香料产生的芳香。
可在本发明中用于为上述织物、硬表面、毛发和皮肤的基质中的一种或多种提供有益添加剂的其他油类包括维生素,如维生素E(生育酚酯),改性和未改性的硅油,表面活性剂,织物柔软剂,脂肪族醇,脂肪酸,脂肪族酯等。所述油类可以直接使用或者作为任意上述油类的组合形式使用。
发明详述
适用于本发明的淀粉颗粒的淀粉可以用生淀粉或来自块茎、豆类、谷类和谷物的改性淀粉制成,例如,玉米淀粉、小麦淀粉、米淀粉、蜡质种玉米淀粉、燕麦淀粉、木薯淀粉、蜡质大麦、蜡质米淀粉、甜米淀粉、amoica、马铃薯淀粉、tapioca淀粉、燕麦淀粉、木薯淀粉及其混合物。
适合使用的改性淀粉包括水解淀粉、酸稀释淀粉、长链烃的淀粉酯、乙酸淀粉、辛烯基琥珀酸(octenyl succinate)淀粉及其混合物。
术语“水解淀粉”表示寡糖型材料,如玉米淀粉、麦芽糖糊精和玉米糖浆固体。
用于抑制所述油向颗粒表面迁移的有机化合物优选是具有下式的酰胺-胺:
其中,R1=C12-C30烷基或链烯基,
R2=R1CONH(CH2)m,
R3=(CH2CH2O)pH、CH3或H,
n=1-5,
m=1-5,和
p=1-10。
在式(I)的更优选的软化化合物中,
R1=C16-C22烷基,
n=1-3,
m=1-3,和
p=1.5-3.5。
在上述式中,R1和R2各自独立地是长链烷基或链烯基,具有12-30个碳原子,优选16-22个碳原子,例如,十二烷基、十二碳烯基、十八烷基、十八烯基。通常,R1和R2来自天然油类,其包含脂肪酸或脂肪酸混合物,如椰子油、棕榈油、牛脂、菜油和鱼油。还可以使用化学合成的脂肪酸。优选饱和脂肪酸或脂肪酸混合物,且尤其是氢化牛脂(H-牛脂)酸(又被称作硬牛脂)。一般且优选的是R1和R2来自相同的脂肪酸或脂肪酸混合物。
R3表示(CH2CH2O)pH、CH3或H,或还可以存在其混合物。当R3表示优选的(CH2CH2O)pH基团时,p是表示平均乙氧基化程度的正数,并且优选为1-10,尤其是1.5-6,且最优选为大约2-4,如2.5,n和m各自是1-5的整数,优选2-4,尤其是2。R3表示优选的(CH2CH2O)pH基团的式(I)的化合物在本文中被广义地称作乙氧基化的酰胺-胺,并且术语“羟乙基”同样被用于描述(CH2CH2O)pH基团。
本发明的洗衣店去污剂组合物可以包括选自下列一组的一种表面活性剂或表面活性剂的混合物:阴离子、非离子和阳离子表面活性剂。
任何合适的非离子型去污剂化合物都可以用作本发明洗衣店去污剂组合物中的表面活性剂,所述去污剂的多种成员描述在Detergents and Emulsifiers的各种年鉴中,作者John W.McCutcheon。所述书籍提供了在美国上市的商业非离子型去污剂的化学式和商标,并且基本上所有这样的去污剂都可用于本发明组合物中。不过,高度优选的是,所述非离子型去污剂是环氧乙烷和高级脂肪族醇的缩合产物(尽管还可以使用高级脂肪酸和烷基[辛基、壬基和异辛基]苯酚替代高级脂肪族醇)。所述醇和所得缩合产物的高级酯肪部分,如烷基,正常是线性的,具有10-18个碳原子,优选10-16个碳原子,更优选12-15个碳原子,并且有时候最优选12-14个碳原子。因为所述脂肪族醇正常是以混合物形式商业出售的,所以所提供的碳原子的数目必须是平均数,但在某些场合下,碳原子数目的范围可以是所采用的醇和相应的烷基的实际限度。
所述非离子型去污剂中环氧乙烷(EtO)含量正常在每摩尔高级脂肪族醇3-15摩尔EtO的范围,尽管可以存在高达20摩尔的EtO。优选的是,所述EtO含量为3-10摩尔,且更优选为6-7摩尔,例如,每摩尔高级脂肪族醇(以及每摩尔非离子型去污剂)6.5或7摩尔。与高级脂肪族醇一样,所提供的聚乙氧基化物限度还可以限定缩合产物中存在的EtO基团数目的平均值。合适的非离子型去污剂的例子包括由ShellChemical Company以为商标出售的产品,包括Neodol 25-7、Neodol 23-6.5和Neodol 25-3。
其他有用的非离子型去污剂化合物包括烷基多苷和烷基多糖表面活性剂,这些表面活性剂是众所周知的,并且在现有文献中有广泛描述。
所述去污剂组合物可以包括线性烷基苯磺酸盐阴离子表面活性剂,其中,所述烷基自由基包括大约10-16个碳原子,是直链或支链形式的,且优选12-15个碳原子。合适的合成阴离子表面活性剂的例子是烷基(C4-C20)苯磺酸钠和钾,特别是线性仲烷基(C10-C15)苯磺酸钠。
在本发明液体去污剂组合物中任选包括的其他合适的阴离子型去污剂是硫酸化乙氧基化高级脂肪族醇,其具有式:RO(C2H4O)mSO3M,其中,R是10-18个碳原子的脂肪烷基,m是2-6(优选具有R中碳原子数目的大约1/5-1/2的值),而M是增溶性形成盐的阳离子,如碱金属、铵或高级烷基苯磺酸盐,其中,所述高级烷基具有10-15个碳原子。环氧乙烷在聚乙氧基化高级硫酸链烷醇酯中的比例通常为1-11个环氧乙烷基团,且优选2-5摩尔环氧乙烷/摩尔阴离子型去污剂,最优选3摩尔,尤其是当高级链烷醇具有11-15个碳原子时。
最优选的水溶性阴离子型去污剂化合物是高级烷基苯磺酸,和高级烷基硫酸的铵和取代过的铵(如一、二和三乙醇胺)、碱金属(如钠和钾)和碱土金属(如钙和镁)盐。
助洗剂材料是本发明液体去污组合物的基本成分。具体地讲,大约2%-大约15%的碱金属碳酸盐,如碳酸钠,且优选按重量计大约3%-大约10%。
按重量计大约5%-大约30%量的磷酸盐助洗剂,且具体是碱金属(钠)多磷酸盐是本发明液体去污组合物的组成成分。所述多磷酸盐助洗剂的量优选为大约8%-大约20%。
合适的含磷无机去污助洗剂的例子包括水溶性盐,尤其是碱金属焦磷酸盐、正磷酸盐和多磷酸盐。无机磷酸盐助洗剂的具体例子包括三多磷酸、磷酸和六偏磷酸钠和钾。
在本发明的组合物中可任选地包括沸石A型的硅铝酸盐助洗剂,它通常是水合的。还可以使用水合沸石X和Y,也可使用起着去污助洗剂作用的天然存在的沸石。在各种沸石A产品中,沸石4A通常是优选的,它是一种类型的沸石分子,其中,孔径大小为大约这种类型的沸石在本领域是众所周知的,并且它的生产方法描述于诸如美国专利3,114,603的本领域中。
所述沸石助洗剂通常具有式
(Na2O)x·(Al2O3)y·(SiO2)z·wH2O
其中,x是1,y是0.8-1.2,优选大约1,z是1.5-3.5,优选2或3或大约2,而w是0-9,优选2.5-6。本发明可以使用的沸石的晶体类型包括在以下文献中所描述的那些:“Zeolite Molecular Series”,DonaldBreck著,由John Wiley&Sons于1974年出版,一般的商业化沸石在该文献的第747-749页上的表9.6中列举,该表被收作本文参考。
所述沸石助洗剂应当是一价阳离子交换沸石,即它应当是一价阳离子的硅铝酸盐,如钠、钾、锂(在可应用时)或其他碱金属或铵。具有碱金属阳离子,尤其是钠的沸石是最优选的,正如在上面的式中所示出的。所采用的沸石的特征是具有对钙离子的高的交换能力,通常为每克硅铝酸盐具有大约200-400或以上毫克当量的碳酸钙硬度,优选250-350mg.eg./g.,它是以无水沸石为基础计算的。沸石的优选量为大约8%-大约20%。
在去污剂组合物中可以存在其他成分,以改善其特性,并且,在某些场合下,起着稀释剂或填料的作用。合适的佐剂的说明性例子有酶,以进一步促进从衣物或硬表面清洗某些难以去除的污渍。在所述酶中,最有用的是蛋白酶和淀粉分解酶。其他有用的佐剂是当需要泡沫时的起泡剂,如月桂酸肉豆蔻酸二乙醇酰胺,和当需要时的防沫剂如二甲基硅氧烷流体。同样有用的是聚合物,抗再沉积剂,漂白剂,荧光增白剂,如均二苯代乙烯增白剂,着色剂,如染料和色素和香料。
分析方法
1.干燥织物的加热的SPME顶空分析
固相微量萃取(SPME;Almirall,J.R.;Furton,K.G.In Solid PhaseMicroextraction;A Practical Guide;Scheppers-Wercinski,S.,Ed;MarcelDekker;New York,1999,pp.203-216)是无溶剂的萃取技术,通过这种技术将分析物从基质(如织物)上萃取到聚合物或其他相中,涂敷在熔融的二氧化硅纤维上。SPME与气相层析(GC)偶联,用于对分析物进行解吸和分析。
材料:
1.具有离子阱质谱检测和SPME 0.75mm ID入口衬垫的气相层析仪。
(Varian GC3800/Saturn 2000,装配有Combi Pal自动采样器(AutoSampler)
2.GC柱:CP-SIL-8CB-MS,30mX0.25mmX0.25μm。
3.SPME纤维:100微米聚二甲基硅氧烷(Supelco 57300-U(手工)或57301(自动化))。
4.10mL顶空小瓶,具有卷曲的顶部和Septa Varian MLA201000和MLA200051ML
方法:
1.使用洁净干燥的剪刀从要分析的厚绒布棉毛巾上切割(3)1克的样品(2g用于恶臭)。
2.用玻璃棒将每一个样本插入10mL顶空小瓶中,小心插的足够远,以不破坏SPME纤维。
3.盖上小瓶,并且在室温下让它平衡至少24小时。
4.在自动采样器中在50℃下平衡小瓶至少30分钟。
5.插入纤维,并且在50℃下暴露25分钟。
6.注入气相层析仪,并且在250℃下解吸30分钟。
GC条件:
注射器温度:250℃。
柱流速:1mL/分钟
柱式加热炉:
总运行时间:45分钟
2.厚绒布毛巾的反萃取方法
对所有样品评估来说,在17加仑顶部加载洗衣机中准备24条新的厚绒布手巾(86%棉,14%聚酯),设定为热洗(120°F),使用自来水,采用超大设定。两轮洗涤使用100g无香料的Mexican Viva 2去污剂粉,一次洗涤只使用水,打开额外漂洗开关,将以上方法用于所有洗涤。在所有三个洗涤循环结束之后,在电子衣物干燥器中对所述毛巾进行干燥机干燥,并且平放进行贮存。对用于测试的所有衣物压载物在每一次使用之间以与毛巾相同的方式处理。
表1.去污剂基本组分,B1:
成分名称 | 重量% |
水 | 6 |
C9-C14线性烷基苯磺酸钠 | 17.3 |
硅酸钠 | 7 |
硅氧烷防沫剂1430(Dow Corning) | 0.01 |
三多磷酸五钠 | 36.8 |
硫酸钠 | 36.8 |
酶Savinase 12T(Novo) | 0.29 |
聚丙烯酸钠Alcosperse 412 | 0.9 |
碳酸钠 | 12 |
次要成分 | 平衡到100 |
淀粉颗粒
淀粉/AA.颗粒是使用Capsul淀粉(由National Starch出售的产品)制备的。Capsul是糊精化的蜡质种玉米辛烯基琥珀酸淀粉。所述降解淀粉的糊精化过程使Capsul淀粉与其他类型的淀粉区分开。利用下述方法制备淀粉/AA颗粒:至少提前一天用GREERCO Model No.1L混合器在水中预混合33%Capsul淀粉。让空气沉降出来。从中取出需要的量,并且添加芳香油和熔化的酰胺-胺混合物,并且使用Silverson Model L4R混合器匀浆。将该混合物倒入Armfield FT80 Tall Form喷雾干燥器(Spray Dryer)中,并且在190℃下进行喷雾干燥,采用0.5-1.0巴的雾化压力。
用于制备表4所示出的组合物的淀粉颗粒的组成(所示出的量是重量百分比)如下(表2):
表2.淀粉颗粒组成
*来自International Flavors and Fragrances Inc的Dinasty主要(substantive)香料,其包括以下成分:
浓度Wt% | Clog P | |
丙酸三环葵烯酯(Cyclaprop) | 6.7 | 3.51 |
Nerolin | 2.2 | 3.77 |
铃兰醛(Lilial) | 2.1 | 4.1 |
Isocyclemone E | 11.1 | 5.23 |
己基肉桂醛 | 44.5 | 4.90 |
加乐麝香 | 33.4 | 5.83 |
颗粒淀粉/AA的表面油含量,和与淀粉/二氧化硅的性能比较
研究表明,疏水性添加剂AA能显著减少干燥的淀粉胶囊表面上的香料量(Dinasty主要香料),从2.89%(无AA)降低到0.24%(表3)。与AA相反,另一项研究表明,疏水性改性的二氧化硅(Aerosil R974;现有技术中的优选添加剂,专利申请WO01/05926)不能将表面油的量降低到与酰胺-胺相同的程度(表3)。Aerosil能将淀粉颗粒上的表面油(Dinasty香料)的量从3.09%(无Aerosil)降低到2.38%(有Aerosil)。表面油是通过以下方法测量的:在室温和大气压力下用己烷从被囊化颗粒中萃取,然后进行气相层析。己烷只能萃取颗粒表面的芳香油,而不能萃取颗粒内被囊化的油。
表3.淀粉香料颗粒上的表面油(仅有主要级分)的量。
表面油(wt%) | 表面油(wt%) | |
淀粉* | 3.09 | 2.89 |
淀粉/AA** | 0.24 | |
淀粉/AerosilR974*** | 2.38 |
*颗粒由[Capsul淀粉(65%),Dinasty主要香料(35%)]组成
**颗粒由[Capsul淀粉(60%),二脂肪酰胺-胺(5%),Dinasty主要香料(35%)]组成
***颗粒由[Capsul淀粉(64.29%),Aerosil R974(0.71%),Dinasty主要香料(35%)]组成
表4.组成1和2
1(对照)重量% | 2(淀粉/AA)重量% | ||
B1 | 基本组分珠 | 97.6 | 97.6 |
香料* | 0.31 | 0.31 | |
淀粉/AA**香料颗粒 | - | 1.23* | |
Dinasty***主要级分 | 0.43 | ||
去离子化水 | 到100 | 到100 |
*添加到B1基本组分珠中之后的香料
**所述颗粒包括35%Dinasty主要香料(或配方中的0.43%)(表2)
***所示出的香料组成(表2)
以上配方是在以下条件下使用的:
测试条件:温度为77F,水的硬度为50ppm,洗涤10分钟,漂洗5分钟,洗衣机是Maytag洗衣机,进行3次洗涤循环。织物加载量为12条厚绒布样品(10X10英寸)。样品在使用之前预先洗涤成条。在洗涤之后,样品挂干1和7天。去污剂浓度为78gm。洗涤是这样进行的:用水填充洗衣机,然后添加硬度为50ppm的水,这通过添加250,000ppm水的储备溶液实现。加入产品并且搅拌1分钟。添加样品,洗涤10分钟,并且漂洗5分钟。在洗涤结束之后,挂干样品1和7天,并且切割织物样品用于SPME分析(1gm织物/SPME小瓶,4瓶/产品)。 |
表5.通过固相微量萃取方法观察到的干燥织物表面上的总的香料量(在第7天之后)。
对照 | 3090065 |
淀粉/AA | 4670633 |
如表5所示,与对照(组成1,表4)相比,使用香料颗粒(组成2,表4)能将更多的香料沉积在织物表面上。
Claims (4)
1.含油的淀粉颗粒,其包括:
(a)淀粉,所述淀粉以形成所述颗粒的有效基质的量存在;
(b)芳香油,其所合成分的计算的ClogP至少为3,所述ClogP是计算的辛醇与水分配系数,所述芳香油在与基质接触后,能够为基质提供有益添加剂,和
(c)有效量的有机化合物,其包含抑制所述油向所述淀粉颗粒表面的迁移的季铵化合物,所述化合物通过以下结构表示:
其中,R1和R2各自独立地是H或:
(a)C1-C22亚烷基羧基部分,其具有式-(CH2)eR3,
其中,R3是-NHCOR4;或-OCOR4;或-NR5COR4;且
其中,R4和R5各自独立地是C1-C22烷基或链烯基;且e是1-22的整数;或
(b)C1-C22线性或分支的烷基;或
(c)C1-C22线性或分支的链烯基;或
(d)C2-C22取代过的或未取代过的亚烷氧基;或
(e)C3-C22取代过的或未取代过的亚烷氧基烷基;或
(f)C6-C22取代过的或未取代过的芳氧基;或
(g)C7-C22取代过的或未取代过的亚烷基芳基;或
(h)C7-C22取代过的或未取代过的亚烷氧基芳基;或
(i)C7-C22氧化亚烷基芳基;或
(j)阴离子单位,其具有式:
-(CH2)yR6
其中,R6是-SO3M、-OSO3M、-PO3M、-OPO3M、Cl或其混合物,其中,M是氢,或一个或多个足以满足电荷平衡的形成盐的阳离子,或其混合物;
y是1-大约22的整数;或
(k)包括(a)-(j)中的至少两种的混合物;和
q是0-大约22的整数;
m是0-大约22的整数;
Q是(CH2)m或(CH2CHR7O);
R7独立地是氢、甲基、乙基、丙基或苄基;及其混合物
B是H或OH;且
Y是N;
R8是H或C1-C4烷基;
Z-是平衡阴离子。
2.一种制备如权利要求1所述的含油的淀粉颗粒的方法,其包括以下步骤:
(a)提供淀粉在水中的分散体,以形成淀粉浆;
(b)熔化有效量的有机化合物以形成有机化合物熔化物;
(c)向步骤(b)的有机化合物熔化物中添加芳香油,以形成有机化合物在芳香油中的溶液;
(d)将步骤(c)的溶液添加到步骤(a)的淀粉浆;
(e)通过混合对所得到的浆进行匀浆,以形成均匀的均相混合物;和
(f)对所述均相混合物进行喷雾干燥,以形成含油的淀粉颗粒。
3.一种洗涤织物的方法,其包括以下步骤
(a)形成含有有效量的如权利要求1的含油的淀粉颗粒的水溶液;和
(b)让要洗涤的织物与步骤(a)的水溶液接触。
4.一种洗衣店去污剂组合物,其包括:
(a)至少一种表面活性剂;和
(b)如权利要求1的有效量的含油的淀粉颗粒。
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CN2005800084580A Expired - Fee Related CN1934238B (zh) | 2004-03-18 | 2005-03-17 | 用于向基质送递有益添加剂的含油的淀粉颗粒 |
CN200910246169A Pending CN101724518A (zh) | 2004-03-18 | 2005-03-17 | 用于向基质送递有益添加剂的含油的淀粉颗粒 |
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US (4) | US7279454B2 (zh) |
EP (3) | EP2186874A1 (zh) |
CN (3) | CN1934238B (zh) |
AT (1) | ATE483787T1 (zh) |
AU (3) | AU2005224675B2 (zh) |
BR (1) | BRPI0507270B1 (zh) |
CA (1) | CA2558008C (zh) |
DE (1) | DE602005023966D1 (zh) |
DK (1) | DK1725646T3 (zh) |
HK (1) | HK1094338A1 (zh) |
IL (3) | IL177761A (zh) |
MY (3) | MY145046A (zh) |
NO (1) | NO20064698L (zh) |
PL (1) | PL1725646T3 (zh) |
RU (3) | RU2408667C2 (zh) |
WO (1) | WO2005090538A2 (zh) |
ZA (1) | ZA200607304B (zh) |
Families Citing this family (8)
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US7279454B2 (en) * | 2004-03-18 | 2007-10-09 | Colgate-Palmolive Company | Oil containing starch granules for delivering benefit-additives to a substrate |
US7276472B2 (en) * | 2004-03-18 | 2007-10-02 | Colgate-Palmolive Company | Oil containing starch granules for delivering benefit-additives to a substrate |
EP2145944B1 (en) * | 2008-07-14 | 2014-03-26 | The Procter & Gamble Company | A particle for imparting a fabric-softening benefit to fabrics treated therewith and that provides a desirable suds suppresion |
ES2351836B1 (es) * | 2010-09-07 | 2011-10-10 | Microlitix- Control Microbiologico Integral Slne | Aditivo para materiales polímeros orgánicos y/o aglomerados inorgánicos y procedimiento y usos correspondientes. |
TR201901003T4 (tr) | 2014-11-17 | 2019-02-21 | Unilever Nv | Kumaş İşleme Bileşimi |
CN107001991A (zh) | 2014-11-17 | 2017-08-01 | 荷兰联合利华有限公司 | 织物处理组合物 |
US9347022B1 (en) | 2014-12-17 | 2016-05-24 | The Procter & Gamble Company | Fabric treatment composition |
US20240033193A1 (en) * | 2022-07-27 | 2024-02-01 | Julius Zecchino | Foaming cleanser |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
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US3114603A (en) * | 1960-01-15 | 1963-12-17 | Union Carbide Corp | Process for synthetic zeolite a |
US5246603A (en) | 1991-09-25 | 1993-09-21 | Lever Brothers Company, Division Of Conopco, Inc. | Fragrance microcapsules for fabric conditioning |
US5500138A (en) | 1994-10-20 | 1996-03-19 | The Procter & Gamble Company | Fabric softener compositions with improved environmental impact |
CA2265804A1 (en) * | 1996-09-18 | 1998-03-26 | Athanasios Surutzidis | Process for making particulate laundry additive composition |
CN1136311C (zh) * | 1996-11-04 | 2004-01-28 | 诺沃奇梅兹有限公司 | 枯草杆菌酶变异体和组合物 |
US5905067A (en) * | 1997-02-10 | 1999-05-18 | Procter & Gamble Company | System for delivering hydrophobic liquid bleach activators |
US5858959A (en) * | 1997-02-28 | 1999-01-12 | Procter & Gamble Company | Delivery systems comprising zeolites and a starch hydrolysate glass |
US6221826B1 (en) * | 1997-03-20 | 2001-04-24 | The Procter & Gamble Company | Laundry additive particle having multiple surface coatings |
BR9909803B1 (pt) * | 1998-04-23 | 2008-11-18 | partÍcula de perfume encapsulada e composiÇço detergente particulada para a lavagem de tecidos. | |
CN100360652C (zh) * | 1999-07-20 | 2008-01-09 | 宝洁公司 | 改进的包封的油颗粒 |
US6362159B1 (en) | 1999-10-04 | 2002-03-26 | Unilever Home & Personal Care Usa | Domestic care product |
AU759299B2 (en) | 1999-12-03 | 2003-04-10 | Procter & Gamble Company, The | Delivery system having encapsulated porous carrier loaded with additives, particularly detergent additives such as perfumes |
ATE367430T1 (de) * | 2000-05-11 | 2007-08-15 | Procter & Gamble | Hochkonzentrierte wäscheweichspülerzusammensetzungen und diese enthaltende mittel |
US6620777B2 (en) * | 2001-06-27 | 2003-09-16 | Colgate-Palmolive Co. | Fabric care composition comprising fabric or skin beneficiating ingredient |
US6740631B2 (en) * | 2002-04-26 | 2004-05-25 | Adi Shefer | Multi component controlled delivery system for fabric care products |
WO2003096242A1 (en) * | 2002-05-07 | 2003-11-20 | British Telecommunications Public Limited Company | Method and apparatus for selecting user policies |
US6780834B2 (en) | 2002-07-31 | 2004-08-24 | Colgate-Palmolive Co. | Fabric conditioning compositions containing an amine acid softening compound |
US20040224028A1 (en) * | 2003-05-09 | 2004-11-11 | Popplewell Lewis Michael | Polymer particles and methods for their preparation and use |
US7276472B2 (en) * | 2004-03-18 | 2007-10-02 | Colgate-Palmolive Company | Oil containing starch granules for delivering benefit-additives to a substrate |
US7279454B2 (en) * | 2004-03-18 | 2007-10-09 | Colgate-Palmolive Company | Oil containing starch granules for delivering benefit-additives to a substrate |
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2004
- 2004-03-18 US US10/803,586 patent/US7279454B2/en active Active
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2005
- 2005-03-17 CN CN2005800084580A patent/CN1934238B/zh not_active Expired - Fee Related
- 2005-03-17 DE DE602005023966T patent/DE602005023966D1/de active Active
- 2005-03-17 CA CA2558008A patent/CA2558008C/en not_active Expired - Fee Related
- 2005-03-17 CN CN200910246169A patent/CN101724518A/zh active Pending
- 2005-03-17 EP EP10155016A patent/EP2186874A1/en not_active Withdrawn
- 2005-03-17 AU AU2005224675A patent/AU2005224675B2/en not_active Ceased
- 2005-03-17 DK DK05725897.2T patent/DK1725646T3/da active
- 2005-03-17 CN CN200910246170.7A patent/CN101712911B/zh not_active Expired - Fee Related
- 2005-03-17 RU RU2006136799/04A patent/RU2408667C2/ru not_active IP Right Cessation
- 2005-03-17 PL PL05725897T patent/PL1725646T3/pl unknown
- 2005-03-17 WO PCT/US2005/009106 patent/WO2005090538A2/en active Application Filing
- 2005-03-17 EP EP10155017A patent/EP2184343A1/en not_active Withdrawn
- 2005-03-17 BR BRPI0507270-0A patent/BRPI0507270B1/pt not_active IP Right Cessation
- 2005-03-17 EP EP05725897A patent/EP1725646B1/en not_active Not-in-force
- 2005-03-17 AT AT05725897T patent/ATE483787T1/de not_active IP Right Cessation
- 2005-03-18 MY MYPI20051206A patent/MY145046A/en unknown
- 2005-03-18 MY MYPI2010002770A patent/MY156462A/en unknown
- 2005-03-18 MY MYPI2010002769A patent/MY156463A/en unknown
-
2006
- 2006-08-29 IL IL177761A patent/IL177761A/en not_active IP Right Cessation
- 2006-08-31 ZA ZA200607304A patent/ZA200607304B/en unknown
- 2006-10-17 NO NO20064698A patent/NO20064698L/no not_active Application Discontinuation
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2007
- 2007-02-07 HK HK07101397.0A patent/HK1094338A1/xx not_active IP Right Cessation
- 2007-05-10 US US11/746,921 patent/US7396805B2/en not_active Expired - Lifetime
- 2007-05-10 US US11/746,914 patent/US7396804B2/en not_active Expired - Lifetime
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2008
- 2008-06-09 US US12/135,672 patent/US20080242571A1/en not_active Abandoned
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2010
- 2010-01-11 IL IL203243A patent/IL203243A/en not_active IP Right Cessation
- 2010-01-11 IL IL203245A patent/IL203245A/en not_active IP Right Cessation
- 2010-09-10 RU RU2010137837/04A patent/RU2010137837A/ru not_active Application Discontinuation
- 2010-09-10 RU RU2010137839/04A patent/RU2010137839A/ru not_active Application Discontinuation
- 2010-11-05 AU AU2010241274A patent/AU2010241274B2/en not_active Ceased
- 2010-11-05 AU AU2010241271A patent/AU2010241271B2/en not_active Ceased
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