CN1039706A - Method of making artificial fa vegetable - Google Patents

Method of making artificial fa vegetable Download PDF

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CN1039706A
CN1039706A CN88104926A CN88104926A CN1039706A CN 1039706 A CN1039706 A CN 1039706A CN 88104926 A CN88104926 A CN 88104926A CN 88104926 A CN88104926 A CN 88104926A CN 1039706 A CN1039706 A CN 1039706A
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CN1031562A (en
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黄族和
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黄族和
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Abstract

本发明公开了人造发菜的制造方法。 The present invention discloses a method of producing artificial seaweed. 它是将食用褐藻胶,α熟淀粉及各种营养素溶解后混合成胶液,将胶液在凝固液中拉成0.1-0.2毫米的酷似野生发菜的丝状物。 It is an edible algin, starch and the cooked α nutrients dissolved and mixed into the glue, the glue is drawn to 0.1-0.2 mm resembles wild seaweed filaments in the coagulating liquid.

Description

[0001] 本发明涉及漂白组合物和漂白洗涤组合物。 [0001] The present invention relates to a bleaching composition and bleaching detergent composition.

[0002] 含氯漂白剂的缺点在于其应用受纤维种类限制,不能应用于色布或印花布且具有特殊的气味。 [0002] The disadvantages of chlorine bleaches in its application restricted by the type of fiber, fabric or cloth can be applied to color and has a special smell. 含氧漂白剂无这些缺点,因而近年来得到广泛推广。 Oxygen bleaches without these disadvantages, so widely spread in recent years.

[0003] 具体地说,由于过碳酸钠和过硼酸钠具有极好的漂白性和稳定性,因此,通常作为含氧漂白剂使用。 [0003] Specifically, since sodium perborate and sodium percarbonate having excellent bleach stability and, therefore, generally used as oxygen bleaches.

[0004] 含氧漂白剂的漂白效率比含氯漂白剂差,因此,含氧漂白剂要与各种漂白活化剂同时使用。 [0004] The oxygen bleaches bleaching efficiency inferior to chlorine bleach, therefore, oxygen bleaches to be used in conjunction with various bleach activators. 另外,已对各种活化剂作了研究,这些活性化剂的例子包括腈类,如乙腈、丙二腈、邻苯二甲腈和亚苯酰氨基二乙腈;O-乙酸酯,如葡糖五乙酯、八乙酰基蔗糖、三醋精、山梨醇六乙酸酯、乙酸基苯磺酸酯、氰尿酸三乙酯和氯甲酸甲酯;N-酰化产物,如N,N,N′,N′,-四乙酰基乙二胺、四乙酰基乙内酰联脲、N-苄基咪唑、二-N-乙酰基丁二酮肟、1-苯基-3-乙酰基乙内酰脲、N,N-二乙酰苯胺、N-乙酰基二甘醇亚胺和二乙酰基亚甲基二甲酰胺;酸酐,如邻苯二甲酸酐、琥珀酸酐、苯甲酸酐、戊二酸酐、O-烷基硫酸酐以及羧酸和有机磺酸的混合酸酐、磺酰肟,如二(甲磺酰基)丁二酮肟盐;酰基磷酸酯,如苯甲酰磷酸二乙酯;苯磺酸酯;有机磷叠氮化合物如二苯基膦叠氮化物;二砜如二苯二砜;N-磺酰基咪唑、氨基氰、囟代三唑和氯化N,N-二甲基-N-辛基-N-10碳苯氧基十二 Further, it has been made on the study of various activators, examples of such active agents include nitriles, such as acetonitrile, malononitrile, phthalonitrile and amido phenylene diacetonitrile; 0- acetates, such as glucose ethyl sugar five, eight acetyl sucrose, triacetin, sorbitol hexaacetate, acetoxy benzene sulfonate, triethyl cyanurate, and methyl chloroformate; N-acylated product, such as N, N, N ', N', - tetraacetyl ethylene diamine, tetraacetyl the hydantoin with urea, N- benzyl imidazole, -N- acetylbutyrolactone oxime, 1-phenyl-3-acetyl ethyl hydantoin, N, N- diacetyl aniline, N- acetyl-imine and diethylene glycol diacetyl methylene dicarboxamide; acid anhydrides, such as phthalic anhydride, succinic anhydride, benzoic anhydride, glutaric acid anhydride, O- alkyl sulfate anhydride, and mixed anhydride of carboxylic acid and organic sulfonic acid, a sulfonyl oxime, such as bis (methylsulfonyl) dimethylglyoxime salt; phosphoric acid ester, such as diethyl benzoyl; phenyl sulfonate; organophosphorus compounds such as azide diphenylphosphino azide; such as diphenyl disulfone disulfone; N-sulfonylimidazolide, cyanamide, halogenated triazole and chloride N, N- dimethyl - -N-10 N- octyl phenoxy twelve carbon 基铵。 Ammonium. 但是,即使含氧漂白剂与上述活化剂一起使用,其漂白效率仍较差。 However, even if the oxygen bleaches used together with the activator which is still poor bleaching efficiency.

[0005] 分子中具有 [0005] molecule

基团的已知化合物包括下列化合物: The following compounds known compound groups include:

[0006] [0006]

[0007] [0007]

[0008] 为了开发具有较强的漂白效率的含氧漂白组合物,本发明地发明人进行了研究,并已发现,将过氧化物与特定的阳离子有机过酸前体一起使用可达到此目的。 [0008] In order to develop a strong bleaching efficiency of an oxygen-containing bleaching composition, the present inventors conducted studies, and have found that the cationic organic peroxide with a particular achieves this object by using precursors with acid .

[0009] 本发明的一个目的是提供漂白组合物和漂白洗涤组合物。 [0009] An object of the present invention to provide a bleaching composition and bleaching detergent composition.

[0010] 本发明的另一个目的是提供新的作为所述组合物的活化剂的阳离子化合物。 [0010] Another object of the present invention is to provide a new composition as the composition of a cationic activator compound.

[0011] 本发明提供了一种漂白组合物,该组合物包括(a)一种过氧化物和(b)具有至少一种选自(b-1)和(b-2)基团的有机过酸前体;本发明还提供了另外含有洗涤剂组分的漂白洗涤组合物。 [0011] The present invention provides a bleaching composition, the composition comprising (a) a peroxide and (b) at least one compound selected from (b-1) an organic group, and (b-2) before peracid thereof; the present invention further provides a bleach composition additionally contains washing detergent components.

[0012] 上面定义的有机过酸前体宜包括分别具有通式(b-3)、(b-4)、(b-5)、(b-6)和(b-7)的化合物以及具有至少一个(b-1)和/或(b-2)基团的多亚烷基多胺。 [0012] defined above front body should respectively include organic peracid having the general formula (b-3), (b-4), (b-5), (b-6) and compound (b-7), and having at least one of (b-1) a polyamine and / or (b-2) a polyalkylene group.

[0013] 下面将对优选的前体作详细的定义。 [0013] The following preferred precursor will be defined in detail.

[0014] 一种前体具有通式(b-3),式中,R1为C1~C24烷基、C1~C24链烯基、具有C1~C24烷基的烷芳基、具有取代基的C1~C24烷基、具有取代基的C1~C24链烯基、具有C1~C24烷基和其它取代基的烷芳基,R2和R3各为C1~C3烷基、具有1至3个碳原子的羟烷基、-(C2H4O)nH(n为1至5)、-CH2CN,X是阴离子。 [0014] A precursor having the general formula (b-3), the formula, R1 is C1 ~ C24 alkyl group, C1 ~ C24 alkenyl group, C1 ~ C24 alkyl group having an aryl alkyl group having a substituent of C1 ~ C24 alkyl group, C1 ~ C24 alkenyl having a substituent, an alkyl group having C1 ~ C24 alkyl group and other substituted aryl group, R2 and R3 are each C1 ~ C3 alkyl group, having 1 to 3 carbon atoms, hydroxyalkyl, - (C2H4O) nH (n is 1 to 5), - CH2CN, X is an anion.

[0015] 一种前体具有通式(b-4),式中,R1为C1~C20烷基,C1~C20链烯基、芳基、具有取代基的C1~C20烷基、具有取代基的C1~C20链烯基、具有取代基的芳基,R2和R3各为C1~C3烷基、具有1至3个碳原子有羟烷基或-(C2H4O)nH(n为1至3)。 [0015] A precursor having the general formula (b-4), the formula, R1 is C1 ~ C20 alkyl group, C1 ~ C20 alkenyl group, an aryl group, C1 ~ C20 alkyl group having a substituent group, having a substituent group a C1 ~ C20 alkenyl group, a substituted aryl group, R2 and R3 are each C1 ~ C3 alkyl group, having 1 to 3 carbon atoms or a hydroxyalkyl group - (C2H4O) nH (n is 1-3) .

[0016] 一种前体具有通式(b-5)或(b-6),式中,R1至R5各为氢、C1至C10烷基、C1~C10链烯基、具有取代基的C1~C10烷基,具有取代基的C1~C10链烯基、羧基、磺酰基或氰基,X为阴离子。 [0016] A precursor having the general formula (b-5) or (b-6), the formula, R1 to R5 are each hydrogen, C1 to C10 alkyl, C1 ~ C10 alkenyl group, a substituent having C1 ~ C10 alkyl, substituted C1 ~ C10 alkenyl group, a carboxyl group, a sulfonyl group or a cyano group, X is an anion.

[0017] 一种前体是具有选自(b-1)和(b-2)中至少一个基团的亚烷基二胺化合物或多亚烷基多胺化合物。 [0017] A precursor is selected from (b-1) and (b-2) at least one group of the alkylenediamine or polyalkylene polyamine compound compound.

[0018] 一种前体具有通式(b-7),其中R1、R2、R3和R4各为C1~C6烷基,n为1至16的整数,X为阴离子。 [0018] A precursor having the general formula (b-7), wherein R1, R2, R3 and R4 are each a C1 ~ C6 alkyl, n is an integer of 1 to 16, X is an anion.

[0019] [0019]

[0020] [0020]

[0021] [0021]

[0022] (a)与(b)的摩尔比宜为99.9/0.1至20/80,组分(b)以100份(重量)(b)和5至20份(重量)粘合剂的掺合物的颗粒形式存在于组合物中。 [0022] (a) and (b) is suitably the molar ratio of 99.9 / 0.1 to 20/80, the component (b) are mixed with 100 parts (by weight) (b) and 5 to 20 parts (by weight) of the binder compound is present in particulate form in the composition.

[0023] 本发明提供了具有上面定义的通式(b-7)的阳离子化合物。 [0023] The present invention provides the above defined with formula (b-7) a cationic compound.

[0024] 在本发明中,要求组分(b)具有 [0024] In the present invention, the required component (b) having

三N阳离子基团。 N three cationic groups. 基团(b-2)具有两个(b-1)基团,但只含一个两个基团共用的氮阳离子。 A group (b-2) having two (b-1) a group, but only two groups containing one nitrogen cation in common.

[0025] 下面将参照组分(b)的优选实施方案对本发明作解释说明,组分(b-3) [0025] The following preferred embodiments with reference to component (b) of the present invention will be described explain, the component (b-3)

[0026] [0026]

[0027] 式中,R1为直链或支链C1-24烷基或链烯基或烷芳基(其中烷基部分具有1至24个碳原子),这些基团可被取代;R2和R3各为C1-3烷基或羟烷基、-(C2H4O)1~5H或-CH2-CN,X为阴离子。 [0027] wherein, Rl (wherein the alkyl moiety having 1 to 24 carbon atoms) is a straight-chain or branched-chain C1-24 alkyl or alkenyl or alkyl aryl group, these groups may be substituted; R2 and R3 are each C1-3 alkyl or hydroxyalkyl, - (C2H4O) 1 ~ 5H or -CH2-CN, X is an anion.

[0028] 采用例如使相应的胺和囟代腈反应的方法可容易地制备上述铵盐,可用下列反应式表示: [0028] The corresponding method for example halogenated nitriles and amines may be readily prepared by reaction of the above ammonium salt, the following reaction formula:

[0029] [0029]

[0030] 式中,R1为直链或支链C1-20烷基、链烯基或芳基,这些基团可被取代;R2和R3各为具有1至3个碳原子的烷基或羟烷基或-(C2H4O)1~5H;X [0030] formula, R1 is a straight-chain or branched-chain C1-20 alkyl, alkenyl or aryl group, these groups may be substituted; R2 and R3 are each an alkyl or hydroxyalkyl having 1 to 3 carbon atoms, alkyl or - (C2H4O) 1 ~ 5H; X

为有机或无机阴离子,n为1至3的整数。 An organic or inorganic anion, n is an integer of 1 to 3.

[0031] 在通式(b-4)所示的阳离子化合物中,通式中R1为C1-8烷基或苯基且n为2的化合物是最优选的漂白活化剂。 [0031] In the general formula (b-4) a cationic compound represented by the general formula wherein R1 is C1-8 alkyl or phenyl and the compound wherein n is 2 are most preferred bleach activators.

[0032] 采用例如下列方式,即使叔胺与囟代乙腈以类似于使胺转化为相应的季铵化合物的方法进行反应,可制备通式(b-4)所示的阳离子化合物。 [0032] The following example embodiment, even with the halogenated acetonitrile to tertiary amine is converted to a method similar to the corresponding quaternary ammonium compound by reacting a compound represented by the cation (b-4) may be prepared by the general formula.

[0033] [0033]

[0034] [0034]

[0035] [0035]

[0036] 式中R1-R5各为氢原子、可被取代的直链或支链C1-10烷基或链烯基、羧基、磺酰基或氰基,X-为有机或无机阴离子。 [0036] wherein R1-R5 are each a hydrogen atom, an optionally substituted linear or branched C1-10 alkyl or alkenyl group, a carboxyl group, a sulfonyl group or a cyano group, X- is an organic or inorganic anion.

[0037] 采用例如使相应的吡啶(可任意地被烷基、链烯基、羧基、磺酰基或氰基取代)与囟代腈反应,可容易地制备本发明所用的铵盐,该反应可用下列反应式表示: [0037] for example using a corresponding pyridine (optionally substituted alkyl group, an alkenyl group, a carboxyl group, a sulfonyl group or a cyano group) is reacted with halogenated nitrile, ammonium salts used in the present invention can be easily prepared, the reaction can be the following reaction formula:

[0038] [0038]

[0039] [0039]

[0040] 可任意地被烷基、链烯基、羧基、磺酰基或氰基取代、用作原料的吡啶包括吡啶、2-,3-和4-吡啶甲酸、烟酸、3,5-吡啶羧酸、3-吡啶磺酸和2-,3-和4-氰基吡啶。 [0040] optionally substituted alkyl, substituted alkenyl group, a carboxyl group, a cyano group or a sulfonyl group, as a raw material pyridine include pyridine, 2-, 3- and 4-pyridine carboxylic acid, nicotinic acid, 3,5-pyridine carboxylic acid, sulfonic acid 3-pyridyl and 2-, 3- and 4-cyanopyridine. 其中吡啶和烟酸因效果好,是最优选的。 Wherein the pyridinyl nicotinic acid because of good effect and is most preferable.

[0041] 亚烷基二胺和多亚烷基多胺化合物 [0041] alkylene diamines and polyalkylene polyamine compound

[0042] 这些化合物具有至少一个选自上述(b-1)和(b-2)的基团,换句话说,具有至少一个通式(b-1)或(b-2)所示的季氮原子。 Quaternary [0042] These compounds having at least one substituent selected from (b-1) above, and (b-2) group, in other words, at least one having the general formula (b-1) or (b-2) shown in FIG. Nitrogen atom.

[0043] 本发明的活化剂可由亚烷基二胺或多亚烷基多胺获得。 [0043] The activator of the present invention can be alkylene diamine or polyalkylene polyamine obtained. 具体地说,下列通式所示的亚烷基二胺和多亚烷基多胺 Specifically, as shown in the general formula alkylene diamine and polyalkylene polyamine

[0044] [0044]

[0045] (式中R1为氢原子或低级烷基;R2为直链或支链C2-10亚烷基,n为2至1,000)可作为本发明活化剂的原料。 [0045] (wherein R1 is a hydrogen atom or a lower alkyl group; R2 is a straight-chain or branched alkylene chain C2-10 alkyl, n is from 2 to 000) of the present invention can be used as starting material an activator. 亚烷基二胺的具体例子为1,2-乙二胺,而多亚烷基多胺的例子包括分子量至多为1000的分子量较低的多亚乙基多胺,如二亚乙基三胺、三亚乙基四胺和四亚乙基五胺、三亚丙基四胺、四亚丁基五胺、二亚丁基三胺、二亚己基三胺和三亚己基四胺。 Specific examples of the alkylenediamine is ethylenediamine, and examples of polyalkylene polyamines include lower molecular weight of up to 1000 molecular weight polyethylene polyamines such as diethylene triamine , triethylene tetramine and tetraethylene pentamine, tripropylene tetramine, tetraethylene pentamine butylene, diethylene triamine, bis hexamethylene triamine and triethylene tetramine hexyl.

[0046] 使亚烷基二胺或多亚烷基多胺的氮原子与通式X′-(CH2)-C≡N(X′为囟原子)所示的化合物反应,从成本和效益角度出发最好是与氯代乙腈反应,形成季铵化合物,从而可容易地引入 [0046] The alkylenediamine or polyalkylene polyamine nitrogen atom of formula X - a compound '(CH2) -C≡N (X' is a halogen atom) is shown, and cost-effectiveness preferably starting the reaction with chloroacetonitrile, quaternary ammonium compound is formed so as to be easily introduced

基团。 Group.

[0047] 现在对由用作原料的1,2-乙二胺制备本发明的活化剂的方法作描述。 [0047] Now by the process of the activator prepared ethylenediamine used as starting material in the present invention be described.

[0048] [0048]

[0049] [0049]

[0050] 这些方法仅仅是制备本发明的活化剂方法的例子,除上述方法外,还可用其它方法制备活化剂。 [0050] These methods are merely examples of the preparation of activators method of the present invention, in addition to the above methods, may be prepared by other methods activators. 用作原料的亚烷基二胺或多亚烷基多胺即可以是上述例子所示的伯胺类,也可以是仲胺或叔胺。 Used as starting material alkylenediamine or polyalkylene polyamines may be primary amines i.e. the example shown above, may be secondary or tertiary amines. 获得的活化剂的结构随亚烷基二胺或多亚烷基多胺原料与所用的氯代乙腈和烷基囟的摩尔比而异,因而可制备各种活化剂。 Structure obtained with activator alkylene diamine or polyalkylene polyamine starting material varies with chloroacetonitrile used and the molar ratio of alkyl halide, which can be prepared by various activators.

[0051] 简单地说,在由原料亚烷基二胺或多亚烷基多胺制备本发明的活化剂时,亚烷基二胺或多亚烷基多胺中的至少一个,最好至少二个氮原子被转化成具有下式所示结构的基团: [0051] Briefly, in the preparation of the present invention consists of the activator feed alkylene diamine or polyalkylene polyamine, an alkylene diamine or polyalkylene polyamine is at least one, preferably at least two nitrogen atoms are converted to a group having the structure represented by the following formula:

[0052] [0052]

[0053] 化合物(b-7) [0053] Compound (b-7)

[0054] 这些化合物是最优选的组分(b) [0054] These compounds are most preferred component (b)

[0055] [0055]

[0056] 式中R1、R2、R3和R4各为C1-6烷基,X [0056] wherein R1, R2, R3 and R4 are each C1-6 alkyl, X

为有机或无机阴离子,n为1至16的整数。 An organic or inorganic anion, n is an integer from 1 to 16.

[0057] 本发明的新化合物中,式(b-7)中R1、R2、R3和R4各为C1-3烷基(特别是甲基)且n为1至9的整数的那些化合物特别有价值。 [0057] The novel compounds of the present invention, the formula (b-7) in R1, R2, R3 and R4 are each C1-3 alkyl (especially methyl) and n is an integer of those compounds are particularly 1-9 value.

[0058] 采用例如下述方法可制备本发明具有上述通式的化合物,即使叔亚烷基二胺与乙腈的囟化物按普通胺的季铵化方法进行反应,可容易地制备具有上述通式的化合物,可用下列反应表示: [0058] The compounds of the present invention may be prepared by the following methods having the above formula, for example, even if the tertiary alkylenediamines and acetonitrile halide reaction as quaternary ammonium ordinary method amine, can easily be prepared having the general formula a compound represented by the following reaction:

[0059] [0059]

[0060] 化合物(b-7)是新的,且可用作纺织柔软剂、抗静电剂、杀菌剂和漂白活化剂。 [0060] Compound (b-7) are novel and can be used as textile softeners, antistatic agents, fungicides, and bleach activators.

[0061] 在本发明中,组分(b)由于具有阳离子基团而易于附着在漂白物上。 [0061] In the present invention, component (b) Since having a cationic group and easily attached to the bleaching species. 另外,因为季氮原子是吸电子的,所以-CN基上的碳原子易带正电荷且对漂白起活化作用。 Further, since the quaternary nitrogen atom is electron withdrawing, the carbon atom on the -CN group is positively charged and is easy to play the bleach activation. 因此,组分(b)提供了发生漂白作用的部位,且增强了组合物的漂白效率。 Thus, component (b) Providing the site of bleaching occurred, and enhances the efficiency of the bleaching composition.

[0062] 本发明的活化剂在加入过氧化物前可按普通方法制成颗粒。 [0062] The activator of the present invention prior to addition of the peroxide may be granulated conventional method. 例如,将5至20份(重量),最好是10至100份(重量)的一种或多种粘合剂(在5至60℃,特别是10至40℃具有流动性)加入到100份(重量)的活化剂中,然后将获得的混合物制成颗粒。 For example, 5 to 20 parts (by weight), preferably 10 to 100 parts (by weight) of one or more binders (5 to 60 ℃, in particular 10 to 40 ℃ fluidity) was added to 100 parts (by weight) of the activator, and the mixture obtained is then granulated.

[0063] 所用的粘合剂可以是选自非离子表面活性剂,如聚乙二醇、聚丙二醇、液态石蜡和高级醇中的一种或多种,这些粘合剂在5至60℃,特别是在10至40℃具有流动性。 [0063] The adhesive may be selected from nonionic surfactants such as polyethylene glycol, polypropylene glycol, liquid paraffin and an alcohol of one or more advanced, these binders 5 to 60 ℃, particularly a flowability of 10 to 40 ℃.

[0064] 根据所用的无机过酸前体和粘合剂的种类,从常规方法如挤压造粒、转鼓造粒或压缩造粒中选择合适的方法进行造粒。 [0064] As used in accordance with the inorganic precursors and the kind through an acid binder, from conventional methods such as extrusion granulation, drum granulation or granulation select the appropriate method for compressing granulated. 例如,按挤压造粒法,将已细磨成粒径为150微米或更小的有机过酸前体在普通混合机中均匀混合,将粘合剂逐步加入研磨的前体中,接着充分捏和,然后,将捏和的混合物加入挤压造粒机中以获得颗粒,接着筛分。 For example, according to extrusion granulation method, which has been finely ground to a particle size of 150 microns or less organic peracid precursor is uniformly mixed in an ordinary mixer, was gradually added to the binder precursor is milled, followed by thorough kneaded and, then, the mixture was added and kneaded extruding pelletizer to obtain granules, followed by sieving. 如果需要改进颗粒特性,在筛分前,可用平均主要粒径为0.1微米或更小的细无机粉末(如粉碎的二氧化硅粉末)涂覆在颗粒上。 If you need to improve particle properties before sieving, it can be used an average primary particle diameter of 0.1 m or smaller fine inorganic powder (e.g. pulverized silica powder) coated on the particles.

[0065] 本发明所用的过氧化物宜为过氧化氢或在水溶液中能产生过氧化氢的过氧化物。 [0065] used in the present invention is suitable peroxide is hydrogen peroxide in an aqueous solution or a peroxide that produces hydrogen peroxide.

[0066] 在水溶液中能产生过氧化氢的过氧化物的例子包括碳酸钠-过氧化物氢加合物、三磷酸钠-过氧化氢加合物、焦磷酸钠-过氧化氢加合物、尿素-过氧化氢加合物、4Na2SO4·2H2O2·NaCl、过硼酸钠一水合物、过硼酸钠四水合物、过氧化钠和过氧化钙,其中,碳酸钠-过氧化氢加合物、过硼酸钠一水合物和过硼酸钠四水合物是最优选的。 Examples [0066] a peroxide that produces hydrogen peroxide in aqueous solution include sodium carbonate - hydrogen peroxide adduct, sodium tripolyphosphate - hydrogen peroxide adduct, sodium pyrophosphate - hydrogen peroxide adduct urea - hydrogen peroxide adduct, 4Na2SO4 · 2H2O2 · NaCl, sodium perborate monohydrate, sodium perborate tetrahydrate, sodium peroxide and calcium peroxide, wherein the sodium carbonate - hydrogen peroxide adduct, sodium perborate monohydrate and sodium perborate tetrahydrate is most preferred.

[0067] 根据本发明,过氧化物与特定的上述活化剂的摩尔比通常为99.1/0.1至20/80,最好为99/1至50/50。 [0067] According to the present invention, the molar ratio of peroxide to the specific activator is usually 99.1 / 0.1 to 20/80, preferably 99/1 to 50/50. 组合物宜含1至99%(重量)的组份(a)。 The composition preferably contain 1 to 99% (by weight) of the component (a).

[0068] 除了上述漂白剂外,本发明的漂白洗涤剂组合物可含下列组份: [0068] In addition to the bleaching agents, bleaching detergent composition of the present invention may contain the following components:

[0069] [1]表面活性剂: [0069] [1] Surfactant:

[0070] (1)直链或支链烷基苯磺酸盐,其中烷基部分的平均碳原子数为10-16。 [0070] (1) a straight-chain or branched alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl moiety 10-16.

[0071] (2)烷基或链烯基醚硫酸盐,其中直链或支链烷基或链烯基的平均碳原子数为10-20,分子中平均含0.5-8摩尔环氧乙烷、环氧丙烷或环氧丁烷,环氧乙烷/环氧丙烷的加入比为0.1/9.9-9.9/0.1,或环氧乙烷/环氧丁烷的加入比为0.1/9.9-9.9/0.1。 [0071] (2) alkyl or alkenyl ether sulfates in which the average number of carbon straight or branched chain alkyl or alkenyl group of from 10 to 20 atoms, containing on average per molecule from 0.5 to 8 moles of ethylene oxide , propylene oxide or butylene oxide, ethylene oxide / propylene oxide added is 0.1 / 9.9-9.9 / 0.1, or ethylene oxide / butylene oxide added is 0.1 / 9.9-9.9 / 0.1.

[0072] (3)烷基或链烯基硫酸盐,其中烷基或链烯基的平均碳原子数为10-20。 [0072] (3) alkyl or alkenyl sulfates, wherein the average carbon number of alkyl or alkenyl groups of from 10 to 20 atoms.

[0073] (4)烯烃磺酸盐,分子中的平均碳原子数为10-20。 [0073] (4) olefin sulfonates, average number of carbon atoms in the molecule is from 10-20.

[0074] (5)烷烃磺酸盐,分子中的平均碳原子数为10-20。 [0074] (5) alkane sulfonates, average number of carbon atoms in the molecule is from 10-20.

[0075] (6)饱和或不饱和脂肪酸盐,分子中的平均碳原子数为10-24。 [0075] (6) a saturated or unsaturated fatty acid salts, average number of carbon atoms in the molecule is from 10-24.

[0076] (7)烷基或链烯基醚羧酸盐,其中,烷基或链烯基的平均碳原子数为10-20,分子中平均含0.5-8摩尔环氧乙烷、环氧丙烷或环氧丁烷,环氧乙烷/环氧丙烷的加入比为0.1/9.9-9.9/0.1,环氧乙烷/环氧丁烷的加入比为0.1/9.9至9.9/0.1。 [0076] (7) alkyl or alkenyl ether carboxylic acid salts, wherein the average carbon number of alkyl or alkenyl groups of from 10 to 20 atoms, containing on average per molecule from 0.5 to 8 moles of ethylene oxide, propylene oxide or butylene oxide, ethylene oxide / propylene oxide added is 0.1 / 9.9-9.9 / 0.1, an ethylene oxide / butylene oxide added is from 0.1 / 9.9 to 9.9 / 0.1.

[0077] (8)具有下列通式的α-磺基脂肪酸盐或酯: [0077] (8) having the following general formula α- sulfo fatty acid salts or esters:

[0078] [0078]

[0079] 其中Y为C1-3烷基或相反离子,Z为相反离子,R为C10-20烷基或链烯基。 [0079] wherein Y is a C1-3 alkyl group or counter ion, Z is a counter ion, R is C10-20 alkyl or alkenyl group.

[0080] 阴离子表面活性剂的相反离子的例子可以有碱金属(如钠和钾)离子、碱土金属(如钙和镁)离子、铵离子、含1-3个烷醇基(含2或3个碳原子)的烷醇胺如单乙醇胺、二乙醇胺、三乙醇胺和三异丙醇胺的离子。 [0080] Examples of anionic counter ions of the surfactant may be an alkali metal (e.g. sodium and potassium) ions, alkaline earth metal (e.g. calcium and magnesium) ions, ammonium ions, alkanolamines having 1 to 3 groups (having 2 or 3 carbon atoms) alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine ions.

[0081] (9)具有下列通式的氨基酸型表面活性剂: Amino acid-type surfactants [0081] (9) having the following formula:

[0082] [0082]

[0083] [0083]

[0084] 式中,R1为C8-24烷基或链烯基,R2为氢或C1-2烷基,R3为氨基酸基,X为碱金属离子或碱土金属离子。 [0084] formula, R1 is C8-24 alkyl or alkenyl group, R2 is hydrogen or C1-2 alkyl, R3 is an amino group, X is an alkali metal ion or alkaline earth metal ion.

[0085] [0085]

[0086] 式中,R1、R2和X与上面的含义相同,n为1-5的整数。 [0086] wherein, R1, R2 and X are the same meanings as above, n is an integer of 1-5.

[0087] [0087]

[0088] 式中R1与上面的含义相同,m为1-8的整数。 [0088] wherein R1 is the same meaning as above, m is an integer from 1-8.

[0089] [0089]

[0090] 式中,R1、R3和X与上面的含义相同,R4代表氯、C1-2烷基或羟烷基。 [0090] In the formula, the same R1, R3 and X are the above meaning, R4 represents chlorine, C1-2 alkyl or hydroxyalkyl.

[0091] [0091]

[0092] [0092]

[0093] 式中R2、R3和X与上面的含义相同,R5为具有6-28个碳原子的β-羟基烷基或β-羟基链烯基。 [0093] wherein R2, R3 and X are the same meaning as above, R5 is a hydroxyalkyl group having β- or β- hydroxy alkenyl group of 6-28 carbon atoms.

[0094] [0094]

[0095] 式中R3、R5和X与上面的含义相同。 [0095] wherein R3, R5 and X are the same meaning as above.

[0096] (10)磷酸酯表面活性剂: [0096] (10) a phosphate ester surfactant:

[0097] No1酸性磷酸烷基(或链烯基)酯: [0097] No1 phosphoric acid alkyl (or alkenyl) ester:

[0098] [0098]

[0099] 式中R′为具有8-24个碳原子的烷基或链烯基,n′+m′为3,而n′代表1-2的数。 [0099] wherein R 'is an alkyl or alkenyl group having 8 to 24 carbon atoms, n' + m 'is 3, and n' represents the number 1-2.

[0100] No2磷酸烷基(或链烯基)酯: [0100] No2 acid alkyl (or alkenyl) ester:

[0101] [0101]

[0102] 式中R′与上面的含义相同,n″+m″为3,n″为1-3的数。 [0102] wherein R 'is the same meaning as above, n "+ m" is 3, n "is a number of 1-3.

[0103] No3烷基(或链烯基)磷酸盐: [0103] No3 alkyl (or alkenyl) phosphates:

[0104] [0104]

[0105] 式中R′、n″和m″与上面的含义相同,M为Na、K或Ca。 [0105] wherein R ', n "and m" have the same meaning as above, M being Na, K or Ca.

[0106] (11)下式所示的磺酸型两性表面活性剂: [0106] (11) represented by the following formula sulfonic acid type amphoteric surfactants:

[0107] [0107]

[0108] 式中R11为C8-24烷基或链烯基,R12为C1-4亚烷基,R13为C1~5烷基,R14为C1-4亚烷基或羟基亚烷基。 [0108] wherein R11 is C8-24 alkyl or alkenyl group, R12 is C1-4 alkylene, R13 is C1 ~ 5 alkyl group, R14 is C1-4 alkylene or hydroxy alkylene.

[0109] [0109]

[0110] 式中R11和R14与上面的含义相同,R15和R16各为具有8-24或1-5碳原子的烷基或链烯基。 [0110] wherein R11 and R14 are the same meaning as above, R15 and R16 are each an alkyl or alkenyl group having 8-24 carbon atoms or 1-5.

[0111] [0111]

[0112] 式中R11和R14与上面的含义相同,n1为1-20的整数。 [0112] wherein R11 and R14 are the same meaning as above, n1 is an integer of 1 to 20.

[0113] (12)具有下列通式的Betaine型两性表面活性剂: [0113] (12) Betaine type amphoteric surfactants having the following general formula:

[0114] [0114]

[0115] 式中R21为具有8-24个碳原子的烷基、链烯基、β-羟烷基或β-羟基链烯基,R22为C1-4烷基,R23为具有1-6个碳原子的亚烷基或羟基亚烷基。 [0115] wherein R21 is an alkyl group having 8 to 24 carbon atoms, an alkenyl group, [beta] [beta] hydroxyalkyl or alkenyl hydroxy, R22 is C1-4 alkyl, R23 having from 1 to 6 alkylene or hydroxy alkylene carbon atoms.

[0116] [0116]

[0117] 式中R21和R23与上面的含义相同,n2为1-20的整数。 [0117] wherein R21 and R23 are the same meaning as above, n2 is an integer of 1 to 20.

[0118] [01]

[0119] [0119]

[0120] 式中R21和R23与上面的含义相同,R24为具有2-5个碳原子的羧烷基或羟烷基。 [0120] wherein R21 and R23 are the same meaning as above, R24 is a carboxyalkyl or hydroxyalkyl group having 2-5 carbon atoms.

[0121] (13)聚氧乙烯烷基或链烯基醚,其中烷基或链烯基的平均碳原子数为10-20,加入的环氧乙烷为1-30摩尔。 [0121] (13) polyoxyethylene alkyl or alkenyl ether, wherein the average carbon number of alkyl or alkenyl groups of from 10 to 20 atoms, was added to 30 moles of ethylene oxide.

[0122] (14)聚氧乙烯烷基苯基醚,其中烷基的平均碳原子数为6-12,加入的环氧乙烷为1-25摩尔。 [0122] (14) Polyoxyethylene alkylphenyl ethers wherein the average number of carbon atoms in the alkyl group of 6-12, was added to 25 moles of ethylene oxide.

[0123] (15)聚氧丙烯烷基或链烯基醚,其中烷基或链烯基的平均碳原子数为10-20,加入的环氧丙烷为1-20摩尔。 [0123] (15) polyoxypropylene alkyl or alkenyl ethers wherein the average number of carbon alkyl or alkenyl group of from 10 to 20 atoms, the addition of 1 to 20 moles of propylene oxide.

[0124] (16)聚氧丁烯烷基或链烯基醚,其中烷基或链烯基的平均碳原子数为10-20,加入的环氧丁烷为1-20摩尔。 [0124] (16) polyoxybutylene alkyl or alkenyl ethers wherein the average number of carbon alkyl or alkenyl group of from 10 to 20 atoms, was added to 20 moles of butylene oxide.

[0125] (17)非离子表面活性剂,其中的烷基或链烯基的平均碳原子数为10-20,加入的环氧乙烷和环氧丙烷或环氧乙烷和环氧丁烷的总摩尔数为1-30摩尔,环氧乙烷与环氧丙烷的比例为0.1/9.9至9.9/0.1。 [0125] (17) a non-ionic surfactant, wherein the average carbon number of alkyl or alkenyl groups of from 10 to 20 atoms, the addition of ethylene oxide and propylene oxide or ethylene oxide and butylene total number of moles of 1 to 30 moles, of ethylene oxide and propylene oxide ratio of from 0.1 / 9.9 to 9.9 / 0.1.

[0126] (18)下列通式的高级脂肪酸烷醇酰胺或其烯化氧加合物: [0126] (18) the following general formula or a higher fatty acid alkanolamides alkylene oxide adduct:

[0127] [0127]

[0128] 式中R′11为具有10-20个碳原子的烷基或链烯基,R′12为H或CH3,n3为1-3的整数,m3为0-3的整数。 [0128] wherein R'11 is an alkyl or alkenyl group having 10 to 20 carbon atoms, R'12 is H or CH3, n3 is an integer of 1 to 3, m3 is an integer of 0-3.

[0129] (19)庶糖/脂肪酸酯,包括平均碳原子数为10-20的脂肪酸和蔗糖。 [0129] (19) Sucrose / fatty acid esters, including average number of carbon atoms from 10 to 20 and sucrose fatty acid.

[0130] (20)脂肪酸/甘油单酯,包括平均碳原子数为10-20的脂肪酸和甘油。 [0130] (20) fatty acid / glycerol monoesters comprising average number of carbon atoms of the fatty acids and glycerol 10-20.

[0131] (21)具有下列通式的烷基胺氧化物: [0131] (21) having the following formula alkylamine oxides:

[0132] [0132]

[0133] 式中R′13为具有10-20个碳原子的烷基或链烯基,R′14和R′15各为C1-3烷基。 [0133] wherein R'13 is an alkyl or alkenyl group having 10 to 20 carbon atoms, R'14 and R'15 are each a C1-3 alkyl group.

[0134] (22)具有下式的阳离子表面活性剂: [0134] (22) having a cationic surfactant of formula:

[0135] [0135]

[0136] 式中,R1′、R2′、R3′、和R4′中的至少一个为具有8-24个碳原子的烷基或链烯基,残基为C1~5烷基,X′为囟素。 [0136] In the formula, R1 ', R2', R3 ', and R4' is at least one alkyl or alkenyl group having 8 to 24 carbon atoms, residues C1 ~ 5 alkyl group, X 'is halogen.

[0137] [0137]

[0138] 式中,R1′、R2′、R3′和X′与上述含义相同。 [0138] In the formula, R1 ', R2', R3 'and X' are as defined above.

[0139] [0139]

[0140] 式中,R1′、R2′和X′与上述含义相同,R5′为C2-3亚烷基,n为1-20的整数。 [0140] In the formula, R1 ', R2' and X 'are as defined above, R5' is C2-3 alkylene alkyl, n is an integer from 1-20.

[0141] 组合物可含至少一种上述表面活性剂,其含量至少为10%(重量)。 [0141] composition may contain at least one such surfactant in an amount of at least (by weight) of 10%.

[0142] 优选的表面活性剂是上述表面活性剂1)、2)、3)、4)、5)、6)、11)-No2 12)-No1、13)、14)、15)、17)和18)。 [0142] Preferred surfactants are surfactants above 1), 2), 3), 4), 5), 6), 11) -No2 12) -No1,13), 14), 15), 17 ) and 18).

[0143] [2]二价金属离子螯合剂 [0143] [2] a divalent metal ion chelator

[0144] 组合物可含0-50%(重量)一种或多种选自下列化合物的碱金属盐或烷醇胺盐的助洗剂组分: [0144] The composition may contain 0-50% (wt) of one or more of the following compounds selected from alkali metal salts or alkanolamine salts of builder components of:

[0145] 1)各类磷酸的盐,这些磷酸的例子有原磷酸、焦磷酸、三磷酸、偏磷酸、六偏磷酸和肌醇六磷酸。 [0145] 1) all types of salt of phosphoric acid, are examples of such ortho-phosphoric acid, pyrophosphoric acid, triphosphoric acid, metaphosphoric acid, hexametaphosphoric acid and phytic acid.

[0146] 2)各类膦酸的盐,这些膦酸的例子有乙烷-1,1-二膦酸、乙烷-1,1,2-三膦酸、乙烷-1-羟基-1,1-二膦酸或其衍生物、乙烷-羟基-1,1,2-三膦酸、乙烷-1,2-二羧基-1,2-二膦酸和甲羟基膦酸。 [0146] 2) phosphonic acids of various types, examples of such phosphonic acids are 1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1 , 1-diphosphonic acid or a derivative thereof, ethane - hydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid and hydroxy carboxylic acid.

[0147] 3)膦酰基羧酸的盐,这些膦酰基羧酸的例子有2-膦酰基丁烷-1,2-二羧酸、1-膦酰基丁烷-2,3,4-三羧酸和α-甲基膦酰基琥珀酸。 [0147] 3) salt of phosphonocarboxylic acid, examples of phosphono carboxylic acids are 2-phosphono-butane-1,2-dicarboxylic acid, 1-phosphono-butane-2,3,4-tricarboxylic acid and α- methyl phosphonosuccinic acid.

[0148] 4)氨基酸的盐,这些氨基酸的例子有天冬氨酸、谷氨酸和甘氨酸。 [0148] 4) an amino acid salt, examples of such amino acids are aspartic acid, glutamic acid and glycine.

[0149] 5)氨基多乙酸的盐,这些氨基多乙酸的例子有次氮基二乙酸、亚氨基二乙酸、乙二胺四乙酸、二亚乙基三胺五乙酸、乙二醇醚二胺四乙酸、羟乙基亚氨基二乙酸、三亚乙基四胺六乙酸和dienkolic acid。 [0149] 5) aminopolycarboxylic acid salts, aminopolycarboxylic acid such examples are nitrilotriacetic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriamine pentaacetic acid, glycol ether diamine acid, hydroxyethyl iminodiacetic acid, triethylene tetraamine hexaacetic acid and dienkolic acid.

[0150] 6)高分子电解质,如聚丙烯酸、聚乌头酸、聚衣康酸、聚柠康酸、聚富马酸、聚马来酸、聚中康酸、聚-α-羟基丙烯酸、聚乙烯基膦酸、磺化聚马来酸、马来酐/二异丁烯共聚物、马来酐/苯乙烯共聚物、马来酐/甲基乙烯基醚共聚物、马来酐/乙烯共聚物、马来酐/乙烯交联共聚物、马来酐/乙酸乙烯基酯共聚物、马来酐/丙烯腈共聚物、马来酐/丙烯酸酯共聚物、马来酐/丁二烯共聚物、马来酐/异戊二烯共聚物、由马来酐和一氧化碳衍生的聚-β-酮基羧酸、衣康酸/乙烯共聚物、衣康酸/乌头酸共聚物、衣康酸/马来酸共聚物、衣康酸/丙烯酸共聚物、丙二酸/亚甲基共聚物、中康酸/富马酸共聚物、乙二醇/对苯二酸乙二醇酯共聚物、乙烯基吡咯烷酮/乙酸乙烯酯共聚物、1-丁烯-2,3,4-三羧酸/衣康酸/丙烯酸共聚物、含铵的聚酯聚醛羧酸、环氧琥珀酸的顺式异构 [0150] 6) The polymer electrolyte such as polyacrylic acid, aconitic acid, poly itaconic acid, citraconic acid, polyethylene, polypropylene fumaric acid, polymaleic acid, polymethacrylic mesaconic acid, polymethacrylic -α- hydroxy acid, polyvinylphosphonic acid, sulfonated polymaleic acid, maleic anhydride / diisobutylene copolymer, maleic anhydride / styrene copolymer, maleic anhydride / methyl vinyl ether copolymer, maleic anhydride / ethylene copolymer , maleic anhydride / ethylene crosslinked copolymer, maleic anhydride / vinyl acetate copolymer, maleic anhydride / acrylonitrile copolymer, maleic anhydride / acrylic ester copolymer, maleic anhydride / butadiene copolymer, maleic anhydride / isoprene copolymers derived from maleic anhydride and carbon monoxide, poly -β- ketocarboxylic acid, itaconic acid / ethylene copolymer, itaconic acid / aconitic acid copolymer, itaconic acid / maleic acid copolymer, itaconic acid / acrylic acid copolymer, malonic acid / methylene copolymer, mesaconic acid / fumaric acid copolymer, ethylene glycol / ethylene terephthalate copolymer, ethylene vinyl pyrrolidone / vinyl acetate copolymers, butene-2,3,4-tricarboxylic acid / itaconic acid / acrylic acid copolymer, ammonium-containing polyester polyacetal carboxylate, cis-epoxysuccinate iso construct 体、聚[N,N-二(羧甲基)丙烯酰胺]、聚(羟基羧酸)、淀粉琥珀酸酯、淀粉马来酸酯、淀粉对苯二酸酯、淀粉磷酸酯、二羧酸淀粉、二羧甲基淀粉和纤维素琥珀酸酯。 , Poly [N, N- bis (carboxymethyl) acrylamide], poly (hydroxycarboxylic acid), starch succinate, starch maleate, starch terephthalate, starch phosphates, dicarboxylic acid starch, carboxymethyl starch and cellulose are two succinate.

[0151] 7)非离解高分子化合物,如聚乙二醇、聚乙烯醇、聚乙烯基吡咯烷酮和溶于冷水且尿烷化的聚乙烯醇。 [0151] 7) a non-dissociating polymers, such as polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone and cold water soluble polyvinyl alcohol and urethane.

[0152] 8)二元羧酸的盐,这些二元羧酸的例子有草酸、丙二酸、丁二酯、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸烷-1,10-二羧酸;乙醇酸的盐、硫代乙醇酸的盐,草乙酸的盐、羟基二琥珀酸的盐、羧甲基羟基琥珀酸的盐和羧甲基丙醇二酸的盐;羟基羧酸的盐,这些羟基羧酸的例子有乙醇酸、苹果酸、羟基新戊酸、酒石酸、柠檬酸、乳酸、葡糖酸、粘酸、葡糖醛酸和双醛淀粉氧化物;下列酸的盐:衣康酸、甲基琥珀酸、3-甲基戊二酸、2,2-二甲基丙二酸、富马酸、谷氨酸、1,2,3-丙烷三甲酸、乌头酸、3-丁烯-1,2,3-三甲酸、丁烷-1,2,3,4-四甲酸、乙烷四甲酸、乙烯四甲酸、正链烯基乌头酸、1,2,3,4-环戊烷四甲酸、苯二甲酸、1,3,5-苯三酸、1,2,3-苯三酸、1,2,4,5-苯四酸、苯六甲酸、四氢呋喃-1,2,3,4-四甲酸和四氢呋喃-2,2,5,5-四 [0152] 8) a salt of the dicarboxylic acid, examples of these dicarboxylic acids are oxalic acid, malonic acid, succinic acid ester, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decane-1,10-dicarboxylic acid; salts of glycolic acid, salts of thioglycolic acid, oxalacetic acid salts, salts of hydroxy disuccinic acid, carboxymethyloxysuccinic acid and salts of carboxymethyl tartronate acid; salts of hydroxycarboxylic acid, examples of such hydroxy acids are glycolic acid, malic acid, hydroxypivalic acid, tartaric acid, citric acid, lactic acid, gluconic acid, mucic acid, glucuronic acid and dialdehyde starch oxides; salts of the following acids: itaconic acid, methacrylic acid, 3-methyl glutaric acid, 2,2-dimethyl malonic acid, fumaric acid, glutamic acid, 1,2,3- propane-tricarboxylic acid, aconitic acid, 3-butene-1,2,3-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, ethane tetracarboxylic acid, ethylene tetracarboxylic acid, n-alkenyl Chiu head acid, 1,2,3,4-cyclopentane tetracarboxylic acid, phthalic acid, trimesic acid, 1,2,3-benzenetricarboxylic acid, pyromellitic tetracarboxylic acid, mellitic acid, tetrahydrofuran-1,2,3,4-tetracarboxylic acid and tetrahydrofuran -2,2,5,5 酸;磺化羧酸的盐,这些磺化羧酸的例子有磺基衣康酸、磺基丙三羧酸、磺基丙氨酸、磺基乙酸和磺基琥珀酸;羧甲基化蔗糖、乳糖和棉子糖、羧甲基化的季戊四醇、羧甲基化葡糖酸、多元醇或糖类与马来酐或琥珀酐的缩合物、羟羧酸与马来酐或琥珀酐的缩合物、有机酸盐如CMOS和Builder M。 Acid; salts of sulfonated carboxylic acid, examples of such acids are sulfonated sulfo itaconic acid, sulfopropionic acid, cysteic acid, sulfonic acid and sulfosuccinic acid; carboxymethylated sucrose , lactose and raffinose, carboxymethylated pentaerythritol, carboxymethylated gluconic acid, saccharides or polyhydric alcohols with maleic anhydride or succinic anhydride, condensates of hydroxycarboxylic acids with maleic anhydride or succinic anhydride condensation , organic acid salts such as CMOS and Builder M.

[0153] 9)硅铝酸盐 [0153] 9) of aluminosilicate

[0154] No1具有下式的结晶硅铝酸盐 [0154] No1 having a crystalline aluminosilicate of the formula

[0155] [0155]

[0156] 式中,M′为碱金属原子,M″为与钙可交换的碱土金属原子,X′、Y′和W′为各个组分的摩尔数,通常如下:0.7≤X′≤1.5,0.8≤Y′≤6,W′为正数。 [0156] In the formula, M 'is an alkali metal atom, M "is exchangeable with calcium alkaline earth metal atom, X', Y 'and W' is the number of moles of the individual components, generally as follows: 0.7≤X'≤1.5 , 0.8≤Y'≤6, W 'is a positive number.

[0157] No2具有下列通常的洗涤助洗剂,这是最优选的: [0157] No2 having the conventional detergency builders, which is the most preferred:

[0158] [0158]

[0159] 式中n为1.8-3.0之间的数,W为1-6之间的数。 [0159] wherein n is a number between 1.8-3.0, W is a number between 1-6.

[0160] No3具有下式的非晶形硅铝酸盐 [0160] No3 having the formula amorphous aluminosilicate

[0161] [0161]

[0162] 式中M为钠和/或钾原子,X,Y和W分别代表各组分的摩尔数,其范围如下:0.7≤X≤1.2,1.6≤Y≤2.8,W为包括零的任何正数。 [0162] wherein M is sodium and / or potassium atom, X, Y and W represents the number of moles of each component, the scope of the following: 0.7≤X≤1.2,1.6≤Y≤2.8, W include any zero A positive number.

[0163] No4具有下式的非晶形硅铝酸盐: [0163] No4 having the formula amorphous aluminosilicates:

[0164] [0164]

[0165] [0165]

[0166] 式中M为Na或K、X、Y、Z和W分别代表各组分的摩尔数,其范围如下:0.20≤X≤1.10,0.20≤Y≤4.00,0.001≤Z≤0.80,W为包括零的任何正数。 [0166] wherein M is Na or K, X, Y, Z and W represents the number of moles of each component, the scope of the following: 0.20≤X≤1.10,0.20≤Y≤4.00,0.001≤Z≤0.80, W to include any positive number zero.

[0167] [3]碱或无机电解质: [0167] [3] base or inorganic electrolytes:

[0168] 组合物还可含1-50%(重量),最好为5-30%(重量)的一种或多种碱金属盐,这些盐选自作为碱或无机电解质的下列化合物:硅酸盐、碳酸盐和硫酸盐。 The following compounds [0168] The composition may also contain 1-50% (wt), preferably 5 to 30% (by weight) of one or more alkali metal salts, such as the alkali or inorganic salt is selected from the electrolyte: silica acid salts, carbonates and sulfates. 另外,组合物可含有机碱,如三乙醇胺、二乙醇胺、单乙醇胺和三异丙醇胺。 Further, the composition may contain bases, such as triethanolamine, diethanolamine, monoethanolamine and triisopropanolamine.

[0169] [4]抗再沉淀剂 [0169] [4] anti-redeposition agents

[0170] 组合物可含0.1-5%(重量)的一种或多种用作抗再沉淀剂的下列化合物:聚乙二醇、聚乙烯醇、聚乙烯基吡咯烷酮和羧甲基纤维素。 One kind of [0170] composition may contain 0.1 to 5% (by weight) of one or more of the following compounds as antiredeposition agents: polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone and carboxymethylcellulose.

[0171] [5]酶(该酶在洗涤时主要具有酶化作用)。 [0171] [5] The enzyme (enzyme having the enzymatic action mainly in the wash).

[0172] 可使用下列酶(按酶化反应性质分类): [0172] using the following enzymes (classified according to the nature of the enzymatic reaction):

[0173] 水解酶、水化酶、氧化还原酶、碳链裂解酶、转移酶和异构酶。 [0173] hydrolase, aqueous enzyme, an oxidoreductase, chain carbon lyases, transferases and isomerases. 所有这些酶都可用于本发明。 All of these enzymes may be used in the present invention. 最优选的酶是水解酶,如蛋白酶、酯酶、糖酶和核酸酶。 The most preferred enzymes are hydrolases such as proteases, esterases, carbohydrases and nucleases.

[0174] 蛋白酶的例子有胃蛋白酶、胰蛋白酶、胰凝乳蛋白酶、胶原酶、角蛋白酶、弹性蛋白酶、枯草溶菌素、BPN、木瓜蛋白酶、菠萝蛋白酶、羧肽酶A和B、氨肽酶和曲霉肽酶A和B。 Examples [0174] proteases are pepsin, trypsin, chymotrypsin, collagenase, keratinase, elastase, subtilisin, the BPN, papain, bromelain, carboxypeptidase A and B, and aminopeptidase Aspergillus peptidase A and B.

[0175] 酯酯的例子有胃脂肪酶、胰脂肪酶、植物解脂酶、磷脂酶、胆碱脂酶和磷酸酶。 Examples of the ester [0175] There are gastric lipase, pancreatic lipase, plant lipase, phospholipase, and phosphatase cholinesterase.

[0176] 糖酶包括碱性纤维素酶、麦芽糖酶、蔗糖酶、淀粉酶、果胶酶、溶菌酶、α-葡糖苷酶和β-葡糖苷酶。 [0176] carbohydrases include alkaline cellulase, maltase, sucrase, amylase, pectinase, lysozyme, alpha] -glucosidase and β- glucosidase.

[0177] [6]上蓝剂和萤光染料: [0177] [6] bluing agents and fluorescent dyes:

[0178] 如果需要,可往组合物中加入各种上蓝剂和萤光染料,例如,推荐具有下列结构的化合物: [0178] If desired, may be added various bluing agents and fluorescent dyes to the composition, e.g., a compound having the following structure recommended:

[0179] [0179]

[0180] [0180]

[0181] 和具有下列通式的上蓝剂: [0181] and a bluing agent having the formula:

[0182] [0182]

[0183] 式中D代表蓝色或红紫色残基、单偶氮染料残基、双偶氮染料残基或蒽醌染料残基,X和Y各代表羟基、氨基、可被羟基、磺酸基、羧酸基或烷氧基取代的脂肪族氨基、或可被囟素、羟基,磺基、羧酸基、低级烷基或低级烷氧基取代的芳族或脂环族氨基,R代表氢原子或低级烷基,但下列情况除外:(1)R代表氢原子,X和Y都可同时代表羟基或烷醇胺基,(2)R代表氢原子,X和Y中的一种代表羟基,而另一个代表烷醇胺基,n为大于等于2的整数, [0183] wherein D represents a blue or reddish purple residue, residues of monoazo dye, a disazo dye or an anthraquinone dye residue residue, X and Y each represent a hydroxyl group, an amino group, by a hydroxyl, sulfonic acid group, carboxylic acid group or alkoxy-substituted aliphatic amino group, or an optionally halogen substituted, a hydroxyl group, a sulfo group, a carboxylic acid group, a lower alkyl or lower alkoxy, aromatic or cycloaliphatic amino group, R representatives a hydrogen atom or a lower alkyl group, with the following exceptions: (1) R represents a hydrogen atom, X and Y may represent a hydroxy group or an alkanol amine a representative of (2) R represents a hydrogen atom, X and Y hydroxy, and the other represents an alkanol amine, n-2 is an integer,

[0184] 和下式的上蓝剂: [0184] and a bluing agent of the formula:

[0185] [0185]

[0186] 式中D代表蓝色或红紫色残基,偶氮染料残基或蒽醌染料残基,X和Y可相同或不同,代表烷醇胺基或羟基。 [0186] wherein D represents a blue or reddish purple residue, azo dye residue, or a residue of an anthraquinone dye, X and Y may be the same or different, represent a hydroxyl group or an alkanol amine.

[0187] [7]防结块剂: [0187] [7] Anti-caking agent:

[0188] 在粉末状的洗涤剂组合物中加入下列防结块剂:对苯甲磺酸盐,二甲苯基磺酸盐、乙酸盐、磺基琥珀酸盐、滑石、粉碎的二氧化硅、粘土、硅酸钙(如Micro-Cell of Johns-Manvill CO.)、碳酸钙的氧化镁。 [0188] The following anti-caking agent was added in a powdery detergent composition: terephthalic sulfonates, xylene sulfonates, acetates, sulfosuccinates, talc, silica, pulverized , clay, calcium silicate (such as Micro-Cell of Johns-Manvill CO.), calcium carbonate, magnesium oxide.

[0189] [8]抗氧化剂: [0189] [8] Antioxidant:

[0190] 抗氧化剂包括例如叔丁羟基甲苯、4,4′-亚丁基二(6-叔丁基-3-甲苯酚)、2,2′-亚丁基二(6-叔丁基-4-甲基苯酚、单苯乙烯化甲酚、双苯乙烯化甲酚、单苯乙烯化苯酚、双苯乙烯化苯酚和1,1′-双(4-羟基苯基)环己烷。 [0190] Antioxidants include, for example, t-butylhydroxytoluene, 4,4'-butylidene-bis (6-tert-butyl-3-methylphenol), 2,2'-butylidene-bis (6-tert-butyl-4- methylphenol, styrenated cresol mono, bis styrenated cresol, monostyrenated phenol, styrenated phenol and 1,1'-bis (4-hydroxyphenyl) cyclohexane.

[0191] [9]过氧化物的稳定剂和过氧化氢的加合物 [0191] [9] peroxide stabilizer and hydrogen peroxide adduct

[0192] 漂白洗涤剂组合物中可使用稳定剂,包括镁盐,如硫酸镁、硅酸镁、氯化镁、氟硅酸镁,氧化镁和氢氧化镁,以及硅酸盐,如硅酸钠。 [0192] Bleaching detergent compositions may be used stabilizers including magnesium salts, such as magnesium sulfate, magnesium silicate, magnesium chloride, magnesium fluorosilicate, magnesium oxide and magnesium hydroxide, and silicates such as sodium silicate.

[0193] [10]香料和着色材料 [0193] [10] Perfume and coloring materials

[0194] 下面将参照组分(b)和漂白组合物的制备方法说明本发明。 [0194] The preparation method with reference to component (b) and the bleaching compositions of the present invention is described below. 制备组分(b)的九种化合物,Ⅰ-a和Ⅰ-b落在(b-3)的定义范围内,Ⅱ-a和Ⅱ-b落在(b-4)的定义范围内,Ⅲ-a和Ⅲ-b分别落在(b-5)和(b-6)的定义范围内,(Ⅳ-a)和(Ⅳ-b)落在(b-7)的定义范围内,(Ⅳ-c)落在多亚烷基多胺化合物的定义范围内。 Preparation of component (b) a compound of nine, and the Ⅰ-a fall Ⅰ-b (b-3) of the definition of, and within Ⅱ-a fall Ⅱ-b (b-4) within the definition Ⅲ and within the definition of -a ⅲ-b, respectively, fall within (b-5) and the definition (b-6) a, (Ⅳ-a) and (Ⅳ-b) falls (b-7) a, (IV -C) fall within the definition of polyalkylene polyamine compound.

[0195] 制备实例1 Preparation [0195] Example 1

[0196] 下式化合物的合成 Synthesis of [0196] the compound of the formula

[0197] [0197]

[0198] [0198]

[0199] 将氯乙腈溶于装在100毫升三颈烧瓶中的20毫升丙酮中。 [0199] The apparatus of chloroacetonitrile is dissolved in 100 ml three-necked flask in 20 ml of acetone. 用氮气作载气往溶液中鼓入无水三甲胺,同时用磁性搅拌器搅拌该溶液。 Nitrogen was used as carrier gas to the solution of anhydrous trimethylamine was bubbled into the solution while stirring with a magnetic stirrer. 在连续鼓入三甲胺3小时以使三甲胺的当量为氯乙腈当量的两倍后,密封烧瓶,在室温下搅拌过夜。 After bubbling trimethylamine continuously for 3 hours to equivalents of trimethylamine twice chloroacetonitrile equivalents sealed flask was stirred at room temperature overnight. 过滤分离出产生的白色晶体,得到8.93克化合物(Ⅰ-a),产率为95.3%。 Filter the resulting white crystals were separated to give 8.93 g compound (Ⅰ-a), in a yield of 95.3%.

[0200] 制备实例2 Preparation [0200] Example 2

[0201] 下式化合物的合成 Synthesis of [0201] the compound of the formula

[0202] [0202]

[0203] 在100毫升装有冷却管的二颈烧瓶中加入20毫升乙醇,将10.7克二甲基辛基胺溶于该乙醇中,接着滴加5.42克氯乙腈。 [0203] Add 100 ml two-necked flask equipped with a cooling tube of 20 ml of ethanol, to 10.7 g was dissolved in the ethanol dimethyloctylamine, followed by dropwise addition of 5.42 g of chloroacetonitrile. 滴加完毕,在油浴(温度为90℃)中加热混合物,在乙醇回流条件下进行反应,直到用TLC法证实原料胺消耗完。 Dropwise addition, the mixture was heated in an oil bath (temperature 90 ℃), the reaction is carried out in ethanol under reflux conditions until the starting amine was confirmed by TLC consumed. 蒸馏得到的反应混合物以除去乙醇,得到15.76克上季铵盐,产率为99.3%。 The reaction mixture was distilled to remove the ethanol, to give the quaternary ammonium salt 15.76 g, yield 99.3%.

[0204] 制备实例3 Preparation [0204] Example 3

[0205] 下式化合物的合成 Synthesis of [0205] the compound of the formula

[0206] [0206]

[0207] 将6.0克乙酸2-二甲氨基乙酯溶于装在100毫升二颈烧瓶中的20毫克升丙酮中。 [0207] 6.0 g of acetic acid 2-dimethylamino-ethyl ester in 100 ml of diethyl mounted necked flask 20 mg l of acetone. 在室温下往烧瓶中滴加8.6克氯乙腈。 To the flask was added dropwise 8.6 g of chloroacetonitrile at room temperature. 在该温度下搅拌得到的混合物8小时,并蒸除溶剂。 At this temperature the resulting mixture was stirred for 8 hours and the solvent was distilled off. 用丙酮充分洗涤残余物,蒸除丙酮。 The residue was washed thoroughly with acetone, the acetone was distilled off. 获得7.3克无色油状的阳离子化合物,产率为93%。 To obtain 7.3 g of a cationic compound as a colorless oil, in 93% yield.

[0208] 物理性质: [0208] Physical properties:

[0209] IR(KBr,cm-1) [0209] IR (KBr, cm-1)

[0210] 3382,3016,2968,2908,1746,1479,1377,1233,1050 [0210] 3382,3016,2968,2908,1746,1479,1377,1233,1050

[0211] 1H-NMR(CD3OD,TMS作为内参照物,δ) [0211] 1H-NMR (CD3OD, TMS as internal reference, δ)

[0212] 2.48(3H,s),3.83(6H,s),4.25~4.4(2H,t),4.68~4.85(2H,t),5.4(2H,s) [0212] 2.48 (3H, s), 3.83 (6H, s), 4.25 ~ 4.4 (2H, t), 4.68 ~ 4.85 (2H, t), 5.4 (2H, s)

[0213] 制备实例4 Preparation [0213] Example 4

[0214] 下式化合物的合成 Synthesis of [0214] the compound of the formula

[0215] [0215]

[0216] 将5克苯甲酸2-二甲氨基乙酯溶于装在100毫升二颈烧瓶中的20毫克升丙酮中。 [0216] 5 g of 2-dimethylamino benzoic acid ethyl ester in 100 ml of diethyl mounted necked flask 20 mg l of acetone. 在室温下往烧瓶中滴加5.9氯乙腈。 To the flask was added dropwise at room temperature 5.9 chloroacetonitrile. 在该温度下搅拌得到的混合物8小时,过滤,得到白色晶体。 Stirred at this temperature for 8 hours the resulting mixture was filtered to give white crystals. 用丙酮洗涤晶体,干燥,得到6.17克无色晶状的阳离子化合物,产率为89% The crystals were washed with acetone, and dried to give 6.17 g of colorless crystals of the cationic compound in a yield of 89%

[0217] 物理性质 [0217] Physical properties

[0218] mp 177-180℃ [0218] mp 177-180 ℃

[0219] IR(KBr,cm-1) [0219] IR (KBr, cm-1)

[0220] 3028,2920,1722,1488,1470,1446,1371,1314,1269,1170,1113,1065,1026,975,915,894,708 [0220] 3028,2920,1722,1488,1470,1446,1371,1314,1269,1170,1113,1065,1026,975,915,894,708

[0221] 1H-NMR(CD3OD,TMS作为内参照物,δ) [0221] 1H-NMR (CD3OD, TMS as internal reference, δ)

[0222] 3.9(6H,s),4.4~4.6(2H,t),5.05~5.25(2H,t),7.8~8.0(2H,d),8.35~8.55(2H,d) [0222] 3.9 (6H, s), 4.4 ~ 4.6 (2H, t), 5.05 ~ 5.25 (2H, t), 7.8 ~ 8.0 (2H, d), 8.35 ~ 8.55 (2H, d)

[0223] 制备实例5 Preparation [0223] Example 5

[0224] 化合物(Ⅲ-a)的合成 Synthesis of Compound [0224] (Ⅲ-a) of

[0225] [0225]

[0226] 将10克吡啶溶于20毫升丙酮中,然后在搅拌下往溶液中滴加14.3克氯乙腈。 [0226] 10 g of pyridine dissolved in 20 ml of acetone, and to the solution was added dropwise 14.3 g of chloroacetonitrile under stirring. 在室温下连续搅拌混合物8小时。 The mixture was stirred continuously at room temperature for 8 hours. 得到浅棕色的反应产物混合物,分离混合物,得到18.0克化合物(Ⅲ-a),产率为92.3%。 The reaction product was a pale brown mixture, the mixture was separated to obtain 18.0 g compound (Ⅲ-a), in a yield of 92.3%.

[0227] 制备实例6 Preparation [0227] Example 6

[0228] 合成化合物(Ⅲ-b) [0228] Synthesis of Compound (Ⅲ-b)

[0229] [0229]

[0230] 将10克烟酸和3.4克NaO一起溶于装在配备有冷却管的烧瓶中的100毫升的甲醇中,然后往溶液中滴加9.2克氯乙腈。 [0230] 10 g of nicotinic acid and 3.4 g NaO dissolved together with a flask equipped with a cooling tube mounted in 100 ml of methanol, and then added dropwise to the solution 9.2 g of chloroacetonitrile. 用80℃的油浴加热反应混合物,在甲醇回流的反应条件下反应3小时。 With an oil bath at 80 deg.] C the reaction mixture was heated, under reaction conditions of methanol was refluxed for 3 hours. 蒸除溶剂后,在甲醇中重结晶,获得7.1克产物(Ⅲ-b),产率为54%。 After the solvent was distilled off, and recrystallized from methanol to give 7.1 g product (Ⅲ-b), in 54% yield.

[0231] 制备实例7 Preparation [0231] Example 7

[0232] [0232]

[0233] 在100毫升丙酮中溶解20克(172毫摩尔)氯乙腈,同时在室温下于装有回流管的300毫升二颈烧瓶中用磁性搅拌器搅拌该溶液,往该溶液中滴加39克(516毫摩尔)N,N,N′,N′-四甲基乙二胺于100毫升丙酮中的溶液。 [0233] was dissolved 20 g (172 mmol) of chloroacetonitrile in 100 ml of acetone, and equipped with a 300 ml two-necked flask with a magnetic stirrer, a reflux tube and the solution was stirred at room temperature, to the solution was added dropwise 39 g (516 mmol) N, N, N ', N'- tetramethylethylenediamine in 100 ml of acetone was added. 滴加完毕,在90℃加热混合物,反应90分钟,接着浓缩并冷却。 Dropwise addition, the mixture was heated at 90 ℃, for 90 minutes, then concentrated and cooled. 过滤收集形成的晶体,得到39.37克化合物(Ⅰ-a),产率为85.6%。 The crystals formed were collected by filtration, to give 39.37 g compound (Ⅰ-a), in a yield of 85.6%.

[0234] 熔点:195~200℃(分解) [0234] Melting point: 195 ~ 200 ℃ (decomposition)

[0235] [0235]

[0236] 3022,2944,1482,1455,1410,981,918,906,792. [0236] 3022,2944,1482,1455,1410,981,918,906,792.

[0237] 1H-NMR: [0237] 1H-NMR:

[0238] 3.52(12H,s),4.33(4H,s),4.95(4H,brs). [0238] 3.52 (12H, s), 4.33 (4H, s), 4.95 (4H, brs).

[0239] 制备实例8 Preparation [0239] Example 8

[0240] [0240]

[0241] 除了用57.8克(516毫摩尔)N,N,N′,N′-四甲基-1,6-己二胺代替39克四甲基乙二胺外,重复制备实例7,得到102.8克白色晶状的化合物(Ⅳ-b),产率为80.3%。 [0241] except that 57.8 g (516 mmol) N, N, N ', N'- tetramethyl-1,6-hexanediamine in place of 39 g of tetramethylethylenediamine, the preparation of Example 7 was repeated to give 102.8 g of white crystalline compound (Ⅳ-b), a yield of 80.3%.

[0242] 熔点:201至203℃(分解) [0242] Melting point: 201. To 203 deg.] C (decomposition)

[0243] [0243]

[0244] [0244]

[0245] 2962,2920,1488,1455。 [0245] 2962,2920,1488,1455.

[0246] 1H-NMR: [0246] 1H-NMR:

[0247] 1.05-2.25(8H,m),3.35(12H,s),3.40-3.80(4H,m),4.75(4H,s). [0247] 1.05-2.25 (8H, m), 3.35 (12H, s), 3.40-3.80 (4H, m), 4.75 (4H, s).

[0248] 制备实例9 Preparation [0248] Example 9

[0249] 化合物(Ⅳ-c)的合成 [0249] Synthesis of Compound (Ⅳ-c) of

[0250] 将100克下式表示的胺 [0250] 100 g of the amine represented by the formula

[0251] [0251]

[0252] 溶于装在配备的冷却管的1000毫升三颈烧瓶中的400毫升乙醇中,往该溶液中滴加131.3克氯乙腈。 [0252] dissolved in 400 ml of ethanol contained in 1000 ml three-necked flask equipped with a cooling tube in the middle, to the solution was added dropwise 131.3 g of chloroacetonitrile. 滴加完毕,用油浴(温度为90℃)给获得的混合物加热。 Dropwise addition, an oil bath (temperature 90 ℃) to the mixture was heated. 在回流乙醇的条件下加热得到的混合物24小时,蒸除乙醇,获得177.3克上述胺的季铵盐,转化率为76.6%。 Of ethanol was heated under reflux for 24 hours to obtain a mixture, ethanol was distilled off to obtain 177.3 g quaternary ammonium salts of such amines, the conversion was 76.6%.

[0253] 组合物的实例1至8 Examples [0253] The compositions of 1 to 8

[0254] 如表1所示,使用有机过酸前体Ⅰ-a至Ⅳ-c制备漂白组合物1至8,同时制备对比组合物1至4,用漂白率或漂白程度来测定它们的漂白作用。 [0254] As shown in Table 1, using an organic peracid precursor Ⅰ-a to Ⅳ-c prepared bleaching composition 1-8, while the comparative compositions prepared from 1 to 4, with a degree of bleaching or bleach rates to determine their bleaching effect. 结果列于表Ⅰ中。 The results are set forth in Table Ⅰ.

[0255] 浸渍漂白作用(表1) [0255] impregnated with the bleaching action (Table 1)

[0256] 将过碳酸钠溶于300毫升20℃的水中以制备活性氧浓度为0.05%的溶液。 [0256] The sodium percarbonate 20 ℃ dissolved in 300 ml water to prepare an active oxygen concentration of 0.05% solution. 往溶液中加入活化剂,其用量应使活化剂中C≡N基团的当量为溶液中所含过氧化氢当量的16倍,由此制得漂白组合物。 Activating agent added to the solution, an amount that equivalents activator C≡N groups is contained in the solution over 16-fold equivalents of hydrogen peroxide, whereby a bleaching composition. 将5块用下述方法加工的黑茶沾色布(8×8厘米)在漂白组合物中浸渍30分钟,用水洗,干燥。 5 The following method of processing black tea staining cloth (8 × 8 cm) was immersed in a bleaching composition for 30 minutes, washed with water, and dried. 用下列等式计算黑茶沾色布的漂白率: Black tea is calculated bleachability fabric staining by the following equation:

[0257] 漂白率(%)= (漂白后的反射率-漂白前的反射率)/(白布的反射率-漂白前的反射率) ×100 [0257] Bleaching rate (%) = (reflectance after bleaching - reflectance before bleaching) / (reflectivity of white cloth - reflectance before bleaching) × 100

[0258] 上式中的反射率由NDR-101DP(Nippon Denshoku kogyo K,K制造)采用460钠米的滤色片测定的。 [0258] reflectivity of NDR-101DP (Nippon Denshoku kogyo K, K) situated on the formula using 460 nanometers as measured color filter.

[0259] 黑茶沾色布的加工如下:将80克NITTOH黑茶(黄色包装)在3升去离子水中沸煮约15分钟,通过褪浆漂白棉布过滤所得的混合物。 [0259] Black tea fabric staining process is as follows: 80 g NITTOH black tea (yellow package) was boiled in 3 liters of deionized water for about 15 minutes, the mixture was filtered bleached cotton through the slurry faded. 将棉衬衫布#2003浸渍在获得的滤液中,沸煮15分钟。 The cotton shirting # 2003 was immersed in the filtrate obtained, boiling for 15 minutes. 迅速取出浸渍在滤液中的布并放置约2小时。 Impregnated cloth quickly removed in the filtrate and left for about 2 hours. 使获得的布自然凉干,用水洗至洗液呈无色。 Natural dry cloth so obtained, washed with water until washings were colorless. 对得到的布进行脱水,压剪成测试尺寸(8×8厘米)。 The resulting cloth was dehydrated, cut into test size press (8 × 8 cm).

[0260] 在表1中,(1)所示的化合物具有下列通式: [0260] In Table 1, (1) a compound represented by the following general formula:

[0261] [0261]

[0262] (2)所示的TAED是四乙酰基乙二胺(Hoechst公司生产)。 [0262] (2) TAED is tetraacetylethylenediamine shown (Hoechst Corporation). (3)所示的化合物由Interox公司生产。 A compound represented by formula (3) produced by Interox company. (4)所示的漂白程度是用活性氧浓度为0.05%的溶液测定的。 (4) The degree of bleaching is shown active oxygen concentration of 0.05% of the assay solution.

[0263] 组合物的实例9和10 Examples [0263] The compositions of 9 and 10

[0264] 漂白方法: [0264] bleaching methods:

[0265] 将过氧化氢加入300毫升20℃的水中,以使有效氧浓度为0.05。 [0265] Hydrogen peroxide was added to water 300 ml 20 ℃ so that the effective oxygen concentration is 0.05. 再往其中加入1克碳酸钠。 Thereto was added 1 g of sodium carbonate. 以与过氧化氢摩尔数相等的量往溶液中加入化合物(Ⅳ-a)或(Ⅳ-b),将一块按上述方法加工的黑茶沾色布(10×10厘米)在该溶液中浸渍30分钟进行漂白。 With hydrogen peroxide in an equal molar amount of the number added to the solution Compound (Ⅳ-a) or (Ⅳ-b), the processing as described above a black tea staining cloth (10 × 10 cm) was immersed in the solution 30 minutes of bleaching. 用水洗涤布,干燥。 Cloth was washed with water, and dried. 按上述等式计算漂白率。 Bleaching rate calculated by the above equation. 用有效氯浓度为0.06%的次氯酸钠作为比产物来进行评定。 A chlorine concentration of 0.06% sodium hypochlorite as a ratio of the product to be assessed. 结果列于表2。 The results are shown in Table 2.

[0266] 洗涤剂组合物的实例11至18 Examples [0266] The detergent compositions 11-18

[0267] 将过碳酸钠和表3所示的阳离子化合物加入含作为底物的非离子表面活性剂但不含阴离子表面活性剂的重役型洗涤剂(可从市场上买到)的溶液中,以制备含表3所给组合物的洗涤剂溶液。 [0267] The sodium percarbonate and cationic compounds shown in Table 3 was added as a substrate containing a non-ionic surfactant but no anionic surfactant heavy duty detergent (commercially available from the market) was, in table detergent solution was prepared containing 3 to the composition. 用洗涤剂溶液在Terg-O-Tometer中在20℃下洗涤5块按上述方法加工的黑茶沾色布(8×8厘米)10分钟,用水洗涤,干燥,按上述方法测定漂白率。 With a detergent solution of Terg-O-Tometer washing at 20 ℃ 5 block processing as described above the staining black tea cloth (8 × 8 cm) for 10 minutes, washed with water, dried and the bleaching rate was measured as described above. 结果与对比组合物7至10的数据一起列于表3中。 Data and results comparative compositions 7-10 are shown together in Table 3.

[0268] 实例19 [0268] Example 19

[0269] 按下述方法分别制备不含磷、含少量磷和含大量磷的三种漂白组合物,百分率以重量计。 [0269] were prepared by the following method phosphorous containing small amounts of phosphorus, and three kinds of bleaching compositions containing a large amount of phosphorus, percentages are by weight.

[0270] 不含磷的组合物由下列组份制备:14%线性十二烷基磺酸钠、6%聚氧乙烯(10摩尔EO)C12-13烷基醚、2%硬质牛脂脂肪酸钠盐、5%2go的硅酸钠、10%碳酸钠、25%4A型沸石、10%过碳酸钠、10%阳离子化合物(Ⅳ-a),2%分子量为6000的聚乙二醇、2%蛋白酶、4%水,其余为硫酸钠。 [0270] The composition phosphorous group consisting of the following ingredients was prepared: 14% linear sodium dodecyl sulfate and 6% polyoxyethylene (10 mol EO) C12-13 alkyl ether, 2% hard tallow fatty acid sodium salt, 5% 2go sodium silicate, 10% sodium carbonate, 25% 4A zeolite, 10% sodium percarbonate, 10% of the cationic compound (Ⅳ-a), 2% polyethylene glycol having a molecular weight of 6000, 2% protease, 4% water, the balance being sodium sulfate.

[0271] 含少量磷的组合物由下列组分制备:10%线性十二烷基磺酸钠、2%十二烷基硫酸钠、8%聚氧乙烯(7.7摩尔EO)C12-13烷基醚、2%硬质牛脂脂肪酸的钠盐、5% 1go的硅酸钠、10%碳酸钠、20%4A型沸石、15%焦磷酸钠、10%过硼酸钠、5%阳离子化合物(Ⅳ-a)、1%分子量为11000聚乙二醇、1%亚硫酸钠、2%蛋白酶、4%水,其余的钠。 [0271] small amount of phosphorus-containing composition prepared from the following components: 10% linear sodium dodecyl sulfate, sodium lauryl sulfate 2% and 8% polyoxyethylene (7.7 moles EO) C12-13 alkyl ether, sodium salt 2% hard tallow fatty acid, 5% 1go sodium silicate, 10% sodium carbonate, 20% 4A zeolite, 15% sodium pyrophosphate, sodium perborate 10%, 5% cationic compound (IV- a), 1% polyethylene glycol molecular weight 11,000, 1% sodium sulfite, proteases 2%, 4% water with the balance sodium.

[0272] 含大量磷的组合物由下列组分制备:20%聚氧乙烯(8.6摩尔EO)牛脂醇醚、2%硬质牛脂脂肪酸的钠盐、30%三磷酸钠、10%过硼酸钠、5%阳离子化合物(Ⅳ-a),5% 2go的硅酸钠、10%碳酸钠、1%亚硫酸钠、2%分子量为6000的聚乙二醇、2%蛋白酶、6%水,其余为硫酸钠。 [0272] large amount of phosphorus-containing composition prepared from the following components: 20% Polyoxyethylene (8.6 moles EO) tallow alcohol ethers, the sodium salt of 2% hard tallow fatty acid, 30% sodium tripolyphosphate, 10% sodium perborate 5% cationic compound (Ⅳ-a), 5% sodium silicate 2go of 10% sodium carbonate, sodium sulfite 1%, 2% polyethylene glycol having a molecular weight of 6000, 2% of protease, 6% water, the remainder being sulfuric acid sodium.

[0273] [0273]

[0274] [0274]

[0275] [0275]

[0276] [0276]

[0277] [0277]

[0278] [0278]

Claims (12)

1、一种漂白组合物,该组合物含(a)一种过氧化物和(b)一种具有选自(b-1)和(b-2)中至少一个基团的有机过酸前体。 1, a bleaching composition, said composition comprising (a) a peroxide and (b) having a front (b-1) and (b-2) selected from a group of at least an organic peracid body.
2、权利要求1所述的漂白洗涤剂组合物,该组合物还含洗涤剂组分。 2, bleaching detergent composition according to claim 1, the composition further comprising detergent ingredients.
3、权利要求1所述的组合物,其中所述前体具有通式(b-3),式中R1为C1-24烷基、C1-24链烯基、烷基部分含1~24个碳原子的烷芳基、具有取代基的C1-24烷基、具有取代基的C1-24链烯基、具有C1-24烷基和其它取代基的烷芳基,R2和R3各为C1-3烷基、具有1至3个碳原子的羟烷基、-(C2H4O)nH(n为1至5)、-CH2-CN,X为阴离子。 3. The composition according to claim 1, wherein said precursor has the general formula (b-3), wherein R1 is C1-24 alkyl, C1-24 alkenyl, alkyl moieties containing from 1 to 24 alkaryl carbon atoms, a substituted C1-24 alkyl group, C1-24 alkenyl group having a substituent, an aryl having C1-24 alkyl and alkoxy groups, R2 and R3 substituents are each other C1- 3 alkyl group, a hydroxyalkyl group having 1-3 carbon atoms, - (C2H4O) nH (n is 1 to 5), - CH2-CN, X is an anion.
4、权利要求1所述的组合物,其中所述的前体具有通式(b-4),式中R1为C1-20烷基、C1-20链烯基、芳基、具有取代基的C1-20烷基、具有取代的C1-20链烯基、具有取代基的芳基,R2和R3各为C1-3烷基、具有1至3个碳原子的羟烷基或-(C2H4O)nH(n为1至3)。 4. A composition according to claim 1, wherein said precursor has the general formula (b-4), wherein R1 is C1-20 alkyl, C1-20 alkenyl group, an aryl group having a substituent C1-20 alkyl, a substituted C1-20 alkenyl group, a substituted aryl group, R2 and R3 are each a C1-3 alkyl group, a hydroxyalkyl group having 1-3 carbon atoms or - (C2H4O) nH (n is 1-3).
5、权利要求1的组合物,其中所述前体具有通式(b-5)或(b-6),式中R1至R5各为氢、C1~C10烷基、C1~C10链烯基、具有取代基的C1~C10烷基、具有取代基的C1~C10链烯基、羧基、磺酰基或氰基,X为阴离子。 5. The composition of claim 1 is C1 ~ C10 alkyl group, C1 ~ C10 alkenyl group, wherein said precursor has the general formula (b-5) or (b-6), wherein R1 to R5 are each hydrogen, , C1 ~ C10 alkyl group having a substituent group, substituted C1 ~ C10 alkenyl group, a carboxyl group, a sulfonyl group or a cyano group, X is an anion.
6、权利要求1的组合物,其中所述的前体是具有选自(b-1)和(b-2)中至少一个基团的亚烷基二胺化合物或多亚烷基多胺化合物。 6. The composition as claimed in claim 1, wherein said precursor is selected from an alkylene diamine compound (b-1) and (b-2) at least one group or polyalkylene polyamine compound .
7、权利要求1的组合物,其中所述的前体具有通式(b-7),式中R1、R2、R3和R4各为C1~6烷基、n为1至16的整数,X为阴离子。 7. The composition of claim 1, wherein said precursor having the formula (b-7), wherein R1, R2, R3 and R4 are each C1 ~ 6 alkyl, n is an integer of 1 to 16, X It is an anion.
8、权利要求1的组合物,其中(a)与(b)的摩尔比为99.9/0.1至20/80。 8. The composition of claim 1, wherein (a) the molar ratio of (b) is from 99.9 / 0.1 to 20/80.
9、权利要求1的组合物,该组合物含100份(重量)(b)和5至20份(重量)粘合剂的掺合物的颗粒。 9. A composition as claimed in claim 1, the composition comprising 100 parts particulate blend (by weight) (b) and 5 to 20 parts (by weight) of the binder.
10、具有权利要求7的定义的通式(b-7)的阳离子化合物。 10, (b-7) a cationic compound having the general formula defined in claim 7.
11、权利要求10所述的化合物,式中R1、R2、R3和R4为具有1至3个碳原子的烷基,n为1至9的整数。 11. A compound according to claim 10, wherein R1, R2, R3 and R4 are alkyl having 1 to 3 carbon atoms, n is an integer from 1 to 9.
12、权利要求1所述的化合物,式中R1、R2、R3和R4为甲基,n为1至9的整数。 12. The compound according to claim 1, wherein R1, R2, R3 and R4 is methyl, n is an integer from 1 to 9.
CN88104926A 1988-08-04 1988-08-04 Method of making artificial fa vegetable CN1039706A (en)

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CN88104926A CN1039706A (en) 1988-08-04 1988-08-04 Method of making artificial fa vegetable

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CN88104926A CN1039706A (en) 1988-08-04 1988-08-04 Method of making artificial fa vegetable

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US20080058282A1 (en) 2005-08-30 2008-03-06 Fallon Joan M Use of lactulose in the treatment of autism
US8658163B2 (en) 2008-03-13 2014-02-25 Curemark Llc Compositions and use thereof for treating symptoms of preeclampsia
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Publication number Priority date Publication date Assignee Title
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