CN1875144B - Method for the reactive colouring of leather - Google Patents

Method for the reactive colouring of leather Download PDF

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CN1875144B
CN1875144B CN 200480032106 CN200480032106A CN1875144B CN 1875144 B CN1875144 B CN 1875144B CN 200480032106 CN200480032106 CN 200480032106 CN 200480032106 A CN200480032106 A CN 200480032106A CN 1875144 B CN1875144 B CN 1875144B
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group
leather
colouring
dye
under
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CN 200480032106
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CN1875144A (en )
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L·索莫吉
A·赞波尼
R·施特赖歇尔
H·基佐
R·埃哈德
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巴斯福股份公司
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507Azo dyes
    • C09B62/513Disazo or polyazo dyes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/4401Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
    • C09B62/4403Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
    • C09B62/4411Azo dyes
    • C09B62/4415Disazo or polyazo dyes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/4401Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system
    • C09B62/4403Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with two or more reactive groups at least one of them being directly attached to a heterocyclic system and at least one of them being directly attached to a non-heterocyclic system the heterocyclic system being a triazine ring
    • C09B62/4411Azo dyes
    • C09B62/4416Metal complex azo dyes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09BORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507Azo dyes
    • C09B62/515Metal complex azo dyes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS, OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02Material containing basic nitrogen
    • D06P3/04Material containing basic nitrogen containing amide groups
    • D06P3/32Material containing basic nitrogen containing amide groups leather skins
    • D06P3/3286Material containing basic nitrogen containing amide groups leather skins using reactive dyes

Abstract

The invention relates to a method for the colouring of leather with at least one dye (F), comprising at least one group of formula (A) which may be activated under alkaline conditions, where ---- represents the bond to the remainder of the dye molecule, X is an electron-withdrawing group, k = 1, 2, or 3, n = 0 or 1 and B is a CH=CH2, or CH2-CH2-Q group, where Q is a group which may be cleaved under alkaline conditions, comprising the treatment of the leather with an aqueous liquor, containing at least one dye (F), at a pH value of at least 7.5. The invention further relates to novel dyes whichare particularly suitable for the reactive colouring of leather.

Description

皮革的反应性着色法 Reactive coloring leather

[0001] 本发明涉及将皮革染色的方法,还涉及特别可用于皮革的反应性染色的新型染料。 [0001] The present invention relates to a method of dyeing leather, to novel reactive dyes are particularly useful for the dyeing of leather.

[0002] 鞣制皮革目前是用酸性染料、直接染料、硫化染料或碱性染料染色的。 [0002] Leather tanning is now acid dyes, direct dyes, sulfur dyes or basic dyes. 使用这些染料难以实现高颜色强度和高颜色稳定度,尤其是耐湿和耐汗坚牢度,实际上对于中至高色调深度迄今不可能达到令人满意的标准。 Using these dyes is difficult to achieve a high color intensity and high color stability, particularly moisture and perspiration fastness, in fact, a high depth of shade for the hitherto impossible to achieve a satisfactory standard.

[0003] 为了提高耐汗和耐湿坚牢度,通常用阳离子络合剂处理皮革,其使染料络合并由·此降低其与水接触时的溶度。 [0003] In order to improve the moisture and perspiration fastness, typically leather treated with a cationic complexing agent, by which the dye-complexed reduced solubility at this contact with water. 然而,可实现的耐湿、耐汗和耐擦坚牢度对于强烈色调仍然不足。 However, achieve moisture, perspiration and rub fastness is still insufficient for the strong tone. 此外,由此制成的皮革制品在使用时容易褪色(mark off)。 Furthermore, leather products made therefrom easily fade in use (mark off). 在中至高色调深度下实现高坚牢度还要求非常仔细地选择染料,且所用染料应与所用皮革助剂以及合适的加脂剂和复鞣料的选择相配。 High fastness under medium to high depth of shade also requires very careful selection of the dye, and the dye used should be selected and a suitable auxiliaries leather fatliquoring agents and matched with retanning material. 此外,实现所需的坚牢度通常要求将染料与加脂剂以及有时与复鞣剂在不同的浴液(float)中施用;必需的浴液变化延长了总过程并产生更多的废水。 Further, to achieve the required fastness to the dye generally required and fatliquors and retanning agent may be administered at different bath (float); the bath changes necessary to extend the overall process and produce more waste.

[0004] 由于所用的不同工艺步骤和化学品,用传统皮革染料在酸性水介质中进行的染色操作是复杂、漫长且昂贵的。 [0004] Due to the different process steps and chemicals used, the traditional leather dyed with dye in an acidic aqueous medium operations are complicated, lengthy and expensive. 此外,这些措施不构成上述坚牢度问题的基本解决方法。 In addition, these measures do not constitute a fundamental solution to the above problem fastness. 其原因在于所用传统染料通过离子相互作用连接到皮革上。 The reason is that the conventional dyestuff is connected to the leather by interaction with ions. 碱性水溶液(例如洗液或在耐汗坚牢度测试中)的作用破坏了皮革与染料之间的离子键,因此染料从皮革上分离并染污周围材料,例如相邻织物。 An alkaline aqueous solution (e.g., lotion or perspiration fastness test) destroys the effect of ionic bond between the dyes and leather, and so dye separation from the leather soiling the surrounding material, e.g. adjacent fabric.

[0005] 已经进行了各种努力以通过反应性染色法改进染色的皮革的颜色坚牢度和耐湿性。 [0005] Color fastness has been performed by a variety of efforts to improve the dyeing reactive dyeing of leather and moisture resistance. 反应性染色是指使用含有能与皮革的官能团形成共价化学键的官能团的染料。 Dyeing reactive dye refers to a functional group containing a covalent chemical bond with a functional group capable of forming a leather.

[0006]例如,TC Mullen 在Leather Manufacturer 1964,18 和在J. Soc. Leather,Trades, Chem. 46,1962,162 以及ML Fein 等在J. Am. LeatherChem. Assoc. 65,1970,584-591中描述了使用含有二氯三嗪基团作为反应残基的活性染料。 [0006] For example, TC Mullen in Leather Manufacturer 1964,18 and J. Soc. Leather, Trades, Chem. 46,1962,162 and ML Fein et al J. Am. LeatherChem in. Assoc. 65,1970,584-591 It describes reactive dyes containing a dichlorotriazine group as the reactive residue. 然而,所记录的固色率,也就是化学键合染料的比例仅是适中的,大约70至75%,并且不能解决上述问题。 However, the recorded fixation rate, i.e. the ratio of the dye is chemically bonded only moderate, about 70 to 75%, and does not solve the above problems. 此夕卜,该技术仅限于铬鞋皮革。 Bu this evening, this technique is limited to chrome leather shoes.

[0007] 为了克服上述缺点,DE-A 3529294提出了使用含有至少一个1,3,5-三嗪基(其上连有含有季氮原子的取代基)的用于皮革染色的染料。 [0007] In order to overcome the above disadvantages, DE-A 3529294 proposes the use of 1,3,5-triazine comprising at least one group (on which there is attached a substituted group containing a quaternary nitrogen atom) dyes for dyeing leather. 然而,专利权受让人对作为模型体系的N-乙酰基赖氨酸的研究表明,在其中所述的染色条件下,在染料与N-乙酰基赖氨酸的氨基之间没有明显形成共价键。 However, studies of the assignee patents N- acetyl-lysine as a model system showed that, in the case where the dyeing conditions, between the dye and the amino-N- acetyl-lysine formed were no significant valence bond.

[0008] K. Rosenbusch等在Das Leder 19,1968, 294中描述了对于油鞋革的染色使用Remazol®染料,其含有乙烯基砜基团或在碱的作用下释放出乙烯基砜基团的基团。 [0008] K. Rosenbusch like 19,1968, 294 is described in Das Leder stain for use Remazol® oil shoe dyes containing a vinyl sulfone group or an alkali under the effect of releasing the vinyl sulfone group group. 然而,充分的固色需要在PH ίο下长时间染色。 However, adequate fixation takes a long time dyed at PH ίο. 由于所用染色条件,也就是高pH以及7小时或更长的染色时间,该方法仅能用于已知对碱性稳定的油鞣革的染色。 Since the staining conditions used, i.e. high pH, ​​and 7 hours or longer staining time, the known method can only be used for dyeing alkaline stable oil tanning. 使用其它皮革种类时,所述染色条件会对皮革造成损害。 With other kinds of leather, the leather dyeing conditions will cause damage. 专利权受让人的研究表明,用含有乙烯基砜基团的Remazol®染料不能实现令人满意的固色。 Research indicates that the patent assignee, with a vinyl sulfone dye contains Remazol® group can not achieve satisfactory fixation.

[0009] 总之,用反应性染料将皮革染色的现有方法在中至高色调深度下不能提供85%或更高的良好固色率。 [0009] In short, the conventional method of reactive dyes for dyeing leather does not provide 85 percent or greater of the good fixation at medium to high depth of shade. 现有技术中实现的70至75%的固色率对于高耐湿和耐汗坚牢度和良好的渗移稳定性是不足的,因为必须费力地洗掉未附着的染料以解决此处所述的问题。 70-75% of the prior art fixation implemented for high moisture and perspiration fastness and good stability bleeding is insufficient, because the dye must be laboriously washed away unattached to resolve herein The problem. 在Leather Manufacturer 1964,18-23中也指出了此处所述的用反应性染料将皮革染色的缺点。 In Leather Manufacturer 1964,18-23 also pointed out the shortcomings described herein dyeing leather with reactive dyes. 因此,不用惊讶于用反应性染料将皮革染色的工艺并不成熟。 Thus, not surprising in the process with reactive dyes for dyeing leather is not mature. 相反,目前正在研究不同的在皮革中共价键合染料的方法,例如用多官能醛预处理皮革,该多官能醛含有至少一个能够通过形成键来与染料的反应性基团反应的反应性基团(参看DE 100 44 642 Al)。 In contrast, currently being studied in different methods of leather dyes covalently bonded, e.g. pretreatment leather multifunctional aldehyde, multifunctional aldehyde which comprises at least one key can be formed by a reactive group with a reactive dye of the reactive group group (cf. DE 100 44 642 Al).

[0010] 由于此处所述的缺点,这些方法尤其不适合制造用于特定部分的皮革制品,例如鞋类、服装、汽车、手套和家具,在这些制品中需要中等和高色调深度以及高坚牢度,尤其是耐洗、耐汗、耐擦和耐渗移坚牢度。 [0010] Due to the disadvantages described herein, these methods are not suitable in particular for producing a specific part of the leather articles, such as shoes, clothing, automobiles, furniture and gloves, medium and high depth of shade required, and in these articles GaoJian fastness, especially washing fastness, perspiration resistance, and rub fastness shift resistance to bleeding.

[0011] 本发明的一个目的是提供一种在中等和高色调深度(颜色强度)下将皮革染色至高坚牢度(尤其是耐湿、耐汗和耐擦坚牢度以及高的渗移牢度)的方法。 [0011] An object of the present invention is to provide a high and at medium depth of shade (color intensity) The leather dyed a high fastness (especially moisture, perspiration and rub-off fastness and high fastness to bleeding )Methods. 该方法应该能够在对皮革即使有损害也是很小的条件下进行。 The method should be capable of damaging the leather is very small even under conditions. 更特别地,该方法应该适合制造用于特定部分的皮革制品,例如鞋类、服装、汽车、手套和家具,在这些制品中需要中等和高色调深度以及高坚牢度,尤其是耐洗、耐汗、耐擦和耐渗移坚牢度。 More particularly, the method should be suitable for producing a specific part of the leather articles, such as shoes, clothing, automobiles, furniture and gloves, medium and high required depth of shade and high fastness in these articles, in particular washing, perspiration, scratch fastness and resistance to bleeding.

[0012] 我们意外地发现,在pH为7. 5或更高的水浴液(aqueous float)中使用含有至少一个下式A的官能团的染料F可以实现该目的。 [0012] We have surprisingly found that the use of dyes F contains at least one functional group of the formula A at a pH of 7.5 or higher water bath (aqueous float) may be implemented for this purpose. 实际上,在这些条件下,染色和固色进行得如此迅速以致于4小时或更短的染色时间就足以获得充足的颜色强度和85%或更高的高固色。 In fact, under these conditions, dyeing and fixing proceeded so rapidly that less than 4 hours of dyeing time sufficient to obtain sufficient color intensity and 85% or more higher fixation.

[0013] 由此,本发明提供了一种用至少一种含有至少一个式A的可被碱活化的基团的染料F将皮革染色的方法: [0013] Accordingly, the present invention provides at least one dye of formula F may be alkali-activated group to a method of dyeing leather with at least one of A, comprising:

[0014] [0014]

[0015] 其中 [0015] in which

[0016] ——是指与染料分子的其余部分相连的键; [0016] - refers to a bond connected to the remainder of the dye molecule;

[0017] X是吸电子基团, [0017] X is an electron withdrawing group,

[0018] k 是1、2 或3, [0018] k is 1, 2 or 3,

[0019] η是O或I且 [0019] η is O or I and

[0020] B是CH = CH2基团或CH2-CH2-Q基团,其中Q是可碱分离的基团, [0020] B is a CH = CH2 group or a CH2-CH2-Q group, wherein Q is a separate base group,

[0021] 该方法包括用pH值不小于7. 5、通常8至11、优选8. 5至10. 5、特别是8. 5至10的含有至少一种染料F的水浴液处理皮革。 [0021] The method comprises a pH value of not less than 7.5, usually 8 to 11, preferably from 8.5 to 10.5, particularly those containing at least one dye F water bath of treating leather of 8.5 to 10.

[0022] 此处和下文中,烷基通常是指含有I至6个碳原子、优选含有I至4个碳原子的直链或支链烃基(分别是C1-C6烷基和C1-C4烷基),例如甲基、乙基、丙基、异丙基等。 [0022] Here and hereinbelow, the alkyl group generally refers to contain I to 6 carbon atoms, preferably containing I to 4 carbon atoms, a straight-chain or branched hydrocarbon group (each alkyl group is C1-C6 alkyl and C1-C4 group) such as methyl, ethyl, propyl, isopropyl and the like. 卤烷基是指氢原子完全或部分被卤原子(尤其是氟原子)取代时的如上所述的烷基,例如三氟甲基、三氯甲基、五氟乙基等。 Haloalkyl refers to an alkyl group as described above substituted with a hydrogen atom when totally or partially halogen atom (particularly fluorine atom), such as trifluoromethyl, trichloromethyl, pentafluoroethyl and the like. 烷氧基是指经由氧原子相连的如上所述的烷基。 Alkoxy refers to an alkyl group as described above attached via an oxygen atom. 任选取代的苯基表示苯基可以含有一个或多个,例如1、2、3或4个选自卤素、烷基、烷氧基、硝基、氰基、C00H、SO3H等的取代基。 It represents phenyl optionally substituted phenyl group may contain one or more, e.g., three or four substituents selected from halogen, alkyl, alkoxy, nitro, cyano, C00H, SO3H other substituents. 卤素特别代表氟、氯或溴。 Representative halogen, especially fluorine, chlorine or bromine.

[0023] 吸电子基团X是指对与它们相连的芳基产生-M和/或-I作用的基团。 [0023] The electron withdrawing group X means a group -M is generated and / or -I effect on an aryl group which they are attached. 它们包括,例如,氟或氯、CN、NO2'以及式-C(O) -R1和S (O) 2R2的基团,其中R1和R2独立地代表0H、烷基、卤烷基、烷氧基或任选取代的苯基。 They include, for example, fluorine or chlorine, CN, NO2 'and the formula -C (O) -R1 and S (O) 2R2 group, wherein R1 and R2 independently represent 0H, alkyl, haloalkyl, alkoxy or optionally substituted phenyl group. 当基团A包含多个基团(k> I)时,X基团可以相同或不同。 When the group A comprises a plurality of groups (k> I), X radicals may be the same or different. 优选地,至少一个X基团是羟基磺酰基(S03H)。 Preferably, at least one X is a hydroxyl group a sulfonyl group (S03H).

[0024] 变量k优选为I或2 ;也就是说A基团包含I或2个吸电子基团X。 [0024] The variable k is preferably I or 2; A group that is I or 2 comprising an electron withdrawing group X. 优选地,式A中的η为O ;也就是说,基团A衍生自苯。 Preferably, in the formula η A is O; that is, the group A is derived from benzene. 当η为I时,基团A衍生自萘。 When η is I, the group A is derived from naphthalene. 在这些情况下,SO2-B基团可以与所述至少一个X基团位于相同的苯环上,也可以位于另一苯环上。 In these cases, SO2-B groups may be located on the same phenyl ring with at least one X group can be on the other phenyl ring.

[0025] 可碱分离的基团Q是指在碱性环境下,也就是pH为7.5或更高的情况下,通过消除而形成乙烯基砜基团而分离的基团。 [0025] The base may be an isolated group Q means that in an alkaline environment, i.e. at a pH of 7.5 or higher, the vinyl sulfone group formed by eliminating separate groups. 这种基团的例子是卤素,例如氯、溴或碘,-O-SO3H, -S-SO3H、二烷基氨基、季铵基团(例如三-C1-C4烷基铵、苄基二-C1-C4烷基铵或N-连接的吡啶鐵),以及式R3S (O) 2_、R4S (O) 2-0-, R5C (O) -O-的基团。 Examples of such groups are halogen, such as chlorine, bromine or iodine, -O-SO3H, -S-SO3H, dialkylamino, quaternary ammonium groups (e.g. three -C1-C4 alkyl ammonium, benzyl dimethyl -C1- C4 alkyl ammonium pyridine iron or N- attached), and the formula R3S (O) 2_, R4S (O) 2-0-, R5C (O) -O- groups. 在这些式中,R3、R4和R5独立地为烷基、卤烷基或任选取代的苯基,但R5还可以是氢。 In these formulas, R3, R4 and R5 are independently an alkyl, haloalkyl or optionally substituted phenyl, but R5 may also be hydrogen. Q优选为-O-(CO)CH3基团,尤其是-O-SO3H基团。 Q is preferably -O- (CO) CH3 group, especially -O-SO3H group.

[0026]按照本发明,式 A 中的B 优选为CH = CH2XH2-CH2-OC (O) CH3 基团或CH2-CH2-O-SO3H基团。 [0026] According to the present invention, in formula A and B is preferably CH = CH2XH2-CH2-OC (O) CH3 group or a CH2-CH2-O-SO3H group. 更特别地,基团A选自下列基团Al至A12: More particularly, the group A is selected from the group consisting of Al to A12:

[0027]· [0027] ·

[0028] 其中特别优选至少一个A基团具有式Al、A2或A9时的染料。 [0028] A particularly preferred at least one group having the formula Al, A2 or dye when A9.

[0029] 有利地,本发明的方法中使用的染料包括1、2或3个、优选I或2个前述A基团。 [0029] Advantageously, the dye used in the method of the present invention comprise 1, 2 or 3, preferably I or 2, the A groups. 这种基团A可以但不必是染料生色团的一部分,并且优选通过-NH-或-N = N-基团连接到染料分子上。 Such groups A may, but need not be part of the dye chromophore, and is preferably attached to the dye molecule by -NH- or -N = N- group.

[0030] 一般而言,染料F每染料分子含有一个或多个,例如I至10个,尤其是2至8个赋予染料F水溶性的官能团。 [0030] In general, the dye F per dye molecule contains one or more, for example I to 10, in particular 2 to 8 to impart a water-soluble dye F functional group. 这些基团通常是在弱酸性或碱性pH值、通常高于pH 4的水介质中离解以形成阴离子基团的阴离子或酸性官能团。 These groups are usually weakly acidic or basic pH value, generally higher than pH 4 in an aqueous medium to form an anionic dissociation of an acidic functional group or anionic group. 这些基团的例子是羟基磺酰基(-SO3H)、羧基(COOH)和羟基磺酰氧基(-O-SO3H)以及这些基团的阴离子。 Examples of such groups are anionic hydroxy sulfonyl (-SO3H), carboxyl (COOH) and hydroxy-sulfonyloxy group (-O-SO3H) and these groups. 这些阴离子/酸性基团可以连接到基团A和/或染料分子的其它部分上。 These anionic / acidic groups may be attached to other portions of the group A and / or dye molecules. 当这些基团作为阴离子基团存在于染料F中时,可以意识到染料还包含中和所必需的抗衡离子。 When these groups are present as anionic groups in the dye F may be appreciated further comprising a dye and counter ion necessary. 合适的抗衡离子特别是碱金属离子,尤其是钠、钾和锂离子,以及铵离子,例如源自单-、二-或三乙醇胺的铵离子。 Suitable counter ions, particularly alkali metal ions, especially sodium, potassium and lithium ions, and ammonium ions, for example, from mono -, di - or triethanolamine ammonium ion.

[0031] 还可以使用前述染料F的金属络合物,优选过渡金属络合物,尤其是元素周期表第6至10族的过渡金属的络合物,且特别是Cu、Cr、Fe、Ni、Co、Mn、Zn和Cd的络合物进行本发明的方法。 [0031] The metal complex may also be used in the dye F, preferably transition metal complexes, especially complexes of a transition metal of periodic table group 6 to 10, and in particular Cu, Cr, Fe, Ni , Co, Mn, Zn and Cd complex method of the present invention. 这些金属络合物中过渡金属与染料分子的摩尔比通常为2 : I至I : 2。 The molar ratio of metal complex dye molecules and a transition metal is generally 2: I to I: 2. 一般而言,在这些染料中,金属离子不是经由前述阴离子基团络合,而是经由去质子化的羟基、经由氨基、亚氨基、芳族η -电子体系中所含的氮原子、或经由偶氮基团络合。 Generally, these dyes, metal ions not complexed by the anionic group, but via deprotonated hydroxy, via the amino, imino, aromatic η - a nitrogen atom contained in the electronic system, or via a complex azo group.

[0032] 本发明的方法中典型的染料F选自下列染料种类:酞菁系列的染料、蒽醌染料、偶氮染料、甲月f染料、三苯基二噁嗪染料和三芳基甲烷染料。 [0032] The method of the present invention typically dye F is selected from the following classes of dyes: phthalocyanine series dyes, anthraquinone dyes, azo dyes, formazan f dyes, triphenylmethane dyes, and dioxazine triarylmethane dyes.

[0033] 这种染料F部分可从现有技术中获知,例如,WO 94/18381、EP-A356931、EP-A559617、EP-A 201868、DE-A 19523245、DE-A 19731166、EP 745640、EP-A 889098、EP-A1097971、EP-A 880098,或可以类似地通过已知的制造结构相似的染料的方法制成,这些方法可从此处所列的现有技术以及EP 602562, EP-A 597411, EP-A 592105或DE 4319674中获知。 [0033] Such a dye portion F is known from the prior art, e.g., WO 94/18381, EP-A356931, EP-A559617, EP-A 201868, DE-A 19523245, DE-A 19731166, EP 745640, EP -A 889098, EP-A1097971, EP-a 880098, or the like can be known by a similar method for manufacturing structure of the dye formed, the prior art methods can herein and those listed in EP 602562, EP-a 597411 , EP-A 592105 or DE 4319674 are known.

[0034] 通常以传统的方式通过使式B的氨基化合物与包含可亲核置换基团的染料中间体反应来制备染料F : [0034] Generally in a conventional manner by reacting an amino compound of Formula B to prepare a dye comprising a dye intermediate F reaction nucleophilically displaceable group:

[0035] [0035]

[0036] 可亲核置换基团的例子是卤素,尤其是氯或溴,其如在卤代三嗪中那样连接到芳族部分上,或以卤磺酰基或卤羰基的形式存在。 [0036] Examples of nucleophilically displaceable groups are halogen, especially chlorine or bromine, which is connected as a halogenated triazine as to an aromatic moiety, or a sulfonyl halide in the form of a carbonyl group or a halogen group. 用于此目的的方法是此处所列的现有技术中已知的或可以类似地用于染料F的制备。 The method used for this purpose are listed here in the prior art are known or can be prepared analogously for F dye. 或者,也可以首先将氨基化合物B重氮化,然后偶联到合适的染料中间体上。 Alternatively, the amino compound B is first diazotized and then coupled to a suitable dye intermediates. 氨基化合物B或其重氮盐与染料中间体反应时获得的反应产物可以已经是染料F,或构成染料F中间体,与已知方法类似地将该中间体进一步加工成染料F。 Amino compound B or a reaction product obtained when the reaction dye intermediate diazonium salt with a dye F may already be, or forming dye intermediate F, analogously to known processes and further processed to the dye intermediate F.

[0037] 容易理解的是,在本发明的方法中可以使用染料混合物和纯净染料。 [0037] readily understood that a mixture of dyes can be used in the process and purity of the dye of the present invention. 在皮革上的染色以及前述高坚牢度还必须符合对染色质量的要求,例如渗透性、色调、清洁度、均染性、受损粒的隐匿以及肉面与粒面之间的色调相等度。 Dyeing fastness and high in the leather must also meet the requirements for the quality of the dyeing, e.g. of equal hue between permeability, color, cleanliness, leveling property, and damage to meat particles privileged grain surface . 本发明的发明人根据自己的经验获知,考虑到整体上的性能状况,优选使用染料混合物。 The inventors of the present invention according to their own experience to know, taking into account the performance of the overall situation, it is preferable to use the dye mixture.

[0038] 染料混合物在此不仅指各种染料F的掺混物,还指F染料的合成混合物。 [0038] The dye mixtures herein refers not only to blend various dyes F, and also refers to the synthesis mixture F dyes. 基于染料中的着色有机化学残基,F染料在这些混合物中的比例优选不低于70重量%,尤其不低于90重量%,更优选不低于99重量%。 Dye-based coloring organic chemical residues, the proportion of these dyes F in the mixture is preferably not less than 70% by weight, in particular not less than 90 wt%, more preferably not less than 99 wt%. 除了F染料,本发明的方法中使用的染料混合物可以包含不含基团A的皮革用传统染料。 In addition to F dye, a dye mixture used in the method of the present invention may comprise free leather group A conventional dye. 基于染料中的着色有机化学残基,这些染料的比例通常低于30重量%,尤其低于10重量%,特别是不超过5重量%。 Dye-based coloring organic chemical residues, the proportion of these dyes is generally less than 30 wt%, in particular less than 10% by weight, in particular not more than 5 wt%.

[0039] 当F染料是具有类似色调的F染料的混合物时,每种染料的量通常不低于混合物中染料F总量的10摩尔%,尤其不低于20摩尔%。 [0039] When F is the dye mixture F having a similar hue dye, the amount of each dye is usually not less than 10 mol% of the total dye mixture F, in particular not less than 20 mol%. 其中优选两种染料F的混合物,每种组分具有9 : I至I : 9、尤其是2 : 8至8 : 2的摩尔比。 Preferably wherein the mixture of the two dyes F, each component having a 9: I to I: 9, in particular 2: 1 molar ratio of 2: 8-8.

[0040]同样有用的是具有不同色调的F染料的染料混合物。 [0040] Also useful are dyes a dye mixture F having a different hue. 其一个具体实施方式是例如黑色染料与不同颜色的染料(例如与红色、绿色或蓝色染料)的染料调色。 A specific embodiment thereof is, for example black dyes and dyes of different colors (e.g. red, green or blue dye) toner dye. 当染料与用于调色的一种或多种其它染料混合时,基于染料中的着色有机化学残基,调色染料的量通常为O. I至15摩尔%。 When the dye with one or more of the toner for mixing other dyes, dye-based coloring organic chemical residues, an amount of toner dye is generally O. I to 15 mol%. 另一具体实施方式包括公知的用于三色染色的染料混合物。 Another specific embodiment include well-known dye mixtures for the trichromatic dyeing. 用于三色染色的染料混合物包括3种或多种具有不同色调的染料F。 For trichromatic dyeing dye mixture comprising three or more dyes having different color tones F. 在这种情况下,每种组分通常占混合物中染料F总量的不低于I摩尔%,尤其不低于5摩尔%,例如5至90摩尔%。 In this case, each component generally comprises not less than I mole% of the dye mixture F, in particular not less than 5 mol%, for example 5 to 90 mol%.

[0041] 必须记住,染料可以根据它们的制造方法包含无机盐以及标准剂(standardize!·)。 [0041] It must be remembered, and the dye may comprise an inorganic salt thereof according to the standard method of producing agent (standardize! ·). 这些组分(下文也被称作非着色组分)的分数通常不超过染料的着色和非着色组分总重量的60重量%,并通常为10重量%至50重量%。 The fraction of these components (hereinafter also referred to as a non-colored component) is typically not more than 60 and the weight of the total weight of the colored, non-colored dye component%, and typically 10% by weight to 50% by weight.

[0042] 在本发明的优选具体实施方式中,染料F是偶氮染料,并优选为选自通式I至XV的染料和它们的络合物的偶氮染料: [0042] In a preferred embodiment of the present invention, the azo dye is F, and is preferably selected from the formulas I to XV azo dyes and their complexes:

[0043] Dk1-N = N - [PN = N-IpKk1L-N = N-Dk2] m [0043] Dk1-N = N - [PN = N-IpKk1L-N = N-Dk2] m

(I) (I)

[0044] Dk1-N = N-Napht1 [-N = N-Tk1] r[-N = N-Kk1JJ-N = N-Dk2] n [0044] Dk1-N = N-Napht1 [-N = N-Tk1] r [-N = N-Kk1JJ-N = N-Dk2] n

(II)· (II) ·

[0045] Dk1-N = N-Napht1-N = N-Tk1-N = N-Kk1-N = N-Tk2-N = N-Napht2-N = N-Dk2 [0045] Dk1-N = N-Napht1-N = N-Tk1-N = N-Kk1-N = N-Tk2-N = N-Napht2-N = N-Dk2

(III) (III)

[0046] Dk1-N = N-Kk1-N = N-Tk1-N = N-Kk2-N = N-Dk2 [0046] Dk1-N = N-Kk1-N = N-Tk1-N = N-Kk2-N = N-Dk2

(IV) (IV)

[0047] Dk1-N = N- [PN = N - ] pN aph t1 [ - N = NR] ,-NH-Tr1-NH-Dk2 [0047] Dk1-N = N- [PN = N -] pN aph t1 [- N = NR], -NH-Tr1-NH-Dk2

(V) (V)

[0048] Dk1-N = NP-NH-Tr1-NH-RN = N-Dk2 [0048] Dk1-N = NP-NH-Tr1-NH-RN = N-Dk2

(VI) (VI)

[0049] Dk1-N = N-Napht1-N = N-Tk1-N = NP-NH-Tr1-NH-Dk2 [0049] Dk1-N = N-Napht1-N = N-Tk1-N = NP-NH-Tr1-NH-Dk2

(VII) (VII)

[0050] Dk1-N = N-Napht1-NH-Tr1-NH-P-NH-Tr2-NH-Napht2-N = N-Dk2 [0050] Dk1-N = N-Napht1-NH-Tr1-NH-P-NH-Tr2-NH-Napht2-N = N-Dk2

(VIII) (VIII)

[0051] Dk1-N = N-Napht1-NH-Tr1-NH-Tk1-NH-Tr2-NH-Napht2-N = N-Dk2 [0051] Dk1-N = N-Napht1-NH-Tr1-NH-Tk1-NH-Tr2-NH-Napht2-N = N-Dk2

(IX) (IX)

[0052] Dk1 [-N = N-LJk-NH-Tr1-NH-MN = N-Napht1-N = NP-NH-Tr2-NH-[RN = N-JnDk2 [0052] Dk1 [-N = N-LJk-NH-Tr1-NH-MN = N-Napht1-N = NP-NH-Tr2-NH- [RN = N-JnDk2

(X) (X)

[0053] Dk1-N = N-Kk1-N = N-Tk1-NH-Tr1-NH-Dk2 [0053] Dk1-N = N-Kk1-N = N-Tk1-NH-Tr1-NH-Dk2

(XI) (XI)

[0054] Dk1-N = N - [ P - N = N-JpR-N = N - K k 1 [- N = N-Dk2] n [0054] Dk1-N = N - [P - N = N-JpR-N = N - K k 1 [- N = N-Dk2] n

(XII) (XII)

[0055] Dk1-N = N-Pyr-A (XIII) [0055] Dk1-N = N-Pyr-A (XIII)

[0056] Kk3-N = N-Tk1-N = N-Kk1-N = NA (XIV) [0056] Kk3-N = N-Tk1-N = N-Kk1-N = NA (XIV)

[0057] Dk1-N = NPN = N-Kk1-N = NRN = N-Dk2 (XV) [0057] Dk1-N = NPN = N-Kk1-N = NRN = N-Dk2 (XV)

[0058]其中: [0058] wherein:

[0059] k、n、p和r独立地为O或1,条件是式II中k+n+r = 1、2或3 ; [0059] k, n, p and r are independently O or 1, with the proviso that in formula II k + n + r = 1,2 or 3;

[0060] m 是0、1 或2; [0060] m is 0, 1 or 2;

[0061] Dk1、Dk2独立地代表源自芳胺的基团或代表式A的基团,条件是在式I-XII和XV的每个式中,Dk1和Dk2至少一个代表式A的基团; [0061] Dk1, Dk2 independently represents a group or a group represented by the formula A is derived from an amine, with the proviso that in each of Formulas I-XII and XV Formula in, DK2 Dk1 and at least one representative of the group of formula A ;

[0062] Kk1、Kk2独立地代表单_、二-或三价芳基,其源自苯、萘、吡唑、喹啉、二苯胺、二苯基甲烷、嘧啶、吡啶或二苯醚,并且其可以任选包含一个或多个下列基团作为取代基:so3h、cooh、cn、conh2、oh、nh2、no2、卤素、C1-C4 烷基、C1-C4 羟烷基、羧基-C1-C4 烷基、C1-C4 烷氧基、C1-C4烷基氨基、C1-C4 二烷基氨基、C1-C4烷基氨基羰基X1-C4 二烷基氨基羰基、C1-C4烷基羰基氨基、N-(C1-C4基羰基)-“-(&-(;烷基羰基)氨基、C1-C4烷基氨基羰基氧基、C1-C4 二烷基氨基羰基氧基、C1-C4烷基氨基羰基氨基、C1-C4 二烷基氨基羰基氨基、苯基氨基羰基氧基、苯基氨基羰基氨基、C1-C4烷氧基羰基氨基、C1-C4羟基-C1-C4烷基氨基、羧基-C1-C4烷基氨基、苯基羰基氨基、C1-C4烷基磺酰基、C1-C4羟烷基磺酰基X1-C4烷基氨基磺酰基、C1-C4烷基磺酰基氨基、苯基磺酰基、苯基磺酰基氨基、甲酰胺、式SO2N [0062] Kk1, Kk2 _ independently represent mono, di - or trivalent aromatic radical which is derived from benzene, naphthalene, pyrazole, quinoline, diphenylamine, diphenylmethane, pyrimidine, pyridine or diphenyl ether, and which may optionally contain one or more of the following groups as substituents: so3h, cooh, cn, conh2, oh, nh2, no2, halogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, carboxy -C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, C1-C4 dialkylamino, C1-C4 alkylaminocarbonyl X1-C4 dialkylaminocarbonyl group, C1-C4 alkylcarbonylamino, N - (C1-C4-yl-carbonyl) - '- (& - (; alkylcarbonyl) amino, C1-C4 alkylaminocarbonyl group, C1-C4 dialkylamino, alkylcarbonyloxy, C1-C4 alkylaminocarbonyl amino, C1-C4 dialkylaminocarbonyl group, a phenylaminocarbonyl group, phenylaminocarbonyl group, C1-C4 alkoxycarbonyl group, C1-C4 hydroxy -C1-C4 alkylamino, carboxy -C1- C4 alkylamino, phenylcarbonylamino, C1-C4 alkylsulfonyl, C1-C4 hydroxyalkyl groups X1-C4 alkylsulfonyl alkylaminosulfonyl, C1-C4 alkylsulfonyl group, phenylsulfonyl, benzyl sulfonylamino group, carboxamide, of formula SO2N R56R57的基团,其中R56和R57独立地代表氢、C1-C4烷基、甲酰基、C1-C4烷基羰基、C1-C4烷氧基羰基、NH2-⑶或C1-C4烷基氨基·羰基、C1-C4烷基氨基磺酰基氨基、二-C1-C4烷基氨基磺酰基氨基、苯基磺酰基氨基——其可以在苯环上被一个或两个选自C1-C4烷基、C1-C4烷氧基或卤素的取代基取代、或任选被1、2或3个下列基团:0H、卤素、C1-C4烷基或苯基取代的5-或6-元杂环基、任选在氮上含有苯基或萘基的5-元芳族杂环基一其可以任选包含一个或两个下列基团:0H、SO3H, C1-C4烷基和/或C1-C4烷氧基; Group R56R57, wherein R56 and R57 independently represent hydrogen, C1-C4 alkyl, formyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, NH2-⑶ amino or C1-C4 alkyl-carbonyl , C1-C4 alkylaminosulfonyl group, di -C1-C4 alkylaminosulfonyl group, phenylsulfonyl group - which may be substituted with one or two on the phenyl ring selected from C1-C4 alkyl, C1 -C4 alkoxy or halogen substituents, or optionally 1, 2 or 3 of the following groups: 0H, halogen, C1-C4 alkyl or phenyl-substituted 5- or 6-membered heterocyclic group, phenyl or naphthyl group optionally containing a nitrogen in the 5-membered aromatic heterocyclic group which may optionally comprise a one or two of the following radicals: 0H, SO3H, C1-C4 alkyl and / or C1-C4 alkyl group;

[0063] Kk3是源自苯、嘧啶、吡啶或萘的一价基团,其任选包含I或2个羟基磺酰基并任选包含1、2或3个选自下列基团的其它取代基:S03H、C00H、CN、CONH2、0H、NH2、NO2、卤素、C1-C4烷基、C1-C4羟烷基、羧基-C1-C4烷基、C1-C4烷氧基、C1-C4烷基氨基、C1-C4 二烷基氨基、C1-C4烷基氨基羰基X1-C4 二烷基氨基羰基、C1-C4烷基羰基氨基、N- (C1-C4烷基羰基)-N- (C1-C4烷基羰基)氨基、C1-C4烷基氨基羰基氧基、C1-C4 二烷基氨基羰基氧基、C1-C4烷基氨基羰基氨基、C1-C4 二烷基氨基羰基氨基、苯基氨基羰基氧基、苯基氨基羰基氨基、C1-C4烷氧基羰基氨基、C1-C4羟基-C1-C4烷基氨基、羧基-C1-C4烷基氨基、苯基羰基氨基、C1-C4烷基磺酰基、C1-C4羟烷基磺酰基、C1-C4烷基磺酰基氨基、苯基磺酰基、苯基磺酰基氨基、甲酰胺、式SO2NR56R57的基团,其中R56和R57独立地代表氢X1-C4烷基、甲酰基X1-C4烷基羰基 [0063] Kk3 is derived from benzene, pyrimidine, pyridine or naphthalene monovalent radical, optionally containing I or 2 hydroxyl group and optionally further substituted sulfonyl group containing 1, 2 or 3 substituents selected from the group consisting of : S03H, C00H, CN, CONH2,0H, NH2, NO2, halogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, carboxy -C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkyl group amino, C1-C4 dialkylamino, C1-C4 alkylaminocarbonyl X1-C4 dialkylaminocarbonyl group, C1-C4 alkylcarbonylamino, N- (C1-C4 alkyl-carbonyl) -N- (C1- C4 alkylcarbonyl) amino, C1-C4 alkylaminocarbonyl group, C1-C4 dialkylamino, alkylcarbonyloxy, C1-C4 alkylaminocarbonyl group, C1-C4 dialkylaminocarbonyl group, phenylamino carbonyl group, phenylaminocarbonyl group, C1-C4 alkoxycarbonyl group, C1-C4 hydroxy -C1-C4 alkylamino, carboxy -C1-C4 alkylamino, phenylcarbonylamino, C1-C4 alkyl group sulfonyl, C1-C4 hydroxyalkyl alkylsulfonyl, C1-C4 alkylsulfonylamino, phenylsulfonyl, phenylsulfonylamino, formamide, a group of the formula SO2NR56R57, wherein R56 and R57 independently represent hydrogen X1 -C4 alkyl, formyl X1-C4 alkylcarbonyl 、C1-C4烷氧基羰基、NH2-CO或C1-C4烷基氨基羰基、C1-C4烷基氨基磺酰基氨基、二-C1-C4烷基氨基磺酰基氨基、苯基磺酰基氨基一其可以在苯环上被一个或两个选自C1-C4烷基、C1-C4烷氧基或卤素的取代基取代、或任选被1、2或3个下列基团:0H、卤素、C1-C4烷基或苯基取代的5-或6-元杂环基、任选在氮上含有苯基或萘基的5-元芳族杂环基一其可以任选包含一个或两个下列基团:0H、S03H、C1-C4烧基和/或C1-C4烧氧基; , C1-C4 alkoxycarbonyl, NH2-CO or C1-C4 alkylaminocarbonyl, C1-C4 alkylaminosulfonyl group, di -C1-C4 alkylaminosulfonyl group, a phenylsulfonyl group which on the phenyl ring may be substituted with one or two substituents selected from C1-C4 alkyl, C1-C4 alkoxy or halogen, or optionally substituted by 1, 2 or 3 of the following groups: 0H, halogen, a C1 -C4 alkyl or phenyl-substituted 5- or 6-membered heterocyclic group, optionally substituted on the nitrogen a phenyl or naphthyl group, a 5-membered aromatic heterocyclic group which may optionally comprise a one or two of the following group: 0H, S03H, C1-C4 group, and burn / burn or C1-C4 alkoxy;

[0064] Tk1, Tk2独立地代表二价芳基,其源自苯、二苯胺、联苯、二苯基甲烷、2-苯基苯并咪唑、苯基磺酰基苯、苯基氨基磺酰基苯、均二苯代乙烯或苯基氨基羰基苯,它们各自任选包含一个或多个下列基团作为取代基:so3H、cooh, OH、NH2, NO2,齒素、C1-C4烷基; [0064] Tk1, Tk2 independently represents a divalent aromatic group derived from benzene, diphenylamine, biphenyl, diphenylmethane, 2-phenyl-benzimidazole, benzene phenylsulfonyl, phenylamino-benzene , stilbene phenyl or phenyl aminocarbonyl, each of which optionally contain one or more of the following groups as substituents: so3H, cooh, OH, NH2, NO2, teeth prime, C1-C4 alkyl;

[0065] L、M、P和R独立地代表源自苯或萘的二价芳基,它们各自可任选包含一个或多个,例如,1、2、3、4或5个下列基团作为取代基:S03H、C00H、CN、CONH2、0H、NH2、NO2、卤素、C1-C4烷基、C1-C4羟烷基、羧基-C1-C4烷基、C1-C4烷氧基X1-C4烷基氨基、C1-C4 二烷基氨基、C1-C4烷基氨基羰基、C1-C4 二烷基氨基羰基、C1-C4烷基羰基氨基、N- (C1-C4烷基羰基)-N- (C1-C4烷基羰基)氨基、C1-C4烷基氨基羰基氧基、C1-C4 二烷基氨基羰基氧基X1-C4烷基氨基羰基氨基、C1-C4 二烷基氨基羰基氨基、苯基氨基羰基氧基、苯基氨基羰基氨基、C1-C4烷氧基羰基氨基、C1-C4羟基-C1-C4烷基氨基、羧基-C1-C4烷基氨基、苯基羰基氨基、C1-C4烷基磺酰基、C1-C4烷基氨基磺酰基、C1-C4-烷基磺酰基、C1-C4烷基磺酰基氨基、苯基磺酰基、苯基磺酰基氨基、甲酰胺、式SO2NR56R57的基团,其中R56和R57独立地代表氢'C1-C4烷基 [0065] L, M, P and R independently represents a benzene or naphthalene derived from a divalent aromatic group, each of which may optionally contain one or more, e.g., 4 or 5 of the following groups as the substituent group: S03H, C00H, CN, CONH2,0H, NH2, NO2, halogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, carboxy -C1-C4 alkyl, C1-C4 alkoxy X1-C4 alkylamino, C1-C4 dialkylamino, C1-C4 alkylaminocarbonyl, C1-C4 dialkylaminocarbonyl group, C1-C4 alkylcarbonylamino, N- (C1-C4 alkyl-carbonyl) -N- (C1-C4 alkyl) amino group, C1-C4 alkylaminocarbonyl group, C1-C4 dialkylamino carbonyl group X1-C4 alkylaminocarbonyl group, C1-C4 dialkylaminocarbonyl group, phenyl aminocarbonyl group, a phenylaminocarbonyl group, C1-C4 alkoxycarbonyl group, C1-C4 hydroxy -C1-C4 alkylamino, carboxy -C1-C4 alkylamino, phenylcarbonylamino, C1-C4 alkylsulfonyl, C1-C4 alkylaminosulfonyl, C1-C4- alkylsulfonyl, C1-C4 alkylsulfonylamino, phenylsulfonyl, phenylsulfonylamino, formamide, a radical of formula SO2NR56R57 group, wherein R56 and R57 independently represent hydrogen 'C1-C4 alkyl group 、甲酰基X1-C4烷基羰基、C1-C4烷氧基羰基、NH2-CO或C1-C4烷基氨基羰基、C1-C4烷基氨基磺酰基氨基、二-C1-C4烷基氨基磺酰基氨基、苯基磺酰基氨基——其可以在苯环上被一个或两个选自C1-C4烷基、C1-C4烷氧基或卤素的取代基取代、或任选被1、2或3个下列基团:0H、卤素、C1-C4烷基或苯基取代的5-或6-元杂环基、任选在氮上含有苯基或萘基的5-元芳族杂环基一其可以任选包含一个或两个下列基团:0H、SO3H, C1-C4烷基和/或C1-C4烷氧基; , Formyl X1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, NH2-CO or C1-C4 alkylaminocarbonyl, C1-C4 alkylaminosulfonyl group, di -C1-C4 alkylaminosulfonyl amino, phenylsulfonylamino - which may be substituted with one or two on the phenyl ring selected from C1-C4 alkyl, C1-C4 alkoxy or halogen substituents, or optionally substituted by 1, 2 or 3 one of the following groups: 0H, halogen, C1-C4 alkyl or phenyl-substituted 5- or 6-membered heterocyclic group, optionally substituted 5-membered aromatic heterocyclic group containing a phenyl or naphthyl group on the nitrogen which may optionally contain one or two of the following radicals: 0H, SO3H, C1-C4 alkyl and / or C1-C4 alkoxy;

[0066] Napht1, Napht2独立地代表源自萘的二价基团,其包含I或2个羟基磺酰基,并可·以任选包含1、2或3个选自下列基团的其它取代基:0H、NH2, C1-C4烷基氨基、C1-C4 二烷基氨基、C1-C4烷基磺酰基氨基、苯基磺酰基氨基、4-甲基苯基磺酰基氨基X1-C4烷基氨基磺酰基、二-C1-C4烷基氨基磺酰基、苯基氨基磺酰基、4-甲基苯基氨基磺酰基和NHC(O)Rx基团,其中Rx是氢、C1-C4烷基、马来酰基或苯基; [0066] Napht1, Napht2 independently represents a divalent group derived from naphthalene, comprising I or 2 hydroxyl sulfonyl group, and can optionally comprise other · to group 1, 2 or 3 substituents selected from the group consisting of : 0H, NH2, C1-C4 alkylamino, C1-C4 dialkylamino, C1-C4 alkylsulfonylamino, phenylsulfonylamino, 4-methylphenyl sulfonylamino X1-C4 alkylamino sulfonyl, di -C1-C4 alkylaminosulfonyl group, aminosulfonyl phenyl, 4-methylphenyl group, and a sulfamoyl NHC (O) Rx groups wherein Rx is hydrogen, C1-C4 alkyl, MA to an acyl group or a phenyl group;

[0067] Pyr代表吡唑-I,4-二基,其通过氮原子连接到A基团上,并任选包含I或2个选自卤素、C1-C4烷基、羟基或C1-C4烷氧基的取代基; [0067] Pyr Representative pyrazole -I, 4- diyl, which is connected to the A radical through a nitrogen atom, and optionally comprising I or 2 substituents selected from halogen, C1-C4 alkyl, hydroxy or C1-C4 alkyl alkoxy substituents;

[0068] Tr1, Tr2独立地代表I,3,5-三嗪-2,4-二基,其任选进一步含有卤素原子、甲基、或甲氧基作为取代基。 [0068] Tr1, Tr2 independently represent I, 3,5- triazine-2,4-diyl, which optionally further contain a halogen atom, a methyl group or a methoxy group as a substituent.

[0069] 此处和下文中,C1-C4烷基(以及C1-C4烷氧基X1-C4烷基氨基、二-C1-C4烷基氨基、C1-C4烷基磺酰基、C1-C4羟烷基磺酰基X1-C4烷基氨基磺酰基、C1-C4烷基氨基羰基、二-C1-C4烷基氨基磺酰基、二-C1-C4烷基氨基羰基和C1-C4烷基羰基氨基等基团中的烷基部分)是指直链或支链脂族烃基,例如甲基、乙基、正丙基、异丙基、正丁基等基团。 [0069] Here and hereinbelow, C1-C4 alkyl (C1-C4 alkoxy group, and X1-C4 alkylamino, di -C1-C4 alkylamino, C1-C4 alkylsulfonyl, C1-C4 hydroxyalkyl X1-C4 alkylsulfonyl alkylaminosulfonyl, C1-C4 alkylaminocarbonyl, di -C1-C4 alkylaminosulfonyl, di -C1-C4 alkylaminocarbonyl and C1-C4 alkylcarbonylamino, etc. in the alkyl moiety) refers to a straight or branched chain aliphatic hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl group.

[0070] C1-C4羟烷基是指含有OH基团的C1-C4烷基,例如2-羟乙基。 [0070] C1-C4 hydroxyalkyl refers to a C1-C4 alkyl containing OH groups, such as 2-hydroxyethyl. 相应地,C1-C4羟烷基氨基是指在烷基中含有OH基团的C1-C4烷基氨基,例如2-羟乙基氨基。 Accordingly, C1-C4 hydroxy alkyl amino means a C1-C4 alkylamino OH group in the alkyl group, such as 2-hydroxyethyl group.

[0071] C1-C4羧基烷基代表含有羧基(C00H基团)的C1-C4烷基,例如羧甲基(CH2COOH)和 [0071] C1-C4 alkyl represents carboxy C1-C4 alkyl containing a carboxyl group (C00 H group), for example, carboxymethyl (CH2COOH) and

2-羧乙基(CH2CH2COOH)。 2-carboxyethyl (CH2CH2COOH). 相应地,C1-C4羧基烷基氨基是指在烷基部分含有羧基(C00H基团)的C1-C4烷基氨基,例如羧甲基氨基(NH-CH2COOH)和2-羧乙基氨基(NH-CH2CH2C00H)。 Accordingly, C1-C4 carboxyalkyl group means the alkyl portion contains a carboxyl group (C00 H group) C1-C4 alkyl group, such as carboxymethyl amino (NH-CH2COOH), and 2-carboxyethyl amino (NH -CH2CH2C00H).

[0072] 5-或6-元杂环基通常包含I、2或3个选自氮、氧和硫的杂原子、尤其是I或2个氮原子和任选地氧或硫原子作为环组元,并可以是饱和、不饱和或芳族的。 [0072] 5- or 6-membered heterocyclic groups typically contain I, 2 or 3 hetero atoms selected from nitrogen, oxygen and sulfur, especially I or 2 nitrogen atoms and optionally an oxygen or sulfur atom as a ring group membered and may be saturated, unsaturated or aromatic. 饱和杂环基的例子是吗啉基、哌啶基、哌嗪基和吡咯烷基。 Examples of saturated heterocyclyl groups are morpholinyl, piperidinyl, piperazinyl and pyrrolidinyl. 芳族杂环基的例子是吡啶基、吡咯基、噁唑基、噻唑基等等。 Examples of aromatic heterocyclic groups are pyridyl, pyrrolyl, oxazolyl, thiazolyl and the like.

[0073] 式I至XV的染料可以游离形式、其盐形式使用,并且当通过重氮基-N = N-连接在一起的两个基团各自包含位于重氮基邻位的OH、COOH或NH2基团时,作为金属络合物使用。 [0073] Formula I to XV of the dye may be in free form, salt form thereof, and when the two groups are linked together via diazo each comprising -N = N- OH group located ortho to the diazo, COOH or when NH2 group using metal complex.

[0074] 式I至XIII和XV的染料中基团DK1和DK2分别来自芳胺DK1-NH2和DK2-NH2,下文也被称作重氮鎗组分。 [0074] Formula I to XIII and XV of the dye groups DK1 and DK2 are from aromatic amines and DK1-NH2 DK2-NH2, hereinafter also referred to as the diazo component gun. 胺DK1-NH2和DK2-NH2通常为任选取代的苯胺、任选取代的α -或β -萘胺或任选取代的氨基喹啉。 DK1-NH2 amine, and generally DK2-NH2 optionally substituted aniline, optionally substituted α - or β - naphthylamine or optionally substituted amino quinoline. 相应地,基团DK1和DK2通常为独立地源自苯、萘或喹啉的基团,其中萘、喹啉和苯任选包含一个或多个,例如1、2或3个取代基。 Accordingly, DK1 and DK2 groups typically are independently derived from benzene, naphthalene or quinoline radical, wherein naphthalene, quinoline and benzene optionally comprise one or more, for example 1, 2 or 3 substituents. 取代基的例子为下列基团:S03H、COOH, OH、NH2, NO2, CN、CONH2,卤素、C「C4 烷基、C1-C4 羟烷基、羧基-C1-C4 烷基、C1-C4烷氧基、C1-C4烷基氨基、C1-C4 二烷基氨基、C1-C4烷基氨基羰基、C1-C4 二烷基氨基羰基、C1-C4烷基氨基羰基氧基、C1-C4 二烷基氨基羰基氧基、C1-C4烷基氨基羰基氨基、C1-C4二烷基氨基羰基氨基、苯基氨基羰基氧基、苯基氨基羰基氨基、C1-C4烷氧基羰基氨基、C1-C4烷基羰基氨基、N- (C1-C4烷基羰基)-N- (C1-C4烷基羰基)氨基、C1-C4羟基-C1-C4烷基氨基、羧基-C1-C4烷基氨基、苯基羰基氨基、C1-C4烷基磺酰基、C1-C4羟烷基磺酰基、C1-C4烷基氨基磺酰基、C1-C4烷基磺酰基氨基、苯基磺酰基、苯基磺酰基氨基、甲酰胺、SO2NR56R57,其中R56和R57独立地代表氢X1-C4烷基、甲酰基X1-C4烷基羰基、C1-C4烷氧基羰基、NH2-COX1-C4烷基氨基羰基、或任选被1、2或3个下列基团:0H、齒素、C1-C4 Examples of the substituent of the following groups: S03H, COOH, OH, NH2, NO2, CN, CONH2, halo, C "C4 alkyl, C1-C4 hydroxyalkyl, carboxy -C1-C4 alkyl, C1-C4 alkyl alkoxy, C1-C4 alkylamino, C1-C4 dialkylamino, C1-C4 alkylaminocarbonyl, C1-C4 dialkylaminocarbonyl group, C1-C4 alkylaminocarbonyl group, C1-C4 dioxane aminocarbonyl group, C1-C4 alkylaminocarbonyl group, C1-C4 dialkylaminocarbonyl group, a phenylaminocarbonyl group, phenylaminocarbonyl group, C1-C4 alkoxycarbonyl group, C1-C4 alkylcarbonylamino, N- (C1-C4 alkyl-carbonyl) -N- (C1-C4 alkyl) amino group, C1-C4 hydroxy -C1-C4 alkylamino, carboxy -C1-C4 alkylamino, phenyl arylcarbonylamino, C1-C4 alkylsulfonyl, C1-C4 hydroxyalkyl alkylsulfonyl, C1-C4 alkylaminosulfonyl, C1-C4 alkylsulfonylamino, phenylsulfonyl, phenylsulfonylamino, carboxamide, SO2NR56R57, wherein R56 and R57 independently represent hydrogen X1-C4 alkyl, formyl X1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, NH2-COX1-C4 alkylaminocarbonyl group, or optionally two or three of the following groups: 0H, teeth prime, C1-C4 烷基或苯基取代的5-或6-元杂环基、任选在氮上含有苯基或萘基的5-元芳族杂环基一其可以任选包含一个或两个下列基团:0H、S03H、C1-C4烧基、和/或C1-C4烧氧基; Alkyl or phenyl-substituted 5- or 6-membered heterocyclic group, optionally containing a phenyl or naphthyl group on the nitrogen in the 5-membered aromatic heterocyclic group which may optionally comprise a one or two of the following radicals : 0H, S03H, C1-C4 group burning and / or burn C1-C4 alkoxy;

[0075] 可用的胺DK1-NH2和DK2-NH2进一步包括4_氨基_1_苯基吡唑,其中吡唑环以及苯·基环含有一个或多个,例如1、2或3个前述类型的取代基或B-SO2-基团,其中B定义如上。 [0075] Useful amines DK1-NH2 and further comprising DK2-NH2 4_ amino _1_ phenylpyrazole, wherein cycloalkyl and phenyl-pyrazole rings contain one or more, for example 1, 2 or 3 of the aforementioned type substituents or a group B-SO2-, wherein B is as defined above. 在这些情况下,Dk1或DK2特别代表吡唑-4-基,其在位置I含有苯基或式A的基团,并任选含有I或2个选自卤素、C1-C4烷基、羟基、C00H、羟基磺酰基或C1-C4烷氧基的取代基。 In these cases, the Special Representative Dk1 or DK2-pyrazol-4-yl, in which position I contains a phenyl group or the formula A, and optionally comprising I or 2 substituents selected from halogen, C1-C4 alkyl, hydroxy , C00H, hydroxysulfonyl or C1-C4 alkoxy substituents.

[0076] 优选地,Dk1或DK2独立地为源自任选取代的苯胺、任选取代的α -或β -萘胺的基团,或独立地为A基团。 [0076] Preferably, DK2 Dk1 or independently from an optionally substituted aniline, optionally substituted α - or β - naphthyl amine group, or A is a group independently.

[0077] 合适的胺DK1-NH2和DK2-NH2的例子是下示化合物DKl至DK39 : [0077] Suitable examples DK1-NH2 amine and DK2-NH2 is a compound shown below to DKl DK39:

[0078] [0078]

[0081] 式DK21至DK25中的Q基团表示氢、C1-C4烷基、羧基-C1-C4烷基、C1-C4羟烷基、C1-C4烷氧基或苯基羰基。 [0081] Formula DK21 through DK25 Q is a group represented by hydrogen, C1-C4 alkyl, carboxy -C1-C4 alkyl, C1-C4 hydroxyalkyl, C1-C4 alkoxy group or a phenylcarbonyl group.

[0082] 合适的重氮组分进一步包括下文所示的萘胺DK40至59 :4_氨基_3_羟基萘-I磺酸(DK40)、4_氨基-3-羟基-6-硝基萘-I-磺酸(DK41)、6_氨基-4-羟基萘_2_磺酸(Y酸,DK42)、4_氨基-5-羟基萘-I-磺酸(Chicago S酸,DK43)、4_氨基-5-羟基萘-2,7- 二磺酸(H酸DK44)、4_氨基-5-羟基萘-1,7- 二磺酸(K酸,DK45)、8_氨基萘-2-磺酸(克列氏酸7,DK46)、6_氨基萘-I-磺酸(D酸,DK47)、4_氨基萘-2,7-磺酸(DK48)、5_氨基萘-2-磺酸(01(49)、7-氨基-4,8-二羟基萘-2-磺酸(DK50)、2_氨基-5-羟基萘-1,7-二磺酸(DK51)、3-氨基-5-羟基萘-2,7-二磺酸(DK52)、3_ 氨基-1,5-二磺酸(DK53)、 [0082] Suitable diazo components further comprises naphthylamine DK40 to 59 shown below: 4_ _3_ hydroxynaphthalene amino acid -I (DK40), 4_ amino-3-hydroxy-6-nitronaphthalene -I- acid (DK41), 6_-amino-4-hydroxy-naphthalene sulfonic acid _2_ (Y acids, DK42), 4_ -I- amino-5-hydroxy-naphthalene sulfonic acid (Chicago S acid, DK43), 4_-amino-5-hydroxy-naphthalene-2,7-disulfonic acid (H acid DK44), 4_-amino-5-hydroxynaphthalene-1,7-disulfonic acid (K acid, DK45), 8_ aminonaphthalene - 2-sulfonic acid (Cleve's acid 7, DK46), 6_ aminonaphthalene -I- acid (D acid, DK47), 4_ amino acid naphthalene-2,7 (DK48), 5_ aminonaphthalene - 2-sulfonic acid (01 (49), 7-amino-4,8-dihydroxy-naphthalene-2-sulfonic acid (DK50), 2_-amino-5-hydroxynaphthalene-1,7-disulfonic acid (DK51), 3-amino-5-hydroxy-naphthalene-2,7-disulfonic acid (DK52), 3_-amino-1,5-disulfonic acid (DK53),

7-氨基萘-I-磺酸(DK54)、4-氨基萘-I-磺酸(DK55)、5-氨基萘-I-磺酸(DK56)、7_氨基萘-I,3,5-三磺酸(DK57)、4-氨基-3-羟基-7-[(4-甲基苯基)磺酰基氨基]-萘_1_磺酸(DK58)和7-氨基-4-羟基萘-2-磺酸(J酸,DK59)。 7-amino-naphthalene sulfonic acid -I- (DK54), 4- amino-naphthalene-sulfonic acid -I- (DK55), 5- aminonaphthalene -I- acid (DK56), 7_ aminonaphthalene -I, 3,5- trisulfonate (DK57), 4- amino-3-hydroxy-7 - [(4-methylphenyl) sulfonylamino] - naphthalene sulfonic acid _1_ (DK58) and 7-amino-4-hydroxy-naphthalene - 2-sulfonic acid (J acid, DK59).

[0083] 合适的单胺DK1-NH2和DK2-NH2的例子是下示化合物DK60至DK83 : [0083] Suitable examples of monoamine DK1-NH2 and DK2-NH2 is a compound shown below DK60 to DK83:

[0084] [0084]

[0085] [0085]

[0086] 作为Kk1和Kk2基团,原则上可以使用所有单_、二-或三价基团,作为Kk3基团,可以使用源自任选取代的苯、萘、吡唑、二苯胺、二苯基甲烷、吡啶、嘧啶或二苯醚的所有单价芳基,它们各自留有1、2或3个自由位置,在这些位置上重氮鎗化合物可以相继偶联一次、两次或三次。 [0086] As Kk1 Kk2 groups and can be used in principle all single _, di - or trivalent group, as Kk3 group may be derived from the use of optionally substituted benzene, naphthalene, pyrazole, diphenylamine, diphenylmethane, pyridine, pyrimidine or diphenyl ether of all monovalent aryl groups, each consisting of two or three left position, these positions can be sequentially coupling the diazonium compound of the gun once, twice or three times. Kk1、Kk2和Kk3基团所代表的化合物在下文也被称作偶联组分。 Compound Kk1, Kk2 and Kk3 group represented hereinafter also referred to as coupling component.

[0087] 合适的偶联组分是例如源自苯的通式Kk-A的化合物、源自萘的式Kk-B的化合物、源自喹啉的式Kk-C的化合物、源自吡唑的式Kk-D的化合物、源自二苯基甲烷的式Kk-E的化合物、源自二苯胺的式Kk-F的化合物、源自吡啶的式Kk-G的化合物和源自吡啶酮的式Kk-H的化合物: [0087] Suitable coupling components are, for example, a compound derived from benzene of formula Kk-A, a compound derived from a naphthalene of formula Kk-B, the compound of formula quinoline from Kk-C is derived from pyrazole compound of the formula Kk-D, a compound derived from a diphenylmethane of formula Kk-E, the compound derived from diphenylamine of the formula Kk-F, pyridine derived compound of formula Kk-G, and derived from pyridone Kk-H compound of formula:

[0088] [0088]

[0089] 在式Kk-A中,R11代表NH2WHX1-C4烷氧基X1-C4烷基氨基、二-C1-C4烷基氨基、羟基-C1-C4烷基氨基、羧基-C1-C4烷基氨基、C1-C4烷基羰基氨基或苯基氨基,R12代表氢、NH2、OH、C1-C4烷氧基、羟基-C1-C4烷基氨基、羧基-C1-C4烷基氨基、C1-C4烷基氨基、二-C1-C4烷基氨基且R13代表氢、C1-C4烷基、C1-C4烷氧基、C1-C4烷基氨基羰基氧基、C1-C4 二烷基氨基羰基氧基、C1-C4烷基氨基羰基氨基、C1-C4 二烷基氨基羰基氨基、苯基氨基羰基氧基、苯基氨基羰基氨基、C1-C4烷氧基羰基氨基、SO3H, C1-C4烷基磺酰基、C1-C4羟烷基磺酰基、C00H、Cl、Br、F、SO2NR56R57, NO2或NH2,其中R56和R57独立地代表氢、C1-C4烷基、甲酰基、C1-C4烷基羰基、C1-C4烷氧基羰基、NH2-CO, C1-C4烷基氨基羰基。 [0089] In the formula Kk-A, R11 X1-C4 alkylamino Representative NH2WHX1-C4 alkoxy, di -C1-C4 alkylamino group, a hydroxy -C1-C4 alkylamino, carboxy -C1-C4 alkyl amino, C1-C4 alkylcarbonylamino group or phenylamino, R12 represents hydrogen, NH2, OH, C1-C4 alkoxy, hydroxy -C1-C4 alkylamino, carboxy -C1-C4 alkylamino, C1-C4 alkylamino, -C1-C4 alkylamino and R13 represents hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylaminocarbonyl group, C1-C4 dialkylamino, alkylcarbonyloxy , C1-C4 alkylaminocarbonyl group, C1-C4 dialkylaminocarbonyl group, a phenylaminocarbonyl group, phenylaminocarbonyl group, C1-C4 alkoxycarbonyl group, S03H, C1-C4 alkyl sulfonamide acyl, C1-C4 hydroxyalkyl alkylsulfonyl, C00H, Cl, Br, F, SO2NR56R57, NO2, or NH2, where R56 and R57 independently represent hydrogen, C1-C4 alkyl, formyl, C1-C4 alkylcarbonyl group, C1-C4 alkoxycarbonyl, NH2-CO, C1-C4 alkylaminocarbonyl.

[0090] 在式Kk-B中,R14和R15独立地代表氢或具有关于Rn所述的含义之一,但R15还可以代表S03H。 [0090] In the formula Kk-B, R14 and R15 independently represent hydrogen or have one of the meanings respect Rn, R15, but may also represent S03H. R16代表氢、OH、SO3H, C1-C4烷基磺酰基氨基、C1-C4烷基氨基磺酰基、C1-C4烷基氨基磺酰基氨基、二-C1-C4烷基氨基磺酰基氨基、C1-C4烷氧基羰基氨基、苯基磺酰基氨基一其可以在苯环上含有一个或两个选自C1-C4烷基、C1-C4烷氧基或卤素的取代基。 R16 represents hydrogen, OH, SO3H, C1-C4 alkylsulfonylamino group, C1-C4 alkylaminosulfonyl, C1-C4 alkylaminosulfonyl group, di -C1-C4 alkylaminosulfonyl group, C1- C4 alkoxycarbonyl group, a phenylsulfonyl group which may contain one or two substituents selected from C1-C4 alkyl on the phenyl ring, C1-C4 alkoxy or halogen substituent. R17代表氢、OH或SO3H基团。 R17 represents hydrogen, OH or SO3H groups.

[0091] 在式Kk-C中,R18至R2°独立地代表氢、OH或C1-C4烷基。 [0091] In the formula Kk-C, R18 to R2 ° independently represent hydrogen, OH or C1-C4 alkyl.

[0092] 在式Kk-D中,R21代表氢、苯基或萘基,其中后两个基团可以包含1、2或3个选自氢、0H、卤素、C1-C4烷基、S03H、N02和上述基团B-SO2-的取代基。 [0092] In the formula Kk-D, R21 represents hydrogen, phenyl or naphthyl, where the latter two groups may contain 1, 2 or 3 substituents selected from hydrogen, 0H, halogen, C1-C4 alkyl, S03H, N02 above groups and substituents B-SO2-. 在本发明的一个具体实施方式中,R21代表上述基团A之一,尤其是基团Al至A12之一。 In one embodiment of the present invention, R21 represents one of the above-mentioned group A, particularly one of the group Al to A12. R22是氢、COOH或C1-C4烷基。 R22 is hydrogen, COOH or C1-C4 alkyl.

[0093] 在式Kk-E中,R23和R25独立地为氢、C00H、羟基或C1-C4烷基。 [0093] In the formula Kk-E, R23 and R25 are independently hydrogen, C00H, hydroxy or C1-C4 alkyl. R24和R26独立地为氢、羟基或C1-C4烷基。 R24 and R26 are independently hydrogen, hydroxy or C1-C4 alkyl.

[0094] 在式Kk-F中,R27和R29独立地为氢、SO3H, C00H、羟基、或C1-C4烷基。 [0094] In the formula Kk-F, R27 and R29 are independently hydrogen, SO3H, C00H, hydroxy, or C1-C4 alkyl. R28和R3q独立地为氢、羟基或C1-C4烷基。 R3q and R28 are independently hydrogen, hydroxy or C1-C4 alkyl.

[0095]在式 Kk-G 中,R48、R49、R50 和R51 独立地为氢、SO3H, C00H、NH2, CN、羟基或C1-C4 烷基。 [0095] In the formula Kk-G, R48, R49, R50 and R51 are independently hydrogen, SO3H, C00H, NH2, CN, hydroxy, or C1-C4 alkyl.

[0096]在式 Kk-H 中,R52、R53、R54 和R55 独立地为氢、SO3H, C00H、NH2, CN、羟基或C「C4 烷基。 [0096] In the formula Kk-H, R52, R53, R54 and R55 are independently hydrogen, SO3H, C00H, NH2, CN, hydroxy or C "C4 alkyl.

[0097] 式Kk-A的偶联组分的例子是上述苯胺化合物DK3、DK4、DK6、DK7、DKlU DK13、DK14、DK15、DK18、DK21 至DK27、DK29、DK30、DK33、DK36、DK38、DK39、以及水杨酸(Kkl)、 [0097] Examples of the coupling component of formula Kk-A is the above aniline compound DK3, DK4, DK6, DK7, DKlU DK13, DK14, DK15, DK18, DK21 through DK27, DK29, DK30, DK33, DK36, DK38, DK39 and salicylic acid (kkl),

3-氨基苯酚(Kk2)、间苯二酚(Kk3)、3-苯基氨基苯酚(Kk4)、l,3-二氨基苯(Kk5)、3_乙酰基氨基苯胺(Kk6)、2-硝基苯胺(Kk7)、3-( 二乙氨基)苯酚(Kk8)、3-(吗啉-I-基)苯酚(Kk9)、3-( 二乙氨基)苯胺(KklO)、N-乙酰基-3-( 二乙氨基)苯胺(Kkll)、N-(3-羟苯基)甘氨酸(Kkl2)、3-(2-羟乙基)氨基苯酚(Kkl3)、2,4-二氨基甲苯(Kkl4)、2,4-二氨基苯磺酸(Kkl5)、2,4-二氨基-I-硝基苯(Kkl6)、N-(3-氨基-6-甲基苯基)甘氨酸(Kkl7)和2,4-二氨基-5-甲基苯磺酸(Kkl8)、2,4-二氨基-I-羟基苯(Kk54)、2,4-二氨基-I-甲氧基苯(Kk55)、2,4-二氨基-I-氯苯(Kk56)、l,2,4-三氨基苯(Kk57)、3_( 二甲氨基)苯胺(Kk58)、3_ ( 二甲氨基)-I-硝基苯(Kk59)、2_ (N, N-二乙氨基)-4-乙酸基氨基-I-甲氧基苯(Kk60)、2-(N,N-二乙氨基)-4-氨基-I-甲氧基苯(Kk61)、2,4-二氨基-I-苯磺酰胺(Kk62)、2_氨基-4-乙酸基氨基-I-甲氧基苯(K 3-aminophenol (Kk2), resorcinol (Kk3), 3- phenyl-aminophenol (Kk4), l, 3- diaminobenzene (Kk5), 3_ acetylamino aniline (Kk6), 2- nitro aniline (Kk7), 3- (diethylamino) phenol (Kk8), 3- (morpholin--I--yl) phenol (Kk9), 3- (diethylamino) aniline (KklO), N- acetyl - 3- (diethylamino) aniline (Kkll), N- (3- hydroxyphenyl) glycine (Kkl2), 3- (2- hydroxyethyl) aminophenol (Kkl3), 2,4- diaminotoluene (Kkl4 ), 2,4-diamino acid (Kkl5), 2,4- diamino-nitrophenyl -I- (Kkl6), N- (3- amino-6-methylphenyl) glycine (Kkl7) and 2,4-diamino-5-methylbenzenesulfonic acid (Kkl8), 2,4- diamino-hydroxyphenyl -I- (Kk54), 2,4- diamino-methoxybenzene -I- (Kk55), -I- amino-2,4-dichlorobenzene (Kk56), l, 2,4- triaminobenzene (Kk57), 3_ (dimethylamino) aniline (Kk58), 3_ (dimethylamino) -I- nitro benzene (Kk59), 2_ (N, N- diethylamino) -I- amino-4-acetic acid-yl-methoxybenzene (Kk60), 2- (N, N- diethylamino) -4-amino--I- methoxybenzene (Kk61), 2,4- diamino-benzenesulfonamide -I- (Kk62), 2_ -I- amino-4-methoxybenzene acetic acid group (K k63)、2_氨基-4-乙酸基氨基-I-氯苯(Kk64) ,2,4- 二氨基-I-甲基磺酰基苯(Kk65) ,2,4- 二氨基-I-乙基磺酰基苯(Kk66)和2,4_ 二氨基-1-(2-羟乙基)磺酰基苯(Kk67)。 k63), 2_ -I- amino-4-chlorophenyl acetate group (Kk64), 2,4- diamino -I- methyl-benzene (Kk65), 2,4- diamino -I- ethyl -benzene (Kk66) and 2,4_-diamino-1- (2-hydroxyethyl) benzene sulfonamide (Kk67).

[0098] 式Kk-B的偶联组分的例子是2-萘酚(Kkl9)、2-苯基氨基萘(Kk20)、4_甲基-I-萘酚(Kk21)、8-甲氧基氨基羰基-2-萘酚(Kk22)、8_乙酰基氨基_2_萘酚(Kk23)、 [0098] Examples of the coupling component of formula Kk-B are 2-naphthol (Kkl9), 2- phenyl-aminonaphthalene (Kk20), 4_ -I- methyl naphthol (Kk21), 8- methoxy aminocarbonyl-2-naphthol (Kk22), 8_ acetylamino _2_ naphthol (Kk23),

8-甲氨基磺酰基-2-萘酚(Kk24)、8-二甲氨基磺酰基氨-2-萘酚(Kk25)、6-[(4-甲基苯基)磺酰基]氨基-4-羟基萘-2-磺酸(Kk26)、8_苯基氨基萘-I-磺酸(Kk27)、6_氨基-4-羟基萘-2-磺酸(DK42)、4-氨基-5-羟基萘-I-磺酸(DK43)、7-氨基-4-羟基萘-2-磺酸(DK59)、4_氨基-5-羟基萘-2,7- 二磺酸(DK44)、4_氨基-5-羟基萘-1,7- 二磺酸(DK45)、8_氨基萘-2-磺酸(DK46)、6_氨基萘-I-磺酸(DK47)、4_氨基萘-2,7-磺酸©1(48)、4-羟基萘-2,7-二磺酸(故28)、3-羟基萘-2,7-二磺酸(Kk29)、4_ (苯基羰基)氨基-5-羟基萘-2,7- 二磺酸(Kk30)、4,6- 二羟基萘_2_磺酸(Kk31)、4,5- 二羟基萘_2·,7- 二磺酸(Kk32)、4-(苯基羰基)氨基-5-羟基萘-I-磺酸(Kk33)、4_羟基萘-I-磺酸(Kk34) ,4,5- 二羟基萘-I-磺酸(Kk35)、5-氨基萘-2-磺酸(DK49)、7-羟基萘-I,3- 二磺酸(Kk36)、7-氨基-4,8- 二羟基萘-2-磺酸(DK50)、8-羟基萘-I-磺酸(Kk37)、2-氨 8- A aminosulfonyl-2-naphthol (Kk24), 8- dimethylamino sulfonyl amino-2-naphthol (Kk25), 6 - [(4- methylphenyl) sulfonyl] amino-4 hydroxynaphthalene-2-sulfonic acid (Kk26), 8_ -I- phenyl aminonaphthalene acid (Kk27), 6_ amino-4-hydroxynaphthalene-2-sulfonic acid (DK42), 4- amino-5-hydroxy -I- naphthalene sulfonic acid (DK43), 7- amino-4-hydroxynaphthalene-2-sulfonic acid (DK59), 4_-amino-5-hydroxy-naphthalene-2,7-disulfonic acid (DK44), 4_ amino 5-hydroxy-naphthalene-1,7-disulfonic acid (DK45), 8_ aminonaphthalene-2-sulfonic acid (DK46), 6_ aminonaphthalene -I- acid (DK47), 4_ -2-aminonaphthalene, 7- acid © 1 (48), 4- hydroxy-naphthalene-2,7-disulfonic acid (it is 28), 3-hydroxy-naphthalene-2,7-disulfonic acid (Kk29), 4_ (phenylcarbonyl) amino 5-hydroxy-naphthalene-2,7-disulfonic acid (Kk30), 4,6- dihydroxynaphthalene _2_ acid (Kk31), 4,5- dihydroxynaphthalene 2 ·, 7-disulfonic acid ( Kk32), 4- (phenylcarbonyl) -I- amino-5-hydroxy-naphthalene sulfonic acid (Kk33), 4_ -I- hydroxy naphthalene sulfonic acid (Kk34), 4,5- dihydroxynaphthalene sulfonic acid -I- (Kk35), 5- amino-naphthalene-2-sulfonic acid (DK49), 7- hydroxynaphthalene -I, 3- disulfonic acid (Kk36), 7- amino-4,8-dihydroxy naphthalene-2-sulfonic acid ( DK50), 8- hydroxynaphthalene -I- acid (Kk37), 2- ammonia -5-羟基萘-I,7-二磺酸(DK51)、3-氨基-5-羟基萘-2,7-二磺酸(DK52)、3_氨基-1,5-二磺酸(DK53) ,4,6- 二羟基-7-羟基羰基萘-2-磺酸(Kk38)、7_氨基萘-I-磺酸(DK54)、4_氨基萘-I-磺酸(DK55)、5-氨基萘-I-磺酸(01(56)、7-氨基萘-1,3,5-三磺酸(DK57)和4-乙酰基氨基-5-羟基萘_2,7- 二磺酸(Kk39)。 5-hydroxy-naphthalene -I, 7- disulfonate (DK51), 3- amino-5-hydroxy-naphthalene-2,7-disulfonic acid (DK52), 3_-amino-1,5-disulfonic acid (DK53 ), 4,6-dihydroxy naphthalene-2-carbonyl-7-hydroxy acid (Kk38), 7_ aminonaphthalene -I- acid (DK54), 4_ aminonaphthalene -I- acid (DK55), 5 - aminonaphthalene -I- acid (01 (56), 7-amino-1,3,5-naphthalene sulfonic acid (DK57) and 4-acetylamino-5-hydroxynaphthalene-disulfonic acid _2,7- (Kk39).

[0099] 偶联组分Kk-C的例子是2,4- 二羟基喹啉(Kk40)和8_羟基喹啉(Kk41)。 Examples [0099] Kk-C coupling components are 2,4-dihydroxyquinoline (Kk40) and 8_ quinolinol (Kk41).

[0100] 偶联组分Kk-D的例子是3-甲基-5-羟基吡唑(Kk42)、I-苯基_3_甲基_5_羟基吡唑(Kk43)、1-[4-(2_羟基磺酰基氧乙基)-2-羟基磺酰基苯基]-3-甲基-5-羟基吡唑(Kk44)、I-[4-(2-羟基磺酰基氧乙基)-2-羟基磺酰基苯基]-5-羟基吡唑-3-羧酸(Kk45)、 Examples [0100] Kk-D coupling component is 3-methyl-5-hydroxy-pyrazole (Kk42), I- _5_ hydroxy methyl phenyl _3_ pyrazole (Kk43), 1- [4 - (2_ hydroxysulfonyl-oxoethyl) -2-hydroxy-phenyl sulfonyl] -3-methyl-5-hydroxypyrazole (Kk44), I- [4- (2- hydroxy-ethyl sulfonyloxy) -2-hydroxy-phenyl sulfonyl] -5-hydroxy-pyrazole-3-carboxylic acid (Kk45),

I-[4-羟基磺酰基苯基]-5-羟基吡唑-3-羧酸(Kk46)和I-[6-羟基磺酰基萘-2-基]-5-羟基-3-甲基吡唑(Kk47)、1-[4_羟基磺酰基苯基]-3-甲基-5-羟基吡唑(Kk48)。 I- [4- hydroxy-phenyl-sulfonyl] -5-hydroxy-pyrazole-3-carboxylic acid (Kk46) and I- [6- hydroxy-sulfonyl-2-yl] -5-hydroxy-3-methyl-pyrazole oxazole (Kk47), 1- [4_-hydroxy-phenyl sulfonyl] -3-methyl-5-hydroxypyrazole (Kk48).

[0101] Kk-E偶联组分的例子是4,4' - 二羟基二苯基甲烷-3,3' - 二羧酸(Kk49)。 [0101] Examples of coupling component Kk-E 4,4 '- dihydroxydiphenyl methane-3,3' - dicarboxylic acid (Kk49).

[0102] Kk-F偶联组分的例子是4,4' - 二羟基二苯胺(Kk50)。 [0102] Examples of Kk-F coupling component is 4,4 '- dihydroxy-diphenylamine (Kk50).

[0103] Kk-G偶联组分的例子是2,6- 二氨基吡啶(Kk51)。 Examples of the coupling component Kk-G [0103] 2,6-diaminopyridine (Kk51).

[0104] Kk-H偶联组分的例子是I-甲基-2-吡啶酮(Kk52)和3_氰基_4_甲基_6_羟基-I-乙基吡啶酮(Kk53)。 [0104] Examples of Kk-H coupling component is I- methyl-2-pyridone (Kk52) and 3_ cyano _4_ -I- hydroxy ethyl methyl _6_ pyridone (Kk53).

[0105] 合适的Kk3基团特别是源自任选取代的苯或萘的一价基团,例如源自偶联组分Kk-A 和Kk-B 的一价基团,例如源自苯胺化合物DK3、DK4、DK6、DK7、DK11、DK13、DK14、DK15、DK18、DK21 至DK27、DK29、DK30、DK33、DK36、DK38、DK39、DK42 至DK83、Kkl 至Kk48 和Kk51至Kk67的基团。 [0105] Suitable Kk3 groups especially those derived from benzene or naphthalene optionally substituted monovalent group, e.g. a monovalent group derived from a coupling component Kk-A and Kk-B, for example, from the aniline compound DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 through DK27, DK29, DK30, DK33, DK36, DK38, DK39, DK42 through DK83, kkl to Kk48 and Kk51 to Kk67 group.

[0106] 基团Tk1和Tk2分别是源自式Tk1(NH2)2和Tk2(NH2)2的芳胺的二价芳族基团。 [0106] Tk1 and Tk2 are radicals derived from the formula Tk1 (NH2) 2 and Tk2 (NH2) 2 of the aromatic amine divalent aromatic group. 这些二胺在下文中也被称作双偶氮组分。 These diamines hereinafter also referred to as a tetrazo component.

[0107] 合适的双偶氮组分是,例如,源自苯的通式Tk-A的化合物、源自联萘的式Tk-B的化合物、源自苯基苯并咪唑的式Tk-C的化合物、源自二苯基甲烷的式Tk-D的化合物、源自二苯胺的式Tk-E的化合物、源自苯基磺酰基苯的式Tk-F的化合物、源自苯基氨基磺酰基苯的式Tk-G的化合物、源自均二苯代乙烯的式Tk-H的化合物和源自苯基氨基羰基苯的式Tk-J的化合物: [0107] Suitable bis azo component is, for example, benzene-derived compounds of general formula Tk-A, a compound derived from binaphthyl of formula Tk-B, from phenylbenzimidazole formula Tk-C compound, a compound derived from a diphenylmethane of formula Tk-D, the compound of the formula derived from diphenylamine Tk-E, the compound of formula Tk-F phenylsulfonyl derived from benzene, from phenyl sulfamic acylbenzenes compound of formula Tk-G, the compound derived from the stilbene compound of the formula Tk-H and the formula derived from Tk-J phenylaminocarbonyl of benzene:

[0108] [0108]

[0110] 在式Tk-A中,R31代表例如氢、C1-C4烷基、C1-C4烷氧基、COOH或S03H。 [0110] In the formula Tk-A, R31 represents, for example hydrogen, C1-C4 alkyl, C1-C4 alkoxy, COOH or S03H. 优选地,两个NH2基团相互位于对位。 Preferably, the two NH2 groups in the para position to each other. 式Tk-A的化合物的例子是1,4-二氨基苯(Tkl)、1,4_ 二氨基-2-甲氧基苯(Tk2)、2,5-二氨基苯甲酸(Tk3)和2,5-二氨基苯磺酸(Tk4)。 Examples of compounds of formula Tk-A are 1,4-diaminobenzene (Tkl), 1,4_-diamino-2-methoxybenzene (Tk2), 2,5- diaminobenzoic acid (Tk3) and 2, 5-amino acid (Tk4).

[0111] 在式Tk-B中,R32和R33独立地代表例如氢、OH、C1-C4烷基、C1-C4烷氧基、COOH或S03H。 [0111] In the formula Tk-B, R32 and R33 independently represent hydrogen, for example, OH, C1-C4 alkyl, C1-C4 alkoxy, COOH or S03H. 优选地,两个NH2基团位于位4和4'。 Preferably, the two NH2 groups located position 4 and 4 '. 式Tk-B的化合物的例子是4,4' - 二氨基联苯(Tk5)、4,4' - _■氣基-3, 3' - _■甲基联苯(Tk6)、4,4' - _■氣基-3, 3' - _■甲氧基联苯(Tk7)、4,4' - _■氣基-3, 3' - _■轻基联苯(Tk8)、4,4' - _■氣基_3-轻基横酸基联苯(Tk9)、4,4' - 二氨基_3,3' -二(羟基磺酰基)联苯(TklO)和4,4' - 二氨基_3,3' -二羧基联苯(Tkll)。 Examples of compounds of formula Tk-B are 4,4 '- diaminobenzidine (Tk5), 4,4' - _ ■ gas-yl -3, 3 '- _ ■ methyl biphenyl (Tk6), 4,4 '- _ ■ gas-yl -3, 3' - _ ■ methoxy-biphenyl (Tk7), 4,4 '- _ ■ gas-yl -3, 3' - _ ■ light biphenyl (Tk8), 4, 4 '- _ ■ light gas yl _3- acid groups cross-biphenyl (Tk9), 4,4' - diamino _3,3 '- di (hydroxy-sulfonyl) biphenyl (TklO) and 4,4' - diamino _3,3 '- dicarboxy biphenyl (Tkll).

[0112] 在式Tk-C中,R34和R35独立地代表例如氢、OlC1-C4烷基或C1-C4烷氧基。 [0112] In the formula Tk-C, R34 and R35 independently represent hydrogen, for example, OlC1-C4 alkyl or C1-C4 alkoxy. 式Tk-C的化合物的例子是6-氨基-2-[4-氨基苯基]苯并咪唑(Tkl2)。 Examples of compounds of the formula Tk-C is 6-amino-2- [4-aminophenyl] benzimidazole (Tkl2).

[0113] 在式Tk-D中,R36和R37独立地代表例如氢、OH、C1-C4烷基、C1-C4烷氧基、COOH或SO3H0优选地,两个NH2基团位于位4和4'。 [0113] In the formula Tk-D, R36 and R37 independently represent hydrogen, for example, OH, C1-C4 alkyl, C1-C4 alkoxy, COOH or SO3H0 Preferably, two NH2 groups disposed in positions 4 and 4 '. Tk-D化合物的例子是二(4-氨基苯基)甲烷(Tkl3)、二(4-氨基-3-羧基苯基)甲烷(Tkl4)和二(4-氨基-3-甲基苯基)甲烷(Tkl5)。 Examples of Tk-D compounds are bis (4-aminophenyl) methane (Tkl3), bis (4-amino-3-carboxy-phenyl) methane (Tkl4) and bis (4-amino-3-methylphenyl) methane (Tkl5).

[0114] 在式Tk-E中,R38和R39独立地代表例如氢、OH、C1-C4烷基、C1-C4烷氧基、COOH或S03H。 [0114] In the formula Tk-E, R38 and R39 independently represent hydrogen, for example, OH, C1-C4 alkyl, C1-C4 alkoxy, COOH or S03H. 优选地,两个NH2基团位于位4和4'。 Preferably, the two NH2 groups located position 4 and 4 '. Tk-E化合物的例子是(4-氨基苯基)(4'-氨基-2'-羟基磺酰基苯基)胺或4,4' - 二氨基二苯胺-2-磺酸(Tkl6)。 Examples of Tk-E compound is (4-aminophenyl) (2'-hydroxy-4'-amino-sulfonyl) amine or 4,4 '- diamino 2-sulfonic acid (Tkl6).

[0115] 在式Tk-F中,R40和R41独立地代表例如氢、OH、C1-C4烷基、C1-C4烷氧基、COOH或S03H。 [0115] In the formula Tk-F, R40 and R41 independently represent hydrogen, for example, OH, C1-C4 alkyl, C1-C4 alkoxy, COOH or S03H. 优选地,两个NH2基团位于位4和4'。 Preferably, the two NH2 groups located position 4 and 4 '. Tk-F化合物的例子是二- (4-氨基苯基)砜(Tkl7)。 Examples of Tk-F compounds are di - (4-aminophenyl) sulfone (Tkl7).

[0116] 在式Tk-G中,R42和R43独立地代表例如氢、OH、C1-C4烷基、C1-C4烷氧基、COOH或SO3H0优选地,两个NH2基团位于位4和4'。 [0116] In the formula Tk-G, R42 and R43 independently represent hydrogen, for example, OH, C1-C4 alkyl, C1-C4 alkoxy, COOH or SO3H0 Preferably, two NH2 groups disposed in positions 4 and 4 '. Tk-G化合物的例子N- (4'-氨基苯基)_4_氨基苯磺酰胺(Tk18)。 Examples of the compound N- Tk-G (4'-aminophenyl) amino-benzenesulfonamide _4_ (Tk18).

[0117] 在式Tk-H中,R44和R45独立地代表例如氢、OH、C1-C4烷基、COOH或S03H。 [0117] In the formula Tk-H, R44 and R45 independently represent hydrogen, for example, OH, C1-C4 alkyl group, COOH or S03H. 优选地,两个NH2基团位于位4和4'。 Preferably, the two NH2 groups located position 4 and 4 '. Tk-H化合物的一个例子是1,2- 二(4-氨基-2-羟基磺酰基苯基)乙烯(flavonic acid, Tkl9)。 An example of Tk-H compounds are 1,2-bis (2-hydroxy-4-amino sulfonyl phenyl) ethylene (flavonic acid, Tkl9).

[0118] 在式Tk-J中,R46和R47独立地代表例如氢、OH、C1-C4烷基、C1-C4烷氧基、COOH或S03H。 [0118] In the formula Tk-J, R46 and R47 independently represent hydrogen, for example, OH, C1-C4 alkyl, C1-C4 alkoxy, COOH or S03H. 优选地,两个NH2基团位于位4和4'。 Preferably, the two NH2 groups located position 4 and 4 '. Tk-J化合物的例子是N-(4'-氨基苯基)_4_氨基苯甲酰胺(Tk20)。 Examples of Tk-J compounds are N- (4'- aminophenyl) _4_ aminobenzamide (Tk20).

[0119] 优选的Napht1和Napht2基团符合通式Napht-II : [0119] Preferred Napht1 Napht2 group corresponding to the formula and Napht-II:

[0120] [0120]

[0121] 其中R1和R2独立地为氢、OH、NH2或NHC(O)R3,其中R3是氢、C1-C4烷基、马来酰基或苯基,并且R1和R2中至少一个不是氢,一一代表与偶氮基团连接的键,s和t代表O或 [0121] wherein R1 and R2 are independently hydrogen, OH, NH2 or NHC (O) R3, wherein R3 is hydrogen, C1-C4 alkyl, maleyl or phenyl and at least one of R1 and R2 is not hydrogen, eleven represents the bond attached azo groups, s and t represents O or

I。 I. s+t的和优选为I或2。 and s + t is preferably I or 2.

[0122] 合适的Napht1和Napht2基团包括下示基团11_1至11_14 : [0122] Suitable Napht1 and Napht2 groups include groups shown below 11_1 to 11_14:

[0123] 2-羟基磺酰基-4-羟基萘-3,6- 二基(11_1), [0123] 2-hydroxy-4- hydroxy-3,6-diyl (11_1),

[0124] 6-氨基-2-羟基磺酰基-4-羟基萘-3,5_ 二基(I 1-2), [0124] 6-amino-2-hydroxy-4- hydroxy-naphthalene-diyl -3,5_ (I 1-2),

[0125] I-羟基磺酰基-5-羟基萘-4,6- 二基(I 1-3), [0125] I- methanesulfonyl-hydroxy-5-hydroxy-naphthalene-4,6-diyl (I 1-3),

[0126] 4-氨基-I-羟基磺酰基-5-羟基萘-3,6- 二基(11_4), [0126] -I- hydroxy-4-sulfonyl-5-hydroxy-3,6-diyl (11_4),

[0127] 2-羟基磺酰基-4-羟基萘-3,7- 二基(I 1-5), [0127] 2-Hydroxy-4- yl-3,7-dihydroxynaphthalene (I 1-5),

[0128] 7-氨基-2-羟基磺酰基-4-羟基萘-3,8- 二基(I 1-6), [0128] 7-Amino-2-hydroxy-4- hydroxy-naphthalene-3,8-diyl (I 1-6),

[0129] 5-羟基-2,7-二羟基磺酰基萘-4,6-二基(11-7), [0129] 5-hydroxy-2,7-dihydroxy-4,6-naphthalene sulfonyl group (11-7),

[0130] 4-氨基-5-羟基-2,7-二羟基磺酰基萘-3,6-二基(11-8), [0130] 4-amino-5-hydroxy-2,7-dihydroxy-3,6-diyl sulfonyl (11-8),

[0131] 5-羟基-I,7-二羟基磺酰基萘-4,6-二基(11_9), [0131] 5-hydroxy -I, 7- dihydroxy-4,6-naphthalene sulfonyl group (11_9),

[0132] 4-氨基-5-羟基-I,7-二羟基磺酰基萘-3,6-二基(11-10), [0132] 4-amino-5-hydroxy -I, 7- dihydroxy-3,6-diyl sulfonyl group (11-10),

[0133] 2-羟基磺酰基萘-5,8-二基(11-11), [0133] 2-hydroxy-5,8-naphthalene sulfonyl group (11-11),

[0134] 2-氨基-5-羟基-I,7-二羟基磺酰基萘-3,6-二基(11-12), [0134] 2-amino-5-hydroxy -I, 7- dihydroxy-3,6-diyl sulfonyl group (11-12),

[0135] 5-羟基-2,7-二羟基磺酰基萘-3,6-二基(11-13), [0135] 5-hydroxy-2,7-dihydroxy-3,6-diyl sulfonyl group (11-13),

[0136] 3-氨基-5-羟基-2,7-二羟基磺酰基萘-4,6-二基(11-14), [0136] 3-amino-5-hydroxy-2,7-dihydroxy-4,6-naphthalene sulfonyl group (11-14),

[0137] 2-羟基磺酰基萘-5,8-二基(11-15)和 [0137] 2-hydroxy-5,8-naphthalene sulfonyl group (11-15) and

[0138] I-羟基磺酰基萘-5,8-二基(11-16)。 [0138] I--hydroxy-5,8-naphthalene sulfonyl group (11-16).

[0139] 基团L、M、P和R是源自苯或萘的二价基团,例如源自式Kk-A和Kk-B的偶联组分的基团,以及源自前述重氮组分并仍然具有可使重氮鎗化合物偶联到其上的自由位置的基团O 其例子是苯胺化合物DK3、DK4、DK6、DK7、DK11、DK13、DK14、DK15、DK18、DK21 至DK27、DK29、DK30、DK33、DK36、DK38、DK39,和DK60 至DK83 以及萘胺DK42 至DK59。 [0139] group L, M, P and R are derived from benzene or naphthalene divalent group, e.g. a group derived from a coupling component of formula Kk-A and Kk-B, and from the diazo diazo component and still having a gun can be coupled to the free compound on which the position of the group O which is an example of an aniline compound DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 through DK27, DK29, DK30, DK33, DK36, DK38, DK39, DK83 and DK60 through DK42 to naphthylamine and DK59.

[0140] 在式I至XV的前述化合物中特别优选通式Ila、IIIa和IVa的染料: [0140] In the compounds of formulas I to XV particularly preferred in the general formula Ila, IIIa and IVa dyes:

[0141 ] Dk1-N = N-Napht1-N = N-Tk1 [-N = N-Kk1] k [-N = N-Dk2] n (IIa) [0141] Dk1-N = N-Napht1-N = N-Tk1 [-N = N-Kk1] k [-N = N-Dk2] n (IIa)

[0142] Dk1-N = N-Napht1-N = N-Tk1-N = N-Kk1-N = N-Tk2-N = N-Napht2-N = N-Dk2 [0142] Dk1-N = N-Napht1-N = N-Tk1-N = N-Kk1-N = N-Tk2-N = N-Napht2-N = N-Dk2

[0143] (IIIa) [0143] (IIIa)

[0144] Dk1-N = N-Napht1-N = N-Tk1-N = N-Napht2-N = N-Dk2 (IVa) [0144] Dk1-N = N-Napht1-N = N-Tk1-N = N-Napht2-N = N-Dk2 (IVa)

[0145]在式 Ila、IIIa 和IVa 中,Dk1 >Dk2> Napht1、Napht2、Kk1、TK1、Tk2 和Kk1 各自定义如上,但Dk1和Dk2基团之一或这二者代表如上所述式A的基团,并特别是代表Al至A12中的一个基团。 [0145] In formulas Ila, IIIa and IVa are, Dk1> Dk2> Napht1, Napht2, Kk1, TK1, Tk2 and Kk1 each as defined above, but both or one of the groups described above Dk1 and representatives of formula A DK2 group, and in particular Al to A12 represent one group. 数η和k是O或1,条件是n+k = I或2。 Η and k is the number 1 or O, with the proviso that n + k = I or 2. 当k = O时,式IIa中的Tk1不代表源自二苯基胺的基团,此时这些化合物是新型的。 When k = O, Tk1 in formula IIa does not represent a diphenylamine-derived radical, at this time these compounds are novel. 因此,这些化合物及其混合物同样构成本发明的部分主题。 Thus, compounds and mixtures of these components likewise subject matter of the present invention.

[0146] 染料II和IIa的特别优选具体实施方式包括通式IIb的染料 [0146] Particularly preferred dyes II and IIa Specific embodiments include dyes of the general formula IIb

[0147] Dk1-N = N-Napht1-N = N-Tk1-N = N-Kk1 [-N = N-Dk2Jn (IIb) [0147] Dk1-N = N-Napht1-N = N-Tk1-N = N-Kk1 [-N = N-Dk2Jn (IIb)

[0148] 其中A、Dk2、Napht1和Kk1各自定义如上,η是O或1,且其中Tk1代表源自联苯、二苯基甲烷、2-苯基苯并咪唑、苯基磺酰基苯、苯基氨基磺酰基苯、二苯胺、均二苯代乙烯或苯基氨基羰基苯的二价基团,并任选包含一个或多个下列基团作为取代基:S03H、C00H, 0H、NH2、NO2、齒素、C1-C4烷基,但当η = O时Tk1不代表源自二苯胺的基团,且Dk2基团还可以代表如上所述的式A的基团。 [0148] wherein A, Dk2, Napht1 Kk1 and are each as defined above, [eta] is O or 1, and wherein Tk1 representatives from biphenyl, diphenylmethane, 2-phenylbenzimidazole-phenyl-benzene, benzene amino-benzene, diphenylamine, stilbene or phenylaminocarbonyl divalent benzene group, and optionally comprising one or more of the following groups as substituents: S03H, C00H, 0H, NH2, NO2 teeth Su, C1-C4 alkyl, but when η = O group does not represent Tk1 from diphenylamine and Dk2 group of formula a may also represent a group described above. 通式IIb的染料,尤其是它们的混合物,是本发明的特别优选的主题。 Dye of formula IIb, especially mixtures thereof, are particularly preferred subject matter of the present invention.

[0149] 在通式IIa、IIb、IIIa和IVa的本发明的染料中,特别优选的是Tk1和/或Tk2基团中至少一个代表下式的基团时的染料: [0149] In the dyes of the invention of formula IIa, IIb, IIIa, and IVa, particularly preferred is a dye when Tk1 and / or at least Tk2 group represents a group of the formula:

[0150] [0150]

…Οά-κΌ… ... Οά-κΌ ...

[0151] 其中一--代表与偶氮基团连接的键。 [0151] where a - represents the bond to the azo group is attached.

[0152] 在通式Ila、lib、IIIa和IVa的化合物中,特别优选的是Napht1和/或Napht2代表上述通式Napht-II的二价基团并特别具有此处所述的具体含义时的染料。 [0152] In the general formula Ila, lib, IIIa and IVa of the compounds, particularly preferred are Napht1 and / or when Napht2 Napht-II represents the average divalent radical and, in particular having a specific meaning herein dye.

[0153] 在通式Ila、lib、IIIa和IVa的化合物中,特别优选的是Dk1和Dk2基团之一或这二者代表上述Al至A12基团之一时的染料。 [0153] In the compounds of formula Ila, lib, IIIa and IVa, particularly preferred are one or both Dk1 and Dk2 group represented by the Al to the dye at one of the groups A12.

[0154] 在通式IIb的染料中,Kk1代表例如源自式版1至故67、01(3、01(4、01(6、01(7、01(11、DK13、DK14、DK15、DK18、DK21 to DK27、DK29、DK30、DK33、DK36、DK38、DK39 或DK42 至DK83的偶联组分的基团。在式Ila、IIb和IIIa的染料中,尤其优选的是Kk1源自Kk-A化合物时的染料。 [0154] In the general formula IIb, dyes, Kk1 formula represents, for example from 1 to Edition so 67,01 (3,01 (4,01 (6,01 (7,01 (11, DK13, DK14, DK15, DK18 , DK21 to DK27, DK29, DK30, DK33, DK36, DK38, DK39 group or to the coupling component DK42 DK83 in formula Ila, IIb and IIIa of dyes, particularly preferred are derived from Kk-a Kk1 when the dye compound.

[0155] 特别优选的是通式IIb的染料的混合物。 [0155] Particularly preferred is a mixture of dyes of the general formula IIb. 染料IIb的混合物包括两种或多种,例如 IIb dye mixture comprises two or more, e.g.

2、3或4种染料lib。 3 or 4 dyes lib. 每种IIb染料的量不低于染料F总量的10摩尔%,尤其不低于20摩尔%。 IIb amount of each dye is not less than 10 mol% of the total dye F, in particular not less than 20 mol%. 优选两种染料F的混合物,其中每种组分的摩尔比为9 : I至I : 9,尤其是2 : 8至8 : 2,更优选3 : 7至7 : 3。 F is preferably a mixture of two dyes, wherein the molar ratio of each component is 9: I to I: 9, especially 2: 8-8: 2, more preferably 3: 7 to 7: 3. 特别优选的具体实施方式包括每种染料仅在Kk1基团上不同时的染料IIb混合物。 Particularly preferred embodiments include IIb dyes of each dye mixture are not only simultaneously in Kk1 group.

[0156] 按照本发明使用的通式I至IV的偶氮染料及其金属络合物是按照传统方法制备的,该方法包括多步重氮化/偶联次序,其通过相继的重氮化/偶联构成染料,也就是说,各个重氮基或NH基团结构单元的连接依次进行;或通过汇集合成构成染料,也就是生成已经包含重氮基或NH基团的染料部分,并然后任选通过偶联或双偶氮组分,经由进一步重氮化/偶联与同样已经包含一个或多个重氮基的染料的其它部分连接。 [0156] I to IV azo dyes and metal complexes are prepared in a conventional manner as in the general formula of the present invention, the method comprises a multistep diazotization / coupling sequence, by sequential diazotization / dye conjugate configuration, i.e., connected to the respective diazo or NH group of the structural unit sequentially; or by convergent synthesis dyes configuration, i.e. contains already generated diazo dye moiety or a NH group, and then or optionally by coupling tetrazo component / coupling has also been linked to other portions comprises one or more diazo dye via a further diazotization.

[0157] 在相继重氮化/偶联过程中,例如,首先将重氮鎗组分Dk1和Dk2重氮化并分别偶联到Napht1和Napht2Ik1或Kk2上或偶联到P或R基团上,然后再将反应产物重氮化并偶联到另一偶联组分(partner)上,任选重复该操作直至构成染料。 [0157] In the successive diazotizing / coupling process, for example, first diazo component gun Dk1 and Dk2 and are diazotized and coupled onto Napht1 Napht2Ik1 or Kk2 or P or conjugated to R groups on and then the reaction product is further diazotized and coupled onto the coupling component (Partner), optionally repeating this operation until the dye configuration. 或者,在相继合成中,也可以使第一偶联的反应产物依次与一种或多种重氮鎗化合物反应。 Alternatively, the successive synthesis, the reaction product may be coupled to a first order reaction with one or more diazo compounds gun.

[0158] 相继偶联可以包括首先将双偶氮组分Tk1 (NH2)2或Tk2 (NH2)2转化成相应的四氮鎗盐,然后依次与Kk1IAapht^Napht2等偶联组分反应,然后进一步进行重氮化/偶联反应。 [0158] sequentially coupling may include a first tetrazo component Tk1 (NH2) 2 or Tk2 (NH2) 2 is converted to the corresponding gun tetrazolium salt, followed by reaction with Kk1IAapht ^ Napht2 other coupling components, and further diazotization / coupling reactions.

[0159] 两种或多种F染料的混合物不仅可以将所需混合组分掺合而制备,还可以通过使用合成F染料所用的原材料的混合物而制备。 [0159] a mixture of two or more dyes F can only be prepared by mixing the desired components are blended, it may also be prepared by using a mixture of raw materials used in the synthesis of dyes F. 可以例如通过在合成中中和两种或多种胺Dk1-NH2, Dk2-NH2或A-NH2的混合物、两种或多种偶联组分H-Kk1和H-Kk2的混合物、两种或多种双偶氮组分(H2N)2-Tk1和(H2N)2-Tk2的混合物或两种或多种不同化合物Napth1H2和Napth2H2的混合物来制备偶氮染料I至XV的混合物。 For example, by two or more neutralizing amines Dk1-NH2,, in the synthesis mixture Dk2-NH2 or A-NH2 mixture of two or more coupling components H-Kk1 and H-Kk2 of two or more tetrazo component (H2N) 2-Tk1 azo dye to the mixture prepared and I to XV (of H2N) 2-Tk2 mixture of two or more different compounds or a mixture Napth1H2 and the Napth2H2. 当然,也可以使用三种或更多种组分的混合物。 Of course, also possible to use a mixture of three or more components.

[0160] 为了保持混合物中F染料的所需混合比,F染料的合成可以使用各种原材料的混·合物,其中每种原材料的存在量不低于混合物的10摩尔%,尤其不低于20摩尔%,更优选不低于30摩尔%。 [0160] In order to maintain the desired mixing ratio of the mixture of dyes F, F synthetic dyes may be used various materials-mixture thereof, wherein each starting material is present in an amount of not less than 10 mol% of the mixture, in particular not less than 20 mol%, more preferably not less than 30 mol%. 在两种原材料的混合物中,例如在两种偶联组分H-Kk(I)和H-Kk(2)的混合物的情况下,或在两种重氮组分的情况下,或在两种混合双偶氮组分的情况下,混合物中每种组分的摩尔比为9 : I至I : 9,尤其是8 : 2至2 : 8,更优选为3 : 7至7 : 3。 In the mixture of the two raw materials, for example, in both the case of mixtures of coupling components H-Kk (I) and H-Kk (2) or, in the case where the two kinds of the diazo component, or two case admixture tetrazo component, the molar ratio of each component in the mixture is 9: I to I: 9, in particular 8: 2 to 2: 8, more preferably 3: 7 to 7: 3.

[0161] 现在参照通式IIb的染料的制备举例解释通式I至XV的偶氮染料的制备。 [0161] Referring now to the preparation of formula IIb dyes I to XV illustrates the preparation of azo dyes of the formula explained. 可以按照传统方式改变用于此目的的方法以构成通式I至XV的其它偶氮染料。 The method used for this purpose may be varied in a conventional manner to form the formulas I to XV, other azo dyes. 通式IIb的染料可以例如如下制备:第一步骤,将双偶氮成分Tk1项下的二氨基化合物Tk1 (NH2)2双偶氮化并然后首先偶联到Napht1基团项下的Napht1H2萘化合物上。 Formula IIb dyes may be prepared, for example, as follows: a first step of the tetrazo component diamino compound Tk1 (NH2) under Tk1 Item 2 tetrazotized and then coupled to the first Napht1H2 naphthalene compounds under item group Napht1 on. 然后,将由此获得的重氮鎗化合物H-Napht1-N = N-Tk1-N2+分别偶联到重氮鎗化合物Dk1-N2+或A-N2+上以获得化合物Dk1-N = N-Napht1-N = N-Tk1-N2+或AN = N-Napht1-N = N-Tk1-N2' 将该化合物偶联到偶联组分Kk1H上以获得其中η = O的式IIb的化合物。 Then, diazo gun compound thus obtained H-Napht1-N = N-Tk1-N2 +, respectively coupled to the diazonium gun compound Dk1-N2 +, or A-N2 + on to obtain compound Dk1-N = N-Napht1-N = N-Tk1-N2 + or AN = N-Napht1-N = N-Tk1-N2 'conjugating the compound to a coupling component Kk1H to obtain a compound of the formula wherein η = O is IIb. 或者,可以将重氮鎗化合物H-Napht1-N=N-Tk1-N2+偶联到偶联组分Kk1H上以获得化合物H-Napht1-N = N-Tk1-N = N-Kk10在其上偶联重氮鎗化合物Dk1-N2+或A-N2+以获得η = O时的式IIb的染料。 Alternatively, the gun diazo compound H-Napht1-N = N-Tk1-N2 + is coupled to the coupling component to obtain a compound Kk1H H-Napht1-N = N-Tk1-N = N-Kk10 even on its gun with diazo compound Dk1-N2 +, or a-N2 + O to obtain η = formula IIb when the dye.

[0162] 也可以通过分别将化合物Dk1-N2+或A-N2+偶联到Napht1H2化合物上以获得式Dk1-N=N-Napht1-H或AN = N-Napht1-H的化合物,由此制备式IIb的染料。 [0162] can also separately the compound Dk1-N2 +, or A-N2 + is coupled to an AN-compound of formula Dk1-N = N-Napht1-H or = N-Napht1-H, whereby the upper Napht1H2 preparation of compounds of formula IIb the dye. 然后将该化合物偶联到二氨基化合物Tk1(NH2)2的双偶氮组分Tk1的母体双偶氮化产物上以分别获得化合物Dk1-N = N-Napht1-N = N-Tk1-N2+ 或AN = N-Napht1-N = N-Tk1-N2' 将该化合物偶联到Kk1H偶联组分上以获得其中η = O的式IIb的染料。 Then the parent product disazo compound coupled to diamino compound Tk1 (NH2) tetrazo component Tk1 compound 2 Dk1-N = N-Napht1-N = N-Tk1-N2 + or respectively AN = N-Napht1-N = N-Tk1-N2 'conjugating the compound to a coupling component Kk1H wherein η = O to obtain the dye of formula IIb.

[0163] 也可以如下制备通式IIb的染料:首先将双偶氮组分Tk1的母体二氨基化合物Tk1 (NH2)2双偶氮化,然后先偶联到Kk1H偶联组分上以获得化合物+N2-Tk1-N = N-Kk1,然后·将其偶联到Napht1H2化合物上以获得式H-Napht1-N = N-Tk1-N = N-Kk1的化合物。 [0163] may also be prepared by a dye of formula IIb: first parent diamino compound of the tetrazo component Tk1 Tk1 (NH2) 2 of tetrazo and coupling to the first coupling component to obtain a compound Kk1H + N2-Tk1-N = N-Kk1, and · the formula to obtain a compound H-Napht1-N = N-Tk1-N = N-Kk1 which is coupled to the Napht1H2 compound. 在其上偶联重氮鎗化合物Dk1-N2+或A-N2+以获得η = O的式IIb的化合物。 Coupling the gun on which the diazo compound Dk1-N2 +, or A-N2 + η = O to obtain a compound of Formula IIb. 或者,可以将化合物+N2-Tk1-N = N-Kk1 偶联到化合物Dk1-N = N-Napht1-H 或AN = N-Napht1-H 上以获得η=O的式IIb的染料。 Alternatively, the compound + N2-Tk1-N = N-Kk1 coupled to compound Dk1-N = N-Napht1-H or the AN = N-Napht1-H η = O to obtain a dye of the formula IIb.

[0164] 在进一步反应阶段,然后可以将Dk2-N2+化合物偶联到η = O的式IIb的化合物上以获得η = I的式IIb的染料。 [0164] a compound of a further reaction stage in and Dk2-N2 + compounds may be coupled to the Formula IIb η = O η = I to obtain a dye of the formula IIb.

[0165] 也可以如下制备η = I的通式IIb的染料:首先将式Dk2-NH2的化合物重氮化,然后偶联到Kk1H偶联组分上以获得式Kk1-N = N-Dk2的化合物。 [0165] can also be prepared as follows η = I dye of formula IIb: First, a compound of formula Dk2-NH2 diazotized, then coupled to a coupling component to obtain a formula Kk1H Kk1-N = N-Dk2 of compound. 然后在该化合物上偶联化合物Dk1-N = N-Napht1-N = N-Tk1-N2+ 或AN = N-Napht1-N = N-Tk1-N2+ 以获得η = I 的式IIb的染料。 The compound is then coupled compound Dk1-N = N-Napht1-N = N-Tk1-N2 + or AN = N-Napht1-N = N-Tk1-N2 + η = I to obtain a dye of the formula IIb.

[0166] 也可以如下制备η = I的通式IIb的染料:将双偶氮Tk1的母体二氨基化合物Tk1 (NH2)2双偶氮化并偶联到Kk1-N = N-Dk2化合物上以获得化合物+N2-Tk1-N = N-Kk1-N =N-Dk20然后将该化合物偶联到化合物Dk1-N = N-Napht1H上以获得η = I的式IIb的染料。 [0166] may be prepared by η = dyes of the general formula I, IIb: The parent diamino compound of disazo Tk1 Tk1 (NH2) 2 tetrazotized and coupled to the Kk1-N = N-Dk2 compound to obtain a compound + N2-Tk1-N = N-Kk1-N = N-Dk20 compound is then coupled to the compound Dk1-N = N-Napht1H η = I to obtain a dye of the formula IIb.

[0167] 优选的通式IIb的染料的混合物(其中每种IIb染料在HKk1基团上不同)优选使用两种或多种不同的Kk1偶联组分制备,其中每种组分如上所示。 [0167] A preferred mixture of dyes of the general formula IIb (IIb wherein each of the different dyes on HKk1 group) or more preferably prepared using two different coupling components of Kk1, wherein each of the components shown above.

[0168] 当染料包括三嗪基团Tr1和/或Tr2时,染料的合成还包括式C的三嗪化合物与两种氨基组分的反应 [0168] When the dye includes a triazine group Tr1 and / or Tr2, the synthesis reaction of the dye further comprises a triazine compound of formula C with two kinds of amino component

[0169] [0169]

Rb Rb

N^N N ^ N

(C) (C)

[0170] 其中1^和1^代表卤素,尤其是氯,且Rb代表卤素、甲基或甲氧基。 [0170] and wherein 1 ^ 1 ^ represents halogen, in particular chlorine, and Rb represents halogen, methyl or methoxy. 氨基组分是例如被称作重氮组分的Dk1-NH2和Dk2-NH2 ;被称作双偶氮组分的二胺化合物Tk1(NH2)2和Tk2(NH2)2 ;以及包含伯氨基的染料部分。 For example, the amino component is referred Dk1-NH2 and Dk2-NH2 diazo component; diamine compound is referred to as a tetrazo component of Tk1 (NH2) 2 and Tk2 (NH2) 2; containing a primary amino group, and dye moieties.

[0171] 这些方法是阴离子偶氮染料的现有技术中已知的,并可类似地用于染料I至XV的合成。 [0171] These prior art methods are known in the anionic azo dye, the dye may similarly be used I to XV of synthesis.

[0172] 所得重氮鎗或四氮鎗化合物化合物的重氮化和偶联通常在以传统方式控制pH值的含水反应介质中进行。 [0172] or gun diazotized diazonium compound and coupling four nitrogen gun aqueous reaction medium is usually carried out in a conventional manner to control the pH values.

[0173] 当反应的残基已经包含带有式CH2CH2-Q的B基团的A基团时,反应混合物的pH值优选不超过PH 8,否则Q基团会分离,同时形成乙烯基。 [0173] When the reaction residue already contains a group A with B of the formula CH2CH2-Q group, pH of the reaction mixture is preferably not more than PH 8, or Q groups will be separated, while forming the vinyl.

[0174] 在重氮鎗组分或四氮鎗组分分别偶联到不仅含有OH基团还含有氨基并且具有至少两个可能的偶联部位的式II和Kk-B的萘化合物上时,必须记住,第一偶联在不超过3的PH值下区域选择性地发生在氨基的邻位上,而在大于等于6并优选大于等于8的pH值下,区域选择性偶联发生在OH基团的邻位上。 [0174] Diazo components of the gun or guns tetrazolium component are coupled to further contain not only an OH group and an amino group-containing naphthalene compound having at least two of the upper coupling portion may formula II and Kk-B, and It must be remembered, the first coupling takes place selectively at the ortho position amino group in a region of not more than 3, pH value, and preferably greater than or equal to 6 and at a pH value greater than or equal to 8, the coupling occurs regioselectively ortho to the OH group.

[0175] 胺与三嗪化合物C的反应通常在酸性pH值下进行,优选小于pH 7,尤其是pH I至pH 4。 [0175] reaction of the amine with a triazine compound C is generally carried out at an acidic pH, preferably less than pH. 7, in particular the I pH to pH 4. · ·

[0176] 重氮化/偶联或与三嗪的反应所需的反应温度通常为0°C至50°C,尤其是O至30°C。 [0176] diazotizing / coupling the desired reaction temperature or reaction with the triazine is generally 0 ° C to 50 ° C, in particular O to 30 ° C. 所需反应时间通常为5分钟至2小时,尤其是20分钟至I小时。 The reaction time required is usually 5 minutes to 2 hours, particularly from 20 minutes to I hour.

[0177] 反应通常以化学计量进行;也就是,反应组分以所需的化学计量互相反应。 [0177] The reaction is usually carried out in a stoichiometric; i.e., the reaction components to react with each other stoichiometrically required. 然而,每种反应物也可以在所需化学计量的基础上过量或不足量使用。 However, each reactant may be used in an amount of excess or deficiency based on the desired stoichiometry. 与所需化学计量的偏离通常不超过20摩尔%,尤其不超过10摩尔%。 Deviation from the required stoichiometric amount of usually not more than 20 mol%, in particular not more than 10 mol%. 换言之,对于重氮鎗组分与偶联组分的反应,两种组分的摩尔比为I : I. 2至I. 2 : 1,尤其是I. I : I至I : I. I。 In other words, the gun for the diazo component and the coupling component, the molar ratio of the two components I: I. 2 to I. 2: 1, especially I. I: I to I: I. I. 为了使四氮鎗化合物与2摩尔当量的偶联组分反应,对于每摩尔四氮鎗化合物,偶联组分的用量为I. 6至2. 4摩尔,尤其是I. 8至2. 2摩尔。 In order to make the gun tetrazaindene compound with 2 molar equivalents of a coupling component of the reaction, per mole of guns tetrazaindene compound, the coupling component is used in an amount to I. 6 2. 4 moles, especially 2. I. 8 to 2 Moore.

[0178] 在重氮化/偶联之后,可以以合适的、优选水溶性盐的形式加入化学计量所需量的所需过渡金属盐,并且,如果需要,加热至络合所需的温度,例如40至100°C,由此制备过渡金属络合物。 [0178] After diazotizing / coupling, may be suitable, preferably in the form of water-soluble salt is added stoichiometrically required amount of the desired transition metal salt, and, if necessary, heated to the desired temperature of the complex, for example, 40 to 100 ° C, thereby preparing a transition metal complex.

[0179] 以传统方式,例如通过将含水反应混合物蒸发,尤其是通过喷雾干燥,通过盐析染料并干燥滤饼,从含水反应混合物中分离染料。 [0179] In a conventional manner, e.g. by evaporation of the aqueous reaction mixture, in particular by spray drying, salting and drying the dye cake was separated from the dye aqueous reaction mixture. 可以将优选仍然潮湿的滤饼再溶解,优选溶于水中,并进行渗滤和/或超滤,从而使合成中制成的无机盐贫化和/或使溶液富含染料。 Preferred may be still moist filter cake is dissolved, preferably dissolved in water, and subjected to diafiltration and / or ultrafiltration, thereby to prepare a synthetic inorganic salts-depleted and / or enriched with dye solution. 然后,通过喷雾干燥从溶液中回收由此提纯的染料。 Then, thus recovered dried dye purified from the solution by spraying.

[0180]为了制备染料的液体品种或液体制品,可以将蒸发或喷雾干燥获得的染料滤饼或粉末溶于例如水、水-溶剂混合物、含水酸或含水碱中,在这种情况下含水酸和含水碱还可以含有溶剂。 [0180] In order to prepare a liquid or liquid product varieties dye, the dye may be a powder or a cake obtained by evaporation or spray-drying for example, water soluble, water - solvent mixture, aqueous acid or aqueous alkali, aqueous acid in which case and aqueous base may further contain a solvent. 此处可用的溶剂特别包括水混溶性溶剂,例如C1-C4链烷醇、有机羧酸(例如甲酸、乙酸和丙酸)、链烷醇胺、二链烷醇胺和三链烷醇胺(例如乙醇胺、二乙醇胺、三乙醇胺)以及酰胺(例如甲酰胺、乙酰胺、二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮、二甲亚砜等)。 Solvents usable herein include, in particular water-miscible solvents such as C1-C4 alkanols, organic carboxylic acids (e.g. formic acid, acetic acid and propionic acid), alkanolamines, dialkanolamines and trialkanolamines ( such as ethanolamine, diethanolamine, triethanolamine) and amides (e.g. formamide, acetamide, dimethylformamide, dimethylacetamide, N- methylpyrrolidone, dimethyl sulfoxide, etc.). 还可以直接由反应溶液或通过超滤和喷雾干燥制备染料的液体制品。 The reaction may also be directly from the solution or liquid article drying the dye was prepared by ultrafiltration and spray. 然后为了获得足够高的染料浓度和液体品种的稳定性,可能必须进行渗滤和/或超滤操作,以使合成过程中生成的无机盐贫化并使溶液浓缩。 Then, in order to obtain a sufficiently high stability of the dye concentration and liquid species, may be subjected to diafiltration and / or ultrafiltration operation, so that the inorganic salts generated during synthesis and lean solution was concentrated.

[0181] 本发明的方法包括在至少7. 5的pH值下的染色步骤。 Method [0181] The present invention includes the step of dyeing at a pH of at least 7.5. 为此,在pH值为至少7. 5且优选至少8. O并包含至少一种上述类型的染料F的水浴液中处理待染色的皮革。 For this purpose, at a pH of at least 7.5 and preferably at least 8. O bath comprising water and at least one of the above types of dyes F in the dyed leather to be treated. 浴液的pH值通常不超过pH 11,优选不超过pH 10.5。 float pH typically does not exceed pH 11, preferably not more than pH 10.5. 更特别地,浴液的pH值为8. 5至10。 More particularly, pH of the bath is from 8.5 to 10. 碱性PH值确保染料固定在皮革上,因为在这些条件下,基团A与皮革的氨基反应以形成共价键。 Alkaline PH value to ensure that the dye is fixed on the leather, because in these conditions, the reaction of an amino group A and leather to form a covalent bond.

[0182] 为了获得固色所需的碱性pH值,可以使用任何合意的碱和缓冲体系。 [0182] In order to obtain the desired alkaline pH fixation, any desirable base and a buffer system. 例子是碱金属碳酸盐和碳酸氢盐,例如碳酸钠、碳酸钾和碳酸氢钠,以及碱金属氢氧化物,例如氢氧化钠水溶液、硅酸钠、焦磷酸盐,例如焦磷酸钠或焦磷酸钾,磷酸三钾、磷酸三钠、硼砂/氢氧化钠水溶液缓冲剂和磷酸盐缓冲剂。 Examples are alkali metal carbonates and bicarbonates such as sodium carbonate, potassium carbonate and bicarbonate, and alkali metal hydroxides such as aqueous sodium hydroxide, sodium silicate, sodium pyrophosphate, sodium pyrophosphate or pyrophosphate e.g. potassium phosphate, tripotassium phosphate, trisodium phosphate, borax / sodium hydroxide solution buffer and phosphate buffer.

[0183] 固定染料所需的温度有利地为不超过60°C,尤其是不超过50°C,更优选不超过40°C,以便温和地将皮革染色。 [0183] required for dye fixing temperature is advantageously not more than 60 ° C, especially not more than 50 ° C, more preferably not more than 40 ° C, in order to gently dyeing leather. 染色温度通常为至少10°C,优选至少20°C,尤其是至少30°C,以获得足够的反应速率并可由此加速染色过程。 The dyeing temperature is typically at least 10 ° C, preferably at least 20 ° C, in particular at least 30 ° C, in order to obtain a sufficient reaction rate can thereby accelerating the dyeing process. 但原则上较低的温度也可行。 But lower temperatures are also possible in principle. 用于有机鞣制的皮革的温度范围优选为15至50°C,特别是30至40°C。 For tanned leather Organic temperature range is preferably from 15 to 50 ° C, in particular 30 to 40 ° C. 用于金属氧化物鞣制的皮革的优选温度范围是15至60°C,特别是30至50°C。 The preferred temperature range for the metal oxide tanned leather from 15 to 60 ° C, in particular 30 to 50 ° C.

[0184] 充分的固色通常需要O. 5至4小时的处理时间,这取决于pH值和温度。 [0184] sufficient fixation O. 5 typically requires processing time to 4 hours, depending on pH and temperature. 本领域技术人员能够通过进行简单的常规实验确定所用特定染料所需的处理时间。 Those skilled in the art to the processing time required by the particular dye determined by simple routine experimentation. 尤其是在9. 5至 Especially 9.5 to

11、尤其是9. 5至10. 5的强碱性pH值下,染色时间优选不超过2小时,例如O. 5至2小时。 11, especially in strongly alkaline pH of 9.5 to 10.5, the dyeing time is preferably less than 2 hours, e.g. O. 5 to 2 hours. · ·

[0185] 染色可以在存在外加的盐(例如芒硝)的情况下进行。 Case where [0185] Dyeing can be applied salts (e.g. Glauber's salt) in the presence of.

[0186] 除了按照本发明使用的染料F外,浴液还可包括传统的酸或直接染料。 [0186] F except in accordance with the present invention the dye, an acid bath may further comprise conventional or direct dyes. 然而,它们的比例优选不超过浴液中染料总量的10重量%,尤其不超过5重量% (在每种情况下都以染料的有机化学着色组分进行计算)。 However, their proportion is preferably not more than 10% by weight of the total amount of the dye bath, in particular not more than 5 wt% (all in Organic Chemistry dye coloring component was calculated in each case).

[0187] 所用染料F的量取决于所需的色调深度并且通常为所用皮革或中间制品削匀重的至少O. 2重量%,通常至少O. 5重量%,尤其是至少I重量%,此处所述的量是以包括合成盐和任何标准剂在内的染料为基础的。 [0187] The amount of dye used depends on the depth of shade required F and generally at least 2 O. weight of shaved weight of leather or intermediate product used, usually at least O.. 5% by weight, in particular at least I wt.%, This the amount of said salt is synthetic and includes any agent, including standard-based dye. 基于着色的有机化学组分,所用染料的量通常不低于所用皮革或中间制品削匀重的O. I重量%,通常不低于O. 3重量%,尤其是不低于O. 5重量%。 Organic chemistry based coloring components, the amount of dye used is usually not less than or intermediate product shaved leather weight O. I% by weight, usually not less than O. 3% by weight, in particular not less than O. 5 wt. %. 以有机化学组分+合成盐和任何标准剂的混合物进行计算,染料用量通常最高达20重量% ;或以着色的有机化学组分进行计算并以削匀重为基础时,染料用量通常最高达15重量%,但也可以使用更大的量。 Mixture of organic chemical components are calculated to + Synthesis salts and any standard agent, the dye is generally used in an amount up to 20 wt%; calculated as the time or colored organic chemical components and to shaved weight basis, the amount of dye is typically up to 15 wt%, but larger amounts may be used. 为了获得中至高色调深度,染料F的用量取决于染料的摩尔消光系数和染料的分子量,并且以皮革或中间制品的削匀重为基础并以有机化学组分+合成盐和任何标准剂的混合物进行计算时,为2重量%至20重量%,通常3重量%至20重量%,尤其是4重量%至20重量%,或者以皮革或中间制品的削匀重为基础并以着色的有机化学组分进行计算时,为I重量%至15重量%,通常I. 5至10重量%,尤其是2重量%至10重量%。 In order to obtain the amount of medium to high depth of shade, it depends dyes dye F molar extinction coefficient and molecular weight of the dye, and to cut leather intermediate products or uniform basis weight and the mixture of organic chemistry component + Synthesis of salts and any standard agent when calculated as a 2% by weight to 20% by weight, usually 3% to 20% by weight, in particular 4 wt% to 20 wt%, or leather or to cut the intermediate product and is uniform basis weight colored organic chemistry when the component is calculated as I wt% to 15 wt%, typically I. 5 to 10 wt%, especially 2 wt% to 10 wt%.

[0188] 水浴液可以包括常规的阴离子染色助剂、非离子表面活性剂以及湿部法(wet-end)化学品,例如常用于复鞣的鞣料,例如聚合复鞣料、合成复鞣料、植物鞣料以及加脂剂和疏水剂。 [0188] Water bath may include conventional anionic dye assistant, a nonionic surfactant and a wet end process (wet-end) chemicals, such as commonly used in the tanning retanning, for example polymeric retanning material, synthetic retanning , vegetable tanning and fatliquoring agents and water repellent.

[0189] 本发明的方法可用的复鞣料包括所有的市售体系,例如: [0189] The method of the present invention may include all commercial retanning material systems, for example:

[0190] I.植物鞣料,例如含羞草、栗子、白雀树; [0190] I. vegetable tanning materials, e.g. mimosa, chestnut, quebracho;

[0191] 2.矿物鞣料,例如铬、铁、铝和锆鞣料; [0191] 2. The mineral tanning material, such as chromium, iron, aluminum and zirconium tanning;

[0192] 3.填料,例如层状硅酸盐、糖类、聚糖,例如淀粉和面粉; [0192] 3. The filler, for example layered silicates, sugars, polysaccharides, such as starch and wheat flour;

[0193] 4.合成鞣料(合成鞣剂),例如EP 0459168、EP 0520182、US 5,342,916 和US5,186,846中描述的物质,例如: [0193] 4. Synthesis of tanning (syntans) such substances EP 0459168, EP 0520182, US 5,342,916 and US5,186,846 described in, for example:

[0194] a.萘磺酸-甲醛缩合产物, [0194] a naphthalenesulfonic acid - formaldehyde condensation products,

[0195] b.苯酚磺酸-甲醛缩合产物, [0195] b phenolsulfonic acid - formaldehyde condensation products,

[0196] c.萘磺酸和/或苯酚磺酸与羟基芳基砜(例如二(羟苯基)砜)和甲醛的缩合产物, [0196] c. Naphthalenesulfonic acid and / or phenolsulfonic acid with hydroxy aromatic sulfones (e.g., bis (hydroxyphenyl) sulfone) and condensation products of formaldehyde,

[0197] d.萘磺酸和/或苯酚磺酸与低聚砜(经由砜桥连接并可以被例如-OH或403!1取代的多环芳族化合物的混合物)和甲醛的共缩合产物, [0197] d. Naphthalenesulfonic acid and / or phenolsulfonic acid with oligomeric sulfone (sulfone are connected via bridges and may be a mixture of e.g. -OH or 403! 1-substituted polycyclic aromatic compound) and formaldehyde co-condensation products,

[0198] e.萘磺酸、苯酚磺酸与甲醛、和与含N的化合物以及合适时与羟基芳基砜或与低聚砜的共缩合产物。 [0198] e. Naphthalenesulfonic acid, phenolsulfonic acid with formaldehyde, and a N-containing aromatic hydroxy compound and a sulfone or sulfone co-oligomeric condensation products as appropriate.

[0199] 含N的化合物的例子是脲、三聚氰胺、三聚氰胺衍生物,例如羟基-C2-C2tl-烷基三聚氰胺、二_轻基-C2-C2tl-烧基二聚氰胺或二_轻基-C2-C2tl-烧基二聚氰胺、轻基芳基二聚氰胺或在N-原子上含有一至三个聚环氧烷链的三聚氰胺;蜜勒胺(2,5,8_三氨基_1,3,4,6,7,9,9b-七氮杂非那烯heptaazaphenalene)或蜜勒胺衍生物,例如轻基-C2-C2tl-烧基蜜勒胺或在N-原子上含有聚环氧烷侧链的蜜勒胺;胍胺(6-取代的2,4_ 二氨基-1,3,5-三嗪),例如苯胍胺、乙酰胍胺、癸酰胍胺或异丁胍胺;胍胺衍生物,例如N-羟基-C2-C2tl-烷基胍胺,以及在N-原子上含有一个或两个聚环氧烷链的胍胺,和二氰二酰胺,· [0199] Examples of N-containing compounds are urea, melamine, melamine derivatives, such as hydroxy alkyl melamine -C2-C2tl-, _ two light burn-yl group -C2-C2tl- melamine two light-yl or di _ - C2-C2tl- burn-yl two melamine, two light aryl melamine or melamine containing one to three polyalkylene oxide chains on the N- atom; melem (2,5,8_ triamino _ 1,3,4,6,7,9,9b- seven-aza-phenalene heptaazaphenalene) or melem derivatives, such as light burned yl group -C2-C2tl- melem or on the N- atom containing poly alkylene side chains melem; guanamine (6-substituted 2,4_-diamino-1,3,5-triazine), such as benzoguanamine, acetoguanamine, benzoguanamine or iso-decanoyl guanidine amine; guanamine derivatives such as N- hydroxysuccinimide -C2-C2tl- alkyl guanamines, guanidines and amines having one or two polyalkylene oxide chains on the N- atom, and dicyandiamide, ·

[0200] f· 4. a至4. e物质与Cr (III)化合物的混合物; [0200] The mixture f · 4. a substance to 4. e Cr (III) compound;

[0201] 5.树脂鞣料;例如: [0201] The resin tanning; for example:

[0202] a.萘磺酸与甲醛的含亚硫酸盐的缩合产物, [0202] a. A sulfite-containing condensation products of naphthalenesulfonic acid with formaldehyde,

[0203] b.苯基磺酸与甲醛的含亚硫酸盐的缩合产物, [0203] b. Phenyl sulfonic acid and formaldehyde condensation products containing sulfite,

[0204] c. 5a与5b的混合物; . [0204] c 5a and 5b of the mixture;

[0205] 6.聚合鞣料,其在性质上可以是阴离子、阳离子或两性的。 [0205] 6. A polymeric tanning material, in which can be anionic, cationic or amphoteric. 阴离子聚合鞣料可以含有,例如,羧基,阳离子聚合鞣料可以含有,例如,氨基,两性聚合鞣料不仅含阳离子基团,还含阴离子基团。 Anionic polymeric tanning material may contain, for example, a carboxyl group, a cationic polymeric tanning material may contain, for example, an amino group, an amphoteric polymeric tanning material containing only a cationic group, further containing an anionic group. 根据PH值,两性聚合物在性质上可以是阴离子或阳离子型的。 The value of PH, in the amphoteric polymer can be anionic or cationic. 聚合鞣料的例子是: Examples of polymeric tanning material are:

[0206] a.丙烯酸和甲基丙烯酸的均聚物和共聚物, [0206] a. Acrylic and methacrylic homopolymers and copolymers,

[0207] b.丙烯酸和/或甲基丙烯酸与丙烯酸C1-C3tl烷基酯和/或甲基丙烯酸C1-C3tl烷基酯的均聚物和共聚物, [0207] b. Of acrylic acid and / or homopolymers and copolymers of methacrylic acid and C1-C3tl alkyl esters and / or methacrylic acid esters of C1-C3tl alkyl,

[0208] c.丙烯酸C1-C3tl烷基酯和/或甲基丙烯酸C1-C3tl烷基酯与含阳离子或阴离子/酸性基团的单体的官能化共聚物, [0208] c. Alkyl acrylate, C1-C3tl ester and / or methacrylic acid alkyl esters with C1-C3tl functional copolymer containing monomers having cationic or anionic / acidic groups, and

[0209] d.烯键式不饱和二羧酸酐(例如马来酸酐)与C3-C4tl- α -烯烃(例如丙烯、I- 丁烯、I-己烯、I-辛烯、二异丁烯、I-癸烯等)的共聚物, . [0209] d ethylenically unsaturated dicarboxylic anhydride (e.g. maleic anhydride) with C3-C4tl- α - olefins (e.g. propylene, I- butene, I- hexene, I- octene, diisobutylene, the I - decene, etc.) copolymer,

[0210] e. 二羧酸酐-苯乙烯共聚物, . [0210] e dicarboxylic anhydride - styrene copolymer,

[0211] f.烯键式不饱和腈(例如丙烯腈和甲基丙烯腈),如果合适与其它单烯键式不饱和单体(例如丙烯酸、甲基丙烯酸、丙烯酰胺、甲基丙烯酰胺或(甲基)丙烯酸C1-Cltl-烷基酯)的均聚物和共聚物, [0211] f. Ethylenically unsaturated nitriles (e.g. acrylonitrile and methacrylonitrile), if appropriate with other monoethylenically unsaturated monomers (e.g. acrylic acid, methacrylic acid, acrylamide, methacrylamide or (meth) acrylic acid alkyl esters of C1-Cltl-) homopolymers and copolymers,

[0212] 在EP-A 1335029和WO 96/15276中描述了聚合鞣料的例子,在这方面,这两个文献都经此引用并入本文。 [0212] Examples of polymeric tanning material is described in EP-A 1335029 and in WO 96/15276, in this regard, these two documents are incorporated herein by reference.

[0213] 7.醒,例如: [0213] 7. The wake up, for example:

[0214] a.甲醒, [0214] a. A wake,

[0215] b.戊二醛, [0215] b. Glutaraldehyde,

[0216] c.如TO 03/095681中所述的低聚醛, [0216] c. As in the oligomerization TO 03/095681 aldehyde,

[0217] d.如Bibliothek des Leders 卷3, Umschau Verlag, 1984,第26-27 页所述的生成醛的鞣料,其例子为噁唑烷和鱗化合物; . [0217] d as Bibliothek des Leders volume 3, Umschau Verlag, 1984, pages 26-27 tanning material according to aldehydes, examples of oxazolidine compound and scale;

[0218] 8.如US 5,186,846中所述的分散剂,例如: [0218] 8. US 5,186,846 in the dispersing agent, for example:

[0219] a.萘磺酸-醛缩合产物和 [0219] a naphthalenesulfonic acid - formaldehyde condensation products and

[0220] b.木素磺酸盐。 [0220] b. Lignosulfonate.

[0221] 可用的鞋料进一步包括所有市售鞋料,例如Ullmann' s EncyclopediaofIndustrial Chemistry,卷A 15 第259-282 页,尤其是268 页以下,第5 版(1990) ,VerlagChemie Weinheim中所述的铬鞋料、矿物鞋料、合成鞋剂、聚合鞋料和植物鞋料。 [0221] further comprises a feed shoe available all commercially available footwear materials, e.g. Ullmann 's EncyclopediaofIndustrial Chemistry, volume A 15 on pages 259-282, in particular the following page 268, fifth edition (1990), VerlagChemie Weinheim described in chromium shoe materials, mineral shoe materials, synthetic shoes, polymeric materials and plant shoe shoes materials. 市售鞋料还可以是I.-8.下所述的鞣料类型的混合物。 Commercially available materials may also be shoe I.-8. Tanning mixture according to the type.

[0222] 可用加脂剂包括皮革制造中所有常规加脂剂,尤其是所有市售加脂剂。 [0222] Available fatliquors include all conventional fatliquor leather manufacture, especially all commercially available fatliquor. 加脂剂自然包括至少一种基于烃,例如基于天然或合成蜡、天然或合成油或天然或合成脂肪的疏水物质。 Greasing agent comprises at least one hydrocarbon-based nature, for example based on natural or synthetic waxes, natural or synthetic oils or fats of natural or synthetic hydrophobic materials. 基于聚异丁烯的物质也可用作加脂剂的烃原料。 Polyisobutylene-based materials can also be used as the hydrocarbon feedstock fatliquors. 下文更详细描述的加脂剂烃原料可以被化学改性,例如: Fatliquor hydrocarbon feedstock described in more detail hereinafter may be chemically modified, for example:

[0223] I.硫酸化 [0223] I. sulfated

[0224] 2.磺化 [0224] 2. Sulfonated

[0225] 3.亚硫酸化 [0225] 3. sulphited

[0226] 4.磺化氧化 [0226] 4. The sulfoxidation

[0227] 5.氯磺化 [0227] 5. chlorosulfonated

[0228] 6.乙氧基化或通常酯化 [0228] 6. typically esterified ethoxylated or

[0229] 加脂剂的烃原料也可以含有非官能化组分的混合物、官能化组分与非官能化组分的混合物或官能化组分的混合物。 [0229] fatliquor hydrocarbon feed mixture, the non-functionalized component and functional component of non-functionalized or functionalized components of the mixture may contain a mixture of components.

[0230] 可用于加脂剂的天然蜡包括蜂蜡、软木蜡、褐煤蜡和巴西棕榈蜡。 [0230] can be used fatliquoring agents include natural waxes beeswax, cork wax, montan wax and carnauba wax.

[0231] 可用于加脂剂的合成蜡包括: Synthetic waxes [0231] fatliquoring agents can be used include:

[0232]-可例如通过乙烯的自由基聚合或乙烯与例如(甲基)丙烯酸的自由基共聚或通过齐格勒-纳塔催化获得的聚乙烯蜡和乙烯共聚物蜡; [0232] - may be, for example, radical polymerization of ethylene or ethylene with (meth) acrylic acid by radical copolymerization or by Ziegler - Natta catalysed polyethylene waxes and ethylene copolymer waxes;

[0233]-聚异丁烯蜡; [0233] - polyisobutylene wax;

[0234]-石蜡,也就是含有12或更多碳原子并通常具有25至45°C的熔点的烃的混合物。 [0234] - Paraffin, i.e. containing 12 or more carbon atoms and usually a mixture of hydrocarbons having a melting point of 25 to 45 ° C to. 这些石蜡可以例如在精炼厂或裂化厂中获得,并且被本领域技术人员称作疏松石蜡和sasol腊;以及 These paraffins can be obtained, for example in a cracker or a refinery, and is referred to as slack wax and sasol wax skilled in the art; and

[0235]-褐煤酯蜡。 [0235] - montan ester wax.

[0236] 可用于加脂剂的天然油特别包括室温液体甘油三酸酯,例如鱼油、牛脚油、橄榄油、棉籽油、蓖麻油、向日葵油和花生油。 Natural oils [0236] may be used include in particular fatliquors triglycerides liquid at room temperature, such as fish oil, beef foot oil, olive oil, cottonseed oil, castor oil, sunflower oil and arachis oil.

[0237] 可用于加脂剂的合成油特别包括轻油、石蜡油、官能化石蜡,例如氯化或氯磺化石蜡,以及聚亚烷基二醇,例如聚乙二醇。 Synthetic [0237] may be used include in particular fatliquors gas oil, paraffin oil, paraffin wax functionalized, e.g. chlorosulfonated or chlorinated paraffin, and polyalkylene glycols such as polyethylene glycol.

[0238] 可用于加脂剂的天然脂肪特别包括室温固体天然甘油三酸酯,例如羊毛脂、紫胶蜡以及它们的混合物。 [0238] can be used fatliquoring agents include natural fatty particularly natural triglycerides solid at room temperature, such as lanolin, shellac wax, and mixtures thereof.

[0239] 在WO 03/023070中描述了基于聚异丁烯的加脂剂的例子。 [0239] Examples described fatliquors based on polyisobutylene in WO 03/023070.

[0240] 在WO 03/023069中描述了加脂剂的其它例子。 [0240] Other examples are described in the fatliquor in WO 03/023069.

[0241] 除了烃原料,加脂剂可以进一步包含表面活性物质。 [0241] In addition to the hydrocarbon feedstock, refatting agents may further comprise surface-active substances. 这些包括用于皮革制造的加脂剂、鞣料、疏水剂和其它助剂中存在的所有乳化剂。 These include all emulsifiers for fatliquoring agents, tanning, hydrophobing agents and other additives present in the leather manufacturing. 表面活性物质在性质上可以是非离子、阴离子、阳离子或两性离子型的。 Surface active in nature can be nonionic, anionic, cationic or zwitterionic. 本发明的加脂剂宜使用非离子或阴离子物质作为乳化齐U,优选使用脂肪醇(也就是含有10至25个碳原子的醇混合物)或含有5至100个环氧烷基团的烷氧基化脂肪醇作为非离子乳化剂,或使用它们的硫酸盐或磷酸盐作为阴离子乳化剂,尤其是使用阴离子乳化剂的钠盐、钾盐或铵盐。 Fatliquor is preferable to use nonionic or anionic species of the present invention as a homogeneous emulsion U, preferably fatty alcohols (i.e. an alcohol mixture containing 10 to 25 carbon atoms), or alkoxy of from 5 to 100 alkylene oxide groups fatty alcohol group as the nonionic emulsifier, or their sulfates or phosphates as anionic emulsifiers, anionic emulsifiers especially sodium, potassium or ammonium salts.

[0242] 可用于本发明的方法的疏水剂包括已知用于皮革制造的所有疏水剂,尤其是如M. Hollstein, Bibliothek des Leders,卷4-Defatting, fatliquoringandhydrophobicization of leather, 1983 中所述的市售体系。 Water repellent process [0242] can be used in the present invention include all known water repellent for leather, in particular as M. Hollstein, Bibliothek des Leders, volume 4-Defatting, fatliquoringandhydrophobicization of leather, in the city of 1983 sale system.

[0243] 市售产品特别包括一种或多种下述组分: [0243] Commercially available products include, in particular one or more of the following components:

[0244] 1. α-烯烃与二羧酸酐(例如马来酸酐)的共聚物 [0244] 1. α- olefin with a dicarboxylic anhydride (e.g. maleic anhydride) copolymer

[0245] 2.石蜡 [0245] 2. Paraffin

[0246] 3.轻油 [0246] 3. The gas oil

[0247] 4.简单硅氧烷 [0247] 4. Simple silicone

[0248] 5.官能化硅氧烷 [0248] The functional siloxane

[0249] 6.乳化剂 [0249] 6. Emulsifier

[0250] 疏水剂可以进一步包括对加脂剂所述的任何组分。 [0250] hydrophobizing agent may further comprise any component of the fatliquors.

[0251]除了其它加脂剂成分,例如在 EP-A 213480、WO 95/22627、W098/04748、ΕΡ-Α1087021和WO 01/68584中还详尽描述了基于硅氧烷的疏水剂和基于α -烯烃与二羧酸酐的共聚物的疏水剂。 [0251] Among other fatliquor ingredients, for example, in EP-A 213480, WO 95/22627, W098 / 04748, ΕΡ-Α1087021 and WO 01/68584 also describes in detail based on the hydrophobic agent and silicone-based α - a copolymer of an olefin and water repellent dicarboxylic acid anhydride. 在WO 93/17130和ΕΡ-Α372746中可以找到疏水剂的其它例子。 Other examples can be found in WO 93/17130 hydrophobic agent and the ΕΡ-Α372746.

[0252] 所用鞣剂、加脂剂和疏水剂的种类和量按传统方式取决于要制造的皮革制品的种类、鞣制类型(矿物鞣或无金属鞣)、所需触觉状况和所需物理性质。 [0252] The haptic conditions and desired physical properties tanning agent used, the type and amount of the hydrophobic agent and fatliquoring agent in a conventional manner depending on the kind of the leather articles to be produced, the type of tanning (metal-free mineral tanning or tanning), the desired .

[0253] 因此,鞣料以下列量用于皮革制造: [0253] Thus, in the following amounts for tanning leather:

[0254] 聚合鞣料(配制为溶液)的量最多达20重量%,通常为3-8重量%和/或 The amount of [0254] polymeric tanning material (formulated as a solution) is up to 20% by weight, typically 3-8 wt% and / or

[0255] 合成鞣剂(以粉末计算)的量最多达30重量%,通常4-12重量%和/或 [0255] The amount of synthetic tanning agent (powder basis) up to 30 wt%, generally 4-12 wt%, and / or

[0256] 树脂鞣料(以粉末计算)的量最多达15重量%,通常3-6重量%,和/或植物鞣料的量最多达30重量%,通常4-12重量%, [0256] The resin tanning material (calculated as a powder) in an amount up to 15 wt%, typically up to 30 wt% 3-6 wt%, and / or amount of vegetable tanning materials, typically 4-12% by weight,

[0257] 鞋料总量通常最多达40重量% ,例如4重量%至40重量% ,通常10重量%至40重量%,所有百分比都以皮革的湿重为基数。 [0257] Typically up to the total feed shoe 40 wt%, for example 4 wt% to 40 wt%, typically 10 wt% to 40 wt%, all percentages are by weight of wet leather base.

[0258] 加脂剂和疏水剂通常以下列量使用:最多达20重量%、通常6-12重量%的加脂齐U,最多达20重量%、通常4-8重量%的疏水剂,各自以皮革的湿重为基数。 [0258] fatliquoring agent and hydrophobic agent are usually in the following amounts: up to 20% by weight, typically 6-12% by weight of refatting homogeneous U, up to 20% by weight, typically 4-8% by weight of a hydrophobic agent, each the wet weight of leather as the base.

[0259] 染色可以在一个阶段进行,也可以分2个阶段进行。 [0259] Dyeing can be carried out in one stage, two stages may be carried out. 在两级染色中,首先在第一阶段用PH值低于7. 5、例如pH 3至7. 4并优选pH值为4至7. 4的含染料的浴液处理皮革。 In two dyeing, at first in a first stage with a PH value of less than 7.5, for example from 3 to 7.4 and preferably pH pH value of the dye bath containing from 4 to 7.4 of treating leather. 该步骤用于使染料均匀分配在皮革横截面上。 This step is used to evenly distribute the dye in the leather cross section. 然后,在第二阶段中,以上述方式在至少8、例如8至11、尤其是8. 5至10. 5、尤其是8. 5至10的pH值下将染料固定。 Then, in a second stage, the above-described manner of at least 8, e.g. 8-11, especially from 8.5 to 10.5, in particular at a pH of from 8.5 to 10 fixing dyes. 还可以在一步法中进行染色,即在固色阶段之前没有分配阶段。 May also be dyed in one step, i.e. not assigned a stage prior to fixation stage.

[0260] 尽管不是绝对必要,但在染色操作之后可以进行洗涤以去除未化学键合的染料以及染料中的杂质,例如不含A基团的染料。 [0260] Although not absolutely necessary, but after the dyeing operation may be washed to remove unbound dye, and a dye chemically bonded impurities such as dyes free of A group. 不是绝对需要该洗涤的原因在于染料固色在许多情况下已经是定量或几乎定量的。 The reason is not absolutely necessary that the dye fixation washed in many cases is already quantitative or almost quantitative. 如果进行然后的洗涤,可以用水将染色后的皮革洗涤一次至多次,例如I至6次,尤其是I至4次。 If then washed can be washed with water after dyeing the leather one to several times, for example I to 6, especially I to 4 times. 水的量通常不超过中间制品削匀重的300重量%,例如100重量%至300重量%。 The amount of water typically does not exceed an intermediate article shaved weight of 300 wt%, e.g. 100% to 300% by weight. 单个洗涤步骤的持续时间通常为5至60分钟,尤其是10至30分钟。 Duration of a single wash step is usually 5 to 60 minutes, in particular from 10 to 30 minutes.

[0261] 洗涤操作可以类似地采用非离子、阴离子、阳离子或两性离子助剂。 [0261] washing operation may similarly be employed nonionic, anionic, cationic or zwitterionic agents. 优选市售离子助剂,例如基于聚乙烯基甲酰胺、聚乙烯基吡咯烷酮、乙烯基吡咯烷酮-乙烯基咪唑共聚物或基于二羧酸或二羧酸酐与胺的缩合产物或萘磺酸与甲醛的缩合产物。 Commercially available ionic additives is preferably, for example based on polyvinyl formamide, polyvinyl pyrrolidone, vinyl pyrrolidone - vinyl imidazole or copolymers based on dicarboxylic acids, or condensation products of naphthalenesulfonic acid with formaldehyde or dicarboxylic anhydride with an amine condensation products. 在EP 0459168,EP0520182、US 5,342,916 和US 5,186,846 中描述了这些助剂。 In EP 0459168, EP0520182, US 5,342,916, and US 5,186,846 describes these additives.

[0262] 当染料中包含有色副产物或当固色过程中形成了有色副产物时,助剂的使用特别敏感。 [0262] When dyes or colored by-products comprising fixing process when colored by-products are formed, particularly sensitive to use of adjuvants. 助剂确保所有有色次要成分的定量或基本定量去除只需要不超过三次洗涤,可能仅两次洗涤或理想地一次洗涤。 Adjuvants ensure quantitative or substantially quantitative removal of all of the colored secondary component, no more than washed three times, washed twice may only be washed once or over.

[0263] 包括复鞣、加脂和后处理在内的皮革染色以传统方式进行,例如通过在转鼓或在桨叶(paddle)中染色而进行。 [0263] comprises retanning, fatliquoring and the dyeing of leather, including the post-treatment in a conventional manner, for example by dyeing in a drum or a paddle (paddle). 这些方法在现有技术中有详尽的描述,例如在"Bibliothekdes Leders ",卷3 (tanning agents, tanning andretanning) These methods are fully described in the prior art, for example, in "Bibliothekdes Leders", Volume 3 (tanning agents, tanning andretanning)

[1985],卷4 (defatting,fatliquoring and hydrophobicization inleather manufacture) [1985], Volume 4 (defatting, fatliquoring and hydrophobicization inleather manufacture)

[1987]及卷5(thedyeing of leather) [1987] and the roll 5 (thedyeing of leather)

[1987]UmschauVerlag ; " Leather Technicians Handbook ",·1983, JH Sharphouse 著,Leather Producers Association 出版;和"Fundamentals ofLeatherManufacturing" , 1993, E. Heidenmann 著,Eduard Roether KG 出版。 [1987] UmschauVerlag; "Leather Technicians Handbook", · 1983, JH Sharphouse forward, Leather Producers Association publication; and "Fundamentals ofLeatherManufacturing", 1993, E. Heidenmann forward, Eduard Roether KG publishing.

[0264] 染色通常在预鞣之后进行,也就是在复鞣之前、之中或之后进行。 [0264] After pre-tanning staining usually carried out, that is, before retanning, during or after. 染色操作可以与复鞣操作在相同的浴中进行,也可以在不同的浴中进行。 Dyeing operation can be performed in the same bath with the retanning operation, may be performed in a different bath. 染色操作优选在复鞣之前进行。 Dyeing operation preferably before retanning. 优选在鞣制之后并在复鞣和加脂之前进行上述一个或多个洗涤步骤。 The one or more washing step is preferably performed before and after the retanning and fatliquoring tanning.

[0265] 通常在染色和复鞣操作之后进行加脂操作以将皮革调节至所需的触觉性能。 [0265] Generally fatliquoring operation after dyeing and retanning leather operation to adjust to the desired tactile properties. 然而,复鞣和加脂也可以在一个工艺步骤中进行。 However, retanning and fatliquoring process may be carried out in one step. 加脂步骤可以在湿部操作的任何阶段进行,并优选在湿部操作的最后进行。 Fatliquoring step may be performed at any stage of the wet end operations and is preferably carried out in the last portion of wet operation.

[0266] 通常,加脂和复鞣都在操作的最后通过酸化进行固定,也就是在染色和任何复鞣和加脂之后进行最后酸化。 [0266] Generally, retanning and fatliquoring operations are fixed by final acidification, which is carried out after acidification the final dyeing and any retanning and fatliquoring. 通常,为了进行酸化,加入酸,尤其是甲酸,将水处理浴的PH值调节至3.7以下的值。 Typically, for acidification, adding an acid, in particular formic acid, the PH value of the water bath is adjusted to a value of 3.7 or less.

[0267] 本发明的方法原则上可用于染色所有类型的皮革,即还没有复鞣的中间制品,例如金属氧化物鞣制的皮革(用氧化铬鞣制的湿铬鞣革和用氧化铝鞣制的湿法白鞣)和有机鞣制的(例如醛鞣的)皮革(白湿皮)、或植物鞣皮革,以及已经复鞣过的中间制品,例如树皮鞣革或坯革。 [0267] In principle, the method according to the present invention may be used for dyeing all types of leather, i.e. not yet retanned intermediate product, such as wet leather metal oxide tanned (wet chrome tanning chromium tanned and alumina tanned method tanning white) and organic tanning (e.g. aldehyde tanned) leather (wet-white leather), or vegetable tanned leather, and it has been retanned intermediate product, e.g. bark tanning or crust.

[0268] 本发明的方法特别可以制造用于任何皮革制品(例如鞋类、服装、汽车、手套和家具部分)的染色皮革。 [0268] The method of the present invention can be manufactured especially for dyeing leather any leather (e.g. shoes, clothing, automobiles, furniture and gloves portion). 本发明的方法也可以制造皮包革和用于配件的爬行动物皮革。 The method of the present invention may also be used for producing bags and leather accessories reptile leather. 按照传统方式,通过选择适用于特定制品的助剂、加脂剂、疏水剂和复鞣料来获得特定皮革制品所需的触觉、机械和物理性能。 In a conventional manner, by selecting a particular article suitable auxiliaries, refatting agents, hydrophobing agents and retanning leather to obtain specific desired article tactile, mechanical and physical properties.

[0269] 按照本发明的方法染色的皮革即使在非常高的色调深度下也具有优异的坚牢度。 [0269] The dyeing method according to the present invention, the leather even at very high depth of shade has excellent fastness. 耐擦坚牢度,尤其是耐洗、耐汗和耐渗移坚牢度特别好,这在通过传统方法染色的皮革中非常难,甚至不可能实现。 Rub fastness, especially washing, perspiration fastness and resistance to Bleeding particularly good, which is very difficult by conventional methods of dyeing leather, or even impossible. 在渗移牢度试验中,即使在高湿度和高温下(也就是高于50°C,例如60至100°C ),按照本发明染色的皮革不会或几乎不会被接触材料染污。 In the bleeding fastness test, even at high humidity and high temperatures (i.e. above 50 ° C, for example, 60 to 100 ° C), according to the present invention, leather dyed with little or no contact with the material being soiled.

[0270] 经由UV/VIS光谱法和HPLC进行的定量和定量测定表明,本发明的染料产生85至100%并通常高于90%的固色度。 [0270] quantitative and quantitative assay was performed via UV / VIS spectroscopy and HPLC indicated that the dye of the present invention produces 85 to 100%, and typically greater than 90% of a solid color.

[0271 ] 下列实施例对本发明进行举例说明。 [0271] The following examples of the present invention is illustrated.

[0272] 制备例: [0272] Preparation Example:

[0273] 实施例Ia : [0273] Example Ia:

[0274] [0274]

[0275] I)使I摩尔MSP (3- (2_硫酸根合乙基磺酰基)_6_氨基苯磺酸)悬浮在冰水中并在pH < I和0-5 °C下用过量亚硝酸钠和盐酸重氮化。 [0275] I) of I molar MSP (3- (2_ sulfato ethylsulfonyl) amino acid _6_) and treated with excess nitrous acid was suspended at pH <I and 0-5 ° C in ice water diazotization and sodium hydrochloride. 将I摩尔Y -酸溶于25重量%氢氧化钠水溶液,然后加入21重量%盐酸将pH值调节至I以下。 The molar I Y - acid was dissolved in 25 wt% aqueous sodium hydroxide solution, followed by addition of 21 wt% hydrochloric acid the pH was adjusted to I or less. Y-酸沉淀,形成悬浴液。 Y- acid precipitation is formed hanging bath. 将重氮化MSP倾倒入悬浴液中。 MSP diazonium suspension was poured into the bath. 然后将反应混合物在pH < I下搅拌I小时直至重氮化MSP或游离Y-酸不可检测。 The reaction mixture was stirred for I h or until free Y- MSP diazotized at pH <I undetectable acid. 此后,加入15重量%的碳酸钠溶液以使pH值升至3-8。 Thereafter, 15 wt% sodium carbonate solution to bring the pH was raised to 3-8.

[0276] 2)在pH< I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,6-二硝基-2-氨基苯酚重氮化,然后添加到步骤I)中获得的反应混合物中。 The reaction [0276] 2) with excess sodium nitrite and hydrochloric acid I molar 4,6-dinitro-2-aminophenol diazotized at pH <I and 0_5 ° C, and then added to step I) obtained in mixture. 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 在反应完成后,在反应混合物中加入O. 20-0. 30摩尔硫酸铬(III)并然后搅拌I小时。 After completion of the reaction, O. 20-0. 30 mol of chromium (III) sulfate in the reaction mixture and then stirred for I hour. 加入NaCl使染料盐析并通过抽吸滤出。 NaCl was added and the dye salted out is filtered off with suction.

[0277] 按照与实施例Ia类似的方式,可以获得通式Dk-N = N-Napht-N = NA的染料(即r = k = 0,n=l时通式II的染料)的金属络合物,其中Dk代表源自重氮组分DKl至DK9、DK13、DK14、DK26、DK27、DK39 至DK41 或DK58 或Al 至A12 的基团,Napht 代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 和11-14 之一,且A 代表基团Al 至A12 之一。 [0277] Following a similar manner to Example Ia embodiment, the formula may be obtained Dk-N = N-Napht-N = NA dye (i.e., r = k = 0, n = dyes of the general formula II when l) metal complex thereof, wherein Dk represents a diazo component derived from DKl to DK9, DK13, DK14, DK26, DK27, DK39 through DK41 or DK58 or a group of Al to A12, Napht Representative divalent group 11-2,11-4 , 11-6,11-8,11-10,11-12 and 11-14, and A represents a group one of Al to A12. 基团AN = N-的偶联在基团11-2、11-4、11-6、11-8、11-10、11-12和11-14的氨基的邻位进行。 AN = N- group in the coupling of the amino group ortho to 11-2,11-4,11-6,11-8,11-10,11-12 and 11-14. 其例子列在下表I中。 Examples listed in Table I below.

[0278] 实施例2a : [0278] Example 2a:

[0279] 按照与实施例Ia所述的方法进行反应,不同的是不进行然后与铬盐的反应。 [0279] was reacted in the manner described in Example Ia, except that the reaction was not carried out with the chromium salt and then.

[0280] 按照与实施例2a类似的方式,可以获得通式Dk-N = N-Napht-N = NA的染料(即r = k = 0,n = I时通式II的染料),其中Dk代表源自重氮组分DKl至DK83或源自Al至A12 的基团,Napht 代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 和11-14 之一,且A代表基团Al至A12之一。 [0280] In a similar manner as Example 2a embodiment, can be general formula Dk-N = N-Napht-N = NA dye (i.e., r = k = 0, n = dyes I as formula II), wherein Dk Representative from the diazo components DK83 DKl to or derived from the group of Al to A12, Napht Representative divalent group and 11-2,11-4,11-6,11-8,11-10,11-12 11-14, and A represents a group one of Al to A12. 基团AN = N-的偶联在基团11-2、11-4、11-6、11-8、11-10、11-12和11-14的氨基的邻位进行。 AN = N- group in the coupling of the amino group ortho to 11-2,11-4,11-6,11-8,11-10,11-12 and 11-14. 其例子列在下表I中。 Examples listed in Table I below.

[0281]表 I [0281] TABLE I

[0282] [0282]

〔0283〕 实例3 : [0283] Example 3:

[0285] I)在pH< I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,6-二硝基-2-氨基苯酚重氮化。 [0285] I) the molar I 4,6-dinitro-2-aminophenol diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C. 将I摩尔Y-酸溶于25重量%氢氧化钠水溶液,然后加入21重量%盐酸将pH值调节至I以下。 The acid was dissolved in 25 I Y- molar wt% aqueous sodium hydroxide, followed by addition of 21 wt% hydrochloric acid the pH was adjusted to I or less. Y-酸沉淀,形成悬浴液。 Y- acid precipitation is formed hanging bath. 将重氮化4,6-二硝基-2-氨基苯酚倾倒入悬浴液中。 The diazotized 4,6-dinitro-2-aminophenol suspension was poured into the bath. 然后将反应混合物在PH < I下搅拌I小时直至重氮化4,6- 二硝基-2-氨基苯酚或游离Y-酸不可检测。 The reaction mixture was stirred at PH <I I hour until diazotized 4,6-dinitro-2-aminophenol or free acid Y- undetectable. 此后,加入15重量%的碳酸钠溶液以使pH值升至3-8。 Thereafter, 15 wt% sodium carbonate solution to bring the pH was raised to 3-8.

[0286] 2)使I摩尔MSP悬浮在冰水中,并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,然后添加到步骤I)中获得的反应混合物中。 [0286] 2) reacting I mole of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C, and then added to step I) obtained in the reaction mixture. 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,加入NaCl,由此沉淀出染料,抽吸滤出该染料。 After completion of the reaction, NaCl, thereby precipitating a dye, the dye is filtered off with suction.

[0287] 按照与实施例3类似的反式,可以获得通式Dk-N = N-Napht-N = NA的染料和它们的金属络合物(即r = k = 0,n = I时通式II的染料),其中Dk代表源自重氮组分DKl至DK83 的基团,Napht 代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 和11-14 之一,且A代表基团Al至A12之一。 [0287] Similarly as in Example 3 trans, can be obtained of the general formula Dk-N = N-Napht-N = NA dyes and metal complexes thereof (i.e., r = k = 0, n = I pass when a dye of formula II), where Dk represents a diazo component derived from DK83 to DKl group, Napht represents a divalent group 11-2,11-4,11-6,11-8,11-10,11- and one 1211-14, and A represents one of the groups Al to A12. 基团AN = N-的偶联在基团11-2、11-4、11-6、11-8、11-10、11-12和11-14的羟基的邻位进行。 AN = N- group in the coupling of ortho hydroxyl groups and 11-2,11-4,11-6,11-8,11-10,11-12 11-14.

[0288] 实施例4a : [0288] Example 4a:

[0289] [0289]

[0290]方法 A [0290] Method A

[0291] I)使I摩尔三氯-I,3,5-三嗪悬浮在0_5°C的水中。 [0291] I) of I mole of trichloromethyl -I, 3,5- triazine was suspended in water of 0_5 ° C. 将I摩尔H酸溶于25重量%氢氧化钠水溶液并逐滴添加到PH值为1-4的三氯三嗪悬浴液中,然后搅拌30分钟。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide and added dropwise to the PH value of 1-4 trichlorotriazine suspension bath, then stirred for 30 minutes.

[0292] 2)使I摩尔MSP悬浮在冰水中并添加到步骤I)获得的反应混合物中。 [0292] 2) reacting I mole of MSP was suspended in ice-water and add to step I) the reaction mixture obtained. 此后,加入碳酸钠将PH值调节至5-8之间,然后搅拌I小时。 Thereafter, sodium carbonate was added to adjust the PH value to 5-8, and then stirred for I hour.

[0293] 3)在pH < I和0-5 °C下用过量亚硝酸钠和盐酸将I摩尔5_硝基_2_氨基苯酚重氮化,并添加到步骤2)获得的反应混合物中。 [0293] 3) with excess sodium nitrite and hydrochloric acid 5_ I molar _2_ nitro aminophenol was diazotized at pH <I and 0-5 ° C, and added to step 2) the reaction mixture obtained in . 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,在反应混合物中加入O. 20-0. 30摩尔硫酸铬(III)并然后搅拌I小时。 After completion of the reaction, O. 20-0. 30 mol of chromium (III) sulfate in the reaction mixture and then stirred for I hour. 加入NaCl使染料盐析并通过抽吸滤出。 NaCl was added and the dye salted out is filtered off with suction.

[0294]方法 B [0294] Method B

[0295] I)使I摩尔三氯三嗪悬浮在0_5°C的水中。 [0295] I) of I mole of trichlorotriazine was suspended in water of 0_5 ° C. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并逐滴添加到pH值为1-4的三氯三嗪悬浴液中,然后搅拌30分钟。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide, and added dropwise to a pH of 1-4 trichlorotriazine suspension bath, then stirred for 30 minutes.

[0296] 2)在pH < I和0-5 °C下用过量亚硝酸钠和盐酸将I摩尔5_硝基_2_氨基苯酚重氮化,并添加到步骤I)获得的反应混合物中。 [0296] 2) at pH <I and 0-5 ° C with excess sodium nitrite and hydrochloric acid 5_ I molar _2_ nitro aminophenol was diazotized and added to step I) obtained in the reaction mixture . 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0297] 3)使I摩尔MSP悬浮在冰水中并添加到步骤2)获得的反应混合物中。 [0297] 3) reacting I mole of MSP was suspended in ice-water and added to step 2) the reaction mixture obtained. 此后,力口入碳酸钠将PH值调节至5-8之间,然后搅拌I小时。 Thereafter, sodium carbonate force mouth PH value is adjusted to between 5-8 and stirred for I hour. 反应完成后,在反应混合物中加入O. 20-0. 30摩尔硫酸铬(III)并然后搅拌I小时。 After completion of the reaction, O. 20-0. 30 mol of chromium (III) sulfate in the reaction mixture and then stirred for I hour. 加入NaCl使染料盐析并通过抽吸滤出。 NaCl was added and the dye salted out is filtered off with suction.

[0298] 按照与实施例4a类似的方式,可以获得通式Dk_N = N-Napht-NH-Tr-NH-A的染料(即r = P = O时通式V的染料)的金属络合物,其中Dk是源自重氮组分DKl至DK9、DK13、DK14、DK26、DK27、DK39-DK41、DK58 的基团,Napht 代表二价基团11-1、11-3、11-5、11-7、11-9、II-Il 和11-13 之一,Tr 是2-氯-1,3, 5-三嗪-4,6- 二基,且A 代表基团Al 至A12之一。 [0298] Following a similar manner to Example 4a, the formula can be obtained Dk_N = N-Napht-NH-Tr-NH-A dye (i.e., r = P = O when a dye of formula V) of the metal complex wherein the diazo component is derived from the DKl Dk to DK9, DK13, DK14, DK26, DK27, DK39-DK41, DK58 group, representing a divalent radical 11-1,11-3,11-5,11 Napht -7,11-9, II-Il and one 11-13, Tr is 2-chloro-1,3,5-triazine-4,6-diyl group, and A represents one of the groups Al to A12. 基团Dk-N = N-的偶联在基团11-1、11-3、11-5、11-7、11-9、II-Il 和11-13 的羟基的邻位进行。 Radicals Dk-N = N- group in the coupling 11-1,11-3,11-5,11-7,11-9, II-Il and vicinal hydroxyl groups were 11-13.

[0299] 实施例5a : [0299] Example 5a:

[0300] 按照实施例4a中所述的方法进行反应,不同的是不进行然后与铬盐的反应。 [0300] reaction was carried out according to the method described in Example 4a embodiment, except that the reaction was not carried out with the chromium salt and then.

[0301] 实施例5b: [0301] Example 5b:

[0303]方法 A [0303] Method A

[0304] I)在pH < I和0-5°C下用过量亚硝酸钠和盐酸将I摩尔5_硝基_2_氨基苯酚重氮化,并使其与I摩尔克列氏酸7在25重量%氢氧化钠水溶液中的溶液反应。 [0304] I) at pH <I and 0-5 ° C with excess sodium nitrite and hydrochloric acid 5_ I molar _2_ nitro aminophenol was diazotized and reacted with I Mo Erke's acid 7 the reaction solution was 25 wt% aqueous solution of sodium hydroxide. 保持pH值低于3。 PH was maintained below 3.

[0305] 2)使I摩尔三氯三嗪悬浮在0_5°C的水中。 [0305] 2) reacting I mole of trichlorotriazine was suspended in water of 0_5 ° C. 将步骤I)获得的反应混合物逐滴添加到PH值为1-4的该悬浴液中,然后搅拌30分钟。 The reaction mixture from step I) obtained added dropwise to the suspension PH value 1-4 bath, then stirred for 30 minutes.

[0306] 3)使I摩尔MSP悬浮在冰水中并添加到步骤2)获得的反应混合物中。 [0306] 3) reacting I mole of MSP was suspended in ice-water and added to step 2) the reaction mixture obtained. 此后,加入碳酸钠将PH值调节至5-8之间,然后搅拌I小时。 Thereafter, sodium carbonate was added to adjust the PH value to 5-8, and then stirred for I hour. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0307]方法 B [0307] Method B

[0308] I)使I摩尔三氯三嗪悬浮在0_5°C的水中。 [0308] I) of I mole of trichlorotriazine was suspended in water of 0_5 ° C. 使I摩尔MSP悬浮在冰水中并添加到pH值为1-4的三氯三嗪悬浴液中,然后搅拌30分钟。 So that I mol of MSP was suspended in ice-water and added to a pH of 1-4 trichlorotriazine suspension bath, then stirred for 30 minutes.

[0309] 2)在pH < I和0-5 °C下用过量亚硝酸钠和盐酸将I摩尔5_硝基_2_氨基苯酚重氮化,并使其与I摩尔克列氏酸7在25重量%氢氧化钠水溶液中的溶液反应。 [0309] 2) at pH <I and 0-5 ° C with excess sodium nitrite and hydrochloric acid 5_ I molar _2_ nitro aminophenol was diazotized and reacted with I Mo Erke's acid 7 the reaction solution was 25 wt% aqueous solution of sodium hydroxide. 保持pH值低于3。 PH was maintained below 3.

[0310] 3)将步骤2)获得的产物加入步骤I)获得的反应混合物中。 [0310] 3) The reaction mixture product of step 2) was added to obtain a step I) obtained. 此后加入碳酸钠将pH值调节至5-8之间,然后搅拌I小时。 After addition of sodium carbonate the pH was adjusted to between 5-8 and stirred for I hour. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction. [0311 ] 按照与实施例5a和5b类似的方式,可以获得通式Dk1-N = N-Napht-NH-Tr-NH-Dk2的染料和它们的金属络合物(即r = P = O时通式V的染料),其中Dk1和Dk2各自代表源自重氮组分DKl至DK83的基团或源自Al至A12的基团,条件是Dk1或Dk2中至少一个代表式A 的基团,Napht 代表二价基团11-1、11-3、11-5、11-7、11-9、11-11、11-13、11-15 和11-16之一,Tr是2-氯-1,3,5-三嗪-4,6- 二基,且A代表基团Al至A12之一。 [0311] When the embodiments 5a and 5b according to a similar embodiment, the formula may be obtained Dk1-N = N-Napht-NH-Tr-NH-Dk2 dyes and metal complexes thereof (i.e., r = P = O a dye of formula V), wherein each represent Dk1 and Dk2 from the diazo components to DKl DK83 group or from a group of Al to A12, with the proviso that at least one of Dk1 Dk2 or represents a group of formula a, Napht represents a divalent group, and one of 11-16 11-1,11-3,11-5,11-7,11-9,11-11,11-13,11-15, Tr is 2-chloro - 1,3,5-triazine-4,6-diyl group, and A represents one of the groups Al to A12. 基团Dk1-N=N-的偶联在基团11-1、11-3、11-5、11-7、11_9、II-Il和11-13的羟基的邻位进行。 Group Dk1-N = N- group in the coupling 11-1,11-3,11-5,11-7,11_9, II-Il and vicinal hydroxyl groups were 11-13.

[0312] 实施例6a: [0312] Example 6a:

[0313] [0313]

[0314]方法 A [0314] Method A

[0315] I)使I摩尔三氯三嗪悬浮在0_5°C的水中。 [0315] I) of I mole of trichlorotriazine was suspended in water of 0_5 ° C. 将I摩尔Y酸溶于25重量%氢氧化钠水溶液,并逐滴添加到pH值为1-4的三氯三嗪悬浴液中,然后搅拌30分钟。 The acid was dissolved in 25 mol of Y I wt% aqueous sodium hydroxide, and added dropwise to a pH of 1-4 trichlorotriazine suspension bath, then stirred for 30 minutes.

[0316] 2)使I摩尔邻氨基苯甲酸悬浮在冰水中并添加到步骤I)获得的反应混合物中。 [0316] 2) reacting I mole of anthranilic acid was suspended in ice water and added to the step I) the reaction mixture obtained. 此后,加入碳酸钠将PH值调节至5-8之间,然后搅拌I小时。 Thereafter, sodium carbonate was added to adjust the PH value to 5-8, and then stirred for I hour.

[0317] 3)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔H酸重氮化,并添加到步骤2)获得的反应混合物中。 [0317] 3) The I molar H acid diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C, and added to step 2) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0318] 4)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并添加到步骤3)获得的反应混合物中。 [0318] 4) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water, and added to step 3) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0319]方法 B [0319] Method B

[0320] I)使I摩尔三氯三嗪悬浮在0_5°C的水中。 [0320] I) of I mole of trichlorotriazine was suspended in water of 0_5 ° C. 将I摩尔Y酸溶于25重量%氢氧化钠水溶液,并逐滴添加到pH值为1-4的三氯三嗪悬浴液中,然后搅拌30分钟。 The acid was dissolved in 25 mol of Y I wt% aqueous sodium hydroxide, and added dropwise to a pH of 1-4 trichlorotriazine suspension bath, then stirred for 30 minutes.

[0321] 2)使I摩尔邻氨基苯甲酸悬浮在冰水中并添加到步骤I)获得的反应混合物中。 [0321] 2) reacting I mole of anthranilic acid was suspended in ice water and added to the step I) the reaction mixture obtained. 此后,加入碳酸钠将PH值调节至5-8之间,然后搅拌I小时。 Thereafter, sodium carbonate was added to adjust the PH value to 5-8, and then stirred for I hour.

[0322] 3)将I摩尔H酸溶于25重量%氢氧化钠水溶液,并用I. 1-1-5摩尔乙酸酐乙酰化。 [0322] 3) The I mol of H acid was dissolved in 25 wt% aqueous sodium hydroxide, and treated with acetic anhydride molar I. 1-1-5 acetylation.

[0323] 4)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并添加到步骤3)获得的反应混合物中。 [0323] 4) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water, and added to step 3) the reaction mixture obtained. 加入碳酸钠将pH值设定并保持在4至7之间。 The addition of sodium carbonate the pH is set and kept between 4 to 7. 偶联完成后,加入21重量%盐酸将pH值调节至I以下,并将反应混合物加热至85-95°C。 After the coupling is complete, the addition of 21 wt% hydrochloric acid the pH was adjusted to I, and the reaction mixture was heated to 85-95 ° C. 乙酰基在该过程中分离。 Acetyl separated in the process.

[0324] 5)在pH < I和0_5°C下用过量亚硝酸钠和盐酸使步骤4)获得的产物重氮化,并添加到步骤2)获得的反应混合物中。 [0324] 5) at pH <I 0_5 ° C and the excess sodium nitrite and hydrochloric acid in step 4) the product obtained is diazotized and added to step 2) the reaction mixture obtained. 加入碳酸钠将pH值设定并保持在4至7之间。 The addition of sodium carbonate the pH is set and kept between 4 to 7. 反应完成后,将反应混合物超滤并干燥。 After completion of the reaction, the reaction mixture was ultrafiltered and dried.

[0325] 按照与实施例6a 类似的方式,可以获得通式A_N = NPN =N-NaDht1-NH-Tr-NH-Dk的染料和它们的金属络合物(即r = 0、p = I且P = Napht2时通式V的染料),其中Dk代表源自重氮组分DKl至DK83的基团,P和Napht1独立地代表二价基团11-1、11-3、11-5、11-7、11-9、11-11、11-13、11-15 和11-16 之一或源自重氮组分DK3、DK4、DK6、DK7、DK11、DK13、DK14、DK15、DK18、DK21 至DK2 7、DK29、DK30、DK3 3、DK36、DK38 或DK39的基团,Tr是2-氯-I,3,5-三嗪-4,6- 二基,且A代表基团Al至A12之一。 [0325] In a similar manner as in Example 6a embodiment, the formula may be obtained A_N = NPN = N-NaDht1-NH-Tr-NH-Dk dyes and metal complexes thereof (i.e., r = 0, p = I and P = Napht2 dyes of the general formula V), where Dk represents a diazo component derived from DK83 to DKl group, P and Napht1 independently represent a divalent group 11-1,11-3,11-5,11 11-16 and one or -7,11-9,11-11,11-13,11-15 from the diazo components DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 to DK2 7, DK29, DK30, DK3 3, DK36, DK38 or DK39 group, Tr is 2-chloro -I, 3,5- triazine-4,6-diyl group, and a represents a group Al to A12 one. 基团AN=N-和AN = N-Napht2-N = N-的偶联分别在Napht2和Napht1中轻基的邻位进行。 AN = N- group and AN = N-Napht2-N = N- ortho coupled respectively Napht2 and Napht1 Light group is. 其例子列在下表2中。 Examples thereof are listed in Table 2 below.

[0326]表 2 : [0326] Table 2:

[0327] [0327]

[0328] 实施例7 : [0328] Example 7:

[0329] [0329]

[0330] I)使I摩尔三氯三嗪悬浮在0_5°C的水中,并将I摩尔对胺酸(paramineacid)加入PH值为1-4的该悬浴液中,然后搅拌30分钟。 [0330] I) of I mole of trichlorotriazine 0_5 ° C was suspended in water, and I mole of leucine (paramineacid) was added to the suspension bath PH value 1-4, then stirred for 30 minutes.

[0331] 2)使I摩尔邻氨基苯甲酸悬浮在冰水中并添加到步骤I)获得的反应混合物中。 [0331] 2) reacting I mole of anthranilic acid was suspended in ice water and added to the step I) the reaction mixture obtained. 此后,加入碳酸钠将pH值调节至5-8之间,然后搅拌I小时。 Thereafter, sodium carbonate was added to adjust the pH to between 5-8 and stirred for I hour. 在pH < I和0-5°C下加入过量亚硝酸钠和盐酸以使反应产物重氮化。 Was added excess sodium nitrite and hydrochloric acid at pH <I to 0-5 ° C and the reaction product is diazotized.

[0332] 3)将I摩尔K酸溶于25重量%氢氧化钠水溶液,并添加到步骤2)获得的反应混合物中。 [0332] 3) The I molar K acid was dissolved in 25 wt% aqueous sodium hydroxide, and added to the reaction mixture in step 2) obtained. 保持pH值低于2。 PH was maintained below 2.

[0333] 4)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下添加过量亚硝酸钠和盐酸以进行重氮化。 [0333] 4) reacting I mole of MSP suspended and added excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water to carry out diazotization. 然后,将重氮化的MSP添加到步骤3)获得的反应混合物中。 Then, add the diazotized MSP to step 3) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液以使PH值保持在3至8之间。 10 wt% aqueous sodium hydroxide solution was added to make the PH value was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0334] 按照与实施例7类似的方式,可以获得通式AN = N-Napht1-N = NR-NH-Tr-NH-Dk的染料和它们的金属络合物(即P = O且r = I时通式V的染料),其中Dk代表源自重氮组分DKl 至DK83 的基团,Napht1 代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 和11-14之一,R代表Dk21,其中Q = H或代表源自Kk5和Kkl4至Kkl6的二价基团,Tr是2-氯-I,3,5-三嗪-4,6- 二基,且A代表基团Al至A12之一。 [0334] Following a similar manner to Example 7, may be obtained of formula AN = N-Napht1-N = NR-NH-Tr-NH-Dk dyes and metal complexes thereof (i.e., P = O, and r = when V is a dye of formula I), where Dk represents a diazo component derived from DK83 to DKl group, Napht1 represents a divalent group 11-2,11-4,11-6,11-8,11-10 one of 11-12 and 11-14, R DK21 representatives, where Q = H or represents a divalent group derived from a radical and Kk5 Kkl4 to the Kkl6, Tr is 2-chloro -I, 3,5- triazin-4 , 6-diyl group, and A represents one of the groups Al to A12. 基团AN = N-的偶联在Napht1中羟基的邻位进行。 AN = N- group in the coupling of the hydroxyl group ortho Napht1.

[0335] 实施例8 : [0335] Example 8:

[0336] [0336]

[0337] I)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并与I摩尔甲胺非他明(metamine)的水溶液反应。 [0337] I) of I molar excess MSP suspended and diazotized with sodium nitrite and hydrochloric acid in ice water at pH <I and 0_5 ° C, and reacted with I mole metamine (metamine) aqueous solution. 保持pH值低于3。 PH was maintained below 3.

[0338] 2)使I摩尔三氯三嗪悬浮在0-5°C的水中,并将该悬浴液在pH I至4下与步骤I)获得的反应混合物混合30分钟。 [0338] 2) reacting I mole of trichlorotriazine was suspended in water to 0-5 ° C, and the reaction mixture was suspended in a mixed bath to lower the pH I I step 4) obtained for 30 minutes.

[0339] 3)使I摩尔对胺酸悬浮在冰水中,并添加到步骤2)获得的反应混合物中。 [0339] 3) reacting I mole of amine acid was suspended in ice-water, and added to step 2) the reaction mixture obtained. 此后,加入碳酸钠将PH值设定在5-8之间,然后搅拌I小时。 Thereafter, PH value is set between the addition of sodium carbonate to 5-8, and then stirred for I hour. 在pH < I和0-5°C下加入过量亚硝酸钠和盐酸以使反应产物重氮化。 Was added excess sodium nitrite and hydrochloric acid at pH <I to 0-5 ° C and the reaction product is diazotized.

[0340] 4)将O. 5摩尔H酸溶于25重量%氢氧化钠水溶液,并添加到步骤3)获得的反应混合物中。 [0340] 4) The O. 5 mol of H acid was dissolved in 25 wt% aqueous sodium hydroxide, and added to the reaction mixture in step 3) obtained. 使PH值在2以下保持I小时,然后加入碳酸钠调节至3-8之间,并保持I小时。 PH value was maintained at 2 or less I h, then sodium carbonate was added was adjusted to between 3-8 and kept I h. 反应完成后,将反应混合物超滤并干燥。 After completion of the reaction, the reaction mixture was ultrafiltered and dried.

[0341] 按照与实施例8类似的方式,可以获得通式AN = NR-NH-Tr-NH-PN = N-Napht-N = NP-NH-Tr-NH-RN = NA 和它们的金属络合物(即Dk1 = Dk2 = A 且k = η = I 时通式X 的染料),其中Napht 代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 和11-14之一,R代表其中Q = H的Dk21,或代表源自Kk5和Kkl4至Kkl6的二价基团,R代表源自DK22 至DK25 的二价基团或代表二价基团II-1、II-3、II-5、II-7、II-9、II-11、II-13、II-15或11-16之一,Tr是2-氯-1,3,5-三嗪-4,6- 二基,且A代表基团Al至A12之一。 [0341] Following a similar manner to Example 8, can be obtained of the general formula AN = NR-NH-Tr-NH-PN = N-Napht-N = NP-NH-Tr-NH-RN = NA and a metal complex thereof compound (i.e. Dk1 = Dk2 = a and k = η = I when the dyes of general formula X), wherein Napht 11-2,11-4,11-6,11-8,11-10 represents a divalent group, one of 11-12 and 11-14, R where Q = H behalf of Dk21, or represents a divalent group derived from a radical and Kk5 Kkl4 to the Kkl6, R a divalent group derived from a representative of a divalent or DK22 through DK25 of group II-1, II-3, II-5, II-7, II-9, II-11, II-13, or one of 11-16 II-15, Tr is 2-chloro-1,3, 4,6-triazine-diyl group, and A represents one of the groups Al to A12.

[0342] 实施例9a : [0342] Example 9a:

[0343] [0343]

[0344] I)将I摩尔对硝基苯胺溶于21重量%盐酸,然后在pH < I和0_5°C下用过量亚硝酸钠重氮化,然后添加到I摩尔邻氨基苯甲酸和冰水的悬浴液中。 [0344] I) The I mol of p-nitroaniline was dissolved in 21 wt% hydrochloric acid and diazotized with excess sodium nitrite at pH <I and 0_5 ° C, and then added to I mole of anthranilic acid and ice water, suspension bath. 然后在pH < 2且T< 10°c下将反应混合物搅拌I小时。 Then the pH <2 and T I h the reaction mixture was stirred <at 10 ° c.

[0345] 2)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并与I摩尔克列氏酸7在25重量%氢氧化钠水溶液中的溶液反应。 [0345] 2) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid in ice water at pH <I and 0_5 ° C, and with 7 I Mo Erke's acid in 25 wt% sodium hydroxide the reaction solution is an aqueous solution. 保持pH值低于3。 PH was maintained below 3.

[0346] 3)使I摩尔三氯三嗪悬浮在0-5°C的水中,并将该悬浴液在pH I至4下与步骤I)获得的反应混合物混合30分钟。 [0346] 3) reacting I mole of trichlorotriazine was suspended in water to 0-5 ° C, and the reaction mixture was suspended in a mixed bath to lower the pH I I step 4) obtained for 30 minutes.

[0347] 4)将步骤2)获得的产物添加到步骤3)获得的反应混合物中。 [0347] 4) Adding the product of step 2) to the reaction mixture obtained in step 3) obtained. 此后加入碳酸钠将pH值调节至5-8之间,然后搅拌I小时。 After addition of sodium carbonate the pH was adjusted to between 5-8 and stirred for I hour. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0348] 按照与实施例9a 类似的方式,可以获得通式Dk1-N = NP-NH-Tr-NH-RN =N-Dk2的染料和它们的金属络合物(即通式VI的染料),其中Dk1和Dk2各自代表源自重氮组分DKl至DK83的基团,或代表源自Al至A12的基团,其中Dk1或Dk2中至少一个代表式A 的基团,P 和R 代表源自DK3、DK4、DK6、DK7、DK11、DK13、DK14、DK15、DK18、DK21 至DK27、DK29、DK30、DK33、DK36、DK38、DK39 或DK60 至DK83 的二价基团,或代表二价基团11-1、11-3、11-5、11-7、11-9、11-11、11-13、11-15 或11-16,Tr 是2-氯-1,3,5-三嗪-4,6-二基,且A代表基团Al至A12之一。 [0348] 9a in accordance with a similar manner, the general formula Dk1-N = NP-NH-Tr-NH-RN = N-Dk2 dyes and metal complexes thereof (i.e. a dye of the general formula VI) Example wherein Dk1 and Dk2 each represent a radical derived from a diazo component DK83 DKl to, from or on behalf of a group of Al to A12, wherein at least Dk2 Dk1 or represents a group of formula a, P, and R represents a source since DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 through DK27, DK29, DK30, DK33, DK36, DK38, DK39, or a divalent group DK60 through DK83 or represents a bivalent radical 11-1,11-3,11-5,11-7,11-9,11-11,11-13,11-15 or 11-16, Tr is 2-chloro-1,3,5-triazine 4,6-diyl group, and A represents one of the groups Al to A12. 基团AN = N-的偶联在基团11_1、11_3、11_5、11_7、 AN = N- groups in the coupling groups 11_1,11_3,11_5,11_7,

11-9、II-Il和11-13中羟基的邻位进行。 11-9, II-Il and hydroxyl groups ortho to be 11-13. 这些染料的例子列在表3中。 Examples of these dyes listed in Table 3.

[0349]表 3 : [0349] Table 3:

[0350] [0350]

[0353] I)使I摩尔三氯三嗪悬浮在0-5°C的水中,预先将I摩尔H酸溶于25重量%氢氧化钠水溶液,然后与该悬浴液在pH I至4下混合,然后搅拌30分钟。 [0353] I) of I mole of trichlorotriazine 0-5 ° C was suspended in water in advance of I molar H acid was dissolved in 25 wt% aqueous sodium hydroxide solution, then the pH of the suspension in the bath 4 to the I were mixed and then stirred for 30 minutes.

[0354] 2)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并添加到步骤I)获得的反应混合物中。 [0354] 2) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water, and added to step I) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0355] 3)使O. 5摩尔4,4-二氨基二苯基磺酰胺悬浮在水中,并添加到步骤2)获得的反应混合物中。 [0355] 3) reacting O. 5 moles of 4,4-diphenyl-sulfonamide was suspended in water, and added to step 2) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,力口入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, the force mouth NaCl and precipitated dye is filtered off with suction.

[0356] 按照与实施例10类似的方式,可以获得通式AN = N-Napht-NH-Tr-NH-Tk-NH-Tr-NH-Napht-N = NA和它们的金属络合物(即Dk1 = Dk2 = A时通式IX的染料),其中Napht代表二价基团11-1、11-3、11-5、11-7、11-9、11-11 或11-13,Tr 是2-氯-1,3, 5-三嗪-4,6-二基,Tk代表源自双偶氮组分Tkl至Tk20的二价基团,且A代表基团Al至A12之一。 [0356] Example 10 Following a similar manner, the general formula AN = N-Napht-NH-Tr-NH-Tk-NH-Tr-NH-Napht-N = NA and metal complexes thereof (i.e. Dk1 = Dk2 = a when the dye of formula IX), wherein Napht represents a divalent group 11-1,11-3,11-5,11-7,11-9,11-11 or 11-13, Tr is 2-chloro-1,3,5-triazine-4,6-represents a group, derived from a tetrazo component Tk Tk20 Tkl to a divalent group, and a represents one of the groups Al to A12. 基团AN = N-的偶联在Napht中羟基的邻位进行。 AN = N- group in the coupling of the hydroxyl group in ortho Napht.

[0357]实施例 Ila: [0357] Example Ila:

[0359] I)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化。 [0359] I) at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid I mol 4,4_ diamino diphenyl sulfonamide tetrazotized. 将I摩尔J酸溶于25重量%氢氧化钠水溶液,并逐滴添加到双偶氮化的4,4-二氨基二苯基磺酰胺的溶液中。 The I J mol wt acid was dissolved in 25% aqueous sodium hydroxide, and added dropwise to the tetrazo of 4,4-diphenyl-sulfonic acid amide in solution. 在该过程中,加入盐酸使pH值保持在3以下。 In this process, addition of hydrochloric acid the pH was maintained at 3 or less.

[0360] 2)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0360] 2) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water. 然后,将反应混合物添加到步骤I)获得的反应混合物中。 Then, the reaction mixture was added to step I) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使PH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8.

[0361] 3)将I摩尔甲胺非他明添加到步骤2)获得的反应混合物中,并加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 [0361] 3) The I molar metamine added to step 2) the reaction mixture obtained, and 10 wt% aqueous sodium hydroxide solution the pH was maintained between 3-8.

[0362] 4)使I摩尔三氯三嗪悬浮在0-5°C的水中。 [0362] 4) reacting I mole of trichlorotriazine was suspended in water to 0-5 ° C. 将该悬浴液定量加入I摩尔邻氨基苯甲酸中,然后在PH 1-4下搅拌30分钟。 The suspension was added I mole float quantitative anthranilic acid, followed by stirring at PH 1-4 30 minutes.

[0363] 5)将步骤4)获得的产物添加到步骤3)获得的反应混合物中。 [0363] 5) The Step 4) was added to the product obtained in step 3) the reaction mixture obtained. 此后,加入碳酸钠将PH值设定在5至8之间,然后搅拌I小时。 Thereafter, sodium carbonate was added to PH value is set between 5 to 8, and then stirred for I hour. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0364]实施例 Ilb : [0364] Example Ilb:

[0365] [0365]

[0366] I)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0366] I) of I molar excess MSP suspended and diazotized with sodium nitrite and hydrochloric acid in ice water at pH <I and 0_5 ° C. 将I摩尔J酸溶于25重量%氢氧化钠水溶液,并添加到重氮化MSP的反应混合物中。 The I J mol wt acid was dissolved in 25% aqueous sodium hydroxide, and added to the reaction mixture of diazotized MSP. 保持pH值低于2。 PH was maintained below 2.

[0367] 2)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化,并添加到步骤I)获得的反应混合物中。 [0367] 2) with excess hydrochloric acid and sodium nitrite mol 4,4_ I diamino diphenyl sulfonamide tetrazotized at pH <I and 0_5 ° C, and added to step I) obtained in the reaction mixture . 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0368] 3)将I摩尔甲胺非他明添加到步骤2)获得的反应混合物中,并加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 [0368] 3) The I molar metamine added to step 2) the reaction mixture obtained, and 10 wt% aqueous sodium hydroxide solution the pH was maintained between 3-8.

[0369] 4)使I摩尔三氯三嗪悬浮在0-5°C的水中。 [0369] 4) reacting I mole of trichlorotriazine was suspended in water to 0-5 ° C. 将该悬浴液定量加入I摩尔邻氨基苯甲酸中,然后在PH 1-4下搅拌30分钟。 The suspension was added I mole float quantitative anthranilic acid, followed by stirring at PH 1-4 30 minutes.

[0370] 5)将步骤4)获得的产物添加到步骤3)获得的反应混合物中。 [0370] 5) The Step 4) was added to the product obtained in step 3) the reaction mixture obtained. 此后,加入碳酸钠将PH值设定在5至8之间,然后搅拌I小时。 Thereafter, sodium carbonate was added to PH value is set between 5 to 8, and then stirred for I hour. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0371] 按照与实施例Ila和Ilb类似的方式,可以获得通式A_N = N-Napht-N = N-Tk-N=NP-NH-Tr-NH-Dk和它们的金属络合物(即Dk1 = A时通式VII的染料),其中Dk代表源自重氮组分DKl 至DK83 的基团,Napht 代表二价基团11-1、11-3、11-5、11-7、11-9、11-11或11-13,Tr是2-氯-1,3,5-三嗪-4,6-二基,Tk代表源自双偶氮组分Tkl至Tk20的二价基团,且A代表基团Al至A12之一。 [0371] Following Example Ila and Ilb similar embodiment, the formula may be obtained A_N = N-Napht-N = N-Tk-N = NP-NH-Tr-NH-Dk and their metal complexes (i.e. when Dk1 = a dye of general formula VII), where Dk represents a diazo component derived from DK83 to DKl group, Napht represents a divalent group 11-1,11-3,11-5,11-7,11 -9,11-11 or 11-13, Tr is 2-chloro-1,3,5-triazine-4,6-diyl, representatives from a tetrazo component Tk Tkl to a divalent group Tk20 and A represents a group to one of Al A12. 当反应如实施例I Ia所述进行时,基团AN = N-的偶联在Napht中轻基的邻位进行,当反应如实施例Ilb所述进行时,该偶联在Napht中氨基的邻位进行。 When the reaction is performed as I Ia Example AN = ortho to the group for coupling the N- Napht Light group when the reaction was performed as described in Example Ilb embodiment, the coupling of the amino group in Napht o bits.

[0374]方法 A [0374] Method A

[0375] I)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化。 [0375] I) at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid I mol 4,4_ diamino diphenyl sulfonamide tetrazotized. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并逐滴添加到双偶氮化的4,4-二氨基二苯基磺酰胺的溶液中。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide, and added dropwise to the tetrazo solution of 4,4-diphenyl the sulfonamide. 在该过程中,加入盐酸使pH值保持在3以下。 In this process, addition of hydrochloric acid the pH was maintained at 3 or less.

[0376] 2)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0376] 2) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water. 然后,将反应混合物添加到步骤I)获得的反应混合物中。 Then, the reaction mixture was added to step I) the reaction mixture obtained. 加入15重量%碳酸钠水溶液使PH值保持在3至8之间。 15 wt% aqueous sodium carbonate was added to make the PH value was maintained between 3-8.

[0377] 3)将I摩尔甲胺非他明添加到步骤2)获得的反应混合物中,并加入15重量%碳酸钠水溶液使PH值保持在3至8之间。 [0377] 3) The I molar metamine added to the reaction mixture in step 2) obtained and 15 wt% aqueous sodium carbonate was added to make the PH value was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0378]方法 B [0378] Method B

[0379] I)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化。 [0379] I) at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid I mol 4,4_ diamino diphenyl sulfonamide tetrazotized. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并逐滴添加到双偶氮化的4, The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide, and added dropwise to the tetrazo of 4,

4- 二氨基二苯基磺酰胺的反应混合物中。 The reaction mixture was diamino-diphenyl the sulfonamide. 保持pH值低于3。 PH was maintained below 3.

[0380] 2)将I摩尔甲胺非他明酸添加到步骤I)获得的反应混合物中,并加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 [0380] 2) adding I metamine molar acid to the reaction mixture from step I) obtained, and 10 wt% aqueous sodium hydroxide to maintain the pH between 3-8.

[0381] 3)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0381] 3) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water. 然后,将反应混合物添加到步骤2)获得的反应混合物中。 Then, the reaction mixture was added to the reaction mixture in step 2) obtained. 加入10重量%氢氧化钠水溶液使PH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0382] 按照与实施例12a 类似的方式,可以获得通式A_N = N-Napht1-N = N-Tk-N =N-Kk的染料(即r = k= l且n = 0时通式II的染料),其中Kk代表源自偶联组分Kkl至Kk67、DK3、DK4、DK6、DK7、DKll、DK13、DK14、DK15、DK18、DK21 至DK27、DK29、DK30、DK33、DK36、DK38、DK39 或DK42 至DK83 的基团,Napht1 代表二价基团11-2、11-4、11-6、11-8、 [0382] In a similar manner as Example 12a embodiment, the formula may be obtained A_N = N-Napht1-N = N-Tk-N = N-Kk dye (i.e., r = k = l and n = 0, the general formula II dyes), which is derived from coupling components Kk represents Kkl to Kk67, DK3, DK4, DK6, DK7, DKll, DK13, DK14, DK15, DK18, DK21 through DK27, DK29, DK30, DK33, DK36, DK38, DK39 or a group of DK42 through DK83, Napht1 11-2,11-4,11-6,11-8 represents a divalent group,

II-10、II-12和11-14之一,Tk代表源自双偶氮组分Tkl至Tk20的基团,且A代表基团Al至A12之一。 II-10, II-12 and 11-14, on behalf of a tetrazo component is derived from Tk to Tk20 Tkl group, and A represents one of the groups Al to A12. 基团AN = N-的偶联在Napht1中羟基的邻位进行。 AN = N- group in the coupling of the hydroxyl group ortho Napht1. 其例子列在表4中。 Examples thereof are listed in Table 4.

[0383]表 4 [0383] TABLE 4

[0384] [0384]

VV VV

[0385]实施例 12gw : [0385] Example 12gw:

[0386]方法 A [0386] Method A

[0387] I)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化。 [0387] I) at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid I mol 4,4_ diamino diphenyl sulfonamide tetrazotized. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并逐滴添加到双偶氮化的4,4-二氨基二苯基磺酰胺的溶液中。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide, and added dropwise to the tetrazo solution of 4,4-diphenyl the sulfonamide. 加入盐酸使pH值保持在3以下。 Hydrochloric acid was added The pH was maintained at 3 or less.

[0388] 2)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0388] 2) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water. 然后,将该反应混合物添加到步骤I)获得的反应混合物中。 Then, the reaction mixture was added to step I) the reaction mixture obtained. 加入15重量%碳酸钠溶液使PH值保持在3至8之间。 15 wt% sodium carbonate solution was added to make the PH value was maintained between 3-8.

[0389] 3)将O. 45摩尔甲胺非他明酸和O. 55摩尔2,4-二氨基-I-甲氧基苯同时添加到步骤2)获得的反应混合物中,并加入15重量%碳酸钠溶液使pH值保持在3至8之间。 [0389] 3) The O. 45 mol metamine O. 55 mol of acid and 2,4-diamino-methoxybenzene -I- simultaneously added to the reaction mixture in step 2) obtained and added 15 weight % sodium carbonate solution pH was maintained between 3-8. 反应完成后,将反应混合物超滤并喷雾干燥。 After completion of the reaction, the reaction mixture was ultrafiltered and spray dried.

[0390]方法 B [0390] Method B

[0391] I)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化。 [0391] I) at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid I mol 4,4_ diamino diphenyl sulfonamide tetrazotized. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并逐滴添加到双偶氮化的4,4- 二氨基二苯基磺酰胺的反应混合物中。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide solution, and the reaction mixture was added dropwise to the tetrazo of 4,4-diphenyl the sulfonamide. 保持pH值低于3。 PH was maintained below 3.

[0392] 2)将O. 45摩尔甲胺非他明酸和O. 55摩尔2,4-二氨基-I-甲氧基苯同时添加到步骤I)获得的反应混合物中,并加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 [0392] 2) The O. 45 mol metamine O. 55 mol of acid and 2,4-diamino-methoxybenzene -I- added simultaneously to step I) the reaction mixture obtained, and 10 wt. % aqueous sodium hydroxide solution the pH was maintained between 3-8.

[0393] 3)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0393] 3) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water. 然后,将该反应混合物添加到步骤2)获得的反应混合物中。 Then, the reaction mixture was added to the reaction mixture in step 2) obtained. 加入10重量%氢氧化钠水溶液使PH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0394] 按照与实施例12gw类似的方式,可以制备通式AN = N-Napht1-N = N-Tk-N =N-Kk的表4a染料混合物(η = O时的式IIb),在这种情况下,AN = N-基团偶联到Napht1中羟基的邻位上。 [0394] Following a similar manner to Example 12gw embodiment, may be prepared by the general formula AN = N-Napht1-N = N-Tk-N = Table 4a dye mixtures of N-Kk (formula when η = O IIb), in which the case, AN = N- group is coupled to the hydroxyl group ortho Napht1.

[0395]表 4a : [0395] Table 4a:

[0396] [0396]

[0397] *括号中的值是指各个偶联组分互相之间的摩尔比。 [0397] * Values ​​in parentheses refer to the molar ratio between the individual coupling components to each other.

[0398]实施例 13a : [0398] Example 13a:

[0399] [0399]

[0400] I)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0400] I) of I molar excess MSP suspended and diazotized with sodium nitrite and hydrochloric acid in ice water at pH <I and 0_5 ° C. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并添加到重氮化的MSP中。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide, and added to the diazotized MSP. 保持pH值低于2。 PH was maintained below 2.

[0401] 2)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化,并添加到步骤I)获得的反应混合物中。 [0401] 2) with excess hydrochloric acid and sodium nitrite mol 4,4_ I diamino diphenyl sulfonamide tetrazotized at pH <I and 0_5 ° C, and added to step I) obtained in the reaction mixture . 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0402] 3)将I摩尔甲胺非他明酸添加到步骤2)获得的反应混合物中,并加入10重量%氢氧化钠水溶液使PH值保持在3至8之间。 [0402] 3) adding a molar I metamine acid to Step 2) the reaction mixture obtained, and 10 wt% aqueous sodium hydroxide PH value was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0403] 按照与实施例13a 类似的方式,可以获得通式A_N = N-Napht1-N = N-Tk-N =N-Kk的染料(即r = k= l且n = 0时通式II的染料),其中Kk代表源自偶联组分Kkl至Kk64、DK3、DK4、DK6、DK7、DKll、DK13、DK14、DK15、DK18、DK21 至DK27、DK29、DK30、DK33、DK36、DK38、DK39 或DK42 至DK83 的基团,Napht 代表二价基团11-2、11-4、11-6、11-8、11-10、11-12和11-14之一,Tk代表源自双偶氮组分Tkl至Tk20的二价基团,且A代表基团Al至A12之一。 [0403] In a similar manner as in Example 13a, the formula can be obtained A_N = N-Napht1-N = N-Tk-N = N-Kk dye (i.e., r = k = l and n = 0, the general formula II dyes), which is derived from coupling components Kk represents Kkl to Kk64, DK3, DK4, DK6, DK7, DKll, DK13, DK14, DK15, DK18, DK21 through DK27, DK29, DK30, DK33, DK36, DK38, DK39 DK42 through DK83 or a group of one Napht 11-2,11-4,11-6,11-8,11-10,11-12 represents a divalent group, and 11-14, representatives from Tk Coupole Tkl Tk20 nitrogen component to a divalent group, and a represents one of the groups Al to A12. 基团AN = N-的偶联在Napht1中氨基的邻位进行。 AN = N- group in the coupling of the amino group ortho to the Napht1.

[0404]表 5 : [0404] Table 5:

[0405] [0405]

[0406]实施例 13gw [0406] Example 13gw

[0407] I)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0407] I) of I molar excess MSP suspended and diazotized with sodium nitrite and hydrochloric acid in ice water at pH <I and 0_5 ° C. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并添加到重氮化的MSP的反应混合物中。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide, and added to the reaction mixture of the diazotized MSP. 保持PH值低于2。 Maintaining the PH value below 2.

[0408] 2)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化,并添加到步骤I)获得的反应混合物中。 [0408] 2) with excess hydrochloric acid and sodium nitrite mol 4,4_ I diamino diphenyl sulfonamide tetrazotized at pH <I and 0_5 ° C, and added to step I) obtained in the reaction mixture . 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0409] 3)将O. 45摩尔甲胺非他明酸和O. 55摩尔2,4_ 二氨基_1_甲氧基苯添加到步骤2)获得的反应混合物中,并加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 [0409] 3) The O. 45 mol metamine acid and O. 55 mol 2,4_ diamino _1_ methoxybenzene Step 2 was added to the reaction mixture) obtained, and 10 wt% hydrogen aqueous sodium hydroxide solution the pH was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0410] 按照与实施例13gw类似的方式,可以获得通式AN = N-Napht1-N = N-Tk-N =N-Kk的表5a染料混合物(η = O时的式IIb),在这种情况下,AN = N-基团的偶联在Napht1中氨基的邻位上进行。 [0410] Following a similar manner to Example 13gw embodiment can be obtained of the general formula AN = N-Napht1-N = N-Tk-N = Table 5a dye mixtures of N-Kk (formula when η = O IIb), in which the case, AN = N- group is coupled in the ortho-position of the amino group Napht1.

[0411]表 5a : [0411] Table 5a:

[0412] [0412]

[0413] *括号中的值是指各个偶联组分互相之间的摩尔比。 [0413] * Values ​​in parentheses refer to the molar ratio between the individual coupling components to each other.

[0414] 实施例14 : [0414] Example 14:

[0415] [0415]

[0416] I)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化。 [0416] I) at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid I mol 4,4_ diamino diphenyl sulfonamide tetrazotized. 将I摩尔甲胺非他明酸溶于25重量%氢氧化钠水溶液,并逐滴添加到双偶氮化的4,4-二氨基二苯基磺酰胺的反应混合物中。 The I molar metamine acid was dissolved in 25 wt% aqueous sodium hydroxide solution, and the reaction mixture was added dropwise to the tetrazo of 4,4-diphenyl the sulfonamide. 加入15重量%碳酸钠溶液使反应混合物的pH值保持在2-3之间。 Was added 15 wt% sodium carbonate solution to make the reaction mixture pH was maintained between 2-3.

[0417] 2)将I摩尔H酸溶于25重量%氢氧化钠水溶液,并添加到步骤I)获得的反应混合物中,并加入15重量%碳酸钠水溶液使反应混合物的pH值保持在2-4之间。 [0417] 2) The I mol of H acid was dissolved in 25 wt% aqueous sodium hydroxide, and added to step I) the reaction mixture obtained, and 15 wt% aqueous sodium carbonate solution was added so that pH of the reaction mixture is maintained at 2- between 4.

[0418] 3)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,然后添加到步骤2)获得的反应混合物中。 [0418] 3) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water, and added to step 2) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0419] 实施例15 : [0419] Example 15:

[0420] [0420]

[0421] I)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化。 [0421] I) at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid I mol 4,4_ diamino diphenyl sulfonamide tetrazotized. 将I摩尔甲胺非他明酸溶于25重量%氢氧化钠水溶液,并逐滴添加到双偶氮化的4,4-二氨基二苯基磺酰胺的反应混合物中。 The I molar metamine acid was dissolved in 25 wt% aqueous sodium hydroxide solution, and the reaction mixture was added dropwise to the tetrazo of 4,4-diphenyl the sulfonamide. 加入15重量%碳酸钠溶液使反应混合物的pH值保持在2-3之间。 Was added 15 wt% sodium carbonate solution to make the reaction mixture pH was maintained between 2-3.

[0422] 2)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0422] 2) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并添加到重氮化的MSP的反应混合物中。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide, and added to the reaction mixture of the diazotized MSP. 保持PH值低于2。 Maintaining the PH value below 2.

[0423] 3)将步骤2获得的反应混合物添加到步骤I)获得的反应混合物中。 [0423] 3) The reaction mixture obtained in Step 2 was added to step I) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使PH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0424]实施例 16a : [0424] Example 16a:

[0425] [0425]

[0426] I)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化。 [0426] I) at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid I mol 4,4_ diamino diphenyl sulfonamide tetrazotized. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并逐滴添加到双偶氮化的4,4- 二氨基二苯基磺酰胺的反应混合物中。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide solution, and the reaction mixture was added dropwise to the tetrazo of 4,4-diphenyl the sulfonamide. 加入15重量%碳酸钠溶液使反应混合物的pH值保持在2-3之间。 Was added 15 wt% sodium carbonate solution to make the reaction mixture pH was maintained between 2-3.

[0427] 2)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,然后添加到步骤I)获得的反应混合物中。 The reaction mixture was [0427] 2) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water, then added to step I) obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0428] 3)在步骤2)获得的反应混合物中加入I摩尔间苯二酚,并加入10重量%氢氧化钠水溶液使PH值保持在3-8之间。 [0428] 3) I mol of resorcinol was added to the reaction mixture in step 2) obtained and was added 10 wt% aqueous sodium hydroxide PH value was maintained between 3-8.

[0429] 4)将I摩尔对硝基苯胺溶于21重量%盐酸,然后在pH < I和0_5°C下用过量亚硝酸钠重氮化,然后添加到步骤3)获得的反应混合物中。 [0429] 4) The I mol of p-nitroaniline was dissolved in 21 wt% hydrochloric acid and diazotized with excess sodium nitrite at pH <I and 0_5 ° C, and then added to step 3) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使PH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0430]实施例 17a : [0430] Example 17a:

[0431] [0431]

[0432] I)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0432] I) of I molar excess MSP suspended and diazotized with sodium nitrite and hydrochloric acid in ice water at pH <I and 0_5 ° C. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并添加到重氮化的MSP的反应混合物中。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide, and added to the reaction mixture of the diazotized MSP. 保持PH值低于2。 Maintaining the PH value below 2.

[0433] 2)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化。 [0433] 2) at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid I mol 4,4_ diamino diphenyl sulfonamide tetrazotized. 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0434] 3)在步骤2)获得的反应混合物中加入I摩尔间苯二酚,并加入10重量%氢氧化钠水溶液使PH值保持在3-8之间。 [0434] 3) I mol of resorcinol was added to the reaction mixture in step 2) obtained and was added 10 wt% aqueous sodium hydroxide PH value was maintained between 3-8.

[0435] 4)将I摩尔对硝基苯胺溶于21重量%盐酸,然后在pH < I和0_5°C下用过量亚硝酸钠重氮化,然后添加到步骤3)获得的反应混合物中。 [0435] 4) The I mol of p-nitroaniline was dissolved in 21 wt% hydrochloric acid and diazotized with excess sodium nitrite at pH <I and 0_5 ° C, and then added to step 3) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使PH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0436] 实施例18 : [0436] Example 18:

[0437] [0437]

[0438] I)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化。 [0438] I) at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid I mol 4,4_ diamino diphenyl sulfonamide tetrazotized. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并逐滴添加到双偶氮化的4,4- 二氨基二苯基磺酰胺的反应混合物中。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide solution, and the reaction mixture was added dropwise to the tetrazo of 4,4-diphenyl the sulfonamide. 加入15重量%碳酸钠溶液使反应混合物的pH值保持在2-3之间。 Was added 15 wt% sodium carbonate solution to make the reaction mixture pH was maintained between 2-3.

[0439] 2)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,然后添加到步骤I)获得的反应混合物中。 The reaction mixture was [0439] 2) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water, then added to step I) obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0440] 3)将I摩尔对硝基苯胺溶于21重量%盐酸,然后在pH < I和0_5°C下用过量亚硝酸钠重氮化。 [0440] 3) The I mol of p-nitroaniline was dissolved in 21 wt% hydrochloric acid and diazotized with excess sodium nitrite at pH <I and 0_5 ° C. 在pH > 12下将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液,然后在10°C以下将重氮化的对硝基苯胺在30分钟内逐滴添加到该溶液中,加入10重量%氢氧化钠水溶液使PH值保持在9以上。 At pH> 12 to I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide solution at below 10 ° C and diazotized p-nitroaniline was added dropwise to the solution over 30 minutes, 10 wt% aqueous sodium hydroxide PH value is maintained at 9 or more.

[0441] 4)将步骤3)获得的反应混合物添加到步骤2)获得的反应混合物中。 [0441] 4) The step 3) was added to the reaction mixture obtained in step 2) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使PH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0442] 实施例19 : [0442] Example 19:

[0443] [0443]

[0444] I)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0444] I) of I molar excess MSP suspended and diazotized with sodium nitrite and hydrochloric acid in ice water at pH <I and 0_5 ° C. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并添加到重氮化的MSP的反应混合物中。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide, and added to the reaction mixture of the diazotized MSP. 保持PH值低于2。 Maintaining the PH value below 2.

[0445] 2)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化,并添加到步骤I)获得的反应混合物中。 [0445] 2) with excess hydrochloric acid and sodium nitrite mol 4,4_ I diamino diphenyl sulfonamide tetrazotized at pH <I and 0_5 ° C, and added to step I) obtained in the reaction mixture . 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0446] 3)将I摩尔对硝基苯胺溶于21重量%盐酸,然后在pH < I和0_5°C下用过量亚硝酸钠重氮化。 [0446] 3) The I mol of p-nitroaniline was dissolved in 21 wt% hydrochloric acid and diazotized with excess sodium nitrite at pH <I and 0_5 ° C. 在pH > 12下将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液,然后在10°C以下将重氮化的对硝基苯胺在30分钟内逐滴添加到该溶液中,加入10重量%氢氧化钠水溶液使PH值保持在9以上。 At pH> 12 to I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide solution at below 10 ° C and diazotized p-nitroaniline was added dropwise to the solution over 30 minutes, 10 wt% aqueous sodium hydroxide PH value is maintained at 9 or more.

[0447] 4)将步骤3)获得的反应混合物添加到步骤2)获得的反应混合物中。 [0447] 4) The step 3) was added to the reaction mixture obtained in step 2) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使PH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0448] 实施例20 : [0448] Example 20:

[0449] [0449]

[0450] I)将I摩尔对硝基苯胺溶于21重量%盐酸,然后在pH < I和0_5°C下用过量亚硝酸钠重氮化。 [0450] I) The I mol of p-nitroaniline was dissolved in 21 wt% hydrochloric acid and diazotized with excess sodium nitrite at pH <I and 0_5 ° C. 在pH > 12下将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液,然后在10°C以下将重氮化的对硝基苯胺在30分钟内逐滴添加到该溶液中,加入10重量%氢氧化钠水溶液使PH值保持在9以上。 At pH> 12 to I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide solution at below 10 ° C and diazotized p-nitroaniline was added dropwise to the solution over 30 minutes, 10 wt% aqueous sodium hydroxide PH value is maintained at 9 or more.

[0451] 2)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化,并添加到步骤I)获得的反应混合物中。 [0451] 2) with excess hydrochloric acid and sodium nitrite mol 4,4_ I diamino diphenyl sulfonamide tetrazotized at pH <I and 0_5 ° C, and added to step I) obtained in the reaction mixture . 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0452] 3)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0452] 3) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并添加到组分DKl至DK83或源自Al至A12的基团,Dk1或Dk2中至少一个代表式A的基团,Kk代表源自偶联组分Kk2、Kk3、Kk5、Kk6、Kkl4、Kkl5、Kkl6、Kk49 或Kk50 的二价基团,Napht1 代表二价基团11-2、11-4、11-6、II-8、II-10、II-12和11-14之一,Tk代表源自双偶氮组分Tkl至Tk20的二价基团,且A代表基团Al至A12之一。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide, and added to the components to DKl DK83 or from a group of Al to A12, at least Dk2 Dk1 or represents a group of formula A, representatives from Kk coupling components Kk2, Kk3, Kk5, Kk6, Kkl4, Kkl5, Kkl6, Kk49 Kk50 or a divalent group and represents a divalent group Napht1 11-2,11-4,11-6, II-8, II -10, II-12 and 11-14, one representative from a tetrazo component Tk Tk20 Tkl to a divalent group, and a represents one of the groups Al to A12. 基团Dk1-N = N-的偶联在Napht1中氨基的邻位进行。 Group Dk1-N = N- The coupling of the amino group in the ortho Napht1. 其例子是下表7所列的染料和金属络合物。 Examples thereof are metal complex dyes listed in Table 7 below.

[0453]表 7 [0453] TABLE 7

[0454] [0454]

[0455] 实施例21 : [0455] Example 21:

[0456] [0456]

[0457] I)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化。 [0457] I) at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid I mol 4,4_ diamino diphenyl sulfonamide tetrazotized. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并逐滴添加到双偶氮化的4,4-二氨基二苯基磺酰胺的反应混合物中。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide solution, and the reaction mixture was added dropwise to the tetrazo of 4,4-diphenyl the sulfonamide. 加入15重量%碳酸钠溶液使该反应混合物的pH值保持在2-3之间。 15 wt% sodium carbonate solution was added so that the pH of the reaction mixture was maintained between 2-3.

[0458] 2)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,然后添加到步骤I)获得的反应混合物中。 The reaction mixture was [0458] 2) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water, then added to step I) obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0459] 3)在步骤2)获得的反应混合物中加入O. 5摩尔间苯二酚,并加入10重量%氢氧化钠水溶液使PH值保持在3-8之间。 [0459] 3) O. 5 mol of resorcinol was added to the reaction mixture in step 2) obtained and was added 10 wt% aqueous sodium hydroxide PH value was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0460] 按照与实施例21类似的方式,可以获得通式[AN = N-Napht1-N = N-Tk-N =NJ2-Kk 的染料(即Dk1 = Dk2 = A,Napht1 = Napht2 且Tk1 = Tk2 时通式III 的染料),其中Kk 代表源自偶联组分Kk2、Kk3、Kk5、Kk6、Kkl4、Kkl5、Kkl6、Kk49 或Kk50 的二价基团,Napht1 代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 和11-14 之一,Tk 代表源自双偶氮组分Tkl至Tk20的二价基团,且A代表基团Al至A12之一。 [0460] Example 21 Following a similar manner, the general formula [AN = N-Napht1-N = N-Tk-N = NJ2-Kk dye (i.e. Dk1 = Dk2 = A, Napht1 = Napht2 and Tk1 = Tk2 dye of the general formula III), which is derived from coupling components Kk represents Kk2, Kk3, Kk5, Kk6, Kkl4, Kkl5, Kkl6, Kk49 Kk50 or a divalent group, the divalent group representatives Napht1 11-2 , and 11-14 11-4,11-6,11-8,11-10,11-12, representatives from a tetrazo component Tk Tk20 Tkl to a divalent group, and a represents a group one of Al to A12. 基团AN = N-的偶联在Napht1中轻基的邻位进行。 AN = group ortho to the coupling of N- group is Napht1 Light.

[0461] 实施例22: [0461] Example 22:

[0462] [0462]

[0463] I)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0463] I) of I molar excess MSP suspended and diazotized with sodium nitrite and hydrochloric acid in ice water at pH <I and 0_5 ° C. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并添加到重氮化的MSP的反应混合物中。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide, and added to the reaction mixture of the diazotized MSP. 保持PH值低于2。 Maintaining the PH value below 2.

[0464] 2)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化,并添加到步骤I)获得的反应混合物中。 [0464] 2) with excess hydrochloric acid and sodium nitrite mol 4,4_ I diamino diphenyl sulfonamide tetrazotized at pH <I and 0_5 ° C, and added to step I) obtained in the reaction mixture . 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0465] 3)在步骤2)获得的反应混合物中加入O. 5摩尔间苯二酚,并加入10重量%氢氧化钠水溶液使PH值保持在3-8之间。 [0465] 3) O. 5 mol of resorcinol was added to the reaction mixture in step 2) obtained and was added 10 wt% aqueous sodium hydroxide PH value was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0466] 按照与实施例22类似的方式,可以获得通式[AN = N-Napht1-N = N-Tk-N =NJ2-Kk 的染料(即Dk1 = Dk2 = A,Napht1 = Napht2 且Tk1 = Tk2 时通式III 的染料),其中Kk 代表源自偶联组分Kk2、Kk3、Kk5、Kk6、Kkl4、Kkl5、Kkl6、Kk49 或Kk50 的二价基团,Napht1 代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 和11-14 之一,Tk 代表源自双偶氮组分Tkl至Tk20的二价基团,且A代表基团Al至A12之一。 [0466] In a similar manner as Example 22 can be obtained of the general formula [AN = N-Napht1-N = N-Tk-N = NJ2-Kk dye (i.e. Dk1 = Dk2 = A, Napht1 = Napht2 and Tk1 = Tk2 dye of the general formula III), which is derived from coupling components Kk represents Kk2, Kk3, Kk5, Kk6, Kkl4, Kkl5, Kkl6, Kk49 Kk50 or a divalent group, the divalent group representatives Napht1 11-2 , and 11-14 11-4,11-6,11-8,11-10,11-12, representatives from a tetrazo component Tk Tk20 Tkl to a divalent group, and a represents a group one of Al to A12. 基团AN = N-的偶联在Napht1中氨基的邻位进行。 AN = N- group in the coupling of the amino group ortho to the Napht1.

[0467] 实施例23 : [0467] Example 23:

[0468] [0468]

[0469] I)将I摩尔Y酸溶于25重量%氢氧化钠水溶液,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并逐滴添加到I摩尔邻氨基苯甲酸的水溶液中。 [0469] I) The acid was dissolved in 25 mol of Y I wt% sodium hydroxide aqueous solution with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C, and added dropwise to I mole of anthranilic aqueous formic acid. 加入10重量%氢氧化钠水溶液使反应混合物的pH值保持在5至10之间。 10 wt% aqueous sodium hydroxide was added to make the reaction mixture was maintained at a pH value between 5-10.

[0470] 2)将I摩尔H酸溶于25重量%氢氧化钠水溶液,并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0470] 2) The I mol of H acid was dissolved in 25 wt% aqueous sodium hydroxide solution, and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C. 将该反应混合物与步骤I)获得的反应混合物混合。 The reaction mixture was The reaction mixture of step I) to obtain a mixture. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0471] 3)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,然后添加到步骤2)获得的反应混合物中。 [0471] 3) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water, and added to step 2) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0472] 按照与实施例23类似的方式,可以获得通式AN = N-Napht1-N = N-Napht2-N =N-Kk的染料(即P = l、n = 0、P = Napht1且R = Napht2时通式XII的染料),其中Kk代表源自偶联组分Kkl至Kk48或Kk51至Kk67的二价基团,Napht1和Napht2各自代表二价基团11-1、11-3、11-5、11-7、11-9、II-II、11-13 或11-15 之一,且A 代表基团Al 至A12 之一。 [0472] Example 23 Following a similar manner, the general formula AN = N-Napht1-N = N-Napht2-N = N-Kk dye (i.e., P = l, n = 0, P = Napht1 and R = Napht2 dyes of the general formula XII), which is derived from coupling components Kk represents Kkl to Kk48 or a divalent radical of Kk51 to Kk67, Napht1 Napht2 and each represents a divalent group 11-1,11-3,11 -5,11-7,11-9, II-II, 11-1311-15 or one, and A represents a group one of Al to A12. 基团Napht1-N = N-的偶联在Napht2中轻基的邻位进行。 Group ortho Napht1-N = N- in the light coupling in the group were Napht2.

[0473] 实施例24 : [0473] Example 24:

[0474] [0474]

[0475] 1)将1摩尔Y酸溶于25重量%氢氧化钠水溶液,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并逐滴添加到I摩尔3-苯基氨基苯酚的水溶液中。 [0475] 1) Y 1 mol of acid was dissolved in 25 wt% aqueous sodium hydroxide solution, with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C, and added dropwise to I mole of 3-phenylsulfonyl an aqueous solution of phenol group. 加入10重量%氢氧化钠水溶液使反应混合物的pH值保持在5至10之间。 10 wt% aqueous sodium hydroxide was added to make the reaction mixture was maintained at a pH value between 5-10.

[0476] 2)将I摩尔克列氏7酸溶于25重量%氢氧化钠水溶液。 [0476] 2) The I Mo Erke column 7's acid was dissolved in 25 wt% aqueous sodium hydroxide. 同时,使I摩尔MSP悬浮在冰水中并在pH < I和0-5°C下用过量亚硝酸钠和盐酸重氮化,然后添加到克列氏酸7溶液中,同时保持pH值低于2。 Meanwhile, the I molar MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid in ice water at pH <I and 0-5 ° C, then added to 7 Cleve's acid solution while maintaining the pH below 2.

[0477] 3)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将步骤2)获得的反应混合物重氮化。 [0477] 3) The reaction step 2) to obtain a mixture of diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C. 将该反应混合物与步骤I)获得的反应混合物混合。 The reaction mixture was The reaction mixture of step I) to obtain a mixture. 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0478] 按照与实施例24类似的方式,可以获得通式AN = N-Napht1-N = N-Napht2-N =N-Kk的染料(即P = l、n = 0、P = Napht1且R = Napht2时通式XII的染料),其中Kk代表源自偶联组分Kkl至Kk48或Kk51至Kk67的二价基团,Napht1和Napht2各自代表二价基团11-1、11-3、11-5、11-7、11-9、II-II、11-13 或11-15 之一,且A 代表基团Al 至A12 之一。 [0478] In a similar manner as Example 24, obtained formula AN = N-Napht1-N = N-Napht2-N = N-Kk dye (i.e., P = l, n = 0, P = Napht1 and R = Napht2 dyes of the general formula XII), which is derived from coupling components Kk represents Kkl to Kk48 or a divalent radical of Kk51 to Kk67, Napht1 Napht2 and each represents a divalent group 11-1,11-3,11 -5,11-7,11-9, II-II, 11-1311-15 or one, and A represents a group one of Al to A12. 基团AN = N-Napht1-N = N-的偶联在Napht2中轻基的邻位进行。 Group AN = N-Napht1-N = N- vicinal coupling in light in the substrate is Napht2.

[0479] 实施例25 : [0479] Example 25:

[0480] [0480]

[0481] I)将I摩尔克列氏7酸溶于25重量%氢氧化钠水溶液。 [0481] I) I Mo Erke the column 7's acid was dissolved in 25 wt% aqueous sodium hydroxide. 同时,使I摩尔MSP悬浮在冰水中并在pH < I和0-5°C下用过量亚硝酸钠和盐酸重氮化,然后添加到克列氏酸7溶液中,同时保持pH值低于2。 Meanwhile, the I molar MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid in ice water at pH <I and 0-5 ° C, then added to 7 Cleve's acid solution while maintaining the pH below 2.

[0482] 2)将I摩尔H酸溶于25重量%氢氧化钠水溶液。 [0482] 2) The I mol of H acid was dissolved in 25 wt% aqueous sodium hydroxide. 同时,使步骤I)获得的反应混合物悬浮在冰水中,并在pH < I和0-5 °C下用过量亚硝酸钠和盐酸重氮化,然后添加到H酸溶液中。 Meanwhile, in step I) the reaction mixture obtained was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0-5 ° C, then added to the H acid solution. 加入10重量%氢氧化钠水溶液使pH值保持在I至4之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH at between I to 4.

[0483] 3)在pH < I和0-5 °C下用过量亚硝酸钠和盐酸将5_硝基_2_氨基苯酚重氮化,然后添加到步骤2)获得的反应混合物中。 [0483] 3) nitro _2_ 5_ aminophenol was diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0-5 ° C, then added to step 2) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在 10 wt% aqueous sodium hydroxide was added maintaining the pH at

3-8之间。 3-8. 反应完成后,在反应混合物中加入O. 20-0. 30摩尔硫酸铬(III)并搅拌I小时。 After completion of the reaction, O. 20-0. 30 mol of chromium (III) sulfate in the reaction mixture and stirred for I h. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0484] 实施例26 : [0484] Example 26:

[0485] 与实施例25所述方法类似地进行制备,但是在最后步骤中不进行金属络合反应。 [0485] The method of preparation was carried out similarly to Example 25, but without the metal complexation reaction in the last step.

[0486] 按照与实施例25和26类似的方式,可以获得通式A_N = N-Napht1-N = N-Napht2-N=N-Dk的染料和它们的金属络合物(即P = m = l、p = Napht1且Kk1 = Napht2时通式I的染料),其中Dk代表源自重氮组分DKl至DK9、DK13、DK14、DK26、DK27、DK39至DK41和DK58 的基团,Napht1 代表二价基团11-1、11-3、11-5、11-7、11-9、11-11、11-13、11-15 或1116 之一,Napht2 代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 或11-14 之一,且A代表基团Al至A12之一。 [0486] Following Example 25 and 26 in a similar manner, the general formula A_N = N-Napht1-N = N-Napht2-N = N-Dk dyes and metal complexes thereof (i.e., P = m = l, p = Napht1 Kk1 = Napht2 and dyes of the general formula I), where Dk represents a diazo component derived from DKl to DK9, DK13, DK14, DK26, DK27, DK39 and DK58 through DK41 group, Napht1 Representing or one divalent group 11-1,11-3,11-5,11-7,11-9,11-11,11-13,11-15 1116, representing a divalent radical 11-2,11 Napht2 or one -4,11-6,11-8,11-10,11-12 11-14, and A represents a group to one of Al A12. 基团AN = N-Napht1-N = N-的偶联在Napht2中氨基的邻位进行。 Group AN = N-Napht1-N = N- The coupling of the amino group in the ortho Napht2.

[0487] 实施例27 : [0487] Example 27:

[0488] [0488]

[0489] I)将I摩尔对硝基苯胺溶于21重量%盐酸,然后在pH < I和0_5°C下用过量亚硝酸钠重氮化。 [0489] I) The I mol of p-nitroaniline was dissolved in 21 wt% hydrochloric acid and diazotized with excess sodium nitrite at pH <I and 0_5 ° C. 同时,将I摩尔H酸溶于25重量%氢氧化钠水溶液,然后加入21重量%盐酸使H酸沉淀。 Meanwhile, the I mol of H acid was dissolved in 25 wt% aqueous sodium hydroxide, followed by addition of 21 wt% hydrochloric acid to precipitate H acid. 将H酸悬浴液添加到重氮化的对硝基苯胺中并保持pH值低于2。 The H-acid suspension is added to the bath diazotized p-nitroaniline and the pH was maintained below 2. 反应在I小时后结束。 After I hour the reaction is completed.

[0490] 2)将I摩尔克列氏酸7溶于25重量%氢氧化钠水溶液。 [0490] 2) The I Mo Erke's acid 7 was dissolved in 25 wt% aqueous sodium hydroxide solution. 同时,使I摩尔MSP悬浮在冰水中并在pH< I和0-5°C下用过量亚硝酸钠和盐酸重氮化,加入克列氏酸7溶液,同时保持pH值低于2。 Meanwhile, the I molar MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0-5 ° C in ice water, 7 Jia Ruke's acid solution while maintaining the pH below 2.

[0491] 3)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将步骤2)获得的反应混合物重氮化,并添加到步骤I)获得的产物中。 The product [0491] 3) The reaction step 2) to obtain a mixture of diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C, and added to step I) obtained. 加入10重量%氢氧化钠水溶液使pH值保持在5至8之间,然后搅拌I小时。 10 wt% aqueous sodium hydroxide was added maintaining the pH between 5 and 8, and then stirred for I hour. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0492] 按照与实施例27类似的方式,可以获得通式AN = N-Napht1-N = N-Napht2-N =N-Dk的染料(即P = m = 1、P = Napht1且Kk1 = Napht2时通式I的染料),其中Dk代表源自重氮组分DKl 至DK83 的基团,Napht1 代表二价基团II-1、II-3、II-5、II-7、II-9、II-11、11-13、11-15 或1116 之一,Napht2 代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 或11-14之一,且A代表基团Al至A12之一。 [0492] In a similar manner as Example 27, obtained formula AN = N-Napht1-N = N-Napht2-N = N-Dk dye (i.e., P = m = 1, P = Napht1 and Kk1 = Napht2 when the dye of general formula I), where Dk represents a diazo component derived from DK83 to DKl group, Napht1 represents a divalent group II-1, II-3, II-5, II-7, II-9, II-11,11-13,11-15 or one 1116, Napht2 represents a divalent group of 11-14 or 11-2,11-4,11-6,11-8,11-10,11-12 a, and a represents one of the groups Al to A12. 基团AN = N-Napht1-N = N-的偶联在Napht2中羟基的邻位进行。 Group AN = N-Napht1-N = N- in ortho coupling Napht2 the hydroxyl group.

[0493]实施例 28a : [0493] Example 28a:

[0494] [0494]

[0495] I)将I摩尔H酸溶于25重量%氢氧化钠水溶液,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0495] I) of I molar H acid was dissolved in 25 wt% aqueous sodium hydroxide solution, diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C. 在PH > 12下将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液,然后在10°C以下在30分钟内逐滴添加,由此将该溶液与重氮化的H酸混合,同时加入10重量%氢氧化钠水溶液使pH值保持在9以上。 In the PH> 12 the next I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide solution was then added dropwise over 30 minutes at below 10 ° C, whereby the solution was mixed with diazotized H acid, simultaneously a 10 wt% aqueous sodium hydroxide solution the pH was maintained at 9 or more.

[0496] 2)在pH< I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,6-二硝基-2-氨基苯酚重氮化,并添加到步骤I)获得的反应混合物中。 [0496] 2) with excess sodium nitrite and hydrochloric acid I molar 4,6-dinitro-2-aminophenol diazotized at pH <I and 0_5 ° C, and added to step I) the reaction mixture obtained in. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0497] 3)将I摩尔克列氏7酸溶于25重量%氢氧化钠水溶液。 [0497] 3) The I Mo Erke column 7's acid was dissolved in 25 wt% aqueous sodium hydroxide. 同时,使I摩尔MSP悬浮在冰水中并在pH < I和0-5°C下用过量亚硝酸钠和盐酸重氮化,然后添加到克列氏酸7溶液中,同时保持pH值低于2。 Meanwhile, the I molar MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid in ice water at pH <I and 0-5 ° C, then added to 7 Cleve's acid solution while maintaining the pH below 2.

[0498] 4)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将步骤3)获得的反应混合物重氮化。 [0498] 4) with excess sodium nitrite and hydrochloric acid in step 3 at pH <I and 0_5 ° C) the reaction mixture obtained diazotized. 将该反应混合物与步骤2)获得的反应混合物混合。 The reaction mixture in step 2) the reaction mixture obtained in the mixing. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,在反应混合物中加入O. 40-0. 60摩尔硫酸铁(III)并搅拌I小时。 After completion of the reaction, O. 40-0. 60 mol of ferric sulfate (III) in the reaction mixture and stirred for I h. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0499] 按照与实施例28a类似的方式,可以获得通式A_N = N-Napht1-N = N-Napht2-N=N-Kk-N = N-Dk 的染料(即p = n= I、P = Napht1 且R = Napht2 时通式XII 的染料)的金属络合物,其中Dk代表源自重氮组分DKl至DK9、DK13、DK14、DK26、DK27、DK39至DK41和DK58 的基团,Napht1 代表二价基团11-1、11-3、11-5、11-7、11-9、11-11、11-13、11-15或1116 之一,Napht2 代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 或11-14 之一,Kk代表源自Kk2、Kk3、Kk49或Kk50的二价基团,且A代表基团Al至A12之一。 [0499] Following a similar manner to Example 28a, may be obtained of the general formula A_N = N-Napht1-N = N-Napht2-N = N-Kk-N = N-Dk dye (i.e. p = n = I, P R = Napht2 = Napht1 and dyes of the general formula XII) metal complexes, where Dk represents a radical derived from a diazo component DKl to DK9, DK13, DK14, DK26, DK27, DK39 and DK58 through DK41 group, Napht1 or one represents a divalent group 11-1,11-3,11-5,11-7,11-9,11-11,11-13,11-15 1116, representing a divalent group 11-2 Napht2 , or one of 11-14 11-4,11-6,11-8,11-10,11-12, Kk representatives from Kk2, Kk3, Kk49 Kk50 or a divalent group, and a represents a group Al to one of A12. 基团AN=N-Napht1-N = N-的偶联在Napht2中轻基的邻位进行。 Group AN = N-Napht1-N = N- vicinal coupling in light in the substrate is Napht2.

[0500]实施例 28b : [0500] Example 28b:

[0501] 按照实施例28a中描述的方法进行反应,不同的是不存在随后与铁盐的反应。 [0501] reaction was carried out according to the procedure described in Example 28a, except that the subsequent reaction with the presence of iron salts.

[0502] 按照与实施例28b 类似的方式,可以获得通式AN = N-Napht1-N = N-Napht2-N=N-Kk-N = N-Dk 的染料(即p = n= 1、P = Napht1 且R = Napht2 时通式XII 的染料),其中Dk代表源自重氮组分DKl至DK83或源自Al至A12的基团,Napht1代表二价基团II-1、11-3、11-5、11-7、11-9、11-11、11-13、11-15 或1116 之一,Napht2 代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 或11-14 之一,Kk 代表源自Kk2、Kk3、Kk5、Kk6、Kkl4、Kkl5、Kkl6、Kk49或Kk50的二价基团,且A代表基团Al至A12之一。 [0502] Following a similar manner to Example 28b, may be obtained of formula AN = N-Napht1-N = N-Napht2-N = N-Kk-N = N-Dk dye (i.e. p = n = 1, P R = Napht2 = Napht1 and dyes of the general formula XII), where Dk represents a diazo component derived from DK83 DKl to or from a group of Al to A12, Napht1 represents a divalent group II-1,11-3, or one 11-5,11-7,11-9,11-11,11-13,11-15 1116, on behalf of Napht2 11-2,11-4,11-6,11-8 divalent group, or one of 11-10,11-12 11-14, Kk representatives from Kk2, Kk3, Kk5, Kk6, Kkl4, Kkl5, Kkl6, Kk49 Kk50 or a divalent group, and a represents a group of Al to A12 one. 基团AN = N-Napht1-N = N-的偶联在Napht2中羟基的邻位进行。 Group AN = N-Napht1-N = N- in ortho coupling Napht2 the hydroxyl group.

[0503]实施例 29a : [0503] Example 29a:

[0505] I)在pH< I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,6-二硝基-2-氨基苯酚重氮化。 [0505] I) the molar I 4,6-dinitro-2-aminophenol diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C. 在pH > 12下将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液,然后将该溶液与在10°C以下在30分钟内逐滴加入的重氮化的4,6- 二硝基-2-氨基苯酚混合,同时加入10重量%氢氧化钠水溶液使pH值保持在9以上。 At pH> 12 to I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide solution, then with a solution of 4,6-dinitro added dropwise over 30 minutes at below 10 ° C diazotized mixed-2-aminophenol, while adding 10 wt% aqueous sodium hydroxide solution the pH was maintained at 9 or more.

[0506] 2)将I摩尔H酸溶于25重量%氢氧化钠水溶液,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并添加到步骤I)获得的反应混合物中。 [0506] 2) The I mol of H acid was dissolved in 25 wt% aqueous sodium hydroxide solution, with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C, and added to step I) the reaction mixture obtained in. 加入10重量%氢氧化钠水溶液使PH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8.

[0507] 3)将I摩尔克列氏7酸溶于25重量%氢氧化钠水溶液。 [0507] 3) The I Mo Erke column 7's acid was dissolved in 25 wt% aqueous sodium hydroxide. 同时,使I摩尔MSP悬浮在冰水中并在pH < I和0-5°C下用过量亚硝酸钠和盐酸重氮化,然后添加到克列氏酸7溶液中,同时保持pH值低于2。 Meanwhile, the I molar MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid in ice water at pH <I and 0-5 ° C, then added to 7 Cleve's acid solution while maintaining the pH below 2.

[0508] 4)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将步骤3)获得的反应混合物重氮化。 [0508] 4) with excess sodium nitrite and hydrochloric acid in step 3 at pH <I and 0_5 ° C) the reaction mixture obtained diazotized. 将该反应混合物与步骤2)获得的反应混合物混合。 The reaction mixture in step 2) the reaction mixture obtained in the mixing. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,在反应混合物中加入O. 40-0. 60摩尔硫酸铁(III)并搅拌I小时。 After completion of the reaction, O. 40-0. 60 mol of ferric sulfate (III) in the reaction mixture and stirred for I h. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0509] 按照与实施例29a类似的方式,可以获得通式A_N = N-Napht1-N = N-Napht2-N =N-Kk-N = N-Dk 的染料(即p = n= I、P = Napht1 且R = Napht2 时通式XII 的染料)的金属络合物,其中Dk代表源自重氮组分DKl至DK9、DK13、DK14、DK26、DK27、DK39至DK41和DK58 的基团,Napht1 代表二价基团11-1、11-3、11-5、11-7、11-9、11-11、11-13、11-15或1116 之一,Napht2 代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 或11-14 之一,Kk代表源自Kk2、Kk3、Kk49或Kk50的二价基团,且A代表基团Al至A12之一。 [0509] Following a similar manner to Example 29a, may be obtained of the general formula A_N = N-Napht1-N = N-Napht2-N = N-Kk-N = N-Dk dye (i.e. p = n = I, P R = Napht2 = Napht1 and dyes of the general formula XII) metal complexes, where Dk represents a radical derived from a diazo component DKl to DK9, DK13, DK14, DK26, DK27, DK39 and DK58 through DK41 group, Napht1 or one represents a divalent group 11-1,11-3,11-5,11-7,11-9,11-11,11-13,11-15 1116, representing a divalent group 11-2 Napht2 , or one of 11-14 11-4,11-6,11-8,11-10,11-12, Kk representatives from Kk2, Kk3, Kk49 Kk50 or a divalent group, and a represents a group Al to one of A12. 基团AN=N-Napht1-N = N-的偶联在Napht2中轻基的邻位进行。 Group AN = N-Napht1-N = N- vicinal coupling in light in the substrate is Napht2.

[0510]实施例 29b : [0510] Example 29b:

[0511] 按照实施例29a中描述的方法进行反应,不同的是不存在随后与铁盐的反应。 [0511] reaction was carried out according to the procedure described in Example 29a, except that the subsequent reaction with the presence of iron salts.

[0512] 按照与实施例29b 类似的方式,可以获得通式AN = N-Napht1-N = N-Napht2-N=N-Kk-N = N-Dk 的染料(即p = n= 1、P = Napht1 且R = Napht2 时通式XII 的染料),其中Dk代表源自重氮组分DKl至DK83或源自Al至A12的基团,Napht1代表二价基团II-1、11-3、11-5、11-7、11-9、11-11、11-13、11-15 或1116 之一,Napht2 代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 或11-14 之一,Kk 代表源自Kk2、Kk3、Kk5、Kk6、Kkl4、Kkl5、Kkl6、Kk49或Kk50的二价基团,且A代表基团Al至A12之一。 [0512] Following a similar manner to Example 29b, may be obtained of formula AN = N-Napht1-N = N-Napht2-N = N-Kk-N = N-Dk dye (i.e. p = n = 1, P R = Napht2 = Napht1 and dyes of the general formula XII), where Dk represents a diazo component derived from DK83 DKl to or from a group of Al to A12, Napht1 represents a divalent group II-1,11-3, or one 11-5,11-7,11-9,11-11,11-13,11-15 1116, on behalf of Napht2 11-2,11-4,11-6,11-8 divalent group, or one of 11-10,11-12 11-14, Kk representatives from Kk2, Kk3, Kk5, Kk6, Kkl4, Kkl5, Kkl6, Kk49 Kk50 or a divalent group, and a represents a group of Al to A12 one. 基团AN = N-Napht1-N = N-的偶联在Napht2中羟基的邻位进行。 Group AN = N-Napht1-N = N- in ortho coupling Napht2 the hydroxyl group.

[0513] 实施例30: [0513] Example 30:

[0515] I)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化。 [0515] I) at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid I mol 4,4_ diamino diphenyl sulfonamide tetrazotized. 将I摩尔H酸溶于25重量%氢氧化钠水溶液,并逐滴添加到双偶氮化的4,4- 二氨基二苯基磺酰胺的反应混合物中。 The acid was dissolved in 25 mol of H I wt% aqueous sodium hydroxide solution, and the reaction mixture was added dropwise to the tetrazo of 4,4-diphenyl the sulfonamide. 保持pH值低于3。 PH was maintained below 3.

[0516] 2)将I摩尔对硝基苯胺溶于21重量%盐酸,然后在pH < I和0_5°C下用过量亚硝酸钠重氮化,并添加到步骤I)获得的反应混合物中。 [0516] 2) The I mol of p-nitroaniline was dissolved in 21 wt% hydrochloric acid and diazotized with excess sodium nitrite at pH <I and 0_5 ° C, and added to step I) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0517] 3)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0517] 3) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water. 将I摩尔K酸溶于25重量%氢氧化钠溶液并添加到重氮化的MSP中。 The K I mol wt acid was dissolved in 25% sodium hydroxide solution and added to the diazotized MSP. 保持pH值低于2。 PH was maintained below 2.

[0518] 4)将步骤3)获得的产物添加到步骤2)获得的反应混合物中。 [0518] 4) The step 3) is added to the product obtained in step 2) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使PH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0519] 按照与实施例30类似的方式,可以获得通式Dk1-N = N-Napht1-N = N-Tk-N =N-Napht2-N = N-Dk2的染料和它们的金属络合物(即通式IV的染料),其中Dk1和Dk2各自代表源自重氮组分DKl至DK83或源自Al至A12的基团,Dk1或Dk2中至少一个代表式A的基团,Napht1 和Napht2 各自代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 或11-14之一,且Tk代表源自Tkl至Tk20的二价基团。 [0519] Following a similar manner to Example 30, Dk1-N = N-Napht1-N = N-Tk-N = N-Napht2-N = N-Dk2 dyes and their metal complexes may be obtained of the general formula (i.e., the dye of formula IV), wherein Dk1 and Dk2 each represent a diazo component derived from the A12 or DK83 DKl to a group, the groups Dk2 Dk1 or at least one representative from Al to formula a, Napht1 and Napht2 each represents a divalent group or 11-2,11-4,11-6,11-8,11-10,11-12 11-14, and represents a divalent group derived from Tk to Tkl of Tk20. 基团Dk1-N = N-的偶联在Napht1中羟基的邻位进行,且Dk2-N = N-的偶联在Napht2中氨基的邻位进行。 Group Dk1-N = N- coupling the hydroxyl group ortho to be Napht1 and Dk2-N = N- The coupling of the amino group in the ortho Napht2.

[0520] 实施例31 : [0520] Example 31:

[0521] 重氮化的MSP中。 [0521] MSP in the diazotized. 保持pH值低于2。 PH was maintained below 2.

[0522] 4)将步骤3)获得的反应混合物添加到步骤2)获得的反应混合物中。 [0522] 4) The step 3) was added to the reaction mixture obtained in step 2) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使PH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0523] 按照与实施例16a和18类似的方式,可以获得通式Dk1-N = N-Napht1-N = N-Tk-N=N-Kk-N = N-Dk2的染料和它们的金属络合物(即r = k = n= l时通式II的染料),其中Dk1和Dk2各自代表源自重氮组分DKl至DK83或源自Al至A12的基团,Dk1或Dk2中至少一个代表式A的基团,Kk代表源自偶联组分Kk2、Kk3、Kk5、Kk6、Kkl4、Kkl5、Kkl6、Kk49或Kk50 的二价基团,Napht1 代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 和ΙΙ-14之一,Tk代表源自双偶氮组分Tkl至Tk20的二价基团,且A代表基团Al至Α12之一。 [0523] Following Example 18 and 16a similar embodiment can be obtained of the general formula Dk1-N = N-Napht1-N = N-Tk-N = N-Kk-N = N-Dk2 dyes and metal complexes thereof compound (i.e., when r = k = n = l of a dye of formula II), wherein each represent Dk1 and Dk2 DKl from the diazo components to or from Al to A12 DK83 group, at least one Dk1 or Dk2 a is a group represented by the formula, derived from the coupling component Kk Representative Kk2, Kk3, Kk5, Kk6, Kkl4, Kkl5, Kkl6, Kk49 Kk50 or a divalent group, the divalent group representatives Napht1 11-2,11- 4,11-6,11-8,11-10,11-12 ΙΙ-14 and one representative from a tetrazo component Tk Tk20 Tkl to a divalent group, and a represents a group to Al Α12 one. 基团Dki-N = N-的偶联在Napht1中羟基的邻位进行。 Group Dki-N = N- in ortho coupling Napht1 the hydroxyl group. 其例子是下表6所列的染料和金属络合物。 Examples thereof are metal complex dyes listed in Table 6 below.

[0524]表 6 : [0524] Table 6:

[0525] [0525]

[0526] 按照与实施例17a、19和20类似的方式,可以获得通式Dk1-N = N-Napht1-N =N-Tk-N = N-Kk-N = N-Dk2的染料和它们的金属络合物(即r = k = η = I时通式II的染料),其中Dk1和Dk2各自代表源自重氮 [0526] and according to Example 20 in a similar manner, the formula can be obtained Dk1-N = N-Napht1-N = N-Tk-N = N-Kk-N = N-Dk2 dye 17a, 19 and their metal complexes (i.e., r = k = η = I the dyes of the general formula II), wherein each represent Dk1 and Dk2 derived from the diazo

[0527] [0527]

[0528] I)将I摩尔对硝基苯胺溶于21重量%盐酸,然后在pH < I和0_5°C下用过量亚硝酸钠重氮化。 [0528] I) The I mol of p-nitroaniline was dissolved in 21 wt% hydrochloric acid and diazotized with excess sodium nitrite at pH <I and 0_5 ° C. 在其中加入I摩尔H酸,同时保持pH值低于2。 I molar H added thereto an acid, keeping the pH below 2.

[0529] 2)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4_ 二氨基二苯基磺酰胺双偶氮化,并添加到步骤I)获得的反应混合物中。 [0529] 2) with excess hydrochloric acid and sodium nitrite mol 4,4_ I diamino diphenyl sulfonamide tetrazotized at pH <I and 0_5 ° C, and added to step I) obtained in the reaction mixture . 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0530] 3)使I摩尔MSP悬浮在冰水中并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0530] 3) reacting I mole of MSP suspended and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C in ice water. 将I摩尔K酸溶于25重量%氢氧化钠溶液并添加到重氮化的MSP中。 The K I mol wt acid was dissolved in 25% sodium hydroxide solution and added to the diazotized MSP. 保持pH值低于2。 PH was maintained below 2.

[0531] 4)将步骤3)获得的产物添加到步骤2)获得的反应混合物中。 [0531] 4) The step 3) is added to the product obtained in step 2) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使PH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0532] 按照与实施例31类似的方式,可以获得通式Dk1-N = N-Napht1-N = N-Tk-N =N-Napht2-N = N-Dk2的染料和它们的金属络合物(即通式IV的染料),其中Dk1和Dk2各自代表源自重氮组分DKl至DK83或源自Al至A12的基团,Dk1或Dk2中至少一个代表式A的基团,Napht1 和Napht2 各自代表二价基团11-2、11-4、11-6、11-8、11-10、11-12 或11-14之一,且Tk代表源自Tkl至Tk20的二价基团。 [0532] In a similar manner as in Example 31, Dk1-N = N-Napht1-N = N-Tk-N = N-Napht2-N = N-Dk2 dye can be obtained and their metal complexes of the general formula (i.e., the dye of formula IV), wherein Dk1 and Dk2 each represent a diazo component derived from the A12 or DK83 DKl to a group, the groups Dk2 Dk1 or at least one representative from Al to formula a, Napht1 and Napht2 each represents a divalent group or 11-2,11-4,11-6,11-8,11-10,11-12 11-14, and represents a divalent group derived from Tk to Tkl of Tk20. 基团Dk1-N = N-和Dk2-N = N-的偶联分别在Napht1和Napht2中氨基的邻位进行。 Group and Dk1-N = N- Dk2-N = N- coupling respectively in ortho Napht2 Napht1 and amino groups.

[0533] 实施例32 : [0533] Example 32:

[0534] [0534]

[0535] 在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,6_ 二硝基_2_氨基苯酚重氮化,并与I摩尔4-(β-硫酸根合乙基磺酰基)吡唑酸2(Kk44)偶联。 [0535] at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid I mol 4,6_ dinitro _2_ aminophenol was diazotized with I mole of 4- (β- sulfato B ylsulfonyl) pyrazole acid 2 (Kk44) conjugated. 使pH值保持在2至7之间。 The pH was maintained between 2-7. 偶联完成后,在反应混合物中加入O. 20-0. 30摩尔硫酸铬(III)并搅拌I小时。 After coupling was complete, O. 20-0. 30 mol of chromium (III) sulfate in the reaction mixture and stirred for I h. 然后将反应混合物在40°C蒸发。 The reaction mixture was evaporated at 40 ° C.

[0536] 按照与实施例32类似的方式,可以获得通式Dk-N = N-Pyr-A的染料(即通式XIII的染料)的金属络合物,其中Dk代表源自重氮组分DKl至DK9、DK13、DK14、DK26、DK27、DK39至DK41或DK58的基团,Pyr代表5-羟基-3-甲基吡唑_1,4_ 二基或5-羟基-3-羧基吡唑-1,4- 二基,且A代表经由Pyr的氮连接的基团Al至A12之一。 [0536] In a similar manner as Example 32, the formula can be obtained Dk-N = N-Pyr-A dye (i.e. a dye of formula XIII) metal complexes, where Dk represents a diazo component derived from DKl to DK9, DK13, DK14, DK26, DK27, DK39 through DK41 or group of DK58, Pyr represents 5-hydroxy-3-methyl-pyrazol-_1,4_ diyl or 3-carboxy-pyrazol-5-hydroxy - Al 1,4- diyl group, and a represents a nitrogen Pyr connected via one to A12.

[0537] 实施例33 : [0537] Example 33:

[0538] 按照实施例32中描述的方法进行反应,不同的是不存在随后与铬盐的反应。 [0538] reaction was carried out according to the method described in Example 32, except that the subsequent reaction with chromium salts are absent.

[0539] 按照与实施例33类似的方式,可以获得通式Dk-N = N-Pyr-A的染料(即通式XIII的染料),其中Dk代表源自重氮组分DKl至DK83的基团,Pyr代表5-羟基-3-甲基吡唑-I, [0539] In a similar manner as Example 33, the formula can be obtained Dk-N = N-Pyr-A dye (i.e. a dye of formula XIII), where Dk represents a diazo component from the group DKl to DK83 group, Pyr represents 5-hydroxy-3-methylpyrazole -I,

4-二基或5-羟基-3-羧基吡唑-I,4-二基,且A代表通过Pyr的氮连接的基团Al至A12 Al 4- diyl group or 3-carboxy-5-hydroxy-pyrazole -I, 4- diyl group, and A represents a nitrogen Pyr connected through to A12

之一O One O

[0540]实施例 34a : [0540] Example 34a:

[0541] [0541]

[0542] I)在pH < I和0-5°C下用过量亚硝酸钠和盐酸将I摩尔5_硝基_2_氨基苯酚重氮化。 [0542] I) the molar 5_ I _2_ nitro aminophenol was diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0-5 ° C. 在pH> 12下将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液,将该溶液与在10°C以下在30分钟内逐滴加入的重氮化5-硝基-2-氨基苯酚混合,同时加入10重量%氢氧化钠水溶液使PH值保持在9以上。 At pH> 12 to I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide, and the solution was added dropwise over 30 minutes at below 10 ° C diazotized 5-nitro-2-amino phenol mixed while adding 10 wt% aqueous sodium hydroxide PH value is maintained at 9 or more.

[0543] 2)使I摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并添加到步骤I)获得的反应混合物中。 [0543] 2) reacting I mole of MSP was suspended in ice-water, diazotized at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid, and added to step I) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,在反应混合物中加入O. 40-0. 60摩尔硫酸铁(III)并搅拌I小时。 After completion of the reaction, O. 40-0. 60 mol of ferric sulfate (III) in the reaction mixture and stirred for I h. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0544]实施例 35a : [0544] Example 35a:

[0545] 按照实施例34a中描述的方法进行反应,不同的是不存在随后与铁盐的反应。 [0545] reaction was carried out according to the method described in Example 34a, except that the subsequent reaction with the presence of iron salts.

[0546] 实施例36 : [0546] Example 36:

[0547] [0547]

[0548] I)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔MSP重氮化。 [0548] I) at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid and diazotized MSP I mol. 将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液,将该溶液与在10°C以下在30分钟内逐滴加入的重氮化的MSP混合,同时加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 The I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide, the solution was added drop-by-MSP diazotized mixed over 30 minutes at below 10 ° C, while adding an aqueous solution of 10 wt% sodium hydroxide the pH was maintained between 3-8.

[0549] 2)使I摩尔5-硝基-2-氨基苯酚悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并添加到步骤I)获得的反应混合物中。 [0549] 2) reacting I mole of 5-nitro-2-aminophenol was suspended in ice-water, diazotized pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid, and added to step I) obtained in the reaction mixture. 加入10重量%氢氧化钠水溶液使PH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8. 反应完成后,在反应混合物中加入O. 40-0. 60摩尔硫酸铁(III)并搅拌I小时。 After completion of the reaction, O. 40-0. 60 mol of ferric sulfate (III) in the reaction mixture and stirred for I h. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0550] 实施例37 : [0550] Example 37:

[0551] 按照实施例36中描述的方法进行反应,不同的是不存在随后与铁盐的反应。 [0551] reaction was carried out according to the method described in Example 36, except that the subsequent reaction with the presence of iron salts.

[0552] 按照与实施例34a和36类似的方式,可以获得通式Dk_N = N-Kk-N = NA的染料(即P = O且m = I时通式I的染料)的金属络合物,其中Dk代表源自重氮组分DKl至DK9、DK13、DK14、DK26、DK27、DK39 至DK41 或DK58 的基团,Kk 代表源自Kk2、Kk3、Kk49 或Kk50的二价基团,且A代表基团Al至A12之一。 [0552] Following Example 36 and 34a similar embodiment, the formula may be obtained Dk_N = N-Kk-N = NA dye (i.e., P = O and m = I dye of the general formula I) is a metal complex , where Dk represents a radical derived from a diazo component DKl to DK9, DK13, DK14, DK26, DK27, DK39 through DK41 or DK58 group, representatives from Kk Kk2, Kk3, Kk49 Kk50 or a divalent group, and a It represents a group one of Al to A12. 其例子列在表8中。 Examples thereof are listed in Table 8.

[0553] 表8 [0553] TABLE 8

[0554] [0554]

[0555] 按照与实施例35a和37类似的方式,可以获得通式Dk_N = N-Kk-N = NA的染料(即P = O且m = I时通式I的染料),其中Dk代表源自重氮组分DKl至DK83的基团,Kk代表源自Kk2、Kk3、Kk49或Kk50的二价基团,且A代表基团Al至Al2之一。 [0555] Following Example 37 and 35a similar embodiment, the formula may be obtained Dk_N = N-Kk-N = NA dye (i.e., P = O and m = I dye of the general formula I), where Dk represents a source since diazo component to DKl DK83 group, representatives from Kk Kk2, Kk3, Kk49 Kk50 or a divalent group, and a represents one of the groups Al to Al2. 其例子列在表9中。 Examples thereof are listed in Table 9.

[0556]表 9 : [0556] Table 9:

[0557] [0557]

[0560]方法 A : [0560] Method A:

[0561] I)在pH< I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,6-二硝基-2-氨基苯酚重氮化。 [0561] I) the molar I 4,6-dinitro-2-aminophenol diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C. 在pH > 12下将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液,将该溶液与在> 10°c在30分钟内逐滴加入的重氮化的4,6_ 二硝基-2-氨基苯酚混合,同时加入10重量%氢氧化钠水溶液使pH值保持在9以上。 At pH> 12 to I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide, the solution with at> 10 ° c is added dropwise over 30 minutes diazotized 4,6_ dinitro - 2-aminophenol were mixed while adding 10 wt% aqueous sodium hydroxide solution the pH was maintained at 9 or more.

[0562] 2)使I摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,然后添加到步骤I)获得的反应混合物中。 [0562] 2) reacting I mole of MSP was suspended in ice-water, diazotized at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid, and then added to step I) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0563] 3)将I摩尔对硝基苯胺溶于21重量%盐酸,此后在pH < I和0_5°C下用过量亚硝酸钠重氮化并添加到步骤2)获得的反应混合物中。 [0563] 3) The I mol of p-nitroaniline was dissolved in 21 wt% hydrochloric acid, thereafter diazotized and added to step 2) the reaction mixture obtained with excess sodium nitrite at pH <I and 0_5 ° C. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,在反应混合物中加入O. 40-0. 60摩尔硫酸铁(III)并搅拌I小时。 After completion of the reaction, O. 40-0. 60 mol of ferric sulfate (III) in the reaction mixture and stirred for I h. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0564]方法 B : [0564] Method B:

[0565] I)将I摩尔对硝基苯胺溶于21重量%盐酸,此后在pH < I和0_5°C下用过量亚硝酸钠重氮化。 [0565] I) The I mol of p-nitroaniline was dissolved in 21 wt% hydrochloric acid, thereafter diazotized with excess sodium nitrite at pH <I and 0_5 ° C. 在PH > 12下将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液。 In the PH> 12 the next I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide. 将该溶液与在10°C以下在30分钟内逐滴加入的重氮化的对硝基苯胺混合,同时加入10重量%氢氧化钠水溶液使pH值保持在9以上。 This mixed solution was added dropwise over 30 minutes at below 10 ° C diazotized p-nitroaniline, while adding 10 wt% aqueous sodium hydroxide solution the pH was maintained at 9 or more.

[0566] 2)使I摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,然后添加到步骤I)获得的反应混合物中。 [0566] 2) reacting I mole of MSP was suspended in ice-water, diazotized at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid, and then added to step I) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0567] 3)在pH< I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,6-二硝基-2-氨基苯酚重氮化,并添加到步骤2)获得的反应混合物中。 [0567] 3) with excess sodium nitrite and hydrochloric acid I molar 4,6-dinitro-2-aminophenol diazotized at pH <I and 0_5 ° C, and added to step 2) the reaction mixture obtained in. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,在反应混合物中加入O. 40-0. 60摩尔硫酸铁(III)并搅拌I小时。 After completion of the reaction, O. 40-0. 60 mol of ferric sulfate (III) in the reaction mixture and stirred for I h. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0568]实施例 39a : [0568] Example 39a:

[0569] 按照实施例38中描述的方法进行反应,不同的是不存在随后与铁盐的反应。 [0569] reaction was carried out according to the method described in Example 38, except that the subsequent reaction with the presence of iron salts.

[0570]实施例 40a : [0570] Example 40a:

[0572]方法 A : [0572] Method A:

[0573] I)将I摩尔对硝基苯胺溶于21重量%盐酸,此后在pH < I和0_5°C下用过量亚硝酸钠重氮化。 [0573] I) The I mol of p-nitroaniline was dissolved in 21 wt% hydrochloric acid, thereafter diazotized with excess sodium nitrite at pH <I and 0_5 ° C. 在PH > 12下将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液。 In the PH> 12 the next I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide. 将该溶液与在10°C以下在30分钟内逐滴加入的重氮化的对硝基苯胺混合,同时加入10重量%氢氧化钠水溶液使pH值保持在9以上。 This mixed solution was added dropwise over 30 minutes at below 10 ° C diazotized p-nitroaniline, while adding 10 wt% aqueous sodium hydroxide solution the pH was maintained at 9 or more.

[0574] 2)在pH< I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,6-二硝基-2-氨基苯酚重氮化,然后添加到步骤I)获得的反应混合物中。 [0574] 2) with excess sodium nitrite and hydrochloric acid I molar 4,6-dinitro-2-aminophenol diazotized at pH <I and 0_5 ° C, and then added to step I) the reaction mixture obtained in. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0575] 3)使I摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并加入步骤2)获得的反应混合物中。 [0575] 3) reacting I mole of MSP was suspended in ice-water, diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C, and the addition step 2) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,在反应混合物中加入O. 40-0. 60摩尔硫酸铁(III)并搅拌I小时。 After completion of the reaction, O. 40-0. 60 mol of ferric sulfate (III) in the reaction mixture and stirred for I h. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0576]方法 B : [0576] Method B:

[0577] I)使I摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0577] I) of I mol of MSP was suspended in ice-water, diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C. 将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液。 The I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide. 将该溶液与在10°C以下在30分钟内逐滴加入的重氮化MSP混合,同时加入10重量%氢氧化钠水溶液使pH值保持在6至7之间。 And the solution was added dropwise below 10 ° C within 30 minutes diazotized MSP mixed while adding 10 wt% aqueous sodium hydroxide solution the pH was maintained between 6-7.

[0578] 2)在pH< I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,6-二硝基-2-氨基苯酚重氮化,然后添加到步骤I)获得的反应混合物中。 [0578] 2) with excess sodium nitrite and hydrochloric acid I molar 4,6-dinitro-2-aminophenol diazotized at pH <I and 0_5 ° C, and then added to step I) the reaction mixture obtained in. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0579] 3)将I摩尔对硝基苯胺溶于21重量%盐酸,此后在pH < I和0_5°C下用过量亚硝酸钠重氮化,并添加到步骤2)获得的反应混合物中。 [0579] 3) The I mol of p-nitroaniline was dissolved in 21 wt% hydrochloric acid, thereafter diazotized with excess sodium nitrite at pH <I and 0_5 ° C, and added to step 2) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,在反应混合物中加入O. 40-0. 60摩尔硫酸铁(III)并搅拌I小时。 After completion of the reaction, O. 40-0. 60 mol of ferric sulfate (III) in the reaction mixture and stirred for I h. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0580]实施例 41a : [0580] Example 41a:

[0581] 按照实施例40中描述的方法进行反应,不同的是不存在随后与铁盐的反应。 [0581] reaction was carried out according to the method described in Example 40, except that the subsequent reaction with the presence of iron salts.

[0582]按照与实施例38a和40a类似的方式,可以获得通式&1—N=N_俨—N=N>Dk2的染料 [0582] Examples 38a and 40a in accordance with a manner similar embodiment can be obtained of the general formula & 1-N = N_ Yan -N = N> Dk2 dye

N=NA N = NA

(即P = O且m = 2时通式I的染料)的金属络合物,其中Dk1和Dk2各自代表源自重氮组分DKl至DK83的基团,基团Dk1或Dk2中至少一个代表源自重氮组分DKl至DK9、DK13、DK14、DK26、DK27、DK39至DK41或DK58的基团,Kk代表源自Kk2或Kk3的三价基团,且A代表基团Al至A12之一。 (I.e., P = O and m = 2 dyes of the general formula I) metal complexes, wherein each represent Dk1 and Dk2 from the diazo components DK83 DKl to a group of at least one representative of the group Dk1 or Dk2 from the diazo components DKl to DK9, DK13, DK14, DK26, DK27, DK39 through DK41 or DK58 group, Kk Representative trivalent group derived from Kk2 or Kk3, and a represents a group Al to A12 . 其例子列在表10中。 Examples listed in Table 10.

[17890] [17890]

[0585]按照与实施例39a和41a类似的方式,可以获得通Sd1cln=nI1^n=nW2的染料 [0585] as in Example 39a and 41a in a similar manner, can be obtained through Sd1cln = nI1 ^ n = nW2 dye

N=NA N = NA

(即P = O且m = 2时通式I的染料),其中Dk1和Dk2各自代表源自重氮组分DKl至DK83 (I.e., P = O and m = 2 dyes of the general formula I), wherein each represent Dk1 and Dk2 from the diazo components to DKl DK83

的基团,Kk代表源自Kk2、Kk3或Kk5的三价基团,且A代表基团Al至A12之一。 Group, representatives from Kk Kk2, Kk3 Kk5 or trivalent group, and A represents one of the groups Al to A12. 其例子列在表11中。 Examples thereof are listed in Table 11.

[0586]表 11: [0586] Table 11:

[0587] [0587]

[0590]方法 A : [0590] Method A:

[0591] I)将I摩尔H酸溶于25重量%氢氧化钠水溶液,并在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0591] I) of I molar H acid was dissolved in 25 wt% aqueous sodium hydroxide solution, and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C. 在PH > 12下将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液。 In the PH> 12 the next I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide. 将该溶液与在10°C以下在30分钟内逐滴加入的重氮化H酸混合,同时加入10重量%氢氧化钠水溶液使PH值保持在9以上。 This solution was added dropwise over 30 minutes at below 10 ° C diazotized H acid are mixed while adding 10 wt% aqueous sodium hydroxide solution maintained at a PH value of 9 or more.

[0592] 2)使I摩尔5-硝基-2-氨基苯酚悬浮在冰水中,然后在pH < I和0_5°C下用过量亚硝酸钠重氮化,然后添加到步骤I)获得的反应混合物中。 [0592] 2) reacting I mole of 5-nitro-2-aminophenol was suspended in ice water and diazotized with excess sodium nitrite at pH <I and 0_5 ° C, and then added to step I) obtained by reaction of mixture. 加入10重量%氢氧化钠水溶液使PH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8.

[0593] 3)使I摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并添加到步骤2)获得的反应混合物中。 [0593] 3) reacting I mole of MSP was suspended in ice-water, diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C, and added to step 2) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,在反应混合物中加入O. 40-0. 60摩尔硫酸铁(III)并搅拌I小时。 After completion of the reaction, O. 40-0. 60 mol of ferric sulfate (III) in the reaction mixture and stirred for I h. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0594]方法 B : [0594] Method B:

[0595] I)将I摩尔H酸溶于25重量%氢氧化钠水溶液,并用I. 1_1. 5摩尔乙酸酐乙酰化。 [0595] I) of I molar H acid was dissolved in 25 wt% aqueous sodium hydroxide solution, and dried I. 1_1. 5 mol of acetic anhydride acetylation.

[0596] 2)使I摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并添加到步骤I)获得的反应混合物中。 [0596] 2) reacting I mole of MSP was suspended in ice-water, diazotized at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid, and added to step I) the reaction mixture obtained. 加入碳酸钠使PH值保持在4至7之间。 Addition of sodium carbonate PH value was maintained between 4 to 7. 偶联完成后,加入21重量%盐酸将pH值调节至I以下,并将反应混合物加热至85-95°C。 After the coupling is complete, the addition of 21 wt% hydrochloric acid the pH was adjusted to I, and the reaction mixture was heated to 85-95 ° C. 这使乙酰基分离。 This separation makes acetyl.

[0597] 3)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将步骤2)获得的产物重氮化,并添加到I摩尔间苯二酚水溶液中。 [0597] 3) The product of step 2) is obtained diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C, and I mol of resorcinol was added to the aqueous solution. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0598] 4)使I摩尔5-硝基-2-氨基苯酚悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并添加到步骤3)获得的反应混合物中。 [0598] 4) reacting I mole of 5-nitro-2-aminophenol was suspended in ice-water, diazotized pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid, and added to step 3) obtained in the reaction mixture. 加入10重量%氢氧化钠水溶液使PH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8. 反应完成后,在反应混合物中加入O. 40-0. 60摩尔硫酸铁(III)并搅拌I小时。 After completion of the reaction, O. 40-0. 60 mol of ferric sulfate (III) in the reaction mixture and stirred for I h. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0599]实施例 43a : [0599] Example 43a:

[0600] 按照实施例42a中描述的方法进行反应,不同的是不存在随后与铁盐的反应。 [0600] reaction was carried out according to the procedure described in Example 42a, except that the subsequent reaction with the presence of iron salts.

[0601] 实施例44: [0601] Example 44:

[0602] [0602]

[0603] I)将I摩尔克列氏酸7溶于25重量%氢氧化钠水溶液。 [0603] I) The I Mo Erke's acid 7 was dissolved in 25 wt% aqueous sodium hydroxide solution. 同时,使I摩尔MSP悬浮在冰水中,在ρΗ< I和0-5°C下用过量亚硝酸钠和盐酸重氮化,然后添加到克列氏酸7的溶液中,同时保持pH值低于2。 Meanwhile, the I mol of MSP was suspended in ice-water, treated with excess sodium nitrite and hydrochloric acid at ρΗ <I and 0-5 ° C, then added to the solution Cleve's acid 7 while keeping the pH low to 2.

[0604] 2)在pH < I和0-5°C下用过量亚硝酸钠和盐酸将步骤I)获得的产物重氮化。 [0604] 2) with excess sodium nitrite and hydrochloric acid at pH <I and 0-5 ° C in step I) the product obtained diazotized. 然后将反应混合物添加到I摩尔间苯二酚水溶液中。 The reaction mixture was then added to an aqueous solution of I mol of resorcinol. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0605] 3)使I摩尔5-硝基-2-氨基苯酚悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并添加到步骤2)获得的反应混合物中。 [0605] 3) reacting I mole of 5-nitro-2-aminophenol was suspended in ice-water, diazotized pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid, and added to step 2) obtained in the reaction mixture. 加入10重量%氢氧化钠水溶液使PH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8. 反应完成后,在反应混合物中加入O. 40-0. 60摩尔硫酸铁(III)并搅拌I小时。 After completion of the reaction, O. 40-0. 60 mol of ferric sulfate (III) in the reaction mixture and stirred for I h. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0606] 实施例45 : [0606] Example 45:

[0607] 按照实施例44中描述的方法进行反应,不同的是不存在随后与铁盐的反应。 [0607] reaction was carried out according to the method described in Example 44, except that the subsequent reaction with the presence of iron salts.

[0608]实施例 46a : [0608] Example 46a:

[0609] [0609]

[0610]方法 A : [0610] Method A:

[0611] I)使I摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0611] I) of I mol of MSP was suspended in ice-water, diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C. 将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液。 The I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide. 将该溶液与在10°C以下在30分钟内逐滴加入的重氮化MSP混合,同时加入10重量%氢氧化钠水溶液使pH值保持在6至8之间。 And the solution was added dropwise below 10 ° C within 30 minutes diazotized MSP mixed while adding 10 wt% aqueous sodium hydroxide solution the pH was maintained between 6-8.

[0612] 2)将I摩尔H酸溶于25重量%氢氧化钠水溶液,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化并添加到步骤I)获得的反应混合物中。 [0612] 2) The I mol of H acid was dissolved in 25 wt% aqueous sodium hydroxide, and added to the diazotization step I) is obtained with excess sodium nitrite and hydrochloric acid at pH <I 0_5 ° C and the reaction mixture . 加入10重量%氢氧化钠水溶液使PH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8.

[0613] 3)使I摩尔5-硝基-2-氨基苯酚悬浮在冰水中,此后在pH < I和0_5°C下用过量亚硝酸钠重氮化,然后添加到步骤2)获得的反应混合物中。 [0613] 3) reacting I mole of 5-nitro-2-aminophenol was suspended in ice-water, thereafter diazotized with excess sodium nitrite at pH <I and 0_5 ° C, then added to step 2) obtained in the reaction mixture. 加入10重量%氢氧化钠水溶液使PH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8. 反应完成后,在反应混合物中加入O. 40-0. 60摩尔硫酸铁(III)并搅拌I小时。 After completion of the reaction, O. 40-0. 60 mol of ferric sulfate (III) in the reaction mixture and stirred for I h. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0614]方法 B : [0614] Method B:

[0615] I)使I摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0615] I) of I mol of MSP was suspended in ice-water, diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C. 将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液。 The I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide. 将该溶液与在10°C以下在30分钟内逐滴加入的重氮化MSP混合,同时加入10重量%氢氧化钠水溶液使pH值保持在6至8之间。 And the solution was added dropwise below 10 ° C within 30 minutes diazotized MSP mixed while adding 10 wt% aqueous sodium hydroxide solution the pH was maintained between 6-8.

[0616] 2)将I摩尔H酸溶于25重量%氢氧化钠水溶液,并用I. 1_1. 5摩尔乙酸酐乙酰化。 [0616] 2) The I mol of H acid was dissolved in 25 wt% aqueous sodium hydroxide solution, and dried I. 1_1. 5 mol of acetic anhydride acetylation.

[0617] 3)使I摩尔5-硝基-2-氨基苯酚悬浮在冰水中,并在pH < I和0_5°C下用过量亚硝酸钠重氮化,并添加到步骤2)获得的反应混合物中。 [0617] 3) reacting I mole of 5-nitro-2-aminophenol was suspended in ice-water, and the pH <I and 0_5 ° C with excess sodium nitrite, and added to step 2) obtained in the reaction mixture. 加入碳酸钠使pH值保持在4至7之间。 Addition of sodium carbonate The pH was maintained between 4 to 7. 偶联完成后,加入21重量%盐酸将pH值调节至I以下,并将反应混合物加热至85-95 °C。 After the coupling is complete, the addition of 21 wt% hydrochloric acid the pH was adjusted to I, and the reaction mixture was heated to 85-95 ° C. 这使乙酰基分离。 This separation makes acetyl.

[0618] 4)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将步骤3)获得的产物重氮化,并添加到3-8之间的步骤I)获得的反应混合物中,然后加入10重量%氢氧化钠水溶液。 [0618] 4) at pH <I 0_5 ° C and the excess sodium nitrite and hydrochloric acid in step 3) The product obtained diazotized and added to between the step 3-8 I) the reaction mixture obtained, 10 wt% aqueous sodium hydroxide was then added. 反应完成后,在反应混合物中加入O. 40-0. 60摩尔硫酸铁(III)并搅拌I小时。 After completion of the reaction, O. 40-0. 60 mol of ferric sulfate (III) in the reaction mixture and stirred for I h. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0619]实施例 47a: [0619] Example 47a:

[0620] 按照实施例46a中描述的方法进行反应,不同的是不存在随后与铁盐的反应。 [0620] reaction was carried out according to the procedure described in Example 46a, except that the subsequent reaction with the presence of iron salts.

[0621] 实施例48: [0621] Example 48:

[0622] [0622]

[0623] I)使I摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0623] I) of I mol of MSP was suspended in ice-water, diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C. 将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液。 The I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide. 将该溶液与在10°C以下在30分钟内逐滴加入的重氮化的MSP混合,同时加入10重量%氢氧化钠水溶液使pH值保持在6至8之间。 The solution was mixed with MSP added dropwise over 30 minutes at below 10 ° C diazotized, while adding 10 wt% aqueous sodium hydroxide solution the pH was maintained between 6-8.

[0624] 2)使I摩尔5-硝基-2-氨基苯酚悬浮在冰水中,并在pH < I和0_5 °C下用过量亚硝酸钠重氮化,并与I摩尔克列氏酸7 —起加入25重量%氢氧化钠水溶液中,同时保持pH值低于2。 [0624] 2) reacting I mole of 5-nitro-2-aminophenol was suspended in ice-water, and the pH <I and 0_5 ° C with excess sodium nitrite, and the I Mo Erke's acid 7 - from 25 wt% aqueous sodium hydroxide was added while maintaining the pH below 2.

[0625] 3)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将步骤2)获得的产物重氮化,然后添加到步骤I)获得的反应混合物中。 [0625] 3) The product of step 2) is obtained by diazotisation at pH <I 0_5 ° C and the excess sodium nitrite and hydrochloric acid, and then added to step I) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3-8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0626] 按照与实施例42a、44和46a类似的方式,可以获得通式Dk1-N = N-Napht-N =N-Kk-N = N-Dk2的染料(即P = Napht、p = I且m = I时通式I的染料)的金属络合物,其中Dk1和Dk2各自代表源自重氮组分DKl至DK9、DK13、DK14、DK26、DK27、DK39至DK41或DK58或源自Al至A12的基团,Dk1或Dk2中至少一个代表式A的基团,Kk代表源自Kk2或Kk3 的二价基团,且Napht 是式11-1、11-3、11-5、11-7、11-9、11-11、11-13、11-15 或11-16的二价基团。 [0626] as in Example 42a, 44 and 46a in a similar manner, the general formula Dk1-N = N-Napht-N = N-Kk-N = N-Dk2 dye (i.e., P = Napht, p = I and m = dyes of formula I when I) metal complexes, wherein each represent Dk1 and Dk2 from the diazo components DKl to DK9, DK13, DK14, DK26, DK27, DK39 through DK41 or DK58 or from Al group to A12, at least Dk2 Dk1 or represents a group of formula a, Kk representative of a divalent group derived from a Kk2 or Kk3, and Napht formula 11-1,11-3,11-5,11- 7,11-9,11-11,11-13,11-15 11-16 or a divalent group. 其例子列在表12中。 Examples thereof are listed in Table 12.

[0629] 按照与实施例43a、45、47a和48类似的方式,可以获得通式Dk1-N = N-Napht-N =N-Kk-N = N-Dk2的染料(即P = Napht、P = I且m = I时通式I的染料),其中Dk1和Dk2各自代表源自重氮组分DKl至DK83或源自Al至A12的基团,Dk1或Dk2中至少一个代表式A的基团,Kk代表源自Kk2、Kk3、Kk5、Kk49或Kk50的二价基团,且Napht是式11-1、11-3、11-5、11-7、11-9、11-11、11-13、11-15 或11-16 的二价基团。 [0629] Following Example 43a, 45,47a, and 48 in a similar manner, the formula can be obtained Dk1-N = N-Napht-N = N-Kk-N = N-Dk2 dye (i.e., P = Napht, P = I m = I and a dye of the general formula I), wherein each represent Dk1 and Dk2 from the diazo components DKl to DK83 or from a group of Al to A12, or Dk2 Dk1 representative of at least a group of the formula a group, representatives from Kk Kk2, Kk3, Kk5, Kk49 Kk50 or a divalent group of the formula and Napht 11-1,11-3,11-5,11-7,11-9,11-11,11 -13,11-15 11-16 or a divalent group. 其例子列在表13 中。 Examples listed in Table 13.

[0630]表 13 [0630] TABLE 13

[0631] [0631]

[0632]实施例 49a : [0632] Example 49a:

[0633] [0633]

[0634] I)在pH< I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4'-二氨基联苯基-3,3' - 二羧酸双偶氮化,并在5至11的pH值下与I摩尔水杨酸反应。 [0634] I) at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid I mole of 4,4'-diamino-biphenyl-3,3 '- dicarboxylic acid tetrazotized and It is reacted with I mole of salicylic acid at pH values ​​of 5 to 11.

[0635] 2)在pH > 12下将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液。 [0635] 2) at pH> 12 under the I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide. 将该溶液与在10°C以下在30分钟内逐滴加入的步骤I)获得的反应产物混合,在此期间加入10重量%氢氧化钠水溶液使pH值保持在9以上。 The reaction product solution was added dropwise to step over 30 minutes at below 10 ° C to I) obtained by mixing, during which time 10 wt% aqueous sodium hydroxide solution the pH was maintained at 9 or more.

[0636] 3)使I摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0636] 3) reacting I mole of MSP was suspended in ice-water, diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C. 随后,将该重氮化MSP添加到步骤2)获得的反应混合物中,同时加入10重量%氢氧化钠水溶液使PH值保持在5至8之间。 Subsequently, the diazotized MSP added to step 2) the reaction mixture obtained, while adding 10 wt% aqueous sodium hydroxide PH value was maintained between 5 to 8. 反应完成后,在反应混合物中加入I摩尔硫酸铜(II)并在70°C搅拌I小时。 After completion of the reaction, the molar I (II) sulfate in the reaction mixture and stirred at 70 ° C I h. 加入NaCl使染料沉淀并通过抽吸滤出。 NaCl was added and the precipitated dye is filtered off with suction.

[0637]实施例 50a : [0637] Example 50a:

[0638] 按照实施例49a中描述的方法进行反应,不同的是不存在随后与铜盐的反应。 [0638] reaction was carried out according to the procedure described in Example 49a, except that the subsequent reaction with the absence of copper salts.

[0639] 实施例51 : [0639] Example 51:

[0640] [0640]

[0641] I)在pH < I和0_5°C下用过量亚硝酸钠和盐酸将I摩尔4,4' - 二氨基苯甲酰苯胺双偶氮化,并在PH 5-11下与I摩尔水杨酸反应。 [0641] I) at pH <I and 0_5 ° C with excess sodium nitrite and hydrochloric acid I mole of 4,4 '- diamino benzanilide tetrazotized and at PH 5-11 mol and I salicylic acid.

[0642] 2)使I摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0642] 2) reacting I mole of MSP was suspended in ice-water, diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C. 将I摩尔间苯二酚溶于50重量%氢氧化钠水溶液。 The I mol of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide. 在10°C以下在30分钟内将重氮化MSP逐滴加入其中,同时加入10重量%氢氧化钠水溶液使pH值保持在6-8之间。 At below 10 ° C over 30 minutes diazotized MSP was added dropwise thereto, while adding 10 wt% aqueous sodium hydroxide solution the pH was maintained between 6-8.

[0643] 3)将步骤2)获得的产物添加到步骤I)获得的反应混合物中,同时加入10重量%氢氧化钠水溶液使PH值保持在5至8之间。 [0643] 3) Adding the product of step 2) obtained in the step I) the reaction mixture obtained, while adding 10 wt% aqueous sodium hydroxide PH value was maintained between 5 to 8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0644] 按照与实施例49a、50a和51类似的方式,可以获得通式Kk3-N = N-Tk-N = N-Kk1-N=NA的染料和它们的金属络合物(即通式XIV的染料),其中Kk3代表源自重氮组分Kkl至Kk48或Kk51至Kk67的基团,或代表Dk42至Dk83,Tk代表源自TKl至TK20的二价基团,Kk1代表源自Kk2、Kk3、Kk5、Kk49或Kk50的二价基团,且A代表基团Al至A12之一。 [0644] accordance 49a, 50a, and 51 in a similar manner, the general formula Kk3-N = N-Tk-N = N-Kk1-N = NA dyes and their metal complexes Example (i.e., Formula dyes XIV), wherein representatives from the diazo components Kkl Kk3 to Kk48 group or Kk51 to Kk67 or on behalf Dk42 to DK83, representative of a divalent group derived from Tk to TKl TK20 and Kk1 derived from Kk2 representatives, Kk3, Kk5, Kk49 Kk50 or a divalent group, and a represents one of the groups Al to A12. 其例子列在表14中。 Examples thereof are listed in Table 14.

[0645]表 14 : [0645] Table 14:

[0646] [0646]

[0649] I)将2摩尔H酸溶于25重量%氢氧化钠水溶液,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并添加到I摩尔3,3'-二羟基二苯胺的水溶液中。 [0649] I) to 2 mol of H acid was dissolved in 25 wt% aqueous sodium hydroxide solution, with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C, and added to 3,3 mol I aqueous dihydroxydiphenyl aniline. 加入10重量%氢氧化钠水溶液使pH值保持在3至10之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-10.

[0650] 2)使2摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并添加到步骤I)获得的反应混合物中。 [0650] 2) reacting 2 mol of MSP was suspended in ice-water, diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C, and added to step I) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0651] 按照与实施例52a类似的方式,可以获得通式Dk1-N = N_p_N = N-Kk1-N = NRN=N-Dk2的染料和它们的金属络合物(通式XV的染料),其中Dk1和Dk2代表源自重氮组 [0651] In a similar manner as Example 52a embodiment, the formula may be obtained Dk1-N = N_p_N = N-Kk1-N = NRN = N-Dk2 dyes and their metal complexes (Formula XV dyes), wherein Dk1 and Dk2 representatives from diazo group

分DKl至DK83或源自Al至A12的基团,Dk1或Dk2中至少一个代表式A的基团,Kk代表源自Kk2、Kk3、Kk5、Kk49 或Kk50 的二价基团,且P 和R 各自代表式11-1、11-3、11-5、11-7、11-9、II-Il和11-13的二价基团。 DKl DK83 points to, or derived from the group Al to A12, at least Dk2 Dk1 or represents a group of formula A, Kk representatives from Kk2, Kk3, Kk5, Kk49 Kk50 or divalent radical, and P and R each represents formula 11-1,11-3,11-5,11-7,11-9, II-Il, and a divalent group 11-13. 其例子列在表15中。 Examples listed in Table 15.

[0652]表 15 : [0652] Table 15:

[0653] [0653]

[0654]实施例 53a : [0654] Example 53a:

[0655] [0655]

[0656] I)使I摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并添加到I摩尔克列氏酸7的碱性溶液中。 [0656] I) of I mol of MSP was suspended in ice-water, diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C, and added to the I Mo Erke's acid 7 in an alkaline solution. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8.

[0657] 2)使I摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并添加到I摩尔8-氨基萘-I-磺酸(Dk56)的碱性溶液中。 [0657] 2) reacting I mole of MSP was suspended in ice-water, diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C, and added to 8-amino-naphthalene -I- I mole acid (Dk56 ) alkaline solution. 加入10重量%氢氧化钠水溶液使PH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8.

[0658] 3)在pH < I和0-5°C下用过量亚硝酸钠和盐酸将步骤I)获得的产物重氮化并在30分钟内添加到I摩尔3,3'- 二羟基二苯胺的碱性溶液中。 [0658] 3) at pH <I 0-5 ° C and excess sodium nitrite and hydrochloric acid in step I) the product obtained is diazotized and added to I mole of 3,3'-dihydroxybenzophenone in 30 minutes aniline alkaline solution. 加入10重量%氢氧化钠水溶液使PH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to make the PH value was maintained between 3-8.

[0659] 4)在pH < I和0-5°C下用过量亚硝酸钠和盐酸将步骤2)获得的产物重氮化并添加到步骤3)获得的反应混合物中,同时加入10重量%氢氧化钠水溶液使pH值保持在5至8之间。 [0659] 4) The product of step 2) is diazotized and added to the obtained step 3) the reaction mixture obtained with excess sodium nitrite and hydrochloric acid at pH <I and 0-5 ° C, while adding 10 wt% aqueous sodium hydroxide solution the pH was maintained between 5 to 8. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0660] 按照与实施例53a类似的方式,可以获得通式Dk1-N = N_P_N = N-Kk1-N = NRN=N-Dk2的染料和它们的金属络合物(通式XV的染料),其中Dk1和Dk2代表源自重氮组分DKl至DK83或源自Al至A12的基团,Dk1或Dk2中至少一个代表式A的基团,Kk代表源自Kk2、Kk3、Kk5、Kk49或Kk50的二价基团,且P和R各自代表式11-15或11-16的二价基团或源自重氮组分DK3、DK4、DK6、DK7、DK11、DK13、DK14、DK15、DK18、DK22 至DK27、DK29、DK30、DK33、DK36、DK38或DK39的二价基团。 [0660] In a similar manner as Example 53a embodiment, the formula may be obtained Dk1-N = N_P_N = N-Kk1-N = NRN = N-Dk2 dyes and their metal complexes (Formula XV dyes), wherein Dk1 and Dk2 representatives from the diazo components DKl to DK83 or from a group of Al to A12, at least Dk2 Dk1 or represents a group of formula a, Kk representatives from Kk2, Kk3, Kk5, Kk49 or Kk50 divalent group, and P and R each represents a divalent radical of formula or 11-16 or 11-15 from the diazo components DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK22 through DK27, DK29, DK30, DK33, DK36, DK38 DK39 or a divalent group. 其例子列在表16中。 Examples thereof are listed in Table 16.

[0661]表 16 : [0661] Table 16:

[0662] [0662]

[0663] 实施例54 : [0663] Example 54:

[0664] [0664]

[0665] I)在70_80°C将2摩尔邻氨基苯甲酸溶于硫酸(96% ),并与O. 5_0. 6摩尔甲醛反应。 [0665] I) at 70_80 ° C 2 moles of anthranilic acid dissolved in sulfuric acid (96%), and reacted with O. 5_0. 6 moles of formaldehyde. 在70-80°C 2小时后,加入冰将反应混合物冷却至大约0°C,并在pH < I和0_5°C下用过量亚硝酸钠和盐酸将所得产物双偶氮化。 After 70-80 ° C 2 h, ice was added and the reaction mixture was cooled to approximately 0 ° C, and the resulting product was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C. 在PH > 12下将I. 8-2. 2摩尔间苯二酚溶于50重量%氢氧化钠水溶液,并将该溶液与在5°C以下在30分钟内逐滴加入的双偶氮化化合物混合,在此期间加入10重量%氢氧化钠水溶液使pH值保持在8以上。 In the PH> 12 at the I. 8-2. 2 moles of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide solution, and the solution was added dropwise to the tetrazo of 30 minutes at below 5 ° C compound is mixed, during which time aqueous 10 wt% sodium hydroxide solution the pH was maintained at 8 or more.

[0666] 2)使2摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化,并添加到步骤I)获得的反应混合物中。 [0666] 2) reacting 2 mol of MSP was suspended in ice-water, diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C, and added to step I) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,将反应溶液加热至80°C,并加入2摩尔CuS04。 After completion of the reaction, the reaction solution was heated to 80 ° C, was added 2 mol CuS04. 然后将所得反应混合物蒸发以获得络合染料。 The resulting reaction mixture was evaporated to obtain a complex dyes.

[0667] 实施例55 : [0667] Example 55:

[0668] 按照实施例54中描述的方法进行反应,不同的是不存在随后与铜盐的反应。 [0668] reaction was carried out according to the method described in Example 54, except that the subsequent reaction with the absence of copper salts.

[0669] 实施例56 : [0669] Example 56:

[0670] [0670]

[0671] I)在70_80°C将2摩尔邻氨基苯甲酸溶于硫酸(96% ),并与O. 5_0. 6摩尔甲醛反应。 [0671] I) at 70_80 ° C 2 moles of anthranilic acid dissolved in sulfuric acid (96%), and reacted with O. 5_0. 6 moles of formaldehyde. 在70-80°C 2小时后,加入冰将反应混合物冷却至大约0°C,并在pH < I和0_5°C下用过量亚硝酸钠和盐酸将所得产物双偶氮化。 After 70-80 ° C 2 h, ice was added and the reaction mixture was cooled to approximately 0 ° C, and the resulting product was tetrazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C.

[0672] 2)使2摩尔MSP悬浮在冰水中,在pH < I和0_5°C下用过量亚硝酸钠和盐酸重氮化。 [0672] 2) reacting 2 mol of MSP was suspended in ice-water, diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0_5 ° C. 将2摩尔间苯二酚溶于50重量%氢氧化钠水溶液。 2 mole of resorcinol was dissolved in 50 wt% aqueous sodium hydroxide. 在10°C以下在30分钟内将重氮化的MSP逐滴加入其中,在此期间加入10重量%氢氧化钠水溶液使pH值保持在6至8之间。 At below 10 ° C over 30 minutes diazotized MSP added dropwise, during which time aqueous 10 wt% sodium hydroxide solution the pH was maintained between 6-8.

[0673] 3)将步骤I)获得的反应产物添加到步骤2)获得的反应混合物中。 The reaction product [0673] 3) in step I) obtained in Step 2 was added to) the reaction mixture obtained. 加入10重量%氢氧化钠水溶液使pH值保持在3至8之间。 10 wt% aqueous sodium hydroxide was added to maintain the pH between 3-8. 反应完成后,将反应溶液加热至80°C,并加入2摩尔CuS04。 After completion of the reaction, the reaction solution was heated to 80 ° C, was added 2 mol CuS04. 然后将所得反应混合物蒸发至干以获得络合染料。 The resulting reaction mixture was evaporated to dryness to obtain a complex dyes.

[0674] 实施例57 : [0674] Example 57:

[0675] 按照实施例56a中描述的方法进行反应,不同的是不存在随后与铜盐的反应。 [0675] reaction was carried out according to the method described in Example 56a in the embodiment, except that the subsequent reaction with the absence of copper salts.

[0676] 按照与实施例54和56类似的方式,可以获得通式Dk1-N = N-Kk1-N = N-Tk1-N =N-Kk2-N = N-Dk2的染料(通式IV的染料)的金属络合物,其中Dk1和Dk2代表源自重氮组分DKl至DK83或源自Al至A12的基团,基团Dk1或Dk2中至少一个代表式A的基团,Tk1代表源自了1^3、了1^4、了1^8至了1^11、了1^14、了1^16或了1^19的二价基团,且Kk1以及Kk2独立地代表源自Kk2、Kk3、Kk5、Kk49 或Kk50 的二价基团或式11-2、11-4、11-6、11-8、11-10、11-12 或II-14的二价基团。 [0676] 54 and 56 in accordance with a similar manner to Example embodiment, the formula may be obtained Dk1-N = N-Kk1-N = N-Tk1-N = N-Kk2-N = N-Dk2 dye (formula IV dye) metal complexes, wherein Dk1 and Dk2 representatives from the diazo components DKl to DK83 or from a group of Al to A12, or Dk2 Dk1 group in at least one representative of the group of formula a, representative of the source Tk1 since the 1 ^ 3 ^ 4 1, 1 ^ 8 to 11 ^ 1, 14 ^ 1, 16 ^ 1, or a divalent group of 1 ^ 19, and Kk1 from and independently represent Kk2 Kk2, Kk3, Kk5, Kk49 Kk50 or a divalent group or a divalent group of the formula II-14 or the 11-2,11-4,11-6,11-8,11-10,11-12.

[0677] 按照与实施例55和57类似的方式,可以获得通式Dk1-N = N-Kk1-N = N-Tk1-N =N-Kk2-N = N-Dk2的染料(通式IV的染料),其中Dk1和Dk2代表源自重氮组分DKl至DK83或源自Al至A12的基团,基团Dk1或Dk2中至少一个代表式A的基团,Tk1代表源自Tkl至Tk20的二价基团,且Kk1以及Kk2独立地代表源自Kk2、Kk3、Kk5、Kk49或Kk50的二价基团或式11-2、11-4、11-6、11-8、11-10、11-12 或11-14 的二价基团。 [0677] and according to Example 57 in a similar manner, the formula can be obtained Dk1-N = N-Kk1-N = N-Tk1-N = N-Kk2-N = N-Dk2 dye (of the formula IV 55 dyes), wherein representatives from the diazo components Dk1 and Dk2 DK83 DKl to or derived from groups Al to A12, and a group of at least a Dk2 Dk1 or represents a group of formula a, from the representative Tk1 through Tk20 of Tkl divalent group, and independently represent Kk1 and Kk2 from Kk2, Kk3, Kk5, a divalent radical of formula or Kk49 or Kk50 11-2,11-4,11-6,11-8,11-10, 11-12 or 11-14 divalent radical.

[0678] 实施例58 : [0678] Example 58:

[0679] [0679]

[0680] I)将I摩尔克列氏酸7溶于25重量%氢氧化钠水溶液。 [0680] I) The I Mo Erke's acid 7 was dissolved in 25 wt% aqueous sodium hydroxide solution. 同时,使I摩尔MSP悬浮在冰水中,并在pH < I和0-5°C下用过量亚硝酸钠和盐酸重氮化,然后添加到克列氏酸7的溶液中,同时保持PH值低于2。 Meanwhile, the I mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0-5 ° C, then added to the solution Cleve's acid 7 while maintaining the PH value less than 2.

[0681] 2)在pH < I和0-5°C下用过量亚硝酸钠和盐酸将步骤I)获得的产物重氮化。 [0681] 2) with excess sodium nitrite and hydrochloric acid at pH <I and 0-5 ° C in step I) the product obtained diazotized. 然后在pH 3-8下与I摩尔甲胺非他明反应。 I then with trimethylamine molar at pH 3-8 non-amphetamine response. 反应完成后,加入NaCl使染料沉淀并通过抽吸滤出。 After completion of the reaction, addition of NaCl and precipitated dye is filtered off with suction.

[0682] 按照与实施例58类似的方式,可以获得通式AN = N-Napht-N = N-Kk的染料(即P = Naptht,P = I且m = O时通式I的染料),其中Napht代表源自DK42至DK59的基团,Kk代表源自Kkl至Kk48或Kk51至Kk67的基团,且A代表基团Al至A12之一。 [0682] Example 58 Following a similar manner, the general formula AN = N-Napht-N = N-Kk dye (i.e., P = Naptht, P = I m = I and O when a dye of formula), wherein Napht representatives from DK42 to DK59 group, Kk Kkl representatives from group to group or Kk48 Kk51 to Kk67, and a represents a group one of Al to A12. 其例子列在表17中。 Examples thereof are listed in Table 17.

[0683]表 17 : [0683] Table 17:

[0684] [0684]

[0685]实施例 59a : [0685] Example 59a:

[0686] [0686]

[0687] 将I摩尔克列氏酸7溶于25重量%氢氧化钠水溶液。 [0687] The I Mo Erke's acid 7 was dissolved in 25 wt% aqueous sodium hydroxide solution. 同时,使I摩尔MSP悬浮在冰水中,并在pH< I和0-5°C下用过量亚硝酸钠和盐酸重氮化,然后添加到克列氏酸7的溶液中,同时保持PH值低于2。 Meanwhile, the I mol of MSP was suspended in ice water and diazotized with excess sodium nitrite and hydrochloric acid at pH <I and 0-5 ° C, then added to the solution Cleve's acid 7 while maintaining the PH value less than 2. 反应完成后,将染料溶液喷雾干燥。 After completion of the reaction, the dye solution was spray-dried.

[0688] 按照与实施例59a类似的方式,可以获得通式A_N = N-Kk的染料(即P = m = O时通式I的染料),其中Kk代表源自Kkl至Kk48或Kk51至Kk67的基团或源自Dk3、DK4、DK6、DK7、DK11、DK13、DK14、DK15、DK18、DK21 至DK27、DK29、DK30、DK33、DK36、DK38、DK39或Dk42至Dk83的基团,且A代表基团Al至A12之一。 [0688] In a similar manner as Example 59a embodiment, the formula may be obtained A_N = N-Kk dye (i.e., P = m = O dyes of the general formula I), wherein Kk represents Kk48 to or derived from Kkl Kk51 to Kk67 or a group derived from Dk3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 through DK27, DK29, DK30, DK33, DK36, DK38, DK39 or Dk42 to Dk83 group, and a represents one of the groups Al to A12. 根据反应的pH值,基团AN = N-的偶联不仅在Dk42至Dk57和在Dk59中羟基的邻位进行,还在氨基的邻位进行。 The pH of the reaction, AN = N- group coupled to Dk57 Dk42 only in the ortho position and the hydroxyl group in Dk59 ortho amino group is still. 其例子列在表18中。 Examples thereof are listed in Table 18.

[0689]表 18 : [0689] Table 18:

[0690] [0690]

[0691]染色配方(prescription): [0691] dyeing recipe (prescription):

[0692] 份数按重量计。 [0692] parts, by weight. 关于鞣料、疏水剂、加脂剂和助剂的所有数据均以市售产品为基础。 On tanning, water repellent, fatliquoring agents and auxiliaries are all data based on a commercially available product. 关于染料的数据是以有色的有机化学成分、由于合成条件而存在的任何盐(合成盐)与存在的任何标准剂的总量为基础的。 Data on the dye is a colored organic chemical composition, the total amount of any salt (Synthesis salts thereof) with any standard agent is present due to the synthesis conditions exist based.

[0693] 固色率通过染色浴液的HPLC分析定性测定并通过UV-VIS光谱法定量测定。 [0693] Fixation dye bath by HPLC analysis and qualitative determination by UV-VIS spectrum measured quantitatively. 为此,在染色之后(pH < 7),在固色60分钟、120分钟、180分钟后(pH > 7)取每种洗液浴液的5毫升样品,并用I毫升甲酸溶液调节至PH 3-4。 To do this, after staining (pH <7), the fixing 60 minutes, 120 minutes and after 180 minutes (pH> 7) 5 ml samples were taken for each wash bath, and treated with I ml of formic acid solution was adjusted to PH 3 -4. 通过HPLC分析样品的染料及其水解产物。 Dyes and by HPLC analysis of the hydrolyzate samples. 所用HPLC 柱是来自Macherey-Nagel 的Nucleodur C18 Gravity 3 μ , CC70/2 和Hypersil120-50DS,CC100/2。 The HPLC column was a Macherey-Nagel Nucleodur from the C18 Gravity 3 μ, CC70 / 2 and Hypersil120-50DS, CC100 / 2. 所用洗脱剂是乙腈/缓冲剂(I. 6克硫酸氢四丁铵,6克三水合磷酸氢二钾,在I升水中)。 As used eluent is acetonitrile / buffer (I. 6 g of tetrabutylammonium hydrogen sulfate, 6 grams of dipotassium hydrogen phosphate trihydrate, in I liter of water).

[0694] 按照下列国际公认的标准测定坚牢度: [0694] Determination of fastness according to the following internationally recognized standards:

[0695] 耐汗坚牢度:按照Veslic C4260 [0695] Perspiration Fastness: according Veslic C4260

[0696]耐洗度: 按照DIN EN ISO 15703 [0696] Washing of: in accordance with DIN EN ISO 15703

[0697] 渗移牢度: 按照DIN EN ISO 15701以及在与DIN EN ISO 15701类似的条件下在85°C和95%的湿度下储存16小时· [0697] Bleeding Fastness: according to DIN EN ISO 15701, and stored at-85 ° C and 95% humidity under conditions similar to DIN EN ISO 15701 16 hours

[0698] 耐擦度: 按照DIN EN ISO 105-X12 (Crockmeter,用纺织棉摩擦)以及按照DIN EN ISO 11640 (Veslic,用毡摩擦) [0698] abrasion of: (Crockmeter, cotton textile friction) and according to DIN EN ISO 11640 (Veslic, the felt rubs) in accordance with DIN EN ISO 105-X12

[0699] Maeser : 按照ASTM D 2099 [0699] Maeser: according to ASTM D 2099

[0700]针入度计: 按照DIN EN ISO 5403 [0700] penetrometer: according to DIN EN ISO 5403

[0701] 水蒸气渗透性:按照DIN EN ISO 14268 [0701] water vapor permeability: according to DIN EN ISO 14268

[0702]抗挠性: 按照DIN EN ISO 5402 [0702] flex resistance: according to DIN EN ISO 5402

[0703] 缝合拉出试验:按照DIN 5331 [0703] suture pull-out test: in accordance with DIN 5331

[0704]抗撕强度: 按照DIN EN ISO 3377 [0704] Tear strength: according to DIN EN ISO 3377

[0705]拉伸强度: 按照DIN EN ISO 3376 [0705] Tensile strength: according to DIN EN ISO 3376

[0706] 染色配方I : [0706] staining formula I:

[0707] a)在30°C下,将削匀厚度为I. I毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0707] a) at 30 ° C, shaved thickness of 100 parts by weight of block I. I I mm in the conventional organic-tanned cow leather with 200 parts of water in a drum and washed for 20 min. 然后使用150份水、2份分散剂和5份来自实施例2d的染料在pH 4. 4和30°C下染色60分钟。 Then 150 parts of water, 2 parts of a dispersant and 5 parts of the dye from Example 2d embodiment dyeing at pH 4. 4 and 30 ° C 60 min. 在60分钟的转鼓加工过程中,逐份添加100份15%碳酸钠溶液以使PH值在40°C保持在10. O至10. 2之间,从而固定染料。 60 minutes drumming process, by portionwise addition of 100 parts of 15% sodium carbonate solution to make the PH value at 40 ° C was maintained between 10.2 to 10. O, to fix the dye. 然后6次在40°C在200份水中洗涤10分钟。 Then 6 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 7的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.7.

[0708] b)将由此染色的皮革在由100份水、2份聚合鞣料和2份天然基加脂剂构成的新制浴液中在35°C复鞣30分钟。 [0708] b) The leather dyed in a freshly thus the float 100 parts of water, 2 parts of polymeric tanning material and 2 parts of natural aliphatic radical agent constituted retanning at 35 ° C for 30 minutes. 然后将浴液与15份液体合成鞣料、6份聚合鞣料、10份Tara植物鞣料混合并转鼓加工20分钟。 The float is then 15 parts of the liquid synthetic tanning material, 6 parts of polymeric tanning, vegetable tanning mixing 10 parts by Tara and drummed for 20 minutes. 然后在35°C在相同的浴液中用8份鱼油基加脂剂和2份卵磷脂基加脂剂通过转鼓加工2小时将皮革加脂。 Then at 35 ° C in the same float with 8 parts by radical addition of fish oil and 2 parts of lecithin fatliquor aliphatic radical fatliquoring agent by drumming for two hours. 最后,用2份浓甲酸将皮革酸化至pH Finally, 2 parts of concentrated formic acid was acidified to pH leather

3. 6,并转鼓加工两次10分钟,再转鼓加工一次30分钟。 3.6, and drumming for 10 minutes twice, once before drumming for 30 minutes. 再将染色的、复鞣和加脂的皮革在15°C用冷水漂洗10分钟,然后伸展,在室温下悬浮干燥过夜、修整、刮软和拉紧。 The dyed and retanning and fatliquoring leather rinsed with cold water for 10 minutes at 15 ° C, and then stretched, dried at room temperature overnight and suspended, trimming, staked and strained.

[0709] 所得皮革具有鲜艳的深红色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0709] The leather obtained had a brilliant crimson, and having excellent washing, perspiration resistance, scratch resistance and bleeding fastness.

[0710] 染色配方2: [0710] 2 staining formula:

[0711] a)在30°C下,将削匀厚度为I. I毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0711] a) at 30 ° C, shaved thickness of 100 parts by weight of block I. I I mm in the conventional organic-tanned cow leather with 200 parts of water in a drum and washed for 20 min. 然后使用150份水、2份分散剂和5份来自实施例2a的染料在pH 4. 4和30°C下染色60分钟。 Then 150 parts of water, 2 parts of a dispersant and 5 parts of the dye from Example 2a dyeing at pH 4. 4 and 30 ° C 60 min. 在60分钟的转鼓加工过程中,逐份添加15份固体碳酸钠以使pH值在40°C保持10. 0,从而固定染料。 60 minutes drumming process, 15 parts by portionwise addition of solid sodium carbonate to maintain a pH of 10.0 at 40 ° C, to fix the dye. 然后4次在40°C在200份水中洗涤10分钟。 Then four times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 7的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.7. 然后如染色配方I的部分b)中所述进行处理。 Then dyeing prescription I, part b) was treated in the.

[0712] 所得皮革具有鲜艳的深红色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0712] The leather obtained had a brilliant crimson, and having excellent washing, perspiration resistance, scratch resistance and bleeding fastness.

[0713] 染色配方3: [0713] 3 staining formula:

[0714] a)在30°C下,将削匀厚度为I. I毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0714] a) at 30 ° C, shaved thickness of 100 parts by weight of block I. I I mm in the conventional organic-tanned cow leather with 200 parts of water in a drum and washed for 20 min. 然后使用150份水、2份分散剂和5份来自实施例24的染料在pH 4. 4和30°C下染色60分钟。 Then 150 parts of water, 2 parts of a dispersant and 5 parts of the dye from Example 24 is dyed at pH 4. 4 and 30 ° C 60 min. 在60分钟的转鼓加工过程中,逐份添加100份15%碳酸钠溶液以使PH值在50°C保持10. 0,从而固定染料。 60 minutes drumming process, by portionwise addition of 100 parts of 15% sodium carbonate solution was added to 10.0 PH value held at 50 ° C, to fix the dye. 然后4次在40°C在200份水中洗涤10分钟。 Then four times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 7的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.7. 然后如染色配方I的部分b)中所述进行处理。 Then dyeing prescription I, part b) was treated in the.

[0715] 所得皮革具有鲜艳的深红色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0715] The leather obtained had a brilliant crimson, and having excellent washing, perspiration resistance, scratch resistance and bleeding fastness. · ·

[0716] 染色配方4: [0716] staining formula 4:

[0717] 在30°C下,将削匀厚度为I. I毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0717] at 30 ° C, shaved thickness of 100 parts by weight of block I. I I mm in the conventional organic-tanned cow leather with 200 parts of water in a drum and washed for 20 min. 然后使用150份水、2份分散剂和5份来自实施例58a的染料在pH 4. 4和30°C下染色60分钟。 Then 150 parts of water, 2 parts of a dispersant and 5 parts of the dye from Example 58a embodiment dyeing at pH 4. 4 and 30 ° C 60 min. 在90分钟的转鼓加工过程中,逐份添加100份15%碳酸钠溶液以使PH值在40°C保持10. 0,从而固定染料。 90 minutes drumming process, by portionwise addition of 100 parts of 15% sodium carbonate solution was added to 10.0 PH value held at 40 ° C, to fix the dye. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 7的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.7. 然后如染色配方I的部分b)中所述进行处理。 Then dyeing prescription I, part b) was treated in the.

[0718] 所得皮革具有鲜艳的深红色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0718] The leather obtained had a brilliant crimson, and having excellent washing, perspiration resistance, scratch resistance and bleeding fastness.

[0719] 染色配方5: [0719] staining formula 5:

[0720] 在30°C下,将削匀厚度为I. I毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0720] at 30 ° C, shaved thickness of 100 parts by weight of block I. I I mm in the conventional organic-tanned cow leather with 200 parts of water in a drum and washed for 20 min. 然后使用150份水、2份分散剂和5份来自实施例58b的染料在pH 4. 4和30°C下染色60分钟。 Then 150 parts of water, 2 parts of a dispersant and 5 parts of the dye from Example 58b embodiment dyeing at pH 4. 4 and 30 ° C 60 min. 在60分钟的转鼓加工过程中,逐份添加100份15%碳酸钠溶液以使PH值在40°C保持10. 0,从而固定染料。 60 minutes drumming process, by portionwise addition of 100 parts of 15% sodium carbonate solution was added to 10.0 PH value held at 40 ° C, to fix the dye. 在添加碳酸钠溶液的同时,分3次加入一共15份芒硝。 The addition of sodium carbonate solution at the same time, a total of three times was added 15 parts of Glauber's salt. 然后5次在40°C在200份水中洗涤10分钟。 Then 5 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 7的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.7. 然后如染色配方I的部分b)中所述进行处理。 Then dyeing prescription I, part b) was treated in the.

[0721] 所得皮革具有鲜艳的深红色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0721] The leather obtained had a brilliant crimson, and having excellent washing, perspiration resistance, scratch resistance and bleeding fastness.

[0722] 染色配方6 : [0722] staining formula 6:

[0723] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0723] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用150份水、2份分散剂和5份来自实施例59a的染料在pH 4. I和30°C下染色60分钟。 Then 150 parts of water, 2 parts of a dispersant and 5 parts of the dye from Example 59a embodiment dyeing at pH 4. I and 30 ° C 60 min. 在180分钟的转鼓加工过程中,逐份添加100份硼砂缓冲剂以使PH值在40°C保持在7. 9至9. O之间,从而固定染料。 180 minutes drumming process, by portionwise addition of 100 parts of borax buffer to PH value at 40 ° C was maintained between 7.9 to 9. O, to fix the dye. 然后5次在40°C在200份水中洗涤10分钟。 Then 5 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 6份甲酸以达到4. 3的pH值。 200 parts of water was added and O. 6 parts of formic acid to reach a pH of 4.3. 然后如染色配方I的部分b)中所述进行处理。 Then dyeing prescription I, part b) was treated in the.

[0724] 所得皮革具有鲜艳的深红色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0724] The leather obtained had a brilliant crimson, and having excellent washing, perspiration resistance, scratch resistance and bleeding fastness.

[0725] 染色配方7 : [0725] staining formula 7:

[0726] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0726] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用150份水、2份分散剂和5份来自实施例59e的染料在pH 4. I和30°C下染色60分钟。 Then 150 parts of water, 2 parts of a dispersant and 5 parts of the dye from Example 59e embodiment dyeing at pH 4. I and 30 ° C 60 min. 在180分钟的转鼓加工过程中,一次性添加30份15%碳酸钠溶液以使pH值在40°C保持在9. 4-9. 9之间,从而固定染料。 180 minutes drumming process, a one-time addition of 30 parts of a 15% solution of sodium carbonate to bring the pH was maintained between 9 4-9. 9 at 40 ° C, to fix the dye. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 5的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.5. 然后如染色配方I的部分b)中所述进行处理。 Then dyeing prescription I, part b) was treated in the.

[0727] 所得皮革具有鲜艳的深红色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0727] The leather obtained had a brilliant crimson, and having excellent washing, perspiration resistance, scratch resistance and bleeding fastness.

[0728] 染色配方8 : [0728] staining formula 8:

[0729] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0729] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用150份水、2份分散剂和5份来自实施例2b的染料在pH 4. I和30°C下染色60分钟。 Then 150 parts of water, 2 parts of a dispersant and 5 parts of the dye from Example 2b dyeing at pH 4. I and 30 ° C 60 min. 在180分钟的转鼓加工过程中,逐份添加100份硼砂缓冲剂以使PH值在40°C保持在8. O至9. O之间,从而固定染料。 180 minutes drumming process, by portionwise addition of 100 parts of borax buffer to make the PH value was maintained between 40 ° C 8. O to 9. O, to fix the dye. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 5的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.5. 然后如染色配方I的部分b)中所述进行处理。 Then dyeing prescription I, part b) was treated in the.

[0730] 所得皮革具有深蓝色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0730] The leather obtained has a dark blue color and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance. · ·

[0731] 染色配方9: [0731] staining formula 9:

[0732] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0732] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用150份水、2份分散剂和5份来自实施例2k的染料在pH 4. 2和30°C下染色60分钟。 Then 150 parts of water, 2 parts of a dispersant and 5 parts of the dye from Example 2k embodiment dyeing at pH 4. 2 and 30 ° C 60 min. 在180分钟的转鼓加工过程中,一次性添加30份15%碳酸钠溶液以使PH值在40°C保持在9. 4-9. 9之间,从而固定染料。 180 minutes drumming process, a one-time addition of 30 parts of 15% sodium carbonate solution to make the PH value was maintained between 9 4-9. 9 at 40 ° C, to fix the dye. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 8的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.8. 然后如染色配方I的部分b)中所述进行处理。 Then dyeing prescription I, part b) was treated in the.

[0733] 所得皮革具有深蓝色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0733] ​​The leather obtained has a dark blue color and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0734] 染色配方10 : [0734] staining formula 10:

[0735] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0735] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用100份水、2份分散剂和5份来自实施例Ila的染料在pH 4. 2和30°C下染色30分钟。 Then 100 parts of water, 2 parts of a dispersant and 5 parts of the dye from Example Ila embodiment dyeing at pH 4. 2 and 30 ° C 30 min. 在180分钟的转鼓加工过程中,逐份添加20份15%碳酸钠溶液以使PH值在40°C保持在8. 6-9. 3之间,从而固定染料。 180 minutes drumming process, by portionwise addition of 20 parts of 15% sodium carbonate solution to make the PH value was maintained between 40 ° C 8. 6-9. 3, to fix the dye. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 8的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.8. 然后如染色配方I的部分b)中所述进行处理。 Then dyeing prescription I, part b) was treated in the.

[0736] 所得皮革具有深枣红色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0736] The leather obtained had a deep maroon, and has excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0737] 染色配方11: [0737] staining formula 11:

[0738] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0738] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用150份水、2份分散剂和5份来自实施例12ae的染料在pH 4. 3和30°C下染色45分钟。 Then 150 parts of water, 2 parts of a dispersant and 5 parts of a dye from Example 12ae dyed at pH 4. 3 and 30 ° C 45 min. 在240分钟的转鼓加工过程中,逐份添加40份7%碳酸氢钠溶液以使PH值在40°C保持在7. 3-8. 2之间,从而固定染料。 240 minutes drumming process, by portionwise addition of 40 parts of 7% sodium bicarbonate solution to make the PH value at 40 ° C was maintained between 7. 3-8. 2, to fix the dye. 然后6次在40°C在200份水中洗涤10分钟。 Then 6 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和I. 2份甲酸以达到3. 9的pH值。 200 parts of water was added and I. 2 parts of formic acid to reach a pH of 3.9. 然后如染色配方I的部分b)中所述进行处理。 Then dyeing prescription I, part b) was treated in the.

[0739] 所得皮革具有鲜艳的深蓝色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0739] The leather obtained had a brilliant deep blue, and has excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0740] 染色配方12 : [0740] staining formula 12:

[0741] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0741] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用150份水、2份分散剂和5份来自实施例13c的染料在pH 4. I和30°C下染色30分钟。 Then 150 parts of water, 2 parts of a dispersant and 5 parts of a dye from Example 13c dyed at pH 4. I and 30 ° C 30 min. 逐份添加40份7%碳酸氢钠溶液以将pH值调节至 By portionwise addition of 40 parts of 7% sodium bicarbonate solution to adjust the pH to

7. 9-8. 1,从而固定染料并进行60分钟的转鼓加工,然后分3次加入15份芒硝,并使转鼓加工在pH 8. 1-9. O下再继续120分钟。 7. 9-8. 1, to fix the dye and drumming for 60 minutes, then three times with 15 parts of Glauber's salt, and drumming. At O was continued at pH 8. 1-9 120 minutes. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和I. O份甲酸以达到3. 8的pH值。 200 parts of water was added and I. O parts of formic acid to reach a pH of 3.8. 然后如染色配方I的部分b)中所述进行处理。 Then dyeing prescription I, part b) was treated in the.

[0742] 所得皮革具有深绿色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0742] The leather obtained has a dark green, and has excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0743] 染色配方13 : [0743] staining formula 13:

[0744] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0744] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用150份水、2份分散剂和5份来自实施例12η的染料在pH 4. 2和30°C下染色45分钟。 Then 150 parts of water, 2 parts of a dispersant and 5 parts of a dye from Example 12η dyed at pH 4. 2 and 30 ° C 45 min. 逐份添加20份15%碳酸钠溶液以将pH值调节至 By portionwise addition of 20 parts of 15% sodium carbonate solution to adjust the pH to

8. 4-9. 2,从而固定染料并进行120分钟的转鼓加工。 8. 4-9. 2, and fix the dye was drummed for 120 minutes. 然后2次在40°C在200份水中洗涤10分钟。 Then 2 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和I. I份甲酸以达到3. 9的pH值。 200 parts of water was added and I. I parts of formic acid to reach a pH of 3.9. 然后如染色配方I的部分b)中·所述进行处理。 Then dyeing prescription portion I b) · in the processing.

[0745] 所得皮革具有黑色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0745] The leather obtained had a black and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0746] 染色配方14 : [0746] staining formula 14:

[0747] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0747] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用150份水、2份分散剂和5份来自实施例13i的染料在pH 4. 2和30°C下染色60分钟。 Then 150 parts of water, 2 parts of a dispersant and 5 parts of a dye from Example 13i dyed at pH 4. 2 and 30 ° C 60 min. 逐份添加21份15%碳酸钠溶液以将pH值调节至8. 8-9. 3,从而固定染料并进行180分钟的转鼓加工。 By portionwise addition of 21 parts of 15% sodium carbonate solution to adjust the pH to 8. 8-9. 3, to fix the dye and 180 minutes drumming. 然后6次在40°C在200份水中洗涤10分钟。 Then 6 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 5的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.5. 然后如染色配方I的部分b)中所述进行处理。 Then dyeing prescription I, part b) was treated in the.

[0748] 所得皮革具有深绿色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0748] The leather obtained has a dark green, and has excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0749] 染色配方15 : [0749] staining formula 15:

[0750] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0750] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用150份水和5份来自实施例59e的染料在pH 4. I和30°C下染色60分钟。 Then 150 parts of water and 5 parts of the dye from Example 59e embodiment dyeing at pH 4. I and 30 ° C 60 min. 逐份添加21份15%碳酸钠溶液以将pH值调节至8. 8-9. 3,从而固定染料并进行180分钟的转鼓加工。 By portionwise addition of 21 parts of 15% sodium carbonate solution to adjust the pH to 8. 8-9. 3, to fix the dye and 180 minutes drumming. 然后6次在40°C在200份水中洗涤10分钟。 Then 6 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 5的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.5. 然后如染色配方I的部分b)中所述进行处理。 Then dyeing prescription I, part b) was treated in the.

[0751] 所得皮革具有鲜艳的深红色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0751] The leather obtained had a brilliant crimson, and having excellent washing, perspiration resistance, scratch resistance and bleeding fastness.

[0752] 染色配方16 : [0752] staining formula 16:

[0753] 在35°C下,将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在装有200份水和O. I份甲酸的转鼓中洗涤10分钟,然后在由100份水、2份甲酸钠、I份乙酸钠、O. 5份碳酸氢钠和I份分散剂构成的浴液中在35°C中和120分钟。 [0753] at 35 ° C, the shaved I. 8 mm thickness was 100 parts by weight of the block I chrome-tanned bovine leather conventional with 200 parts of water and washed with O. I drum parts formic acid for 10 minutes, then 100 parts of water, 2 parts of sodium formate, sodium acetate, parts I, bath O. 5 parts of sodium bicarbonate, and I part of a dispersant is at 35 ° C and 120 minutes. 脱酸浴液从而具有5. O的pH。 Deacidifying float 5. O with the pH. 然后将皮革在35°C用200份水洗涤10分钟。 The leather is then washed at 35 ° C for 10 minutes 200 parts of water. 将由此中和的皮革在由30份水和2份聚合鞣料构成的新制浴液中在30°C复鞣30分钟。 The thus neutralized by the leather in a freshly float 30 parts of water and 2 parts of polymeric tanning material constituted retanning at 30 ° C for 30 minutes. 然后将浴液与2份疏水加脂剂混合。 The float was then added and mixing 2 parts of a hydrophobic fatliquor. 再进行30分钟的转鼓加工,然后加入5份砜型鞣料和4份树脂型鞣料,然后再转鼓加工60分钟。 Then drummed for 30 minutes, followed by addition of 5 parts of a sulfone type tanning material and 4 parts of a resin type tanning material and then drumming for 60 minutes. 最后,用O. 5%甲酸将皮革酸化至pH 4.0,并转鼓加工10分钟一次,30分钟一次。 Finally, the leather O. 5% formic acid was acidified to pH 4.0, and drummed 10 minutes, 30 minutes.

[0754] 在pH 4. 8和35°C下,将皮革在由150份水、2份分散剂、5份来自59f的染料和O. 2份碳酸氢钠构成的新制浴液中染色90分钟。 [0754] at pH 4. 8 and 35 ° C, float leather dyed in a freshly made 150 parts of water, 2 parts of a dispersant, 5 parts of dye from 59f and 2 parts of sodium bicarbonate O. consisting of 90 minutes . 逐份添加40份15%碳酸钠溶液以将pH值调节到9. O至9. 3之间,从而固定染料,并在40°C进行180分钟的转鼓加工。 By portionwise addition of 40 parts of 15% sodium carbonate solution to adjust the pH to between 9.3 to 9. O, to fix the dye and drumming for 180 minutes at 40 ° C. 然后6次在40°C在200份水中洗涤10分钟。 Then 6 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 5的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.5.

[0755] 在55°C,在由100份水、4. 5份基于亚硫酸化鱼油和合成油的混合加脂剂、O. 5份羊毛脂基加脂剂构成的新浴液中转鼓加工40分钟,从而将皮革加脂。 [0755] at 55 ° C, 100 parts by water, 4.5 parts of a mixed fatliquor based sulfited fish oil and synthetic oils, O. Drummed new bath 5 parts of lanolin aliphatic radical agent comprising for 40 minutes to the fatliquoring. 然后用I. 5份浓甲酸酸化至pH 3. 5并转鼓加工40分钟。 Then acidified with 5 parts of concentrated formic acid to pH 3. 5 I. and drummed for 40 minutes. 再将染色和加脂的皮革用15°C的冷水漂洗10分钟,然后伸展,在室温下悬浮干燥过夜、修整、刮软和拉紧。 The dyed and fatliquored leather rinsed with cold water 15 ° C for 10 minutes, and then stretching, suspension dried overnight at room temperature, trimmed, staked and strained.

[0756] 所得皮革具有鲜艳的深红色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0756] The leather obtained had a brilliant crimson, and having excellent washing, perspiration resistance, scratch resistance and bleeding fastness.

[0757] 染色配方17 : [0757] staining formula 17:

[0758] 在35°C下,将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在装有200份水和O. I份甲酸的转鼓中洗涤10分钟,然后在由100份水、2份甲酸钠、I份乙酸钠、I. 5份碳酸氢钠和I份分散剂构成的浴液中在35°C中和120分钟。 [0758] at 35 ° C, the shaved I. 8 mm thickness was 100 parts by weight of the block I chrome-tanned bovine leather conventional with 200 parts of water and washed with O. I drum parts formic acid for 10 minutes, then 100 parts of water, 2 parts of sodium formate, sodium acetate, parts I, I. I float 5 parts of sodium bicarbonate and a part of a dispersant at 35 ° C and 120 minutes. 脱酸浴液具有6. 3的pH值。 Deacidifying float having a pH of 6.3. 然后将皮革在35°C用200份水洗涤10分钟。 The leather is then washed at 35 ° C for 10 minutes 200 parts of water. · ·

[0759] 在pH 5. 6和30°C下,将皮革在由150份水和5份来自实施例35g的染料构成的新制浴液中染色60分钟。 [0759] at pH 5. 6 and 30 ° C, 150 parts by leather of water and 5 parts of a freshly float from Example 35g configuration dye dyed for 60 minutes. 逐份添加13份15%碳酸钠溶液以将浴液的pH值调节到8. 5-9. I之间,然后在40°C转鼓加工180分钟。 By portionwise addition of 13 parts of 15% sodium carbonate solution, the pH of the float was adjusted to 8. 5-9. Between I, and then processed at 40 ° C drum 180 minutes. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和I. 5份甲酸以达到4. 8的pH值。 200 parts of water was added and I. 5 parts of formic acid to reach a pH of 4.8.

[0760] 将由此染色的皮革在由30份水和2份聚合鞣料构成的新制浴液中在30°C复鞣30分钟。 [0760] The leather dyed in a freshly thus the float 30 parts of water and 2 parts of polymeric tanning material constituted retanned at 30 ° C 30 min. 然后将浴液与2份疏水加脂剂混合。 The float was then added and mixing 2 parts of a hydrophobic fatliquor. 在再30分钟的转鼓加工时间后,加入5份砜型鞣料和4份树脂型鞣料,然后再转鼓加工60分钟。 After a further 30 minutes drumming time, adding 5 parts of a sulfone type tanning material and 4 parts of a resin type tanning material and then drumming for 60 minutes. 最后,用O. 5份甲酸将皮革酸化至pH4. 4,并转鼓加工10分钟一次,30分钟一次。 Finally, the leather O. 5 parts of formic acid was acidified to pH4. 4, 10 minutes and drummed for 30 minutes. 在用100份水洗涤10分钟后,在由100份水、4. 5份基于亚硫酸化鱼油和合成油的混合加脂剂、O. 5份羊毛脂基加脂剂构成的新浴液中通过在55°C转鼓加工40分钟来将皮革加脂。 After washing with 100 parts of water for 10 minutes, by 100 parts of water, 4.5 parts of the mixed fresh bath fatliquor based sulphited fish oil and synthetic oil, O. 5 parts of lanolin aliphatic radical agent consisting of by processing at 55 ° C for 40 minutes the drum fatliquoring. 然后用I. 5份浓甲酸酸化至pH 3. 5并转鼓加工40分钟。 Then acidified with 5 parts of concentrated formic acid to pH 3. 5 I. and drummed for 40 minutes. 再将染色和加脂的皮革用15°C的冷水漂洗10分钟,然后伸展,在室温下悬浮干燥过夜、修整、刮软和拉紧。 The dyed and fatliquored leather rinsed with cold water 15 ° C for 10 minutes, and then stretching, suspension dried overnight at room temperature, trimmed, staked and strained.

[0761] 所得皮革具有鲜艳的深红色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0761] The leather obtained had a brilliant crimson, and having excellent washing, perspiration resistance, scratch resistance and bleeding fastness.

[0762] 染色配方18 : [0762] staining formula 18:

[0763] 在35°C下,将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在装有200份水和O. I份甲酸的转鼓中洗涤10分钟,然后在由100份水、2份甲酸钠、I份乙酸钠、I. 5份碳酸氢钠和I份分散剂构成的浴液中在35°C中和120分钟。 [0763] at 35 ° C, the shaved I. 8 mm thickness was 100 parts by weight of the block I chrome-tanned bovine leather conventional with 200 parts of water and washed with O. I drum parts formic acid for 10 minutes, then 100 parts of water, 2 parts of sodium formate, sodium acetate, parts I, I. I float 5 parts of sodium bicarbonate and a part of a dispersant at 35 ° C and 120 minutes. 该脱酸浴液从而具有6. 5的PH值。 The deacidifying float having a PH value of 6.5. 然后将皮革在35°C用200份水洗涤10分钟。 The leather is then washed at 35 ° C for 10 minutes 200 parts of water.

[0764] 在pH 5. 9和30°C下,将皮革在由150份水和5份来自实施例35h的染料构成的新制浴液中染色45分钟。 [0764] at pH 5. 9 and 30 ° C, 150 parts by leather of water and 5 parts of the dye from the dye freshly float 35h embodiment constructed in 45 minutes. 逐份添加15份15%碳酸钠溶液以将浴液的pH值调节到8. 8-9. 6之间,然后在50°C转鼓加工120分钟。 By portionwise addition of 15 parts of 15% sodium carbonate solution to pH of the float was adjusted to between 8 8-9. 6, 50 ° C and then processed drum 120 minutes. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 5份甲酸以达到5. I的pH值。 200 parts of water was added and O. 5 parts of formic acid to reach a pH of 5. I.

[0765] 将由此染色的皮革在由30份水和2份聚合鞣料构成的新制浴液中在30°C复鞣30分钟。 [0765] The leather dyed in a freshly thus the float 30 parts of water and 2 parts of polymeric tanning material constituted retanned at 30 ° C 30 min. 然后将浴液与2份疏水加脂剂混合。 The float was then added and mixing 2 parts of a hydrophobic fatliquor. 在再30分钟的转鼓加工时间后,加入5份砜型鞣料和4份树脂型鞣料,然后再转鼓加工60分钟。 After a further 30 minutes drumming time, adding 5 parts of a sulfone type tanning material and 4 parts of a resin type tanning material and then drumming for 60 minutes. 最后,用I. O份甲酸将皮革酸化至pH4. 1,并转鼓加工10分钟一次,30分钟一次。 Finally, the leather parts of formic acid I. O and acidified to pH4. 1, 10 minutes and drummed for 30 minutes. 在用100份水洗涤10分钟后,在由100份水、4. 5份基于亚硫酸化鱼油和合成油的混合加脂剂、O. 5份羊毛脂基加脂剂构成的新浴液中通过在55°C转鼓加工40分钟来将皮革加脂。 After washing with 100 parts of water for 10 minutes, by 100 parts of water, 4.5 parts of the mixed fresh bath fatliquor based sulphited fish oil and synthetic oil, O. 5 parts of lanolin aliphatic radical agent consisting of by processing at 55 ° C for 40 minutes the drum fatliquoring. 然后用I. 5份浓甲酸酸化至pH 3. 5并转鼓加工40分钟。 Then acidified with 5 parts of concentrated formic acid to pH 3. 5 I. and drummed for 40 minutes. 再将染色和加脂的皮革用15°C的冷水漂洗10分钟,然后伸展,在室温下悬浮干燥过夜、修整、刮软和拉紧。 The dyed and fatliquored leather rinsed with cold water 15 ° C for 10 minutes, and then stretching, suspension dried overnight at room temperature, trimmed, staked and strained.

[0766] 所得皮革具有深棕色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0766] The leather obtained has a dark brown, and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0767] 染色配方19 : [0767] staining formula 19:

[0768] 在35°C下,将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在装有200份水和O. I份甲酸的转鼓中洗涤10分钟,然后在由100份水、2份甲酸钠、I份乙酸钠、I. 5份碳酸氢钠和I份分散剂构成的浴液中在35°C中和120分钟。 [0768] at 35 ° C, the shaved I. 8 mm thickness was 100 parts by weight of the block I chrome-tanned bovine leather conventional with 200 parts of water and washed with O. I drum parts formic acid for 10 minutes, then 100 parts of water, 2 parts of sodium formate, sodium acetate, parts I, I. I float 5 parts of sodium bicarbonate and a part of a dispersant at 35 ° C and 120 minutes. 该脱酸浴液从而具有6. 6的PH值。 The deacidifying float having a PH value of 6.6. 然后将皮革在35°C用200份水洗涤10分钟。 The leather is then washed at 35 ° C for 10 minutes 200 parts of water.

[0769] 在pH 6. O和30°C下,将皮革在由150份水和5份来自实施例12a的染料构成的新制浴液中染色60分钟。 [0769] at pH 6. O and 30 ° C, 150 parts by leather of water and 5 parts of a freshly float from Example 12a consisting of a dye staining for 60 minutes. 逐份添加18份15%碳酸钠溶液以将浴液的pH值调节到8. 8-9. 8之间,然后在50°C转鼓加工120分钟。 By portionwise addition of 18 parts of 15% sodium carbonate solution to pH of the float was adjusted to between 8-9 8. 8, 50 ° C and then processed drum 120 minutes. 然后2次在40°C在200份水中洗涤10分钟。 Then 2 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入·200份水和O. 5份甲酸以达到5. O的pH值。 · 200 parts of water were added and O. 5 parts of formic acid to reach a pH of 5. O.

[0770] 将由此染色的皮革在由30份水和2份聚合鞣料构成的新制浴液中在30°C复鞣30分钟。 [0770] The leather dyed in a freshly thus the float 30 parts of water and 2 parts of polymeric tanning material constituted retanned at 30 ° C 30 min. 然后将浴液与2份疏水加脂剂混合。 The float was then added and mixing 2 parts of a hydrophobic fatliquor. 在再30分钟的转鼓加工时间后,加入5份砜型鞣料和4份树脂型鞣料,然后再转鼓加工60分钟。 After a further 30 minutes drumming time, adding 5 parts of a sulfone type tanning material and 4 parts of a resin type tanning material and then drumming for 60 minutes. 最后,用I. O份甲酸将皮革酸化至pH4. 1,并转鼓加工10分钟一次,30分钟一次,20分钟两次。 Finally, the leather parts of formic acid I. O and acidified to pH4. 1, and drummed 10 minutes, 30 minutes, 20 minutes twice. 在用200份水洗涤10分钟后,在由100份水、4. 5份基于亚硫酸化鱼油和合成油的混合加脂剂、O. 5份羊毛脂基加脂剂构成的新浴液中通过在55°C转鼓加工40分钟来将皮革加脂。 After washing with 200 parts of water over 10 min, by 100 parts of water, 4.5 parts based on the new hybrid fatliquor float sulfited fish oil and synthetic oils, O. 5 parts of lanolin aliphatic radical agent consisting of by processing at 55 ° C for 40 minutes the drum fatliquoring. 然后用I. 5份浓甲酸酸化至pH Then acidified with 5 parts of concentrated formic acid to pH I.

3. 4并转鼓加工40分钟。 3.4 and drumming for 40 minutes. 再将染色和加脂的皮革用15°C的冷水漂洗10分钟,然后伸展,在室温下悬浮干燥过夜、修整、刮软和拉紧。 The dyed and fatliquored leather rinsed with cold water 15 ° C for 10 minutes, and then stretching, suspension dried overnight at room temperature, trimmed, staked and strained.

[0771] 所得皮革具有黑色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0771] The leather obtained had a black and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0772] 染色配方20 : [0772] staining formula 20:

[0773] 在35°C下,将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在装有200份水和O. I份甲酸的转鼓中洗涤10分钟,然后在由100份水、2份甲酸钠、I份乙酸钠、I. 5份碳酸氢钠和I份分散剂构成的浴液中在35°C中和120分钟。 [0773] at 35 ° C, the shaved I. 8 mm thickness was 100 parts by weight of the block I chrome-tanned bovine leather conventional with 200 parts of water and washed with O. I drum parts formic acid for 10 minutes, then 100 parts of water, 2 parts of sodium formate, sodium acetate, parts I, I. I float 5 parts of sodium bicarbonate and a part of a dispersant at 35 ° C and 120 minutes. 该脱酸浴液因而具有6. 4的PH值。 The deacidifying float therefore has a PH value of 6.4. 然后将皮革在35°C用200份水洗涤10分钟。 The leather is then washed at 35 ° C for 10 minutes 200 parts of water.

[0774] 在pH 5. 7和30°C下,将皮革在由150份水和4. 25份来自实施例17h的染料构成的新制浴液中染色90分钟。 [0774] at pH 5. 7 and 30 ° C, in the leather 150 parts of water and 4.25 parts of a dye from a freshly float 17h stained embodiment constituted embodiment 90 minutes. 逐份添加16份15%碳酸钠溶液以将浴液的pH值调节到8. 6-9. 3之间,然后在50°C转鼓加工180分钟。 By portionwise addition of 16 parts of 15% sodium carbonate solution to pH of the float was adjusted to between 6-9 8. 3, 50 ° C and then processed drum 180 minutes. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 7的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.7.

[0775] 将由此染色的皮革在由30份水和2份聚合鞣料构成的新制浴液中在30°C复鞣30分钟。 [0775] The leather dyed in a freshly thus the float 30 parts of water and 2 parts of polymeric tanning material constituted retanned at 30 ° C 30 min. 然后将浴液与2份疏水加脂剂混合。 The float was then added and mixing 2 parts of a hydrophobic fatliquor. 在再30分钟的转鼓加工时间后,加入5份砜型鞣料和4份树脂型鞣料,然后再转鼓加工60分钟。 After a further 30 minutes drumming time, adding 5 parts of a sulfone type tanning material and 4 parts of a resin type tanning material and then drumming for 60 minutes. 最后,用O. 5份甲酸将皮革酸化至pH Finally, the leather O. 5 parts of formic acid was acidified to pH

4. 7,并转鼓加工10分钟一次,30分钟一次。 4.7, and drummed 10 minutes, 30 minutes. 在用200份水在40°C洗涤10分钟后,在由100份水、4. 5份基于亚硫酸化鱼油和合成油的混合加脂剂、O. 5份羊毛脂基加脂剂构成的新浴液中通过在55°C转鼓加工40分钟来将皮革加脂。 With 200 parts of water after a 10 minute wash at 40 ° C, 100 parts by water, 4.5 parts of fish oil and sulfite-based mixed synthetic fatliquor, O. 5 parts of lanolin aliphatic radical agent comprising fresh bath for 40 minutes by the fatliquoring to 55 ° C in a drum. 然后用I. 5份浓甲酸酸化至pH 3. 7并转鼓加工40分钟。 Then acidified with 5 parts of concentrated formic acid to pH 3. 7 I. and drummed for 40 minutes. 再将染色和加脂的皮革用15°C的冷水漂洗10分钟,然后伸展,在室温下悬浮干燥过夜、修整、刮软和拉紧。 The dyed and fatliquored leather rinsed with cold water 15 ° C for 10 minutes, and then stretching, suspension dried overnight at room temperature, trimmed, staked and strained.

[0776] 所得皮革具有黑色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0776] The leather obtained had a black and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0777] 染色配方21 : [0777] staining formula 21:

[0778] 在35°C下,将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在装有200份水和O. I份甲酸的转鼓中洗涤10分钟,然后在由100份水、2份甲酸钠、I份乙酸钠、I. 5份碳酸氢钠和I份分散剂构成的浴液中在35°C中和120分钟。 [0778] at 35 ° C, the shaved I. 8 mm thickness was 100 parts by weight of the block I chrome-tanned bovine leather conventional with 200 parts of water and washed with O. I drum parts formic acid for 10 minutes, then 100 parts of water, 2 parts of sodium formate, sodium acetate, parts I, I. I float 5 parts of sodium bicarbonate and a part of a dispersant at 35 ° C and 120 minutes. 该脱酸浴液从而具有6. 4的PH值。 The deacidifying float having a PH value of 6.4. 然后将皮革在35°C用200份水洗涤10分钟。 The leather is then washed at 35 ° C for 10 minutes 200 parts of water.

[0779] 在pH 5. 4和30°C下,将皮革在由150份水和10份来自实施例25的染料构成的新制浴液中染色45分钟。 [0779] at pH 5. 4 and 30 ° C, in the leather and 150 parts of water 10 parts of the dye from the dye bath freshly configuration of embodiment 25 embodiment 45 minutes. 逐份添加20份15%碳酸钠溶液以将浴液的pH值调节到8. 4-9. I之间,然后在50°C转鼓加工120分钟。 By portionwise addition of 20 parts of 15% sodium carbonate solution, the pH of the float was adjusted to 8. 4-9. Between I, 50 ° C and then processed drum 120 minutes. 然后2次在40°C在200份水中洗涤10分钟。 Then 2 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 6的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.6.

[0780] 将由此染色的皮革在由30份水和2份聚合鞣料构成的新制浴液中在30°C复鞣30分钟。 [0780] The leather dyed in a freshly thus the float 30 parts of water and 2 parts of polymeric tanning material constituted retanned at 30 ° C 30 min. 然后将浴液与2份疏水加脂剂混合。 The float was then added and mixing 2 parts of a hydrophobic fatliquor. 在再30分钟的转鼓加工时间后,加入5份砜型鞣料和4份树脂型鞣料,然后再转鼓加工60分钟。 After a further 30 minutes drumming time, adding 5 parts of a sulfone type tanning material and 4 parts of a resin type tanning material and then drumming for 60 minutes. 最后,用O. 5份甲酸将皮革酸化至pH·4. 7,并转鼓加工10分钟一次,30分钟一次。 Finally, the leather O. 5 parts of formic acid was acidified to pH · 4. 7, and drummed 10 minutes, 30 minutes. 在用200份水在40°C洗涤10分钟后,在由100份水、4. 5份基于亚硫酸化鱼油和合成油的混合加脂剂、O. 5份羊毛脂基加脂剂构成的新浴液中通过在55°C转鼓加工40分钟来将皮革加脂。 With 200 parts of water after a 10 minute wash at 40 ° C, 100 parts by water, 4.5 parts of fish oil and sulfite-based mixed synthetic fatliquor, O. 5 parts of lanolin aliphatic radical agent comprising fresh bath for 40 minutes by the fatliquoring to 55 ° C in a drum. 然后用I. 5份浓甲酸酸化至pH 3. 7并转鼓加工40分钟。 Then acidified with 5 parts of concentrated formic acid to pH 3. 7 I. and drummed for 40 minutes. 再将染色和加脂的皮革在15°C用冷水漂洗15分钟,然后伸展,在室温下悬浮干燥过夜、修整、刮软和拉紧。 The dyed and fatliquored leather rinsed with cold water for 15 minutes at 15 ° C, and then stretched, dried at room temperature overnight and suspended, trimming, staked and strained.

[0781] 所得皮革具有深黑色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0781] The leather obtained has a dark, and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0782] 染色配方22 : [0782] staining formula 22:

[0783] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0783] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用由150份水、2份分散剂和10份来自实施例32的染料构成的浴液在PH 4. 3和30°C下染色60分钟。 Then used by 150 parts of water, 2 parts of a dispersant and 10 parts of the dye from Example embodiment float 32 constituting the dyed at PH 4. 3 and 30 ° C 60 min. 然后逐份添加27份15%碳酸钠溶液以使浴液的PH值在40°C达到8. 7至9. 3之间并在180分钟的转鼓加工过程中保持该pH值。 27 parts by portionwise addition of 15% sodium carbonate solution was added to the bath in the PH value reaches 40 ° C and the pH is maintained at 180 minutes drumming process between 8.7 to 9.3. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 2的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.2. 如染色配方I的部分b)中所述进行复鞣/加脂/机械操作。 Formulation I, such as dyeing in part b) the retanning / fatliquoring / mechanical operations.

[0784] 所得皮革具有深黑色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0784] The leather obtained has a dark, and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0785] 染色配方23 : [0785] staining formula 23:

[0786] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0786] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用由150份水和10份来自实施例40b的染料构成的浴液在PH 4. 3和30°C下染色60分钟。 Then used by 10 parts of water and 150 parts of a dye bath of Example 40b constituting PH 4. 3 staining at 30 ° C 60 and the minutes from the embodiment. 然后逐份添加27份15%碳酸钠溶液以使浴液的pH值在40°C达到8. 7至9. 3之间并在180分钟的转鼓加工过程中保持该pH值。 Was then added portionwise 27 parts of a 15% solution of sodium carbonate to bring the pH of the float was reached at 40 ° C and the pH is maintained at 180 minutes drumming process between 8.7 to 9.3. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和O. 7份甲酸以达到4. 3的pH值。 200 parts of water was added and O. 7 parts of formic acid to reach a pH of 4.3. 如染色配方I的部分b)中所述进行复鞣/加脂/机械操作。 Formulation I, such as dyeing in part b) the retanning / fatliquoring / mechanical operations.

[0787] 所得皮革具有深棕色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0787] The leather obtained has a dark brown, and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0788] 染色配方24 : [0788] staining formula 24:

[0789] 在35°C下,将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在装有200份水和O. I份甲酸的转鼓中洗涤10分钟,然后在由100份水、2份甲酸钠、I份乙酸钠、I. 5份碳酸氢钠和I份分散剂构成的浴液中在35°C中和120分钟。 [0789] at 35 ° C, the shaved I. 8 mm thickness was 100 parts by weight of the block I chrome-tanned bovine leather conventional with 200 parts of water and washed with O. I drum parts formic acid for 10 minutes, then 100 parts of water, 2 parts of sodium formate, sodium acetate, parts I, I. I float 5 parts of sodium bicarbonate and a part of a dispersant at 35 ° C and 120 minutes. 该脱酸浴液从而具有6. 4的PH值。 The deacidifying float having a PH value of 6.4. 然后将皮革在35°C用200份水洗涤10分钟。 The leather is then washed at 35 ° C for 10 minutes 200 parts of water.

[0790] 在pH6. I和30°C下,将皮革在由150份水和4. 25份来自实施例42g的染料构成的新制浴液中染色60分钟。 [0790] In pH6. I and 30 ° C, in the leather and 150 parts of water 4.25 parts of the dye from the dye bath freshly embodiment configuration of 42g for 60 minutes. 逐份添加3份15%碳酸钠溶液以将浴液的pH值调节到8. 5-9. I之间,然后在50°C转鼓加工180分钟。 3 parts by portionwise addition of 15% sodium carbonate solution to pH of the float was adjusted to 8. 5-9. Between I, 50 ° C and then processed drum 180 minutes. 然后4次在40°C在200份水中洗涤10分钟。 Then four times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和I. 5份甲酸以达到4. 3的pH值。 200 parts of water was added and I. 5 parts of formic acid to reach a pH of 4.3.

[0791] 将由此染色的皮革在由30份水和2份聚合鞣料构成的新制浴液中在30°C复鞣30分钟。 [0791] The leather dyed in a freshly thus the float 30 parts of water and 2 parts of polymeric tanning material constituted retanned at 30 ° C 30 min. 然后将浴液与2份疏水加脂剂混合。 The float was then added and mixing 2 parts of a hydrophobic fatliquor. 在再30分钟的转鼓加工时间后,加入5份砜型鞣料和4份树脂型鞣料,然后再转鼓加工60分钟。 After a further 30 minutes drumming time, adding 5 parts of a sulfone type tanning material and 4 parts of a resin type tanning material and then drumming for 60 minutes. 最后,用2. O份甲酸将皮革酸化至pH3. 8,并转鼓加工10分钟一次,30分钟三次。 Finally, the leather 2. O parts of formic acid was acidified to pH3. 8, 10 minutes and drummed for 30 minutes three times. 在用200份水在40°C洗涤10分钟后,在由100份水、4. 5份基于亚硫酸化鱼油和合成油的混合加脂剂、O. 5份羊毛脂基加脂剂构成的新浴液中通过在55°C转鼓加工40分钟来将皮革加脂。 With 200 parts of water after a 10 minute wash at 40 ° C, 100 parts by water, 4.5 parts of fish oil and sulfite-based mixed synthetic fatliquor, O. 5 parts of lanolin aliphatic radical agent comprising fresh bath for 40 minutes by the fatliquoring to 55 ° C in a drum. 然后用I. 5份浓甲酸酸化至pH 3. 3并转鼓加工40分钟。 Then acidified with 5 parts of concentrated formic acid to pH 3. 3 I. and drummed for 40 minutes. 再将染色和加脂的皮革用15°C的冷水漂洗15分钟,然后伸展,减压,在室温下悬浮干燥过夜、修整、刮软和拉紧。 The dyed and fatliquored leather rinsed with cold water 15 ° C for 15 minutes, and then stretching under reduced pressure, the suspension was dried at room temperature overnight, conditioned, staked and strained.

[0792] 所得皮革具有深棕色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0792] The leather obtained has a dark brown, and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance. · ·

[0793] 染色配方25 : [0793] staining formula 25:

[0794] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0794] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用由150份水和4. 25份来自实施例43a的染料构成的浴液在PH 4. 2和30°C下染色60分钟。 Then 150 parts of water and is used by 4.25 parts of the dye from Example 43a float embodiment of the configuration of the dyeing PH 4. 2 and at 30 ° C 60 min. 逐份添加30份15%碳酸钠溶液以使浴液的pH值在40°C达到8. 5至9. 4之间并在180分钟的转鼓加工过程中保持该pH值。 By portionwise addition of 30 parts of a 15% solution of sodium carbonate to bring the pH of the float was reached at 40 ° C and the pH is maintained at 180 minutes drumming process between 8.5 to 9.4. 然后2次在40°C在200份水中洗涤10分钟。 Then 2 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和I. 4份甲酸以达到4. O的pH值。 200 parts of water was added and I. 4 parts of formic acid to reach a pH of 4. O. 如染色配方I的部分b)中所述进行复鞣/加脂/机械操作。 Formulation I, such as dyeing in part b) the retanning / fatliquoring / mechanical operations.

[0795] 所得皮革具有棕色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0795] The leather obtained has a brown, and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0796] 染色配方26 : [0796] staining formula 26:

[0797] 在35°C下,将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在装有200份水和O. I份甲酸的转鼓中洗涤10分钟,然后在由100份水、2份甲酸钠、I份乙酸钠、I. 5份碳酸氢钠和I份分散剂构成的浴液中在35°C中和120分钟。 [0797] at 35 ° C, the shaved I. 8 mm thickness was 100 parts by weight of the block I chrome-tanned bovine leather conventional with 200 parts of water and washed with O. I drum parts formic acid for 10 minutes, then 100 parts of water, 2 parts of sodium formate, sodium acetate, parts I, I. I float 5 parts of sodium bicarbonate and a part of a dispersant at 35 ° C and 120 minutes. 该脱酸浴液从而具有6. 2的PH值。 The deacidifying float having a PH value of 6.2. 然后将皮革在35°C用200份水洗涤10分钟。 The leather is then washed at 35 ° C for 10 minutes 200 parts of water.

[0798] 在pH5. 3和30°C下,将皮革在由150份水和11. 5份来自实施例Ic的染料构成的新制浴液中染色60分钟。 [0798], 60 minutes in the dyeing leather freshly dye bath consisting of Example Ic at pH5. 3 and 30 ° C consisting of 150 parts of water and 11.5 parts from embodiment. 逐份添加28份15%碳酸钠溶液以将浴液的pH值调节到8. 8-9. 3之间,然后在50°C转鼓加工180分钟。 By portionwise addition of 28 parts of 15% sodium carbonate solution to pH of the float was adjusted to between 8-9 8. 3, 50 ° C and then processed drum 180 minutes. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和I. O份甲酸以达到4. 5的pH值。 200 parts of water was added and I. O parts of formic acid to reach a pH of 4.5.

[0799] 将由此染色的皮革在由30份水和2份聚合鞣料构成的新制浴液中在30°C复鞣30分钟。 [0799] The leather dyed in a freshly thus the float 30 parts of water and 2 parts of polymeric tanning material constituted retanned at 30 ° C 30 min. 然后将浴液与2份疏水加脂剂混合。 The float was then added and mixing 2 parts of a hydrophobic fatliquor. 在再30分钟的转鼓加工时间后,加入5份砜型鞣料和4份树脂型鞣料,然后再转鼓加工60分钟。 After a further 30 minutes drumming time, adding 5 parts of a sulfone type tanning material and 4 parts of a resin type tanning material and then drumming for 60 minutes. 最后,用2. O份甲酸将皮革酸化至pH3. 8,并转鼓加工10分钟一次,30分钟三次。 Finally, the leather 2. O parts of formic acid was acidified to pH3. 8, 10 minutes and drummed for 30 minutes three times. 在用200份水在40°C洗涤10分钟后,在由100份水、4. 5份基于亚硫酸化鱼油和合成油的混合加脂剂、O. 5份羊毛脂基加脂剂构成的新浴液中通过在55°C转鼓加工40分钟来将皮革加脂。 With 200 parts of water after a 10 minute wash at 40 ° C, 100 parts by water, 4.5 parts of fish oil and sulfite-based mixed synthetic fatliquor, O. 5 parts of lanolin aliphatic radical agent comprising fresh bath for 40 minutes by the fatliquoring to 55 ° C in a drum. 然后用I. 5份浓甲酸酸化至pH 4. O并转鼓加工40分钟。 Then acidified with 5 parts of concentrated formic acid to pH 4. O and I. drummed for 40 minutes. 再将染色和加脂的皮革用15°C的冷水漂洗15分钟,然后伸展,减压,在室温下悬浮干燥过夜、修整、刮软和拉紧。 The dyed and fatliquored leather rinsed with cold water 15 ° C for 15 minutes, and then stretching under reduced pressure, the suspension was dried at room temperature overnight, conditioned, staked and strained.

[0800] 所得皮革具有深黑色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0800] The leather obtained has a dark, and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0801] 染色配方27: [0801] staining formula 27:

[0802] 在35°C下,将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在装有200份水和O. I份甲酸的转鼓中洗涤10分钟,然后在由100份水、2份甲酸钠、I份乙酸钠、I. 5份碳酸氢钠和I份分散剂构成的浴液中在35°C中和120分钟。 [0802] at 35 ° C, the shaved I. 8 mm thickness was 100 parts by weight of the block I chrome-tanned bovine leather conventional with 200 parts of water and washed with O. I drum parts formic acid for 10 minutes, then 100 parts of water, 2 parts of sodium formate, sodium acetate, parts I, I. I float 5 parts of sodium bicarbonate and a part of a dispersant at 35 ° C and 120 minutes. 该脱酸浴液从而具有6. 2的PH值。 The deacidifying float having a PH value of 6.2. 然后将皮革在35°C用200份水洗涤10分钟。 The leather is then washed at 35 ° C for 10 minutes 200 parts of water.

[0803] 在pH 5. 3和30°C下,将皮革在由150份水和14. 3份来自实施例6c的染料构成的新制浴液中染色60分钟。 [0803] at pH 5. 3 and 30 ° C, in the leather 150 parts of water and 14.3 parts of the dye from the dye bath freshly Example 6c configuration of embodiment 60 minutes. 逐份添加28份15%碳酸钠溶液以将浴液的pH值调节到8. 7-9. 3之间,然后在50°C转鼓加工180分钟。 By portionwise addition of 28 parts of 15% sodium carbonate solution to pH of the float was adjusted to between 7-9 8. 3, 50 ° C and then processed drum 180 minutes. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和I. O份甲酸以达到4. 6的pH值。 200 parts of water was added and I. O parts of formic acid to reach a pH of 4.6.

[0804] 将由此染色的皮革在由30份水和2份聚合鞣料构成的新制浴液中在30°C复鞣30分钟。 [0804] The leather dyed in a freshly thus the float 30 parts of water and 2 parts of polymeric tanning material constituted retanned at 30 ° C 30 min. 然后将浴液与2份疏水加脂剂混合。 The float was then added and mixing 2 parts of a hydrophobic fatliquor. 在再30分钟的转鼓加工时间后,加入5份砜型鞣料和4份树脂型鞣料,然后再转鼓加工60分钟。 After a further 30 minutes drumming time, adding 5 parts of a sulfone type tanning material and 4 parts of a resin type tanning material and then drumming for 60 minutes. 最后,用I. 8份甲酸将皮革酸化至pH4.0,并转鼓加工10分钟一次,30分钟三次。 Finally, the leather I. 8 parts of formic acid was acidified to pH 4.0, and drumming for 10 minutes, 30 minutes three times. 在用200份水在40°C洗涤10分钟后,在由100·份水、4. 5份基于亚硫酸化鱼油和合成油的混合加脂剂、O. 5份羊毛脂基加脂剂构成的新浴液中通过在55°C转鼓加工40分钟来将皮革加脂。 With 200 parts of water after a 10 minute wash at 40 ° C, in a 100-parts of water, 4.5 parts of a mixed fatliquor based sulfited fish oil and synthetic oils, O. 5 parts of lanolin aliphatic radical agent comprising new bath for 40 minutes by machining the fatliquoring drum at 55 ° C. 然后用I. 5份浓甲酸酸化至pH 3. 3并转鼓加工40分钟。 Then acidified with 5 parts of concentrated formic acid to pH 3. 3 I. and drummed for 40 minutes. 再将染色和加脂的皮革用15°C的冷水漂洗15分钟,然后伸展,减压,在室温下悬浮干燥过夜、修整、刮软和拉紧。 The dyed and fatliquored leather rinsed with cold water 15 ° C for 15 minutes, and then stretching under reduced pressure, the suspension was dried at room temperature overnight, conditioned, staked and strained.

[0805] 所得皮革具有深黑色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0805] The leather obtained has a dark, and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0806] 染色配方28 : [0806] staining formula 28:

[0807] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0807] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用由150份水、2份分散剂和11. 5份来自实施例6d的染料构成的浴液在PH 4. 3和30°C下染色60分钟。 150 parts of water is then used by, float parts 2 and 11.5 parts of dispersant from Example 6d dye staining embodiment constituting PH 4. 3 and at 30 ° C 60 min. 逐份添加30份15%碳酸钠溶液以在180分钟的转鼓加工过程中在40°C将pH值保持在8. 8至9. 2之间。 By portionwise addition of 30 parts of 15% sodium carbonate solution, the pH value at 40 ° C for 180 minutes in the drum during processing was maintained between 8.8 to 9.2. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和I. O份甲酸以达到4. 4的pH值。 200 parts of water was added and I. O parts of formic acid to reach a pH of 4.4. 如染色配方I的部分b)中所述进行复鞣/加脂/机械操作。 Formulation I, such as dyeing in part b) the retanning / fatliquoring / mechanical operations.

[0808] 所得皮革具有深黑色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0808] The leather obtained has a dark, and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0809] 染色配方29 : [0809] staining formula 29:

[0810] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0810] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用150份水、2份分散剂和14. 3份来自实施例9f的染料在pH 4. 3和30°C下染色60分钟。 Then 150 parts of water, 2 parts of a dispersant, and 14.3 parts of the dye from Example 9f embodiment dyeing at pH 4. 3 and 30 ° C 60 min. 逐份添加30份15%碳酸钠溶液以在180分钟的转鼓加工过程中使浴液的PH值在40°C保持8. 7至9. 2之间。 By portionwise addition of 30 parts of a 15% solution of sodium carbonate in 180 minutes drumming process, to the bath is maintained between the PH value of 8.7 to 9.2 at 40 ° C. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和I. O份甲酸以达到4. 5的pH值。 200 parts of water was added and I. O parts of formic acid to reach a pH of 4.5. 如染色配方I的部分b)中所述进行复鞣/加脂/机械操作。 Formulation I, such as dyeing in part b) the retanning / fatliquoring / mechanical operations.

[0811] 所得皮革具有深黑色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0811] The leather obtained has a dark, and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0812] 染色配方30: [0812] staining formula 30:

[0813] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0813] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用由150份水和11. 5份来自实施例If的染料构成的浴液在pH 4. 3和30°C下染色60分钟。 Then 150 parts of water and is used by 11.5 parts of a dye bath consisting of Example If dyed at pH 4. 3 30 ° C 60 and the minutes from the embodiment. 在180分钟的转鼓加工过程中,逐份添加30份15%碳酸钠溶液以使浴液的pH值在40°C保持在8. 8至9. 4之间,从而固定染料。 180 minutes drumming process, by portionwise addition of 30 parts of a 15% solution of sodium carbonate to bring the pH of the bath at 40 ° C was maintained between 8.8 to 9.4, to fix the dye. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和I. O份甲酸以达到4. 6的pH值。 200 parts of water was added and I. O parts of formic acid to reach a pH of 4.6. 如染色配方I的部分b)中所述进行复鞣/加脂/机械操作。 Formulation I, such as dyeing in part b) the retanning / fatliquoring / mechanical operations.

[0814] 所得皮革具有深黑色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0814] The leather obtained has a dark, and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0815] 染色配方31: [0815] staining formula 31:

[0816] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0816] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用由150份水和14. 3份来自实施例12q的染料构成的浴液在pH 4. 3和30°C下染色60分钟。 Then 150 parts of water and is used by 14.3 parts of the dye of Example 12q constituting float dyeing at pH 4. 3 30 ° C 60 and the minutes from the embodiment. 在180分钟的转鼓加工过程中,逐份添加30份15%碳酸钠溶液以使浴液的pH值在40°C保持在8. 6至9. 3之间,从而固定染料。 180 minutes drumming process, by portionwise addition of 30 parts of a 15% solution of sodium carbonate to bring the pH of the float was maintained at 40 ° C between 8.6 to 9.3, to fix the dye. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和I. O份甲酸以达到4. 6的pH值。 200 parts of water was added and I. O parts of formic acid to reach a pH of 4.6. 如染色配方I的部分b)中所述进行复鞣/加脂/机械操作。 Formulation I, such as dyeing in part b) the retanning / fatliquoring / mechanical operations.

[0817] 所得皮革具有深黑色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0817] The leather obtained has a dark, and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance. · ·

[0818] 染色配方32: [0818] staining formula 32:

[0819] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0819] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后逐份添加30份15%碳酸钠溶液将由150份水、2份分散剂和8份来自实施例12s的染料构成的新浴液的pH值立即调节至> 8. 5,并在220分钟的转鼓加工过程中在40°C将pH值保持在8. 7至9. 2之间以固定染料。 30 parts by portionwise addition of 15% sodium carbonate solution immediately adjusted by 150 parts of water, 2 parts of a dispersing agent and 8 parts of the dye bath pH value from the new configuration of Embodiment Example 12s to> 8.5, and 220 minutes the pH was maintained between 8.7 to 9.2 in order to fix the dye at 40 ° C during the drumming. 然后3次在40°C在200份水中洗涤10分钟。 Then 3 times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和I. O份甲酸以达到4. 5的pH值。 200 parts of water was added and I. O parts of formic acid to reach a pH of 4.5.

[0820] 如染色配方I的部分b)中所述进行复鞣/加脂/机械操作。 [0820] The dye of formula I in part b) the retanning / fatliquoring / mechanical operations.

[0821] 所得皮革具有深黑色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0821] The leather obtained has a dark, and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0822] 染色配方33 : [0822] staining formula 33:

[0823] 在35°C下,将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在装有200份水和O. I份甲酸的转鼓中洗涤10分钟,然后在由100份水、2份甲酸钠、I份乙酸钠、I. 5份碳酸氢钠和I份分散剂构成的浴液中在35°c中和120分钟。 [0823] at 35 ° C, the shaved I. 8 mm thickness was 100 parts by weight of the block I chrome-tanned bovine leather conventional with 200 parts of water and washed with O. I drum parts formic acid for 10 minutes, then 100 parts of water, 2 parts of sodium formate, sodium acetate, parts I, I. I float 5 parts of sodium bicarbonate and a part of a dispersant at 35 ° c and 120 minutes. 该脱酸浴液从而具有6. 4的PH值。 The deacidifying float having a PH value of 6.4. 然后将皮革在35°C用200份水洗涤10分钟。 The leather is then washed at 35 ° C for 10 minutes 200 parts of water.

[0824] 逐份添加23份15 %碳酸钠溶液将由150份水和8份来自实施例12的染料构成新制浴液的pH值立即调节至> 8. 5,并在240分钟的转鼓加工过程中在50°C保持在8. 7至 [0824] 23 parts by portionwise addition of 15% sodium carbonate solution, the pH of a freshly constituted by 150 parts of water and the float 8 parts of the dye from Example 12 is immediately adjusted to> 8.5, and 240 minutes drumming process maintained at 50 ° C and 8.7 to

9. 5之间以固定染料。 Between 9.5 to fix the dye. 然后4次在40°C在200份水中洗涤10分钟。 Then four times at 40 ° C and washed with 200 parts of water for 10 minutes. 加入200份水和I. I份甲酸以达到4. 2的pH值。 200 parts of water was added and I. I parts of formic acid to reach a pH of 4.2.

[0825] 将由此染色的皮革在由30份水和2份聚合鞣料构成的新制浴液中在30°C复鞣30分钟。 [0825] The leather dyed in a freshly thus the float 30 parts of water and 2 parts of polymeric tanning material constituted retanned at 30 ° C 30 min. 然后将浴液与2份疏水加脂剂混合。 The float was then added and mixing 2 parts of a hydrophobic fatliquor. 在再30分钟的转鼓加工时间后,加入5份砜型鞣料和4份树脂型鞣料,然后再转鼓加工60分钟。 After a further 30 minutes drumming time, adding 5 parts of a sulfone type tanning material and 4 parts of a resin type tanning material and then drumming for 60 minutes. 最后,用2. O份甲酸将皮革酸化至pH3. 8,并转鼓加工10分钟一次,30分钟三次。 Finally, the leather 2. O parts of formic acid was acidified to pH3. 8, 10 minutes and drummed for 30 minutes three times. 在用200份水在40°C洗涤10分钟后,在由100份水、4. 5份基于亚硫酸化鱼油和合成油的混合加脂剂、O. 5份羊毛脂基加脂剂构成的新浴液中通过在55°C转鼓加工40分钟来将皮革加脂。 With 200 parts of water after a 10 minute wash at 40 ° C, 100 parts by water, 4.5 parts of fish oil and sulfite-based mixed synthetic fatliquor, O. 5 parts of lanolin aliphatic radical agent comprising fresh bath for 40 minutes by the fatliquoring to 55 ° C in a drum. 然后用I. 5份浓甲酸酸化至pH 3. 3并转鼓加工40分钟。 Then acidified with 5 parts of concentrated formic acid to pH 3. 3 I. and drummed for 40 minutes. 再将染色和加脂的皮革用15°C的冷水漂洗15分钟,然后伸展,减压,在室温下悬浮干燥过夜、修整、刮软和拉紧。 The dyed and fatliquored leather rinsed with cold water 15 ° C for 15 minutes, and then stretching under reduced pressure, the suspension was dried at room temperature overnight, conditioned, staked and strained.

[0826] 所得皮革具有深黑色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0826] The leather obtained has a dark, and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0827] 染色配方34 : [0827] staining formula 34:

[0828] 在30°C下,将削匀厚度为I. O毫米的I块100重量份的传统有机鞣牛皮革在装有200份水的转鼓中洗涤20分钟。 [0828] at 30 ° C, shaved thickness of 100 parts by weight of the block I mm I. O-tanned cow leather of conventional organic was washed with 200 parts of water in a tumbler for 20 minutes. 然后使用由150份水、2份分散剂和7份来自实施例12u的染料构成的浴液在PH 4. 3和30°C下染色60分钟。 Then, 2 parts of a dispersant and 7 parts of the dye from Example 12u embodiment float composed of 150 parts of water dyed at PH 4. 3 and 30 ° C 60 min. 在200分钟的转鼓加工过程中,逐份添加30份15%碳酸钠溶液以使浴液的pH值在40°C保持在8. 6至9. 3之间,从而固定染料。 In 200 minutes drumming process, by portionwise addition of 30 parts of a 15% solution of sodium carbonate to bring the pH of the float was maintained at 40 ° C between 8.6 to 9.3, to fix the dye. 在改变浴液后,加入200份水和1.0份甲酸以将pH值设为4.5。 After changing the bath, were added 200 parts of water and 1.0 parts of formic acid to the pH value to 4.5. 如染色配方I的部分b)中所述进行复鞣/加脂/机械操作。 Formulation I, such as dyeing in part b) the retanning / fatliquoring / mechanical operations.

[0829] 所得皮革具有深黑色,并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0829] The leather obtained has a dark, and having excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0830] 染色配方35 : [0830] staining formula 35:

[0831] 在35°C下,将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在装有200份水和O. I份甲酸的转鼓中洗涤10分钟,然后在由100份水、2份甲酸钠、I份乙酸钠、I. 5份碳酸氢钠和I份分散剂构成的浴液中在35°C中和120分钟。 [0831] at 35 ° C, the shaved I. 8 mm thickness was 100 parts by weight of the block I chrome-tanned bovine leather conventional with 200 parts of water and washed with O. I drum parts formic acid for 10 minutes, then 100 parts of water, 2 parts of sodium formate, sodium acetate, parts I, I. I float 5 parts of sodium bicarbonate and a part of a dispersant at 35 ° C and 120 minutes. 该脱酸浴液从而具有6. 4的PH值。 The deacidifying float having a PH value of 6.4. 然后将皮革在35°C用200份水洗涤10分钟。 The leather is then washed at 35 ° C for 10 minutes 200 parts of water.

[0832] 在pH 6. 3和30°C下,将皮革在由150份水和7份来自实施例13η的染料构成的新·制浴液中染色60分钟。 [0832] at pH 6. 3 and 30 ° C, in the leather 150 parts of water and 7 parts prepared from the new-dye bath 13η embodiment constituted dyed for 60 minutes. 逐份添加23份15%碳酸钠溶液以将浴液的pH值调节到8. 7-9. 5之间,从而固定染料,然后在50°C转鼓加工210分钟。 By portionwise addition of 23 parts of 15% sodium carbonate solution to pH of the float was adjusted to between 7-9 8. 5, thereby fixing the dye, 50 ° C and then processed drum 210 minutes. 浴液改变后,加入200份水和I. O份甲酸将pH值设为4.3。 After changing the bath, were added 200 parts of water and I. O parts of formic acid to the pH 4.3.

[0833] 将由此染色的皮革在由30份水和2份聚合鞣料构成的新制浴液中在30°C复鞣30分钟。 [0833] The leather dyed in a freshly thus the float 30 parts of water and 2 parts of polymeric tanning material constituted retanned at 30 ° C 30 min. 然后将浴液与2份疏水加脂剂混合。 The float was then added and mixing 2 parts of a hydrophobic fatliquor. 在再30分钟的转鼓加工时间后,加入5份砜型鞣料和4份树脂型鞣料,然后再转鼓加工60分钟。 After a further 30 minutes drumming time, adding 5 parts of a sulfone type tanning material and 4 parts of a resin type tanning material and then drumming for 60 minutes. 最后,用2. O份甲酸将皮革酸化至pH3. 8,并转鼓加工10分钟一次,30分钟三次。 Finally, the leather 2. O parts of formic acid was acidified to pH3. 8, 10 minutes and drummed for 30 minutes three times. 在用200份水在40°C洗涤10分钟后,在由100份水、4. 5份基于亚硫酸化鱼油和合成油的混合加脂剂、O. 5份羊毛脂基加脂剂构成的新浴液中通过在55°C转鼓加工40分钟来将皮革加脂。 With 200 parts of water after a 10 minute wash at 40 ° C, 100 parts by water, 4.5 parts of fish oil and sulfite-based mixed synthetic fatliquor, O. 5 parts of lanolin aliphatic radical agent comprising fresh bath for 40 minutes by the fatliquoring to 55 ° C in a drum. 然后用I. 5份浓甲酸酸化至pH 3. 3并转鼓加工40分钟。 Then acidified with 5 parts of concentrated formic acid to pH 3. 3 I. and drummed for 40 minutes. 再将染色和加脂的皮革用15°C的冷水漂洗15分钟,然后伸展,减压,在室温下悬浮干燥过夜、修整、刮软和拉紧。 The dyed and fatliquored leather rinsed with cold water 15 ° C for 15 minutes, and then stretching under reduced pressure, the suspension was dried at room temperature overnight, conditioned, staked and strained.

[0834] 染色配方36 : [0834] staining formula 36:

[0835] 在35°C下,将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在装有300份水的转鼓中洗涤10分钟,然后在由100份水、2份甲酸钠、I份乙酸钠和2. 2份碳酸氢钠构成的浴液中在40°C中和120分钟。 [0835] at 35 ° C, I. shaved thickness of 8 mm, 100 parts by weight of the block I conventionally chrome-tanned cow leather was washed with 300 parts of water in the drum for 10 minutes, then 100 parts of water by , 2 parts of sodium formate bath, the I and 2.2 parts of sodium acetate constituted parts of sodium bicarbonate at 40 ° C and 120 minutes. 该脱酸浴液从而具有7. 2的pH值。 The deacidifying float having a pH value of 7.2. 将该脱酸浴液与 The deacidifying float and

10. 5份染料12bj混合并在pH6. 9和40°C下染色30分钟。 10.5 parts of the dye 12bj mixed and dyed at pH6. 9 and 40 ° C 30 min. 逐份添加8份碳酸钠以将浴液的PH值调节到9. 2-9. 7之间,然后在40°C转鼓加工75分钟。 8 parts by portionwise addition of sodium carbonate to the bath PH value was adjusted to between 2-9 9. 7, 40 ° C and then processed in the drum for 75 minutes. 然后两次在40°C在300份水中进行20分钟的洗涤操作。 Then twice at 40 ° C for 20 minutes washing operation in 300 parts of water. 加入200份水和I. 2份甲酸以达到3. 9的pH值。 200 parts of water was added and I. 2 parts of formic acid to reach a pH of 3.9.

[0836] 将由此染色的皮革在由100份水和2份聚合鞣料构成的新制浴液中在30°C复鞣30分钟。 [0836] The leather dyed in a freshly thus the float 100 parts of water and 2 parts of polymeric tanning material constituted retanned at 30 ° C 30 min. 然后将浴液与2份疏水加脂剂混合。 The float was then added and mixing 2 parts of a hydrophobic fatliquor. 在再30分钟的转鼓加工时间后,加入5份砜型鞣料和4份树脂型鞣料,然后再转鼓加工60分钟。 After a further 30 minutes drumming time, adding 5 parts of a sulfone type tanning material and 4 parts of a resin type tanning material and then drumming for 60 minutes. 将复鞣浴液与4. 5份基于亚硫酸化鱼油和合成油的混合加脂剂和O. 5份羊毛脂基加脂剂混合,并通过在55°C转鼓加工40分钟来将皮革加脂。 Retanning float lanolin aliphatic radical agent is mixed with 4.5 parts of fish oil and sulfite-based mixed synthetic fatliquor and O. 5 parts, and by processing for 40 minutes at 55 ° C leather drum greasing. 然后用I. 6份浓甲酸酸化至pH 3. 6并转鼓加工45分钟。 Then acidified with 6 parts of concentrated formic acid to pH 3. 6 I. and drummed for 45 minutes. 再将染色和加脂的皮革用300份20°C的冷水洗涤10分钟,然后伸展,在70°C减压,在室温下悬浮干燥过夜、修整、刮软和拉紧。 The dyed and fatliquored leather was washed with 300 parts of cold water at 20 ° C for 10 minutes, and then stretching under reduced pressure at 70 ° C, was suspended at room temperature overnight, conditioned, staked and strained.

[0837] 所得皮革是烟黑色的并具有优异的耐洗、耐汗、耐擦和耐渗移坚牢度。 [0837] The leather obtained black smoke and has excellent washing resistance, perspiration resistance, rub fastness and bleeding resistance.

[0838] 按照类似的方式进行表19所述的染色。 [0838] Table 19 staining in a similar manner.

[0839]表 19 [0839] Table 19

[0840] [0840]

[0841] 现在将参照用于制造最重要的制品部分(鞋类、服装、汽车、手套和家具)的染色皮革的制品配方更详细地举例说明本发明的方法。 [0841] Referring now be formulated for the most important articles of the article portion (footwear, clothing, automobiles, furniture and glove) leather dyed in more detail illustrate the method of the present invention. 然而,本发明的方法并不限于这5种皮革部分;例如,本发明也可以制造皮包革和用于配件的爬行动物皮革。 However, the method of the present invention is not limited to these five leather portion; e.g., the present invention can also be manufactured bag leather and leather for accessories reptiles.

[0842] 在下列制品配方中,份数是按重量计。 [0842] In the following product formulation, parts are by weight. 提供的所有信息都涉及商业材料。 All information provided involve commercial material. 关于鞣料、疏水剂、加脂剂和助剂的所有数据均以市售产品为基础。 On tanning, water repellent, fatliquoring agents and auxiliaries are all data based on a commercially available product. 关于染料的数据是以有色的有机化学成分、由于合成条件而存在的任何盐(合成盐)与存在的任何标准剂的总量为基础的。 Data on the dye is a colored organic chemical composition, the total amount of any salt (Synthesis salts thereof) with any standard agent is present due to the synthesis conditions exist based. 在制品配方中,对于湿部法的化学品使用下列缩写。 In the article formulation for wet-end chemicals law following abbreviations are used.

[0843] 商业加脂剂(F)的主要成分: [0843] Commercial fatliquor (F) of the main components:

[0844] Fl :植物油和亚硫酸化鱼油的水乳状液。 [0844] Fl: vegetable oils and fish oil sulfite aqueous emulsion.

[0845] F2 :基于阴离子乙烯基聚合物的钠盐和非离子表面活性剂(乙氧基化的油酸)的含水制剂。 [0845] F2: aqueous preparation based on nonionic surfactant and sodium anionic vinyl polymer (ethoxylated oleic acid).

[0846] F3 :基于改性的脂肪酸的含水制剂。 [0846] F3: aqueous preparation based on a fatty acid-modified.

[0847] F4 :基于合成油和乙氧基化脂肪醇的磷酸酯(包括脂肪醇磺酸酯和丁基二甘醇)的含水制剂。 [0847] F4: aqueous preparation based on synthetic oil and phosphate esters of ethoxylated fatty alcohols (fatty alcohol sulfonates and comprising butyl diglycol) a.

[0848] F5 :基于亚硫酸氢化鱼油(钠盐)和氯磺化石蜡油的水解产物、乙氧基化异十三烷的含水制剂。 [0848] F5: based on hydrogenated fish oil hydrolyzate sulfite (sodium salt) and the chlorosulfonated paraffin oil, ethoxylated isotridecyl aqueous preparation of the.

[0849] F6 :基于磺化植物油的钠盐和改性合成油和聚合物的含水制剂。 [0849] F6: aqueous preparation of sulfonated vegetable oils, synthetic oils and the sodium and the modified polymer.

[0850] F7 :基于硫酸化脂肪酸酯的含水制剂。 [0850] F7: aqueous preparation based on a sulfated fatty acid ester.

[0851] F8 :基于非离子表面活性剂、亚硫酸化油(钠盐)的含水制剂。 [0851] F8: based on nonionic surfactants, sulfited oil (sodium salt) in an aqueous formulation.

[0852] F9 :以在溶剂/水中的铵盐制剂形式的基于石蜡磺酸酯、磷酸烷基酯和硫酸单烷基酯的表面活性剂混合物。 [0852] F9: paraffin sulfonates, alkyl phosphates, and mixtures in a solvent / water formulation of ammonium sulfate based surfactant monoalkyl esters.

[0853] 商业疏水剂(H)的主要成分: [0853] commercial water repellent (H) of the main components:

[0854] Hl :基于石蜡、官能化聚硅氧烷、N-油酰肌氨酸钠盐的含水制剂。 [0854] Hl: paraffin-based, functional polysiloxane, N- oleoyl sarcosine sodium salt in aqueous formulations.

[0855] Η2 :基于石蜡、改性硅氧烷、N-油酰肌氨酸钠盐的含水制剂。 [0855] Η2: paraffin-based aqueous formulations, modified silicone, N- oleoyl sarcosine sodium salt.

[0856] Η3 :基于石蜡和阴离子表面活性剂的含水制剂。 [0856] Η3: paraffin-based formulations and aqueous anionic surfactant.

[0857] Η4 :基于官能化聚硅氧烷和乳化剂体系的含水制剂。 [0857] Η4: an aqueous based formulation functionalized polysiloxane and an emulsifier system.

[0858] Η5 :基于用乙烯基聚合物的盐改性的硅氧烷的含水制剂。 [0858] Η5: aqueous preparation with salt-modified siloxane-based polymer of vinyl.

[0859] Η6 :基于用阴离子表面活性剂官能化的聚硅氧烷的含水制剂。 [0859] Η6: aqueous preparation with an anionic surfactant-based functional polysiloxane.

[0860] Η7 :基于官能化聚硅氧烷的含水制剂。 [0860] Η7: an aqueous based formulation functionalized polysiloxane.

[0861] HS :基于石蜡和阴离子表面活性剂钠盐的含水制剂。 [0861] HS: paraffin-based formulations and aqueous anionic surfactant is a sodium salt.

[0862] 下文中使用的“混合物”在鞣料和助剂方面不仅指通过将各组分在室温和大气压下混合制成的混合物,还包括通过在升高的温度和压力下短时间或长时间混合制成的混合物。 [0862] Hereinafter use "mixture" means not only in terms of tanning aids and by mixing the components at room temperature and atmospheric pressure, the mixture was made, a short or long by further comprising at elevated temperature and pressure mixing time the mixture was prepared.

[0863] 商业复鞣剂(G)的主要成分: [0863] commercial retanning agent (G) is a main component:

[0864] Gl :苯酚磺酸、甲醛和苯胺的钠盐形式的缩合产物。 [0864] Gl: sodium salt of a condensation product of phenolsulfonic acid, formaldehyde and aniline.

[0865] G2 :苯酚磺酸、甲醛和苯胺的缩合产物的钠盐的含水制剂。 [0865] G2: aqueous preparation of the sodium salt of a condensation product of phenolsulfonic acid, formaldehyde and aniline.

[0866] G3 :苯酚磺酸、甲醛、三聚氰胺、脲和苯胺的缩合产物的钠-铵盐与基于丙烯酸和碱性单体的两性加成共聚物的混合物的含水制剂。 [0866] G3: phenolsulfonic acid, sodium formaldehyde condensation products, melamine, urea and aniline - ammonium salt mixture of addition copolymer based on acrylic acid and amphiphilic monomer aqueous alkaline formulation.

[0867] G4 :苯酚、苯酚磺酸和甲醛的缩合产物的铵盐的含水制剂。 [0867] G4: phenol, condensation products of aqueous preparation of the ammonium salt of phenolsulfonic acid and formaldehyde.

[0868] G5 :基于二羟基二苯基砜、苯酚磺酸、脲和甲醛的缩合产物的钠盐。 [0868] G5: sodium salt of a condensation product based on dihydroxy diphenyl sulfone, phenolsulfonic acid, urea and formaldehyde are.

[0869] G6 :基于二羟基二苯基砜、苯酚磺酸、脲和甲醛的缩合产物的钠-铵盐的水溶液。 [0869] G6: a condensation product of sodium based on the dihydroxy diphenyl sulfone, phenolsulfonic acid, urea and formaldehyde - the aqueous ammonium salt.

[0870] G7:钠盐形式的基于二羟基二苯基砜、苯酚磺酸、脲和甲醛的高分子量缩合产物。 [0870] G7: Based on the high molecular weight sodium salt dihydroxydiphenyl sulfone, phenolsulfonic acid, urea and formaldehyde condensation products.

[0871] G8 :基于二羟基二苯基砜、脲和甲醛低分子量缩合产物的钠-铵盐与二苯基砜与甲醛的低分子量缩合产物的混合物的含水制剂。 [0871] G8: condensation product based on dihydroxydiphenyl sulfone, urea and formaldehyde of low molecular weight sodium - salt mixture of low molecular weight and diphenyl sulfone formaldehyde condensation product with an aqueous formulation.

[0872] G9 :基于改性石蜡(C16-C34-烷基磺酰氯)的脂肪鞣料。 [0872] G9: fat-based tanning modified paraffin (C16-C34- alkylsulfonyl chlorine).

[0873] GlO :基于丙烯酸与丙烯腈和胺的共聚物的含水制剂。 [0873] GlO: aqueous preparation based on copolymers of acrylic acid with acrylonitrile and the amine.

[0874] Gll :萘磺酸-三聚氰胺缩合物与羟基甲烷磺酸盐和脲的混合物。 [0874] Gll: naphthalene sulfonic acid - with a mixture of melamine condensates and urea-hydroxy methanesulfonate.

[0875] G12 :戊二醛在水中的24重量%溶液。 [0875] G12: Glutaraldehyde solution 24% by weight of water.

[0876] G13 :戊二醛在水中的50重量%溶液。 [0876] G13: Glutaraldehyde solution 50% by weight of water.

[0877] G14 :基于醛基聚合鞣剂的含有含水溶剂的制剂(甲醛与戊二醛的缩合产物)。 [0877] G14: Formulation (the condensation product of formaldehyde and glutaraldehyde) containing aqueous solvent, an aldehyde-based polymeric tanning agent.

[0878] G15 :基于丙烯酸与丙烯腈的共聚物的含水制剂。 [0878] G15: aqueous preparation based on copolymers of acrylic acid and of acrylonitrile.

[0879] G16 :基于低分子量聚丙烯酸(Mn < 8000,数均)的含水制剂。 [0879] G16: aqueous preparation based on a low molecular weight polyacrylic acid (Mn <8000, number average).

[0880] G17 :基于高分子量聚丙烯酸(Mn > 40000,数均)的含水制剂。 [0880] G17: polyacrylic acid (Mn> 40000, number average) based on the high molecular weight aqueous formulation.

[0881] G18 :基于聚甲基丙烯酸的含水制剂。 [0881] G18: aqueous preparation based on polymethacrylic acid.

[0882] G19 :马来酸与苯乙烯的共聚物的含水制剂。 [0882] G19: aqueous preparation of the copolymer of maleic acid and styrene.

[0883] G20 :铬合成鞣剂(基于芳族低聚砜和铬制剂的缩合产物混合物)。 [0883] G20: Synthesis of chrome tanning agent (based on the condensation products of aromatic sulfones and the oligomerization mixture of chromium formulation).

[0884] G21 : Tara ο [0884] G21: Tara ο

[0885] G22 :含羞草。 [0885] G22: mimosa.

[0886] G23 :栗子。 [0886] G23: chestnuts.

[0887] G24 :具有24重量%的CF2O3含量和40%的碱度的轻掩蔽铬鞣料。 [0887] G24: chrome tanning material having a light-mask 24 wt% CF2O3 content of 40% and alkalinity.

[0888] G25 :四(羟甲基)鱗氯化物和硫酸盐的液体制剂。 [0888] G25: tetrakis (hydroxymethyl) liquid formulation chloride and sulfate scales.

[0889] G26 :4,4_ 二甲基-1,3-噁唑烷。 [0889] G26: 4,4_-dimethyl-1,3-oxazolidine.

[0890] G27 : I-氮杂-3,7_ 二氧二环~5~ 乙基[3. 3. O]辛烷。 [0890] G27: I- aza-bicyclo -3,7_ dioxo ~ 5 ~ ethyl [3. 3. O] octane.

[0891] G28 :基于脲和甲醛的缩聚产物与基于苯酚和甲醛的缩聚产物的混合物。 [0891] G28: based on condensation products of urea and formaldehyde polycondensation product based on a mixture of phenol and formaldehyde.

[0892] G29 :甲醛的30重量%水溶液。 [0892] G29: 30 wt% aqueous solution of formaldehyde.

[0893] G30 :基于14重量%的氢氧化铝(以Al2O3计算)和3重量%的铬盐(以Cr2O3计算)的矿物鞣料混合物。 [0893] G30: 14 wt% based on aluminum hydroxide mineral tanning material mixture (calculated in Al2O3) and 3 wt% of chromium salt (calculated as Cr2O3) is.

[0894] 商业助剂(HM)的主要成分: [0894] Commercial additives (HM) main components:

[0895] HMl :羟基甲烷磺酸盐与由萘磺酸、脲和甲醛形成的缩合产物的钠盐的混合物。 [0895] HMl: a mixture of hydroxy sulfonate condensation product formed from naphthalenesulfonic acid, sodium salt, urea and formaldehyde.

[0896] HM2:乙氧基化烷基胺(C16-C18)的混合物。 [0896] HM2: ethoxylated alkyl amine (C16-C18) mixtures thereof.

[0897] HM3 :部分水解的聚-N-乙烯基甲酰胺的含水制剂,略呈阳离子型。 [0897] HM3: aqueous preparation of poly -N- vinylformamide partially hydrolyzed, slightly cationic.

[0898] HM4 :阴离子改性的加成共聚物的含水制剂。 [0898] HM4: aqueous preparation of the anionically modified addition copolymer.

[0899] HM5:羟甲基化的脲。 [0899] HM5: methylolated urea.

[0900] HM6 :基于钠盐形式的芳族磺酸、苯酚、甲醛和脲的混合物。 [0900] HM6: based on sodium salt of aromatic sulfonic acid, phenol, formaldehyde and urea.

[0901] HM7 :阳离子型含氨基的缩聚物的含水制剂。 [0901] HM7: preparation of an aqueous amino group-containing cationic polycondensate.

[0902] 按照下列国际公认的标准测定坚牢度: [0902] Determination of fastness according to the following internationally recognized standards:

[0903] 耐汗坚牢度:按照Veslic C4260 [0903] Perspiration Fastness: according Veslic C4260

[0904]耐洗度: 按照DIN EN ISO 15703 [0904] Washing of: in accordance with DIN EN ISO 15703

[0905] 渗移牢度:按照DIN EN ISO 15701以及在与DIN EN ISO 15701类似的条件下在85°C和95%的湿度下储存16小时 [0905] Bleeding Fastness: according to DIN EN ISO 15701, and stored at 85 ° C and humidity of 95% under the similar DIN EN ISO 15701 16 hours

[0906]耐擦度: 按照DIN EN ISO 105-X12 (Crockmeter,用纺织棉摩擦) [0906] abrasion degree: according to DIN EN ISO 105-X12 (Crockmeter, cotton textile friction)

[0907] 以及按照DIN EN ISO 11640 (Veslic,用毡摩擦) [0907] and according to DIN EN ISO 11640 (Veslic, the felt friction)

[0908] Maeser : 按照ASTM D 2099 [0908] Maeser: according to ASTM D 2099

[0909]针入度计: 按照DIN EN ISO 5403 [0909] penetrometer: according to DIN EN ISO 5403

[0910] 水蒸气渗透性:按照DIN EN ISO 14268 [0910] water vapor permeability: according to DIN EN ISO 14268

[0911]抗挠性: 按照DIN EN ISO 5402 [0911] flex resistance: according to DIN EN ISO 5402

[0912] 缝合拉出试验:按照DIN 5331 [0912] suture pull-out test: in accordance with DIN 5331

[0913]抗撕强度: 按照DIN EN ISO 3377 [0913] Tear strength: according to DIN EN ISO 3377

[0914]拉伸强度: 按照DIN EN ISO 3376 [0914] Tensile strength: according to DIN EN ISO 3376

[0915] A鞋面革配方 [0915] A shoe upper leather recipe

[0916] 鞋面革配方1: [0916] upper leather recipe 1:

[0917] 将削匀厚度为2. O毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由150份水、2份甲酸钠和I份乙酸钠构成的浴液中转鼓加工5分钟,然后与2份碳酸氢钠混合并在40°C中和10分钟。 100 parts [0917] The shaved thickness of I mm 2. O bulk weight in a conventional chrome-tanned bovine leather in 35 ° C water bath was washed with 200 parts of 10 minutes and then at 40 ° C in 150 parts of water by a , 2 parts of sodium formate drum bath and I part of sodium acetate configuration processing for 5 minutes and then mixed with 2 parts of sodium bicarbonate and 40 ° C in 10 minutes. 该脱酸浴液从而具有7. 3的pH值。 The deacidifying float having a pH value of 7.3. 将该脱酸浴液与4. 6份染料Ie混合并在pH 6. 8和40°C下染色30分钟。 The dye mixture Ie deacidifying float and stained with 4.6 parts at pH 6. 8 and 40 ° C 30 min. 每次少许地添加总共6份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,并将皮革在40°C转鼓加60分钟。 Each addition of a total of 6 parts of sodium carbonate to bring the pH of the float 9 for fixation between 2-9. 6, and leather processing drum at 40 ° C for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤两次,一共洗涤30分钟。 After float change, the leather was washed twice each time, a total of 30 minutes and washed with 300 parts of water. 在30分钟的过程中,在300份水的浴液中逐份添加总共O. 5份甲酸以达到6. 5的pH值。 In the course of 30 minutes in the bath by 300 parts of water was added in parts of a total of O. 5 parts of formic acid to reach a pH of 6.5.

[0918] 将由此染色的皮革在由200份水和5份加脂和鞣制疏水剂H5构成的新制浴液中在40°C复鞣20分钟。 [0918] The leather thus dyed in a freshly float of 200 parts of water and 5 parts of tanning and fatliquoring hydrophobicizer H5 of retanning at 40 ° C 20 min. 在20分钟的过程中,添加O. 5份甲酸以达到5. O的pH值。 In the course of 20 minutes, add O. 5 parts of formic acid to reach a pH of 5. O. 使用3份聚合鞣料G15,在40°C进行复鞣30分钟。 Using 3 parts of polymeric tanning material G15, retanning at 40 ° C 30 min. 然后将浴液与5份疏水剂H2和O. 3份助剂HM4的混合物混合。 Then 3 parts of auxiliary HM4 mixture of 5 parts of the float and H2 O. mixing hydrophobic agent. 在再60分钟的转鼓加工时间后,在60分钟的过程中每次少许地添加总共2. 5份甲酸以将PH值酸化至3. 7。 After another 60 minutes drumming time, each addition of a total 2.5 parts of formic acid was acidified to PH value to 3.7 in the course of 60 minutes. 然后在由150份水和O. 5份甲酸构成的新制浴液中在30°C转鼓加工10分钟。 Then 150 parts of water by a float freshly O. 5 parts of formic acid and of the processing drum at 30 ° C for 10 min. 然后添加5份铬鞣料G24以再次铬鞣90分钟。 Was then added to 5 parts of chrome tanning material G24 chrome again for 90 minutes. 获得3. 6的pH值。 A pH value of 3.6. 最后,将皮革在300份水中在30°C洗涤10分钟,该洗涤进行两次。 Finally, the leather was washed twice in the washing 30 ° C 10 minutes 300 parts of water.

[0919] 将由此染色、复鞋和疏水的皮革搭马(horse up)过夜、然后伸展,在60°C减压处理3分钟,在室温下悬浮干燥过夜,修整,刮软并在60°C真空干燥2分钟。 [0919] The thus dyed, shoes and hydrophobic complex horsed (horse up) overnight and then stretching, 3 minutes at 60 ° C under reduced pressure, suspension dried overnight at room temperature, trimmed, and staked at 60 ° C vacuum dried for 2 minutes.

[0920] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的疏水鞋面革。 [0920] This having excellent washing resistance, perspiration resistance, bleeding and hydrophobic shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的鞋面革。 A shoe upper leather in one of Examples Ia to 59k dyes embodiment in an analogous manner.

[0921] 鞋面革配方2: [0921] upper leather recipe 2:

[0922] 将削匀厚度为2. O毫米的1块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由150份水、2份甲酸钠和1份乙酸钠构成的浴液中转鼓加工5分钟,然后与2份碳酸氢钠混合并在40°C中和10分钟。 100 parts by weight of a [0922] shaved thickness of 2. O mm chrome-tanned cow leather of conventional 35 ° C in a bath of 200 parts of water washed for 10 minutes and then at 40 ° C in 150 parts of water by a , 2 parts of sodium formate drum bath and 1 part of sodium acetate configuration of processing for 5 minutes and then mixed with 2 parts of sodium bicarbonate and 40 ° C in 10 minutes. 该脱酸浴液从而具有7. 3的pH值。 The deacidifying float having a pH value of 7.3. 将该脱酸浴液与7. 5份染料2f混合并在pH 6.8和401:下染色30分钟。 The deacidifying float 7.5 parts of dye 2f and mixed with pH 6.8 and 401: dyeing for 30 minutes. 每次少许地添加总共8份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,并将皮革在40°C转鼓加工60分钟。 Each addition of a total of 8 parts of sodium carbonate to bring the pH of the float 9 for fixation between 2-9. 6, and the leather in the drum 40 ° C for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤两次,一共洗涤30分钟。 After float change, the leather was washed twice each time, a total of 30 minutes and washed with 300 parts of water. 在30分钟的过程中,在300份水的浴液中逐份添加总共O. 5份甲酸以达到6. 5的pH值。 In the course of 30 minutes in the bath by 300 parts of water was added in parts of a total of O. 5 parts of formic acid to reach a pH of 6.5.

[0923] 将由此染色的皮革在由200份水和5份加脂和鞣制疏水剂H5构成的新制浴液中在40°C复鞣20分钟。 [0923] The leather thus dyed in a freshly float of 200 parts of water and 5 parts of tanning and fatliquoring hydrophobicizer H5 of retanning at 40 ° C 20 min. 在20分钟的过程中,添加O. 5份甲酸以达到5. O的pH值。 In the course of 20 minutes, add O. 5 parts of formic acid to reach a pH of 5. O. 使用3份聚合鞣料G15,在40°C进行复鞣20分钟。 Using 3 parts of polymeric tanning material G15, retanning at 40 ° C 20 min. 然后,在浴液中加入5份复鞣料Gl,然后再进行30分钟转鼓加工。 Then, 5 parts of retanning material Gl in the bath, and then for 30 minutes drumming. 然后将浴液与6份疏水剂H2和O. 3份助剂HM4的混合物混合。 Then 3 parts of auxiliary HM4 mixture of 6 parts of the float and H2 O. mixing hydrophobic agent. 在再60分钟的转鼓加工时间后,在60分钟的过程中每次少许地添加总共2. 5份甲酸以将pH值酸化至3. 6。 After another 60 minutes drumming time, each addition of a total 2.5 parts of formic acid to the pH value is acidified to 3.6 in the course of 60 minutes. 然后在由150份水和O. 5份甲酸构成的新制浴液中在30°C转鼓加工10分钟。 Then 150 parts of water by a float freshly O. 5 parts of formic acid and of the processing drum at 30 ° C for 10 min. 然后添加5份铬鞣料G24以再次铬鞣90分钟。 Was then added to 5 parts of chrome tanning material G24 chrome again for 90 minutes. 获得3. 6的pH值。 A pH value of 3.6. 最后,将皮革在300份水中在30°C洗涤10分钟,该洗涤进行两次。 Finally, the leather was washed twice in the washing 30 ° C 10 minutes 300 parts of water. · ·

[0924] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在60°C减压处理3分钟,在室温下悬浮干燥过夜,修整,刮软并在60°C真空干燥2分钟。 [0924] The thus dyed, retanned and hydrophobic horsed overnight and then stretching, 3 minutes at 60 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo at 60 ° C 2 minutes .

[0925] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的疏水鞋面革。 [0925] This having excellent washing resistance, perspiration resistance, bleeding and hydrophobic shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的鞋面革。 A shoe upper leather in one of Examples Ia to 59k dyes embodiment in an analogous manner.

[0926] 鞋面革配方3 : [0926] upper leather recipe 3:

[0927] 将削匀厚度为2. O毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由150份水、2份甲酸钠和I份乙酸钠构成的浴液中转鼓加工5分钟,然后与2份碳酸氢钠混合并在40°C中和10分钟。 100 parts [0927] The shaved thickness of I mm 2. O bulk weight in a conventional chrome-tanned bovine leather in 35 ° C water bath was washed with 200 parts of 10 minutes and then at 40 ° C in 150 parts of water by a , 2 parts of sodium formate drum bath and I part of sodium acetate configuration processing for 5 minutes and then mixed with 2 parts of sodium bicarbonate and 40 ° C in 10 minutes. 该脱酸浴液从而具有7. 3的pH值。 The deacidifying float having a pH value of 7.3. 将该脱酸浴液与5. I份染料3混合并在pH 6. 8和40°C下染色30分钟。 The deacidifying float 5. I was mixed with 3 parts of the dye and dyed at pH 6. 8 and 40 ° C 30 min. 每次少许地添加总共6份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,并将皮革在40°C转鼓加工60分钟。 Each addition of a total of 6 parts of sodium carbonate to bring the pH of the float 9 for fixation between 2-9. 6, and the leather in the drum 40 ° C for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤两次,一共洗涤30分钟。 After float change, the leather was washed twice each time, a total of 30 minutes and washed with 300 parts of water. 在30分钟的过程中,在300份水的浴液中逐份添加总共O. 5份甲酸以达到6. 5的pH值。 In the course of 30 minutes in the bath by 300 parts of water was added in parts of a total of O. 5 parts of formic acid to reach a pH of 6.5.

[0928] 将由此染色的皮革在由200份水和5份加脂和鞣制疏水剂H5构成的新制浴液中在40°C复鞣20分钟。 [0928] The leather thus dyed in a freshly float of 200 parts of water and 5 parts of tanning and fatliquoring hydrophobicizer H5 of retanning at 40 ° C 20 min. 在20分钟的过程中,添加O. 5份甲酸以达到5. O的pH值。 In the course of 20 minutes, add O. 5 parts of formic acid to reach a pH of 5. O. 使用3份聚合鞣料G15,在40°C进行复鞣20分钟。 Using 3 parts of polymeric tanning material G15, retanning at 40 ° C 20 min. 然后,在该液体中加入5份复鞣料Gll以再转鼓加工30分钟。 Then, 5 parts of retanning material Gll in the liquid and then processed to the drum for 30 minutes. 然后将浴液与6份疏水剂H2和O. 3份助剂HM4的混合物混合。 Then 3 parts of auxiliary HM4 mixture of 6 parts of the float and H2 O. mixing hydrophobic agent. 在再60分钟的转鼓加工时间后,在60分钟的过程中每次少许地添加总共2. 5份甲酸以将pH值酸化至3. 6。 After another 60 minutes drumming time, each addition of a total 2.5 parts of formic acid to the pH value is acidified to 3.6 in the course of 60 minutes. 然后在由150份水和O. 5份甲酸构成的新制浴液中在30°C转鼓加工10分钟。 Then 150 parts of water by a float freshly O. 5 parts of formic acid and of the processing drum at 30 ° C for 10 min. 然后添加5份铬鞣料G24以再次铬鞣90分钟。 Was then added to 5 parts of chrome tanning material G24 chrome again for 90 minutes. 获得3. 7的pH值。 A pH value of 3.7. 最后,将皮革在300份水中在30°C洗涤10分钟,该洗涤进行两次。 Finally, the leather was washed twice in the washing 30 ° C 10 minutes 300 parts of water.

[0929] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在60°C减压处理3分钟,在室温下悬浮干燥过夜,修整,刮软并在60°C真空干燥2分钟。 [0929] The thus dyed, retanned and hydrophobic horsed overnight and then stretching, 3 minutes at 60 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo at 60 ° C 2 minutes .

[0930] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的疏水鞋面革。 [0930] This having excellent washing resistance, perspiration resistance, bleeding and hydrophobic shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的鞋面革。 A shoe upper leather in one of Examples Ia to 59k dyes embodiment in an analogous manner.

[0931] 鞋面革配方4: [0931] upper leather recipe 4:

[0932] 将削匀厚度为I. 3-1. 4毫米的I块100重量份的传统有机鞣牛皮革在30°C在由300份水构成的浴液中洗涤15分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工10分钟。 [0932] shaved thickness of I. 3-1. 4 mm I 100 parts by weight of the block in the conventional organic-tanned cow leather 30 ° C in a bath of 300 parts of water washed for 15 minutes and then at 35 ° C drumming in a float of 100 parts of water and I. 5 parts of sodium formate in 10 minutes. 该浴液具有4. 2-4. 6的pH值。 The bath had a pH of 4. 2-4. 6. 将该浴液与8. 5份染料4d混合,然后在pH 5.5和35°C下染色60分钟。 8.5 parts of the dye bath and mixed 4d, then stained in [deg.] At pH 5.5 and C 60 minutes 35. 在20分钟的过程中,每次少许地添加总共3份碳酸氢钠以达到7. 3-7. 8的pH值。 In the course of 20 minutes, each addition of a total of 3 parts of sodium bicarbonate to reach a pH of 7. 3-7. 8. 为了固色,逐份添加总共8份碳酸钠并在35°C转鼓加工60分钟,从而使浴液的PH值达到9. 2-9. 6之间。 For fixation by portionwise addition of a total of 8 parts of sodium carbonate and processed at 35 ° C the drum for 60 minutes so that the float reaches PH value between 2-9 9. 6. 浴液改变之后,每次用300份水和I. 5份HM3在40°C将皮革洗涤两次,一共洗涤50分钟。 After float change, 5 parts HM3 each leather was washed twice in a total of 40 ° C 50 minutes 300 parts of water and I.. 在70分钟的过程中,在200份水的浴液中逐份添加总共2份甲酸以在40°C保持4. 3-4. 6的pH值。 In the course of 70 minutes in the bath by 200 parts of water was added in parts of a total of 2 parts of formic acid to maintain the pH 4. 3-4. 6 at 40 ° C.

[0933] 将由此染色的皮革在由100份水、6份聚合鞣料G18和I. 5份加脂剂F6构成的新制浴液中在35°C复鞣30分钟。 [0933] The leather thus dyed by 100 parts of water, and 6 parts of polymeric tanning material G18 I. 5 parts fresh float fatliquor F6 constituted retanning at 35 ° C for 30 minutes. 在加入10份复鞣料G18并转鼓加工60分钟后,通过添加10份植物鞣料G22和10份复鞣料G4并在35°C转鼓加工60分钟以完成鞣制。 After addition of 10 parts of retanning material G18 and drumming for 60 minutes and 60 minutes to complete the processing by adding 10 parts of tanning vegetable tanning material G22 and 10 parts of retanning material G4 drum at 35 ° C. 将浴液与5. 5份加脂剂F6混合并将皮革在35°C加脂90分钟。 The F6 bath and mixed with 5.5 parts of fatliquor leather fatliquoring at 35 ° C for 90 minutes. 为了固定加脂剂,加入100份40°C的热水并转鼓加工20分钟,然后经50分钟加入甲酸以达到3. 5的pH值。 To fix the fatliquor, was added 100 parts of hot water of 40 ° C and drumming for 20 minutes, then formic acid is added over 50 minutes to reach a pH of 3.5. 然后漂洗15分钟。 Then rinse for 15 minutes. · ·

[0934] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在45°C减压处理4分钟,在室温下悬浮干燥过夜,修整,刮软并真空干燥。 [0934] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, for 4 minutes at 45 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo.

[0935] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的白湿(wetihite)鞋面革。 [0935] This having excellent washing resistance, perspiration resistance, bleeding and rub-off fastness wet white (wetihite) upper leather. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的白湿鞋面革。 Wet-white leather shoe upper can be manufactured in one embodiment to 59k Ia dyes embodiment in an analogous manner.

[0936] 鞋面革配方5 : [0936] upper leather recipe 5:

[0937] 将削匀厚度为I. 3-1. 4毫米的I块100重量份的传统有机鞣牛皮革在30°C在由300份水构成的浴液中洗涤15分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工10分钟。 [0937] shaved thickness of I. 3-1. 4 mm I 100 parts by weight of the block in the conventional organic-tanned cow leather 30 ° C in a bath of 300 parts of water washed for 15 minutes and then at 35 ° C drumming in a float of 100 parts of water and I. 5 parts of sodium formate in 10 minutes. 该浴液具有4. 2-4. 6的pH值。 The bath had a pH of 4. 2-4. 6. 将该浴液与10份染料5b混合,然后在pH 5.5和35°C下染色60分钟。 The bath is admixed with 10 parts of dye 5b, and then dyed at pH 5.5 and 35 ° C 60 min. 在20分钟的过程中,每次少许地添加总共3份碳酸氢钠以达到7. 3-7. 8的pH值。 In the course of 20 minutes, each addition of a total of 3 parts of sodium bicarbonate to reach a pH of 7. 3-7. 8. 为了固色,逐份添加总共9份碳酸钠并在35°C转鼓加工60分钟,从而使浴液的PH值达到9. 2-9. 6之间。 For fixation by portionwise addition of a total of 9 parts of sodium carbonate and processed at 35 ° C the drum for 60 minutes so that the float reaches PH value between 2-9 9. 6. 浴液改变之后,每次用300份水在40°C将皮革洗涤三次,一共洗涤60分钟。 After float change, at 40 ° C each time the leather was washed with a total of 60 minutes and washed three times with 300 parts of water. 在70分钟的过程中,在200份水的浴液中逐份添加总共2份甲酸以在40°C保持4. 3-4. 6的pH值。 In the course of 70 minutes in the bath by 200 parts of water was added in parts of a total of 2 parts of formic acid to maintain the pH 4. 3-4. 6 at 40 ° C.

[0938] 将由此染色的皮革在由100份水、6份聚合鞣料G18和I. 5份加脂剂F6构成的新制浴液中在35°C复鞣30分钟。 [0938] The leather thus dyed by 100 parts of water, and 6 parts of polymeric tanning material G18 I. 5 parts fresh float fatliquor F6 constituted retanning at 35 ° C for 30 minutes. 在加入10份复鞣料G18并转鼓加工60分钟后,通过添加10份植物鞣料G22和10份复鞣料G4并在35°C转鼓加工60分钟以完成鞣制。 After addition of 10 parts of retanning material G18 and drumming for 60 minutes and 60 minutes to complete the processing by adding 10 parts of tanning vegetable tanning material G22 and 10 parts of retanning material G4 drum at 35 ° C. 将浴液与5. 5份加脂剂F6混合并将皮革在35°C加脂90分钟。 The F6 bath and mixed with 5.5 parts of fatliquor leather fatliquoring at 35 ° C for 90 minutes. 为了固定加脂剂,加入100份40°C的热水并转鼓加工20分钟,然后经50分钟加入甲酸以达到3. 5的pH值。 To fix the fatliquor, was added 100 parts of hot water of 40 ° C and drumming for 20 minutes, then formic acid is added over 50 minutes to reach a pH of 3.5. 然后漂洗15分钟。 Then rinse for 15 minutes.

[0939] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在45°C减压处理4分钟,在室温下悬浮干燥过夜,修整,刮软并真空干燥。 [0939] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, for 4 minutes at 45 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo.

[0940] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的白湿鞋面革。 [0940] This having excellent washing resistance, perspiration resistance, bleeding and white shoe upper leather wet abrasion fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的白湿鞋面革。 Wet-white leather shoe upper can be manufactured in one embodiment to 59k Ia dyes embodiment in an analogous manner.

[0941] 鞋面革配方6 : [0941] upper leather recipe 6:

[0942] 将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由150份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,然后与I. 5份碳酸氢钠混合并在40°C中和10分钟。 100 parts by weight of the block I [0942] shaved I. 8 mm in thickness conventionally chrome-tanned bovine leather bath at 35 ° C in 200 parts of water washed for 10 minutes and then at 40 ° C in 150 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes and then mixed with I. 5 parts of sodium bicarbonate and 40 ° C in 10 minutes. 进一步加入15份碳酸氢钠和3份HM4,然后进一步转鼓加工15分钟。 Further added 15 parts of sodium bicarbonate and 3 parts of HM4, and then further drumming for 15 minutes. 该脱酸浴液从而具有7. 6的pH值。 The deacidifying float having a pH value of 7.6. 将该脱酸浴液与9份染料6c混合并在pH 7. 2和40°C下染色90分钟。 The deacidifying float was admixed with 9 parts of dye 6c and dyed at pH 7. 2 and 40 ° C 90 min. 每次少许地添加总共8份碳酸钠以使浴液的PH值达到9. 3-9. 9之间以固色,并将皮革在40°C转鼓加工60分钟。 Each addition of a total of 8 parts of sodium carbonate to make the PH value of the float for fixation between 9. 3-9. 9, and the leather in the drum 40 ° C for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 在60分钟的过程中,在200份水的浴液中逐份添加总共2份甲酸以达到4. 5的pH值。 In the course of 60 minutes, 200 parts of water in the bath by the portionwise addition of a total of 2 parts of formic acid to reach a pH of 4.5.

[0943] 将由此染色的皮革在由80份水和4份聚合鞣料G15构成的新制浴液中在45°C复鞣30分钟。 [0943] The leather dyed in a freshly thus the float 80 parts of water and 4 parts of polymeric tanning material G15 of retanning constituting at 45 ° C 30 min. 在添加5份植物鞣料G22和3份树脂鞣料Gll后,转鼓加工再继续进行40分钟。 After the addition of 5 parts of vegetable tanning material G22 and 3 parts of resin tanning material Gll, drumming was continued for 40 minutes. 为了加脂,然后将该浴液与6份疏水剂Hl和O. 4份助剂HM4的混合物混合。 For fatliquoring, then 4 parts of a mixture of auxiliary HM4 float and 6 parts mixing water repellent and O. Hl. 在再90分钟的转鼓加工时间后,加入70份60°C的热水,转鼓加工10分钟,然后在60分钟的过程中逐份添加总共5份甲酸以将pH值酸化至3. 4。 After another 90 minutes drumming time, 70 parts of hot water of 60 ° C, drumming for 10 minutes and then 5 parts by portionwise addition of a total acid value was acidified to pH 3.4 to 60 minutes in the course of . 用200份水在30 V冼洚10分钟后,将皮革在由200份水、I份疏水剂H6和O. 2份助剂H4构成的新制浴液中在30°C转鼓加工20分钟。 With 200 parts of water at 30 V for 10 minutes Sin flood, float the leather in a freshly made 200 parts of water, and the I parts water repellent H6 H4 O. 2 parts of adjuvants consisting of 30 ° C in the processing bowl for 20 min. 然后添加4份铬鞣料G24将皮革再次铬鞣过夜。 It was then added 4 parts of chrome tanning material G24 chrome tanned leather again overnight. 浴液的pH值为3. 4。 The bath pH is 3.4. 最后,将皮革在200份水中在30°C洗涤10分钟,该洗涤进行两次。 Finally, the leather was washed at 30 ° C 10 minutes, and the washing is performed twice in 200 parts of water.

[0944] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在50°C减压处理6分钟,在室温下悬浮干燥过夜,修整,刮软并在50°C真空干燥2分钟。 [0944] The thus dyed, retanned and hydrophobic horsed overnight and then stretching processing under reduced pressure at 50 ° C 6 minutes, and resuspended at room temperature overnight, conditioned, staked and dried in vacuo at 50 ° C 2 minutes . · ·

[0945] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的疏水鞋面革。 [0945] This having excellent washing resistance, perspiration resistance, bleeding and hydrophobic shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的疏水鞋面革。 May be made hydrophobic shoe upper leather dyed with one of the dyes of Examples Ia to 59k embodiment in an analogous manner.

[0946] 鞋面革配方7 : [0946] upper leather recipe 7:

[0947] 将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由150份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,然后与I. 5份碳酸氢钠混合并在40°C中和10分钟。 100 parts by weight of the block I [0947] shaved I. 8 mm in thickness conventionally chrome-tanned bovine leather bath at 35 ° C in 200 parts of water washed for 10 minutes and then at 40 ° C in 150 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes and then mixed with I. 5 parts of sodium bicarbonate and 40 ° C in 10 minutes. 进一步加入I. 5份碳酸氢钠和3份HM4,然后进一步转鼓加工15分钟。 I. 5 parts of sodium hydrogencarbonate was further added, and 3 parts of HM4, and then further drumming for 15 minutes. 该脱酸浴液从而具有7. 6的pH值。 The deacidifying float having a pH value of 7.6. 将该脱酸浴液与11. 5份染料7混合并在pH 7. 2和40°C下染色90分钟。 The deacidifying float 7 11.5 parts of the dye is mixed and dyed at pH 7. 2 and 40 ° C 90 min. 每次少许地添加总共10份碳酸钠以使浴液的PH值达到9. 3-9. 9之间以固色,并将皮革在40°C转鼓加工60分钟。 Each addition of a total 10 parts of sodium carbonate to make the PH value of the float for fixation between 9. 3-9. 9, and the leather in the drum 40 ° C for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 在60分钟的过程中,在200份水的浴液中逐份添加总共2份甲酸以达到4. 6的pH值。 In the course of 60 minutes, 200 parts of water in the bath by the portionwise addition of a total of 2 parts of formic acid to reach a pH of 4.6.

[0948] 将由此染色的皮革在由80份水和4份聚合鞣料G15构成的新制浴液中在45°C复鞣30分钟。 [0948] The leather dyed in a freshly thus the float 80 parts of water and 4 parts of polymeric tanning material G15 of retanning constituting at 45 ° C 30 min. 在添加5份植物鞣料G22和3份树脂鞣料Gll后,转鼓加工再继续进行40分钟。 After the addition of 5 parts of vegetable tanning material G22 and 3 parts of resin tanning material Gll, drumming was continued for 40 minutes. 为了加脂,然后将该浴液与6份疏水剂Hl和O. 4份助剂HM4的混合物混合。 For fatliquoring, then 4 parts of a mixture of auxiliary HM4 float and 6 parts mixing water repellent and O. Hl. 在再90分钟的转鼓加工时间后,加入70份60°C的热水,转鼓加工10分钟,然后在60分钟的过程中逐份添加总共5份甲酸以将pH值酸化至3. 3。 After another 90 minutes drumming time, 70 parts of hot water of 60 ° C, drumming for 10 minutes and then 5 parts by portionwise addition of a total acid value of the pH was acidified to 3.3 in the course of 60 minutes . 用200份水在30V冼洚10分钟后,将皮革在由100份水和3份助剂G24构成的新制浴液中在30°C转鼓加工过夜。 With 200 parts of water in the flood Sin 30V for 10 minutes, the leather will float in a freshly made 100 parts of water and 3 parts of additives consisting of G24 overnight at 30 ° C drumming. 在用200份水在30V洗洚10分钟后,在由10份水和2份疏水剂H6构成的新制浴液中在30°C转鼓加工20分钟。 After washing with 200 parts of water flood 10 min at 30V, float in a freshly made 10 parts of water and 2 parts of a hydrophobic agent consisting of H6 processing drum at 30 ° C for 20 min. 然后添加3份铬鞣料G24将皮革再次铬鞣90分钟。 It was then added 3 parts of Chrome tanning leather tanning material G24 again for 90 minutes. 浴液的pH值为3. 4。 The bath pH is 3.4. 最后,将皮革在200份水中在30°C洗涤10分钟,该洗涤进行两次。 Finally, the leather was washed at 30 ° C 10 minutes, and the washing is performed twice in 200 parts of water.

[0949] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在50°C减压处理6分钟,在室温下悬浮干燥过夜,修整,刮软并在50°C真空干燥2分钟。 [0949] The thus dyed, retanned and hydrophobic horsed overnight and then stretching processing under reduced pressure at 50 ° C 6 minutes, and resuspended at room temperature overnight, conditioned, staked and dried in vacuo at 50 ° C 2 minutes .

[0950] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的疏水鞋面革。 [0950] This having excellent washing resistance, perspiration resistance, bleeding and hydrophobic shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的疏水鞋面革。 May be made hydrophobic shoe upper leather dyed with one of the dyes of Examples Ia to 59k embodiment in an analogous manner.

[0951] 鞋面革配方8: [0951] upper leather recipe 8:

[0952] 将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过20分钟每次少许地添加总共3份碳酸氢钠,中和为7. 7的pH值。 100 parts by weight of the block I [0952] shaved I. 8 mm in thickness conventionally chrome-tanned bovine leather bath at 35 ° C in 200 parts of water washed for 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which time over 20 minutes addition of a total of 3 parts of sodium bicarbonate, and a pH of 7.7. 在加入 Joining

I. 5份HM2后,将皮革在40°C转鼓加工5分钟,然后在酸化液体中加入6. 5份染料8,然后在pH 7. 5和40°C下染色40分钟。 I. After 5 parts of HM2, the leather was 5 minutes at 40 ° C drum, and then acidified by adding 6.5 parts of the dye in the liquid 8, and then dyed at pH 7. 5 and 40 ° C 40 min. 每次少许地添加总共7. I份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工90分钟。 Each addition of a total 7. I parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 90 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 在90分钟的过程中,在200份水的浴液中每次少许地添加总共2份甲酸以达到4. 3的pH值。 In the course of 90 minutes, in a float of 200 parts of water per addition of a total of 2 parts of formic acid to reach a pH of 4.3.

[0953] 将由此染色的皮革在由80份水和3份聚合鞣料G15构成的新制浴液中在45°C复鞣40分钟。 [0953] The leather thus dyed in a freshly float composed of 80 parts water and 3 parts of polymeric tanning material G15 of retanning constituting at 45 ° C 40 min. 添加3份复鞣料Gl、3份植物鞣料G22和3份树脂鞣料Gll将皮革在45°C复鞣60分钟。 Was added 3 parts of retanning material Gl, 3 parts of vegetable tanning material G22 and 3 parts of resin tanning material Gll leather retanned at 45 ° C for 60 minutes. 加入70份60°C的热水后,将皮革在60°C转鼓加工20分钟,并在添加2. 5份加脂剂F7和2. 5份加脂剂F4后将皮革在60°C加脂60分钟。 After addition of 70 parts of hot water of 60 ° C, the leather was for 20 minutes at 60 ° C drum, and adding 2.5 parts of fatliquor F7 and after 2.5 parts of fatliquor F4 leather at 60 ° C fatliquoring 60 minutes. 在60分钟的过程中每次少许地添加总共4份甲酸以便将皮革酸化至3. 5的pH值。 Each addition of a total of 4 parts of formic acid to the leather was acidified to a pH of 3.5 in the course of 60 minutes. 然后漂洗15分钟。 Then rinse for 15 minutes.

[0954] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在60°C减压处理2分钟,在室温下悬浮干燥过夜,修整,刮软并在60°C真空干燥2分钟。 [0954] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, 2 minutes at 60 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo at 60 ° C 2 minute.

[0955] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的鞋面革。 [0955] This having excellent washing resistance, perspiration resistance, bleeding and the shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的鞋面革。 A shoe upper leather in one of Examples Ia to 59k dyes embodiment in an analogous manner.

[0956] 鞋面革配方9 : [0956] upper leather recipe 9:

[0957] 将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过20分钟每次少许地添加总共3份碳酸氢钠,并中和为7. 7的pH值。 100 parts by weight of the block I [0957] shaved I. 8 mm in thickness conventionally chrome-tanned bovine leather bath at 35 ° C in 200 parts of water washed for 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which time over 20 minutes addition of a total of 3 parts of sodium bicarbonate, and neutralized to a pH value of 7.7. 在加入I. 5份HM2后,将皮革在40°C转鼓加工5分钟,然后在酸化浴液中加入4份染料%,然后在pH 7. 5和40°C下染色40分钟。 After addition of I. 5 parts of HM2, the leather was 5 minutes at 40 ° C drum, followed by addition of 4% in parts of dye bath acidified, and then dyed at pH 7. 5 and 40 ° C 40 min. 每次少许地添加总共5份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工90分钟。 Addition of a total per 5 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 90 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过90分钟在200份水的浴液中每次少许地添加总共2份甲酸以达到4. 3的pH值。 Little at a time over 90 minutes to a total of 2 parts of formic acid was added in 200 parts of water bath, at a pH of 4.3.

[0958] 将由此染色的皮革在由80份水和3份聚合鞣料G17构成的新制浴液中在45°C复鞣40分钟。 [0958] The leather thus dyed in a freshly float composed of 80 parts water and 3 parts of polymeric tanning material G17 of retanning constituting at 45 ° C 40 min. 添加3份复鞣料G7、2份植物鞣料G22、2份植物鞣料G23和3份树脂鞣料Gll将皮革在45°C复鞣60分钟。 Was added 3 parts of retanning material G7,2 parts of vegetable tanning G22,2 parts of vegetable tanning material G23 and 3 parts of resin tanning material Gll leather retanned at 45 ° C for 60 minutes. 加入70份60°C的热水后,将皮革在60°C转鼓加工20分钟,并在添加2. 5份加脂剂F7和2. 5份加脂剂F4后将皮革在60°C加脂60分钟。 After addition of 70 parts of hot water of 60 ° C, the leather was for 20 minutes at 60 ° C drum, and adding 2.5 parts of fatliquor F7 and after 2.5 parts of fatliquor F4 leather at 60 ° C fatliquoring 60 minutes. 在60分钟的过程中每次少许地添加总共4份甲酸以便将皮革酸化至3. 5的pH值。 Each addition of a total of 4 parts of formic acid to the leather was acidified to a pH of 3.5 in the course of 60 minutes. 然后漂洗15分钟。 Then rinse for 15 minutes.

[0959] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在60°C减压处理2分钟,在室温下悬浮干燥过夜,修整,刮软并在60°C真空干燥2分钟。 [0959] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, 2 minutes at 60 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo at 60 ° C 2 minute.

[0960] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的鞋面革。 [0960] This having excellent washing resistance, perspiration resistance, bleeding and the shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的鞋面革。 A shoe upper leather in one of Examples Ia to 59k dyes embodiment in an analogous manner.

[0961] 鞋面革配方10 : [0961] shoe upper leather recipe 10:

[0962] 将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过20分钟每次少许地添加总共3份碳酸氢钠,并中和为7. 7的pH值。 100 parts by weight of the block I [0962] shaved I. 8 mm in thickness conventionally chrome-tanned bovine leather bath at 35 ° C in 200 parts of water washed for 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which time over 20 minutes addition of a total of 3 parts of sodium bicarbonate, and neutralized to a pH value of 7.7. 在加入I. 5份HM2后,将皮革在40°C转鼓加工5分钟,然后在酸化浴液中加入6. 9份染料10,然后在pH 7. 5和40°C下染色40分钟。 After addition of I. 5 parts of HM2, the leather was 5 minutes at 40 ° C drum, followed by addition of 6.9 parts of the dye bath 10 in acidified, and then dyed at pH 7. 5 and 40 ° C 40 min. 每次少许地添加总共7. 2份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工90分钟。 Each addition of a total 7.2 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 90 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过90分钟在200份水的浴液中每次少许地添加总共2份甲酸以达到4. 3的pH值。 Little at a time over 90 minutes to a total of 2 parts of formic acid was added in 200 parts of water bath, at a pH of 4.3.

[0963] 将由此染色的皮革在由80份水和5份聚合鞣料G18构成的新制浴液中在45°C复鞣40分钟。 [0963] The leather thus dyed in a freshly float composed of 80 parts water and 5 parts of polymeric tanning material G18 of retanning constituting at 45 ° C 40 min. 添加3份复鞣料Gl、2份植物鞣料G22和4份聚合鞣料GlO将皮革在45°C复鞣60分钟。 Was added 3 parts of retanning material Gl, 2 parts of vegetable tanning material G22 and 4 parts of polymeric tanning material GlO leather retanned at 45 ° C for 60 minutes. 加入70份60°C的热水后,将皮革在60°C转鼓加工20分钟,并在添加4. 5份加脂剂F5和O. 5份加脂剂F8后将皮革在60°C加脂60分钟。 After addition of 70 parts of hot water of 60 ° C, the leather was for 20 minutes at 60 ° C drum, and after adding 5 parts of 4.5 parts of fatliquor F5 and F8 O. leather fatliquors at 60 ° C fatliquoring 60 minutes. 在60分钟的过程中每次少许地添加总共4份甲酸以便将皮革酸化至3. 5的pH值。 Each addition of a total of 4 parts of formic acid to the leather was acidified to a pH of 3.5 in the course of 60 minutes. 然后漂洗15分钟。 Then rinse for 15 minutes.

[0964] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在60°C减压处理2分钟,在室温下悬浮干燥过夜,修整,刮软并在60°C真空干燥2分钟。 [0964] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, 2 minutes at 60 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo at 60 ° C 2 minute.

[0965] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的鞋面革。 [0965] This having excellent washing resistance, perspiration resistance, bleeding and the shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的鞋面革。 A shoe upper leather in one of Examples Ia to 59k dyes embodiment in an analogous manner. · ·

[0966] 鞋面革配方11: [0966] upper leather recipe 11:

[0967] 将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过20分钟每次少许地添加总共3份碳酸氢钠,并中和为7. 7的pH值。 100 parts by weight of the block I [0967] shaved I. 8 mm in thickness conventionally chrome-tanned bovine leather bath at 35 ° C in 200 parts of water washed for 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which time over 20 minutes addition of a total of 3 parts of sodium bicarbonate, and neutralized to a pH value of 7.7. 在加入I. 5份HM2后,将皮革在40°C转鼓加工5分钟,然后在脱酸浴液中加入9份染料11b,然后在pH 7. 5和40°C下染色40分钟。 After addition of I. 5 parts of HM2, the leather was drum at 40 ° C for 5 minutes and then added to the deacidifying float 9 parts of dye 11b, and then dyed at pH 7. 5 and 40 ° C 40 min. 每次少许地添加总共9. 5份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工90分钟。 Each addition of a total 9.5 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 90 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过90分钟在200份水的浴液中每次少许地添加总共2份甲酸以达到4. 3的pH值。 Little at a time over 90 minutes to a total of 2 parts of formic acid was added in 200 parts of water bath, at a pH of 4.3.

[0968] 将由此染色的皮革在由80份水、I. 5份复鞣料G13和2. 5份聚合鞣料G16构成的新制浴液中在45°C复鞣40分钟。 [0968] The leather thus dyed in a freshly made 80 parts of water float, I. 5 parts of retanning material G13 and 2.5 parts of polymeric tanning material G16 of retanning constituting at 45 ° C 40 min. 添加3份复鞣料Gl、3份植物鞣料G22和3份树脂鞣料Gll将皮革在45°C复鞣60分钟。 Was added 3 parts of retanning material Gl, 3 parts of vegetable tanning material G22 and 3 parts of resin tanning material Gll leather retanned at 45 ° C for 60 minutes. 加入70份60°C的热水后,将皮革在60°C转鼓加工20分钟,并在添加4. 5份加脂剂F5和O. 5份加脂剂F8后将皮革在60°C力口脂60分钟。 After addition of 70 parts of hot water of 60 ° C, the leather was for 20 minutes at 60 ° C drum, and after adding 5 parts of 4.5 parts of fatliquor F5 and F8 O. leather fatliquors at 60 ° C lipid force port 60 minutes. 在60分钟的过程中每次少许地添加总共4份甲酸以便将皮革酸化至3. 5的pH值。 Each addition of a total of 4 parts of formic acid to the leather was acidified to a pH of 3.5 in the course of 60 minutes. 然后冷漂洗15分钟。 Then rinsed cold for 15 minutes.

[0969] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在60°C减压处理2分钟,在室温下悬浮干燥过夜,修整,刮软并在60°C真空干燥2分钟。 [0969] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, 2 minutes at 60 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo at 60 ° C 2 minute.

[0970] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的鞋面革。 [0970] This having excellent washing resistance, perspiration resistance, bleeding and the shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的鞋面革。 A shoe upper leather in one of Examples Ia to 59k dyes embodiment in an analogous manner.

[0971] 鞋面革配方12: [0971] upper leather recipe 12:

[0972] 将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过20分钟每次少许地添加总共3份碳酸氢钠,并中和为7. 7的pH值。 100 parts by weight of the block I [0972] shaved I. 8 mm in thickness conventionally chrome-tanned bovine leather bath at 35 ° C in 200 parts of water washed for 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which time over 20 minutes addition of a total of 3 parts of sodium bicarbonate, and neutralized to a pH value of 7.7. 在加入I. 5份HM2后,将皮革在40°C转鼓加工5分钟,然后在脱酸浴液中加入8. 5份染料12d,然后在pH 7. 5和40°C下染色40分钟。 I. After the addition of 5 parts of HM2, the leather was drum at 40 ° C for 5 minutes and then deacidifying float 12 d were added 8.5 parts of dye, and then dyed at pH 7. 5 and 40 ° C 40 minutes . 每次少许地添加总共9份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工90分钟。 Each addition of a total of 9 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 90 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过90分钟在200份水的浴液中每次少许地添加总共2份甲酸以达到4. 3的pH值。 Little at a time over 90 minutes to a total of 2 parts of formic acid was added in 200 parts of water bath, at a pH of 4.3.

[0973] 将由此染色的皮革在由80份水、I. 5份复鞣料G13和2. 5份聚合鞣料G16构成的新制浴液中在45°C复鞣40分钟。 [0973] The leather thus dyed in a freshly made 80 parts of water float, I. 5 parts of retanning material G13 and 2.5 parts of polymeric tanning material G16 of retanning constituting at 45 ° C 40 min. 添加8份复鞣料G2、3份聚合鞣料G19和3份树脂鞣料Gll将皮革在45°C复鞣60分钟。 Addition of 8 parts of retanning material G2,3 parts of polymeric tanning material G19 and 3 parts of resin tanning material Gll leather retanned at 45 ° C for 60 minutes. 加入70份60°C的热水后,将皮革在60°C转鼓加工20分钟,并在添加4. 5份加脂剂F5和O. 5份加脂剂F8后将皮革在60°C力口脂60分钟。 After addition of 70 parts of hot water of 60 ° C, the leather was for 20 minutes at 60 ° C drum, and after adding 5 parts of 4.5 parts of fatliquor F5 and F8 O. leather fatliquors at 60 ° C lipid force port 60 minutes. 在60分钟的过程中每次少许地添加总共4份甲酸以便将皮革酸化至3. 5的pH值。 Each addition of a total of 4 parts of formic acid to the leather was acidified to a pH of 3.5 in the course of 60 minutes. 然后冷漂洗15分钟。 Then rinsed cold for 15 minutes.

[0974] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在60°C减压处理2分钟,在室温下悬浮干燥过夜,修整,刮软并在60°C真空干燥2分钟。 [0974] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, 2 minutes at 60 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo at 60 ° C 2 minute.

[0975] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的鞋面革。 [0975] This having excellent washing resistance, perspiration resistance, bleeding and the shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的鞋面革。 A shoe upper leather in one of Examples Ia to 59k dyes embodiment in an analogous manner. · ·

[0976] 鞋面革配方12 : [0976] upper leather recipe 12:

[0977] 将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过20分钟每次少许地添加总共3份碳酸氢钠,并中和为7. 7的pH值。 100 parts by weight of the block I [0977] shaved I. 8 mm in thickness conventionally chrome-tanned bovine leather bath at 35 ° C in 200 parts of water washed for 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which time over 20 minutes addition of a total of 3 parts of sodium bicarbonate, and neutralized to a pH value of 7.7. 在加入I. 5份HM2后,将皮革在40°C转鼓加工5分钟,然后在脱酸浴液中加入8份染料12at,然后在pH 7. 5和40°C下染色40分钟。 After addition of I. 5 parts of HM2, the leather was drum at 40 ° C for 5 minutes and then added to the deacidifying float 12at 8 parts of dye, and then dyed at pH 7. 5 and 40 ° C 40 min. 每次少许地添加总共9份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工90分钟。 Each addition of a total of 9 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 90 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过90分钟在200份水的浴液中每次少许地添加总共2份甲酸以达到4. 3的pH值。 Little at a time over 90 minutes to a total of 2 parts of formic acid was added in 200 parts of water bath, at a pH of 4.3.

[0978] 将由此染色的皮革在由80份水、I份复鞣料G13和3份聚合鞣料G16构成的新制浴液中在45°C复鞣40分钟。 [0978] The leather thus dyed in a freshly made 80 parts of water float, I retanning material parts 3 parts of polymeric tanning material G13 and G16 of retanning configuration at 45 ° C 40 min. 添加I. 5份助剂HM4、3份聚合鞣料G19和3份聚合鞣料GlO将皮革在45°C复鞣60分钟。 I. 5 parts of additives added HM4,3 parts of polymeric tanning material G19 and 3 parts of polymeric tanning material GlO leather retanned at 45 ° C for 60 minutes. 加入70份60°C的热水后,将皮革在60°C转鼓加工20分钟,并在添加I. 5份加脂剂F2和3. 5份疏水剂H3后将皮革在60°C加脂60分钟。 After addition of 70 parts of hot water of 60 ° C, the leather was for 20 minutes at 60 ° C drum, and adding 5 parts of fatliquor I. F2 and after 3.5 parts of water repellent leather H3 added at 60 ° C grease 60 minutes. 在60分钟的过程中每次少许地添加总共4份甲酸以便将皮革酸化至3. 5的pH值。 Each addition of a total of 4 parts of formic acid to the leather was acidified to a pH of 3.5 in the course of 60 minutes. 然后冷漂洗10分钟。 Then rinsed cold for 10 minutes.

[0979] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在60°C减压处理2分钟,在室温下悬浮干燥过夜,修整,刮软并在60°C真空干燥2分钟。 [0979] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, 2 minutes at 60 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo at 60 ° C 2 minute.

[0980] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的鞋面革。 [0980] This having excellent washing resistance, perspiration resistance, bleeding and the shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的鞋面革。 A shoe upper leather in one of Examples Ia to 59k dyes embodiment in an analogous manner.

[0981] 鞋面革配方14 : [0981] upper leather recipe 14:

[0982] 将削匀厚度为I. 3毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过20分钟每次少许地添加总共3份碳酸氢钠,并中和为7. 7的pH值。 100 parts [0982] shaved I. 3 mm in thickness by weight of I-block in a conventional chrome-tanned bovine leather in 35 ° C water bath was washed with 200 parts of 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which time over 20 minutes addition of a total of 3 parts of sodium bicarbonate, and neutralized to a pH value of 7.7. 在加入 Joining

I. 5份HM2后,将皮革在40°C转鼓加工5分钟,然后在脱酸浴液中加入8份染料12bx,然后在pH 7. 5和40°C下染色40分钟。 After I. 5 parts of HM2, the leather was drum at 40 ° C for 5 minutes and then added to the deacidifying float 12BX 8 parts of dye, and then dyed at pH 7. 5 and 40 ° C 40 min. 每次少许地添加总共8. 5份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工90分钟。 Each addition of a total 8.5 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 90 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过90分钟在200份水的浴液中每次少许地添加总共2份甲酸以达到4. 3的pH值。 Little at a time over 90 minutes to a total of 2 parts of formic acid was added in 200 parts of water bath, at a pH of 4.3.

[0983] 将由此染色的皮革在由80份水和I份复鞣料G13构成的新制浴液中复鞣10分钟。 [0983] The thus dyed leather retanned in a freshly made 80 parts of water and float I G13 constituting parts of retanning material for 10 minutes. 添加4份铬鞣料G24、2份复鞣料Gl、l份加脂剂Fl将皮革在35°C复鞣40分钟。 Was added 4 parts of chrome tanning material G24,2 parts retanning Gl, l Fl parts fatliquor leather retanned at 35 ° C for 40 minutes. 加入I份甲酸钠并转鼓加工20分钟。 I was added and drumming parts of sodium formate 20 min. 在已经加入O. 3份碳酸氢钠后,再将皮革复鞣90分钟。 Having O. 3 parts of sodium bicarbonate was added, and then the leather retanned for 90 minutes. 在300份水中在35°C洗涤10分钟后,将皮革在由100份水和I. 5份甲酸钠构成的新制浴液中在35°C中和10分钟。 In 300 parts of water after a 10 minute wash in 35 ° C, float to the leather in a freshly I. 5 parts of water and 100 parts of sodium formate at 35 ° C in 10 minutes. 将中和浴液与O. 5份碳酸氢钠混合,然后转鼓加工30分钟。 The bath and mixed with O. 5 parts of sodium bicarbonate, then drummed for 30 minutes. 在用5份聚合鞣料G18复鞣30分钟后,添加5份复鞣料G5和3份复鞣料Gl以完成皮革的鞣制。 After polymerization tanning G18 retanning with 5 parts of 30 minutes, 5 parts and 3 parts of retanning material G5 Gl retanning material to complete the tanning of leather. 在40分钟的转鼓加工时间后,将浴液用100份60°C的热水稀释,然后在60°C转鼓加工10分钟。 After 40 minutes drumming time, 100 parts of the float was diluted with water to 60 ° C, 60 ° C and then processed in the drum for 10 minutes. 在添加3. 5份加脂剂Fl和3. 5份疏水剂H3后将皮革在60°C加脂60分钟。 Added 3.5 parts of fatliquor Fl and 3.5 parts of the hydrophobic agent after H3 leather fatliquoring at 60 ° C for 60 minutes. 经过60分钟每次少许地添加总共4份甲酸以酸化至3. 5的pH值。 Little at a time over 60 minutes a total of 4 parts of formic acid was added to acidify to a pH of 3.5. 然后冷漂洗10分钟。 Then rinsed cold for 10 minutes.

[0984] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在60°C减压处理2分钟,在室温下悬浮干燥过夜,修整,刮软并在60°C真空干燥2分钟。 [0984] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, 2 minutes at 60 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo at 60 ° C 2 minute. · ·

[0985] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的柔软鞋面革。 [0985] This having excellent washing resistance, perspiration resistance, bleeding and soft shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的柔软鞋面革。 It may be made flexible shoe upper leather dyed with Example 59k Ia to one embodiment of the dye in a similar manner.

[0986] 鞋面革配方15 : [0986] upper leather recipe 15:

[0987] 将削匀厚度为I. 3毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过20分钟每次少许地添加总共3份碳酸氢钠,并中和为7. 7的pH值。 100 parts [0987] shaved I. 3 mm in thickness by weight of I-block in a conventional chrome-tanned bovine leather in 35 ° C water bath was washed with 200 parts of 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which time over 20 minutes addition of a total of 3 parts of sodium bicarbonate, and neutralized to a pH value of 7.7. 在加入I. 5份HM2后,将皮革在40°C转鼓加工5分钟,然后在脱酸浴液中加入8份染料混合物12gz,然后在pH 7. 5和40°C下染色40分钟。 After addition of I. 5 parts of HM2, the leather was drum at 40 ° C for 5 minutes and then added to the deacidifying float 8 parts of the dye mixture 12gz, and then dyed at pH 7. 5 and 40 ° C 40 min. 每次少许地添加总共8. 5份碳酸钠以使浴液的PH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工90分钟。 Each addition of a total 8.5 parts of sodium carbonate to make the PH value to reach between the float 9. 2-9. 6 for fixation, 40 ° C and then processed in the drum for 90 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过90分钟在200份水的浴液中每次少许地添加总共2份甲酸以达到4. 3的pH值。 Little at a time over 90 minutes to a total of 2 parts of formic acid was added in 200 parts of water bath, at a pH of 4.3.

[0988] 将由此染色的皮革在由80份水和I. 5份复鞣料G14构成的新制浴液中复鞣10分钟。 [0988] The thus dyed leather retanned in a freshly made 80 parts of water and float I. 5 parts of retanning material constituting G14 for 10 minutes. 添加6份铬合成鞣剂G20和I份加脂剂Fl将皮革在35°C复鞣40分钟。 Was added 6 parts of chrome and syntan G20 I Fl parts fatliquor leather retanned at 35 ° C for 40 minutes. 加入I份甲酸钠并转鼓加工20分钟。 I was added and drumming parts of sodium formate 20 min. 在已经加入O. 3份碳酸氢钠后,再将皮革复鞣90分钟。 Having O. 3 parts of sodium bicarbonate was added, and then the leather retanned for 90 minutes. 在300份水中在35V洗洚10分钟后,将皮革在由100份水和I. 5份甲酸钠构成的新制浴液中在35°C中和10分钟。 After 300 parts of water for 10 minutes and washed flood 35V, the leather by the float in a freshly I. 5 parts of water and 100 parts of sodium formate at 35 ° C in 10 minutes. 将中和浴液与O. 5份碳酸氢钠混合,然后转鼓加工30分钟。 The bath and mixed with O. 5 parts of sodium bicarbonate, then drummed for 30 minutes. 在用6份聚合鞣料G18复鞣30分钟后,添加6份复鞣料G5和6份复鞣料G3以完成皮革的鞣制。 After polymerization tanning G18 retanning with 6 parts of 30 minutes, 6 parts 6 parts of retanning material G5 and G3 retanning material to complete the tanning of leather. 在40分钟的转鼓加工时间后,将浴液用100份60°C的热水稀释,然后在60°C转鼓加工10分钟。 After 40 minutes drumming time, 100 parts of the float was diluted with water to 60 ° C, 60 ° C and then processed in the drum for 10 minutes. 在添加3. 5份加脂剂Fl和3. 5份疏水剂H3后将皮革在60°C加脂60分钟。 Added 3.5 parts of fatliquor Fl and 3.5 parts of the hydrophobic agent after H3 leather fatliquoring at 60 ° C for 60 minutes. 经过60分钟每次少许地添加总共4份甲酸以酸化至3. 5的pH值。 Little at a time over 60 minutes a total of 4 parts of formic acid was added to acidify to a pH of 3.5. 然后冷漂洗10分钟。 Then rinsed cold for 10 minutes.

[0989] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在60°C减压处理2分钟,在室温下悬浮干燥过夜,修整,刮软并在60°C真空干燥2分钟。 [0989] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, 2 minutes at 60 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo at 60 ° C 2 minute.

[0990] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的柔软鞋面革。 [0990] This having excellent washing resistance, perspiration resistance, bleeding and soft shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的柔软鞋面革。 It may be made flexible shoe upper leather dyed with Example 59k Ia to one embodiment of the dye in a similar manner.

[0991] 鞋面革配方16 : [0991] upper leather recipe 16:

[0992] 将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过20分钟每次少许地添加总共3份碳酸氢钠,并中和为7. 4的pH值。 100 parts by weight of the block I [0992] shaved I. 8 mm in thickness conventionally chrome-tanned bovine leather bath at 35 ° C in 200 parts of water washed for 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which time over 20 minutes addition of a total of 3 parts of sodium bicarbonate, and neutralized to a pH value of 7.4. 在加入I. 5份HM2后,将皮革在40°C转鼓加工5分钟,然后在脱酸浴液中加入7份染料混合物12hf,然后在pH 7. 5和40°C下染色40分钟。 After addition of I. 5 parts of HM2, the leather was drum at 40 ° C for 5 minutes and then added to the deacidifying float 7 parts of dye mixture 12hf, and then dyed at pH 7. 5 and 40 ° C 40 min. 每次少许地添加总共8份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工90分钟。 Each addition of a total of 8 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 90 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过90分钟在200份水的浴液中每次少许地添加总共4份甲酸以达到3. 7的pH值。 Little at a time over 90 minutes to add a total of 4 parts of formic acid in 200 parts of water bath, at a pH of 3.7.

[0993] 将由此染色的皮革在由80份水、I. 5份醛鞣料G13和6份聚合鞣料G18构成的新制浴液中在45°C复鞣40分钟。 [0993] The leather thus dyed in a freshly made 80 parts of water float, I. 5 parts and 6 parts of aldehyde tanning material G13 G18 composed of polymeric tanning material in retanning 45 ° C 40 min. 然后添加8份复鞣料G2、2份聚合鞣料G19和3份树脂鞣料GlI,再在45°C在60分钟内完成鞣革。 Then added 8 parts of retanning material G2,2 parts of polymeric tanning material G19 and 3 parts of resin tanning material GlI, then complete tanning in 60 minutes at 45 ° C. 然后将浴液与70份60°C的热水稀释,然后在60V转鼓加工20分钟。 Float then diluted with 70 parts of hot water of 60 ° C, then processed in the drum 60V for 20 minutes. 在添加6. 5份加脂剂Fl和3. 5份加脂剂F3后将皮革在60°C加脂60分钟。 Added 6.5 parts of fatliquor after Fl, and 3.5 parts of fatliquor F3 leather fatliquoring at 60 ° C for 60 minutes. 经过60分钟每次少许地添加总共4份甲酸以酸化至pH 3.5。 Little at a time over 60 minutes a total of 4 parts of formic acid was added to acidify to pH 3.5. 然后冷漂洗10分钟。 Then rinsed cold for 10 minutes.

[0994] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在60°C减压处理2分钟,在室温下悬浮干燥过夜,修整,刮软并在60°C真空干燥2分钟。 [0994] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, 2 minutes at 60 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo at 60 ° C 2 minute.

[0995] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的柔软鞋面革。 [0995] This having excellent washing resistance, perspiration resistance, bleeding and soft shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的柔软鞋面革。 It may be made flexible shoe upper leather dyed with Example 59k Ia to one embodiment of the dye in a similar manner.

[0996] 鞋面革配方17 : [0996] upper leather recipe 17:

[0997] 将削匀厚度为I. 5毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过25分钟每次少许地添加总共3份碳酸氢钠,并中和为7. 6的pH值。 100 parts of the [0997] thickness of shaved I I. 5 mm bulk weight in a conventional chrome-tanned bovine leather in 35 ° C water bath was washed with 200 parts of 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes over 25 minutes after each addition of a total of 3 parts of sodium bicarbonate, and neutralized to a pH value of 7.6. 在脱酸浴液中加入9份染料混合物12hr,然后在pH 7. 5和40°C下染色40分钟。 Was added 9 parts of the dye mixture 12hr deacidifying float before dyeing at pH 7. 5 and 40 ° C 40 min. 每次少许地添加总共9份固体碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工90分钟。 Each addition of a total of 9 parts of solid sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 90 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过90分钟在200份水的浴液中每次少许地添加总共4份甲酸以达到3. 5的pH值。 Little at a time over 90 minutes to add a total of 4 parts of formic acid in 200 parts of water bath, at a pH of 3.5.

[0998] 将由此染色的皮革在由100份水和4份醛鞣料G12构成的新制浴液中在35°C转鼓加工10分钟。 [0998] The leather thus dyed in a fresh bath of water and 4 parts of 100 parts of aldehyde tanning material G12 in the configuration of the processing drum 35 ° C for 10 min. 此后加入6份铬鞣料G24和2份复鞣料G1,再在35°C复鞣50分钟。 After addition of 6 parts of chrome tanning material G24 and 2 parts of retanning material G1, then retanned at 35 ° C for 50 minutes. 然后将浴液与I份甲酸钠混合,再转鼓加工10分钟。 The bath is then mixed with sodium formate parts I, then drummed for 10 minutes. 添加I. 5份加脂剂Fl后,将皮革在35°C转鼓加工90分钟。 After the addition of fatliquor I. 5 parts of Fl, the leather was drum at 35 ° C for 90 minutes. 使浴液滴出并将皮革用300份水在45V洗洚10分钟。 The float was dropped and the leather was washed with 300 parts of water for 10 minutes flood 45V.

[0999] 然后,将皮革在由70份水和2份疏水剂H3构成的新制浴液中在45°C预加脂15分钟。 [0999] Then, the leather will float in a freshly made 70 parts of water and 2 parts of a hydrophobic agent consisting of pre-H3 grease 45 ° C 15 min. 然后添加2份甲酸钠、I份碳酸氢钠和3份助剂HM4,再转鼓加工30分钟。 Then added 2 parts of sodium formate, I part of sodium bicarbonate and 3 parts of auxiliary HM4, then drummed for 30 minutes. 将该中和浴液与12份复鞣料G6混合,然后在10分钟的转鼓加工时间后,加入2份聚合鞣料G19,然后再在50分钟的过程中完成鞣革。 The G6 and mixed with 12 parts of retanning bath, then after 10 minutes drumming time, was added 2 parts of polymeric tanning material G19, and then completed in the course of tanning in 50 minutes. 将复鞣浴液与4份加脂剂F4、4份加脂剂Fl和2份加脂剂F6混合,再在45°C加脂60分钟。 The retanning float and 4 parts of fatliquor F4,4 fatliquor Fl parts and 2 parts of fatliquor F6 mixed, fatliquoring at 45 ° C for 60 minutes. 在60分钟的过程中每次少许地添加总共4份甲酸以酸化至pH 3. 5。 Each addition of a total of 4 parts of formic acid in the course of 60 minutes to acidified to pH 3. 5. 然后使浴液滴出并将皮革冷漂洗5分钟。 Thereafter, the float drops and the leather rinsed cold for 5 minutes.

[1000] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在55°C减压处理I分钟,在室温下悬浮干燥过夜,修整,刮软、干转鼓加工过夜并用绷革框干燥。 [1000] The thus dyed, retanned and hydrophobic horsed overnight and then stretching process I min at 55 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked, dry drummed overnight and toggle box dry.

[1001] 这产生具有干燥鼓干燥(dry-drumming)的粒面和优异的耐洗、耐汗、耐渗移和耐擦坚牢度的柔软鞋面革。 [1001] This produces a drying drum drying (dry-drumming) grain and excellent washing resistance, perspiration resistance, bleeding and soft shoe upper leather scuff fastness. 可以按照类似方式制造具有干燥鼓干燥粒面并用实施例Ia至59k的染料之一染色的柔软鞋面革。 Soft shoe upper leather can be produced by one of the dyes stain 59k Examples Ia to an embodiment of the drying drum having a grain and dried in a similar manner.

[1002] 鞋面革配方18 : [1002] upper leather recipe 18:

[1003] 将削匀厚度为2. I毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过25分钟每次少许地添加总共3份碳酸氢钠,并中和为7. 6的pH值。 100 parts [1003] 2. shaved thickness of I mm by weight of I-block in a conventional chrome-tanned bovine leather in 35 ° C water bath was washed with 200 parts of 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes over 25 minutes after each addition of a total of 3 parts of sodium bicarbonate, and neutralized to a pH value of 7.6. 在脱酸浴液中加入7. 5份染料混合物13b,然后在pH 7. 5和40°C下染色30分钟。 Was added 7.5 parts of the dye mixture 13b deacidifying float before dyeing at the pH 7.5 and 40 ° C 30 min. 每次少许地添加总共8份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工75分钟。 Each addition of a total of 8 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 75 minutes. 浴液改变之后,每次用300份水将皮革洗涤两次,一共洗涤60分钟。 After float change, the leather was washed twice each time, washed with a total of 60 minutes 300 parts of water.

[1004] 将由此染色的皮革在由80份水和3份醛鞣料G12构成的新制浴液中在45°C转鼓加工30分钟。 [1004] The leather thus dyed in a freshly float composed of 80 parts water and 3 parts of an aldehyde tanning material G12 in the configuration of the processing drum 45 ° C for 30 minutes. 此后加入5份复鞣料G5并将皮革在45°C复鞣30分钟。 After adding 5 parts of the leather and the retanning material G5 retanning at 45 ° C for 30 minutes. 然后将浴液与I份加脂剂Fl和I份加脂剂F4混合并将皮革在45°C预加脂40分钟。 I then float to the parts of fatliquor Fl and F4 fatliquor parts I and mixed at 45 ° C pre leather fatliquoring for 40 minutes. 然后添加70份55°C的热水并在55°C转鼓加工20分钟。 Was then added 70 parts of hot water of 55 ° C at 55 ° C and the processing drum 20 min. 在55分钟的过程中,逐份添加I. 5份甲酸以达到5. O的PH值。 In the course of 55 minutes, I. 5 parts by portionwise addition of formic acid PH value of 5. O. 使浴液滴出并将皮革用300份水在45V洗洚10分钟。 The float was dropped and the leather was washed with 300 parts of water for 10 minutes flood 45V.

[1005] 然后,将皮革在由100份水和2份疏水剂H3构成的新制浴液中在45°C转鼓加工15分钟。 [1005] Then, the leather will float in a freshly made 100 parts of water and 2 parts of a hydrophobic agent consisting of H3 processing drum at 45 ° C for 15 min. 此后添加2份聚合鞣料G19。 After addition of 2 parts of polymeric tanning material G19. 在15分钟的转鼓加工时间后,添加2份聚合鞣料G15,并再在30分钟的过程中完成鞣革。 After drumming time of 15 minutes, 2 parts of polymeric tanning material G15 was added, and then complete the tanning in the course of 30 minutes. 将复鞣浴液与2. 5份加脂剂Fl、4份加脂剂F4、l份加脂剂F3和I份加脂剂F2混合,再在45°C加脂60分钟。 The retanning float with 2.5 parts of fatliquor Fl, 4 parts of fatliquor F4, l parts of fatliquor F3 and F2 hybrid fatliquor parts I, and then at 45 ° C fatliquoring for 60 minutes. 在60分钟的过程中每次少许地添加总共4份甲酸以酸化至pH 3.5。 Each addition of a total of 4 parts of formic acid in the course of 60 minutes to acidify to pH 3.5. 然后使浴液滴出并将皮革冷漂洗5分钟。 Thereafter, the float drops and the leather rinsed cold for 5 minutes. · ·

[1006] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在40°C湿拉紧干燥,修整,刮软、干转鼓加工过夜并用绷革框干燥。 [1006] The thus dyed, retanned and hydrophobic horsed overnight and then stretched at 40 ° C wet-strained dried, conditioned, staked, dry drummed overnight and toggle frame dried.

[1007] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的鞣池鞋面革。 [1007] This having excellent washing resistance, perspiration resistance, bleeding and the shoe upper leather tanning pool scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的鞣池鞋面革。 Shoe upper leather tanning pool may be manufactured in one embodiment to 59k Ia dyes embodiment in an analogous manner.

[1008] 鞋面革配方19 : [1008] upper leather recipe 19:

[1009] 将削匀厚度为2. I毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过20分钟每次少许地添加总共3份碳酸氢钠,并中和为7. 7的pH值。 100 parts [1009] 2. shaved thickness of I mm by weight of I-block in a conventional chrome-tanned bovine leather in 35 ° C water bath was washed with 200 parts of 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which time over 20 minutes addition of a total of 3 parts of sodium bicarbonate, and neutralized to a pH value of 7.7. 在脱酸浴液中加入5. 9份染料13ae,然后在pH 7. 5和40°C下染色40分钟。 Was added 5.9 parts of dye 13ae deacidifying float before dyeing at pH 7. 5 and 40 ° C 40 min. 每次少许地添加总共6. 5份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工90分钟。 Each addition of a total 6.5 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 90 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过60分钟在200份水的浴液中每次少许地添加总共4份甲酸以达到3. 6的pH值。 Little at a time over 60 minutes to add a total of 4 parts of formic acid in 200 parts of water bath, at a pH of 3.6.

[1010] 将由此染色的皮革在由80份水和I份醛鞣料G13和3份聚合鞣料G16构成的新制浴液中在45°C转鼓加工60分钟。 [1010] The leather thus dyed in a fresh bath of water and 80 parts of an aldehyde tanning material parts I and 3 parts of polymeric tanning material G13 G16 in the configuration of the processing drum 45 ° C for 60 minutes. 此后添加O. 5份碳酸氢钠,然后在30分钟转鼓加工时间后,加入5份聚合鞣料G18,再在45°C复鞣30分钟。 O. After 5 parts of sodium bicarbonate was added, then after 30 minutes drumming time of 5 parts of polymeric tanning material G18, and then retanned at 45 ° C for 30 minutes. 然后将该浴液与O. 8份助剂HM5、3份聚合鞣料G17和2份聚合鞣料G19混合,并在45°C完成鞣革60分钟。 Then the bath and O. 8 parts adjuvant HM5,3 parts of polymeric tanning material G17 and G19 mixing 2 parts of polymeric tanning material, in leather tanning and completed 45 ° C 60 min. 然后添加70份水,再在60°C转鼓加工10分钟。 70 parts of water were then added, and then the processing drum at 60 ° C for 10 min. 将复鞣浴液与2. 5份加脂剂F6、l. 5份疏水剂H3和I. 5份加脂剂F2混合,再在45°C加脂60分钟。 The retanning float with 2.5 parts of fatliquor F6, l. 5 parts of a hydrophobic agent and H3 I. 5 parts of fatliquor F2 mixed, fatliquoring at 45 ° C for 60 minutes. 然后在60分钟的过程中每次少许地添加总共4份甲酸以达到3. 5的pH值。 Then each addition of a total of 4 parts of formic acid in the course of 60 minutes to achieve a pH value of 3.5. 然后使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float drops and the leather briefly rinsed cold.

[1011] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在60°C减压处理2分钟,在室温下悬浮干燥,修整,刮软并在60°C真空干燥2分钟。 [1011] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, 2 minutes at 60 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 60 ° C 2 minutes .

[1012] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的纯聚合基鞋面革。 [1012] This having excellent washing resistance, perspiration resistance, bleeding and the pure polymeric matrix shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的纯聚合基鞋面革。 Pure polymeric matrix may be fabricated shoe upper leather dyed with one embodiment of Ia to 59k in a similar manner.

[1013] 鞋面革配方20: [1013] upper leather recipe 20:

[1014] 将削匀厚度为2. O毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过20分钟每次少许地添加总共3份碳酸氢钠,并中和为7. 8的pH值。 100 parts [1014] The shaved thickness of I mm 2. O bulk weight in a conventional chrome-tanned bovine leather in 35 ° C water bath was washed with 200 parts of 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which time over 20 minutes addition of a total of 3 parts of sodium bicarbonate, and neutralized to a pH value of 7.8. 在脱酸浴液中加入4. 8份染料13dt后,将皮革在pH 7. 6和40°C下染色35分钟。 After the addition of 4.8 parts of the dye 13dt deacidifying float the leather was dyed at pH 7. 6 and 40 ° C 35 min. 每次少许地添加总共6份碳酸钠以使浴液的pH值达到9. 4-9. 9之间以固色,然后在40°C转鼓加工60分钟。 Each addition of a total of 6 parts of sodium carbonate to bring the pH reaches between the float 9. 4-9. 9 for fixation, 40 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过60分钟在200份水的浴液中每次少许地添加总共2份甲酸以达到4. 3的pH值。 Little at a time over 60 minutes is added a total of 2 parts of formic acid in 200 parts of water bath, at a pH of 4.3.

[1015] 将由此染色的皮革在由80份水和I. 5份疏水剂H3构成的新制浴液中转鼓加工20分钟。 [1015] The thus dyed leather drummed in a freshly float composed of 80 parts of water and H3 I. 5 parts of a hydrophobic agent consisting of 20 minutes. 然后加入5份聚合鞣料G18,再在40分钟的转鼓加工时间后,添加I份助剂HM5和5份聚合鞣料G18。 Then 5 parts of polymeric tanning material G18, followed after 40 minutes drumming time, add I and 5 parts of adjuvants HM5 parts of polymeric tanning material G18. 再在45°C转鼓加工30分钟,然后添加3份聚合鞣料G19,再在45°C复鞣60分钟。 Reprocessing 30 minutes 45 ° C drum, and then add 3 parts of polymeric tanning material G19, followed retanning 45 ° C for 60 minutes. 然后添加70份水,再在60°C转鼓加工10分钟。 70 parts of water were then added, and then the processing drum at 60 ° C for 10 min. 将复鞣浴液与2. 5份加脂剂F6、·O. 5份疏水剂H3和I. 5份加脂剂F2混合,再在60。 The retanning float with 2.5 parts of fatliquor F6, · O. 5 parts of a hydrophobic agent and H3 I. 5 parts of fatliquor F2 mixed, at 60. . 加脂60分钟。 Fatliquoring 60 minutes. 然后在60分钟的过程中每次少许地添加总共4份甲酸以达到3. 4的pH值。 Then each addition of a total of 4 parts of formic acid in the course of 60 minutes to achieve a pH value of 3.4. 然后使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float drops and the leather briefly rinsed cold.

[1016] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在60°C减压处理2分钟,在室温下悬浮干燥,修整,刮软并在60°C真空干燥2分钟。 [1016] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, 2 minutes at 60 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 60 ° C 2 minutes .

[1017] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的纯聚合基鞋面革。 [1017] This having excellent washing resistance, perspiration resistance, bleeding and the pure polymeric matrix shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的纯聚合基鞋面革。 Pure polymeric matrix may be fabricated shoe upper leather dyed with one embodiment of Ia to 59k in a similar manner.

[1018] 鞋面革配方21: [1018] upper leather recipe 21:

[1019] 将削匀厚度为2. 2毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过20分钟每次少许地添加总共3份碳酸氢钠,并中和为7. 8的pH值。 100 parts [1019] The shaved thickness of 2.2 mm by weight of the block I conventionally chrome-tanned bovine leather bath at 35 ° C in 200 parts of water washed for 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which time over 20 minutes addition of a total of 3 parts of sodium bicarbonate, and neutralized to a pH value of 7.8. 在脱酸浴液中加入7. 7份染料混合物13hb,然后在pH 7. 6和40°C下染色35分钟。 Was added 7.7 parts of the dye mixture 13hb deacidifying float before dyeing at pH 7. 6 and 40 ° C 35 min. 每次少许地添加总共8份碳酸钠以使浴液的pH值达到9. 5-10. O之间以固色,然后在40°C转鼓加工55分钟。 Each addition of a total of 8 parts of sodium carbonate to bring the pH of the float was reached 9. 5-10. For fixation between O, 40 ° C and then processed in the drum for 55 minutes. 浴液改变之后,每次用300份水将皮革洗涤两次,一共洗涤60分钟。 After float change, the leather was washed twice each time, washed with a total of 60 minutes 300 parts of water. 经过60分钟在200份水的浴液中每次少许地添加总共2份甲酸以达到4. 4的pH值。 Little at a time over 60 minutes is added a total of 2 parts of formic acid in 200 parts of water bath, at a pH of 4.4.

[1020] 将由此染色的皮革在由80份水和I. 5份疏水剂H3构成的新制浴液中转鼓加工15分钟。 [1020] The thus dyed leather drummed in a freshly float composed of 80 parts of water and H3 I. 5 parts of a hydrophobic agent consisting of 15 minutes. 然后加入5份聚合鞣料G18,再在40分钟的转鼓加工时间后,添加I份助剂HM5、3份聚合鞣料G17、3份植物鞣料G23和2份鞣料G11。 Then 5 parts of polymeric tanning material G18, followed after 40 minutes drumming time, add auxiliary I HM5,3 parts parts parts G17,3 2 parts of vegetable tanning and tanning material G23 G11 polymeric tanning material. 再在45°C转鼓加工30分钟,然后添加3份聚合鞣料G19,再在45°C复鞣60分钟。 Reprocessing 30 minutes 45 ° C drum, and then add 3 parts of polymeric tanning material G19, followed retanning 45 ° C for 60 minutes. 然后添加70份水,再在60°C转鼓加工10分钟。 70 parts of water were then added, and then the processing drum at 60 ° C for 10 min. 将复鞣浴液与2. 5份加脂剂F7和2份加脂剂F4混合,再在60°C加脂60分钟。 The retanning float with 2.5 parts of fatliquor F7 and 2 parts of fatliquor F4 mixed, fatliquoring at 60 ° C for 60 minutes. 然后在60分钟的过程中每次少许地添加总共4份甲酸以达到3. 5的pH值。 Then each addition of a total of 4 parts of formic acid in the course of 60 minutes to achieve a pH value of 3.5. 然后使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float drops and the leather briefly rinsed cold.

[1021] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在60°C减压处理2分钟,在室温下悬浮干燥,修整,刮软并在60°C真空干燥2分钟。 [1021] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, 2 minutes at 60 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 60 ° C 2 minutes .

[1022] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的鞋面革。 [1022] This having excellent washing resistance, perspiration resistance, bleeding and the shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的鞋面革。 A shoe upper leather in one of Examples Ia to 59k dyes embodiment in an analogous manner.

[1023] 鞋面革配方22 : [1023] upper leather recipe 22:

[1024] 将削匀厚度为I. 9毫米的I块100重量份的传统铬鞣牛皮革在35°C在由200份水构成的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后在20分钟的过程中逐份添加总共3份碳酸氢钠以达到7. 8的中和pH值。 100 parts of the [1024] thickness of shaved I I. 9 mm bulk weight in a conventional chrome-tanned bovine leather 35 ° C in a bath consisting of 200 parts of water washed for 10 minutes and then at 40 ° C in a 100 parts of water and the float bowl I. 5 parts of sodium formate and processing for 5 minutes, after which a total of 3 parts by portionwise addition of sodium bicarbonate and the pH value of 7.8 in the course of 20 minutes. 将该脱酸浴液与10. 5份染料混合物13hp混合,然后在pH 7. 6和40°C下染色20分钟。 The deacidifying float 13hp dye mixture is mixed with 10.5 parts, and then dyed at pH 7. 6 and 40 ° C 20 min. 每次少许地添加总共9份碳酸钠以使浴液的pH值达到9. 5-10. 0之间以固色,然后在40。 Each addition of a total of 9 parts of sodium carbonate to bring the pH reaches between the float 9. 5-10. 0 for fixation, then 40. . 转鼓加工70分钟。 Drumming for 70 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过60分钟在200份水的浴液中逐份添加2份甲酸以达到4. 3的pH值。 Over 60 minutes by portionwise addition of 2 parts of formic acid to reach a pH of 4.3 in a float of 200 parts of water.

[1025] 将由此染色的皮革在由80份水和3份聚合鞣料G19构成的新制浴液中转鼓加工5分钟。 [1025] The thus dyed leather drummed in a freshly float composed of 80 parts water and 3 parts of polymeric tanning material G19 constituting 5 minutes. 然后加入6份复鞣料G2,再在30分钟的转鼓加工时间后,添加5份聚合鞣料G18、3份聚合鞣料G19和4份复鞣料G2。 Was then added 6 parts of retanning material G2, then after 30 minutes drumming time, the addition of 5 parts of polymeric tanning material G18,3 parts of polymeric tanning material G19 and 4 parts of retanning material G2. 再在45°C转鼓加工60分钟,然后添加70份水,并在65°C转鼓加工20分钟。 Reprocessing 60 minutes 45 ° C drum, and then 70 parts of water was added, and the processing drum at 65 ° C for 20 min. 将复鞣浴液与3份加脂剂Fl和2份加脂剂F2混合,再在65°C加脂60分钟。 The retanning float with 3 parts of fatliquor Fl 2 parts of fatliquor F2 and mixed, and then at 65 ° C fatliquoring for 60 minutes. 然后在60分钟的过程中毎次少许地添加总共4份甲酸以达到3.6的pH值。 Then in the course of 60 minutes every time addition of a total of 4 parts of formic acid to reach a pH of 3.6. 然后使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float drops and the leather briefly rinsed cold.

[1026] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥3分钟,用220规格的金刚砂纸进行正绒面革处理(nubucked),除尘并用绷革框干燥。 [1026] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 3 minutes , nubucked process (nubucked) 220 specifications with emery paper, dust and toggle frame dried.

[1027] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的直纹(direct-route)正绒面鞋面革。 [1027] This having excellent washing resistance, perspiration resistance, bleeding and rub-off fastness ruled (direct-route) nubuck shoe upper leather. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的直纹正绒面鞋面革。 Dyed with one of the dyes of Examples Ia to 59k in a similar manner nubuck shoe upper leather.

[1028] 鞋面革配方23 : [1028] upper leather recipe 23:

[1029] 将削匀厚度为2. 0毫米的I块100重量份的传统铬鞣牛皮革在35°C在由200份水构成的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后在20分钟的过程中逐份添加总共3份碳酸氢钠以达到7. 6的中和pH值。 Parts of [1029] shaved thickness of 2.0 mm by weight of I-block 100 in a conventional chrome-tanned bovine leather 35 ° C in a bath of 200 parts of water washed for 10 minutes and then at 40 ° C in a 100 parts of water and the float bowl I. 5 parts of sodium formate and processing for 5 minutes, after which a total of 3 parts by portionwise addition of sodium bicarbonate and the pH of 7.6 in the course of 20 minutes. 将该脱酸浴液与6. I份染料混合物13hw混合,然后在pH 7. 5和40°C下染色15分钟。 The deacidifying float 6. I admixed with parts of the dye mixture 13hw, and then dyed at pH 7. 5 and 40 ° C 15 min. 毎次少许地添加总共8份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加エ90分钟。 Once every addition of a total of 8 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, then add Ester drum at 40 ° C for 90 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 在60分钟的过程中在200份水的浴液中逐份添加2份甲酸以达到4. 2的pH值。 By portionwise addition of 2 parts of formic acid to reach a pH of 4.2 in the course of 60 minutes in a float of 200 parts of water.

[1030] 将由此染色的皮革在由80份水和I份醛鞣料G13构成的新制浴液中转鼓加工3分钟。 [1030] The thus dyed leather drummed in a freshly made 80 parts of water and float I G13 constituting parts of aldehyde tanning material for 3 minutes. 加入3份聚合鞣料G19后,将皮革再转鼓加工30分钟。 After addition of 3 parts of polymeric tanning material G19, then the leather was drummed for 30 minutes. 然后添加0. 8份碳酸氢钠。 Was then added 0.8 parts of sodium bicarbonate. 转鼓加工30分钟,然后在再转鼓加工30分钟之前、之后添加3份疏水剂H5,用5份聚合鞣料G18复鞣30分钟。 Drumming for 30 minutes and then 30 minutes before processing, after the addition of 3 parts of water repellent H5, with 5 parts of polymeric tanning material G18 for 30 minutes and then retanning drum. 将复鞣浴液与5份疏水剂Hl和0. 5份助剂HM4混合,然后在45°C加脂60分钟。 The retanning float was admixed with 5 parts of a hydrophobic agent and 0.5 parts of Hl auxiliary HM4, and then at 45 ° C fatliquoring for 60 minutes. 然后加入70份水,再在65°C转鼓加工20分钟。 70 parts of water were then added, and then processed at 65 ° C the drum for 20 minutes. 然后在60分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 It was then added portionwise 4 parts of formic acid to reach a pH of 3.5 in the course of 60 minutes. 此后使浴液滴出。 Thereafter the float was dropped. 将皮革在由150份水和0. 5份甲酸构成的新制浴液中在30°C转鼓加工10分钟。 The leather float in a freshly made 150 parts of water and 0.5 parts of formic acid at 30 ° C in the processing drum 10 min. 添加5份铬鞣料G24将疏水化在30°C固定90分钟。 Add 5 parts of chrome tanning material G24 hydrophobized fixed at 30 ° C for 90 minutes. 然后用300份水洗涤10分钟一次,此后将皮革在由300份水和0. 2份甲酸构成的浴液中转鼓加工10分钟。 Then washed once with 300 parts of water for 10 minutes, thereafter the leather was drummed in a float of 300 parts of water and 0.2 parts of formic acid for 10 minutes. 将皮革浙干并将皮革简单冷漂洗。 Zhejiang dry the leather and the leather briefly rinsed cold.

[1031] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥3分钟,用220规格的金刚砂纸进行正绒面革处理,除尘并用绷革框干燥。 [1031] The thus dyed, retanned and hydrophobic horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 3 minutes. nubucked treated with 220 gauge emery paper, dust and toggle frame dried.

[1032] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的疏水直纹正绒面鞋面革。 [1032] This having excellent washing resistance, perspiration resistance, bleeding and hydrophobic nubuck shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的疏水直纹正绒面鞋面革。 Dyed with one of the dyes of Examples Ia to 59k in a similar manner as hydrophobic nubuck shoe upper leather.

[1033] 鞋面革配方24 : [1033] upper leather recipe 24:

[1034] 将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在35°C在由200份水构成的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后在20分钟的过程中逐份添加总共3份碳酸氢钠以达到7. 5的中和pH值。 100 parts of the [1034] thickness was shaved I block I. 8 mm chrome-tanned bovine leather weight of conventional 35 ° C in a bath of 200 parts of water by a 10 minute wash, and then at 40 ° C in a 100 parts of water and the float bowl I. 5 parts of sodium formate and processing for 5 minutes, after which a total of 3 parts by portionwise addition of sodium bicarbonate and a pH of 7.5 in the course of 20 minutes. 将该脱酸浴液与9. 2份染料14混合,然后在pH 7. 5和40°C下染色25分钟。 The deacidifying float 9.2 is mixed with 14 parts of the dye, and then dyed at pH 7. 5 and 40 ° C 25 min. 每次少许地添加总共9份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工50分钟。 Each addition of a total of 9 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 50 minutes. 浴液改变之后,每次用300份水将皮革洗涤两次,一共洗涤60分钟。 After float change, the leather was washed twice each time, washed with a total of 60 minutes 300 parts of water. 在60分钟的过程中在200份水的浴液中逐份添加2份甲酸以达到4. 3的pH值。 By portionwise addition of 2 parts of formic acid to reach a pH of 4.3 in a float of 200 parts of water in the course of 60 minutes.

[1035] 将由此染色的皮革在由80份水和3份聚合鞣料G19构成的新制浴液中转鼓加工15分钟。 [1035] The thus dyed leather drummed in a freshly float composed of 80 parts water and 3 parts of polymeric tanning material constituting G19 for 15 minutes. 此后,加入2份疏水剂Hl。 Thereafter, 2 parts of a hydrophobic agent Hl. 转鼓加工15分钟,然后加入5份聚合鞣料G18、3份复鞣料Gl和I份聚合鞣料G19,然后复鞣30分钟。 Drumming for 15 minutes, followed by addition of 5 parts of polymeric tanning material G18,3 parts Gl and I retanning material G19 parts of polymeric tanning, retanning and 30 minutes. 将复鞣浴液与4份疏水剂Hl和0. 3份助剂HM4混合,然后在45°C加脂60分钟。 The retanning float was admixed with 4 parts of a hydrophobic agent and 0.3 parts of Hl auxiliary HM4, and then at 45 ° C fatliquoring for 60 minutes. 然后加入70份水,再在65°C转鼓加工20分钟。 70 parts of water were then added, and then processed at 65 ° C the drum for 20 minutes. 然·后在60分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 Then 4 parts · by portionwise addition of formic acid to reach a pH of 3.5 in the course of 60 minutes. 此后使浴液滴出。 Thereafter the float was dropped. 将皮革在由150份水和0. 5份甲酸构成的新制浴液中在30°C转鼓加工10分钟。 The leather float in a freshly made 150 parts of water and 0.5 parts of formic acid at 30 ° C in the processing drum 10 min. 添加5份铬鞣料G24将疏水化在30°C固定90分钟。 Add 5 parts of chrome tanning material G24 hydrophobized fixed at 30 ° C for 90 minutes. 然后用300份水洗涤10分钟一次,此后将皮革在由300份水和0. 2份甲酸构成的浴液中转鼓加工10分钟。 Then washed once with 300 parts of water for 10 minutes, thereafter the leather was drummed in a float of 300 parts of water and 0.2 parts of formic acid for 10 minutes. 将皮革浙干并将皮革简单冷漂洗。 Zhejiang dry the leather and the leather briefly rinsed cold.

[1036] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥3分钟,用220规格的金刚砂纸进行正绒面革处理,除尘并用绷革框干燥。 [1036] The thus dyed, retanned and hydrophobic horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 3 minutes. nubucked treated with 220 gauge emery paper, dust and toggle frame dried.

[1037] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的疏水直纹正绒面鞋面革。 [1037] This having excellent washing resistance, perspiration resistance, bleeding and hydrophobic nubuck shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的疏水直纹正绒面鞋面革。 Dyed with one of the dyes of Examples Ia to 59k in a similar manner as hydrophobic nubuck shoe upper leather.

[1038] 鞋面革配方25 : [1038] upper leather recipe 25:

[1039] 将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在35°C在由200份水构成的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后在20分钟的过程中逐份添加总共3份碳酸氢钠以达到7. 5的中和pH值。 100 parts of the [1039] thickness was shaved I block I. 8 mm chrome-tanned bovine leather weight of conventional 35 ° C in a bath of 200 parts of water by a 10 minute wash, and then at 40 ° C in a 100 parts of water and the float bowl I. 5 parts of sodium formate and processing for 5 minutes, after which a total of 3 parts by portionwise addition of sodium bicarbonate and a pH of 7.5 in the course of 20 minutes. 将该脱酸浴液与6. 8份染料15混合,然后在pH 7. 5和40°C下染色30分钟。 The deacidifying float 6.8 is mixed with 15 parts of dye, and then dyed at pH 7. 5 and 40 ° C 30 min. 每次少许地添加总共8份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工90分钟。 Each addition of a total of 8 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 90 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 在90分钟的过程中在200份水的浴液中逐份添加5份甲酸以达到3. 0的pH值。 In the course of 90 minutes by portionwise addition of 5 parts of formic acid in the bath 200 parts of water to achieve a pH value of 3.0.

[1040] 将由此染色的皮革在由80份水和0. 4份甲酸构成的新制浴液中转鼓加工10分钟。 [1040] The thus dyed leather drummed in a freshly float composed of 80 parts of water and 0.4 parts of formic acid for 10 minutes. 然后加入I份复鞣料G14,再转鼓加工30分钟。 I then added parts retanning material G14, before drumming for 30 minutes. 然后加入4份铬鞣料G24和2份复鞣料G28。 Followed by addition of 4 parts of chrome tanning material G24 and 2 parts of retanning material G28. 在30分钟的转鼓加工时间后,添加0. 5份甲酸钠,再重新铬鞣60分钟。 After drumming time of 30 minutes, 0.5 parts of sodium formate was added, and then re-tanning 60 minutes. 将该浴液与100份水混合,再转鼓加工过夜。 The float mixed with 100 parts of water before drumming overnight. 然后使浴液滴出。 Thereafter, the float drops out.

[1041] 将皮革在由80份水、I. 5份甲酸钠和0. 5份碳酸氢钠构成的新制浴液中在30°C转鼓加工30分钟。 [1041] The leather float in a freshly made 80 parts of water, I. 5 parts of sodium bicarbonate and 0.5 parts of the configuration of the processing drum 30 ° C for 30 minutes. 然后加入2份聚合鞣料G19。 2 parts of polymeric tanning material G19 were then added. 在15分钟的转鼓加工时间后,加入2份疏水剂H1,再转鼓加工15分钟。 After drumming time of 15 minutes, was added 2 parts of hydrophobic agent H1, then drummed for 15 minutes. 加入5份聚合鞣料G18,并转鼓加工30分钟,然后为完成鞣革,添加4份复鞣料G28和3份复鞣料Gl I,然后再复鞣30分钟。 Was added 5 parts of polymeric tanning material G18, and drumming for 30 minutes and then to complete the tanning, retanning material was added 4 parts of 3 parts of retanning material G28 and Gl I, and then 30 minutes of retanning. 将复鞣浴液与4份疏水剂Hl和o. 3份助剂HM4混合,然后加脂60分钟。 The retanning float and 4 parts of a hydrophobic agent and Hl o. 3 parts of auxiliary HM4 mixed and fatliquoring for 60 minutes. 然后在该浴液中加入70份水,再在65°C转鼓加エ20分钟。 70 parts of water were then added in the bath, and then added to the drum Ester at 65 ° C for 20 min. 然后在45分钟的过程中逐份添加总共3. 5份甲酸以达到3. 5的pH值。 It was then added portionwise a total of 3.5 parts of formic acid to reach a pH of 3.5 in the course of 45 minutes. 将皮革在由150份水和0. 5份甲酸构成的新制浴液中在30°C转鼓加工10分钟。 The leather float in a freshly made 150 parts of water and 0.5 parts of formic acid at 30 ° C in the processing drum 10 min. 添加5份铬鞣料G24将疏水化在30°C固定90分钟。 Add 5 parts of chrome tanning material G24 hydrophobized fixed at 30 ° C for 90 minutes. 然后用300份水洗涤10分钟一次,此后将皮革在由300份水和0. 2份甲酸构成的浴液中转鼓加工10分钟。 Then washed once with 300 parts of water for 10 minutes, thereafter the leather was drummed in a float of 300 parts of water and 0.2 parts of formic acid for 10 minutes. 将皮革浙干并将皮革简单冷漂洗。 Zhejiang dry the leather and the leather briefly rinsed cold.

[1042] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥3分钟,用220规格的金刚砂纸进行正绒面革处理,除尘并用绷革框干燥。 [1042] The thus dyed, retanned and hydrophobic horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 3 minutes. nubucked treated with 220 gauge emery paper, dust and toggle frame dried.

[1043] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的疏水直纹正绒面鞋面革。 [1043] This having excellent washing resistance, perspiration resistance, bleeding and hydrophobic nubuck shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的疏水直纹正绒面鞋面革。 Dyed with one of the dyes of Examples Ia to 59k in a similar manner as hydrophobic nubuck shoe upper leather.

[1044] 鞋面革配方26 :· [1044] upper leather recipe 26: -

[1045] 将削匀厚度为I. 9毫米的I块100重量份的传统铬鞣牛皮革在35°C在由200份水构成的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后在20分钟的过程中逐份添加总共3份碳酸氢钠以达到7. 6的中和pH值。 100 parts of the [1045] thickness of shaved I I. 9 mm bulk weight in a conventional chrome-tanned bovine leather 35 ° C in a bath consisting of 200 parts of water washed for 10 minutes and then at 40 ° C in a 100 parts of water and the float bowl I. 5 parts of sodium formate and processing for 5 minutes, after which a total of 3 parts by portionwise addition of sodium bicarbonate and the pH of 7.6 in the course of 20 minutes. 将该脱酸浴液与8. 8份染料16j混合,然后在pH 7. 5和40°C下染色40分钟。 The deacidifying float was admixed with 8.8 parts of dye 16j, and then dyed at pH 7. 5 and 40 ° C 40 min. 每次少许地添加总共8份碳酸钠以使浴液的pH值达到9. 1-9. 7之间以固色,然后在40°C转鼓加工60分钟。 Each addition of a total of 8 parts of sodium carbonate to bring the pH reaches between the float 9. 1-9. 7 for fixation, 40 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤两次,一共洗涤60分钟。 After float change, the leather was washed twice each time, washed with a total of 60 minutes 300 parts of water. 在60分钟的过程中在200份水的浴液中逐份添加2份甲酸以达到4. 2的pH值。 By portionwise addition of 2 parts of formic acid to reach a pH of 4.2 in the course of 60 minutes in a float of 200 parts of water.

[1046] 将由此染色的皮革在由80份水和I份复鞣料G14构成的新制浴液中转鼓加工5分钟。 [1046] The thus dyed leather drummed in a freshly made 80 parts of water and float I G14 of retanning material constituting parts 5 minutes. 然后加入2份聚合鞣料G19,再在15分钟的转鼓加工时间后,添加5份聚合鞣料G18。 Then 2 parts of polymeric tanning material G19, followed after 15 minutes drumming time, the addition of 5 parts of polymeric tanning material G18. 再在45°C转鼓加工40分钟,然后添加3份植物鞣料G22和3份复鞣料G28,再在45°C复鞣60分钟。 And then for 40 minutes at 45 ° C drum, and then add 3 parts 3 parts of vegetable tanning material G22 and G28 of retanning material, and then retanned at 45 ° C for 60 minutes. 然后加入70份水,再在60°C转鼓加工10分钟。 70 parts of water were then added, and then the processing drum at 60 ° C for 10 min. 将复鞣浴液与2. 5份加脂剂Fl和2. 5份疏水剂H3混合并在50°C加脂60分钟。 The retanning float with 2.5 parts of fatliquor Fl and 2.5 parts of a hydrophobic agent and fatliquoring H3 mixed at 50 ° C 60 min. 然后在60分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 It was then added portionwise 4 parts of formic acid to reach a pH of 3.5 in the course of 60 minutes. 然后使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float drops and the leather briefly rinsed cold.

[1047] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥3分钟,用220规格的金刚砂纸进行正绒面革处理,除尘并用绷革框干燥。 [1047] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 3 minutes , nubucked treatment, dust with size of 220 emery paper and toggle frame dried.

[1048] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的直纹正绒面鞋面革。 [1048] This having excellent washing resistance, perspiration resistance, bleeding and nubuck shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的直纹正绒面鞋面革。 Dyed with one of the dyes of Examples Ia to 59k in a similar manner nubuck shoe upper leather.

[1049] 鞋面革配方27 : [1049] upper leather recipe 27:

[1050] 将削匀厚度为I. 9毫米的I块100重量份的传统铬鞣牛皮革在35°C在由200份水构成的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后在20分钟的过程中逐份添加总共3份碳酸氢钠以达到7. 6的中和pH值。 100 parts of the [1050] thickness of shaved I I. 9 mm bulk weight in a conventional chrome-tanned bovine leather 35 ° C in a bath consisting of 200 parts of water washed for 10 minutes and then at 40 ° C in a 100 parts of water and the float bowl I. 5 parts of sodium formate and processing for 5 minutes, after which a total of 3 parts by portionwise addition of sodium bicarbonate and the pH of 7.6 in the course of 20 minutes. 将该脱酸浴液与9份染料17b混合,然后在pH 7. 5和40°C下染色40分钟。 The deacidifying float was admixed with 9 parts of dye 17b, and then dyed at pH 7. 5 and 40 ° C 40 min. 毎次少许地添加总共9. 5份碳酸钠以使浴液的pH值达到9. 2-9. 8之间以固色,然后在40°C转鼓加工60分钟。 Once every addition of a total 9.5 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 8 for fixation, 40 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤两次,一共洗涤60分钟。 After float change, the leather was washed twice each time, washed with a total of 60 minutes 300 parts of water. 在60分钟的过程中在200份水的浴液中逐份添加2份甲酸以达到4. 3的pH值。 By portionwise addition of 2 parts of formic acid to reach a pH of 4.3 in a float of 200 parts of water in the course of 60 minutes.

[1051] 将由此染色的皮革在由80份水和I份复鞣料G14构成的新制浴液中在45°C转鼓加工5分钟。 [1051] The leather thus dyed in a freshly made 80 parts of water and float I G14 of retanning material constituting parts of the processing drum at 45 ° C for 5 minutes. 然后加入2份聚合鞣料G19,再在15分钟的转鼓加工时间后,添加5份聚合鞣料G18。 Then 2 parts of polymeric tanning material G19, followed after 15 minutes drumming time, the addition of 5 parts of polymeric tanning material G18. 再在45°C转鼓加工40分钟,然后添加4份树脂鞣料G28和4份树脂鞣料Gl I,再在45°C复鞣60分钟。 And then for 40 minutes at 45 ° C drum, and then 4 parts of resin tanning material was added 4 parts of resin tanning material G28 and Gl I, and then retanned at 45 ° C for 60 minutes. 然后加入70份水,再在60°C转鼓加工10分钟。 70 parts of water were then added, and then the processing drum at 60 ° C for 10 min. 将复鞣浴液与2. 5份加脂剂Fl和2. 5份疏水剂H3混合并在55°C加脂60分钟。 The retanning float was admixed with 2.5 parts of fatliquor Fl and 2.5 parts of a hydrophobic agent and fatliquoring H3 at 55 ° C 60 min. 然后在60分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 It was then added portionwise 4 parts of formic acid to reach a pH of 3.5 in the course of 60 minutes. 然后使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float drops and the leather briefly rinsed cold.

[1052] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥3分钟,用220规格的金刚砂纸进行正绒面革处理,除尘并用绷革框干燥。 [1052] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 3 minutes , nubucked treatment, dust with size of 220 emery paper and toggle frame dried.

[1053] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的直纹正绒面鞋面革。 [1053] This having excellent washing resistance, perspiration resistance, bleeding and nubuck shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的直纹正绒面鞋面革。 Dyed with one of the dyes of Examples Ia to 59k in a similar manner nubuck shoe upper leather.

[1054] 鞋面革配方28 : [1054] upper leather recipe 28:

[1055] 将削匀厚度为I. 9毫米的I块100重量份的传统铬鞣牛皮革在35°C在由200份水构成的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后在20分钟的过程中逐份添加总共3份碳酸氢钠以达到7. 6的中和pH值。 100 parts of the [1055] thickness of shaved I I. 9 mm bulk weight in a conventional chrome-tanned bovine leather 35 ° C in a bath consisting of 200 parts of water washed for 10 minutes and then at 40 ° C in a 100 parts of water and the float bowl I. 5 parts of sodium formate and processing for 5 minutes, after which a total of 3 parts by portionwise addition of sodium bicarbonate and the pH of 7.6 in the course of 20 minutes. ·将该脱酸浴液与5份染料19混合,然后在pH 7. 5和40°C下染色40分钟。 · The acid was mixed with 19 parts of 5 float off the dye, and then dyed at pH 7. 5 and 40 ° C 40 min. 毎次少许地添加总共6. 5份碳酸钠以使浴液的pH值达到9. 2-9. 8之间以固色,然后在40°C转鼓加工65分钟。 Once every addition of a total 6.5 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 8 for fixation, 40 ° C and then processed in the drum for 65 minutes. 浴液改变之后,每次用300份水将皮革洗涤两次,一共洗涤60分钟。 After float change, the leather was washed twice each time, washed with a total of 60 minutes 300 parts of water. 在60分钟的过程中在200份水的浴液中逐份添加总共2份甲酸以达到4. 3的pH值。 By portionwise addition of a total of 2 parts of formic acid to reach a pH of 4.3 in a float of 200 parts of water in the course of 60 minutes.

[1056] 将由此染色的皮革在由80份水和I份复鞣料G14构成的新制浴液中在45°C转鼓加工5分钟。 [1056] The leather thus dyed in a freshly made 80 parts of water and float I G14 of retanning material constituting parts of the processing drum at 45 ° C for 5 minutes. 然后加入2份聚合鞣料G19,再在15分钟的转鼓加工时间后,添加5份聚合鞣料G18。 Then 2 parts of polymeric tanning material G19, followed after 15 minutes drumming time, the addition of 5 parts of polymeric tanning material G18. 再在45°C转鼓加工40分钟,然后添加2份植物鞣料G22和4份树脂鞣料G28,再在45°C复鞣60分钟。 And then for 40 minutes at 45 ° C drum, and then 2 parts of vegetable tanning material was added 4 parts of resin tanning material G22 and G28, and then retanned at 45 ° C for 60 minutes. 然后加入70份水,再在60°C转鼓加工10分钟。 70 parts of water were then added, and then the processing drum at 60 ° C for 10 min. 将复鞣浴液与2. 5份加脂剂Fl和2. 5份疏水剂H3混合并在60°C加脂60分钟。 The retanning float was admixed with 2.5 parts of fatliquor Fl and 2.5 parts of a hydrophobic agent and fatliquoring H3 at 60 ° C 60 min. 然后在50分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 It was then added portionwise 4 parts of formic acid to reach a pH of 3.5 in the course of 50 minutes. 然后使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float drops and the leather briefly rinsed cold.

[1057] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥3分钟,用220规格的金刚砂纸进行正绒面革处理,除尘并用绷革框干燥。 [1057] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 3 minutes , nubucked treatment, dust with size of 220 emery paper and toggle frame dried.

[1058] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的直纹正绒面鞋面革。 [1058] This having excellent washing resistance, perspiration resistance, bleeding and nubuck shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的直纹正绒面鞋面革。 Dyed with one of the dyes of Examples Ia to 59k in a similar manner nubuck shoe upper leather.

[1059] 鞋面革配方29 : [1059] upper leather recipe 29:

[1060] 将削匀厚度为I. 9毫米的I块100重量份的传统铬鞣牛皮革在35°C在由200份水构成的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后在20分钟的过程中逐份添加总共3份碳酸氢钠以达到7. 6的中和pH值。 Parts of [1060] shaved thickness of I mm I. 9 wt block 100 conventionally chrome-tanned bovine leather float at 35 ° C in 200 parts of water by a 10 minute wash, and then at 40 ° C in a 100 parts of water and the float bowl I. 5 parts of sodium formate and processing for 5 minutes, after which a total of 3 parts by portionwise addition of sodium bicarbonate and the pH of 7.6 in the course of 20 minutes. 将该脱酸浴液与7. I份染料22混合,然后在pH 7. 5和40°C下染色40分钟。 The deacidifying float 7. I dye is mixed with 22 parts, and then dyed at pH 7. 5 and 40 ° C 40 min. 每次少许地添加总共8份碳酸钠以使浴液的pH值达到9. 2-9. 8之间以固色,然后在40°C转鼓加工60分钟。 Each addition of a total of 8 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 8 for fixation, 40 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤两次,一共洗涤60分钟。 After float change, the leather was washed twice each time, washed with a total of 60 minutes 300 parts of water. 在60分钟的过程中在200份水的浴液中逐份添加3份甲酸以达到3. 9的pH值。 By portionwise addition of 3 parts of formic acid to reach a pH of 3.9 in the course of 60 minutes in a float of 200 parts of water.

[1061] 将由此染色的皮革在由80份水和2份复鞣料G29构成的新制浴液中在45°C转鼓加工20分钟。 [1061] The leather dyed in a freshly thus the float 80 parts of water and 2 parts of retanning material G29 in the configuration of the processing drum 45 ° C for 20 min. 然后加入2份聚合鞣料G19,再在15分钟的转鼓加工时间后,添加5份聚合鞣料G18。 Then 2 parts of polymeric tanning material G19, followed after 15 minutes drumming time, the addition of 5 parts of polymeric tanning material G18. 再在45°C转鼓加工40分钟,然后添加4份树脂鞣料G28和4份树脂鞣料G11,再在45°C复鞣60分钟。 And then for 40 minutes at 45 ° C drum, and then 4 parts of resin tanning material was added 4 parts of resin tanning material G28 and G11, and then retanned at 45 ° C for 60 minutes. 然后加入70份水,再在60°C转鼓加工10分钟。 70 parts of water were then added, and then the processing drum at 60 ° C for 10 min. 将复鞣浴液与2. 5份加脂剂Fl和2. 5份疏水剂H3混合并在55°C加脂60分钟。 The retanning float was admixed with 2.5 parts of fatliquor Fl and 2.5 parts of a hydrophobic agent and fatliquoring H3 at 55 ° C 60 min. 然后在60分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 It was then added portionwise 4 parts of formic acid to reach a pH of 3.5 in the course of 60 minutes. 然后使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float drops and the leather briefly rinsed cold.

[1062] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥3分钟,用220规格的金刚砂纸进行正绒面革处理,除尘并用绷革框干燥。 [1062] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 3 minutes , nubucked treatment, dust with size of 220 emery paper and toggle frame dried.

[1063] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的直纹正绒面鞋面革。 [1063] This having excellent washing resistance, perspiration resistance, bleeding and nubuck shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的直纹正绒面鞋面革。 Dyed with one of the dyes of Examples Ia to 59k in a similar manner nubuck shoe upper leather.

[1064] 鞋面革配方30 : [1064] upper leather recipe 30:

[1065] 将削匀厚度为2. 0毫米的I块100重量份的传统铬鞣牛皮革在35°C在由200份水构成的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓·加工5分钟,此后在20分钟的过程中逐份添加总共3份碳酸氢钠以达到7. 6的中和pH值。 Parts of [1065] shaved thickness of 2.0 mm by weight of I-block 100 in a conventional chrome-tanned bovine leather 35 ° C in a bath of 200 parts of water washed for 10 minutes and then at 40 ° C in a 100 parts of water and I. 5 parts of sodium formate drum-processing bath for 5 minutes, after which the course of 20 minutes by portionwise addition of a total of 3 parts of sodium bicarbonate and a pH of 7.6. 将该脱酸浴液与7. 2份染料24混合,然后在pH 7. 5和40°C下染色40分钟。 The deacidifying float 7.2 is mixed with 24 parts of the dye, and then dyed at pH 7. 5 and 40 ° C 40 min. 每次少许地添加总共8份碳酸钠以使浴液的pH值达到9. 2-9. 8之间以固色,然后在40°C转鼓加工60分钟。 Each addition of a total of 8 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 8 for fixation, 40 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤两次,一共洗涤60分钟。 After float change, the leather was washed twice each time, washed with a total of 60 minutes 300 parts of water. 在60分钟的过程中在200份水的浴液中逐份添加4份甲酸以达到4. 0的pH值。 In the course of 60 minutes by portionwise addition of 4 parts of 200 parts of formic acid in the bath water to a pH of 4.0.

[1066] 将由此染色的皮革在由80份水和3份复鞣料G25构成的新制浴液中在45°C转鼓加工5分钟。 [1066] The leather thus dyed in a freshly float composed of 80 parts water and 3 parts of retanning material G25 in the configuration of the processing drum 45 ° C for 5 minutes. 然后加入2份聚合鞣料G19,再在15分钟的转鼓加工时间后,添加5份聚合鞣料G18。 Then 2 parts of polymeric tanning material G19, followed after 15 minutes drumming time, the addition of 5 parts of polymeric tanning material G18. 再在45°C转鼓加工40分钟,然后添加4份树脂鞣料G28和4份树脂鞣料Gl I,再在45°C复鞣60分钟。 And then for 40 minutes at 45 ° C drum, and then 4 parts of resin tanning material was added 4 parts of resin tanning material G28 and Gl I, and then retanned at 45 ° C for 60 minutes. 然后加入70份水,再在60°C转鼓加工10分钟。 70 parts of water were then added, and then the processing drum at 60 ° C for 10 min. 将复鞣浴液与2. 5份加脂剂Fl和2. 5份疏水剂H3混合并在55°C加脂60分钟。 The retanning float was admixed with 2.5 parts of fatliquor Fl and 2.5 parts of a hydrophobic agent and fatliquoring H3 at 55 ° C 60 min. 然后在60分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 It was then added portionwise 4 parts of formic acid to reach a pH of 3.5 in the course of 60 minutes. 然后使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float drops and the leather briefly rinsed cold.

[1067] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥3分钟,用220规格的金刚砂纸进行正绒面革处理,除尘并用绷革框干燥。 [1067] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 3 minutes , nubucked treatment, dust with size of 220 emery paper and toggle frame dried.

[1068] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的直纹正绒面鞋面革。 [1068] This having excellent washing resistance, perspiration resistance, bleeding and nubuck shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的直纹正绒面鞋面革。 Dyed with one of the dyes of Examples Ia to 59k in a similar manner nubuck shoe upper leather.

[1069] 鞋面革配方31: [1069] upper leather recipe 31:

[1070] 将削匀厚度为2. 0毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,然后在25分钟的过程中毎次少许地添加总共3份碳酸氢钠以达到7. 7的中和pH值。 100 parts [1070] The shaved thickness of 2.0 mm by weight of the block I conventionally chrome-tanned bovine leather bath at 35 ° C in 200 parts of water washed for 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, then a total of 3 parts of sodium bicarbonate was added in the course of 25 minutes in a little at every time in order to achieve a pH of 7.7 and a. 将该脱酸浴液与4. 9份染料28a混合,然后在pH 7. 5和40°C下染色30分钟。 The deacidifying float 28a 4.9 parts of dye mixed with, and then dyed at pH 7. 5 and 40 ° C 30 min. 每次少许地添加总共6. 8份碳酸钠以使浴液的pH值达到9. 5-10. 0之间以固色,然后在40°C转鼓加工60分钟。 Little at a time to add a total of 6.8 parts of sodium carbonate to bring the pH reaches between the float 9. 5-10. 0 for fixation, 40 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤两次,一共洗涤60分钟。 After float change, the leather was washed twice each time, washed with a total of 60 minutes 300 parts of water. 在50分钟的过程中在200份水的浴液中逐份添加总共I. 5份甲酸以达到5. 5的pH值。 It was added portionwise a total of I. 5 parts of formic acid to reach a pH of 5.5 in a float of 200 parts of water in the course of 50 minutes.

[1071] 将由此染色的皮革在由80份水和5份疏水剂H5构成的新制浴液中在45°C转鼓加エ20分钟。 [1071] The leather thus dyed in a freshly float composed of 80 parts water and 5 parts of a hydrophobic agent consisting of H5 added Ester drum at 45 ° C for 20 min. 然后加入5份聚合鞣料G18,再在40分钟的转鼓加工时间后,添加5份疏水剂Hl和0. 3份助剂HM4。 Then 5 parts of polymeric tanning material G18, followed after 40 minutes drumming time, adding 5 parts of a hydrophobic agent, and 0.3 parts of Hl auxiliary HM4. 在45°C加脂60分钟后,加入70份水,再在60°C转鼓加工10分钟。 After fatliquoring 45 ° C for 60 minutes was added 70 parts of water, and then the processing drum at 60 ° C for 10 min. 在60分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 In the course of 60 minutes by portionwise addition of 4 parts of formic acid to reach a pH of 3.5. 此后使浴液滴出并将皮革在由150份水和0. 5份甲酸构成的新制浴液中转鼓加工5分钟。 Thereafter, the float was dropped and the leather drummed in a freshly 150 parts of water by a float and 0.5 parts of formic acid for 5 minutes. 添加5份铬鞣料G24,然后固色90分钟。 Add 5 parts of chrome tanning material G24, then fixing for 90 minutes. 最后,将皮革在30°C用300份水漂洗10分钟,此漂洗进行两次。 Finally, the leather rinsed at 30 ° C for 10 minutes 300 parts of water, this rinse twice.

[1072] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥过夜,修整,刮软并在55°C真空干燥2分钟。 [1072] The thus dyed, retanned and hydrophobic horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo at 55 ° C 2 minutes .

[1073] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的疏水鞋面革。 [1073] This having excellent washing resistance, perspiration resistance, bleeding and hydrophobic shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的疏水鞋面革。 May be made hydrophobic shoe upper leather dyed with one of the dyes of Examples Ia to 59k embodiment in an analogous manner.

[1074] 鞋面革配方32 : [1074] upper leather recipe 32:

[1075] 将削匀厚度为I. 9毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,然后在25分钟的过程中毎次少许地添加总共3份碳酸氢钠并达到7. 7的中和pH值。 100 parts of the [1075] thickness of shaved I I. 9 mm bulk weight in a conventional chrome-tanned bovine leather in 35 ° C water bath was washed with 200 parts of 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes and then added to reach a total of 3 parts of sodium hydrogen carbonate and the pH value of 7.7 and in the course of 25 minutes in a little at every time. 在该脱酸浴液中加入9. I份染料30,然后在pH 7. 6和40°C下染色40分钟。 9. I was added 30 parts of the dye deacidifying float before dyeing at pH 7. 6 and 40 ° C 40 min. 每次少许地添加总共9. 2份固体碳酸钠以使浴液的pH值达到9. 3-9. 8之间以固色,然后在40°C转鼓加工·60分钟。 Each addition of a total 9.2 parts of solid sodium carbonate to bring the pH of the float 9 reaches between 3-9. 8 for fixation, then drummed at 40 ° C-60 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过50分钟在150份水的浴液中每次少许地添加总共2份甲酸以达到4. 3的pH值。 50 minutes after each addition of a total of 2 parts of formic acid in 150 parts of water bath, at a pH of 4.3.

[1076] 将由此染色的皮革在由80份水、I. 5份复鞣料G13和2份聚合鞣料G19构成的新制浴液中在45°C转鼓加工40分钟。 [1076] The leather thus dyed in a freshly made 80 parts of water float, I. 5 parts 2 parts of retanning material G13 and G19 constituting the polymeric tanning material processed at 45 ° C the drum for 40 minutes. 然后加入0. 7份碳酸氢钠以在20分钟的转鼓加工时间后获得5. 5的pH值。 0.7 parts of sodium hydrogencarbonate was then added to obtain a pH value of 5.5 after 20 minutes drumming time. 然后加入3份疏水剂Hl和0. 2份助剂HM4,此后转鼓加工20分钟。 Then 3 parts of a hydrophobic agent, and 0.2 parts of Hl auxiliary HM4, after drumming for 20 minutes. 加入6份聚合鞣料G18后,再复鞣30分钟。 After addition of 6 parts of polymeric tanning material G18, retanning further 30 minutes. 为了将皮革加脂,添加5份疏水剂Hl和0. 3份助剂HM4,并转鼓加工60分钟。 To fatliquoring, adding 5 parts of a hydrophobic agent, and 0.3 parts of Hl auxiliary HM4, and drummed for 60 minutes. 然后加入70份水。 Then 70 parts of water was added. 在60°C转鼓加工10分钟后,在60分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 After drumming 60 ° C for 10 minutes, in the course of 60 minutes by portionwise addition of 4 parts of formic acid to reach a pH of 3.5. 此后使浴液滴出并将皮革在由150份水和0. 5份甲酸构成的新制浴液中转鼓加工5分钟。 Thereafter, the float was dropped and the leather drummed in a freshly 150 parts of water by a float and 0.5 parts of formic acid for 5 minutes. 添加5份铬鞣料G24,然后固色90分钟。 Add 5 parts of chrome tanning material G24, then fixing for 90 minutes. 最后,将皮革在30°C用300份水漂洗10分钟,此漂洗进行两次。 Finally, the leather rinsed at 30 ° C for 10 minutes 300 parts of water, this rinse twice.

[1077] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥过夜,修整,刮软并在55°C真空干燥2分钟。 [1077] The thus dyed, retanned and hydrophobic horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo at 55 ° C 2 minutes .

[1078] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的疏水的柔软鞋面革。 [1078] This having excellent washing resistance, perspiration resistance, bleeding soft shoe upper leather hydrophobic and scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的疏水的柔软鞋面革。 Dyed with one of the dyes of Examples Ia to 59k in a similar manner as hydrophobic soft shoe upper leather.

[1079] 鞋面革配方33: [1079] upper leather recipe 33:

[1080] 将削匀厚度为2. 0毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,然后在25分钟的过程中毎次少许地添加总共3份碳酸氢钠以达到7. 7的中和pH值。 100 parts [1080] The shaved thickness of 2.0 mm by weight of the block I conventionally chrome-tanned bovine leather bath at 35 ° C in 200 parts of water washed for 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, then a total of 3 parts of sodium bicarbonate was added in the course of 25 minutes in a little at every time in order to achieve a pH of 7.7 and a. 将该脱酸浴液与9. 9份染料32混合,然后在pH 7. 6和40°C下染色40分钟。 The float 32 deacidifying mixed with 9.9 parts of dye, and then dyed at pH 7. 6 and 40 ° C 40 min. 逐份添加总共 Collate add a total of

10. 0份碳酸钠以使浴液的pH值达到9. 2-9. 7之间以固色,然后在40°C转鼓加工60分钟。 10.0 parts of sodium carbonate to bring the pH of the float for fixation between 9. 2-9. 7, 40 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用总共300份水将皮革洗涤两次,一共洗涤60分钟。 After float change, the leather was washed twice each time, washed with a total of 60 minutes with a total of 300 parts of water. 在50分钟的过程中在200份水的浴液中逐份添加总共I. 5份甲酸以达到5. 4的pH值。 It was added portionwise a total of I. 5 parts of formic acid to reach a pH of 5.4 in a float of 200 parts of water in the course of 50 minutes.

[1081] 将由此染色的皮革在由80份水和3份聚合鞣料G19构成的新制浴液中在45°C转鼓加工15分钟。 [1081] The leather thus dyed in a freshly float composed of 80 parts water and 3 parts of polymeric tanning material G19 in the configuration of the processing drum 45 ° C for 15 min. 然后加入I. 5份疏水剂H1,然后转鼓加工15分钟。 Followed by addition of a hydrophobic agent I. 5 parts H1, then drummed for 15 minutes. 加入5份聚合鞣料G18,然后再复鞣30分钟。 Was added 5 parts of polymeric tanning material G18, and then 30 minutes of retanning. 然后加入2份植物鞣料G22、2份复鞣料Gl、2份树脂鞣料G28和3份复鞣料Gl I,再转鼓加工30分钟。 Then 2 parts of vegetable tanning retanning of Gl G22,2 parts, 2 parts, and 3 parts of resin tanning material G28 of retanning material Gl I added, then drummed for 30 minutes. 为了将皮革加脂,添加4. 5份疏水剂Hl和0. 3份助剂HM4,并转鼓加工60分钟。 To fatliquoring, was added 4.5 parts of a hydrophobic agent, and 0.3 parts of Hl auxiliary HM4, and drummed for 60 minutes. 然后加入70份水。 Then 70 parts of water was added. 在60°C转鼓加工10分钟后,在50分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 After drumming 60 ° C for 10 minutes, in the course of 50 minutes by portionwise addition of 4 parts of formic acid to reach a pH of 3.5. 此后使浴液滴出并将皮革在由150份水和 Thereafter, the float was dropped and the leather by 150 parts of water and

0. 5份甲酸构成的新制浴液中转鼓加工10分钟。 0.5 parts of formic acid the drum float freshly processed for 10 minutes. 添加5份铬鞣料G24,然后固色90分钟。 Add 5 parts of chrome tanning material G24, then fixing for 90 minutes. 此后用300份水在30°C洗涤10分钟一次,并用由300份水和0. 2份甲酸构成的浴液洗涤ー After washing with 300 parts of water at 30 ° C 10 minutes, the bath and treated with 300 parts of water and 0.2 parts of formic acid was washed ー

次。 Times. 最后,将皮革简单漂洗。 Finally, the leather briefly rinsed.

[1082] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥2分钟。 [1082] The thus dyed, retanned and hydrophobic horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 2 min.

[1083] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的疏水鞋面革。 [1083] This having excellent washing resistance, perspiration resistance, bleeding and hydrophobic shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的疏水鞋面革。 May be made hydrophobic shoe upper leather dyed with one of the dyes of Examples Ia to 59k embodiment in an analogous manner.

[1084] 鞋面革配方34 : [1084] upper leather recipe 34:

[1085] 将削匀厚度为I. 8-2. 0毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加エ5分钟,然后在25分钟的过程中每次少许地添加总共3份碳酸氢钠以达到7. 7的中和pH值。 [1085] shaved thickness of I. 8-2. 0 mm I 100 parts by weight of a conventional block chrome-tanned bovine leather bath at 35 ° C in 200 parts of water washed for 10 minutes and then at 40 ° C in a float of 100 parts of water and I. 5 parts of sodium formate plus Ester 5 minutes and then each addition of a total of 3 parts of sodium bicarbonate in the course of 25 minutes to achieve a pH of 7.7 and in the. 将该脱酸浴液与6. 8份染料34p混合,然后在pH 7.6和40で下染色40分钟。 The dye mixture deacidifying float 34p and 6.8 parts, and then dyed at 40 で the pH 7.6 and 40 min. 逐份添加总共7. 5份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,并在40°C转鼓加工90分钟。 Total added portionwise 7.5 parts of sodium carbonate to bring the pH of the float 9 for fixation between 2-9. 6, and the processing drum at 40 ° C for 90 minutes. 浴液改变之后,每次用总共300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with a total of 300 parts of water. 在60分钟的过程中在200份水的浴液中逐份添加总共2份甲酸以达到4. 3的pH值。 By portionwise addition of a total of 2 parts of formic acid to reach a pH of 4.3 in a float of 200 parts of water in the course of 60 minutes.

[1086] 将由此染色的皮革在由80份水、I份复鞣料G14和2份聚合鞣料G19构成的新制浴液中在45°C转鼓加工40分钟。 [1086] The leather thus dyed in a freshly made 80 parts of water float, I retanning material parts 2 parts of polymeric tanning material G14 and G19 in the configuration of the processing drum 45 ° C for 40 minutes. 然后加入0. 8份碳酸氢钠以获得5. 6的pH值。 0.8 parts of sodium hydrogencarbonate was then added to obtain a pH value of 5.6. 然后添加3份疏水剂H5和0. 15份腿4,并转鼓加工20分钟。 It was then added 3 parts of a hydrophobic agent and 0.15 parts H5 leg 4, and drummed for 20 minutes. 加入5份聚合鞣料G18,然后再复鞣30分钟。 Was added 5 parts of polymeric tanning material G18, and then 30 minutes of retanning. 然后加入2份复鞣料Gl、2份植物鞣料G22和2份树脂鞣料G28,并转鼓加工30分钟。 Then 2 parts of retanning material Gl, 2 parts of vegetable tanning material and 2 parts of resin tanning material G22 G28, and drummed for 30 minutes. 为了将皮革加脂,添加5份疏水剂Hl和0. 15份助剂HM4,并转鼓加工60分钟。 To fatliquoring, adding 5 parts of a hydrophobic agent and 0.15 parts of Hl auxiliary HM4, and drummed for 60 minutes. 然后加入70份水。 Then 70 parts of water was added. 在60°C转鼓加工10分钟后,在40分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 After drumming 60 ° C for 10 minutes, in the course of 40 minutes by portionwise addition of 4 parts of formic acid to reach a pH of 3.5. 此后使浴液滴出并将皮革在由150份水和0. 5份甲酸构成的新制浴液中转鼓加エ10分钟。 Thereafter, the float was added dropwise and the leather 10 minutes in a freshly Ester 150 parts of water by a float and 0.5 parts of formic acid the drum. 添加5份铬鞣料G24,然后固色90分钟。 Add 5 parts of chrome tanning material G24, then fixing for 90 minutes. 此后用300份水在30°C洗涤10分钟一次,并用由300份水和0.2份甲酸构成的浴液洗涤一次。 After washing once with 300 parts of water 300 parts of water by a float and 0.2 part of formic acid used in the washing 30 ° C 10 minutes, and. 最后,将皮革简单漂洗。 Finally, the leather briefly rinsed.

[1087] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥2分钟。 [1087] The thus dyed, retanned and hydrophobic horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 2 min.

[1088] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的疏水鞋面革。 [1088] This having excellent washing resistance, perspiration resistance, bleeding and hydrophobic shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的疏水鞋面革。 May be made hydrophobic shoe upper leather dyed with one of the dyes of Examples Ia to 59k embodiment in an analogous manner.

[1089] 鞋面革配方35 : [1089] upper leather recipe 35:

[1090] 将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在30°C在300份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过25分钟每次少许地添加总共3份碳酸氢钠,并达到7. 7的中和pH值。 100 parts of the [1090] thickness was shaved I block I. 8 mm chrome-tanned bovine leather weight of conventional 30 ° C in a bath of 300 parts of water, washed for 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which little at a time over 25 minutes to add a total of 3 parts of sodium bicarbonate, and a neutralization a pH of 7.7. 在脱酸浴液中加入8. I份染料36后,将皮革在pH 7. 6和40°C下染色50分钟。 8. I was added in parts of the dye after the deacidifying float 36, the dyeing leather at pH 7. 6 and 40 ° C 50 min. 每次少许地添加总共8. 7份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工60分钟。 Each addition of a total 8.7 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过60分钟在150份水的浴液中毎次少许地添加总共I. 5份甲酸以达到5. 3的pH值。 Over 60 minutes once every addition of a total I. 5 parts of formic acid to achieve a pH of 5.3 in the bath 150 parts of water.

[1091] 将由此染色的皮革在由100份水和3份疏水剂H5构成的新制浴液中预加脂20分钟。 [1091] The leather dyed in a freshly thus the float 100 parts of water and 3 parts of a hydrophobic agent consisting of a pre-H5 fatliquoring 20 minutes. 然后添加5份聚合鞣料G18,此后转鼓加工40分钟。 It was then added 5 parts of polymeric tanning material G18, after drumming for 40 minutes. 添加3份聚合鞣料G16后,再复鞣30分钟。 After the addition of 3 parts of polymeric tanning material G16, and then 30 minutes of retanning. 此后,添加2份聚合鞣料G19,并经过30分钟完成鞣革。 Thereafter, 2 parts of polymeric tanning material G19 was added, and after 30 minutes to complete tanning. 将复鞣浴液与5份疏水剂Hl和0. 5份助剂HM4混合,然后加脂60分钟。 The retanning float was admixed with 5 parts of a hydrophobic agent and 0.5 parts of Hl auxiliary HM4, and fatliquoring for 60 minutes. 然后添加100份水。 100 parts of water was then added. 在60°C转鼓加工10分钟后,经过55分钟逐份添加4份甲酸以达到3. 5的pH值。 After drumming 60 ° C for 10 minutes after 55 minutes by portionwise addition of 4 parts of formic acid to reach a pH of 3.5. 然后使浴液滴出并将皮革在由120份水和0. 5份甲酸构成的新制浴液中转鼓加工10分钟。 Thereafter, the float drops and the leather drummed in a float of 120 parts of fresh water and 0.5 parts of formic acid for 10 minutes. 添加5份铬鞣料G24,然后固色90分钟。 Add 5 parts of chrome tanning material G24, then fixing for 90 minutes. 然后将皮革在30°C用300份水洗涤10分钟,此洗涤进行两次。 The leather is then washed at 30 ° C for 10 minutes 300 parts of water, washed twice this.

[1092] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥3分钟。 [1092] The thus dyed, retanned and hydrophobic horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 3 min.

[1093] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的纯聚合基疏水鞋面革。 [1093] This having excellent washing resistance, perspiration resistance, bleeding and the hydrophobic polymeric matrix pure shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的纯聚合基疏水鞋面革。 Pure hydrophobic polymeric matrix may be fabricated shoe upper leather dyed with one embodiment of Ia to 59k in a similar manner.

[1094] 鞋面革配方36 : [1094] upper leather recipe 36:

[1095] 将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在30°C在300份水·的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过25分钟每次少许地添加总共3份碳酸氢钠,并达到7. 7的中和pH值。 100 parts of the [1095] thickness was shaved I I. 8 mm bulk weight chrome-tanned bovine leather in a conventional 30 ° C in 300 parts of water-washing bath of 10 minutes and then at 40 ° C in 100 parts of water bath and the drum I. 5 parts of sodium formate and processing for 5 minutes, after which little at a time over 25 minutes to add a total of 3 parts of sodium bicarbonate, and a neutralization a pH of 7.7. 在脱酸浴液中加入5. 7份染料35v后,将皮革在pH 7. 6和40°C下转鼓加工50分钟。 After the addition of 5.7 parts of dye 35v deacidifying float, the leather was drummed at pH 7. 6 and 40 ° C 50 min. 每次少许地添加总共6. 5份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工60分钟。 Each addition of a total 6.5 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过60分钟在150份水的浴液中毎次少许地添加总共I. 5份甲酸以达到5. 3的pH值。 Over 60 minutes once every addition of a total I. 5 parts of formic acid to achieve a pH of 5.3 in the bath 150 parts of water.

[1096] 将由此染色的皮革在由100份水和2份疏水剂H5构成的新制浴液中预加脂20分钟。 [1096] The leather dyed in a freshly thus the float 100 parts of water and 2 parts of a hydrophobic agent consisting of a pre-H5 fatliquoring 20 minutes. 然后添加5份聚合鞣料G18,此后转鼓加工40分钟。 It was then added 5 parts of polymeric tanning material G18, after drumming for 40 minutes. 添加3份聚合鞣料Gl后,再复鞣30分钟。 After the addition of 3 parts of polymeric tanning material Gl, and then 30 minutes of retanning. 此后,添加2份聚合鞣料G22,并经过30分钟完成鞣革。 Thereafter, 2 parts of polymeric tanning material G22 was added, and after 30 minutes to complete tanning. 将复鞣浴液与5份疏水剂Hl和0. 5份助剂HM4混合,然后加脂60分钟。 The retanning float was admixed with 5 parts of a hydrophobic agent and 0.5 parts of Hl auxiliary HM4, and fatliquoring for 60 minutes. 然后添加100份水。 100 parts of water was then added. 在60°C转鼓加工10分钟后,经过55分钟逐份添加4份甲酸以达到3.5的pH值。 After drumming 60 ° C for 10 minutes after 55 minutes by portionwise addition of 4 parts of formic acid to achieve a pH of 3.5. 此后使浴液滴出并将皮革在由120份水和0. 5份甲酸构成的新制浴液中转鼓加工10分钟。 Thereafter, the float was dropped and the leather drummed in a float of 120 parts of fresh water and 0.5 parts of formic acid for 10 minutes. 添加5份铬鞣料G24,然后固色90分钟。 Add 5 parts of chrome tanning material G24, then fixing for 90 minutes. 然后将皮革在30°C用300份水洗涤10分钟,此洗涤进行两次。 The leather is then washed at 30 ° C for 10 minutes 300 parts of water, washed twice this.

[1097] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥3分钟。 [1097] The thus dyed, retanned and hydrophobic horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 3 min.

[1098] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的疏水鞋面革。 [1098] This having excellent washing resistance, perspiration resistance, bleeding and hydrophobic shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的疏水鞋面革。 May be made hydrophobic shoe upper leather dyed with one of the dyes of Examples Ia to 59k embodiment in an analogous manner.

[1099] 鞋面革配方37 : [1099] upper leather recipe 37:

[1100] 将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在30°C在300份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过25分钟每次少许地添加总共3份碳酸氢钠,并达到7. 7的中和pH值。 100 parts of the [1100] thickness was shaved I block I. 8 mm chrome-tanned bovine leather weight of conventional 30 ° C in a bath of 300 parts of water, washed for 10 minutes and then at 40 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which little at a time over 25 minutes to add a total of 3 parts of sodium bicarbonate, and a neutralization a pH of 7.7. 在脱酸浴液中加入7. 8份染料38o后,将皮革在pH 7. 6和40°C下转鼓加工50分钟。 After the addition of 7.8 parts of dye 38o deacidifying float, the leather was drummed at pH 7. 6 and 40 ° C 50 min. 每次少许地添加总共8. I份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在40°C转鼓加工60分钟。 Each addition of a total 8. I parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 40 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过60分钟在150份水的浴液中毎次少许地添加总共2份甲酸以达到4. 5的pH值。 Over 60 minutes once every addition of a total of 2 parts of formic acid in 150 parts of water bath, at a pH of 4.5.

[1101] 将由此染色的皮革在由100份水、I. 5份复鞣料G14、I. 5份聚合鞣料G16和I. 5份复鞣料G19构成的新制浴液中转鼓加工40分钟。 [1101] The leather thus dyed by 100 parts of water, I. 5 parts of retanning material G14, I. Freshly float 5 parts of polymeric tanning material G16 and G19 I. 5 parts of retanning material consisting of 40 minutes of drumming . 添加2份植物鞣料G22和3份植物鞣料G28,然后鞣制60分钟以完成鞣制。 Was added 2 parts of vegetable tanning material and 3 parts of vegetable tanning material G22 G28, tanning and tanning 60 minutes to complete. 将复鞣浴液与6份疏水剂Hl和0. 5份助剂HM4混合,然后加脂90分钟。 The retanning float was admixed with 6 parts of a hydrophobic agent and 0.5 parts of Hl auxiliary HM4, and fatliquoring for 90 minutes. 然后添加100份水。 100 parts of water was then added. 在60°C转鼓加工10分钟后,经过50分钟逐份添加4份甲酸以达到3. 5的pH值。 After drumming 60 ° C for 10 minutes after 50 minutes by portionwise addition of 4 parts of formic acid to reach a pH of 3.5. 此后使浴液滴出并将皮革在由120份水和0. 5份甲酸构成的新制浴液中转鼓加工5分钟。 Thereafter, the float was dropped and the leather drummed in a float of 120 parts of fresh water and 0.5 parts of formic acid for 5 minutes. 添加5份铬鞣料G24,然后固色90分钟。 Add 5 parts of chrome tanning material G24, then fixing for 90 minutes. 然后将皮革在30°C用300份水洗涤10分钟,此洗涤进行两次。 The leather is then washed at 30 ° C for 10 minutes 300 parts of water, washed twice this.

[1102] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥3分钟。 [1102] The thus dyed, retanned and hydrophobic horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 3 min.

[1103] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的疏水鞋面革。 [1103] This having excellent washing resistance, perspiration resistance, bleeding and hydrophobic shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的疏水鞋面革。 May be made hydrophobic shoe upper leather dyed with one of the dyes of Examples Ia to 59k embodiment in an analogous manner.

[1104] 鞋面革配方38: [1104] upper leather recipe 38:

[1105] 将削匀厚度为2. 0毫米的I块100重量份的传统铬鞣牛皮革在35°C在由200份水构成的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加エ5分钟,此后在20分钟的过程中逐份添加总共3份碳酸氢钠以达到7. 6的中和pH值。 Parts of [1105] shaved thickness of 2.0 mm by weight of I-block 100 in a conventional chrome-tanned bovine leather 35 ° C in a bath of 200 parts of water washed for 10 minutes and then at 40 ° C in a 100 parts of water and the float bowl I. 5 parts of sodium formate plus Ester 5 minutes, after which a total of 3 parts by portionwise addition of sodium bicarbonate and the pH of 7.6 in the course of 20 minutes. 将该脱酸浴液与9. 2份染料40d混合,然后在pH 7. 5和40°C下染色40分钟。 The deacidifying float 9.2 parts of dye mixed with 40d, and then dyed at pH 7. 5 and 40 ° C 40 min. 毎次少许地添·加总共9. 3份碳酸钠以使浴液的pH值达到9. 2-9. 8之间以固色,然后在40°C转鼓加工60分钟。 · Added a little at every time a total of 9.3 parts of sodium carbonate was added to bring the pH of the float for fixation between 9 2-9. 8, 40 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤两次,一共洗涤60分钟。 After float change, the leather was washed twice each time, washed with a total of 60 minutes 300 parts of water. 在60分钟的过程中在200份水的浴液中逐份添加总共3. 5份甲酸以达到3. 8的pH值。 Was added portionwise a total of 3.5 parts of formic acid to reach a pH of 3.8 in a float of 200 parts of water in the course of 60 minutes.

[1106] 将由此染色的皮革在由80份水和3份复鞣料G26构成的新制浴液中在45°C转鼓加工60分钟。 [1106] The leather thus dyed in a freshly float composed of 80 parts water and 3 parts of retanning material G26 in the configuration of the processing drum 45 ° C for 60 minutes. 然后加入2份聚合鞣料G19,再在15分钟的转鼓加工时间后,添加5份聚合鞣料G18。 Then 2 parts of polymeric tanning material G19, followed after 15 minutes drumming time, the addition of 5 parts of polymeric tanning material G18. 再在45°C转鼓加工40分钟,然后添加4份树脂鞣料G28和4份树脂鞣料G11,再在45°C转鼓加工60分钟。 And then for 40 minutes at 45 ° C drum, and then 4 parts of resin tanning material was added 4 parts of resin tanning material G28 and G11, and then the processing drum at 45 ° C for 60 minutes. 然后加入70份水,再在60°C转鼓加工10分钟。 70 parts of water were then added, and then the processing drum at 60 ° C for 10 min. 将复鞣浴液与 The retanning float and

2. 5份加脂剂Fl和2. 5份疏水剂H3混合,然后在55°C加脂60分钟。 2.5 parts of fatliquor Fl and 2.5 parts hydrophobicizer H3 and fatliquoring at 55 ° C for 60 minutes. 然后在60分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 It was then added portionwise 4 parts of formic acid to reach a pH of 3.5 in the course of 60 minutes. 然后使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float drops and the leather briefly rinsed cold.

[1107] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥3分钟,用220规格的金刚砂纸进行正绒面革处理,除尘并用绷革框干燥。 [1107] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 3 minutes , nubucked treatment, dust with size of 220 emery paper and toggle frame dried.

[1108] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的直纹正绒面鞋面革。 [1108] This having excellent washing resistance, perspiration resistance, bleeding and nubuck shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的直纹正绒面鞋面革。 Dyed with one of the dyes of Examples Ia to 59k in a similar manner nubuck shoe upper leather.

[1109] 鞋面革配方39: [1109] upper leather recipe 39:

[1110] 将削匀厚度为2. I毫米的I块100重量份的传统铬鞣牛皮革在35°C在由200份水构成的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后在20分钟的过程中逐份添加总共3份碳酸氢钠以达到7. 6的中和pH值。 100 parts [1110] 2. shaved thickness of I mm by weight of I-block in a conventional chrome-tanned bovine leather 35 ° C in a bath of 200 parts of water washed for 10 minutes and then at 40 ° C in a 100 parts of water and the float bowl I. 5 parts of sodium formate and processing for 5 minutes, after which a total of 3 parts by portionwise addition of sodium bicarbonate and the pH of 7.6 in the course of 20 minutes. 将该脱酸浴液与8份染料391混合,然后在pH 7. 5和40°C下染色40分钟。 The dye mixture deacidifying float 391 and 8 parts, and then dyed at pH 7. 5 and 40 ° C 40 min. 每次少许地添加总共8. 6份碳酸钠以使浴液的pH值达到9. 2-9. 8之间以固色,然后在40°C转鼓加工60分钟。 Each addition of a total 8.6 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 8 for fixation, 40 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤两次,一共洗涤60分钟。 After float change, the leather was washed twice each time, washed with a total of 60 minutes 300 parts of water. 在60分钟的过程中在200份水的浴液中逐份添加总共3. 5份甲酸以达到3. 8的pH值。 Was added portionwise a total of 3.5 parts of formic acid to reach a pH of 3.8 in a float of 200 parts of water in the course of 60 minutes.

[1111] 将由此染色的皮革在由80份水和3. 5份复鞣料G27构成的新制浴液中在45°C转鼓加工50分钟。 [1111] The leather thus dyed in a freshly float composed of 80 parts of water and 3.5 parts of retanning material G27 in the configuration of the processing drum 45 ° C for 50 minutes. 然后加入2份聚合鞣料G19,再在15分钟的转鼓加工时间后,添加5份聚合鞣料G18。 Then 2 parts of polymeric tanning material G19, followed after 15 minutes drumming time, the addition of 5 parts of polymeric tanning material G18. 再在45°C转鼓加工40分钟,然后添加4份树脂鞣料G28和4份树脂鞣料Gl I,再在45°C转鼓加工60分钟。 And then for 40 minutes at 45 ° C drum, and then 4 parts of resin tanning material was added 4 parts of resin tanning material G28 and Gl I, and then processed at 45 ° C the drum for 60 minutes. 然后加入70份水,再在60°C转鼓加工10分钟。 70 parts of water were then added, and then the processing drum at 60 ° C for 10 min. 将复鞣浴液与2. 5份加脂剂Fl和2. 5份疏水剂H3混合,然后在55°C加脂60分钟。 The retanning float was admixed with 2.5 parts of fatliquor Fl and 2.5 parts of water repellent H3, then at 55 ° C fatliquoring for 60 minutes. 然后在60分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 It was then added portionwise 4 parts of formic acid to reach a pH of 3.5 in the course of 60 minutes. 然后使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float drops and the leather briefly rinsed cold.

[1112] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在55°C减压处理4分钟,在室温下悬浮干燥,修整,刮软并在55°C真空干燥3分钟,用220规格的金刚砂纸进行正绒面革处理,除尘并用绷革框干燥。 [1112] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, for 4 minutes at 55 ° C under reduced pressure, the suspension was dried at room temperature, trimmed, staked and dried in vacuo at 55 ° C 3 minutes , nubucked treatment, dust with size of 220 emery paper and toggle frame dried.

[1113] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的直纹正绒面鞋面革。 [1113] This having excellent washing resistance, perspiration resistance, bleeding and nubuck shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的直纹正绒面鞋面革。 Dyed with one of the dyes of Examples Ia to 59k in a similar manner nubuck shoe upper leather.

[1114] 鞋面革配方40: [1114] upper leather recipe 40:

[1115] 将削匀厚度为I. 8毫米的I块100重量份的传统铬鞣牛皮革在30°C在300份水的浴液中洗涤10分钟,然后在40°C在由100份水、I. 5份鞣料Gl和I份助剂HM7构成的浴液中转鼓加工60分钟。 [1115] shaved thickness of 100 mm I. 8 parts by weight of the block I conventionally chrome-tanned bovine leather bath at 30 ° C in 300 parts of water, washed for 10 minutes and then at 40 ° C in 100 parts of water by a , I bath. Gl. 5 parts of tanning material and auxiliary parts HM7 configuration I drummed for 60 minutes. 然后将浴液与I. 5份甲酸钠混合,然后在40°C转鼓加工30分钟。 Bath was then mixed with I. 5 parts of sodium formate, 40 ° C and then processed in the drum for 30 minutes. 此后经过25分钟每次少许地添加总共3份碳酸氢钠,并达到7. 6的中和pH值。 Over 25 minutes after each addition of a total of 3 parts of sodium bicarbonate, and a neutralization a pH of 7.6. 在脱酸浴液·中加入8. 0份染料13ae,然后在pH 7. 0和40°C下染色45分钟。 Was added 8.0 parts of dye 13ae · deacidifying float then dyed at pH 7. 0 and 40 ° C 45 min. 每次少许地添加总共7. 5份碳酸钠以使浴液的PH值达到9. 2-9. 5之间以固色,然后在40°C转鼓加工60分钟。 Each addition of a total 7.5 parts of sodium carbonate to make the PH value to reach between the float 9. 2-9. 5 for fixation, 40 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 经过60分钟在200份水的浴液中每次少许地添加总共4份甲酸以达到3. 6的pH值。 Little at a time over 60 minutes to add a total of 4 parts of formic acid in 200 parts of water bath, at a pH of 3.6.

[1116] 将由此染色的皮革在由80份水、I份醛鞣料G13和3份聚合鞣料G16构成的新制浴液中在45°C复鞣60分钟。 [1116] The thus dyed leather by 80 parts of water, I parts of aldehyde tanning material G13 and 3 parts of polymeric tanning material freshly float G16 constituted retanning at 45 ° C for 60 minutes. 然后加入0. 5份碳酸氢钠,再在30分钟的转鼓加工时间后加入5份聚合鞣料G18,并在45°C再复鞣30分钟。 It was then added 0.5 parts of sodium hydrogen carbonate was added 5 parts of polymeric tanning material G18 after 30 minutes drumming time, and then retanned at 45 ° C 30 min. 然后将浴液与0. 8份助剂HM5、3份聚合鞣料G17和2份聚合鞣料G19混合,再在45°C鞣制60分钟至完成。 Bath and then 0.8 parts of polymeric tanning material parts auxiliary HM5,3 G17 2 parts of polymeric tanning material G19 were mixed and then made 60 minutes at 45 ° C to complete the tanning. 然后加入70份水,再在60°C转鼓加工10分钟。 70 parts of water were then added, and then the processing drum at 60 ° C for 10 min. 将复鞣浴液与2. 5份加脂剂F6、l. 5份疏水剂H3和I. 5份加脂剂F2混合,并在45°C加脂60分钟。 The retanning float with 2.5 parts of fatliquor F6, l. 5 parts of a hydrophobic agent and H3 I. 5 parts of fatliquor F2 mixed, and fatliquoring at 45 ° C for 60 minutes. 在60分钟的过程中毎次少许地添加总共4份甲酸以达到PH 3.5。 In the course of 60 minutes every time the addition of a total of 4 parts of formic acid PH 3.5. 此后,使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float was dropped and the leather briefly rinsed cold.

[1117] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,在60°C减压处理2分钟,在室温下悬浮干燥过夜,修整,刮软并在60°C真空干燥2分钟。 [1117] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, 2 minutes at 60 ° C under reduced pressure, was suspended at room temperature overnight, conditioned, staked and dried in vacuo at 60 ° C 2 minute.

[1118] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的鞋面革。 [1118] This having excellent washing resistance, perspiration resistance, bleeding and the shoe upper leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的鞋面革。 A shoe upper leather in one of Examples Ia to 59k dyes embodiment in an analogous manner.

[1119] 家具革配方I: [1119] Furniture leather recipe I:

[1120] 将削匀厚度为I. I毫米的I块100重量份的传统铬鞣牛皮革在30°C在300份水的浴液中洗涤10分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过25分钟每次少许地添加总共3份碳酸氢钠,并达到7. 8的中和pH值。 100 parts by weight of the block I conventionally chrome-tanned bovine leather [1120] I. shaved thickness of I mm at 30 ° C the bath was washed with 300 parts of water for 10 minutes and then at 35 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which little at a time over 25 minutes to add a total of 3 parts of sodium bicarbonate, and a neutralization a pH of 7.8. 加入I. 5份HM2后,将皮革转鼓加工5分钟。 After addition of I. 5 parts of HM2, the leather was drummed for 5 minutes. 然后在脱酸浴液中加入10. 5份染料41c,然后在pH7. 3和35°C下染色30分钟。 Followed by addition of 10.5 parts of dye 41c deacidifying float before dyeing at pH7. 3 and 35 ° C 30 min. 然后添加0. 5份碳酸氢钠并转鼓加工60分钟。 0.5 parts of sodium hydrogencarbonate was then added and drumming for 60 minutes. 每次少许地添加总共9. 5份碳酸钠以使浴液的pH值达到9. 3-9. 5之间以固色,然后在35°C转鼓加工60分钟。 Each addition of a total 9.5 parts of sodium carbonate to bring the pH reaches between the float 9. 3-9. 5 for fixation, 35 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革在40°C洗涤两次,一共洗涤60分钟。 After float change, each time washed twice at 40 ° C, the leather was washed with a total of 60 minutes with 300 parts of water. 经过60分钟在200份水的浴液中每次少许地添加总共3份甲酸以达到3. 7的pH值。 Little at a time over 60 minutes a total of 3 parts of formic acid was added in 200 parts of water bath, at a pH of 3.7.

[1121] 将由此染色的皮革在由150份水和2份复鞣料G13构成的新制浴液中在45°C转鼓加工60分钟。 [1121] The leather thus dyed in 150 parts of water by a float freshly and 2 parts of retanning material G13 in the configuration of the processing drum 45 ° C for 60 minutes. 然后加入2份聚合鞣料G18。 2 parts of polymeric tanning material G18 were then added. 在60分钟的转鼓加工时间后,添加I. 5份碳酸氢钠。 After 60 minutes drumming time, I. 5 parts of sodium bicarbonate was added. 再在45°C转鼓加工20分钟,然后加入2份加脂剂Fl和0. 2份助剂HM4,再加脂20分钟。 Reprocessing 45 ° C for 20 minutes the drum, followed by addition of 2 parts of fatliquor Fl and 0.2 parts of auxiliary HM4, refatting 20 minutes. 将浴液与5份复鞣料G5、3份植物鞣料G22和2份树脂鞣料Gll混合,然后复鞣60分钟。 The float and 5 parts of retanning G5,3 parts of vegetable tanning material G22 and 2 parts of resin tanning material Gll mixed, and then retanned for 60 minutes. 将复鞣浴液与7份加脂剂Fl和3份加脂剂F6混合,然后在45°C加脂60分钟。 The retanning float and 7 parts of fatliquor Fl and 3 parts of fatliquor F6 mixed, then at 45 ° C fatliquoring for 60 minutes. 然后在45分钟的过程中逐份添加5份甲酸以达到3. 5的pH值。 5 parts by portionwise addition of formic acid to reach a pH of 3.5 in the course of 45 minutes. 此后,使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float was dropped and the leather briefly rinsed cold.

[1122] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿拉紧并用绷革框干燥,修整,刮软并干转鼓加工。 [1122] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretched, wet-strained and toggle frame dried, conditioned, staked and dry drummed.

[1123] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的家具革。 [1123] This having excellent washing resistance, perspiration resistance, bleeding and furniture leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的家具革。 Furniture leather in Example Ia to 59k one dye which is in a similar manner.

[1124] 家具革配方2: [1124] Furniture leather recipe 2:

[1125] 将削匀厚度为I. 0-1. I毫米的I块100重量份的传统有机鞣牛皮革在30°C在300份水的浴液中洗涤15分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工10分钟。 [1125] shaved thickness of I. 0-1. I 100 parts by weight of the block I mm in the conventional organic-tanned cow leather bath at 30 ° C in 300 parts of water washed for 15 minutes and then at 35 ° C by the processing in a float of 100 parts of water and I. 5 parts of sodium formate 10 min. 该浴液具有4. 2-4. 6的pH值。 The bath had a pH of 4. 2-4. 6. 将该浴液与8. 7份染料42g混合,然后在pH·5. 5和35°C下染色40分钟。 The bath is 8.7 parts of dye mixed with 42g, and then dyed at pH · 5. 5 and 35 ° C 40 min. 然后在20分钟的过程中逐份添加总共3份碳酸氢钠以达到7. 3-7. 8的pH值。 Then a total of 3 parts by portionwise addition of sodium bicarbonate pH of 7. 3-7. 8 in the course of 20 minutes. 为了固色,逐份添加总共9份碳酸钠以使浴液的pH值达到9. 2-9. 6之间,然后在35°C转鼓加工60分钟。 For fixation by portionwise addition of a total of 9 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6, 35 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水和I. 5份助剂HM3将皮革在40°C洗涤两次,一共洗涤60分钟。 After float change, each time with 300 parts of water and additives I. 5 parts HM3 The leather was washed twice at 40 ° C, washed with a total of 60 minutes. 在60分钟的过程中,在200份水的浴液中逐份添加总共2份甲酸以在40°C保持4. 3-4. 6的pH值。 In the course of 60 minutes, 200 parts of water by the bath in parts of a total of 2 parts of formic acid was added to maintain the pH 4. 3-4. 6 at 40 ° C.

[1126] 将由此染色的皮革在由100份水、3份聚合鞣料G18和I. 5份加脂剂F6构成的新制浴液中在35°C复鞣30分钟。 [1126] The leather thus dyed by 100 parts of water, and 3 parts of polymeric tanning material G18 I. 5 parts fresh float fatliquor F6 constituted retanning at 35 ° C for 30 minutes. 然后加入6份聚合鞣料G18和10份复鞣料G18,然后在35°C转鼓加工60分钟。 It was then added 6 parts of polymeric tanning material G18 and 10 parts of retanning material G18, 35 ° C and then processed in the drum for 60 minutes. 添加I. 5份加脂剂F6并转鼓加工30分钟后,添加6份聚合鞣料G18和10份复鞣料G8,并在35°C复鞣60分钟。 After the addition I. 5 parts of fatliquor F6 and drumming for 30 minutes was added 6 parts of polymeric tanning material G18 and 10 parts of retanning material G8, and 35 ° C retanned for 60 minutes. 将复鞣浴液与10份加脂剂F6混合,然后在35°C加脂60分钟。 The retanning float with 10 parts of fatliquor F6 mixed and fatliquoring at 35 ° C for 60 minutes. 为了固定加脂剂,加入100份45°C的热水,并在20分钟的转鼓加工时间后,在50分钟的过程中添加甲酸以达到3. 5的pH值。 To fix the fatliquor, was added 100 parts of hot water of 45 ° C, and after 20 minutes drumming time of formic acid was added in the course of 50 minutes to achieve a pH value of 3.5. 此后用300份水洗涤15分钟。 After washing with 300 parts of water for 15 minutes.

[1127] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿拉紧,用绷革框干燥,修整,刮软,干转鼓加工并拉紫。 [1127] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretched, wet-strained, toggle frame dried, conditioned, staked, dry drummed and pull purple.

[1128] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的白湿家具革。 [1128] This having excellent washing resistance, perspiration resistance, bleeding and white furniture leather wet abrasion fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的白湿家具革。 Wet-white leather furniture can be produced in one of Examples Ia to 59k dyes embodiment in an analogous manner.

[1129] 家具革配方3: [1129] Furniture leather recipe 3:

[1130] 将削匀厚度为I. 0-1. I毫米的I块100重量份的传统有机鞣牛皮革在30°C在300份水的浴液中洗涤15分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加エ10分钟。 [1130] shaved thickness of I. 0-1. I 100 parts by weight of the block I mm in the conventional organic-tanned cow leather bath at 30 ° C in 300 parts of water washed for 15 minutes and then at 35 ° C in a float of 100 parts of water and I. 5 parts of sodium formate plus Ester 10 minutes. 该浴液具有4. 4的pH值。 The bath having a pH of 4.4. 将该浴液与7. 5份染料46e混合,然后在pH 5. 3和35°C下染色45分钟。 7.5 parts of the dye bath and mixed 46e, then stained and pH 5. 3 at 35 ° C 45 min. 在20分钟的过程中逐份添加总共3份碳酸氢钠以达到7. 3-7. 8的pH值。 In the course of 20 minutes by portionwise addition of a total of 3 parts of sodium bicarbonate to reach a pH of 7. 3-7. 8. 为了固色,逐份添加总共8份碳酸钠以使浴液的pH值达到9. 5-10. 0之间,然后在35°C转鼓加工60分钟。 For fixation by portionwise addition of a total of 8 parts of sodium carbonate to bring the pH reaches between the float 9. 5-10. 0, then the processing drum at 35 ° C for 60 minutes. 浴液改变之后,每次用由300份水构成的浴液将皮革在40°C洗涤三次,一共洗涤60分钟。 After float change, the leather in each washed three times with 40 ° C, washed with a total of 60 minutes by a float of 300 parts of water. 在60分钟的过程中,在200份水的浴液中逐份添加总共I. 5份甲酸以在40°C保持4. 7-5.0的pH值。 In the course of 60 minutes, 200 parts of water by the bath in a total parts I. 5 parts of formic acid was added to maintain the pH of 4. 7-5.0 at 40 ° C.

[1131] 将由此染色的皮革在由50份水、15份疏水剂H5和15份聚合鞣料G18构成的新制浴液中在35°C复鞣90分钟。 [1131] The leather thus dyed in a fresh bath of water 50 parts, 15 parts and 15 parts of water repellent H5 polymeric tanning material G18 of retanning constituting at 35 ° C 90 min. 然后加入8份疏水剂H5和6份加脂剂F6,再在35°C加脂150分钟。 Followed by addition of 8 parts water repellent H5 and 6 parts of fatliquor F6, and then at 35 ° C fatliquoring 150 minutes. 然后加入100份45°C的热水,并转鼓加工10分钟。 100 parts of hot water 45 ° C was then added and drummed for 10 minutes. 然后在40分钟的过程中添加3份甲酸以达到3. 5的pH值。 3 parts of formic acid was then added in the course of 40 minutes to achieve a pH value of 3.5. 最后,将皮革简单地用水漂洗。 Finally, the leather was briefly rinsed with water.

[1132] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿拉紧,用绷革框干燥,修整,刮软,干转鼓加工过夜并拉紧。 [1132] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretched, wet-strained, toggle frame dried, conditioned, staked, dry drummed overnight and tensioned.

[1133] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的纯聚合物基白湿家具革。 [1133] This having excellent washing resistance, perspiration resistance, bleeding and pure white polymer based furniture leather wet abrasion fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的纯聚合物基白湿家具革。 Can be dyed with one of the dyes of Examples Ia to 59k embodiment of the pure polymer based wet-white leather furniture in a similar manner.

[1134] 家具革配方4: [1134] Furniture leather recipe 4:

[1135] 将削匀厚度为I. I毫米的I块100重量份的传统铬鞣牛皮革在30°C在300份水的浴液中洗涤10分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过30分钟每次少许地添加总共4份碳酸氢钠,并达到7. 7的中和pH值。 100 parts by weight of the block I conventionally chrome-tanned bovine leather [1135] I. shaved thickness of I mm at 30 ° C the bath was washed with 300 parts of water for 10 minutes and then at 35 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes over 30 minutes after each addition of a total of 4 parts of sodium bicarbonate, and a neutralization a pH of 7.7. 加入I. 5份HM2后,将皮革转鼓加工5分钟。 After addition of I. 5 parts of HM2, the leather was drummed for 5 minutes. 然后在脱酸浴液中加入9份染料43ag,然后在pH 7.4和35°C下染色30分钟。 Deacidifying float was then added to 9 parts of dye 43ag, and then dyed at pH 7.4 and 35 ° C 30 min. 然后添加0. 5份碳酸氢钠并在pH 7. 5下转鼓加工60分钟。 0.5 parts of sodium hydrogencarbonate was then added and drummed for 60 minutes at pH 7. 5. 毎次少许地添加总共9. 8份碳酸钠以使浴液的pH值达到9. 3-9. 8之间以固色,然后在35°C转鼓加工60分钟。 Once every addition of a total 9.8 parts of sodium carbonate to bring the pH of the float for fixation between 9 3-9. 8, 35 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革在40°C洗涤三次,一共洗涤60分钟。 After float change, each time at 40 ° C and washed three times, washed with a total of 60 minutes the leather with 300 parts of water. 经过60分钟在200份水的浴液中每次少许地添加总共I. 8份甲酸以达到4. 6的pH值。 Over 60 minutes every addition of a total I. 8 parts of formic acid in a float of 200 parts of water to achieve a pH value of 4.6.

[1136] 将由此染色的皮革在由150份水和6份复鞣料G18构成的新制浴液中在45°C转鼓加工40分钟。 [1136] The leather thus dyed in 150 parts of water by a float freshly and 6 parts of retanning material G18 in the configuration of the processing drum 45 ° C for 40 minutes. 该浴液的pH值为5. O。 pH value of the bath 5. O. 添加0. 8份碳酸氢钠并转鼓加工20分钟,以使浴液的PH值达到6. 9。 0.8 parts of sodium hydrogen carbonate was added and drumming for 20 minutes to float PH value reaches 6.9. 将复鞣浴液与2份加脂剂Fl和0. 2份助剂HM4混合,然后在45°C预加脂20分钟。 The retanning float was admixed with 2 parts of fatliquor Fl and 0.2 part of auxiliary HM4, and then at 45 ° C pre fatliquoring 20 minutes. 将浴液与3份复鞣料G5、3份植物鞣料G22和2份树脂鞣料Gll混合,然后复鞣60分钟。 The float with 3 parts of retanning material G5,3 parts of vegetable tanning material G22 and 2 parts of resin tanning material Gll mixed, and then retanned for 60 minutes. 将复鞣浴液与7份加脂剂Fl和3份加脂剂F6混合,然后在45°C加脂60分钟。 The retanning float and 7 parts of fatliquor Fl and 3 parts of fatliquor F6 mixed, then at 45 ° C fatliquoring for 60 minutes. 然后在45分钟的过程中逐份添加5份甲酸以达到3. 5的pH值。 5 parts by portionwise addition of formic acid to reach a pH of 3.5 in the course of 45 minutes. 此后,使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float was dropped and the leather briefly rinsed cold.

[1137] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿拉紧并用绷革框干燥,修整,刮软并干转鼓加工。 [1137] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretched, wet-strained and toggle frame dried, conditioned, staked and dry drummed.

[1138] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的家具革。 [1138] This having excellent washing resistance, perspiration resistance, bleeding and furniture leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的家具革。 Furniture leather in Example Ia to 59k one dye which is in a similar manner.

[1139] 家具革配方5: [1139] Furniture leather recipe 5:

[1140] 将削匀厚度为I. I毫米的I块100重量份的传统铬鞣牛皮革在30°C在300份水的浴液中洗涤10分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过30分钟每次少许地添加总共4份碳酸氢钠,并达到7. 7的中和pH值。 100 parts by weight of the block I conventionally chrome-tanned bovine leather [1140] I. shaved thickness of I mm at 30 ° C the bath was washed with 300 parts of water for 10 minutes and then at 35 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes over 30 minutes after each addition of a total of 4 parts of sodium bicarbonate, and a neutralization a pH of 7.7. 加入 Join

I. 5份HM2后,将皮革转鼓加工5分钟。 After I. 5 parts of HM2, the leather was drummed for 5 minutes. 然后在脱酸浴液中加入8份染料47ac,然后在pH7. 5和35°C下染色30分钟。 Followed by addition of 8 parts of dye 47ac deacidifying float, and then dyed at pH7. 5 and 35 ° C 30 min. 然后添加0. 5份碳酸氢钠并在pH 7. 6下转鼓加工60分钟。 0.5 parts of sodium hydrogencarbonate was then added and drummed for 60 minutes at pH 7. 6. 每次少许地添加总共9份碳酸钠以使浴液的pH值达到9. 5-9. 9之间以固色,然后在35°C转鼓加工60分钟。 Each addition of a total of 9 parts of sodium carbonate to bring the pH reaches between the float 9. 5-9. 9 for fixation, 35 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革在40°C洗涤三次,一共洗涤60分钟。 After float change, each time at 40 ° C and washed three times, washed with a total of 60 minutes the leather with 300 parts of water. 经过60分钟在200份水的浴液中毎次少许地添加总共3. 0份甲酸以达到3. 7的pH值。 Over 60 minutes in a float of 200 parts of water were added a little every time a total of 3.0 parts of formic acid to reach a pH of 3.7.

[1141] 将由此染色的皮革在由150份水和I份复鞣料G13构成的新制浴液中在45°C转鼓加工40分钟。 [1141] The leather thus dyed in 150 parts of water by a float freshly I and G13 of retanning material constituting the parts of the processing drum at 45 ° C for 40 minutes. 然后加入6份聚合鞣料G18并在45°C复鞣40分钟。 It was then added 6 parts of polymeric tanning material G18 and retanning at 45 ° C for 40 minutes. 该浴液的pH值为4. 2。 The pH of the bath is 4.2. 添加I. 5份碳酸氢钠并转鼓加工20分钟,以使浴液的pH值达到6. 2。 I. 5 parts of sodium hydrogen carbonate was added and drumming for 20 minutes to float pH reaches 6.2. 将复鞣浴液与2份加脂剂Fl和0. 2份助剂HM4混合,然后在45°C预加脂20分钟。 The retanning float was admixed with 2 parts of fatliquor Fl and 0.2 part of auxiliary HM4, and then at 45 ° C pre fatliquoring 20 minutes. 将浴液与3份复鞣料G5、3份植物鞣料G22和2份树脂鞣料Gll混合,然后复鞣60分钟。 The float with 3 parts of retanning material G5,3 parts of vegetable tanning material G22 and 2 parts of resin tanning material Gll mixed, and then retanned for 60 minutes. 将复鞣浴液与7份加脂剂Fl和3份加脂剂F6混合,然后在45°C加脂60分钟。 The retanning float and 7 parts of fatliquor Fl and 3 parts of fatliquor F6 mixed, then at 45 ° C fatliquoring for 60 minutes. 该浴液的pH值为5. 6。 The pH of the bath is 5.6. 然后在45分钟的过程中逐份添加5份甲酸以达到3. 5的pH值。 5 parts by portionwise addition of formic acid to reach a pH of 3.5 in the course of 45 minutes. 此后,使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float was dropped and the leather briefly rinsed cold.

[1142] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿拉紧并用绷革框干燥,修整,刮软并干转鼓加工。 [1142] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretched, wet-strained and toggle frame dried, conditioned, staked and dry drummed.

[1143] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的家具革。 [1143] This having excellent washing resistance, perspiration resistance, bleeding and furniture leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的家具革。 Furniture leather in Example Ia to 59k one dye which is in a similar manner.

[1144] 家具革配方6: [1144] Furniture leather recipe 6:

[1145] 将削匀厚度为I. I毫米的I块100重量份的传统铬鞣牛皮革在30°C在300份水的浴液中洗涤10分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过30分钟每次少许地添加总共4份碳酸氢钠,并达到7. 7的中和pH值。 100 parts by weight of the block I conventionally chrome-tanned bovine leather [1145] I. shaved thickness of I mm at 30 ° C the bath was washed with 300 parts of water for 10 minutes and then at 35 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes over 30 minutes after each addition of a total of 4 parts of sodium bicarbonate, and a neutralization a pH of 7.7. カロ入I. 5份HM2后,将皮革转鼓加工5分钟。 After the grades ro I. 5 parts of HM2, the leather was drummed for 5 minutes. 然后在脱酸浴液中加入7份染料49b,然后在pH7. 5和35°C下染色30分钟。 Then 7 parts of dye added to the deacidifying float 49b, and then dyed at pH7. 5 and 35 ° C 30 min. 然后添加0. 5份碳酸氢钠并在pH 7. 6下转鼓加工60分钟。 0.5 parts of sodium hydrogencarbonate was then added and drummed for 60 minutes at pH 7. 6. 每次少许地添加总共8份碳酸钠以使浴液的pH值达到9. 5-9. 9之间以固色,然后在35°C转鼓·加工60分钟。 Each addition of a total of 8 parts of sodium carbonate to bring the pH reaches between the float 9. 5-9. 9 for fixation, 35 ° C and then drum-processed for 60 minutes. 浴液改变之后,每次用300份水将皮革在40°C洗涤三次,一共洗涤60分钟。 After float change, each time at 40 ° C and washed three times, washed with a total of 60 minutes the leather with 300 parts of water. 经过60分钟在200份水的浴液中毎次少许地添加总共3. 0份甲酸以达到3. 7的pH值。 Over 60 minutes in a float of 200 parts of water were added a little every time a total of 3.0 parts of formic acid to reach a pH of 3.7.

[1146] 将由此染色的皮革在由150份水和I份复鞣料G13构成的新制浴液中在45°C转鼓加工40分钟。 [1146] The leather thus dyed in 150 parts of water by a float freshly I and G13 of retanning material constituting the parts of the processing drum at 45 ° C for 40 minutes. 添加6份聚合鞣料G18,并在45°C复鞣40分钟。 Was added 6 parts of polymeric tanning material G18, and retanning 45 ° C for 40 minutes. 该浴液的pH值为4. 2。 The pH of the bath is 4.2. 添加I份碳酸氢钠并转鼓加工20分钟。 I part of sodium bicarbonate was added and drummed for 20 minutes. 将复鞣浴液与2份加脂剂Fl混合,并在45°C加脂20分钟。 The retanning float was admixed with 2 parts of fatliquor Fl, and fatliquoring at 45 ° C for 20 min. 将浴液与10份复鞣料G3混合,然后转鼓加工90分钟。 The float 10 parts of retanning material G3 and mixed, and then drummed for 90 minutes. 然后用6份加脂剂Fl和2份加脂剂F6在45°C进行加脂60分钟。 Then 6 parts of fatliquor with Fl and 2 parts of fatliquor F6 fatliquoring 60 minutes at 45 ° C. 然后在45分钟的过程中逐份添加5份甲酸以达到3. 5的pH值。 5 parts by portionwise addition of formic acid to reach a pH of 3.5 in the course of 45 minutes. 此后,使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float was dropped and the leather briefly rinsed cold.

[1147] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿拉紧并用绷革框干燥,修整,刮软并干转鼓加工。 [1147] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretched, wet-strained and toggle frame dried, conditioned, staked and dry drummed.

[1148] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的家具革。 [1148] This having excellent washing resistance, perspiration resistance, bleeding and furniture leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的家具革。 Furniture leather in Example Ia to 59k one dye which is in a similar manner.

[1149] 家具革配方7: [1149] Furniture leather recipe 7:

[1150] 将削匀厚度为I. I毫米的I块100重量份的传统铬鞣牛皮革在30°C在300份水的浴液中洗涤10分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过30分钟每次少许地添加总共3份碳酸氢钠,并达到7. 6的中和pH值。 100 parts by weight of the block I conventionally chrome-tanned bovine leather [1150] I. shaved thickness of I mm at 30 ° C the bath was washed with 300 parts of water for 10 minutes and then at 35 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes over 30 minutes after each addition of a total of 3 parts of sodium bicarbonate, and a neutralization a pH of 7.6. 然后在脱酸浴液中加入5. 5份染料52e,然后在pH 7. 5和35°C下染色40分钟。 It was then added 5.5 parts of dye 52e deacidifying float before dyeing at pH 7. 5 and 35 ° C 40 min. 每次少许地添加总共7份碳酸钠以使浴液的pH值达到9. 2-9. 6之间以固色,然后在35°C转鼓加工60分钟。 Each addition of a total of 7 parts of sodium carbonate to bring the pH of the float 9 reaches between 2-9. 6 for fixation, 35 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革在40°C洗涤三次,一共洗涤60分钟。 After float change, each time at 40 ° C and washed three times, washed with a total of 60 minutes the leather with 300 parts of water. 经过60分钟在150份水的浴液中每次少许地添加总共2. 0份甲酸以达到5. 2的pH值。 Little at a time over 60 minutes to add a total of 2.0 parts of formic acid in 150 parts of water bath, at a pH of 5.2.

[1151] 将由此染色的皮革在由100份水、3份聚合鞣料G18和I. 5份聚合鞣料G19构成的新制浴液中在45°C转鼓加工20分钟。 [1151] The thus freshly dyed leather tanning material G19 float 5 parts of a polymerization process consisting of 45 ° C for 20 minutes by drum 100 parts of water, and 3 parts of polymeric tanning material G18 I.. 将该复鞣浴液与I份加脂剂F6和0. 5份加脂剂F2混合,然后在45°C预加脂20分钟。 The retanning float parts of fatliquor F2 F6 0. 5 parts I and mixed with the fatliquor, at 45 ° C and then pre-fatliquoring 20 minutes. 将浴液与3份聚合鞣料G18、6份复鞣料G8和2份植物鞣料G22混合,然后复鞣60分钟。 The float with 3 parts of polymeric tanning material G18,6 parts retanning material G8 and G22 mixing 2 parts of vegetable tanning, retanning and 60 minutes. 然后用6份加脂剂F6、2份加脂剂F2和I份加脂剂F3在45°C加脂60分钟。 Then treated with 6 parts of fatliquor F6,2 parts of fatliquor F2 and F3 I parts of fatliquor fatliquoring at 45 ° C for 60 minutes. 然后在45分钟的过程中逐份添加4份甲酸以达到3. 5的pH值,然后添加100份水并转鼓加工10分钟。 Then in the course of 45 minutes by portionwise addition of 4 parts of formic acid to reach a pH of 3.5, 100 parts of water were then added and drumming for 10 minutes. 此后,使浴液滴出并将皮革简单冷漂洗。 Thereafter, the float was dropped and the leather briefly rinsed cold.

[1152] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿拉紧并用绷革框干燥,修整,刮软并干转鼓加工。 [1152] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretched, wet-strained and toggle frame dried, conditioned, staked and dry drummed.

[1153] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的家具革。 [1153] This having excellent washing resistance, perspiration resistance, bleeding and furniture leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的家具革。 Furniture leather in Example Ia to 59k one dye which is in a similar manner.

[1154] 家具革配方8: [1154] Furniture leather recipe 8:

[1155] 将削匀厚度为I. I毫米的I块100重量份的传统铬鞣牛皮革在30°C在300份水的浴液中洗涤10分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过25分钟每次少许地添加总共3份碳酸氢钠,并达到7. 6的中和pH值。 100 parts by weight of the block I conventionally chrome-tanned bovine leather [1155] I. shaved thickness of I mm at 30 ° C the bath was washed with 300 parts of water for 10 minutes and then at 35 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which little at a time over 25 minutes to add a total of 3 parts of sodium bicarbonate, and a neutralization a pH of 7.6. 然后在脱酸浴液中加入6份染料53b,然后在pH 7. 5和35°C下染色50分钟。 6 parts of the dye is then added to the deacidifying float 53b, and then dyed at pH 7. 5 and 35 ° C 50 min. 每次少许地添加总共7份固体碳酸钠以使浴液的pH值达到9. 5-10. 0之间以固色,然后在35°C转鼓加工60分钟。 Each addition of a total of 7 parts of solid sodium carbonate to bring the pH reaches between the float 9. 5-10. 0 for fixation, 35 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革在40°C洗涤三次,一共洗涤60分钟。 After float change, each time at 40 ° C and washed three times, washed with a total of 60 minutes the leather with 300 parts of water. 经过60·分钟在150份水和2. 2份甲酸的浴液中每次少许地达到4. 9的pH值。 After 60-minutes each float of 150 parts of water and 2.2 parts of formic acid in a little at a pH of 4.9.

[1156] 将由此染色的皮革在由100份水和2份复鞣料G14构成的新制浴液中转鼓加工30分钟。 [1156] The thus dyed leather drummed in a freshly float consisting of 100 parts of water and 2 parts of retanning material constituting G14 for 30 minutes. 然后加入5份聚合鞣料G18,再在45°C复鞣40分钟。 Then 5 parts of polymeric tanning material G18, retanning and then at 45 ° C 40 min. 将复鞣浴液与2份加脂剂F6和I份加脂剂F2混合,然后在45°C预加脂20分钟。 The retanning float with 2 parts of fatliquor F6 parts I and fatliquor F2 mixed, at 45 ° C and then pre-fatliquoring 20 minutes. 将浴液与6份复鞣料G2、2份植物鞣料G22和2份树脂鞣料G28混合,然后复鞣60分钟。 The float and 6 parts of retanning material G2,2 parts of vegetable tanning material G22 and G28 mixing 2 parts of resin tanning material, and then retanned for 60 minutes. 然后用8份加脂剂F6、2份加脂剂F2和I份加脂剂F3在45°C加脂60分钟。 Then 8 parts of fatliquor F6,2 parts of fatliquor F2 and F3 I parts of fatliquor fatliquoring at 45 ° C for 60 minutes. 在45分钟的过程中逐份添加4份甲酸以达到3. 5的pH值,此后加入100份水并转鼓加工10分钟。 In the course of 45 minutes by portionwise addition of 4 parts of formic acid to reach a pH of 3.5, after which 100 parts of water were added and drummed for 10 minutes. 然后将浴液排出并将皮革简单冷漂洗。 The bath is then discharged and the leather briefly rinsed cold.

[1157] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿拉紧并用绷革框干燥,修整,刮软并干转鼓加工。 [1157] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretched, wet-strained and toggle frame dried, conditioned, staked and dry drummed.

[1158] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的家具革。 [1158] This having excellent washing resistance, perspiration resistance, bleeding and furniture leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的家具革。 Furniture leather in Example Ia to 59k one dye which is in a similar manner.

[1159] 家具革配方9: [1159] Furniture leather recipe 9:

[1160] 将削匀厚度为I. I毫米的I块100重量份的传统铬鞣牛皮革在30°C在300份水的浴液中洗涤10分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过25分钟每次少许地添加总共3份碳酸氢钠,并达到7. 8的中和pH值。 100 parts by weight of the block I conventionally chrome-tanned bovine leather [1160] I. shaved thickness of I mm at 30 ° C the bath was washed with 300 parts of water for 10 minutes and then at 35 ° C in 100 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which little at a time over 25 minutes to add a total of 3 parts of sodium bicarbonate, and a neutralization a pH of 7.8. 然后在脱酸浴液中加入5. 7份染料58b,然后在pH 7. 7和35°C下染色60分钟。 It was then added 5.7 parts of the dye 58b in the deacidifying float, and then dyed at pH 7. 7 and 35 ° C 60 min. 每次少许地添加总共9份碳酸钠以使浴液的pH值达到9. 5-10. 0之间以固色,然后在35°C转鼓加工60分钟。 Each addition of a total of 9 parts of sodium carbonate to bring the pH reaches between the float 9. 5-10. 0 for fixation, 35 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革在40°C洗涤三次,一共洗涤60分钟。 After float change, each time at 40 ° C and washed three times, washed with a total of 60 minutes the leather with 300 parts of water. 经过60分钟在150份水的浴液中每次少许地添加总共2. 3份甲酸以达到5. 0的pH值。 Little at a time over 60 minutes to add a total of 2.3 parts of formic acid in 150 parts of water bath, at a pH of 5.0.

[1161] 将由此染色的皮革在由100份水和2份复鞣料G14构成的新制浴液中转鼓加工30分钟。 [1161] The thus dyed leather drummed in a freshly float consisting of 100 parts of water and 2 parts of retanning material constituting G14 for 30 minutes. 然后加入6份聚合鞣料G18,再在45°C复鞣40分钟。 It was then added 6 parts of polymeric tanning material G18, retanning and then at 45 ° C 40 min. 将复鞣浴液与2份加脂剂Fl混合,然后在45°C预加脂20分钟。 The retanning float was admixed with 2 parts of fatliquor Fl, and then pre-butter 45 ° C 20 min. 将浴液与4份复鞣料G3和2份植物鞣料G22混合,然后转鼓加工60分钟。 The bath was mixed with 4 parts of retanning material G3 and 2 parts of vegetable tanning material G22, and drumming for 60 minutes. 添加2份聚合鞣料G19,然后再复鞣20分钟。 Was added 2 parts of polymeric tanning material G19, retanning and then 20 minutes. 在复鞣浴液中加入6份加脂剂Fl、4份加脂剂F6和I份加脂剂F3,然后在45°C加脂60分钟。 It was added 6 parts of fatliquor bath retanning Fl, 4 parts of fatliquor F6 and F3 fatliquor parts I, at 45 ° C and then 60 minutes fatliquoring. 在45分钟的过程中逐份添加4份甲酸以达到3.5的pH值,此后加入100份水并转鼓加工10分钟。 In the course of 45 minutes by portionwise addition of 4 parts of formic acid to achieve a pH of 3.5, after which 100 parts of water were added and drummed for 10 minutes. 然后将浴液排出并将皮革简单冷漂洗。 The bath is then discharged and the leather briefly rinsed cold.

[1162] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿拉紧并用绷革框干燥,修整,刮软并干转鼓加工。 [1162] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretched, wet-strained and toggle frame dried, conditioned, staked and dry drummed.

[1163] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的家具革。 [1163] This having excellent washing resistance, perspiration resistance, bleeding and furniture leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的家具革。 Furniture leather in Example Ia to 59k one dye which is in a similar manner.

[1164] 汽车革配方I: [1164] Automotive leather recipe I:

[1165] 将削匀厚度为I. 2-1. 3毫米的I块100重量份的传统铬鞣牛皮革在30°C在300份水的浴液中洗涤10分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过25分钟每次少许地添加总共3份碳酸氢钠,并达到7. 8的中和pH值。 [1165] shaved thickness of I. 2-1. 3 mm I block 100 parts by weight of a conventional chrome-tanned bovine leather bath at 30 ° C in 300 parts of water, washed for 10 minutes and then at 35 ° C by the processing in a float of 100 parts of water and I. 5 parts of sodium formate for 5 minutes each time over 25 minutes after addition of a total of 3 parts of sodium bicarbonate, and a neutralization a pH of 7.8. 添加I. 5份HM2后,将皮革转鼓加工5分钟。 After the addition I. 5 parts of HM2, the leather was drummed for 5 minutes. 然后在脱酸浴液中加入4. 7份染料59d,然后在PH 7. 3和35°C下染色30分钟。 It was then added 4.7 parts of the dye 59d deacidifying float, and then dyed at PH 7. 3 and 35 ° C 30 min. 然后加入0. 5份碳酸氢钠并在pH7. 4下转鼓加工60分钟。 0.5 parts of sodium hydrogencarbonate was then added and drummed for 60 minutes at pH7. 4. 毎次少许地添加总共5份碳酸钠以使浴液的pH值达到9. 4-9. 8之间以固色,然后在35°C转鼓加工60分钟。 Addition of a total times every 5 parts of sodium carbonate to bring the pH of the float for fixation between 9 4-9. 8, 35 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革在40°C洗涤三次,一共洗涤60分钟。 After float change, each time at 40 ° C and washed three times, washed with a total of 60 minutes the leather with 300 parts of water. 经过60分钟在200份水的浴液中逐份添加总共3份甲酸以达到3. 7的pH值。 Over 60 minutes by portionwise addition of a total of 3 parts of formic acid to reach a pH of 3.7 in the bath 200 parts of water.

[1166] 将由此染色的皮革在由150份水和I. 5份复鞣料G13构成的新制浴液中在45°C转鼓加工60分钟。 [1166] The leather thus dyed in 150 parts of water by a float freshly I. 5 parts of retanning material and G13 constituting the processing drum at 45 ° C for 60 minutes. 然后加入8份聚合鞣料G18,再在45°C复鞣40分钟。 Followed by addition of 8 parts of polymeric tanning material G18, retanning and then at 45 ° C 40 min. 添加I. 5份碳酸氢钠,并在20分钟的转鼓加工时间后,用2份加脂剂Fl和0. 2份助剂HM4在45°C预加脂20分钟。 I. 5 parts of sodium bicarbonate was added, and after 20 minutes drumming time with 2 parts of fatliquor Fl and 0.2 parts of auxiliary HM4 pre butter 45 ° C 20 min. 将浴液与4份复鞣料G5、4份植物鞣料G21和2份树脂鞣料Gll混合,然后复鞣60分钟。 The float and 4 parts of retanning material G5,4 parts 2 parts of vegetable tanning material G21 and Gll mixed resin tanning material, and then retanned for 60 minutes. 将复鞣浴液与7份加脂剂Fl和3份加脂剂F6混合,再在45°C加脂60分钟。 The retanning float and 7 parts of fatliquor Fl and 3 parts of fatliquor F6 mixed, fatliquoring at 45 ° C for 60 minutes. 然后在45分钟的过程中逐份添加5份甲酸以达到3. 5的pH值,此后使浴液滴出并将皮革简单冷漂洗。 5 parts by portionwise addition of formic acid to reach a pH of 3.5 in the course of 45 minutes, after which the float was dropped and the leather briefly rinsed cold.

[1167] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿拉紧并用绷革框干燥,修整,刮软并干转鼓加工。 [1167] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretched, wet-strained and toggle frame dried, conditioned, staked and dry drummed.

[1168] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的汽车革。 [1168] This having excellent washing resistance, perspiration resistance, bleeding and rub-off fastness of automotive leather. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的汽车革。 Example Ia may be dyed with a dye to 59k one embodiment of automotive leather in a similar manner.

[1169] 汽车革配方2: [1169] Automotive leather recipe 2:

[1170] 将削匀厚度为I. 1-1. 2毫米的I块100重量份的传统有机鞣牛皮革在30°C在300份水的浴液中洗涤15分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加エ10分钟。 [1170] shaved thickness of I. 1-1. 2 mm I 100 parts by weight of a conventional block organic-tanned cow leather was washed with 300 parts of 15 minutes in the bath of water at 30 ° C, and then at 35 ° C in a float of 100 parts of water and I. 5 parts of sodium formate plus Ester 10 minutes. 该浴液具有4. 4的pH值。 The bath having a pH of 4.4. 将该浴液与7. 2份染料56混合,然后在pH 4. 5和35°C下染色60分钟。 The float 56 was mixed with 7.2 parts of dye, and then dyed at pH 4. 5 and 35 ° C 60 min. 在20分钟的过程中逐份添加总共3份碳酸氢钠以达到7. 1-7. 6的pH值。 In the course of 20 minutes by portionwise addition of a total of 3 parts of sodium bicarbonate to reach a pH of 7. 1-7. 6. 为了固色,逐份添加总共8份碳酸钠以使浴液的pH值达到9. 6-9. 7之间,然后在35°C转鼓加工90分钟。 For fixation by portionwise addition of a total of 8 parts of sodium carbonate to bring the pH reaches between the float 9. 6-9. 7, 35 ° C and then processed in the drum for 90 minutes. 浴液改变之后,每次用由300份水构成的浴液将皮革在40°C洗涤三次,一共洗涤60分钟。 After float change, the leather in each washed three times with 40 ° C, washed with a total of 60 minutes by a float of 300 parts of water. 经过60分钟在40°C在300份水的浴液中逐份添加总共2份甲酸以达到4. 2的pH值。 Over 60 minutes by portionwise addition of a total of 2 parts of formic acid to reach a pH of 4.2 at 40 ° C in a bath of 300 parts of water.

[1171] 将由此染色的皮革在由100份水和5份聚合鞣料G18构成的新制浴液中在35°C复鞣10分钟。 [1171] The leather thus dyed in 100 parts of water by a float freshly and 5 parts of polymeric tanning material G18 constituted retanning at 35 ° C for 10 min. 然后加入I份加脂剂F6和0. 5份加脂剂F2以便在35°C预加脂20分钟。 I then added parts of fatliquor F6 and 0.5 parts of fatliquor F2 to the pre-fat 35 ° C 20 min. 加入5份聚合鞣料G18和10份复鞣料G8以便复鞣60分钟。 Was added 5 parts of polymeric tanning material G18 and 10 parts of retanning retanning material G8 to 60 minutes. 将复鞣浴液与I份加脂剂F6和0. 5份加脂剂F2混合,以便在35°C加脂30分钟。 The retanning float and I parts of fatliquor F2 F6 0. 5 parts of the mixing and fatliquors, for greasing at 35 ° C 30 min. 然后用5份聚合鞣料G18和10份复鞣料G18和10份复鞣料G8使鞣制经过90分钟完成。 5 parts of polymeric tanning material and then with 10 parts of retanning material G18 and G18 and 10 parts of retanning material G8 so tanned after 90 minutes to complete. 然后在加入加脂剂F6和2份加脂剂F2后,在35°C加脂60分钟。 Then, after Jia Rujia fatliquor F6 and 2 parts of fatliquor F2, fatliquoring at 35 ° C for 60 minutes. 为了固定加脂剂,加入100份45°C的热水,并在20分钟的转鼓加工时间后,在60分钟的过程中添加3份甲酸以达到3. 5的pH值。 To fix the fatliquor, was added 100 parts of hot water of 45 ° C, and after 20 minutes drumming time, 3 parts of formic acid was added in the course of 60 minutes to achieve a pH value of 3.5. 此后将皮革用300份水洗涤15分钟。 300 parts of water, after which the leather is washed for 15 minutes.

[1172] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿拉紧、绷革框干燥,修整,刮软、干转鼓加工并拉紫。 [1172] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretched, wet-strained, toggle frame dried, conditioned, staked, dry drummed and pull purple.

[1173] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的白湿汽车革。 [1173] This having excellent washing resistance, perspiration resistance, bleeding resistance and wet-white leather car rub fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的白湿汽车革。 Wet-white leather automobile can be manufactured in one embodiment to 59k Ia dyes embodiment in an analogous manner.

[1174] 汽车革配方3: [1174] Automotive leather recipe 3:

[1175] 将削匀厚度为I. 1-1. 2毫米的I块100重量份的传统有机鞣牛皮革在30°C在300份水的浴液中洗涤15分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加エ10分钟。 [1175] shaved thickness of I. 1-1. 2 mm I 100 parts by weight of a conventional block organic-tanned cow leather bath at 30 ° C in 300 parts of water washed for 15 minutes and then at 35 ° C in a float of 100 parts of water and I. 5 parts of sodium formate plus Ester 10 minutes. 该浴液具有4. 4的pH值。 The bath having a pH of 4.4. 将该浴液与3. 5份染料54混合,然后在pH 4. 5和35°C下染色40分钟。 The bath is admixed with 3.5 parts of the dye 54, and then dyed at pH 4. 5 and 35 ° C 40 min. 在20分钟的过程中逐份添加总共3份碳酸氢钠以达到7. 6的pH值。 By portionwise addition of a total of 3 parts of sodium bicarbonate to reach a pH of 7.6 in the course of 20 minutes. 为了固色,逐份添加总共5份碳酸钠以使浴液的pH值达到9. 6-9. 7之间,然后在35°C转鼓加工90分钟。 For fixation by portionwise addition of a total of 5 parts of sodium carbonate to bring the pH reaches between the float 9. 6-9. 7, 35 ° C and then processed in the drum for 90 minutes. 浴液改变之后,每次用由300份水将皮革在40°C洗涤三次,一共洗涤60分·钟。 After float change, per 300 parts of water from the leather was washed three times at 40 ° C, washed with a total of 60 minutes Chung. 在60分钟的过程中,在200份水的浴液中逐份添加总共I. 5份甲酸以在40°C保持5. 0的pH值。 In the course of 60 minutes, 200 parts of water by the bath in a total parts I. 5 parts of formic acid was added to maintain the pH of 5.0 at 40 ° C.

[1176] 将由此染色的皮革在由50份水、15份疏水剂H5和15份聚合鞣料G18构成的新制浴液中在35°C复鞣90分钟。 [1176] The leather thus dyed in a fresh bath of water 50 parts, 15 parts and 15 parts of water repellent H5 polymeric tanning material G18 of retanning constituting at 35 ° C 90 min. 然后加入4份疏水剂H5、6份加脂剂F6和4份加脂剂F2,再在35°C加脂150分钟。 Followed by addition of 4 parts water repellent H5,6 parts of fatliquor F6 and 4 parts of fatliquor F2, then at 35 ° C fatliquoring 150 minutes. 然后加入100份45°C的热水,并转鼓加工10分钟。 100 parts of hot water 45 ° C was then added and drummed for 10 minutes. 然后在60分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 It was then added portionwise 4 parts of formic acid to reach a pH of 3.5 in the course of 60 minutes. 最后,将皮革用300份水洗涤15分钟。 Finally, the leather was washed with 300 parts of water over 15 minutes.

[1177] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿拉紧,绷革框干燥,修整,刮软,干转鼓加工过夜,刮软并用绷革框干燥。 [1177] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretched, wet-strained, toggle frame dried, conditioned, staked, dry drummed overnight, staked and toggle frame dried.

[1178] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的纯聚合物基白湿汽车革。 [1178] This having excellent washing resistance, perspiration resistance, bleeding and pure white polymer based automotive leather wet abrasion fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的纯聚合物基白湿汽车革。 Can be dyed with one of the dyes of Examples Ia to 59k embodiment of the pure polymer based wet-white leather car in a similar manner.

[1179] 汽车革配方4: [1179] Automotive leather recipe 4:

[1180] 将削匀厚度为I. 1-1. 2毫米的I块100重量份的传统铬鞣牛皮革在30°C在300份水的浴液中洗涤10分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过30分钟每次少许地添加总共3. 5份碳酸氢钠,并达到7. 6的中和pH值。 [1180] shaved thickness of I. 1-1. 2 mm I 100 parts by weight of a conventional block chrome-tanned bovine leather bath at 30 ° C in 300 parts of water, washed for 10 minutes and then at 35 ° C by the processing in a float of 100 parts of water and 5 parts of sodium formate I. 5 minutes over 30 minutes after each addition of a total 3.5 parts of sodium bicarbonate, and a neutralization a pH of 7.6. 然后在脱酸浴液中加入5. 2份染料51,然后在pH 7. 5和35°C下染色30分钟。 It was then added 5.2 parts of dye deacidifying float 51, and then dyed at pH 7. 5 and 35 ° C 30 min. 然后添加0. 5份碳酸氢钠并在pH 7. 6下转鼓加工60分钟。 0.5 parts of sodium hydrogencarbonate was then added and drummed for 60 minutes at pH 7. 6. 每次少许地添加总共7份碳酸钠以使浴液的PH值达到9. 3-9. 9之间以固色,然后在35°C转鼓加工60分钟。 Little at a time to add a total of 7 parts of sodium carbonate PH value between the float reaches 9. 3-9. 9 for fixation, 35 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革在40°C洗涤三次,一共洗涤60分钟。 After float change, each time at 40 ° C and washed three times, washed with a total of 60 minutes the leather with 300 parts of water. 经过60分钟在200份水的浴液中毎次少许地添加总共3. 5份甲酸以达到3. 5的pH值。 Over 60 minutes in a float of 200 parts of water were added a little every time a total of 3.5 parts of formic acid to reach a pH of 3.5.

[1181] 将由此染色的皮革在由150份水和3份复鞣料G12构成的新制浴液中在45°C转鼓加工10分钟。 [1181] The leather dyed in a freshly thus the float 150 parts of water and 3 parts of retanning material G12 in the configuration of the processing drum 45 ° C for 10 min. 在添加I. 5份加脂剂Fl后,将皮革在45°C预加脂50分钟。 After the addition of fatliquor I. 5 parts of Fl, the leather at 45 ° C pre fatliquoring 50 minutes. 然后添加0. 5份碳酸氢钠并转鼓加工30分钟。 0.5 parts of sodium hydrogencarbonate was then added and drumming for 30 minutes. 将浴液与5份聚合鞣料G18和I. 5份加脂剂Fl混合,然后转鼓加工40分钟。 The float and 5 parts of polymeric tanning material G18 and I. 5 parts of fatliquor Fl mixed, then drummed for 40 minutes. 将复鞣浴液与I. 5份加脂剂Fl和I. 5份加脂剂F2混合,然后在45°C加脂20分钟。 The retanning float and I. 5 parts of fatliquor I. 5 parts of Fl and F2 fatliquor mixed, then at 45 ° C fatliquoring for 20 min. 然后添加8份复鞣料G6、8份复鞣料G8和2份聚合鞣料G19。 Then added 8 parts of retanning material G6,8 parts retanning material G8 and 2 parts of polymeric tanning material G19. 在再60分钟的转鼓加工时间后,添加3份加脂剂Fl、l. 5份加脂剂F6和I. 5份加脂剂F2,然后在45°C加脂90分钟。 After another 60 minutes drumming time, add 3 parts of fatliquor Fl, l. 5 parts of fatliquor F6 and I. 5 parts F2 of fatliquor, then at 45 ° C fatliquoring 90 minutes. 然后在50分钟的过程中逐份添加3. 5份甲酸以达到3. 5的pH值。 It was then added portionwise 3.5 parts of formic acid to reach a pH of 3.5 in the course of 50 minutes. 此后,使浴液滴出并将皮革用300份水洗涤15分钟。 Thereafter, the float was dropped and the leather was washed with 300 parts of water over 15 minutes.

[1182] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿拉紧并用绷革框干燥,修整,刮软并干转鼓加工。 [1182] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretched, wet-strained and toggle frame dried, conditioned, staked and dry drummed.

[1183] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的汽车革。 [1183] This having excellent washing resistance, perspiration resistance, bleeding and rub-off fastness of automotive leather. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的汽车革。 Example Ia may be dyed with a dye to 59k one embodiment of automotive leather in a similar manner.

[1184] 汽车革配方5: [1184] Automotive leather recipe 5:

[1185] 将削匀厚度为I. 1-1. 2毫米的I块100重量份的传统铬鞣牛皮革在30°C在300份水的浴液中洗涤10分钟,然后在35°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过30分钟每次少许地添加总共3. 5份碳酸氢钠,并达到7. 5的中和pH值。 [1185] shaved thickness of I. 1-1. 2 mm I 100 parts by weight of a conventional block chrome-tanned bovine leather bath at 30 ° C in 300 parts of water, washed for 10 minutes and then at 35 ° C by the processing in a float of 100 parts of water and 5 parts of sodium formate I. 5 minutes over 30 minutes after each addition of a total 3.5 parts of sodium bicarbonate, and a neutralization a pH of 7.5. 在脱酸浴液中加入4. 7份染料48,然后在pH 7. 5和35°C下染色30分钟。 4.7 parts of the dye was added to the deacidifying float 48, and then dyed at pH 7. 5 and 35 ° C 30 min. 然后添加0. 5份碳酸氢钠并在pH 7. 6下转鼓加工60分钟。 0.5 parts of sodium hydrogencarbonate was then added and drummed for 60 minutes at pH 7. 6. 姆次少许地添加总共6份固体碳酸钠以使浴液的PH值达到9. 3-9. 9之间以固色,然后在35°C转鼓加工60分钟。 Farm views addition of a total of 6 parts of solid sodium carbonate to make the PH value between the float reaches 9. 3-9. 9 for fixation, 35 ° C and then processed in the drum for 60 minutes. 浴液改变之后,每次用300份水将皮革在40°C洗涤三次,一共洗涤60分钟。 After float change, each time at 40 ° C and washed three times, washed with a total of 60 minutes the leather with 300 parts of water. 经过60分钟在200份水的浴液中每次少许地添加总共I. 5份甲酸以达到5. 5的pH值。 Over 60 minutes every addition of a total I. 5 parts of formic acid in 200 parts of water bath, at a pH of 5.5.

[1186] 将由此染色的皮革在由120份水和6份聚合鞣料G18构成的新制浴液中在45°C转鼓加工5分钟。 [1186] The leather thus dyed in a fresh bath of water and 6 parts of 120 parts of polymeric tanning material G18 in the configuration of the processing drum 45 ° C for 5 minutes. 然后加入2份聚合鞣料G19。 2 parts of polymeric tanning material G19 were then added. 在再5分钟的转鼓加工时间后,添加I. 5份加脂剂Fl并在45°C转鼓加工30分钟。 After an additional 5 minutes drumming time, add I. 5 parts of fatliquor Fl and processed at 45 ° C the drum for 30 minutes. 然后加入I. 5份加脂剂Fl和I份加脂剂F2,再预加脂20分钟。 I. 5 parts was then added fatliquor Fl and I parts of fatliquor F2, then pre fatliquoring 20 minutes. 将浴液与4份聚合鞣料G18混合,然后转鼓加工20分钟。 The float and 4 parts of polymeric tanning material G18 were mixed and then drummed for 20 minutes. 然后添加8份复鞣料G6和8份复鞣料G8。 8 parts of retanning material was then added 8 parts of retanning material G6 and G8. 在40分钟的转鼓加工时间后,添加I份聚合鞣料G19,然后鞣制20分钟至完成。 After 40 minutes drumming time, parts of polymeric tanning material G19 I added, then 20 minutes to complete the tanning. 将复鞣浴液与6份加脂剂Fl和2份加脂剂F2混合,然后在45°C加脂90分钟。 The retanning float and 6 parts of fatliquor Fl and F2 2 parts of fatliquor mixed, then at 45 ° C fatliquoring 90 minutes. 然后在45分钟的过程中逐份添加3. 5份甲酸以达到3. 5的pH值。 It was then added portionwise 3.5 parts of formic acid to reach a pH of 3.5 in the course of 45 minutes. 此后,使浴液滴出并将皮革用300份水洗涤15分钟。 Thereafter, the float was dropped and the leather was washed with 300 parts of water over 15 minutes.

[1187] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿拉紧并用绷革框干燥,修整,刮软并干转鼓加工。 [1187] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretched, wet-strained and toggle frame dried, conditioned, staked and dry drummed.

[1188] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的汽车革。 [1188] This having excellent washing resistance, perspiration resistance, bleeding and rub-off fastness of automotive leather. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的汽车革。 Example Ia may be dyed with a dye to 59k one embodiment of automotive leather in a similar manner.

[1189] 服装革配方I: [1189] garment leather formula I:

[1190] 将削匀厚度为0. 7毫米的I块100重量份的传统铬鞣绵羊革在35°C在300份水的浴液中洗涤10分钟,然后在40°C在由150份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过20分钟每次少许地添加总共3份碳酸氢钠。 100 parts [1190] shaved thickness of 0.7 mm by weight of the block I conventionally chrome-tanned sheepskin bath at 35 ° C in 300 parts of water, washed for 10 minutes and then at 40 ° C in 150 parts of water by a bath and drum I. 5 parts of sodium formate and processing for 5 minutes, after which time over 20 minutes addition of a total of 3 parts of sodium bicarbonate. 然后加入3份助剂HM4并转鼓加工10分钟。 Then 3 parts of auxiliary HM4 and drumming for 10 minutes. 该浴液的pH值为7. 7。 The pH of the bath is 7.7. 将该脱酸浴液与9份染料44混合,然后在pH 7. 4和40°C下染色40分钟。 This mixed deacidifying float 9 with 44 parts of dye, and then dyed at pH 7. 4 and 40 ° C 40 min. 毎次少许地添加总共9份碳酸钠以使浴液的pH值达到9. 6-9. 8之间以固色,并将皮革在40°C转鼓加工60分钟。 Once every addition of a total of 9 parts of sodium carbonate to bring the pH of the float for fixation between 9 6-9. 8, and the leather in the drum 40 ° C for 60 minutes. 浴液改变之后,每次用300份水将皮革在40°C洗涤三次,一共洗涤60分钟。 After float change, each time at 40 ° C and washed three times, washed with a total of 60 minutes the leather with 300 parts of water. 在55分钟的过程中,在150份水的浴液中每次少许地添加总共4份甲酸以达到3. 6的pH值。 In the course of 55 minutes, each addition of a total of 4 parts of formic acid in 150 parts of water bath, at a pH of 3.6.

[1191] 将由此染色的皮革在由150份水和2份复鞣料G14构成的新制浴液中在45°C转鼓加工40分钟。 [1191] The leather thus dyed in 150 parts of water by a float freshly and 2 parts of retanning material G14 in the configuration of the processing drum 45 ° C for 40 minutes. 然后加入2份甲酸钠。 Then 2 parts of sodium formate. 在再20分钟的转鼓加工时间后,添加2份碳酸氢钠并在45°C转鼓加工20分钟。 After another 20 minutes drumming time, 2 parts of sodium hydrogen carbonate was added at 45 ° C and the processing drum 20 min. 该浴液的pH值为5. 2。 The pH of the bath is 5.2. 将该浴液与8份复鞣料G3和2份复鞣料Gll混合,然后转鼓加工40分钟。 The bath is admixed with 8 parts of retanning material G3 and 2 parts of retanning material Gll, then drummed for 40 minutes. 然后加入6份加脂剂Fl、4份加脂剂F3和I份疏水剂H7。 6 parts of fatliquor Fl was then added, 4 parts of fatliquor F3 and I parts water repellent H7. 在20分钟的转鼓加工时间后,添加4份聚合鞣料GlO并转鼓加工20分钟。 After 20 minutes drumming time, 4 parts of polymeric tanning material GlO was added and drummed for 20 minutes. 然后加入6份加脂剂Fl、4份加脂剂F3和I份疏水剂H7。 6 parts of fatliquor Fl was then added, 4 parts of fatliquor F3 and I parts water repellent H7. 在40分钟的加脂时间后,在45分钟的过程中逐份添加5份甲酸以达到3. 5的pH值。 After 40 minutes fatliquoring time, in the course of 45 minutes by portionwise addition of 5 parts of formic acid to reach a pH of 3.5. 此后,使浴液滴出并将皮革用300份水洗涤15分钟。 Thereafter, the float was dropped and the leather was washed with 300 parts of water over 15 minutes.

[1192] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,悬浮干燥,修整,刮软,干转鼓加工并用绷革框干燥。 [1192] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretched, the suspension was dried, conditioned, staked, dry drummed and toggle frame dried.

[1193] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的服装革。 [1193] This having excellent washing resistance, perspiration resistance, bleeding and garment leather scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的服装革。 Garment leather can be produced in one of Examples Ia to 59k dyes embodiment in an analogous manner.

[1194] 服装革配方2: [1194] garment leather recipe 2:

[1195] 将削匀厚度为0. 8-0. 9毫米的I块100重量份的传统铬鞣牛皮革在35°C在200份水的浴液中洗涤10分钟,然后在40°C在由100份水和I. 5份甲酸钠构成的浴液中转鼓加エ5分钟,此后经过25分钟每次少许地添加总共3. 2份碳酸氢钠以达到7. 6的中和pH值。 [1195] shaved thickness of 0. 8-0. 9 mm I-block 100 parts by weight of conventional chrome-tanned bovine leather bath at 35 ° C in 200 parts of water washed for 10 minutes and then at 40 ° C in a float of 100 parts of water and I. 5 parts of sodium formate plus Ester 5 minutes over 25 minutes after each addition of a total 3.2 parts of sodium bicarbonate and a pH of 7.6. 将该脱酸浴液与8份染料混合物12hu混合,然后在pH 7. 5和40°C下染色40分钟。 The deacidifying float 8 parts 12hu dye mixture is mixed with, and then dyed at pH 7. 5 and 40 ° C 40 min. 每次少许地添加总共8. 7份碳酸钠以使浴液的pH值达到9. 6-9. 8之间以固色,并将皮革在40°C·转鼓加工90分钟。 Each addition of a total 8.7 parts of sodium carbonate to bring the pH of the float for fixation between 9 6-9. 8, and the leather in the drum 40 ° C · 90 minutes. 浴液改变之后,每次用300份水将皮革洗涤三次,一共洗涤60分钟。 After float change, the leather was washed three times each, total of 60 minutes and washed with 300 parts of water. 在60分钟的过程中,在200份水的浴液中每次少许地添加总共5份甲酸以达到3. 3的pH值。 In the course of 60 minutes, the addition of a total per 5 parts of formic acid in 200 parts of water bath, at a pH of 3.3.

[1196] 将由此染色的皮革在由100份水和3份复鞣料G12构成的新制浴液中在30°C转鼓加工10分钟。 [1196] The leather dyed in a freshly thus the float 100 parts of water and 3 parts of retanning material G12 in the configuration of the processing drum 30 ° C for 10 min. 添加4份铬鞣料G24和I. 5份助剂HM6,然后在30°C重新铬鞣50分钟。 Was added 4 parts of chrome tanning material G24 I. 5 parts of adjuvants and HM6, and then re-tanning at 30 ° C 50 min. 然后加入I份甲酸钠,再转鼓加工90分钟。 I then added parts of sodium formate, then drummed for 90 minutes. 在加入100份水后,将皮革重新铬鞣过夜。 After the addition of 100 parts of water, re-tanning leather overnight. 然后将浴液浙干并将皮革用300份水在45V洗洚10分钟。 The bath is then dried and the leather was washed Zhejiang flood 45V for 10 min with 300 parts of water. 将皮革在由100份水和I. 5份疏水剂H5构成的新制浴液中转鼓加工20分钟。 The leather was drummed in a freshly float consisting of 100 parts of water and I. 5 parts hydrophobicizer H5 20 minutes. 然后加入5份聚合鞣料G18,在5分钟的转鼓加エ时间后,加入2份复鞣料G5。 Then 5 parts of polymeric tanning material G18, 5 minutes after the time the drum plus Ester, 2 parts of retanning material G5. 再复鞣30分钟后,加入2份聚合鞣料G19,将皮革转鼓加工10分钟,然后加入5份复鞣料G5。 After a further 30 minutes of retanning, was added 2 parts of polymeric tanning material G19, the leather was drummed for 10 minutes and then was added 5 parts of retanning material G5. 再复鞣60分钟后,加入4份疏水剂H8、6份疏水剂H2、7份疏水剂H7和0. 8份助剂HM4,然后在45°C加脂60分钟。 After an additional 60 minutes retanning, was added 4 parts of a hydrophobic agent H8,6 parts water repellent H2,7 H7 parts water repellent additives and 0.8 parts of HM4, and then at 45 ° C fatliquoring for 60 minutes. 然后添加100份水并在60。 100 parts of water was then added at 60. . 转鼓加工10分钟。 Drumming for 10 minutes. 然后在45分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 It was then added portionwise 4 parts of formic acid to reach a pH of 3.5 in the course of 45 minutes. 此后,将浴液浙干并将皮革在由300份水和0. 15份甲酸构成的新制浴液中洗涤15分钟。 Thereafter, the leather was washed and dried float Zhejiang float in a freshly made 300 parts of water and 0.15 parts of formic acid for 15 minutes. 将皮革在由150份水、2份疏水剂H7和0. 2份助剂HM4构成的新制浴液中在30°C转鼓加工20分钟。 The leather float in a freshly made 150 parts of water, 2 parts of a hydrophobic agent and 0.2 parts H7 auxiliary HM4 constituted processing drum at 30 ° C for 20 min. 添加5份矿物鞣料G30,然后固定90分钟。 Add 5 parts of a mineral tanning material G30, and then fixed for 90 minutes. 最后,将皮革用由300份水和0. 2份甲酸构成的浴液洗涤一次,并用由300份水和0. I份甲酸构成的浴液洗涤一次,毎次都在30°C洗涤10分钟。 Finally, the washing bath of 300 parts of water and 0.2 parts of formic acid leather once, and washed with a float of 300 parts of water and 0. I parts of formic acid primary, secondary are washed every 30 ° C for 10 minutes .

[1197] 将由此染色、复鞣和疏水的皮革搭马过夜、然后伸展,湿拉紧并用绷革框干燥,修整,刮软,干转鼓加工并用绷革框干燥。 [1197] The thus dyed, retanned and hydrophobic horsed overnight and then stretched, wet-strained and toggle frame dried, conditioned, staked, dry drummed and toggle frame dried.

[1198] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的疏水摩托车服皮革。 [1198] This having excellent washing resistance, perspiration resistance, bleeding and rub-off fastness hydrophobic motorcycle clothing leather. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的摩托车服皮革。 Dyed with one of the dyes of Examples Ia to 59k in a similar manner motorcycle clothing leather.

[1199] 手套革配方I: [1199] leather gloves formula I:

[1200] 将削匀厚度为0. 5-0. 7毫米的I块100重量份的传统铬鞣山羊革在35°C在300份水的浴液中洗涤10分钟,然后在35°C在由120份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过30分钟每次少许地添加总共3. I份碳酸氢钠。 Goat conventional chrome tanning leather [1200] shaved thickness of 0. 5-0. 7 mm I-block 100 parts by weight of 35 ° C the bath was washed with 300 parts of water for 10 minutes and then at 35 ° C a float in the machining parts of water and 120 I. 5 parts of sodium formate for 5 minutes each time over 30 minutes after addition of a total 3. I parts of sodium bicarbonate. 然后加入3份助剂HM2并转鼓加工5分钟。 Then 3 parts of auxiliary HM2 and drumming for 5 minutes. 该浴液的pH值为7. 8。 The pH of the bath is 7.8. 将该脱酸浴液与10份染料混合物13hi混合,然后在pH 7. 4和35°C下染色40分钟。 The deacidifying float 13hi mixed with 10 parts of the dye mixture, and then dyed at pH 7. 4 and 35 ° C 40 min. 每次少许地添加总共9份碳酸钠以使浴液的pH值达到9. 6-9. 8之间以固色,并将皮革在35°C转鼓加工90分钟。 Each addition of a total of 9 parts of sodium carbonate to bring the pH of the float for fixation between 9 6-9. 8, and the leather in the drum 35 ° C for 90 minutes. 浴液改变之后,每次用300份水和I. 5份助剂HM3将皮革在40°C洗涤两次,一共洗涤50分钟。 After float change, each time with 300 parts of water and additives I. 5 parts HM3 The leather was washed twice at 40 ° C, washed with a total of 50 minutes. 在60分钟的过程中,在200份水的浴液中每次少许地添加总共3份甲酸以达到3. 4的pH值。 In the course of 60 minutes, each addition of a total of 3 parts of formic acid in 200 parts of water bath, at a pH of 3.4.

[1201] 将由此染色的皮革在由150份水和I. 5份复鞣料G13构成的新制浴液中在40°C转鼓加工60分钟。 [1201] The leather thus dyed in 150 parts of water by a float freshly I. 5 parts of retanning material and G13 constituting the processing drum at 40 ° C for 60 minutes. 然后加入I. 5份甲酸钠。 I. 5 parts of sodium were then added. 在20分钟的转鼓加工时间后,添加I份碳酸氢钠并在40°C转鼓加工30分钟。 After 20 minutes drumming time, parts of sodium bicarbonate was added I at 40 ° C and the processing drum 30 minutes. 将该浴液与6份聚合鞣料G18混合,然后转鼓加工40分钟。 The float and 6 parts of polymeric tanning material G18 were mixed and then drummed for 40 minutes. 此后加入6份复鞣料G3,再复鞣30分钟。 After addition of 6 parts of retanning material G3, then 30 minutes of retanning. 然后加入5份疏水剂H3、2份聚合鞣料G19、10份复鞣料G9、4份加脂剂F9和I份碳酸钠,然后复鞣120分钟。 Then 5 parts of a hydrophobic agent H3,2 G19,10 parts parts parts retanning material G9,4 fatliquor F9 I and polymeric tanning material parts of sodium carbonate, and then retanned for 120 minutes. 在45分钟的过程中逐份添加3. 5份甲酸以达到3. 5的pH值。 In the course of 45 minutes by portionwise addition of 3.5 parts of formic acid to reach a pH of 3.5. 然后加入3份疏水剂H4后,转鼓加工20分钟。 After then adding 3 parts of water repellent H4, drumming for 20 minutes. 此后,使浴液滴出并将皮革洗涤两次,毎次都用由300份水和0. 2份甲酸构成的浴液洗涤15分钟。 Thereafter, the bath was dropped and the leather was washed twice, once every 300 parts of the float are washed with water and 0.2 parts of formic acid for 15 minutes.

[1202] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿-拉紧并用绷革框干燥,修整,刮软并干转鼓加工。 [1202] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, wet - strained and toggle frame dried, conditioned, staked and dry drummed.

[1203] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的手套革。 [1203] This having excellent washing resistance, perspiration resistance, bleeding and gloving abrasion fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的手套革。 Leather gloves can be produced in one of Examples Ia to 59k dyes embodiment in an analogous manner.

[1204] 手套革配方2: [1204] glove leather recipe 2:

[1205] 将削匀厚度为0. 5-0. 7毫米的I块100重量份的传统铬鞣山羊革在30°C在300份水的浴液中洗涤10分钟,然后在35°C在由120份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过30分钟每次少许地添加总共3. I份碳酸氢钠。 Conventionally chrome-tanned leather I goat block 100 parts by weight of [1205] shaved thickness of 0. 5-0. 7 mm at 30 ° C the bath was washed with 300 parts of water for 10 minutes and then at 35 ° C a float in the machining parts of water and 120 I. 5 parts of sodium formate for 5 minutes each time over 30 minutes after addition of a total 3. I parts of sodium bicarbonate. 然后加入3份助剂HM2并转鼓加工5分钟。 Then 3 parts of auxiliary HM2 and drumming for 5 minutes. 该浴液的pH值为7. 8。 The pH of the bath is 7.8. 将该脱酸浴液与8份染料混合物13gz混合,然后在pH 7. 4和35°C下染色40分钟。 The deacidifying float 8 parts 13gz dye mixture is mixed with, and then dyed at pH 7. 4 and 35 ° C 40 min. 每次少许地添加总共8份固体碳酸钠以使浴液的pH值达到9. 6-9. 8之间以固色,并将皮革在35°C转鼓加工90分钟。 Each addition of a total of 8 parts of solid sodium carbonate to bring the pH of the float for fixation between 9 6-9. 8, and the leather in the drum 35 ° C for 90 minutes. 浴液改变之后,每次用300份水和I. 5份助剂HM3将皮革在40°C洗涤两次,一共洗涤50分钟。 After float change, each time with 300 parts of water and additives I. 5 parts HM3 The leather was washed twice at 40 ° C, washed with a total of 50 minutes. 在60分钟的过程中,在200份水的浴液中每次少许地添加总共I. 3份甲酸以达到5. 8的pH值。 In the course of 60 minutes, in a float of 200 parts of water per addition of a total I. 3 parts of formic acid to reach a pH of 5.8.

[1206] 将由此染色的皮革在由150份水和4份疏水剂H3构成的新制浴液中转鼓加工20分钟。 [1206] The thus dyed leather drummed in a freshly made float 150 parts of water and 4 parts of a hydrophobic agent consisting of H3 20 minutes. 然后加入8份聚合鞣料G18,再复鞣40分钟,此后,加入8份复鞣料G2,再在40。 Followed by addition of 8 parts of polymeric tanning material G18, retanning and then 40 minutes, after addition of 8 parts of retanning material G2, then at 40. . 转鼓加工30分钟。 Drumming for 30 minutes. 然后添加4份疏水剂H3、0. 5份助剂HM4、8份复鞣料G9、3份加脂剂F9和0. 8份碳酸钠,然后复鞣120分钟。 It was then added 4 parts of a hydrophobic agent H3,0. 5 HM4,8 auxiliary parts parts parts retanning material G9,3 fatliquor F9 and 0.8 parts of sodium carbonate, and then retanned for 120 minutes. 在35分钟的过程中逐份添加3. 5份甲酸以达到3. 5的PH值。 In the course of 35 minutes by portionwise addition of 3.5 parts of formic acid PH value of 3.5. 然后加入3份疏水剂H7和3份助剂HM4,并转鼓加工20分钟。 Then 3 parts of a hydrophobic agent and 3 parts of auxiliary H7 HM4, and drummed for 20 minutes. 此后,使浴液滴出并将皮革洗涤两次,毎次都用由300份水和0. 2份甲酸构成的浴液洗涤15分钟。 Thereafter, the bath was dropped and the leather was washed twice, once every 300 parts of the float are washed with water and 0.2 parts of formic acid for 15 minutes.

[1207] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿-拉紧并用绷革框干燥,修整,刮软并干转鼓加工。 [1207] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, wet - strained and toggle frame dried, conditioned, staked and dry drummed.

[1208] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的手套革。 [1208] This having excellent washing resistance, perspiration resistance, bleeding and gloving abrasion fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的手套革。 Leather gloves can be produced in one of Examples Ia to 59k dyes embodiment in an analogous manner.

[1209] 手套革配方3: [1209] glove leather recipe 3:

[1210] 将削匀厚度为0. 5-0. 7毫米的I块100重量份的传统铬鞣山羊革在30°C在300份水的浴液中洗涤10分钟,然后在35°C在由120份水和I. 5份甲酸钠构成的浴液中转鼓加工5分钟,此后经过30分钟每次少许地添加总共3. I份碳酸氢钠。 Conventionally chrome-tanned leather I goat block 100 parts by weight of [1210] shaved thickness of 0. 5-0. 7 mm for 10 minutes and washed with 300 parts of water bath at 30 ° C, and then at 35 ° C a float in the machining parts of water and 120 I. 5 parts of sodium formate for 5 minutes each time over 30 minutes after addition of a total 3. I parts of sodium bicarbonate. 然后加入3份助剂HM2并转鼓加工5分钟。 Then 3 parts of auxiliary HM2 and drumming for 5 minutes. 该浴液的pH值为7. 8。 The pH of the bath is 7.8. 将该脱酸浴液与8. 2份染料混合物12hb混合,然后在pH 7. 4和35°C下染色40分钟。 The mixing 2 parts of the dye mixture 12hb 8. deacidifying float and then dyed at pH 7. 4 and 35 ° C 40 min. 每次少许地添加总共8份固体碳酸钠以使浴液的pH值达到9. 6-9. 8之间以固色,并将皮革在35°C转鼓加工90分钟。 Each addition of a total of 8 parts of solid sodium carbonate to bring the pH of the float for fixation between 9 6-9. 8, and the leather in the drum 35 ° C for 90 minutes. 浴液改变之后,每次用300份水将皮革在40°C洗涤两次,一共洗涤60分钟。 After float change, each time washed twice at 40 ° C, the leather was washed with a total of 60 minutes with 300 parts of water. 在60分钟的过程中,在200份水的浴液中每次少许地添加总共I. 2份甲酸以达到5. 7的pH值。 In the course of 60 minutes, in a float of 200 parts of water per addition of a total I. 2 parts of formic acid to reach a pH of 5.7.

[1211] 将由此染色的皮革在由100份水、I份疏水剂Hl和0. 2份助剂HM4构成的新制浴液中转鼓加工20分钟。 [1211] The thus dyed leather drummed in a freshly float consisting of 100 parts of water, I water repellent Hl parts and 0.2 parts constituting the auxiliary HM4 20 minutes. 然后加入10份疏水剂H5并转鼓加工5分钟。 Then, 10 parts of water repellent H5 and drummed for 5 minutes. 然后加入10份聚合鞣料G18并复鞣55分钟。 It was then added 10 parts of polymeric tanning material and G18 of retanning for 55 minutes. 将复鞣浴液与5份疏水剂H5、8份疏水剂Hl和0. 8份助剂HM4混合,然后加脂120分钟。 The retanning float 5 parts of a hydrophobic agent and a hydrophobic agent Hl H5,8 parts and 0.8 parts of auxiliary HM4 mixed and fatliquoring 120 minutes. 加入100份水并转鼓加工20分钟后,在50分钟的过程中逐份添加4份甲酸以达到3. 5的pH值。 After addition of 100 parts of water and drumming for 20 minutes by portionwise addition of 4 parts of formic acid in the course of 50 minutes to achieve a pH value of 3.5. 此后,使浴液滴出并将皮革洗涤两次,毎次都用由300份水和0. 2份甲酸构成的浴液洗涤15分钟。 Thereafter, the bath was dropped and the leather was washed twice, once every 300 parts of the float are washed with water and 0.2 parts of formic acid for 15 minutes.

[1212] 将由此染色、复鞣和加脂的皮革搭马过夜、然后伸展,湿-拉紧并用绷革框干燥,修整,刮软并干转鼓加工。 [1212] The thus dyed, retanning and fatliquoring leather was horsed overnight and then stretching, wet - strained and toggle frame dried, conditioned, staked and dry drummed.

[1213] 这产生具有优异的耐洗、耐汗、耐渗移和耐擦坚牢度的纯聚合物基疏水手套革。 [1213] This having excellent washing resistance, perspiration resistance, bleeding and the pure polymer a hydrophobic group gloving scuff fastness. 可以按照类似方式制造用实施例Ia至59k的染料之一染色的手套革。 Leather gloves can be produced in one of Examples Ia to 59k dyes embodiment in an analogous manner. · ·

Claims (14)

  1. 1. 一种用至少ー种染料F将皮革染色的方法,其中染料F含有至少ー个式A的可被碱活化的基团: A species with at least ー a method of dyeing leather dyes F, wherein F contains the dye of formula ー least one group A may be alkali-activated:
    其中-----代表与染料分子相连的键; X是吸电子基团,其选自氟、氯、CN、NO2、式-C(O)-R1和S(O)2R2的基团,其中R1和R2独立地代表0H、烷基、卤烷基、烷氧基或苯基,k是1、2或3,η是O或I且B是CH = CH2基团或CH2-CH2-Q基团,其中Q是可碱分离的基团,其选自卤素、-O-SO3H, -S-SO3H、ニ烷基氨基、三-C1-C4烷基铵、苄基ニ-C1-C4烷基铵、N-连接的吡啶鐵,式R3S(O)2_、R4S(O)2-0-和R5C(O)-O-的基团,其中,R3、R4和R5独立地为烷基、卤烷基或苯基,且R5还可以是氢, 该方法包括用PH值为7. 5至11的含有至少ー种染料F的水浴液处理皮革, 其中染料F选自通式I至XV的染料和这些染料的金属络合物: Dk1-N = N- [PN = N-] /k1 [-N = N-Dk2] m (I) Dk1-N = N-Napht1 [-N = N-Tk1] r [-N = N-Kk1] k [-N = N-Dk2] n (II) Dk1-N = N-Napht1-N = N-Tk1-N = N-Kk1-N = N-Tk2-N = N-Napht2-N = N-Dk2 (III) Dk1-N = N-Kk1-N = N-Tk1-N = N-Kk2-N = N-Dk2(IV) Dk1-N = N- [PN = N-] pNa Wherein ----- represents the bond attached to the dye molecule; X is an electron withdrawing group selected from fluoro, chloro, CN, NO2, formula -C (O) -R1 and S (O) 2R2 group of wherein R1 and R2 independently represent 0H, alkyl, haloalkyl, alkoxy or phenyl, k is 1, 2 or 3, η is I or O and B is CH = CH2 group or a CH2-CH2-Q group, wherein Q is a separate base group, selected from halogen, -O-SO3H, -S-SO3H, ni alkylamino, tri -C1-C4 alkyl ammonium, benzyl -C1-C4 alkyl ni ammonium groups, pyridine iron N- linked formula R3S (O) 2_, R4S (O) 2-0- and R5C (O) -O- group, wherein, R3, R4 and R5 are independently an alkyl group, haloalkyl or phenyl, and R5 can also be hydrogen, which method comprises the PH value of 7.5 to 11 containing at least a water bath ー kinds of treating leather dyes F, wherein F is selected from dyes of the formulas I to XV metal complex dyes, and these dyes: Dk1-N = N- [PN = N-] / k1 [-N = N-Dk2] m (I) Dk1-N = N-Napht1 [-N = N-Tk1 ] r [-N = N-Kk1] k [-N = N-Dk2] n (II) Dk1-N = N-Napht1-N = N-Tk1-N = N-Kk1-N = N-Tk2-N = N-Napht2-N = N-Dk2 (III) Dk1-N = N-Kk1-N = N-Tk1-N = N-Kk2-N = N-Dk2 (IV) Dk1-N = N- [PN = N-] pNa pht1 [-N = NR] ,-NH-Tr1-NH-Dk2 (V) Dk1-N = NP-NH-Tr1-NH-RN = N-Dk2(VI) Dk1-N = N-Napht1-N = N-Tk1-N = NP-NH-Tr1-NH-Dk2(VII) Dk1-N = N-Napht1-NH-Tr1-NH-P-NH-Tr2-NH-Napht2-N = N-Dk2(VIII) Dk1-N = N-Napht1-NH-Tr1-NH-Tk1-NH-Tr2-NH-Napht2-N = N-Dk2 (IX) Dk1 [-N = NL] ,-NH-Tr1-NH-MN = N-Napht1-N = NP-NH-Tr2-NH- [RN = N-] nDk2 (X) Dk1-N = N-Kk1-N = N-Tk1-NH-Tr1-NH-Dk2 (XI) Dk1-N = N- [PN = N - ] PR - N = N - K k 1 [- N = N-Dk2] n(XII)Dk1-N = N-Pyr-A(XIII) Kk3-N = N-Tk1-N = N-Kk1-N = NA(XIV) Dk1-N = NPN = N-Kk1-N = NRN = N-Dk2(XV) 其中: k、η、p和r独立地为O或I,条件是式II中k+n+r = 1、2或3 ; m是0、1或2 ; Dk\Dk2独立地代表源自苯、萘或喹啉的基团,其中萘、喹啉和苯任选包含1、2或3个取代基,其中取代基选自S03H、COOH, OH、NH2、N02、CN、CONH2、卤素、C1-C4烷基、C1-C4羟烷基、羧基-C1-C4烷基、C1-C4烷氧基、C1-C4烷基氨基、C1-C4 ニ烷基氨基、C1-C4烷基氨基羰基、C1-C4 ニ烷基氨基羰基、C1-C4烷基氨基 pht1 [-N = NR], -NH-Tr1-NH-Dk2 (V) Dk1-N = NP-NH-Tr1-NH-RN = N-Dk2 (VI) Dk1-N = N-Napht1-N = N -Tk1-N = NP-NH-Tr1-NH-Dk2 (VII) Dk1-N = N-Napht1-NH-Tr1-NH-P-NH-Tr2-NH-Napht2-N = N-Dk2 (VIII) Dk1 -N = N-Napht1-NH-Tr1-NH-Tk1-NH-Tr2-NH-Napht2-N = N-Dk2 (IX) Dk1 [-N = NL], -NH-Tr1-NH-MN = N- Napht1-N = NP-NH-Tr2-NH- [RN = N-] nDk2 (X) Dk1-N = N-Kk1-N = N-Tk1-NH-Tr1-NH-Dk2 (XI) Dk1-N = N- [PN = N -] PR - N = N - K k 1 [- N = N-Dk2] n (XII) Dk1-N = N-Pyr-A (XIII) Kk3-N = N-Tk1-N = N-Kk1-N = NA (XIV) Dk1-N = NPN = N-Kk1-N = NRN = N-Dk2 (XV) wherein: k, η, p and r are independently O or I, with the proviso that formula II, k + n + r = 1,2 or 3; m is 0, 1 or 2; Dk \ Dk2 represent independently derived from benzene, naphthalene or quinoline radical, wherein naphthalene, quinoline and benzene optionally comprising 2 or 3 substituents, wherein the substituents are selected from S03H, COOH, OH, NH2, N02, CN, CONH2, halogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, carboxy -C1-C4 alkyl , C1-C4 alkoxy, C1-C4 alkylamino, C1-C4 alkylamino Ni, C1-C4 alkylaminocarbonyl, C1-C4 ni alkylaminocarbonyl, C1-C4 alkylamino 羰基氧基、C1-C4 ニ烷基氨基羰基氧基、C1-C4烷基氨基羰基氨基、C1-C4 ニ烷基氨基羰基氨基、苯基氨基羰基氧基、苯基氨基羰基氨基、C1-C4烷氧基羰·基氨基、C1-C4烷基羰基氨基、N- (C1-C4烷基羰基)-N- (C1-C4烷基羰基)氨基、C1-C4羟基-C1-C4烷基氨基、羧基-C1-C4烷基氨基、苯基羰基氨基、C1-C4烷基磺酰基、C1-C4羟烷基磺酰基、C1-C4烷基氨基磺酰基、C1-C4烷基磺酰基氨基、苯基磺酰基、苯基磺酰基氨基、甲酰胺、SO2NR56R57,其中R56和R57独立地代表氢、C1-C4烷基、甲酰基、C1-C4烷基羰基、C1-C4烷氧基羰基、NH2-C0、C1-C4烷基氨基羰基、或任选被1、2或3个下列基团:0H、卤素、C1-C4烷基或苯基取代的5-或6-元杂环基、任选在氮上含有苯基或萘基的5-元芳族杂环基,其可以任选包含ー个或两个下列基团:0H、SO3H, C1-C4烷基或C1-C4烷氧基,I-苯基吡唑-4-基,其中吡唑环以及苯基环含有1 Alkylcarbonyloxy, C1-C4 alkylaminocarbonyl group Ni, C1-C4 alkylaminocarbonyl group, C1-C4 ni alkylaminocarbonyl group, phenylaminocarbonyl group, phenylaminocarbonyl group, C1-C4 · alkoxycarbonylamino group, C1-C4 alkylcarbonylamino, N- (C1-C4 alkyl-carbonyl) -N- (C1-C4 alkyl) amino group, C1-C4 hydroxy -C1-C4 alkylamino , carboxy -C1-C4 alkylamino, phenylcarbonylamino, C1-C4 alkylsulfonyl, C1-C4 hydroxyalkyl alkylsulfonyl, C1-C4 alkylaminosulfonyl, C1-C4 alkylsulfonylamino group, phenylsulfonyl, phenylsulfonylamino, formamide, SO2NR56R57, wherein R56 and R57 independently represent hydrogen, C1-C4 alkyl, formyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, NH2 -C0, C1-C4 alkylaminocarbonyl, or optionally, two or three of the following groups: 0H, halogen, C1-C4 alkyl or phenyl-substituted 5- or 6-membered heterocyclic group, any one of 5-membered aromatic heterocyclic group selected from a phenyl or naphthyl group on the nitrogen, which may optionally contain ー or two of the following radicals: 0H, SO3H, C1-C4 alkyl or C1-C4 alkoxy , I- phenyl-pyrazol-4-yl, wherein the phenyl ring and a pyrazole ring comprising 1 2或3个如上所述取代基, 或代表式A的基团,条件是在式I-XII和XV的每个式中,Dk1和Dk2至少ー个代表式A的基团; Kk\ Kk2独立地代表单_、ニ-或三价芳基,其源自苯、萘、吡唑、喹啉、ニ苯胺、ニ苯基甲烷、嘧啶、吡啶或ニ苯醚,并且其可以任选包含一个或多个下列基团作为取代基:S03H、cooh、cn、conh2、oh、nh2、no2、卤素、C1-C4 烷基、C1-C4 羟烷基、羧基-C1-C4 烷基、C1-C4 烷氧基、C1-C4烷基氨基、C1-C4 ニ烷基氨基、C1-C4烷基氨基羰基、C1-C4 ニ烷基氨基羰基、C1-C4烷基羰基氨基、N- (C1-C4烷基羰基)-N- (C1-C4烷基羰基)氨基、C1-C4烷基氨基羰基氧基、C1-C4 ニ烷基氨基羰基氧基、C1-C4烷基氨基羰基氨基、C1-C4 ニ烷基氨基羰基氨基、苯基氨基羰基氧基、苯基氨基羰基氨基、C1-C4烷氧基羰基氨基、C1-C4羟基-C1-C4烷基氨基、羧基-C1-C4烷基氨基、苯基羰基氨基、C1-C4烷基磺酰基 2 or 3 substituent groups as described above, or represents a group of formula A, with the proviso that in each formula of formula I-XII and XV of, at least Dk1 and Dk2 ー representative group of formula A; Kk \ Kk2 independently _ represents a single, ni - or trivalent aromatic radical which is derived from benzene, naphthalene, pyrazole, quinoline, aniline ni, ni diphenylmethane, pyrimidine, pyridine or diphenyl ether ni, and which may optionally contain one or more of the following groups as substituents: S03H, cooh, cn, conh2, oh, nh2, no2, halogen, C1-C4 alkyl, C1-C4 hydroxyalkyl, carboxy -C1-C4 alkyl, C1-C4 alkyl alkoxy, C1-C4 alkylamino, C1-C4 alkylamino Ni, C1-C4 alkylaminocarbonyl, C1-C4 ni alkylaminocarbonyl, C1-C4 alkylcarbonylamino, N- (C1-C4 alkyl ylcarbonyl) -N- (C1-C4 alkyl) amino group, C1-C4 alkylaminocarbonyl group, C1-C4 alkylaminocarbonyl group Ni, C1-C4 alkylaminocarbonyl group, C1-C4 ni alkylaminocarbonyl group, a phenylaminocarbonyl group, phenylaminocarbonyl group, C1-C4 alkoxycarbonyl group, C1-C4 hydroxy -C1-C4 alkylamino, carboxy -C1-C4 alkylamino, phenyl arylcarbonylamino, C1-C4 alkylsulfonyl 羟基-C1-C4烷基磺酰基、C1-C4烷基氨基磺酰基、C1-C4烷基磺酰基氨基、苯基磺酰基、苯基磺酰基氨基、甲酰胺、式SO2NR56R57的基团,其中R56和R57独立地代表氢、C1-C4烷基、甲酰基、C1-C4烷基羰基、C1-C4烷氧基羰基、NH2-CO或C1-C4烷基氨基羰基、C1-C4烷基氨基磺酰基氨基、ニ-C1-C4烷基氨基磺酰基氨基、苯基磺酰基氨基——其可以在苯环上被一个或两个选自C1-C4烷基、C1-C4烷氧基或卤素的取代基取代、或任选被.1、2或3个下列基团:0H、卤素、C1-C4烷基或苯基取代的5-或6-元杂环基、任选在氮上含有苯基或萘基的5-元芳族杂环基——其可以任选包含ー个或两个下列基团AHAO3HX1-C4烷基或C1-C4烷氧基; Kk3是源自苯、嘧啶、吡啶或萘的ー价基团,其任选包含I或2个羟基磺酰基并任选包含.1、2或3个选自下列基团的其它取代基:S03H、COOH, CN、CONH2、OH、NH2、NO2、卤素、C「C4烷基、C1- Hydroxy -C1-C4 alkylsulfonyl, C1-C4 alkylaminosulfonyl, C1-C4 alkylsulfonylamino, phenylsulfonyl, phenylsulfonylamino, formamide, a radical of formula SO2NR56R57, wherein R56 and R57 independently represent hydrogen, C1-C4 alkyl, formyl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, NH2-CO or C1-C4 alkylaminocarbonyl, C1-C4 alkyl sulfamic acylamino, alkylamino ni -C1-C4 alkylsulfonyl group, a phenylsulfonyl group - which may be substituted with one or two substituents selected from C1-C4 alkyl, C1-C4 alkoxy or halogen in the phenyl ring substituents, or optionally .1,2 or three of the following groups: 0H, halogen, C1-C4 alkyl or phenyl-substituted 5- or 6-membered heterocyclic group, optionally substituted on the nitrogen containing benzene naphthyl group or 5-membered aromatic heterocyclic group - which may optionally contain one or two of the following ー AHAO3HX1-C4 alkyl groups or C1-C4 alkoxy; Kk3 is derived from benzene, pyrimidine, pyridineー naphthalene or a divalent group, optionally containing I or 2 hydroxyl group and optionally further substituted sulfonyl group comprising .1,2 or three substituents selected from the group consisting of: S03H, COOH, CN, CONH2, OH, NH2, NO2, halo, C "C4 alkyl, C1- C4羟烷基、羧基-C1-C4烷基、C1-C4烷氧基、C1-C4烷基氨基、C1-C4 ニ烷基氨基、C1-C4烷基氨基羰基、C1-C4 ニ烷基氨基羰基、C1-C4烷基羰基氨基、N-(C1-C4烷基羰基)-N-(C1-C4烷基羰基)氨基、C1-C4烷基氨基羰基氧基、C1-C4 ニ烷基氨基羰基氧基、C1-C4烷基氨基羰基氨基、C1-C4 ニ烷基氨基羰基氨基、苯基氨基羰基氧基、苯基氨基羰基氨基、C1-C4烷氧基羰基氨基、C1-C4羟基-C1-C4烷基氨基、羧基-C1-C4烷基氨基、苯基羰基氨基、C1-C4烷基磺酰基、羟基-C1-C4烷基磺酰基、C1-C4烷基氨基磺酰基、C1-C4烷基磺酰基氨基、苯基磺酰基、苯基磺酰基氨基、甲酰胺、式SO2NR56R57的基团,其中R56和R57独立地代表氢、C1-C4烷基、甲酰基、C1-C4烷基羰基、C1-C4烷氧基羰基、NH2-CO或C1-C4烷基氨基羰基、C1-C4烷基氨基磺酰基氨基、ニ-C1-C4烷基氨基磺酰基氨基、苯基磺酰基氨基——其可以在苯环上被ー个或两 C4 hydroxyalkyl, carboxy -C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, C1-C4 alkylamino Ni, C1-C4 alkylaminocarbonyl, C1-C4 alkylamino ni carbonyl, C1-C4 alkylcarbonylamino, N- (C1-C4 alkyl-carbonyl) -N- (C1-C4 alkyl) amino gr