CN1875144A - Method for the reactive colouring of leather - Google Patents

Method for the reactive colouring of leather Download PDF

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Publication number
CN1875144A
CN1875144A CNA2004800321064A CN200480032106A CN1875144A CN 1875144 A CN1875144 A CN 1875144A CN A2004800321064 A CNA2004800321064 A CN A2004800321064A CN 200480032106 A CN200480032106 A CN 200480032106A CN 1875144 A CN1875144 A CN 1875144A
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amino
alkyl
group
carbonyl
phenyl
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CNA2004800321064A
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CN1875144B (en
Inventor
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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BASF SE
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BASF SE
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Priority claimed from DE200410041187 external-priority patent/DE102004041187A1/en
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Priority claimed from PCT/EP2004/012231 external-priority patent/WO2005040490A1/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive 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
    • C09B62/503—Reactive 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
    • C09B62/507—Azo dyes
    • C09B62/513—Disazo or polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive 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
    • C09B62/4401—Reactive 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
    • C09B62/4403—Reactive 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
    • C09B62/4411—Azo dyes
    • C09B62/4415—Disazo or polyazo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive 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
    • C09B62/4401—Reactive 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
    • C09B62/4403—Reactive 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
    • C09B62/4411—Azo dyes
    • C09B62/4416—Metal complex azo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive 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
    • C09B62/503—Reactive 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
    • C09B62/507—Azo dyes
    • C09B62/515—Metal complex azo dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/32—Material containing basic nitrogen containing amide groups leather skins
    • D06P3/3286—Material 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 which are particularly suitable for the reactive colouring of leather.

Description

The reactive colouring of leather
The present invention relates to method, also relate to the new dye of the reactive coloration that is particularly useful for leather leather coloring.
Tan leather is to use ACID DYES, direct dyes, SULPHUR DYES or basic dyeing at present.Use these dyestuffs to be difficult to realize high color intensity and high color stability, especially moisture-proof and perspiration fastness, in fact in paramount depth of shade can not reach gratifying standard so far.
In order to improve sweat proof and moisture-proof fastness, handle leather with cation complexing agents usually, it makes the dyestuff complexing and reduces it thus the solubility when contacting with water.Yet attainable moisture-proof, sweat proof and anti-wiping fastness are still not enough for strong tone.In addition, the leather and fur products of making thus fade easily in use (mark off).In realize that high fastness also requires very carefully to select dyestuff under the paramount depth of shade, and used dyestuff should match with used leather agent and suitable fatting agent and the selection of retanning material.In addition, realize that required fastness requires dyestuff usually with fatting agent and use in different body lotion (float) with retanning agent sometimes; Essential body lotion changes and has prolonged total process and produced more waste water.
Because used different process step and chemicals, the dying operation that carries out in acidic aqueous media with the conventional leather dyestuff is complicated, very long and expensive.In addition, these measures do not constitute the basic solution of above-mentioned fastness problem.Its reason is that used conventional dyes is connected on the leather by ionic interaction.The effect of alkaline aqueous solution (for example washing lotion or in perspiration fastness test) has destroyed the ionic bond between leather and the dyestuff, so dyestuff separates and stains material around, for example adjacent fabric from leather.
Various effort have been carried out to improve the color fastness and the moisture-proof of the leather of dyeing by the reactive coloration method.Reactive coloration is meant to use and contains the dyestuff that can form the functional group of covalent chemical bond with the functional group of leather.
For example, T.C.Mullen is at Leather Manufacturer 1964,18 and at J.Soc.Leather, Trades, Chem.46,1962,162 and M.L.Fein etc. at J.Am.LeatherChem.Assoc.65,1970, described among the 584-591 to use and contained the REACTIVE DYES of dichlorotriazine group as reaction residue.Yet, the degree of fixation that is write down, just the ratio of chemical bonding dyestuff only is moderate, and is about 70 to 75%, and can not address the above problem.In addition, this technology only limits to the chrome tanning leather.
In order to overcome above-mentioned shortcoming, DE-A 3529294 has proposed to use the dyestuff that is used for leather coloring that contains at least one 1,3,5-triazines base (being connected with the substituting group that contains quaternary nitrogen atoms on it).Yet patent assignee under the described therein dyeing condition, does not obviously form covalent bond to as studies show that of the N-acetyl group lysine of model system between dyestuff and N-acetyl group lysine amino.
K.Rosenbusch etc. have described in Das Leder 19,1968,294 for the dyeing of chamois leather and have used Remazol_ dyestuff, the group that it contains the vinyl sulfone group or discharge the vinyl sulfone group under the effect of alkali.Yet fixation need be in 10 times long-time dyeing of pH fully.Since used dyeing condition, just high pH and 7 hours or longer dyeing time, and this method only can be used for known dyeing to the stable chamois leather of alkalescence.Use other leather kind time-like, described dyeing condition can cause damage to leather.Studies show that of patent assignee can not be realized gratifying fixation with the Remazol_ dyestuff that contains the vinyl sulfone group.
In a word, with chemically-reactive dyes with the existing method of leather coloring in can not provide 85% or higher good degree of fixation under the paramount depth of shade.It is not enough that 70 to 75% the degree of fixation of realizing in the prior art moves stability for high moisture-proof and perspiration fastness and good oozing, because must wash the dyestuff that do not adhere to arduously off to solve problem described herein.At Leather Manufacturer 1964, also pointed out described herein among the 18-23 with the shortcoming of chemically-reactive dyes with leather coloring.Therefore, need not be surprised at chemically-reactive dyes the technology of leather coloring and immature.On the contrary, studying at present different in leather the method for covalent bonding dyestuff, for example use multifunctional aldehyde preliminary treatment leather, this multifunctional aldehyde contains at least one can be by the reactive group (referring to DE 100 44 642 A1s) of formation key with the reaction-ity group reaction of dyestuff.
Because shortcoming described herein, these methods especially are not suitable for making the leather and fur products that is used for specific part, for example footwear, clothes, automobile, gloves and furniture, need medium and high depth of shade and high fastness in these goods, especially washable, sweat proof, anti-wiping and anti-oozing are moved fastness.
An object of the present invention is to provide a kind of under medium and high depth of shade (color intensity) method with the paramount fastness of leather coloring (especially moisture-proof, sweat proof and anti-wiping fastness and high oozing move fastness).Even this method should be able to also be to carry out under the very little condition leather there being infringement.More particularly, this method should be fit to make the leather and fur products that is used for specific part, for example footwear, clothes, automobile, gloves and furniture need medium and high depth of shade and high fastness in these goods, and especially washable, sweat proof, anti-wiping and anti-oozing are moved fastness.
We are surprised to find that, pH be 7.5 or higher water bath shampoo (aqueous float) in use the dyestuff F of the functional group of containing at least one following formula A can realize this purpose.In fact, under these conditions, dyeing and fixation are carried out so rapidly so that 4 hours or shorter dyeing time just are enough to obtain the color intensity and 85% or higher high fixation of abundance.
Thus, the invention provides the method for the dyestuff F of at least a group that can be activated by alkali that contains at least one formula A of a kind of usefulness with leather coloring:
Wherein
-----be meant key that links to each other with the remainder of dye molecule;
X is an electron withdraw group,
K is 1,2 or 3,
N be 0 or 1 and
B is CH=CH 2Group or CH 2-CH 2-Q group, wherein Q is the group that theobromine separates,
This method comprises that being not less than 7.5, common 8 to 11, preferred 8.5 to 10.5, particularly 8.5 to 10 the water bath shampoo that contains at least a dyestuff F with the pH value handles leather.
Herein and hereinafter, to typically refer to the straight or branched alkyl that contains 1 to 6 carbon atom, preferably contains 1 to 4 carbon atom (be respectively C to alkyl 1-C 6Alkyl and C 1-C 4Alkyl), for example methyl, ethyl, propyl group, isopropyl etc.Alkylhalide group is meant the aforesaid alkyl when hydrogen atom is replaced by halogen atom (especially fluorine atom) wholly or in part, for example trifluoromethyl, trichloromethyl, pentafluoroethyl group etc.Alkoxyl is meant the aforesaid alkyl that links to each other via oxygen atom.It is one or more that the optional phenyl that replaces represents that phenyl can contain, and for example 1,2,3 or 4 is selected from halogen, alkyl, alkoxyl, nitro, cyano group, COOH, SO 3The substituting group of H etc.Halogen special representative fluorine, chlorine or bromine.
Electron withdraw group X be meant to the aryl generation-M that links to each other with them and/or-group of I effect.They comprise, for example, and fluorine or chlorine, CN, NO 2, and formula-C (O)-R 1And S (O) 2R 2Group, R wherein 1And R 2Represent OH, alkyl, alkylhalide group, alkoxyl or the optional phenyl that replaces independently.When group A comprised a plurality of groups (k＞1), the X group can be identical or different.Preferably, at least one X group is hydroxyl sulfonyl (SO 3H).
Variable k is preferably 1 or 2; That is to say that the A group comprises 1 or 2 electron withdraw group X.Preferably, the n among the formula A is 0; That is to say that group A is derived from benzene.When n was 1, group A was derived from naphthalene.In these cases, SO 2-B group can be positioned on the identical phenyl ring with described at least one X group, also can be positioned on another phenyl ring.
The group Q that theobromine separates is meant under alkaline environment, just pH be 7.5 or higher situation under, form the group that the vinyl sulfone group separates by elimination.The example of this group is a halogen, for example chlorine, bromine or iodine ,-O-SO 3H ,-S-SO 3H, dialkyl amido, quaternary ammonium group (three-C for example 1-C 4Alkylammonium, benzyl two-C 1-C 4And formula R the pyridine that alkylammonium or N-connect), 3S (O) 2-, R 4S (O) 2-O-, R 5The group of C (O)-O-.In these formulas, R 3, R 4And R 5Be alkyl, alkylhalide group or the optional phenyl that replaces independently, but R 5It can also be halogen.Q is preferably-O-(CO) CH 3Group, especially-O-SO 3The H group.
According to the present invention, the B among the formula A is preferably CH=CH 2, CH 2-CH 2-O-C (O) CH 3Group or CH 2-CH 2-O-SO 3The H group.More particularly, group A is selected from following groups A1 to A12:
Figure A20048003210600141
Dyestuff when wherein preferred especially at least one A group has formula A1, A2 or A9.
Advantageously, the dyestuff that uses in the method for the present invention comprises 1,2 or 3, preferred 1 or 2 aforementioned A group.This group A can but need not to be the part of dye chromophore, and preferably by-NH-or-the N=N-group is connected on the dye molecule.
Generally speaking, the every dye molecule of dyestuff F contains one or more, for example 1 to 10, especially gives dyestuff F water miscible functional group for 2 to 8.These groups normally in faintly acid or alkaline pH value, usually above the aqueous medium of pH4 in disassociation to form the anion or the acidic functionality of anionic group.The example of these groups is hydroxyl sulfonyl (SO 3H), carboxyl (COOH) and hydroxyl sulfonyloxy (O-SO 3H) and the anion of these groups.These anion/acidic-groups can be connected on the other parts of group A and/or dye molecule.When these groups are present among the dyestuff F as anionic group, can recognize that dyestuff also comprises the necessary counter ion counterionsl gegenions of neutralization.Suitable counter ion counterionsl gegenions are alkali metal ion particularly, especially sodium, potassium and lithium ion, and ammonium ion, for example be derived from single-, two-or the ammonium ion of triethanolamine.
Can also use the metal complex of aforementioned dyestuff F, preferred transition metal complex, the especially complex compound of the transition metal of the periodic table of elements the 6th to 10 family, and particularly the complex compound of Cu, Cr, Fe, Ni, Co, Mn, Zn and Cd carries out method of the present invention.The mol ratio of transition metal and dye molecule is generally 2: 1 to 1: 2 in these metal complexs.Generally speaking, in these dyestuffs, metal ion is not via aforementioned anionic group complexing, but via the hydroxyl of deprotonation, via nitrogen-atoms contained in amino, imino group, the aromatics π-electron system or via the azo group complexing.
Typical dyestuff F is selected from following dyestuff kind in the method for the present invention: the dyestuff of phthalocyanine series, anthraquinone dye, azo dyes, first Dyestuff, three phenyl dioxazine dyestuff and triarylmethane dyes.
This dyestuff F part can be known from prior art, for example, WO 94/18381, EP-A356931, EP-A 559617, EP-A 201868, DE-A 19523245, DE-A 19731166, EP 745640, EP-A 889098, EP-A 1097971, EP-A 880098, or can make by the method for the similar dyestuff of known manufacturing structure similarly, know among the prior art that these methods can be listed from here and EP 602562, EP-A 597411, EP-A 592105 or the DE 4319674.
But react with the dyestuff intermediate that comprises the nucleophilic displacement group by the amino-compound that makes formula B in a conventional manner usually and prepare dyestuff F:
Figure A20048003210600161
But the example of nucleophilic displacement group is a halogen, chlorine or bromine especially, and it or exists with the form of halosulfonyl or halogen carbonyl as be connected to the aromatics part in the halo triazine on.The method that is used for this purpose is listed herein well known in the prior art or can be used for the preparation of dyestuff F similarly.Perhaps, also can be coupled to then on the suitable dyestuff intermediate at first with amino-compound B diazotization.The product that obtains when amino-compound B or its diazol and dyestuff intermediate reaction can be dyestuff F, or constitutes dyestuff F intermediate, similarly this intermediate further is processed into dyestuff F with known method.
Be understood that easily, can use dye mixture and pure dyestuff in the method for the invention.Dyeing on leather and aforementioned high fastness also must meet the requirement to dyeing quality, for example permeability, tone, cleannes, equalization, the concealment of impaired grain and the tone equality between flesh noodles and the grain.The present inventor is known according to the experience of oneself, considers performance condition on the whole, preferably uses dye mixture.
Dye mixture not only refers to the blend of various dyestuff F at this, also refers to the synthetic mixture of F dyestuff.Based on the painted organic chemistry residue in the dyestuff, the ratio of F dyestuff in these mixtures preferably is not less than 70 weight %, especially is not less than 90 weight %, more preferably is not less than 99 weight %.Except the F dyestuff, the dye mixture that uses in the method for the present invention can comprise the leather conventional dyes that does not contain group A.Based on the painted organic chemistry residue in the dyestuff, the ratio of these dyestuffs is usually less than 30 weight %, especially is lower than 10 weight %, particularly is no more than 5 weight %.
When the F dyestuff is that the amount of every kind of dyestuff is not less than 10 moles of % of dyestuff F total amount in the mixture usually, especially is not less than 20 moles of % when having the mixture of F dyestuff of similar tone.The mixture of wherein preferred two kinds of dyestuff F, every kind of component have 9: 1 to 1: 9,2: 8 to 8: 2 mol ratio especially.
The dye mixture that equally usefully has the F dyestuff of different tones.An one specific embodiment is for example dyestuff toning of black dyes and dyes in different colors (for example with red, green or blue dyes).When dyestuff mixed with one or more other dyestuffs that are used to mix colours, based on the painted organic chemistry residue in the dyestuff, the amount of dope dye was generally 0.1 to 15 mole of %.Another specific embodiment comprises the known dye mixture that is used for trichrome stain.The dye mixture that is used for trichrome stain comprises 3 kinds or multiple dyestuff F with different tones.In this case, every kind of component accounts for the 1 mole of % that is not less than of dyestuff F total amount in the mixture usually, especially is not less than 5 moles of %, for example 5 to 90 moles of %.
Must remember that dyestuff can comprise inorganic salts and standard agent (standardizer) according to their manufacture method.The mark of these components (hereinafter also being known as the non-staining component) is no more than 60 weight % of the painted of dyestuff and non-staining component gross weight usually, and is generally 10 weight % to 50 weight %.
In preferred embodiment of the present invention, dyestuff F is an azo dyes, and is preferably and is selected from the azo dyes of general formula I to the dyestuff of XV and their complex compound:
Dk 1-N＝N-[P-N＝N-] pKk 1[-N＝N-Dk 2] m (I)
Dk 1-N＝N-Napht 1[-N＝N-Tk 1] r[-N＝N-Kk 1] k[-N＝N-Dk 2] n (II)
Dk 1-N＝N-Napht 1-N＝N-Tk 1-N＝N-Kk 1-N＝N-Tk 2-N＝N-Napht 2-N＝N-Dk 2 (III)
Dk 1-N＝N-Kk 1-N＝N-Tk 1-N＝N-Kk 2-N＝N-Dk 2 (IV)
Dk 1-N＝N-[P-N＝N-] pNapht 1[-N＝N-R] r-NH-Tr 1-NH-Dk 2 (V)
Dk 1-N＝N-P-NH-Tr 1-NH-R-N＝N-Dk 2 (VI)
Dk 1-N＝N-Napht 1-N＝N-Tk 1-N＝N-P-NH-Tr 1-NH-Dk 2 (VII)
Dk 1-N＝N-Napht 1-NH-Tr 1-NH-P-NH-Tr 2-NH-Napht 2-N＝N-Dk 2 (VIII)
Dk 1-N＝N-Napht 1-NH-Tr 1-NH-Tk 1-NH-Tr 2-NH-Napht 2-N＝N-Dk 2 (IX)
Dk 1[-N＝N-L]k-NH-Tr 1-NH-M-N＝N-Napht 1-N＝N-P-NH-Tr 2-NH-[R-N＝N-] nDk 2 (X)
Dk 1-N＝N-Kk 1-N＝N-Tk 1-NH-Tr 1-NH-Dk 2 (XI)
Dk 1-N＝N-[P-N＝N-] pR-N＝N-Kk 1[-N＝N-Dk 2] n (XII)
Dk 1-N＝N-Pyr-A (XIII)
Kk 3-N＝N-Tk 1-N＝N-Kk 1-N＝N-A (XIV)
Dk 1-N＝N-P-N＝N-Kk 1-N＝N-R-N＝N-Dk 2 (XV)
Wherein:
K, n, p and r are 0 or 1 independently, and condition is k+n+r=1 among the formula II, 2 or 3;
M is 0,1 or 2;
Dk 1, Dk 2Represent the group that is derived from the group of arylamine or represents formula A independently, condition is in each formula of formula I-XII and XV, Dk 1And Dk 2At least one represents the group of formula A;
Kk 1, Kk 2Represent independently single-, two-or trivalent aryl, it is derived from benzene, naphthalene, pyrazoles, quinoline, diphenylamines, diphenyl methane, pyrimidine, pyridine or diphenyl ether, and it can be chosen wantonly and comprises one or more following groups as substituting group: SO 3H, COOH, CN, CONH 2, OH, NH 2, NO 2, halogen, C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, carboxyl-C 1-C 4Alkyl, C 1-C 4Alkoxyl, C 1-C 4Alkyl amino, C 1-C 4Dialkyl amido, C 1-C 4Alkyl amino-carbonyl, C 1-C 4Dialkyl amino carbonyl, C 1-C 4Alkyl-carbonyl-amino, N-(C 1-C 4Alkyl-carbonyl)-N-(C 1-C 4Alkyl-carbonyl) amino, C 1-C 4Alkyl amino carbonyl oxy, C 1-C 4Dialkyl amino carbonyl oxy, C 1-C 4Alkyl amino-carbonyl amino, C 1-C 4Dialkyl amino carbonyl amino, phenyl amino ketonic oxygen base, phenyl amino carbonylamino, C 1-C 4Alkoxycarbonyl amino, C 1-C 4Hydroxyl-C 1-C 4Alkyl amino, carboxyl-C 1-C 4Alkyl amino, phenylcarbonyl group amino, C 1-C 4Alkyl sulphonyl, C 1-C 4Hydroxyalkyl sulfonyl, C 1-C 4Alkyl amino sulfonyl, C 1-C 4Alkyl sulfonyl-amino, phenyl sulfonyl, phenyl sulfonyl amino, formamide, formula SO 2NR 56R 57Group, R wherein 56And R 57Represent hydrogen, C independently 1-C 4Alkyl, formoxyl, C 1-C 4Alkyl-carbonyl, C 1-C 4Alkoxy carbonyl, NH 2-CO or C 1-C 4Alkyl amino-carbonyl, C 1-C 4Alkyl amino sulfonyl amino, two-C 1-C 4Alkyl amino sulfonyl amino, phenyl sulfonyl amino---it can be selected from C by one or two on phenyl ring 1-C 4Alkyl, C 1-C 4The substituting group of alkoxy or halogen replaces or is optional by 1,2 or 3 following groups: OH, halogen, C 1-C 45-that alkyl or phenyl replaces or 6-unit heterocyclic radical, aromatic heterocyclic radical---it can be chosen wantonly and comprise one or two following groups: OH, SO to choose the 5-unit of containing phenyl or naphthyl on nitrogen wantonly 3H, C 1-C 4Alkyl and/or C 1-C 4Alkoxyl;
Kk 3Be the univalent perssad that is derived from benzene, pyrimidine, pyridine or naphthalene, it is chosen wantonly to comprise 1 or 2 hydroxyl sulfonyl and choose wantonly and comprises 1,2 or 3 other substituting group that is selected from following groups: SO 3H, COOH, CN, CONH 2, OH, NH 2, NO 2, halogen, C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, carboxyl-C 1-C 4Alkyl, C 1-C 4Alkoxyl, C 1-C 4Alkyl amino, C 1-C 4Dialkyl amido, C 1-C 4Alkyl amino-carbonyl, C 1-C 4Dialkyl amino carbonyl, C 1-C 4Alkyl-carbonyl-amino, N-(C 1-C 4Alkyl-carbonyl)-N-(C 1-C 4Alkyl-carbonyl) amino, C 1-C 4Alkyl amino carbonyl oxy, C 1-C 4Dialkyl amino carbonyl oxy, C 1-C 4Alkyl amino-carbonyl amino, C 1-C 4Dialkyl amino carbonyl amino, phenyl amino ketonic oxygen base, phenyl amino carbonylamino, C 1-C 4Alkoxycarbonyl amino, C 1-C 4Hydroxyl-C 1-C 4Alkyl amino, carboxyl-C 1-C 4Alkyl amino, phenylcarbonyl group amino, C 1-C 4Alkyl sulphonyl, C 1-C 4Hydroxyalkyl sulfonyl, C 1-C 4Alkyl sulfonyl-amino, phenyl sulfonyl, phenyl sulfonyl amino, formamide, formula SO 2NR 56R 57Group, R wherein 56And R 57Represent hydrogen, C independently 1-C 4Alkyl, formoxyl, C 1-C 4Alkyl-carbonyl, C 1-C 4Alkoxy carbonyl, NH 2-CO or C 1-C 4Alkyl amino-carbonyl, C 1-C 4Alkyl amino sulfonyl amino, two-C 1-C 4Alkyl amino sulfonyl amino, phenyl sulfonyl amino---it can be selected from C by one or two on phenyl ring 1-C 4Alkyl, C 1-C 4The substituting group of alkoxy or halogen replaces or is optional by 1,2 or 3 following groups: OH, halogen, C 1-C 45-that alkyl or phenyl replaces or 6-unit heterocyclic radical, aromatic heterocyclic radical---it can be chosen wantonly and comprise one or two following groups: OH, SO to choose the 5-unit of containing phenyl or naphthyl on nitrogen wantonly 3H, C 1-C 4Alkyl and/or C 1-C 4Alkoxyl;
Tk 1, Tk 2Represent divalent aryl independently; it is derived from benzene, diphenylamines, biphenyl, diphenyl methane, 2-Phenylbenzimidazole, phenyl sulfonyl benzene, phenyl amino sulfonyl benzene, stilbene or phenyl amino carbonyl benzene, and they are chosen wantonly separately and comprise one or more following groups as substituting group: SO 3H, COOH, OH, NH 2, NO 2, halogen, C 1-C 4Alkyl;
L, M, P and R represent the divalent aryl that is derived from benzene or naphthalene independently, and they can be chosen wantonly separately and comprise one or morely, and for example, 1,2,3,4 or 5 following groups is as substituting group: SO 3H, COOH, CN, CONH 2, OH, NH 2, NO 2, halogen, C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, carboxyl-C 1-C 4Alkyl, C 1-C 4Alkoxyl, C 1-C 4Alkyl amino, C 1-C 4Dialkyl amido, C 1-C 4Alkyl amino-carbonyl, C 1-C 4Dialkyl amino carbonyl, C 1-C 4Alkyl-carbonyl-amino, N-(C 1-C 4Alkyl-carbonyl)-N-(C 1-C 4Alkyl-carbonyl) amino, C 1-C 4Alkyl amino carbonyl oxy, C 1-C 4Dialkyl amino carbonyl oxy, C 1-C 4Alkyl amino-carbonyl amino, C 1-C 4Dialkyl amino carbonyl amino, phenyl amino ketonic oxygen base, phenyl amino carbonylamino, C 1-C 4Alkoxycarbonyl amino, C 1-C 4Hydroxyl-C 1-C 4Alkyl amino, carboxyl-C 1-C 4Alkyl amino, phenylcarbonyl group amino, C 1-C 4Alkyl sulphonyl, C 1-C 4Alkyl amino sulfonyl, C 1-C 4Hydroxyalkyl sulfonyl, C 1-C 4Alkyl sulfonyl-amino, phenyl sulfonyl, phenyl sulfonyl amino, formamide, formula SO 2NR 56R 57Group, R wherein 56And R 57Represent hydrogen, C independently 1-C 4Alkyl, formoxyl, C 1-C 4Alkyl-carbonyl, C 1-C 4Alkoxy carbonyl, NH 2-CO or C 1-C 4Alkyl amino-carbonyl, C 1-C 4Alkyl amino sulfonyl amino, two-C 1-C 4Alkyl amino sulfonyl amino, phenyl sulfonyl amino---it can be selected from C by one or two on phenyl ring 1-C 4Alkyl, C 1-C 4The substituting group of alkoxy or halogen replaces or is optional by 1,2 or 3 following groups: OH, halogen, C 1-C 45-that alkyl or phenyl replaces or 6-unit heterocyclic radical, aromatic heterocyclic radical---it can be chosen wantonly and comprise one or two following groups: OH, SO to choose the 5-unit of containing phenyl or naphthyl on nitrogen wantonly 3H, C 1-C 4Alkyl and/or C 1-C 4Alkoxyl;
Napht 1, Napht 2Representative is derived from the divalent group of naphthalene independently, and it comprises 1 or 2 hydroxyl sulfonyl, and can choose wantonly and comprise 1,2 or 3 other substituting group that is selected from following groups: OH, NH 2, C 1-C 4Alkyl amino, C 1-C 4Dialkyl amido, C 1-C 4Alkyl sulfonyl-amino, phenyl sulfonyl amino, 4-aminomethyl phenyl sulfuryl amino, C 1-C 4Alkyl amino sulfonyl, two-C 1-C 4Alkyl amino sulfonyl, phenyl amino sulfonyl, 4-aminomethyl phenyl amino-sulfonyl and NHC (O) R xGroup, wherein R xBe hydrogen, C 1-C 4Alkyl, maleoyl or phenyl;
Pyr represents pyrazoles-1,4-two bases, and it is connected on the A group by nitrogen-atoms, and optional comprise 1 or 2 and be selected from halogen, C 1-C 4Alkyl, hydroxyl or C 1-C 4The substituting group of alkoxyl;
Tr 1, Tr 2Represent 1,3,5-triazines-2 independently, 4-two bases, it is chosen wantonly and further contains halogen atom, methyl or methoxyl group as substituting group.
Herein and hereinafter, C 1-C 4Alkyl (and C 1-C 4Alkoxyl, C 1-C 4Alkyl amino, two-C 1-C 4Alkyl amino, C 1-C 4Alkyl sulphonyl, C 1-C 4Hydroxyalkyl sulfonyl, C 1-C 4Alkyl amino sulfonyl, C 1-C 4Alkyl amino-carbonyl, two-C 1-C 4Alkyl amino sulfonyl, two-C 1-C 4Alkyl amino-carbonyl and C 1-C 4Moieties in the groups such as alkyl-carbonyl-amino) is meant the straight or branched aliphatic hydrocarbyl, for example groups such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl.
C 1-C 4Hydroxyalkyl is meant the C that contains the OH group 1-C 4Alkyl, for example 2-ethoxy.Correspondingly, C 1-C 4Hydroxyalkyl amino is meant the C that contains the OH group in alkyl 1-C 4Alkyl amino, for example 2-hydroxyethylamino.
C 1-C 4The carboxyalkyl representative contains the C of carboxyl (COOH group) 1-C 4Alkyl, for example carboxymethyl (CH 2COOH) and 2-carboxyethyl (CH 2CH 2COOH).Correspondingly, C 1-C 4Carboxyalkyl amino is meant the C that contains carboxyl (COOH group) at moieties 1-C 4Alkyl amino, for example carboxymethylamino (NH-CH 2COOH) and 2-carboxyethyl amino (NH-CH 2CH 2COOH).
5-or 6-unit heterocyclic radical comprises 1,2 or 3 usually and is selected from the hetero atom of nitrogen, oxygen and sulphur, especially 1 or 2 nitrogen-atoms and randomly oxygen or sulphur atom and can be saturated, unsaturated or aromatics as the ring constituent element.The example of saturated heterocyclyl is morpholinyl, piperidyl, piperazinyl and pyrrolidinyl.The example of aromatic heterocyclic radical is pyridine radicals, pyrrole radicals, oxazolyl, thiazolyl or the like.
The dyestuff of formula I to XV can free form, its salt form uses, and as each self-contained OH, COOH or the NH that is positioned at the diazo ortho position of two groups that links together by diazo-N=N- 2During group, use as metal complex.
Group DK in the dyestuff of formula I to XIII and XV 1And DK 2Respectively from arylamine DK 1-NH 2And DK 2-NH 2, hereinafter also be known as diazo component.Amine DK 1-NH 2And DK 2-NH 2Be generally the optional aniline that replaces, the optional α that replaces-or beta-naphthylamine or optional aminoquinoline that replaces.Correspondingly, group DK 1And DK 2Be generally the group that is derived from benzene, naphthalene or quinoline independently, wherein naphthalene, quinoline and benzene optional comprise one or more, 1,2 or 3 substituting group for example.Substituent example is following groups: SO 3H, COOH, OH, NH 2, NO 2, CN, CONH 2, halogen, C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, carboxyl-C 1-C 4Alkyl, C 1-C 4Alkoxyl, C 1-C 4Alkyl amino, C 1-C 4Dialkyl amido, C 1-C 4Alkyl amino-carbonyl, C 1-C 4Dialkyl amino carbonyl, C 1-C 4Alkyl amino carbonyl oxy, C 1-C 4Dialkyl amino carbonyl oxy, C 1-C 4Alkyl amino-carbonyl amino, C 1-C 4Dialkyl amino carbonyl amino, phenyl amino ketonic oxygen base, phenyl amino carbonylamino, C 1-C 4Alkoxycarbonyl amino, C 1-C 4Alkyl-carbonyl-amino, N-(C 1-C 4Alkyl-carbonyl)-N-(C 1-C 4Alkyl-carbonyl) amino, C 1-C 4Hydroxyl-C 1-C 4Alkyl amino, carboxyl-C 1-C 4Alkyl amino, phenylcarbonyl group amino, C 1-C 4Alkyl sulphonyl, C 1-C 4Hydroxyalkyl sulfonyl, C 1-C 4Alkyl amino sulfonyl, C 1-C 4Alkyl sulfonyl-amino, phenyl sulfonyl, phenyl sulfonyl amino, formamide, SO 2NR 56R 57, R wherein 56And R 57Represent hydrogen, C independently 1-C 4Alkyl, formoxyl, C 1-C 4Alkyl-carbonyl, C 1-C 4Alkoxy carbonyl, NH 2-CO, C 1-C 4Alkyl amino-carbonyl or optional by 1,2 or 3 following groups: OH, halogen, C 1-C 45-that alkyl or phenyl replaces or 6-unit heterocyclic radical, aromatic heterocyclic radical---it can be chosen wantonly and comprise one or two following groups: OH, SO to choose the 5-unit of containing phenyl or naphthyl on nitrogen wantonly 3H, C 1-C 4Alkyl and/or C 1-C 4Alkoxyl;
Available amine DK 1-NH 2And DK 2-NH 2Further comprise 4-amino-1-Phenylpyrazole, wherein pyrazoles ring and benzyl ring contain one or more, for example substituting group of 1,2 or 3 aforementioned type or B-SO 2-group, wherein the B definition as above.In these cases, Dk 1Or DK 2Special representative's pyrazoles 4-base, it is 1 group that contains phenyl or formula A in the position, and optionally contains 1 or 2 and be selected from halogen, C 1-C 4Alkyl, hydroxyl, COOH, hydroxyl sulfonyl or C 1-C 4The substituting group of alkoxyl.
Preferably, Dk 1Or DK 2Independently for being derived from the optional aniline that replaces, the optional α that replaces-or the group of beta-naphthylamine, or be the A group independently.
Suitable amine DK 1-NH 2And DK 2-NH 2Example show Compound D K1 to DK39 under being:
Q group among the formula DK21 to DK25 is represented hydrogen, C 1-C 4Alkyl, carboxyl-C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, C 1-C 4Alkoxyl or phenylcarbonyl group.
Naphthylamines DK40 to 59:4-amino shown in suitable diazo component further comprises hereinafter-3-hydroxyl naphthalene-1-sulfonic acid (DK40); 4-amino-3-hydroxyl-6-nitronaphthalene-1-sulfonic acid (DK41); (the γ acid of 6-amino-4-hydroxy naphthalene-2-sulfonic acid; DK42); 4-amino-5-hydroxyl naphthalene-1-sulfonic acid (Chicago S acid; DK43); 4-amino-5-hydroxyl naphthalene-2; 7-disulfonic acid (H acid DK44); 4-amino-5-hydroxyl naphthalene-1; (the K acid of 7-disulfonic acid; DK45); amino naphthalene-2-sulfonic acid (the Cleve's acid 7 of 8-; DK46); 6-amino naphthalenes-1-sulfonic acid (D acid; DK47); 4-amino naphthalenes-2; 7-sulfonic acid (DK48); the amino naphthalene-2-sulfonic acid (DK49) of 5-; 7-amino-4; 8-dihydroxy naphthalene-2-sulfonic acid (DK50); 2-amino-5-hydroxyl naphthalene-1; 7-disulfonic acid (DK51); 3-amino-5-hydroxyl naphthalene-2; 7-disulfonic acid (DK52); 3-amino-1; 5-disulfonic acid (DK53); 7-amino naphthalenes-1-sulfonic acid (DK54); 4-amino naphthalenes-1-sulfonic acid (DK55); 5-amino naphthalenes-1-sulfonic acid (DK56); 7-amino naphthalenes-1; 3; 5-trisulfonic acid (DK57); 4-amino-3-hydroxyl-7-[(4-aminomethyl phenyl) sulfuryl amino]-naphthalene-1-sulfonic acid (DK58) and 7-amino-4-hydroxy naphthalene-2-sulfonic acid (J acid, DK59).
Suitable monoamine DK 1-NH 2And DK 2-NH 2Example show Compound D K60 to DK83 under being:
Figure A20048003210600251
As Kk 1And Kk 2Group, can use in principle that all are single-, two-or trivalent group, as Kk 3Group, can use all unit price aryl that are derived from optional benzene, naphthalene, pyrazoles, diphenylamines, diphenyl methane, pyridine, pyrimidine or the diphenyl ether that replaces, they leave 1,2 or 3 free position separately, on these positions diazonium compound in succession coupling once, twice or three times.Kk 1, Kk 2And Kk 3The compound of group representative also is known as coupling component hereinafter.
The compound of the formula Kk-G that suitable coupling component is compound, the compound that is derived from the formula Kk-B of naphthalene, the compound that is derived from the formula Kk-C of quinoline, the compound that is derived from the formula Kk-D of pyrazoles, the compound that is derived from the formula Kk-E of diphenyl methane, the compound that is derived from the formula Kk-F of diphenylamines that for example are derived from the general formula Kk-A of benzene, be derived from pyridine and be derived from the compound of the formula Kk-H of pyridone:
Figure A20048003210600261
In formula Kk-A, R 11Represent NH 2, OH, C 1-C 4Alkoxyl, C 1-C 4Alkyl amino, two-C 1-C 4Alkyl amino, hydroxyl-C 1-C 4Alkyl amino, carboxyl-C 1-C 4Alkyl amino, C 1-C 4Alkyl-carbonyl-amino or phenyl amino, R 12Represent hydrogen, NH 2, OH, C 1-C 4Alkoxyl, hydroxyl-C 1-C 4Alkyl amino, carboxyl-C 1-C 4Alkyl amino, C 1-C 4Alkyl amino, two-C 1-C 4Alkyl amino and R 13Represent hydrogen, C 1-C 4Alkyl, C 1-C 4Alkoxyl, C 1-C 4Alkyl amino carbonyl oxy, C 1-C 4Dialkyl amino carbonyl oxy, C 1-C 4Alkyl amino-carbonyl amino, C 1-C 4Dialkyl amino carbonyl amino, phenyl amino ketonic oxygen base, phenyl amino carbonylamino, C 1-C 4Alkoxycarbonyl amino, SO 3H, C 1-C 4Alkyl sulphonyl, C 1-C 4Hydroxyalkyl sulfonyl, COOH, Cl, Br, F, SO 2NR 56R 57, NO 2Or NH 2, R wherein 56And R 57Represent hydrogen, C independently 1-C 4Alkyl, formoxyl, C 1-C 4Alkyl-carbonyl, C 1-C 4Alkoxy carbonyl, NH 2-CO, C 1-C 4Alkyl amino-carbonyl.
In formula Kk-B, R 14And R 15Represent hydrogen independently or have about R 11One of described implication, but R 15Can also represent SO 3H.R 16Represent hydrogen, OH, SO 3H, C 1-C 4Alkyl sulfonyl-amino, C 1-C 4Alkyl amino sulfonyl, C 1-C 4Alkyl amino sulfonyl amino, two-C 1-C 4Alkyl amino sulfonyl amino, C 1-C 4Alkoxycarbonyl amino, phenyl sulfonyl amino---it can contain one or two and be selected from C on phenyl ring 1-C 4Alkyl, C 1-C 4The substituting group of alkoxy or halogen.R 17Represent hydrogen, OH or SO 3The H group.
In formula Kk-C, R 18To R 20Represent hydrogen, OH or C independently 1-C 4Alkyl.
In formula Kk-D, R 21Represent hydrogen, phenyl or naphthyl, wherein latter two group can comprise 1,2 or 3 and is selected from hydrogen, OH, halogen, C 1-C 4Alkyl, SO 3H, NO 2With above-mentioned group B-SO 2-substituting group.In a specific embodiment of the present invention, R 21Represent one of above-mentioned group A, especially one of group A1 to A12.R 22Be hydrogen, COOH or C 1-C 4Alkyl.
In formula Kk-E, R 23And R 25Be hydrogen, COOH, hydroxyl or C independently 1-C 4Alkyl.R 24And R 26Be hydrogen, hydroxyl or C independently 1-C 4Alkyl.
In formula Kk-F, R 27And R 29Be hydrogen, SO independently 3H, COOH, hydroxyl or C 1-C 4Alkyl.R 28And R 30Be hydrogen, hydroxyl or C independently 1-C 4Alkyl.
In formula Kk-G, R 48, R 49, R 50And R 51Be hydrogen, SO independently 3H, COOH, NH 2, CN, hydroxyl or C 1-C 4Alkyl.
In formula Kk-H, R 52, R 53, R 54And R 55Be hydrogen, SO independently 3H, COOH, NH 2, CN, hydroxyl or C 1-C 4Alkyl.
The example of the coupling component of formula Kk-A is above-mentioned aniline compound DK3; DK4; DK6; DK7; DK11; DK13; DK14; DK15; DK18; DK21 to DK27; DK29; DK30; DK33; DK36; DK38; DK39; and salicylic acid (Kk1); 3-amino-phenol (Kk2); resorcinol (Kk3); 3-phenyl amino phenol (Kk4); 1; 3-diaminobenzene (Kk5); 3-acetyl-amino aniline (Kk6); 2-nitroaniline (Kk7); 3-(lignocaine) phenol (Kk8); 3-(morpholine-1-yl) phenol (Kk9); 3-(lignocaine) aniline (Kk10); N-acetyl group-3-(lignocaine) aniline (Kk11); N-(3-hydroxyphenyl) glycine (Kk12); 3-(2-ethoxy) amino-phenol (Kk13); 2; 4-diaminotoluene (Kk14); 2; 4-diamino benzene sulfonic acid (Kk15); 2; 4-diaminostilbene-nitrobenzene (Kk16); N-(3-amino-6-aminomethyl phenyl) glycine (Kk17) and 2; 4-diaminourea-5-toluene sulfonic acide (Kk18); 2; 4-diaminostilbene-hydroxy benzenes (Kk54); 2; 4-diaminostilbene-methoxybenzene (Kk55); 2; 4-diaminostilbene-chlorobenzene (Kk56); 1; 2; 4-triaminobenzene (Kk57); 3-(dimethylamino) aniline (Kk58); 3-(dimethylamino)-1-nitrobenzene (Kk59); 2-(N; the N-lignocaine)-4-acetyl-amino-1-methoxybenzene (Kk60); 2-(N; the N-lignocaine)-4-amino-1-methoxybenzene (Kk61); 2; 4-diaminostilbene-benzsulfamide (Kk62); 2-amino-4-acetyl-amino-1-methoxybenzene (Kk63); 2-amino-4-acetyl-amino-1-chlorobenzene (Kk64); 2; 4-diaminostilbene-methyl sulphonyl benzene (Kk65); 2; 4-diaminostilbene-ethylsulfonyl benzene (Kk66) and 2,4-diaminostilbene-(2-ethoxy) sulfonyl benzene (Kk67).
The example of the coupling component of formula Kk-B is beta naphthal (Kk19); 2-phenyl amino naphthalene (Kk20); 4-methyl isophthalic acid-naphthols (Kk21); 8-methoxyl group amino carbonyl-beta naphthal (Kk22); 8-acetyl-amino-beta naphthal (Kk23); 8-methylamino sulfonyl-beta naphthal (Kk24); 8-dimethylamino Herbicidal sulphonylamino-beta naphthal (Kk25); the 6-[(4-aminomethyl phenyl) sulfonyl] amino-4-hydroxy naphthalene-2-sulfonic acid (Kk26); 8-phenyl amino naphthalene-1-sulfonic acid (Kk27); 6-amino-4-hydroxy naphthalene-2-sulfonic acid (DK42); 4-amino-5-hydroxyl naphthalene-1-sulfonic acid (DK43); 7-amino-4-hydroxy naphthalene-2-sulfonic acid (DK59); 4-amino-5-hydroxyl naphthalene-2; 7-disulfonic acid (DK44); 4-amino-5-hydroxyl naphthalene-1; 7-disulfonic acid (DK45); the amino naphthalene-2-sulfonic acid (DK46) of 8-; 6-amino naphthalenes-1-sulfonic acid (DK47); 4-amino naphthalenes-2; 7-sulfonic acid (DK48); 4-hydroxyl naphthalene-2; 7-disulfonic acid (Kk28); 3-hydroxyl naphthalene-2; 7-disulfonic acid (Kk29); 4-(phenylcarbonyl group) amino-5-hydroxyl naphthalene-2; 7-disulfonic acid (Kk30); 4; 6-dihydroxy naphthalene-2-sulfonic acid (Kk31); 4; 5-dihydroxy naphthlene-2; 7-disulfonic acid (Kk32); 4-(phenylcarbonyl group) amino-5-hydroxyl naphthalene-1-sulfonic acid (Kk33); 4-hydroxyl naphthalene-1-sulfonic acid (Kk34); 4; 5-dihydroxy naphthlene-1-sulfonic acid (Kk35); the amino naphthalene-2-sulfonic acid (DK49) of 5-; 7-hydroxyl naphthalene-1; 3-disulfonic acid (Kk36); 7-amino-4; 8-dihydroxy naphthalene-2-sulfonic acid (DK50); 8-hydroxyl naphthalene-1-sulfonic acid (Kk37); 2-amino-5-hydroxyl naphthalene-1; 7-disulfonic acid (DK51); 3-amino-5-hydroxyl naphthalene-2; 7-disulfonic acid (DK52); 3-amino-1; 5-disulfonic acid (DK53); 4; 6-dihydroxy-7-hydroxycarbonyl group naphthalene-2-sulfonic acid (Kk38); 7-amino naphthalenes-1-sulfonic acid (DK54); 4-amino naphthalenes-1-sulfonic acid (DK55); 5-amino naphthalenes-1-sulfonic acid (DK56); 7-amino naphthalenes-1; 3; 5-trisulfonic acid (DK57) and 4-acetyl-amino-5-hydroxyl naphthalene-2,7-disulfonic acid (Kk39).
The example of coupling component Kk-C is 2,4-dihydroxy quinoline (Kk40) and oxine (Kk41).
The example of coupling component Kk-D is 3-methyl-5-hydroxypyrazoles (Kk42); 1-phenyl-3-methyl-5-hydroxypyrazoles (Kk43); 1-[4-(2-hydroxyl sulfonyl oxygen ethyl)-2-hydroxyl sulfonyl phenyl]-3-methyl-5-hydroxypyrazoles (Kk44); 1-[4-(2-hydroxyl sulfonyl oxygen ethyl)-2-hydroxyl sulfonyl phenyl]-5-hydroxypyrazoles-3-carboxylic acid (Kk45); 1-[4-hydroxyl sulfonyl phenyl]-5-hydroxypyrazoles-3-carboxylic acid (Kk46) and 1-[6-hydroxyl sulfonyl naphthalene-2-yl]-5-hydroxy-3-methyl pyrazoles (Kk47); 1-[4-hydroxyl sulfonyl phenyl]-3-methyl-5-hydroxypyrazoles (Kk48).
The example of Kk-E coupling component is 4,4 '-dihydroxy diphenyl methane-3,3 '-dicarboxylic acids (Kk49).
The example of Kk-F coupling component is 4,4 '-dihydroxy diphenylamine (Kk50).
The example of Kk-G coupling component is 2,6-diamino-pyridine (Kk51).
The example of Kk-H coupling component is 1-methyl-2-pyridone (Kk52) and 3-cyano group-4-methyl-6-hydroxyl-1-ethylpyridine ketone (Kk53).
Suitable Kk3 group particularly is derived from the optional benzene that replaces or the univalent perssad of naphthalene, for example be derived from the univalent perssad of coupling component Kk-A and Kk-B, for example be derived from the group of aniline compound DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 to DK27, DK29, DK30, DK33, DK36, DK38, DK39, DK42 to DK83, Kk1 to Kk48 and Kk51 to Kk67.
Group Tk 1And Tk 2Be respectively to be derived from formula Tk 1(NH 2) 2And Tk 2(NH 2) 2The divalent aromatic radical of arylamine.These diamines also are known as the bisazo component hereinafter.
Suitable bisazo component is; for example, be derived from the general formula Tk-A of benzene compound, be derived from the formula Tk-B of dinaphthalene compound, be derived from the formula Tk-C of phenyl benzimidazole compound, be derived from the formula Tk-D of diphenyl methane compound, be derived from the formula Tk-E of diphenylamines compound, be derived from the formula Tk-F of phenyl sulfonyl benzene compound, be derived from the formula Tk-G of phenyl amino sulfonyl benzene compound, be derived from stilbene formula Tk-H compound and be derived from the compound of the formula Tk-J of phenyl amino carbonyl benzene:
Figure A20048003210600291
Figure A20048003210600301
In formula Tk-A, R 31Typical example such as hydrogen, C 1-C 4Alkyl, C 1-C 4Alkoxyl, COOH or SO 3H.Preferably, two NH 2Group is positioned at contraposition mutually.The example of the compound of formula Tk-A is 1,4-diaminobenzene (Tk1), 1,4-diaminourea-2-methoxybenzene (Tk2), 2,5-diaminobenzoic acid (Tk3) and 2,5-diamino benzene sulfonic acid (Tk4).
In formula Tk-B, R 32And R 33Typical example such as hydrogen, OH, C independently 1-C 4Alkyl, C 1-C 4Alkoxyl, COOH or SO 3H.Preferably, two NH 2Group be positioned at the position 4 and 4 '.The example of the compound of formula Tk-B is 4,4 '-benzidine (Tk5), 4,4 '-diaminourea-3; 3 '-dimethyl diphenyl (Tk6), 4; 4 '-diaminourea-3,3 '-dimethoxy-biphenyl (Tk7), 4,4 '-diaminourea-3; 3 '-dihydroxybiphenyl (Tk8), 4; 4 '-diaminourea-3-hydroxyl sulfonyl biphenyl (Tk9), 4,4 '-diaminourea-3,3 '-two (hydroxyl sulfonyl) biphenyl (Tk10) and 4; 4 '-diaminourea-3,3 '-dicarboxylate biphenyl (Tk11).
In formula Tk-C, R 34And R 35Typical example such as hydrogen, OH, C independently 1-C 4Alkyl or C 1-C 4Alkoxyl.The example of the compound of formula Tk-C is 6-amino-2-[4-aminophenyl] benzimidazole (Tk12).
In formula Tk-D, R 36And R 37Typical example such as hydrogen, OH, C independently 1-C 4Alkyl, C 1-C 4Alkoxyl, COOH or SO 3H.Preferably, two NH 2Group be positioned at the position 4 and 4 '.The example of Tk-D compound is two (4-aminophenyl) methane (Tk13), two (4-amino-3-carboxyl phenyl) methane (Tk14) and two (4-amino-3-aminomethyl phenyl) methane (Tk15).
In formula Tk-E, R 38And R 39Typical example such as hydrogen, OH, C independently 1-C 4Alkyl, C 1-C 4Alkoxyl, COOH or SO 3H.Preferably, two NH 2Group be positioned at the position 4 and 4 '.The example of Tk-E compound be (4-aminophenyl) (4 '-amino-2 '-hydroxyl sulfonyl phenyl) amine or 4,4 '-diamino-diphenylamine-2-sulfonic acid (Tk16).
In formula Tk-F, R 40And R 41Typical example such as hydrogen, OH, C independently 1-C 4Alkyl, C 1-C 4Alkoxyl, COOH or SO 3H.Preferably, two NH 2Group be positioned at the position 4 and 4 '.The example of Tk-F compound is two-(4-aminophenyl) sulfone (Tk17).
In formula Tk-G, R 42And R 43Typical example such as hydrogen, OH, C independently 1-C 4Alkyl, C 1-C 4Alkoxyl, COOH or SO 3H.Preferably, two NH 2Group be positioned at the position 4 and 4 '.The example N-of Tk-G compound (4 '-aminophenyl)-4-aminobenzene sulfonamide (Tk18).
In formula Tk-H, R 44And R 45Typical example such as hydrogen, OH, C independently 1-C 4Alkyl, COOH or SO 3H.Preferably, two NH 2Group be positioned at the position 4 and 4 '.An example of Tk-H compound is 1, and 2-two (4-amino-2-hydroxyl sulfonyl phenyl) ethene (flavonic acid, Tk19).
In formula Tk-J, R 46And R 47Typical example such as hydrogen, OH, C independently 1-C 4Alkyl, C 1-C 4Alkoxyl, COOH or SO 3H.Preferably, two NH 2Group be positioned at the position 4 and 4 '.The example of Tk-J compound is N-(4 '-aminophenyl)-4-aminobenzamide (Tk20).
Preferred Napht 1And Napht 2Group general molecular formula Napht-II:
R wherein 1And R 2Be hydrogen, OH, NH independently 2Or NHC (O) R 3, R wherein 3Be hydrogen, C 1-C 4Alkyl, maleoyl or phenyl, and R 1And R 2In at least one is not a hydrogen, the key that is connected with azo group of----representative, s and t represent 0 or 1.S+t and be preferably 1 or 2.
Suitable Napht 1And Napht 2Under comprising, group shows group II-1 to II-14:
2-hydroxyl sulfonyl-4-hydroxyl naphthalene-3,6-two bases (II-1),
6-amino-2-hydroxyl sulfonyl-4-hydroxyl naphthalene-3,5-two bases (II-2),
1-hydroxyl sulfonyl-5-hydroxyl naphthalene-4,6-two bases (II-3),
4-amino-1-hydroxyl sulfonyl-5-hydroxyl naphthalene-3,6-two bases (II-4),
2-hydroxyl sulfonyl-4-hydroxyl naphthalene-3,7-two bases (II-5),
7-amino-2-hydroxyl sulfonyl-4-hydroxyl naphthalene-3,8-two bases (II-6),
5-hydroxyl-2,7-sulfonyldioxy naphthalene-4,6-two bases (II-7),
4-amino-5-hydroxyl-2,7-sulfonyldioxy naphthalene-3,6-two bases (II-8),
5-hydroxyl-1,7-sulfonyldioxy naphthalene-4,6-two bases (II-9),
4-amino-5-hydroxyl-1,7-sulfonyldioxy naphthalene-3,6-two bases (II-10),
2-hydroxyl sulfonyl naphthalene-5,8-two bases (II-11),
2-amino-5-hydroxyl-1,7-sulfonyldioxy naphthalene-3,6-two bases (II-12),
5-hydroxyl-2,7-sulfonyldioxy naphthalene-3,6-two bases (II-13),
3-amino-5-hydroxyl-2,7-sulfonyldioxy naphthalene-4,6-two bases (II-14),
2-hydroxyl sulfonyl naphthalene-5,8-two bases (II-15) and
1-hydroxyl sulfonyl naphthalene-5,8-two bases (II-16).
Group L, M, P and R are the divalent groups that is derived from benzene or naphthalene, for example are derived from the group of the coupling component of formula Kk-A and Kk-B, and are derived from aforementioned diazo component and still have and can make diazonium compound be coupled to the group of the free position on it.Its example is aniline compound DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 to DK27, DK29, DK30, DK33, DK36, DK38, DK39 and DK60 to DK83 and naphthylamines DK42 to DK59.
The dyestuff of special preferred formula Ha, IIIa and IVa in the aforesaid compound of formula I to XV:
Dk 1-N＝N-Napht 1-N＝N-Tk 1[-N＝N-Kk 1] k[-N＝N-Dk 2] n (IIa)
Dk 1-N＝N-Napht 1-N＝N-Tk 1-N＝N-Kk 1-N＝N-Tk 2-N-N-Napht 2-N＝N-Dk 2
(IIIa)
Dk 1-N＝N-Napht 1-N＝N-Tk 1-N＝N-Napht 2-N＝N-Dk 2 (IVa)
In formula Ha, IIIa and IVa, Dk 1, Dk 2, Napht 1, Napht 2, Kk 1, TK 1, Tk 2And Kk 1Each is as above self-defined, but Dk 1And Dk 2One of group or these two are represented the group of formula A as mentioned above, and particularly represent a group among the A1 to A12.Number n and k are 0 or 1, and condition is n+k=1 or 2.When k=0, the Tk among the formula IIa 1Do not represent the group that is derived from diphenylamine, this moment, these compounds were novel.Therefore, the same formation of these compounds and composition thereof part theme of the present invention.
The special preferred embodiment of dyestuff II and IIa comprises the dyestuff of general formula I Ib
Dk 1-N＝N-Napht 1-N＝N-Tk 1-N＝N-Kk 1[-N＝N-Dk 2] n (IIb)
Wherein A, Dk 2, Napht 1And Kk 1Each is as above self-defined, and n is 0 or 1, and Tk wherein 1Representative is derived from the divalent group of biphenyl, diphenyl methane, 2-Phenylbenzimidazole, phenyl sulfonyl benzene, phenyl amino sulfonyl benzene, diphenylamines, stilbene or phenyl amino carbonyl benzene, and optionally comprises one or more following groups as substituting group: SO 3H, COOH, OH, NH 2, NO 2, halogen, C 1-C 4Alkyl, but when n=0 Tk 1Do not represent the group that is derived from diphenylamines, and Dk 2Group can also be represented the group of aforesaid formula A.The dyestuff of general formula I Ib, especially their mixture are particularly preferred themes of the present invention.
In the dyestuff of the present invention of general formula I Ia, IIb, IIIa and IVa, particularly preferably be Tk 1And/or Tk 2Dyestuff when at least one represents the group of following formula in the group:
Wherein----represents the key that is connected with azo group.
In the compound of general formula I Ia, IIb, IIIa and IVa, particularly preferably be Napht 1And/or Napht 2Dyestuff when representing the divalent group of above-mentioned general formula Napht-II and having described herein concrete implication especially.
In the compound of general formula I Ia, IIb, IIIa and IVa, particularly preferably be Dk 1And Dk 2One of group or these two are represented the dyestuff for the moment of above-mentioned A1 to A12 group.
In the dyestuff of general formula I Ib, Kk 1Typical example is as the group of the coupling component that is derived from formula Kk1 to Kk67, DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 to DK27, DK29, DK30, DK33, DK36, DK38, DK39 or DK42 to DK83.In the dyestuff of formula IIa, IIb and IIIa, especially preferred is Kk 1Dyestuff when being derived from the Kk-A compound.
Particularly preferably be the mixture of the dyestuff of general formula I Ib.The mixture of dyestuff IIb comprises two or more, for example 2,3 or 4 kind of dyestuff IIb.The amount of every kind of IIb dyestuff is not less than 10 moles of % of dyestuff F total amount, especially is not less than 20 moles of %.The mixture of preferred two kinds of dyestuff F, wherein the mol ratio of every kind of component is 9: 1 to 1: 9, especially 2: 8 to 8: 2, more preferably 3: 7 to 7: 3.The particularly preferred specific embodiment comprises that every kind of dyestuff is only at Kk 1Asynchronous dyestuff Hb mixture on the group.
General formula I to azo dyes and the metal complex thereof of IV prepares according to conventional method used according to the present invention, this method comprises multistep diazotization/coupling order, it constitutes dyestuff by diazotization/coupling in succession, that is to say that the connection of each diazo or NH unit structure unit is carried out successively; Or by compiling the synthetic dyestuff that constitutes, just generate the dyestuff part that has comprised diazo or NH group, and optional then by coupling or bisazo component, be connected with the other parts that equally comprise one or more diazo dyestuffs via further diazotization/coupling.
In diazotization/coupling process in succession, for example, at first with diazo component Dk 1And Dk 2Diazotization also is coupled to Napht respectively 1And Napht 2, Kk 1Or Kk 2Go up or be coupled on P or the R group, and then with product diazotization and be coupled on another coupling component (partner), optionally repeat this operation until the formation dyestuff.Perhaps, in synthesizing in succession, the product of first coupling is reacted successively with one or more diazonium compounds.
Coupling can comprise at first with bisazo component Tk in succession 1(NH 2) 2Or Tk 2(NH 2) 2Change into corresponding four nitrogen salts, then successively with Kk 1, P, Napht 1, Napht 2Deng the coupling component reaction, further carry out diazotization/coupling reaction then.
The mixture of two or more F dyestuffs not only can prepare required blending ingredients fusion, can also prepare by using the synthetic used raw-material mixture of F dyestuff.Can be for example by two or more amine of neutralization Dk in synthetic 1-NH 2, Dk 2-NH 2Or A-NH 2Mixture, two or more coupling components H-Kk 1And H-Kk 2Mixture, two or more bisazo components (H 2N) 2-Tk 1(H 2N) 2-Tk 2Mixture or two or more different compound N apth 1H 2And Napth 2H 2Mixture prepare the mixture of azo dyes I to XV.Certainly, also can use the mixture of three kinds or more kinds of components.
In order to keep the required mixing ratio of F dyestuff in the mixture, the synthetic of F dyestuff can be used various raw-material mixtures, and wherein every kind of raw-material amount is not less than 10 moles of % of mixture, especially is not less than 20 moles of %, more preferably is not less than 30 moles of %.In two kinds of raw-material mixtures, for example under the situation of the mixture of two kinds of coupling component H-Kk (1) and H-Kk (2), or under the situation of two kinds of diazo components, or under the situation of two kinds of mixing bisazo components, the mol ratio of every kind of component is 9: 1 to 1: 9 in the mixture, especially 8: 2 to 2: 8, more preferably 3: 7 to 7: 3.
Referring now to the preparation of the preparation illustration general formula I of the dyestuff of general formula I Ib to the azo dyes of XV.Can be used for the method for this purpose to constitute general formula I other azo dyes according to the traditional approach change to XV.The dyestuff of general formula I Ib can for example be prepared as follows: first step, and with bisazo composition Tk 1Diamino compounds Tk under 1(NH 2) 2Double couple gallium also at first is coupled to Napht then 1Napht under the group item 1H 2On the naphthalene compound.Then, with thus obtained diazonium compound H-Napht 1-N=N-Tk 1-N 2 +Be coupled to diazonium compound Dk respectively 1-N 2 +Or A-N 2 +Go up to obtain Compound D k 1-N=N-Napht 1-N=N-Tk 1-N2+ or A-N=N-Napht 1-N=N-Tk 1-N 2 +This compound is coupled to coupling component Kk 1H is last to obtain the wherein compound of the formula IIb of n=0.Perhaps, can be with diazonium compound H-Napht 1-N=N-Tk 1-N 2 +Be coupled to coupling component Kk 1H is last to obtain compound H-Napht 1-N=N-Tk 1-N=N-Kk 1Coupling diazonium compound Dk thereon 1-N 2 +Or A-N 2 +The dyestuff of formula IIb during with acquisition n=0.
Also can pass through respectively with Compound D k 1-N 2 +Or A-N 2 +Be coupled to Napht 1H 2On the compound to obtain formula Dk 1-N=N-Napht 1-H or A-N=N-Napht 1The compound of-H, the dyestuff of preparation formula IIb thus.Then this compound is coupled to diamino compounds Tk 1(NH 2) 2Bisazo component Tk 1Parent double couple gallium product on to obtain Compound D k respectively 1-N=N-Napht 1-N=N-Tk 1-N 2 +Or A-N=N-Napht 1-N=N-Tk 1-N 2 +This compound is coupled to Kk 1On the H coupling component to obtain the wherein dyestuff of the formula IIb of n=0.
Also can be prepared as follows the dyestuff of general formula Hb: at first with bisazo component Tk 1Parent diamino compounds Tk 1(NH 2) 2Double couple gallium is coupled to Kk then earlier 1On the H coupling component to obtain compound +N 2-Tk 1-N=N-Kk 1, then it is coupled to Napht 1H 2On the compound to obtain formula H-Napht 1-N=N-Tk 1-N=N-Kk 1Compound.Coupling diazonium compound Dk thereon 1-N 2 +Or A-N 2 +Compound with the formula IIb that obtains n=0.Perhaps, can be with compound +N 2-Tk 1-N=N-Kk 1Be coupled to Compound D k 1-N=N-Napht 1-H or A-N=N-Napht 1The last dyestuff of-H with the formula IIb that obtains n=0.
In the further stage of reaction, then can be with Dk 2-N 2 +Compound is coupled on the compound of formula IIb of n=0 the dyestuff with the formula IIb that obtains n=1.
Also can be prepared as follows the dyestuff of the general formula I Ib of n=1: at first with formula Dk 2-NH 2Compound diazotization, be coupled to Kk then 1On the H coupling component to obtain formula Kk 1-N=N-Dk 2Compound.Coupling compound Dk on this compound then 1-N=N-Napht 1-N=N-Tk 1-N 2 +Or A-N=N-Napht 1-N=N-Tk 1-N 2 +Dyestuff with the formula IIb that obtains n=1.
Also can be prepared as follows the dyestuff of the general formula I Ib of n=1: with bisazo Tk 1Parent diamino compounds Tk 1(NH 2) 2Double couple gallium also is coupled to Kk 1-N=N-Dk 2On the compound to obtain compound +N 2-Tk 1-N=N-Kk 1-N=N-Dk 2Then this compound is coupled to Compound D k 1-N=N-Napht 1The last dyestuff of H with the formula IIb that obtains n=1.
(wherein every kind of IIb dyestuff is at HKk for the mixture of the dyestuff of preferred general formula I Ib 1Difference on the group) preferably uses two or more different Kk 1The coupling component preparation, wherein every kind of component is as implied above.
When dyestuff comprises triazine group Tr 1And/or Tr 2The time, the synthetic reaction that also comprises triaizine compounds and the two kinds of amino groups of formula C of dyestuff
Figure A20048003210600361
R wherein aAnd R cRepresent halogen, especially chlorine, and R bRepresent halogen, methyl or methoxy.Amino group is the Dk that for example is known as diazo component 1-NH 2And Dk 2-NH 2Be known as the diamine compound Tk of bisazo component 1(NH 2) 2And Tk 2(NH 2) 2And the dyestuff part that comprises primary amino radical.
These methods are the well known in the prior art of anion azo dyes, and can be used for the synthetic of dyestuff I to XV similarly.
The diazotization and the coupling of gained diazonium or tetrazotization compound compound are carried out in the water-containing reacting medium of controlling the pH value in a conventional manner usually.
When having comprised, the residue that reacts has formula CH 2CH 2During the A group of the B group of-Q, the pH value of reactant mixture preferably is no more than pH8, otherwise the Q group can separate, and forms vinyl simultaneously.
Diazo component or four nitrogen components be coupled to respectively not only contain the OH group also contain amino and have the formula II of at least two possible coupling sites and the naphthalene compound of Kk-B on the time, must remember, first is coupled at and is no more than 3 pH value lower area and optionally occurs on the amino ortho position, and more than or equal to 6 and be preferably greater than and equal under 8 the pH value, the regioselectivity coupling occurs on the ortho position of OH group.
The reaction of amine and triaizine compounds C is carried out under acid ph value usually, preferably less than pH7, and pH1 to pH4 especially.
Diazotization/coupling or be generally 0 ℃ to 50 ℃, especially 0 to 30 ℃ with the required reaction temperature of the reaction of triazine.The required reaction time is generally 5 minutes to 2 hours, especially 20 minutes to 1 hour.
Reaction is carried out with stoichiometry usually; Just, reactive component is with required stoichiometry interreaction.Yet every kind of reactant also can use excessive or in shortage on required stoichiometric basis.Usually be no more than 20 moles of % with required stoichiometric departing from, especially be no more than 10 moles of %.In other words, for the reaction of diazo component and coupling component, the mol ratio of two kinds of components is 1: 1.2 to 1.2: 1, especially 1.1: 1 to 1: 1.1.In order to make the coupling component reaction of tetrazotization compound and 2 molar equivalents, for every mole of tetrazotization compound, the consumption of coupling component is 1.6 to 2.4 moles, especially 1.8 to 2.2 moles.
After diazotization/coupling, can add the required transition metal salt of stoichiometry aequum with form suitable, preferred water soluble salt, and, if desired, be heated to the required temperature of complexing, for example 40 to 100 ℃, prepare transition metal complex thus.
In a conventional manner, for example, especially,, from aqueous reaction mixture, separate dyestuff by dyestuff and the dry cake of saltouing by spray drying by with the aqueous reaction mixture evaporation.Preferred still moist filter cake can be dissolved again, preferably soluble in water, and carry out diafiltration and/or ultrafiltration, thus make the inorganic salts dilution of making in synthetic and/or make solution be rich in dyestuff.Then, from solution, reclaim the dyestuff of purifying thus by spray drying.
In order to prepare the liquid kind or the flowing product of dyestuff, dyestuff filter cake that evaporation or spray drying can be obtained or powder for example are dissolved in water, water-solvent mixture, aqueous acids or the aqueous bases, and aqueous acids and aqueous bases can also contain solvent in this case.Available herein solvent is particularly including water-miscible solvent, for example C 1-C 4Alkanol, organic carboxyl acid (for example formic acid, acetate and propionic acid), alkanolamine, two alkanolamines and trialkanolamine (for example monoethanolamine, diethanol amine, triethanolamine) and acid amides (for example formamide, acetamide, dimethyl formamide, dimethylacetylamide, N-Methyl pyrrolidone, methyl-sulfoxide etc.).Can also be directly by reaction solution or prepare the flowing product of dyestuff by ultrafiltration and spray drying.In order to obtain the stability of sufficiently high dye strength and liquid kind, diafiltration and/or ultrafiltration may must be carried out then, so that the inorganic salts dilution that generates in the building-up process and make solution concentration.
Method of the present invention is included in the staining procedure under at least 7.5 the pH value.For this reason, be at least 7.5 and preferred at least 8.0 and comprise in the water bath shampoo of dyestuff F of at least a the above-mentioned type and handle leather to be dyeed in the pH value.The pH value of body lotion is no more than pH11 usually, preferably is no more than pH10.5.More particularly, the pH value of body lotion is 8.5 to 10.The alkaline pH value is guaranteed the fixing of dye on leather, because under these conditions, the reaction of the amino of group A and leather is to form covalent bond.
In order to obtain the required alkaline pH value of fixation, can use any desirable alkali and buffering system.Example is alkali carbonate and bicarbonate, for example sodium carbonate, potash and sodium bicarbonate, and alkali metal hydroxide, for example sodium hydrate aqueous solution, sodium metasilicate, pyrophosphate, for example sodium pyrophosphate or potassium pyrophosphate, tripotassium phosphate, tertiary sodium phosphate, borax/sodium hydrate aqueous solution buffer and phosphate buffer.
The required temperature of fixed dye especially is no more than 50 ℃, more preferably no more than 40 ℃, so that leniently with leather coloring advantageously for being no more than 60 ℃.Dyeing temperature is generally at least 10 ℃, and preferably at least 20 ℃, especially at least 30 ℃, to obtain enough reaction rates and can quicken dyeing course thus.But lower in principle temperature is also feasible.The temperature range that is used for the leather of organic tanning is preferably 15 to 50 ℃, particularly 30 to 40 ℃.The preferred range that is used for the leather of metal oxide tanning is 15 to 60 ℃, particularly 30 to 50 ℃.
Fixation needs 0.5 to 4 hour processing time usually fully, and this depends on pH value and temperature.Those skilled in the art can be by carrying out the processing time that simple normal experiment determines that used particular dye is required.Especially under 9.5 to 11, especially 9.5 to 10.5 strong basicity pH value, dyeing time preferably is no more than 2 hours, for example 0.5 to 2 hour.
Dyeing can be carried out under the situation of the salt (for example saltcake) that existence adds.
Except dyestuff F used according to the present invention, body lotion also can comprise traditional acid or direct dyes.Yet their ratio preferably is no more than 10 weight % of dyestuff total amount in the body lotion, especially is no more than 5 weight % (all calculating with the organic chemistry colouring component of dyestuff in each case).
The amount of used dyestuff F depends on required depth of shade and is generally used leather or at least 0.2 weight % of intermediate shaved weight, usually at least 0.5 weight %, especially at least 1 weight %, amount described herein is based on the dyestuff that comprises synthetic salt and any standard agent.Based on painted organic chemistry component, the amount of used dyestuff is not less than 0.1 weight % of used leather or intermediate shaved weight usually, is not less than 0.3 weight % usually, especially is not less than 0.5 weight %.Mixture with organic chemistry component+synthetic salt and any standard agent calculates, and dye dosage is up to 20 weight % usually; Or calculate and when being the basis with the shaved weight, dye dosage is up to 15 weight % usually, but also can use bigger amount with painted organic chemistry component.For paramount depth of shade in obtaining, the consumption of dyestuff F depends on the molar extinction coefficient of dyestuff and the molecular weight of dyestuff, and when calculating based on the shaved weight of leather or intermediate and with the mixture of organic chemistry component+synthetic salt and any standard agent, be 2 weight % to 20 weight %, common 3 weight % to 20 weight %, especially 4 weight % to 20 weight %, when perhaps calculating based on the shaved weight of leather or intermediate and with painted organic chemistry component, be 1 weight % to 15 weight %, common 1.5 to 10 weight %, especially 2 weight % to 10 weight %.
Water bath shampoo can comprise conventional anion dyeing assistant, non-ionic surface active agent and wet end method (wet-end) chemicals, for example is usually used in the tanning material of retanning, for example polymerization retanning material, synthetic retanning material, vegetable tanning material and fatting agent and water-repelling agent.
Method of the present invention can with the retanning material package draw together all commercial system, for example:
1. vegetable tanning material, for example sensitive plant, chestnut, quebracho;
2. mineral tanning agent, for example chromium, iron, aluminium and zirconium tanning material;
3. filler, for example phyllosilicate, carbohydrate, glycan, for example starch and flour;
4. synthetic tanning material (syntans), the material of describing among EP 0459168, EP 0520182, US 5,342,916 and the US 5,186,846 for example, for example:
A. naphthalene sulfonic acids-formaldehyde condensation products,
B. phenolsulfonic acid-formaldehyde condensation products,
C. the condensation product of naphthalene sulfonic acids and/or phenolsulfonic acid and hydroxyaryl sulfone (for example two (hydroxyphenyl) sulfone) and formaldehyde,
D. naphthalene sulfonic acids and/or phenolsulfonic acid and low polysulfones (via the sulfone bridging connect and can by for example-OH or-SO 3The mixture of the polynuclear aromatic compound that H replaces) and the cocondensation product of formaldehyde,
E. naphthalene sulfonic acids, phenolsulfonic acid and formaldehyde and with the compound that contains N and when suitable and the hydroxyaryl sulfone or with the cocondensation product of low polysulfones.
The example that contains the compound of N is urea, melamine, melamine derivative, for example hydroxyl-C 2-C 20-alkyl melamine, two-hydroxyl-C 2-C 20-alkyl melamine or three-hydroxyl-C 2-C 20-alkyl melamine, hydroxyaryl melamine or on the N-atom, contain the melamine of one to three polyalkylene oxide chain; Melem (2,5,8-triamido-1,3,4,6,7,9, non-that alkene of 9b-seven azepines heptaazaphenalene) or melem derivative, for example hydroxyl-C 2-C 20-alkyl melem or on the N-atom, contain the melem of polyalkylene oxide side chain; Guanamines (2 of 6-replacement, 4-diamino-1,3,5-triazines), for example benzoguanamine, acetylguanamine, caprinoyl guanamines or isobutyl guanamines; Guanamines derivative, for example N-hydroxyl-C 2-C 20-alkyl guanamines, and the guanamines and the dicyan diamides that on the N-atom, contain one or two polyalkylene oxide chain,
F.4.a to the mixture of 4.e material and Cr (III) compound;
5. resin tanning material; For example:
A. the condensation product that contains sulphite of naphthalene sulfonic acids and formaldehyde,
B. the condensation product that contains sulphite of phenylbenzimidazole sulfonic acid and formaldehyde,
C.5a with the mixture of 5b;
6. polymerization tanning material, it can be anion, CATION or both sexes in nature.The anionic polymerisation tanning material can contain, for example, carboxyl, the cationic polymerization tanning material can contain, for example, and amino, both sexes polymerization tanning material is the cation group not only, also contains anionic group.According to the pH value, amphiphilic polymers can be an anion or cationic in nature.The example of polymerization tanning material is:
A. the homopolymers of acrylic acid and methacrylic acid and copolymer,
B. acrylic acid and/or methacrylic acid and acrylic acid C 1-C 30Arrcostab and/or methacrylic acid C 1-C 30The homopolymers of Arrcostab and copolymer,
C. acrylic acid C 1-C 30Arrcostab and/or methacrylic acid C 1-C 30The functionalized copolymers of the monomer of Arrcostab and cation or anion/acidic-group,
D. ethylenic unsaturated dicarboxylic acid anhydride (for example maleic anhydride) and C 3-C 40The copolymer of-alpha-olefin (for example propylene, 1-butylene, 1-hexene, 1-octene, diisobutylene, 1-decene etc.),
E. dicarboxylic anhydride-styrol copolymer,
F. ethylenic unsaturated nitrile (for example acrylonitrile and methacrylonitrile) is if suitable and other single ethylenically unsaturated monomers (for example acrylic acid, methacrylic acid, acrylamide, Methacrylamide or (methyl) acrylic acid C 1-C 10-Arrcostab) homopolymers and copolymer,
Described the example of polymerization tanning material in EP-A 1335029 and WO 96/15276, in this respect, these two documents all are incorporated herein by this reference.
7. aldehyde, for example:
A. formaldehyde,
B. glutaraldehyde,
C. the low polyacetals described in WO 03/095681,
D. as Bibliothek des Leders volume 3, Umschau Verlag, the tanning material of the described generation aldehyde of 1984, the 26-27 pages or leaves, its example Wei oxazolidine is with phosphonium compounds;
8. as US 5,186, the dispersant described in 846, for example:
A. naphthalene sulfonic acids-aldehyde condensation products and
B. lignosulphonates.
Available tanning material further comprises all commercially available tanning materials, Ullmann ' s Encyclopediaof Industrial Chemistry for example, volume A 15 259-282 pages or leaves, especially below 268 pages, the 5th edition (1990), the chrome tanning material described in the Verlag Chemie Weinheim, mineral tanning agent, syntans, polymerization tanning material and vegetable tanning material.Commercially available tanning material can also be the mixture of described tanning material type under the 1.-8..
Available fatting agent comprises all conventional fatting agents, especially all commercially available fatting agents in the leather manufacturing.Fatting agent comprises at least a based on hydrocarbon naturally, for example based on the hydrophobic substance of natural or synthetic wax, natural or artificial oil or natural or synthctic fat.The hydrocarbon feed that also can be used as fatting agent based on the material of polyisobutene.Hereinafter the fatting agent hydrocarbon feed can be by chemical modification, for example in greater detail:
1. sulphation
2. sulfonation
3. sulfiting
4. sulfoxidation
5. chlorosulfonation
6. ethoxylation or esterification usually
The hydrocarbon feed of fatting agent also can contain the mixture of mixture, functional ized components and non-functional ized components of non-functional ized components or the mixture of functional ized components.
The native paraffin that can be used for fatting agent comprises beeswax, cork wax, montan wax and Brazil wax.
The synthetic wax that can be used for fatting agent comprises:
-can be for example radical polymerization by ethene or ethene and for example (methyl) acrylic acid free-radical polymerized or Tissuemat E and ethylene copolymer wax by the ziegler-natta catalyzed acquisition;
-polyisobutene wax;
-paraffin just contains 12 or more carbon atoms and have the mixture of hydrocarbon of 25 to 45 ℃ fusing point usually.These paraffin can for example obtain in refinery or cracking plant, and are called slack wax and sasol wax by those skilled in the art; And
-brown coal ester type waxes.
The natural oil that can be used for fatting agent is particularly including the room temperature liquid triglyceride, for example fish oil, hoof oil, olive oil, cottonseed oil, castor oil, sunflower oil and peanut oil.
The artificial oil that can be used for fatting agent is particularly including light oil, paraffin oil, functionalized paraffin, for example chlorination or chlorosulfonation paraffin, and poly alkylene glycol, for example polyethylene glycol.
The natural fat that can be used for fatting agent is particularly including room temperature solid natural glycerin three acid esters, for example lanolin, shellac wax and their mixture.
Example based on the fatting agent of polyisobutene has been described in WO 03/023070.
Other example of fatting agent has been described in WO 03/023069.
Except hydrocarbon feed, fatting agent can further comprise surface reactive material.These comprise all emulsifying agents that the fatting agent, tanning material, water-repelling agent and other auxiliary agent that are used for the leather manufacturing exists.Surface reactive material can be nonionic, anion, CATION or amphoteric ion type in nature.Fatting agent of the present invention should use nonionic or anionic species as emulsifying agent, the preferred alkoxy fatty alcohols that uses fatty alcohol (alcohol mixture that just contains 10 to 25 carbon atoms) or contain 5 to 100 alkylen groups is as nonionic emulsifier, use they sulfate or phosphate as anion emulsifier, especially use sodium salt, sylvite or the ammonium salt of anion emulsifier.
The water-repelling agent that can be used for method of the present invention comprises all water-repelling agents that become known for the leather manufacturing, especially as M.Hollstein, Bibliothek des Leders, volume 4-Defatting, fatliquoringand hydrophobicization of leather, the commercial system described in 1983.
The commercially available prod is particularly including one or more following components:
1. the copolymer of alpha-olefin and dicarboxylic anhydride (for example maleic anhydride)
2. paraffin
3. light oil
4. simple siloxanes
5. functionalized silicone
6. emulsifying agent
Water-repelling agent may further include the described any component of fatting agent.
Except other fatting agent composition, also detailed description the in EP-A 213480, WO 95/22627, WO98/04748, EP-A 1087021 and WO 01/68584 for example based on the water-repelling agent of siloxanes with based on the water-repelling agent of the copolymer of alpha-olefin and dicarboxylic anhydride.In WO 93/17130 and EP-A372746, can find other example of water-repelling agent.
The kind of used tanning agent, fatting agent and water-repelling agent and amount depend on kind, tanning type (mineral are tanned or do not had metal and tan), required sense of touch situation and the required physical property of the leather and fur products that will make by traditional approach.
Therefore, tanning material is used for the leather manufacturing with following amount:
The amount of polymerization tanning material (being formulated as solution) is 20 weight % the most nearly, be generally 3-8 weight % and/or
The amount of syntans (calculating with powder) is 30 weight % the most nearly, usually 4-12 weight % and/or
The amount of resin tanning material (calculating with powder) is 15 weight % the most nearly, and 3-6 weight %, and/or the amount of vegetable tanning material usually is 30 weight % the most nearly, common 4-12 weight %,
The tanning material total amount is 40 weight % the most nearly usually, 4 weight % to 40 weight % for example, and common 10 weight % to 40 weight %, all percentages are radix with the weight in wet base of leather.
Fatting agent and water-repelling agent use with following amount usually: reach the fatting agent of 20 weight %, common 6-12 weight % most, reach the water-repelling agent of 20 weight %, common 4-8 weight % most, the weight in wet base with leather is a radix separately.
Dyeing can be carried out a stage, also can divide 2 stages to carry out.In two-stage dyeing, at first the phase I with pH value be lower than 7.5, for example pH3 to 7.4 and preferred pH values be 4 to 7.4 the body lotion processing leather that contains dyestuff.This step is used to make the dyestuff uniform distribution at the leather cross section.Then, in second stage, in the above described manner under at least 8, for example 8 to 11, especially 8.5 to 10.5, especially 8.5 to 10 pH value with the fixing of dye.Can also in one-step method, dye, promptly not have allocated phase before the stage in fixation.
Although be not imperative, after dying operation, can wash to remove not the dyestuff of chemical bonding and the impurity in the dyestuff, for example do not contain the dyestuff of A group.Not that the reason of this washing of absolute demand is that dye fixing has been quantitatively or almost quantitative in many cases.If carry out washing then, the leather washing after can water will dyeing is once to repeatedly, for example 1 to 6 time, and especially 1 to 4 time.The amount of water is no more than 300 weight % of intermediate shaved weight usually, for example 100 weight % to 300 weight %.The duration of single washing step is generally 5 to 60 minutes, especially 10 to 30 minutes.
Washing operation can adopt nonionic, anion, CATION or amphion auxiliary agent similarly.Preferred commercially available ion auxiliary agent is for example based on polyvinyl formamide, PVP, vinyl pyrrolidone-vinyl imidazole copolymer or based on the condensation product of dicarboxylic acids or dicarboxylic anhydride and amine or the condensation product of naphthalene sulfonic acids and formaldehyde.In EP 0459168, EP 0520182, US 5,342,916 and US 5,186,846, these auxiliary agents have been described.
When comprising coloured accessory substance in the dyestuff or when having formed coloured accessory substance in the fixation process, the use of auxiliary agent is responsive especially.Auxiliary agent guarantees that the quantitative of all coloured submembers or basal ration removal only need be no more than three washings, may only twice washing or once washing ideally.
The leather coloring that comprises retanning, stuffing and post processing carries out in a conventional manner, is for example undertaken by dyeing at rotary drum or in blade (paddle).These methods have detailed description in the prior art, for example at " Bibliothek des Leders ", volume 3 (tanning agents, tanning andretanning) [1985], roll up 4 (defatting, fatliquoring and hydrophobicization inleather manufacture) [1987] and roll up 5 (the dyeing of leather) [1987] UmschauVerlag; " Leather Technicians Handbook ", 1983, the J.H.Sharphouse work, Leather Producers Association publishes; With " Fundamentals of LeatherManufacturing ", 1993, the E.Heidenmann work, Eduard Roether KG publishes.
Dyeing after pretan, carry out usually, just before the retanning, among or carry out afterwards.Dying operation can operate in the identical bath with retanning and carry out, and also can carry out in different baths.Dying operation preferably carried out before retanning.Preferably after tanning and before retanning and stuffing, carry out above-mentioned one or more washing step.
Usually after dyeing and retanning operation, carry out currying leather is adjusted to required tactile property.Yet retanning and stuffing also can be carried out in a processing step.The stuffing step can be carried out in any stage of wet end operation, and preferred carrying out at last in wet end operation.
Usually, stuffing and retanning are just carried out last acidifying all fixing by acidifying at last of operating after dyeing and any retanning and stuffing.Usually, in order to carry out acidifying, add acid, formic acid especially, the pH value that water treatment is bathed is adjusted to the value below 3.7.
All types of leathers can be used for dyeing on the methodological principle of the present invention, the intermediate that does not promptly also have retanning, (for example aldehyde tannage) leather (wet-white leather) or vegetable tanning leather of the leather of metal oxide tanning (with the wet blue of chromium oxide tanning with the wet method aluming of aluminium oxide tanning) and organic tanning for example, and the intermediate of retanning, for example bark or crust leather.
Method of the present invention can be made the colouring leather that is used for any leather and fur products (for example footwear, clothes, automobile, gloves and furniture part) especially.Method of the present invention also can be made the suitcase leather and be used for the reptile leather of accessory.According to traditional approach, by selecting to be applicable to that auxiliary agent, fatting agent, water-repelling agent and the retanning material of particular product obtain the required sense of touch of specific leather and fur products, machinery and physical property.
Even the leather according to method dyeing of the present invention also has excellent fastness under very high depth of shade.Anti-wiping fastness, especially washable, sweat proof and anti-ly ooze that to move fastness good especially, this is very difficult in by the leather of conventional method dyeing, even may not realize.Move in the fastness test oozing,, can or can not be touched material hardly according to the leather of the present invention's dyeing and stain even under high humility and high temperature, (just be higher than 50 ℃, for example 60 to 100 ℃).
Via UV/VIS spectroscopic methodology and HPLC carry out quantitatively and quantitative assay show dyestuff generation 85 to 100% of the present invention and usually above 90% fixation degree.
The following example is illustrated the present invention.
Preparation example:
Embodiment 1a:
Figure A20048003210600461
1) 1 mole of MSP (3-(2-sulfato ethylsulfonyl)-6-aminobenzenesulfonic acid) is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.1 mole of γ-acid is dissolved in 25 weight % sodium hydrate aqueous solutions, adds 21 weight % hydrochloric acid then the pH value is adjusted to below 1.γ-acid precipitation forms outstanding body lotion.Diazotization MSP is poured in the outstanding body lotion.Then reactant mixture is stirred in pH＜1 time and can not detect until diazotization MSP or free γ-acid in 1 hour.After this, add the sodium carbonate liquor of 15 weight % so that the pH value rises to 3-8.
2) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,6-dinitro-2-amino-phenol diazotization adds in the reactant mixture that obtains in the step 1) then.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction is finished, in reactant mixture, add 0.20-0.30 mol sulfuric acid chromium (III) and also stirred then 1 hour.Adding NaCl makes dyestuff saltout and leach by suction.
According to the similar mode of embodiment 1a, the dyestuff that can obtain general formula D k-N=N-Napht-N=N-A (is r=k=0, the dyestuff of general formula I I during n=1) metal complex, wherein the Dk representative is derived from the group of diazo component DK1 to DK9, DK13, DK14, DK26, DK27, DK39 to DK41 or DK58 or A1 to A12, Napht represents one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 and II-14, and A represents one of group A1 to A12.Carry out at the ortho position of the amino that is coupled at group II-2, II-4, II-6, II-8, II-10, II-12 and II-14 of group A-N=N-.Its example is listed in the following table 1.
Embodiment 2a:
According to reacting with the described method of embodiment 1a, different is does not carry out then reaction with chromic salts.
According to the similar mode of embodiment 2a, the dyestuff that can obtain general formula D k-N=N-Napht-N=N-A (is r=k=0, the dyestuff of general formula I I during n=1), wherein Dk represents the group that is derived from diazo component DK1 to DK83 or is derived from A1 to A12, Napht represents one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 and II-14, and A represents one of group A1 to A12.Carry out at the ortho position of the amino that is coupled at group II-2, II-4, II-6, II-8, II-10, II-12 and II-14 of group A-N=N-.Its example is listed in the following table 1.
Table 1
Embodiment number Dk Napht A Metal
1a DK5 DK42 A1 Cr
1b DK41 DK42 A1 Cr
1c DK41 DK44 A1 Cr
1d DK5 DK44 A1 Cr
1e DK3 DK44 A1 Cr
1f DK5 DK43 A7 Cr
2a DK5 DK42 A1 -
2b DK5 DK44 A1 -
2c DK12 DK44 A1 -
2d A1 DK59 A1 -
2e A1 DK44 A1 -
2f A7 DK44 A7 -
2g A4 DK44 A4 -
2h A6 DK44 A6 -
2i A1 DK44 A6 -
2j A1 DK45 A1 -
2k A6 DK45 A6 -
Embodiment 3:
Figure A20048003210600481
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,6-dinitro-2-amino-phenol diazotization.1 mole of γ-acid is dissolved in 25 weight % sodium hydrate aqueous solutions, adds 21 weight % hydrochloric acid then the pH value is adjusted to below 1.γ-acid precipitation forms outstanding body lotion.With diazotization 4,6-dinitro-2-amino-phenol pours in the outstanding body lotion.Then reactant mixture is stirred 1 hour in pH＜1 time until diazotization 4,6-dinitro-2-amino-phenol or free γ-acid can not detect.After this, add the sodium carbonate liquor of 15 weight % so that the pH value rises to 3-8.
2) 1 mole of MSP is suspended in the frozen water, and, adds to then in the reactant mixture that obtains in the step 1) in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction is finished, add NaCl, be settled out dyestuff thus, suction leaches this dyestuff.
According to similar to Example 3 trans, can obtain the dyestuff of general formula D k-N=N-Napht-N=N-A and their metal complex (is r=k=0, the dyestuff of general formula I I during n=1), wherein the Dk representative is derived from the group of diazo component DK1 to DK83, Napht represents one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 and II-14, and A represents one of group A1 to A12.Carry out at the ortho position of the hydroxyl that is coupled at group II-2, II-4, II-6, II-8, II-10, II-12 and II-14 of group A-N=N-.
Embodiment 4a:
Method A
1) 1 mole of three chloro-1,3,5-triazines is suspended in 0-5 ℃ the water.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions and dropwise adds the pH value to, stirred then 30 minutes in the outstanding body lotion of three chlorotriazines of 1-4.
2) make 1 mole of MSP be suspended in the frozen water and add in the reactant mixture that step 1) obtains.After this, add sodium carbonate the pH value is adjusted between the 5-8, stirred then 1 hour.
3) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole of 5-nitro-2-amino-phenol diazotization, and add step 2 to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction is finished, in reactant mixture, add 0.20-0.30 mol sulfuric acid chromium (III) and also stirred then 1 hour.Adding NaCl makes dyestuff saltout and leach by suction.
Method B
1) 1 mole of three chlorotriazine is suspended in 0-5 ℃ the water.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and dropwise adds the pH value to, stirred then 30 minutes in the outstanding body lotion of three chlorotriazines of 1-4.
2) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole of 5-nitro-2-amino-phenol diazotization, and add in the reactant mixture that step 1) obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.
3) make 1 mole of MSP be suspended in the frozen water and add step 2 to) in the reactant mixture that obtains.After this, add sodium carbonate the pH value is adjusted between the 5-8, stirred then 1 hour.After reaction is finished, in reactant mixture, add 0.20-0.30 mol sulfuric acid chromium (III) and also stirred then 1 hour.Adding NaCl makes dyestuff saltout and leach by suction.
According to the similar mode of embodiment 4a, can obtain the metal complex of the dyestuff (dyestuff of general formula V when being r=p=0) of general formula D k-N=N-Napht-NH-Tr-NH-A, wherein Dk is the group that is derived from diazo component DK1 to DK9, DK13, DK14, DK26, DK27, DK39-DK41, DK58, Napht represents one of divalent group II-1, II-3, II-5, II-7, II-9, II-11 and II-13, Tr is a 2-chloro-1,3,5-triazine-4,6-two bases, and A represents one of group A1 to A12.Carry out at the ortho position of the hydroxyl that is coupled at group II-1, II-3, II-5, II-7, II-9, II-11 and II-13 of group Dk-N=N-.
Embodiment 5a:
React according to the method described in the embodiment 4a, different is does not carry out then reaction with chromic salts.
Embodiment 5b:
Figure A20048003210600511
Method A
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole of 5-nitro-2-amino-phenol diazotization, and make itself and the solution reaction of 1 mole of Cleve's acid 7 in 25 weight % sodium hydrate aqueous solutions.Keep the pH value to be lower than 3.
2) 1 mole of three chlorotriazine is suspended in 0-5 ℃ the water.The reactant mixture that step 1) is obtained dropwise adds the pH value to in the outstanding body lotion of being somebody's turn to do of 1-4, stirs then 30 minutes.
3) make 1 mole of MSP be suspended in the frozen water and add step 2 to) in the reactant mixture that obtains.After this, add sodium carbonate the pH value is adjusted between the 5-8, stirred then 1 hour.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
Method B
1) 1 mole of three chlorotriazine is suspended in 0-5 ℃ the water.Make 1 mole of MSP be suspended in the frozen water and add the pH value to, stirred then 30 minutes in the outstanding body lotion of three chlorotriazines of 1-4.
2) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole of 5-nitro-2-amino-phenol diazotization, and make itself and the solution reaction of 1 mole of Cleve's acid 7 in 25 weight % sodium hydrate aqueous solutions.Keep the pH value to be lower than 3.
3) with step 2) product that obtains adds in the reactant mixture that step 1) obtains.After this add sodium carbonate the pH value is adjusted between the 5-8, stirred then 1 hour.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to embodiment 5a and the similar mode of 5b, can obtain general formula D k 1-N=N-Napht-NH-Tr-NH-Dk 2Dyestuff and their metal complex (dyestuff of general formula V when being r=p=0), Dk wherein 1And Dk 2Represent the group that is derived from the group of diazo component DK1 to DK83 or is derived from A1 to A12 separately, condition is Dk 1Or Dk 2In at least one represents the group of formula A, Napht represents one of divalent group II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 and II-16, Tr is a 2-chloro-1,3,5-triazines-4,6-two bases, and A represents one of group A1 to A12.Group Dk 1Carry out at the ortho position of the hydroxyl that is coupled at group II-1, II-3, II-5, II-7, II-9, II-11 and II-13 of-N=N-.
Embodiment 6a:
Method A
1) 1 mole of three chlorotriazine is suspended in 0-5 ℃ the water.1 mole of γ acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and dropwise adds the pH value to, stirred then 30 minutes in the outstanding body lotion of three chlorotriazines of 1-4.
2) make 1 mole of ortho-aminobenzoic acid be suspended in the frozen water and add in the reactant mixture that step 1) obtains.After this, add sodium carbonate the pH value is adjusted between the 5-8, stirred then 1 hour.
3) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole of H acid diazotization, and add step 2 to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.
4) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, and add in the reactant mixture that step 3) obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
Method B
1) 1 mole of three chlorotriazine is suspended in 0-5 ℃ the water.1 mole of γ acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and dropwise adds the pH value to, stirred then 30 minutes in the outstanding body lotion of three chlorotriazines of 1-4.
2) make 1 mole of ortho-aminobenzoic acid be suspended in the frozen water and add in the reactant mixture that step 1) obtains.After this, add sodium carbonate the pH value is adjusted between the 5-8, stirred then 1 hour.
3) 1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and with the acetylation of 1.1-1.5 mole of acetic anhydride.
4) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, and add in the reactant mixture that step 3) obtains.Adding sodium carbonate sets the pH value and remain between 4 to 7.After coupling is finished, add 21 weight % hydrochloric acid the pH value is adjusted to below 1, and reactant mixture is heated to 85-95 ℃.Acetyl group separates in this process.
5) the product diazotization that with excessive nitrite sodium and hydrochloric acid step 4) is obtained down pH＜1 and 0-5 ℃, and add step 2 to) in the reactant mixture of acquisition.Adding sodium carbonate sets the pH value and remain between 4 to 7.After reaction is finished, with reactant mixture ultrafiltration and dry.
According to the similar mode of embodiment 6a, can obtain general formula A-N=N-P-N=N-Napht 1The dyestuff of-NH-Tr-NH-Dk and their metal complex (are r=0, p=1 and P=Napht 2The time general formula V dyestuff), wherein the Dk representative is derived from the group of diazo component DK1 to DK83, P and Napht 1Represent one of divalent group II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 and II-16 independently or be derived from the group of diazo component DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 to DK27, DK29, DK30, DK33, DK36, DK38 or DK39, Tr is a 2-chloro-1,3,5-triazine-4,6-two bases, and A represents one of group A1 to A12.Group A-N=N-and A-N=N-Napht 2The coupling of-N=N-is respectively at Napht 2And Napht 1Carry out at the ortho position of middle hydroxyl.Its example is listed in the following table 2.
Table 2:
Embodiment number A P Napht 1 Dk Metal
6a A1 DK44 DK42 DK4 -
6b A1 DK39 DK43 DK5 Cr
6c A1 DK4 DK42 DK17 Cr
6d A1 DK27 DK59 DK4 Cr
6e A7 DK44 DK42 DK4 -
6f A2 DK44 DK42 DK4 -
6g A4 DK44 DK42 DK4 -
6h A6 DK27 DK59 DK4 -
Embodiment 7:
Figure A20048003210600541
1) 1 mole of three chlorotriazine is suspended in 0-5 ℃ the water, and with 1 mole amino acid (paramineacid) to be added pH value be that this of 1-4 hangs in body lotion, stirred then 30 minutes.
2) make 1 mole of ortho-aminobenzoic acid be suspended in the frozen water and add in the reactant mixture that step 1) obtains.After this, add sodium carbonate the pH value is adjusted between the 5-8, stirred then 1 hour.Add excessive nitrite sodium and hydrochloric acid down so that product diazotization pH＜1 and 0-5 ℃.
3) 1 mole of K acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and adds step 2 to) in the reactant mixture that obtains.Keep the pH value to be lower than 2.
4) 1 mole of MSP is suspended in the frozen water and adds excessive nitrite sodium and hydrochloric acid down to carry out diazotization pH＜1 and 0-5 ℃.Then, diazotizing MSP is added in the reactant mixture of step 3) acquisition.Add 10 weight % sodium hydrate aqueous solutions so that the pH value remains between 3 to 8.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to mode similar to Example 7, can obtain general formula A-N=N-Napht 1The dyestuff of-N=N-R-NH-Tr-NH-Dk and their metal complex (dyestuff of general formula V when being p=0 and r=1), wherein the Dk representative is derived from the group of diazo component DK1 to DK83, Napht 1Represent one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 and II-14, R represents Dk21, and wherein Q=H or representative are derived from the divalent group of Kk5 and Kk14 to Kk16, Tr is a 2-chloro-1,3,5-triazines-4,6-two bases, and A represents one of group A1 to A12.Group A-N=N-is coupled at Napht 1Carry out at the ortho position of middle hydroxyl.
Embodiment 8:
1) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, and with the reactant aqueous solution of 1 mole of methylamine Fei Taming (metamine).Keep the pH value to be lower than 3.
2) 1 mole of three chlorotriazine is suspended in 0-5 ℃ the water, and will hangs the reaction mixture 30 minutes that body lotion obtains in pH 1 to 4 time and step 1).
3) make 1 mole amino acid is suspended in the frozen water, and add step 2 to) in the reactant mixture that obtains.After this, add sodium carbonate the pH value is set between the 5-8, stirred then 1 hour.Add excessive nitrite sodium and hydrochloric acid down so that product diazotization pH＜1 and 0-5 ℃.
4) 0.5 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and adds in the reactant mixture of step 3) acquisition.Make the pH value keeping 1 hour below 2, add sodium carbonate then and be adjusted between the 3-8, and kept 1 hour.After reaction is finished, with reactant mixture ultrafiltration and dry.
According to mode similar to Example 8, the metal complex that can obtain general formula A-N=N-R-NH-Tr-NH-P-N=N-Napht-N=N-P-NH-Tr-NH-R-N=N-A and they (is Dk 1=Dk 2The dyestuff of general formula X when=A and k=n=1), wherein Napht represents one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 and II-14, R represents the wherein Dk21 of Q=H, or representative is derived from the divalent group of Kk5 and Kk14 to Kk16, the R representative is derived from the divalent group of DK22 to DK25 or represents one of divalent group II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 or II-16, Tr is a 2-chloro-1,3,5-triazine-4,6-two bases, and A represents one of group A1 to A12.
Embodiment 9a:
1) 1 mole of paranitroanilinum is dissolved in 21 weight % hydrochloric acid, in pH＜1 and the 0-5 ℃ of following excessive nitrite sodium diazotization of using, adds to then in the outstanding body lotion of 1 mole of ortho-aminobenzoic acid and frozen water then.Under pH＜2 and T＜10 ℃, reactant mixture was stirred 1 hour then.
2) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, and with the solution reaction of 1 mole of Cleve's acid 7 in 25 weight % sodium hydrate aqueous solutions.Keep the pH value to be lower than 3.
3) 1 mole of three chlorotriazine is suspended in 0-5 ℃ the water, and will hangs body lotion the reaction mixture that obtains with step 1) for pH1 to 4 time 30 minutes.
4) with step 2) product that obtains adds in the reactant mixture that step 3) obtains.After this add sodium carbonate the pH value is adjusted between the 5-8, stirred then 1 hour.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to the similar mode of embodiment 9a, can obtain general formula D k 1-N=N-P-NH-Tr-NH-R-N=N-Dk 2Dyestuff and their metal complex (being the dyestuff of general formula VI), Dk wherein 1And Dk 2Representative is derived from the group of diazo component DK1 to DK83 separately, or representative is derived from the group of A1 to A12, wherein Dk 1Or Dk 2In at least one represents the group of formula A, P and R representative are derived from the divalent group of DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 to DK27, DK29, DK30, DK33, DK36, DK38, DK39 or DK60 to DK83, or represent divalent group II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 or II-16, Tr is a 2-chloro-1,3,5-triazine-4,6-two bases, and A represents one of group A1 to A12.Carry out at the ortho position that is coupled at hydroxyl among group II-1, II-3, II-5, II-7, II-9, II-11 and the II-13 of group A-N=N-.The example of these dyestuffs is listed in the table 3.
Table 3:
Embodiment number Dk 1 P R Dk 2 Metal
9a A1 DK46 DK4 DK17 -
9b A1 DK42 DK4 DK19 -
9c DK5 DK42 DK4 A1 Cr
9d DK4 DK43 DK4 A1 Co
9e DK40 DK59 DK22 A1 Cr
9f DK5 DK44 DK22 A1 Cr
9g A7 DK46 DK4 DK17 -
9h DK5 DK42 DK4 A4 Cr
Embodiment 10:
Figure A20048003210600571
1) 1 mole of three chlorotriazine is suspended in 0-5 ℃ the water, in advance 1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, mix for 1 to 4 time at pH with this outstanding body lotion then, stirred then 30 minutes.
2) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, and add in the reactant mixture that step 1) obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) make 0.5 mole 4,4-diamino-diphenyl sulfonamide is suspended in the water, and adds step 2 to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to mode similar to Example 10, the metal complex that can obtain general formula A-N=N-Napht-NH-Tr-NH-Tk-NH-Tr-NH-Napht-N=N-A and they (is Dk 1=Dk 2The dyestuff of general formula I X during=A), wherein Napht represents divalent group II-1, II-3, II-5, II-7, II-9, II-11 or II-13, and Tr is a 2-chloro-1,3,5-triazine-4,6-two bases, the Tk representative is derived from the divalent group of bisazo component Tk1 to Tk20, and A represents one of group A1 to A12.Carry out at the ortho position that is coupled at hydroxyl among the Napht of group A-N=N-.
Embodiment 11a:
Figure A20048003210600581
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium.1 mole of J acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and dropwise adds 4 of double couple gallium to, in the solution of 4-diamino-diphenyl sulfonamide.In this process, add hydrochloric acid the pH value is remained on below 3.
2) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.Then, reactant mixture is added in the reactant mixture of step 1) acquisition.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) add 1 mole of methylamine Fei Taming to step 2) in the reactant mixture that obtains, and add 10 weight % sodium hydrate aqueous solutions the pH value is remained between 3 to 8.
4) 1 mole of three chlorotriazine is suspended in 0-5 ℃ the water.Should hang body lotion and quantitatively add in 1 mole of ortho-aminobenzoic acid, under pH 1-4, stir 30 minutes then.
5) product that step 4) is obtained adds in the reactant mixture of step 3) acquisition.After this, add sodium carbonate the pH value is set between 5 to 8, stirred then 1 hour.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
Embodiment 11b:
Figure A20048003210600591
1) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.1 mole of J acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and adds in the reactant mixture of diazotization MSP.Keep the pH value to be lower than 2.
2) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium, and adding in the reactant mixture that step 1) obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) add 1 mole of methylamine Fei Taming to step 2) in the reactant mixture that obtains, and add 10 weight % sodium hydrate aqueous solutions the pH value is remained between 3 to 8.
4) 1 mole of three chlorotriazine is suspended in 0-5 ℃ the water.Should hang body lotion and quantitatively add in 1 mole of ortho-aminobenzoic acid, under pH 1-4, stir 30 minutes then.
5) product that step 4) is obtained adds in the reactant mixture of step 3) acquisition.After this, add sodium carbonate the pH value is set between 5 to 8, stirred then 1 hour.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to embodiment 11a and the similar mode of 11b, the metal complex that can obtain general formula A-N=N-Napht-N=N-Tk-N=N-P-NH-Tr-NH-Dk and they (is Dk 1The dyestuff of general formula VII during=A), wherein the Dk representative is derived from the group of diazo component DK1 to DK83, Napht represents divalent group II-1, II-3, II-5, II-7, II-9, II-11 or II-13, Tr is a 2-chloro-1,3,5-triazine-4,6-two bases, the Tk representative is derived from the divalent group of bisazo component Tk1 to Tk20, and A represents one of group A1 to A12.When reaction when carrying out as described in the embodiment 11a, carry out at the ortho position that is coupled at hydroxyl among the Napht of group A-N=N-, when reaction when carrying out as described in the embodiment 11b, this is coupled at ortho position amino among the Napht and carries out.
Embodiment 12a:
Method A
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and dropwise adds 4 of double couple gallium to, in the solution of 4-diamino-diphenyl sulfonamide.In this process, add hydrochloric acid the pH value is remained on below 3.
2) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.Then, reactant mixture is added in the reactant mixture of step 1) acquisition.Adding 15 weight % aqueous sodium carbonates remains between 3 to 8 the pH value.
3) add 1 mole of methylamine Fei Taming to step 2) in the reactant mixture that obtains, and add 15 weight % aqueous sodium carbonates the pH value is remained between 3 to 8.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
Method B
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and dropwise adds 4 of double couple gallium to, in the reactant mixture of 4-diamino-diphenyl sulfonamide.Keep the pH value to be lower than 3.
2) 1 mole of methylamine Fei Taming acid is added in the reactant mixture that step 1) obtains, and added 10 weight % sodium hydrate aqueous solutions the pH value is remained between 3 to 8.
3) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.Then, add reactant mixture to step 2) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to the similar mode of embodiment 12a, can obtain general formula A-N=N-Napht 1The dyestuff of-N=N-Tk-N=N-Kk (dyestuff of general formula I I when being r=k=1 and n=0), wherein the Kk representative is derived from the group of coupling component Kk1 to Kk67, DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 to DK27, DK29, DK30, DK33, DK36, DK38, DK39 or DK42 to DK83, Napht 1Represent one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 and II-14, the Tk representative is derived from the group of bisazo component Tk1 to Tk20, and A represents one of group A1 to A12.Group A-N=N-is coupled at Napht 1Carry out at the ortho position of middle hydroxyl.Its example is listed in the table 4.
Table 4
Embodiment number A Napht 1 Tk Kk
12a A1 DK44 Tk18 Kk15
12b A1 DK44 Tk18 Kk5
12c A1 DK44 Tk18 Kk2
12d A1 DK44 Tk18 Kk3
12e A1 DK44 Tk18 Kk6
12f A1 DK44 Tk18 Kk1
12g A1 DK44 Tk18 Kk4
12h A1 DK44 Tk18 Kk7
12i A1 DK44 Tk18 Kk9
12j A1 DK44 Tk18 Kk10
12k A1 DK44 Tk18 Kk14
12l A1 DK44 Tk18 Kk16
12m A1 DK44 Tk18 Kk26
12n A1 DK44 Tk18 K127
12o A1 DK44 Tk18 Kk40
12p A1 DK44 Tk18 Kk46
Embodiment number A Napht 1 Tk Kk
12q A1 DK44 Tk18 Kk48
12r A1 DK44 Tk18 Dk4
12s A1 DK44 Tk18 Dk11
12t A1 DK44 Tk18 Dk18
12u A1 DK44 Tk18 Dk29
12v A1 DK44 Tk18 Dk30
12z A1 DK44 Tk18 Dk39
12aa A1 DK44 Tk16 Kk5
12ab A1 DK44 Tk16 Kk3
12ac A1 DK44 Tk16 Kk4
12ad A1 DK44 Tk16 Dk4
12ae A1 DK44 Tk19 Kk5
12af A1 DK45 Tk18 Kk5
12ag A2 DK44 Tk18 Kk5
12ah A7 DK44 Tk18 Kk15
12ai A4 DK44 Tk18 Kk15
12aj A5 DK45 Tk18 Kk10
12ak A9 DK45 Tk18 Kk14
12al A10 DK45 Tk18 Kk16
12am A11 DK45 Tk18 Kk26
12an A1 DK44 Tk18 Kk11
12ao A1 DK44 Tk18 Kk51
12ap A1 DK44 Tk18 Kk52
12aq A1 DK44 Tk18 Kk53
12ar A1 DK44 Tk18 Kk54
12as A1 DK44 Tk18 Kk55
12at A1 DK44 Tk18 Kk56
12au A1 DK44 Tk18 Kk57
12av A1 DK44 Tk18 Kk58
12aw A1 DK44 Tk18 Kk59
12ax A1 DK44 Tk18 Kk60
12ay A1 DK44 Tk18 Kk61
12az A1 DK44 Tk18 Kk62
12ba A1 DK44 Tk18 Kk63
12bb A1 DK44 Tk18 Kk64
12bc A1 DK44 Tk18 DK66
12bd A1 DK45 Tk18 Kk1
12be A1 DK45 Tk18 Kk2
Embodiment number A Napht 1 Tk Kk
12bf A1 DK45 Tk18 Kk3
12bg A1 DK45 Tk18 Kk4
12bh A1 DK45 Tk18 Kk6
12bi A1 DK45 Tk18 Kk7
12bj A1 DK45 Tk18 Kk10
12bk A1 DK45 Tk18 Kk11
12bl A1 DK45 Tk18 Kk14
12bm A1 DK45 Tk18 Kk15
12bn A1 DK45 Tk18 Kk16
12bo A1 DK45 Tk18 Kk51
12bp A1 DK45 Tk18 Kk53
12bq A1 DK45 Tk18 Kk54
12br A1 DK45 Tk18 Kk55
12bs A1 DK45 Tk18 Kk56
12bt A1 DK45 Tk18 Kk61
12bu A1 DK45 Tk18 Kk62
12bv A1 DK45 Tk18 Kk63
12bw A1 DK45 Tk18 Kk64
12bx A1 DK45 Tk18 DK66
12by A1 DK44 Tk16 Kk10
12bz A1 DK44 Tk16 Kk11
12ca A1 DK44 Tk16 Kk14
12cb A1 DK44 Tk16 Kk15
12cc A1 DK44 Tk16 Kk16
12cd A1 DK44 Tk16 Kk51
12ce A1 DK44 Tk16 Kk53
12cf A1 DK44 Tk16 Kk54
12cg A1 DK44 Tk16 Kk55
12ch A1 DK44 Tk16 Kk56
12ci A1 DK44 Tk16 Kk61
12cj A1 DK44 Tk16 Kk62
12ck A1 DK44 Tk16 Kk63
12cl A1 DK44 Tk16 Kk64
12cm A1 DK44 Tk16 DK66
12cn A1 DK44 Tk19 Kk2
12co A1 DK44 Tk19 Kk3
12cp A1 DK44 Tk19 Kk10
12cq A1 DK44 Tk19 Kk11
Embodiment number A Napht 1 Tk Kk
12cr A1 DK44 Tk19 Kk14
12cs A1 DK44 Tk19 Kk15
12ct A1 DK44 Tk19 Kk16
12cu A1 DK44 Tk19 Kk51
12cv A1 DK44 Tk19 Kk53
12cw A1 DK44 Tk19 Kk54
12cx A1 DK44 Tk19 Kk55
12cy A1 DK44 Tk19 Kk56
12cz A1 DK44 Tk19 Kk61
12da A1 DK44 Tk19 Kk62
12db A1 DK44 Tk19 Kk63
12dc A1 DK44 Tk19 Kk64
12dd A1 DK44 Tk19 DK66
12de A1 DK44 Tk20 Kk2
12df A1 DK44 Tk20 Kk3
12dg A1 DK44 Tk20 Kk5
12dh A1 DK44 Tk20 Kk10
12di A1 DK44 Tk20 Kk11
12dj A1 DK44 Tk20 Kk14
12dk A1 DK44 Tk20 Kk15
12dl A1 DK44 Tk20 Kk16
12dm A1 DK44 Tk20 Kk51
12dn A1 DK44 Tk20 Kk53
12do A1 DK44 Tk20 Kk54
12dp A1 DK44 Tk20 Kk55
12dq A1 DK44 Tk20 Kk56
12dr A1 DK44 Tk20 Kk61
12ds A1 DK44 Tk20 Kk62
12dt A1 DK44 Tk20 Kk63
12du A1 DK44 Tk20 Kk64
12dv A1 DK44 Tk20 DK66
12dw A1 DK45 Tk16 Kk2
12dx A1 DK45 Tk16 Kk3
12dy A1 DK45 Tk16 Kk5
12dz A1 DK45 Tk16 Kk10
12ea A1 DK45 Tk16 Kk11
12eb A1 DK45 Tk16 Kk14
12ec A1 DK45 Tk16 Kk15
Embodiment number A Napht 1 Tk Kk
12ed A1 DK45 Tk16 Kk16
12ee A1 DK45 Tk16 Kk51
12ef A1 DK45 Tk16 Kk53
12eg A1 DK45 Tk16 Kk54
12eh A1 DK45 Tk16 Kk55
12ei A1 DK45 Tk16 Kk56
12ej A1 DK45 Tk16 Kk61
12ek A1 DK45 Tk16 Kk62
12el A1 DK45 Tk16 Kk63
12em A1 DK45 Tk16 Kk64
12en A1 DK45 Tk16 DK66
12eo A1 DK45 Tk19 Kk2
12ep A1 DK45 Tk19 Kk3
12eq A1 DK45 Tk19 Kk5
12er A1 DK45 Tk19 Kk10
12es A1 DK45 Tk19 Kk11
12et A1 DK45 Tk19 Kk14
12eu A1 DK45 Tk19 Kk15
12ev A1 DK45 Tk19 Kk16
12ew A1 DK45 Tk19 Kk51
12ex A1 DK45 Tk19 Kk53
12ey A1 DK45 Tk19 Kk54
12ez A1 DK45 Tk19 Kk55
12fa A1 DK45 Tk19 Kk56
12fb A1 DK45 Tk19 Kk61
12fc A1 DK45 Tk19 Kk62
12fd A1 DK45 Tk19 Kk63
12fe A1 DK45 Tk19 Kk64
12ff A1 DK45 Tk19 DK66
12fg A1 DK45 Tk20 Kk2
12fh A1 DK45 Tk20 Kk3
12fi A1 DK45 Tk20 Kk5
12fj A1 DK45 Tk20 Kk10
12fk A1 DK45 Tk20 Kk11
12fl A1 DK45 Tk20 Kk14
12fm A1 DK45 Tk20 Kk15
12fn A1 DK45 Tk20 Kk16
12fo A1 DK45 Tk20 Kk51
Embodiment number A Napht 1 Tk Kk
12fp A1 DK45 Tk20 Kk53
12fq A1 DK45 Tk20 Kk54
12fr A1 DK45 Tk20 Kk55
12fs A1 DK45 Tk20 Kk56
12ft A1 DK45 Tk20 Kk61
12fu A1 DK45 Tk20 Kk62
12fv A1 DK45 Tk20 Kk63
12fw A1 DK45 Tk20 Kk64
12fx A1 DK45 Tk20 DK66
12fy A1 DK44 Tk16 Kk65
12fz A1 DK44 Tk16 Kk66
12ga A1 DK44 Tk16 Kk67
12gb A1 DK45 Tk16 Kk65
12gc A1 DK45 Tk16 Kk66
12gd A1 DK45 Tk16 Kk67
12ge A1 DK44 Tk18 Kk65
12gf A1 DK44 Tk18 Kk66
12gg A1 DK44 Tk18 Kk67
12gb A1 DK45 Tk18 Kk65
12gi A1 DK45 Tk18 Kk66
12gj A1 DK45 Tk18 Kk67
12gk A1 DK44 Tk19 Kk65
12gl A1 DK44 Tk19 Kk66
12gm A1 DK44 Tk19 Kk67
12gn A1 DK45 Tk19 Kk65
12go A1 DK45 Tk19 Kk66
12gp A1 DK45 Tk19 Kk67
12gq A1 DK44 Tk20 Kk65
12gr A1 DK44 Tk20 Kk66
12gs A1 DK44 Tk20 Kk67
12gt A1 DK45 Tk20 Kk65
12gu A1 DK45 Tk20 Kk66
12gv A1 DK45 Tk20 Kk67
Embodiment 12gw:
Method A
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and dropwise adds 4 of double couple gallium to, in the solution of 4-diamino-diphenyl sulfonamide.Adding hydrochloric acid remains on below 3 the pH value.
2) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.Then, this reactant mixture is added in the reactant mixture of step 1) acquisition.Adding 15 weight % sodium carbonate liquors remains between 3 to 8 the pH value.
3) with 0.45 mole of methylamine Fei Taming acid and 0.55 mole 2,4-diaminostilbene-methoxybenzene adds step 2 simultaneously to) in the reactant mixture of acquisition, and add 15 weight % sodium carbonate liquors the pH value is remained between 3 to 8.After reaction is finished, with reactant mixture ultrafiltration and spray drying.
Method B
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and dropwise adds 4 of double couple gallium to, in the reactant mixture of 4-diamino-diphenyl sulfonamide.Keep the pH value to be lower than 3.
2) with 0.45 mole of methylamine Fei Taming acid and 0.55 mole 2,4-diaminostilbene-methoxybenzene adds in the reactant mixture of step 1) acquisition simultaneously, and adds 10 weight % sodium hydrate aqueous solutions the pH value is remained between 3 to 8.
3) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.Then, add this reactant mixture to step 2) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to the similar mode of embodiment 12gw, can prepare general formula A-N=N-Napht 1The table 4a dye mixture (the formula IIb during n=0) of-N=N-Tk-N=N-Kk, in this case, the A-N=N-group is coupled to Napht 1On the ortho position of middle hydroxyl.
Table 4a:
Embodiment number A Napht 1 Tk Kk *)
12gw A1 DK44 Tk18 Kk15∶Kk55(45∶55)
12gz A1 DK44 Tk18 Kk15∶Kk56(30∶70)
12ha A1 DK44 Tk18 Kk15∶Kk66(80∶20)
12hb A1 DK44 Tk18 Kk5∶Kk10(10∶90)
12hc A1 DK44 Tk18 Kk5∶Kk14(15∶85)
12hd A1 DK44 Tk18 Kk5∶Kk15(60∶40)
12he A1 DK44 Tk18 Kk5∶Kk55(75∶25)
12hf A1 DK44 Tk18 Kk5∶Kk56(40∶60)
12hh A1 DK44 Tk18 Kk5∶Kk67(20∶80)
12hi A1 DK44 Tk18 Kk5∶DK66(50∶50)
12hj A1 DK45 Tk18 Kk15∶Kk55(45∶55)
12hk A1 DK45 Tk18 Kk15∶Kk56(30∶70)
12hl A1 DK45 Tk18 Kk15∶Kk66(80∶20)
12hm A1 DK45 Tk18 Kk5∶Kk10(10∶90)
12hn A1 DK45 Tk18 Kk5∶Kk14(15∶85)
12ho A1 DK45 Tk18 Kk5∶Kk15(60∶40)
12hp A1 DK45 Tk18 Kk5∶Kk55(75∶25)
12hq A1 DK45 Tk18 Kk5∶Kk56(40∶60)
12hr A1 DK45 Tk18 Kk5∶Kk67(20∶80)
12hs A1 DK45 Tk18 Kk5∶DK66(50∶50)
12ht A1 DK44 Tk16 Kk5∶Kk15(45∶55)
12hu A1 DK44 Tk16 Kk15∶Kk55(45∶55)
12hv A1 DK44 Tk19 Kk15∶Kk55(45∶55)
12hw A1 DK44 Tk20 Kk15∶Kk55(45∶55)
*Value in the bracket is meant the mol ratio between each coupling component mutually.
Embodiment 13a:
1) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and adds among the diazotizing MSP.Keep the pH value to be lower than 2.
2) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium, and adding in the reactant mixture that step 1) obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) add 1 mole of methylamine Fei Taming acid to step 2) in the reactant mixture that obtains, and add 10 weight % sodium hydrate aqueous solutions the pH value is remained between 3 to 8.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to the similar mode of embodiment 13a, can obtain general formula A-N=N-Napht 1The dyestuff of-N=N-Tk-N=N-Kk (dyestuff of general formula I I when being r=k=1 and n=0), wherein the Kk representative is derived from the group of coupling component Kk1 to Kk64, DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 to DK27, DK29, DK30, DK33, DK36, DK38, DK39 or DK42 to DK83, Napht represents one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 and II-14, the Tk representative is derived from the divalent group of bisazo component Tk1 to Tk20, and A represents one of group A1 to A12.Group A-N=N-is coupled at Napht 1Carry out at middle amino ortho position.
Table 5:
Embodiment number A Napht 1 Tk Kk
13a A1 DK44 Tk18 Kk15
13b A1 DK44 Tk18 Kk5
13c A1 DK44 Tk18 Kk2
13d A1 DK44 Tk18 Kk3
13e A1 DK44 Tk18 Kk6
13f A1 DK44 Tk18 Kk1
13g A1 DK44 Tk18 Kk4
13h A1 DK44 Tk18 Kk7
13i A1 DK44 Tk18 Kk9
13j A1 DK44 Tk18 Kk10
13k A1 DK44 Tk18 Kk14
13l A1 DK44 Tk18 Kk16
13m A1 DK44 Tk18 Kk26
13n A1 DK44 Tk18 Kk27
Embodiment number A Napht 1 Tk Kk
13o A1 DK44 Tk18 Kk40
13p A1 DK44 Tk18 Kk46
13q A1 DK44 Tk18 Kk48
13r A1 DK44 Tk18 Dk4
13s A1 DK44 Tk18 Dk11
13t A1 DK44 Tk18 Dk18
13u A1 DK44 Tk18 Dk29
13v A1 DK44 Tk18 Dk30
13z A1 DK44 Tk18 Dk39
13aa A1 DK44 Tk16 Kk5
13ab A1 DK44 Tk16 Kk3
13ac A1 DK44 Tk16 Kk4
13ad A1 DK44 Tk16 Dk4
13ae A1 DK44 Tk19 Kk5
13af A1 DK45 Tk18 Kk5
13ag A2 DK44 Tk18 Kk5
13ah A7 DK44 Tk18 Kk15
13ai A4 DK44 Tk18 Kk15
13aj A1 DK44 Tk16 Kk15
13ak A1 DK44 Tk16 Kk34
13al A7 DK44 Tk18 Kk3
13am A7 DK44 Tk18 Kk5
13an A6 DK45 Tk18 Kk10
13ao A8 DK45 Tk18 Kk14
13ap A11 DK45 Tk18 Kk16
13aq A12 DK45 Tk18 Kk26
13ar A1 DK44 Tk18 Kk11
13as A1 DK44 Tk18 Kk51
13at A1 DK44 Tk18 Kk52
13au A1 DK44 Tk18 Kk53
13av A1 DK44 Tk18 Kk54
13aw A1 DK44 Tk18 Kk55
13ax A1 DK44 Tk18 Kk56
13ay A1 DK44 Tk18 Kk57
13az A1 DK44 Tk18 Kk58
13ba A1 DK44 Tk18 Kk59
13bb A1 DK44 Tk18 Kk60
13bc A1 DK44 Tk18 Kk61
Embodiment number A Napht 1 Tk Kk
13bd A1 DK44 Tk18 Kk62
13be A1 DK44 Tk18 Kk63
13bf A1 DK44 Tk18 Kk64
13bg A1 DK44 Tk18 DK66
13bh A1 DK45 Tk18 Kk1
13bi A1 DK45 Tk18 Kk2
13bj A1 DK45 Tk18 Kk3
13bk A1 DK45 Tk18 Kk4
13bl A1 DK45 Tk18 Kk6
13bm A1 DK45 Tk18 Kk7
13bn A1 DK45 Tk18 Kk10
13bo A1 DK45 Tk18 Kk11
13bp A1 DK45 Tk18 Kk14
13bq A1 DK45 Tk18 Kk15
13br A1 DK45 Tk18 Kk16
13bs A1 DK45 Tk18 Kk51
13bt A1 DK45 Tk18 Kk53
13bu A1 DK45 Tk18 Kk54
13bv A1 DK45 Tk18 Kk55
13bw A1 DK45 Tk18 Kk56
13bx A1 DK45 Tk18 Kk61
13by A1 DK45 Tk18 Kk62
13bz A1 DK45 Tk18 Kk63
13ca A1 DK45 Tk18 Kk64
13cb A1 DK45 Tk18 DK66
13cc A1 DK44 Tk16 Kk10
13cd A1 DK44 Tk16 Kk11
13ce A1 DK44 Tk16 Kk14
13cf A1 DK44 Tk16 Kk16
13cg A1 DK44 Tk16 Kk51
13ch A1 DK44 Tk16 Kk53
13ci A1 DK44 Tk16 Kk54
13cj A1 DK44 Tk16 Kk55
13ck A1 DK44 Tk16 Kk56
13cl A1 DK44 Tk16 Kk61
13cm A1 DK44 Tk16 Kk62
13cn A1 DK44 Tk16 Kk63
13co A1 DK44 Tk16 Kk64
Embodiment number A Napht 1 Tk Kk
13cp A1 DK44 Tk16 DK66
13cq A1 DK44 Tk19 Kk2
13cr A1 DK44 Tk19 Kk3
13cs A1 DK44 Tk19 Kk10
13ct A1 DK44 Tk19 Kk11
13cu A1 DK44 Tk19 Kk14
13cv A1 DK44 Tk19 Kk15
13cw A1 DK44 Tk19 Kk16
13cx A1 DK44 Tk19 Kk51
13cy A1 DK44 Tk19 Kk53
13cz A1 DK44 Tk19 Kk54
13da A1 DK44 Tk19 Kk55
13db A1 DK44 Tk19 Kk56
13dc A1 DK44 Tk19 Kk61
13dd A1 DK44 Tk19 Kk62
13de A1 DK44 Tk19 Kk63
13df A1 DK44 Tk19 Kk64
13dg A1 DK44 Tk19 DK66
13dh A1 DK44 Tk20 Kk2
13di A1 DK44 Tk20 Kk3
13dj A1 DK44 Tk20 Kk5
13dk A1 DK44 Tk20 Kk10
13dl A1 DK44 Tk20 Kk11
13dm A1 DK44 Tk20 Kk14
13dn A1 DK44 Tk20 Kk15
13do A1 DK44 Tk20 Kk16
13dp A1 DK44 Tk20 Kk51
13dq A1 DK44 Tk20 Kk53
13dr A1 DK44 Tk20 Kk54
13ds A1 DK44 Tk20 Kk55
13dt A1 DK44 Tk20 Kk56
13du A1 DK44 Tk20 Kk61
13dv A1 DK44 Tk20 Kk62
13dw A1 DK44 Tk20 Kk63
13dx A1 DK44 Tk20 Kk64
13dy A1 DK44 Tk20 DK66
13dz A1 DK45 Tk16 Kk2
13ea A1 DK45 Tk16 Kk3
Embodiment number A Napht 1 Tk Kk
13eb A1 DK45 Tk16 Kk5
13ec A1 DK45 Tk16 Kk10
13ed A1 DK45 Tk16 Kk11
13ee A1 DK45 Tk16 Kk14
13ef A1 DK45 Tk16 Kk15
13eg A1 DK45 Tk16 Kk16
13eh A1 DK45 Tk16 Kk51
13ei A1 DK45 Tk16 Kk53
13ej A1 DK45 Tk16 Kk54
13ek A1 DK45 Tk16 Kk55
13el A1 DK45 Tk16 Kk56
13em A1 DK45 Tk16 Kk61
13en A1 DK45 Tk16 Kk62
13eo A1 DK45 Tk16 Kk63
13ep A1 DK45 Tk16 Kk64
13eq A1 DK45 Tk16 DK66
13er A1 DK45 Tk19 Kk2
13es A1 DK45 Tk19 Kk3
13et A1 DK45 Tk19 Kk5
13eu A1 DK45 Tk19 Kk10
13ev A1 DK45 Tk19 Kk11
13ew A1 DK45 Tk19 Kk14
13ex A1 DK45 Tk19 Kk15
13ey A1 DK45 Tk19 Kk16
13ez A1 DK45 Tk19 Kk51
13fa A1 DK45 Tk19 Kk53
13fb A1 DK45 Tk19 Kk54
13fc A1 DK45 Tk19 Kk55
13fd A1 DK45 Tk19 Kk56
13fe A1 DK45 Tk19 Kk61
13ff A1 DK45 Tk19 Kk62
13fg A1 DK45 Tk19 Kk63
13fh A1 DK45 Tk19 Kk64
13fi A1 DK45 Tk19 DK66
13fj A1 DK45 Tk20 Kk2
13fk A1 DK45 Tk20 Kk3
13fl A1 DK45 Tk20 Kk5
13fm A1 DK45 Tk20 Kk10
Embodiment number A Napht 1 Tk Kk
13fn A1 DK45 Tk20 Kk11
13fo A1 DK45 Tk20 Kk14
13fp A1 DK45 Tk20 Kk15
13fq A1 DK45 Tk20 Kk16
13fr A1 DK45 Tk20 Kk51
13fs A1 DK45 Tk20 Kk53
13ft A1 DK45 Tk20 Kk54
13fu A1 DK45 Tk20 Kk55
13fv A1 DK45 Tk20 Kk56
13fw A1 DK45 Tk20 Kk61
13fx A1 DK45 Tk20 Kk62
13fy A1 DK45 Tk20 Kk63
13fz A1 DK45 Tk20 Kk64
13ga A1 DK45 Tk20 DK66
13gb A1 DK44 Tk16 Kk65
13gc A1 DK44 Tk16 Kk66
13gd A1 DK44 Tk16 Kk67
13ge A1 DK45 Tk16 Kk65
13gf A1 DK45 Tk16 Kk66
13gg A1 DK45 Tk16 Kk67
13gh A1 DK44 Tk18 Kk65
13gi A1 DK44 Tk18 Kk66
13gj A1 DK44 Tk18 Kk67
13gk A1 DK45 Tk18 Kk65
13gl A1 DK45 Tk18 Kk66
13gm A1 DK45 Tk18 Kk67
13gn A1 DK44 Tk19 Kk65
13go A1 DK44 Tk19 Kk66
13gp A1 DK44 Tk19 Kk67
13gq A1 DK45 Tk19 Kk65
13gr A1 DK45 Tk19 Kk66
13gs A1 DK45 Tk19 Kk67
13gt A1 DK44 Tk20 Kk65
13gr A1 DK44 Tk20 Kk66
13gs A1 DK44 Tk20 Kk67
13gt A1 DK45 Tk20 Kk65
13gu A1 DK45 Tk20 Kk66
13gv A1 DK45 Tk20 Kk67
Embodiment 13gw
1) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and adds in the reactant mixture of diazotizing MSP.Keep the pH value to be lower than 2.
2) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium, and adding in the reactant mixture that step 1) obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) with 0.45 mole of methylamine Fei Taming acid and 0.55 mole 2,4-diaminostilbene-methoxybenzene adds step 2 to) in the reactant mixture of acquisition, and add 10 weight % sodium hydrate aqueous solutions the pH value is remained between 3 to 8.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to the similar mode of embodiment 13gw, can obtain general formula A-N=N-Napht 1The table 5a dye mixture (the formula IIb during n=0) of-N=N-Tk-N=N-Kk, in this case, the A-N=N-group be coupled at Napht 1Carry out on the middle amino ortho position.
Table 5a:
Embodiment A Napht 1 Tk Kk *)
13gw A1 DK44 Tk18 Kk15∶Kk55(45∶55)
13gz A1 DK44 Tk18 Kk15∶Kk56(30∶70)
13ha A1 DK44 Tk18 Kk15∶Kk66(80∶20)
13hb A1 DK44 Tk18 Kk5∶Kk10(10∶90)
13hc A1 DK44 Tk18 Kk5∶Kk14(15∶85)
13hd A1 DK44 Tk18 Kk5∶Kk15(60∶40)
13he A1 DK44 Tk18 Kk5∶Kk55(75∶25)
13hf A1 DK44 Tk18 Kk5∶Kk56(40∶60)
13hh A1 DK44 Tk18 Kk5∶Kk67(20∶80)
13hi A1 DK44 Tk18 Kk5∶DK66(50∶50)
13hj A1 DK45 Tk18 Kk15∶Kk55(45∶55)
13hk A1 DK45 Tk18 Kk15∶Kk56(30∶70)
13hl A1 DK45 Tk18 Kk15∶Kk66(80∶20)
13hm A1 DK45 Tk18 Kk5∶Kk10(10∶90)
13hn A1 DK45 Tk18 Kk5∶Kk14(15∶85)
13ho A1 DK45 Tk18 Kk5∶Kk15(60∶40)
Embodiment A Napht 1 Tk Kk *)
13hp A1 DK45 Tk18 Kk5∶Kk55(75∶25)
13hq A1 DK45 Tk18 Kk5∶Kk56(40∶60)
13hr A1 DK45 Tk18 Kk5∶Kk67(20∶80)
13hs A1 DK45 Tk18 Kk5∶DK66(50∶50)
13ht A1 DK44 Tk16 Kk5∶Kk15(45∶55)
13hu A1 DK44 Tk16 Kk15∶Kk55(45∶55)
13hv A1 DK44 Tk19 Kk15∶Kk55(45∶55)
13hw A1 DK44 Tk20 Kk15∶Kk55(45∶55)
*Value in the bracket is meant the mol ratio between each coupling component mutually.
Embodiment 14:
Figure A20048003210600761
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium.1 mole of methylamine Fei Taming acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and dropwise adds 4 of double couple gallium to, in the reactant mixture of 4-diamino-diphenyl sulfonamide.Adding 15 weight % sodium carbonate liquors remains between the 2-3 pH value of reactant mixture.
2) 1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and adds in the reactant mixture that step 1) obtains, and add 15 weight % aqueous sodium carbonates the pH value of reactant mixture is remained between the 2-4.
3) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, add step 2 then to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
Embodiment 15:
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium.1 mole of methylamine Fei Taming acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and dropwise adds 4 of double couple gallium to, in the reactant mixture of 4-diamino-diphenyl sulfonamide.Adding 15 weight % sodium carbonate liquors remains between the 2-3 pH value of reactant mixture.
2) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and adds in the reactant mixture of diazotizing MSP.Keep the pH value to be lower than 2.
3) reactant mixture that step 2 is obtained adds in the reactant mixture of step 1) acquisition.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
Embodiment 16a:
Figure A20048003210600772
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and dropwise adds 4 of double couple gallium to, in the reactant mixture of 4-diamino-diphenyl sulfonamide.Adding 15 weight % sodium carbonate liquors remains between the 2-3 pH value of reactant mixture.
2) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, add to then in the reactant mixture that step 1) obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.
3) in step 2) add 1 mole of resorcinol in the reactant mixture that obtains, and add 10 weight % sodium hydrate aqueous solutions the pH value is remained between the 3-8.
4) 1 mole of paranitroanilinum is dissolved in 21 weight % hydrochloric acid, in pH＜1 and the 0-5 ℃ of following excessive nitrite sodium diazotization of using, adds to then in the reactant mixture of step 3) acquisition then.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
Embodiment 17a:
Figure A20048003210600781
1) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and adds in the reactant mixture of diazotizing MSP.Keep the pH value to be lower than 2.
2) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole of 4,4 diamino-diphenyl sulfonamide double couple gallium.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.
3) in step 2) add 1 mole of resorcinol in the reactant mixture that obtains, and add 10 weight % sodium hydrate aqueous solutions the pH value is remained between the 3-8.
4) 1 mole of paranitroanilinum is dissolved in 21 weight % hydrochloric acid, in pH＜1 and the 0-5 ℃ of following excessive nitrite sodium diazotization of using, adds to then in the reactant mixture of step 3) acquisition then.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
Embodiment 18:
Figure A20048003210600791
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and dropwise adds 4 of double couple gallium to, in the reactant mixture of 4-diamino-diphenyl sulfonamide.Adding 15 weight % sodium carbonate liquors remains between the 2-3 pH value of reactant mixture.
2) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, add to then in the reactant mixture that step 1) obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.
3) 1 mole of paranitroanilinum is dissolved in 21 weight % hydrochloric acid, then in pH＜1 and the 0-5 ℃ of following excessive nitrite sodium diazotization of using.Time 1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions in pH＞12, below 10 ℃ diazotizing paranitroanilinum was dropwise added in this solution in 30 minutes then, adding 10 weight % sodium hydrate aqueous solutions the pH value is remained on more than 9.
4) reactant mixture that step 3) is obtained adds step 2 to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
Embodiment 19:
1) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and adds in the reactant mixture of diazotizing MSP.Keep the pH value to be lower than 2.
2) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium, and adding in the reactant mixture that step 1) obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.
3) 1 mole of paranitroanilinum is dissolved in 21 weight % hydrochloric acid, then in pH＜1 and the 0-5 ℃ of following excessive nitrite sodium diazotization of using.Time 1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions in pH＞12, below 10 ℃ diazotizing paranitroanilinum was dropwise added in this solution in 30 minutes then, adding 10 weight % sodium hydrate aqueous solutions the pH value is remained on more than 9.
4) reactant mixture that step 3) is obtained adds step 2 to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
Embodiment 20:
Figure A20048003210600801
1) 1 mole of paranitroanilinum is dissolved in 21 weight % hydrochloric acid, then in pH＜1 and the 0-5 ℃ of following excessive nitrite sodium diazotization of using.Time 1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions in pH＞12, below 10 ℃ diazotizing paranitroanilinum was dropwise added in this solution in 30 minutes then, adding 10 weight % sodium hydrate aqueous solutions the pH value is remained on more than 9.
2) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium, and adding in the reactant mixture that step 1) obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.
3) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and adds among the diazotizing MSP.Keep the pH value to be lower than 2.
4) reactant mixture that step 3) is obtained adds step 2 to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to embodiment 16a and 18 similar modes, can obtain general formula D k 1-N=N-Napht 1-N=N-Tk-N=N-Kk-N=N-Dk 2Dyestuff and their metal complex (dyestuff of general formula I I when being r=k=n=1), Dk wherein 1And Dk 2Represent the group that is derived from diazo component DK1 to DK83 or is derived from A1 to A12, Dk separately 1Or Dk 2In at least one represents the group of formula A, Kk representative is derived from the divalent group of coupling component Kk2, Kk3, Kk5, Kk6, Kk14, Kk15, Kk16, Kk49 or Kk50, Napht 1Represent one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 and II-14, the Tk representative is derived from the divalent group of bisazo component Tk1 to Tk20, and A represents one of group A1 to A12.Group Dk 1-N=N-is coupled at Napht 1Carry out at the ortho position of middle hydroxyl.Its example is listed dyestuff and a metal complex of following table 6.
Table 6:
Embodiment number Dk 1 Napht 1 Tk Kk Dk2 Metal
16a A1 DK44 Tk18 Kk3 DK17 -
16b A1 DK44 Tk18 Kk3 DK5 Fe
16c A1 DK44 Tk18 Kk3 DK5 Cr
16d A1 DK44 Tk18 Kk3 DK40 -
16e DK17 DK44 Tk18 Kk3 A1 -
16f DK17 DK44 Tk18 Kk3 A7 -
16g DK17 DK44 Tk18 Kk5 A7 -
16h DK5 DK44 Tk18 Kk3 A1 Fe
16i DK5 DK44 Tk18 Kk3 A1 Cr
16j DK5 DK44 Tk16 Kk5 A12 -
16k DK17 DK45 Tk16 Kk3 A10 -
According to embodiment 17a, 19 and 20 similar modes, can obtain general formula D k 1-N=N-Napht 1-N=N-Tk-N=N-Kk-N=N-Dk 2Dyestuff and their metal complex (dyestuff of general formula I I when being r=k=n=1), Dk wherein 1And Dk 2Represent the group that is derived from diazo component DK1 to DK83 or is derived from A1 to A12, Dk separately 1Or Dk 2In at least one represents the group of formula A, Kk representative is derived from the divalent group of coupling component Kk2, Kk3, Kk5, Kk6, Kk14, Kk15, Kk16, Kk49 or Kk50, Napht 1Represent one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 and II-14, the Tk representative is derived from the divalent group of bisazo component Tk1 to Tk20, and A represents one of group A1 to A12.Group Dk 1-N=N-is coupled at Napht 1Carry out at middle amino ortho position.Its example is listed dyestuff and a metal complex of following table 7.
Table 7
Embodiment number Dk 1 Napht 1 Tk Kk Dk 2 Metal
17a A1 DK44 Tk18 Kk3 DK17 -
17b A1 DK44 Tk18 Kk3 DK5 Fe
17c A1 DK44 Tk18 Kk3 DK5 Cr
17d A1 DK44 Tk18 Kk3 DK40 -
17e DK17 DK44 Tk18 Kk3 A1 -
17f DK17 DK44 Tk18 Kk3 A7 -
17g DK17 DK44 Tk18 Kk5 A1 -
17h DK5 DK44 Tk18 Kk3 A1 -
17i DK5 DK44 Tk18 Kk3 A5 -
17j A1 DK44 Tk18 Kk3 A1 -
17k DK5 DK44 Tk16 Kk5 A9 -
17l DK17 DK45 Tk16 Kk3 A11 -
Embodiment 21:
Figure A20048003210600821
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and dropwise adds 4 of double couple gallium to, in the reactant mixture of 4-diamino-diphenyl sulfonamide.Adding 15 weight % sodium carbonate liquors remains between the 2-3 pH value of this reactant mixture.
2) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, add to then in the reactant mixture that step 1) obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.
3) in step 2) add 0.5 mole of resorcinol in the reactant mixture that obtains, and add 10 weight % sodium hydrate aqueous solutions the pH value is remained between the 3-8.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to embodiment 21 similar modes, can obtain general formula [A-N=N-Napht 1-N=N-Tk-N=N] 2The dyestuff of-Kk (is Dk 1=Dk 2=A, Napht 1=Napht 2And Tk 1=Tk 2The time general formula III dyestuff), wherein Kk representative is derived from the divalent group of coupling component Kk2, Kk3, Kk5, Kk6, Kk14, Kk15, Kk16, Kk49 or Kk50, Napht 1Represent one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 and II-14, the Tk representative is derived from the divalent group of bisazo component Tk1 to Tk20, and A represents one of group A1 to A12.Group A-N=N-is coupled at Napht 1Carry out at the ortho position of middle hydroxyl.
Embodiment 22:
Figure A20048003210600831
1) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and adds in the reactant mixture of diazotizing MSP.Keep the pH value to be lower than 2.
2) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium, and adding in the reactant mixture that step 1) obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.
3) in step 2) add 0.5 mole of resorcinol in the reactant mixture that obtains, and add 10 weight % sodium hydrate aqueous solutions the pH value is remained between the 3-8.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to embodiment 22 similar modes, can obtain general formula [A-N=N-Napht 1-N=N-Tk-N=N] 2The dyestuff of-Kk (is Dk 1=Dk 2=A, Napht 1=Napht 2And Tk 1=Tk 2The time general formula III dyestuff), wherein Kk representative is derived from the divalent group of coupling component Kk2, Kk3, Kk5, Kk6, Kk14, Kk15, Kk16, Kk49 or Kk50, Napht 1Represent one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 and II-14, the Tk representative is derived from the divalent group of bisazo component Tk1 to Tk20, and A represents one of group A1 to A12.Group A-N=N-is coupled at Napht 1Carry out at middle amino ortho position.
Embodiment 23:
Figure A20048003210600841
1) 1 mole of γ acid is dissolved in 25 weight % sodium hydrate aqueous solutions, down with excessive nitrite sodium and hydrochloric acid diazotization, and dropwise adds in the aqueous solution of 1 mole of ortho-aminobenzoic acid pH＜1 and 0-5 ℃.Adding 10 weight % sodium hydrate aqueous solutions remains between 5 to 10 the pH value of reactant mixture.
2) 1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.Reaction mixture with this reactant mixture and step 1) acquisition.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, add step 2 then to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to embodiment 23 similar modes, can obtain general formula A-N=N-Napht 1-N=N-Napht 2The dyestuff of-N=N-Kk (is p=1, n=0, P=Napht 1And R=Napht 2The time general formula X II dyestuff), wherein the Kk representative is derived from the divalent group of coupling component Kk1 to Kk48 or Kk51 to Kk67, Napht 1And Napht 2Represent one of divalent group II-1, II-3, II-5, II-7, II-9, II-11, II-13 or II-15 separately, and A represents one of group A1 to A12.Group Napht 1-N=N-is coupled at Napht 2Carry out at the ortho position of middle hydroxyl.
Embodiment 24:
Figure A20048003210600851
1) 1 mole of γ acid is dissolved in 25 weight % sodium hydrate aqueous solutions, down with excessive nitrite sodium and hydrochloric acid diazotization, and dropwise adds in the aqueous solution of 1 mole of 3-phenyl amino phenol pH＜1 and 0-5 ℃.Adding 10 weight % sodium hydrate aqueous solutions remains between 5 to 10 the pH value of reactant mixture.
2) 1 mole of gram Lie Shi, 7 acid are dissolved in 25 weight % sodium hydrate aqueous solutions.Simultaneously, 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, add to then in Cleve's acid 7 solution, keep the pH value to be lower than 2 simultaneously.
3) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with step 2) the reactant mixture diazotization that obtains.Reaction mixture with this reactant mixture and step 1) acquisition.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to embodiment 24 similar modes, can obtain general formula A-N=N-Napht 1-N=N-Napht 2The dyestuff of-N=N-Kk (is p=1, n=0, P=Napht 1And R=Napht 2The time general formula X II dyestuff), wherein the Kk representative is derived from the divalent group of coupling component Kk1 to Kk48 or Kk51 to Kk67, Napht 1And Napht 2Represent one of divalent group II-1, II-3, II-5, II-7, II-9, II-11, II-13 or II-15 separately, and A represents one of group A1 to A12.Group A-N=N-Napht 1-N=N-is coupled at Napht 2Carry out at the ortho position of middle hydroxyl.
Embodiment 25:
Figure A20048003210600861
1) 1 mole of gram Lie Shi, 7 acid is dissolved in 25 weight % sodium hydrate aqueous solutions.Simultaneously, 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, add to then in Cleve's acid 7 solution, keep the pH value to be lower than 2 simultaneously.
2) 1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions.Simultaneously, the reactant mixture that step 1) is obtained is suspended in the frozen water, and in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used, adds to then in the H acid solution.Adding 10 weight % sodium hydrate aqueous solutions remains between 1 to 4 the pH value.
3) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 5-nitro-2-amino-phenol diazotization, add step 2 then to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction is finished, in reactant mixture, add 0.20-0.30 mol sulfuric acid chromium (III) and stirred 1 hour.Adding NaCl makes dye precipitated and leaches by suction.
Embodiment 26:
Be prepared similarly with embodiment 25 described methods, but in the end do not carry out the metal complex reaction in the step.
According to embodiment 25 and 26 similar modes, can obtain general formula A-N=N-Napht 1-N-N-Napht 2The dyestuff of-N=N-Dk and their metal complex (are p=m-1, p=Napht 1And Kk 1=Napht 2The time general formula I dyestuff), wherein Dk representative is derived from the group of diazo component DK1 to DK9, DK13, DK14, DK26, DK27, DK39 to DK41 and DK58, Napht 1Represent one of divalent group II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 or II16, Napht 2Represent one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 or II-14, and A represents one of group A1 to A12.Group A-N=N-Napht 1-N=N-is coupled at Napht 2Carry out at middle amino ortho position.
Embodiment 27:
Figure A20048003210600871
1) 1 mole of paranitroanilinum is dissolved in 21 weight % hydrochloric acid, then in pH＜1 and the 0-5 ℃ of following excessive nitrite sodium diazotization of using.Simultaneously, 1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, adds 21 weight % hydrochloric acid then and make H acid precipitation.Add to the outstanding body lotion of H acid in the diazotizing paranitroanilinum and keep the pH value to be lower than 2.Finish after being reflected at 1 hour.
2) 1 mole of Cleve's acid 7 is dissolved in 25 weight % sodium hydrate aqueous solutions.Simultaneously, 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, add Cleve's acid 7 solution, keep the pH value to be lower than 2 simultaneously.
3) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with step 2) the reactant mixture diazotization that obtains, and add in the product that step 1) obtains.Add 10 weight % sodium hydrate aqueous solutions the pH value is remained between 5 to 8, stirred then 1 hour.Adding NaCl makes dye precipitated and leaches by suction.
According to embodiment 27 similar modes, can obtain general formula A-N=N-Napht 1-N=N-Napht 2The dyestuff of-N=N-Dk (is p=m=1, P=Napht 1And Kk 1=Napht 2The time general formula I dyestuff), wherein Dk representative is derived from the group of diazo component DK1 to DK83, Napht 1Represent one of divalent group II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 or II16, Napht 2Represent one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 or II-14, and A represents one of group A1 to A12.Group A-N=N-Napht 1-N-N-is coupled at Napht 2Carry out at the ortho position of middle hydroxyl.
Embodiment 28a:
Figure A20048003210600881
1) 1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.Time 1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions in pH＞12, in 30 minutes, dropwise adding below 10 ℃ then, thus this solution is mixed with diazotizing H acid, add 10 weight % sodium hydrate aqueous solutions simultaneously the pH value is remained on more than 9.
2) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,6-dinitro-2-amino-phenol diazotization, and adding in the reactant mixture that step 1) obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) 1 mole of gram Lie Shi, 7 acid are dissolved in 25 weight % sodium hydrate aqueous solutions.Simultaneously, 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, add to then in Cleve's acid 7 solution, keep the pH value to be lower than 2 simultaneously.
4) in pH＜1 and 0-5 ℃ of reactant mixture diazotization that with excessive nitrite sodium and hydrochloric acid step 3) is obtained down.With this reactant mixture and step 2) reaction mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction is finished, in reactant mixture, add 0.40-0.60 mol sulfuric acid iron (III) and stirred 1 hour.Adding NaCl makes dye precipitated and leaches by suction.
According to the similar mode of embodiment 28a, can obtain general formula A-N=N-Napht 1-N=N-Napht 2The dyestuff of-N=N-Kk-N=N-Dk (is p=n=1, P=Napht 1And R=Napht 2The time general formula X II dyestuff) metal complex, wherein the Dk representative is derived from the group of diazo component DK1 to DK9, DK13, DK14, DK26, DK27, DK39 to DK41 and DK58, Napht 1Represent one of divalent group II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 or II16, Napht 2Represent one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 or II-14, the Kk representative is derived from the divalent group of Kk2, Kk3, Kk49 or Kk50, and A represents one of group A1 to A12.Group A-N=N-Napht 1-N=N-is coupled at Napht 2Carry out at the ortho position of middle hydroxyl.
Embodiment 28b:
React according to the method for describing among the embodiment 28a, different is does not exist subsequently reaction with molysite.
According to the similar mode of embodiment 28b, can obtain general formula A-N=N-Napht 1-N=N-Napht 2The dyestuff of-N=N-Kk-N=N-Dk (is p=n=1, P=Napht 1And R=Napht 2The time general formula X II dyestuff), wherein the Dk representative is derived from diazo component DK1 to DK83 or is derived from the group of A1 to A12, Napht 1Represent one of divalent group II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 or II16, Napht 2Represent one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 or II-14, the Kk representative is derived from the divalent group of Kk2, Kk3, Kk5, Kk6, Kk14, Kk15, Kk16, Kk49 or Kk50, and A represents one of group A1 to A12.Group A-N=N-Napht 1-N=N-is coupled at Napht 2Carry out at the ortho position of middle hydroxyl.
Embodiment 29a:
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,6-dinitro-2-amino-phenol diazotization.Time 1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions in pH＞12, then with this solution with in 30 minutes, dropwise add below 10 ℃ diazotizing 4,6-dinitro-2-amino-phenol mixes, and adds 10 weight % sodium hydrate aqueous solutions simultaneously the pH value is remained on more than 9.
2) 1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, down with excessive nitrite sodium and hydrochloric acid diazotization, and adds in the reactant mixture that step 1) obtains pH＜1 and 0-5 ℃.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) 1 mole of gram Lie Shi, 7 acid are dissolved in 25 weight % sodium hydrate aqueous solutions.Simultaneously, 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, add to then in Cleve's acid 7 solution, keep the pH value to be lower than 2 simultaneously.
4) in pH＜1 and 0-5 ℃ of reactant mixture diazotization that with excessive nitrite sodium and hydrochloric acid step 3) is obtained down.With this reactant mixture and step 2) reaction mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction is finished, in reactant mixture, add 0.40-0.60 mol sulfuric acid iron (III) and stirred 1 hour.Adding NaCl makes dye precipitated and leaches by suction.
According to the similar mode of embodiment 29a, can obtain general formula A-N=N-Napht 1-N=N-Napht 2The dyestuff of-N=N-Kk-N=N-Dk (is p=n=1, P=Napht 1And R=Napht 2The time general formula X II dyestuff) metal complex, wherein the Dk representative is derived from the group of diazo component DK1 to DK9, DK13, DK14, DK26, DK27, DK39 to DK41 and DK58, Napht 1Represent one of divalent group II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 or II16, Napht 2Represent one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 or II-14, the Kk representative is derived from the divalent group of Kk2, Kk3, Kk49 or Kk50, and A represents one of group A1 to A12.Group A-N=N-Napht 1-N=N-is coupled at Napht 2Carry out at the ortho position of middle hydroxyl.
Embodiment 29b:
React according to the method for describing among the embodiment 29a, different is does not exist subsequently reaction with molysite.
According to the similar mode of embodiment 29b, can obtain general formula A-N=N-Napht 1-N=N-Napht 2The dyestuff of-N=N-Kk-N=N-Dk (is p=n=1, P=Napht 1And R=Napht 2The time general formula X II dyestuff), wherein the Dk representative is derived from diazo component DK1 to DK83 or is derived from the group of A1 to A12, Napht 1Represent one of divalent group II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 or II16, Napht 2Represent one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 or II-14, the Kk representative is derived from the divalent group of Kk2, Kk3, Kk5, Kk6, Kk14, Kk15, Kk16, Kk49 or Kk50, and A represents one of group A1 to A12.Group A-N=N-Napht 1-N=N-is coupled at Napht 2Carry out at the ortho position of middle hydroxyl.
Embodiment 30:
Figure A20048003210600921
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium.1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and dropwise adds 4 of double couple gallium to, in the reactant mixture of 4-diamino-diphenyl sulfonamide.Keep the pH value to be lower than 3.
2) 1 mole of paranitroanilinum is dissolved in 21 weight % hydrochloric acid,, and adds in the reactant mixture of step 1) acquisition then in pH＜1 and 0-5 ℃ of following usefulness excessive nitrite sodium diazotization.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.1 mole of K acid is dissolved in 25 weight % sodium hydroxide solutions and adds among the diazotizing MSP.Keep the pH value to be lower than 2.
4) product that step 3) is obtained adds step 2 to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to embodiment 30 similar modes, can obtain general formula D k 1-N=N-Napht 1-N=N-Tk-N=N-Napht 2-N=N-Dk 2Dyestuff and their metal complex (being the dyestuff of general formula I V), Dk wherein 1And Dk 2Represent the group that is derived from diazo component DK1 to DK83 or is derived from A1 to A12, Dk separately 1Or Dk 2In at least one represents the group of formula A, Napht 1And Napht 2Represent one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 or II-14 separately, and the Tk representative is derived from the divalent group of Tk1 to Tk20.Group Dk 1-N=N-is coupled at Napht 1Carry out at the ortho position of middle hydroxyl, and Dk 2-N=N-is coupled at Napht 2Carry out at middle amino ortho position.
Embodiment 31:
Figure A20048003210600931
1) 1 mole of paranitroanilinum is dissolved in 21 weight % hydrochloric acid, then in pH＜1 and the 0-5 ℃ of following excessive nitrite sodium diazotization of using.Add 1 mole of H acid therein, keep the pH value to be lower than 2 simultaneously.
2) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4-diamino-diphenyl sulfonamide double couple gallium, and adding in the reactant mixture that step 1) obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) 1 mole of MSP is suspended in the frozen water and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization.1 mole of K acid is dissolved in 25 weight % sodium hydroxide solutions and adds among the diazotizing MSP.Keep the pH value to be lower than 2.
4) product that step 3) is obtained adds step 2 to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to embodiment 31 similar modes, can obtain general formula D k 1-N=N-Napht 1-N=N-Tk-N=N-Napht 2-N=N-Dk 2Dyestuff and their metal complex (being the dyestuff of general formula I V), Dk wherein 1And Dk 2Represent the group that is derived from diazo component DK1 to DK83 or is derived from A1 to A12, Dk separately 1Or Dk 2In at least one represents the group of formula A, Napht 1And Napht 2Represent one of divalent group II-2, II-4, II-6, II-8, II-10, II-12 or II-14 separately, and the Tk representative is derived from the divalent group of Tk1 to Tk20.Group Dk 1-N=N-and Dk 2The coupling of-N=N-is respectively at Napht 1And Napht 2Carry out at middle amino ortho position.
Embodiment 32:
Figure A20048003210600941
PH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,6-dinitro-2-amino-phenol diazotization, and with 1 mole of 4-(β-sulfato ethylsulfonyl) pyrazoles acid 2 (Kk44) coupling.The pH value is remained between 2 to 7.After coupling is finished, in reactant mixture, add 0.20-0.30 mol sulfuric acid chromium (III) and stirred 1 hour.Then with reactant mixture 40 ℃ of evaporations.
According to embodiment 32 similar modes, can obtain the metal complex of the dyestuff (being the dyestuff of general formula X III) of general formula D k-N=N-Pyr-A, wherein the Dk representative is derived from the group of diazo component DK1 to DK9, DK13, DK14, DK26, DK27, DK39 to DK41 or DK58, Pyr represents 5-hydroxy-3-methyl pyrazoles-1,4-two bases or 5-hydroxyl-3-carboxyl pyrazoles-1, one of 4-two bases, and the group A1 to A12 that connects via the nitrogen of Pyr of A representative.
Embodiment 33:
React according to the method for describing among the embodiment 32, different is does not exist subsequently reaction with chromic salts.
According to embodiment 33 similar modes, can obtain the dyestuff (being the dyestuff of general formula X III) of general formula D k-N=N-Pyr-A, wherein the Dk representative is derived from the group of diazo component DK1 to DK83, Pyr represents 5-hydroxy-3-methyl pyrazoles-1,4-two bases or 5-hydroxyl-3-carboxyl pyrazoles-1,4-two bases, and A represents one of group A1 to A12 of the nitrogen connection of passing through Pyr.
Embodiment 34a:
Figure A20048003210600951
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole of 5-nitro-2-amino-phenol diazotization.Time 1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions in pH＞12, with this solution with mix at the diazotization 5-nitro-2-amino-phenol that in 30 minutes, dropwise adds below 10 ℃, add 10 weight % sodium hydrate aqueous solutions simultaneously the pH value remained on more than 9.
2) 1 mole of MSP is suspended in the frozen water, down with excessive nitrite sodium and hydrochloric acid diazotization, and adds in the reactant mixture that step 1) obtains pH＜1 and 0-5 ℃.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction is finished, in reactant mixture, add 0.40-0.60 mol sulfuric acid iron (III) and stirred 1 hour.Adding NaCl makes dye precipitated and leaches by suction.
Embodiment 35a:
React according to the method for describing among the embodiment 34a, different is does not exist subsequently reaction with molysite.
Embodiment 36:
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole of MSP diazotization.1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions, with this solution with mix at the diazotizing MSP that in 30 minutes, dropwise adds below 10 ℃, add 10 weight % sodium hydrate aqueous solutions simultaneously the pH value remained between 3 to 8.
2) 1 mole of 5-nitro-2-amino-phenol is suspended in the frozen water, down with excessive nitrite sodium and hydrochloric acid diazotization, and adds in the reactant mixture that step 1) obtains pH＜1 and 0-5 ℃.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction is finished, in reactant mixture, add 0.40-0.60 mol sulfuric acid iron (III) and stirred 1 hour.Adding NaCl makes dye precipitated and leaches by suction.
Embodiment 37:
React according to the method for describing among the embodiment 36, different is does not exist subsequently reaction with molysite.
According to embodiment 34a and 36 similar modes, can obtain the metal complex of the dyestuff (dyestuff of general formula I when being p=0 and m=1) of general formula D k-N=N-Kk-N=N-A, wherein the Dk representative is derived from the group of diazo component DK1 to DK9, DK13, DK14, DK26, DK27, DK39 to DK41 or DK58, the Kk representative is derived from the divalent group of Kk2, Kk3, Kk49 or Kk50, and A represents one of group A1 to A12.Its example is listed in the table 8.
Table 8
Embodiment number Dk Kk A Metal
34a DK1 Kk3 A1 Fe
34b DK2 Kk3 A1 Fe
34c DK3 Kk3 A1 Fe
34d DK4 Kk3 A1 Fe
34e DK4 Kk3 A1 Fe
34f DK5 Kk3 A1 Fe
34g DK6 Kk3 A1 Fe
34h DK7 Kk3 A1 Fe
34i DK8 Kk3 A1 Fe
34j DK9 Kk3 A1 Fe
34k DK13 Kk3 A1 Fe
34l DK14 Kk3 A1 Fe
34m DK27 Kk3 A1 Fe
34n DK39 Kk3 A1 Fe
Embodiment number Dk Kk A Metal
34o DK40 Kk3 A1 Fe
34p DK41 Kk3 A1 Fe
34q DK58 Kk3 A1 Fe
34r DK5 Kk49 A1 Fe
34s DK5 Kk50 A1 Fe
34t DK5 Kk3 A1 Cr
34u DK5 Kk49 A1 Co
34v DK5 Kk50 A1 Cr
34z DK4 Kk3 A3 Fe
34aa DK5 Kk3 A6 Fe
34ab DK6 Kk3 A10 Fe
34ac DK7 Kk3 A11 Fe
According to embodiment 35a and 37 similar modes, can obtain the dyestuff (dyestuff of general formula I when being p=0 and m=1) of general formula D k-N=N-Kk-N=N-A, wherein the Dk representative is derived from the group of diazo component DK1 to DK83, the Kk representative is derived from the divalent group of Kk2, Kk3, Kk49 or Kk50, and A represents one of group A1 to A12.Its example is listed in the table 9.
Table 9:
Embodiment number Dk Kk A
35a DK1 Kk3 A1
35b DK2 Kk3 A1
35c DK3 Kk3 A1
35d DK4 Kk3 A1
35e DK5 Kk3 A1
35f DK6 Kk3 A1
35g DK7 Kk3 A1
35h DK8 Kk3 A1
35i DK9 Kk3 A1
35j DK10 KK3 A1
35k DK12 KK3 A1
35l DK13 Kk3 A1
35m DK14 Kk3 A1
35n DK17 Kk3 A1
Embodiment number Dk Kk A
35o DK27 Kk3 A1
35p DK28 Kk3 A1
35q DK32 Kk3 A1
35r DK39 Kk3 A1
35s DK40 Kk3 A1
35t DK41 Kk3 A1
35u DK42 Kk3 A1
35v DK46 Kk3 A1
35z DK47 Kk3 A1
35aa DK58 Kk3 A1
35ab DK5 Kk49 A1
35ac DK5 Kk50 A1
35ad DK47 Kk49 A1
35ae DK47 Kk50 A1
35af DK4 Kk3 A4
35ag DK5 Kk3 A7
35ah DK6 Kk3 A9
35ai DK7 Kk3 A12
Embodiment 38a:
Figure A20048003210600981
Method A:
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,6-dinitro-2-amino-phenol diazotization.Time 1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions in pH＞12, with this solution with dropwise add in 30 minutes at＞10 ℃ diazotizing 4,6-dinitro-2-amino-phenol mixes, and adds 10 weight % sodium hydrate aqueous solutions simultaneously the pH value is remained on more than 9.
2) 1 mole of MSP is suspended in the frozen water,, adds to then in the reactant mixture of step 1) acquisition in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) 1 mole of paranitroanilinum is dissolved in 21 weight % hydrochloric acid, after this pH＜1 and 0-5 ℃ down with excessive nitrite sodium diazotization and add step 2 to) in the reactant mixture of acquisition.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction is finished, in reactant mixture, add 0.40-0.60 mol sulfuric acid iron (III) and stirred 1 hour.Adding NaCl makes dye precipitated and leaches by suction.
Method B:
1) 1 mole of paranitroanilinum is dissolved in 21 weight % hydrochloric acid, after this in pH＜1 and the 0-5 ℃ of following excessive nitrite sodium diazotization of using.Time 1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions in pH＞12.With this solution with mix at the diazotizing paranitroanilinum that in 30 minutes, dropwise adds below 10 ℃, add 10 weight % sodium hydrate aqueous solutions simultaneously the pH value remained on more than 9.
2) 1 mole of MSP is suspended in the frozen water,, adds to then in the reactant mixture of step 1) acquisition in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,6-dinitro-2-amino-phenol diazotization, and add step 2 to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction is finished, in reactant mixture, add 0.40-0.60 mol sulfuric acid iron (III) and stirred 1 hour.Adding NaCl makes dye precipitated and leaches by suction.
Embodiment 39a:
React according to the method for describing among the embodiment 38, different is does not exist subsequently reaction with molysite.
Embodiment 40a:
Method A:
1) 1 mole of paranitroanilinum is dissolved in 21 weight % hydrochloric acid, after this in pH＜1 and the 0-5 ℃ of following excessive nitrite sodium diazotization of using.Time 1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions in pH＞12.With this solution with mix at the diazotizing paranitroanilinum that in 30 minutes, dropwise adds below 10 ℃, add 10 weight % sodium hydrate aqueous solutions simultaneously the pH value remained on more than 9.
2) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,6-dinitro-2-amino-phenol diazotization adds in the reactant mixture that step 1) obtains then.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) 1 mole of MSP is suspended in the frozen water, pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, and add step 2) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction is finished, in reactant mixture, add 0.40-0.60 mol sulfuric acid iron (III) and stirred 1 hour.Adding NaCl makes dye precipitated and leaches by suction.
Method B:
1) 1 mole of MSP is suspended in the frozen water, in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions.With this solution with mix at the diazotization MSP that in 30 minutes, dropwise adds below 10 ℃, add 10 weight % sodium hydrate aqueous solutions simultaneously the pH value remained between 6 to 7.
2) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,6-dinitro-2-amino-phenol diazotization adds in the reactant mixture that step 1) obtains then.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) 1 mole of paranitroanilinum is dissolved in 21 weight % hydrochloric acid, after this pH＜1 and 0-5 ℃ down with excessive nitrite sodium diazotization, and add step 2 to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction is finished, in reactant mixture, add 0.40-0.60 mol sulfuric acid iron (III) and stirred 1 hour.Adding NaCl makes dye precipitated and leaches by suction.
Embodiment 41a:
React according to the method for describing among the embodiment 40, different is does not exist subsequently reaction with molysite.
According to embodiment 38a and the similar mode of 40a, can obtain general formula
The metal complex of dyestuff (dyestuff of general formula I when being p=0 and m=2), Dk wherein 1And Dk 2Representative is derived from the group of diazo component DK1 to DK83, group Dk separately 1Or Dk 2In at least one representative be derived from the group of diazo component DK1 to DK9, DK13, DK14, DK26, DK27, DK39 to DK41 or DK58, the Kk representative is derived from the trivalent group of Kk2 or Kk3, and A represents one of group A1 to A12.Its example is listed in the table 10.
Table 10
Embodiment number Dk 1 Kk Dk 2 A Metal
38a DK1 KK3 DK17 A1 Fe
38b DK1 KK3 DK5 A1 Fe
38c DK1 KK3 DK10 A1 Fe
38d DK2 KK3 DK17 A1 Fe
38e DK4 KK3 DK17 A1 Cu
38f DK4 KK3 DK12 A1 Co
38g DK4 KK3 DK56 A1 Cr
38h DK5 KK3 DK9 A1 Fe
38i DK5 KK3 DK10 A1 Fe
38j DK5 KK3 DK12 A1 Fe
38k DK5 KK3 DK17 A1 Fe
38l DK5 KK3 DK19 A1 Fe
Embodiment number Dk 1 Kk Dk 2 A Metal
38m DK5 KK3 DK27 A1 Fe
38n DK5 KK3 DK28 A1 Fe
38o DK5 KK3 DK30 A1 Fe
38p DK5 KK3 DK32 A1 Fe
38q DK5 KK3 DK35 A1 Fe
38r DK5 KK3 DK41 A1 Fe
38s DK5 KK3 DK46 A1 Fe
38t DK5 KK3 DK47 A1 Fe
38u DK5 KK3 DK58 A1 Fe
38v DK5 KK3 DK12 A5 Fe
38z DK5 KK3 DK17 A9 Fe
40a DK1 KK3 DK17 A1 Fe
40b DK1 KK3 DK5 A1 Fe
40c DK1 KK3 DK10 A1 Fe
40d DK2 KK3 DK17 A1 Fe
40e DK4 KK3 DK17 A1 Cu
40f DK4 KK3 DK12 A1 Co
40g DK4 KK3 DK56 A1 Cr
40h DK5 KK3 DK9 A1 Fe
40i DK5 KK3 DK10 A1 Fe
40j DK5 KK3 DK12 A1 Fe
40k DK5 KK3 DK17 A1 Fe
40l DK5 KK3 DK19 A1 Fe
40m DK5 KK3 DK27 A1 Fe
40n DK5 KK3 DK28 A1 Fe
40o DK5 KK3 DK30 A1 Fe
40p DK5 KK3 DK32 A1 Fe
40q DK5 KK3 DK35 A1 Fe
40r DK5 KK3 DK41 A1 Fe
40s DK5 KK3 DK46 A1 Fe
40t DK5 KK3 DK47 A1 Fe
40u DK5 KK3 DK58 A1 Fe
40v DK5 KK3 DK12 A4 Fe
40z DK5 KK3 DK17 A11 Fe
According to embodiment 39a and the similar mode of 41a, can obtain general formula Dyestuff (dyestuff of general formula I when being p=0 and m=2), Dk wherein 1And Dk 2Representative is derived from the group of diazo component DK1 to DK83 separately, and the Kk representative is derived from the trivalent group of Kk2, Kk3 or Kk5, and A represents one of group A1 to A12.Its example is listed in the table 11.
Table 11:
Embodiment number Dk 1 Kk Dk 2 A
39a DK1 KK3 DK17 A1
39b DK1 KK3 DK5 A1
39c DK1 KK3 DK10 A1
39d DK2 KK3 DK17 A1
39e DK4 KK3 DK17 A1
39f DK4 KK3 DK12 A1
39g DK4 KK3 DK56 A1
39h DK5 KK3 DK9 A1
39i DK5 KK3 DK10 A1
39j DK5 KK3 DK12 A1
39k DK5 KK3 DK17 A1
39l DK5 KK3 DK19 A1
39m DK5 KK3 DK27 A1
39n DK5 KK3 DK28 A1
39o DK5 KK3 DK30 A1
39p DK5 KK3 DK32 A1
39q DK5 KK3 DK35 A1
39r DK5 KK3 DK41 A1
39s DK5 KK3 DK46 A1
39t DK5 KK3 DK47 A1
39u DK5 KK3 DK58 A1
39v DK5 KK3 DK12 A7
39z DK5 KK3 DK17 A12
41a DK1 KK3 DK17 A1
41b DK1 KK3 DK5 A1
41c DK1 KK3 DK10 A1
41d DK2 KK3 DK17 A1
41e DK4 KK3 DK17 A1
41f DK4 KK3 DK12 A1
41g DK4 KK3 DK56 A1
41h DK5 KK3 DK9 A1
Embodiment number Dk 1 Kk Dk 2 A
41i DK5 KK3 DK10 A1
41j DK5 KK3 DK12 A1
41k DK5 KK3 DK17 A1
41l DK5 KK3 DK19 A1
41m DK5 KK3 DK27 A1
41n DK5 KK3 DK28 A1
41o DK5 KK3 DK30 A1
41p DK5 KK3 DK32 A1
41q DK5 KK3 DK35 A1
41r DK5 KK3 DK41 A1
41s DK5 KK3 DK46 A1
41t DK5 KK3 DK47 A1
41u DK5 KK3 DK58 A1
Embodiment 42a:
Figure A20048003210601041
Method A:
1) 1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.Time 1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions in pH＞12.With this solution with mix in the diazotization H acid that in 30 minutes, dropwise adds below 10 ℃, add 10 weight % sodium hydrate aqueous solutions simultaneously the pH value remained on more than 9.
2) 1 mole of 5-nitro-2-amino-phenol is suspended in the frozen water, in pH＜1 and the 0-5 ℃ of following excessive nitrite sodium diazotization of using, adds to then in the reactant mixture of step 1) acquisition then.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) 1 mole of MSP is suspended in the frozen water, pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, and add step 2 to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction is finished, in reactant mixture, add 0.40-0.60 mol sulfuric acid iron (III) and stirred 1 hour.Adding NaCl makes dye precipitated and leaches by suction.
Method B:
1) 1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and with the acetylation of 1.1-1.5 mole of acetic anhydride.
2) 1 mole of MSP is suspended in the frozen water, down with excessive nitrite sodium and hydrochloric acid diazotization, and adds in the reactant mixture that step 1) obtains pH＜1 and 0-5 ℃.Adding sodium carbonate remains between 4 to 7 the pH value.After coupling is finished, add 21 weight % hydrochloric acid the pH value is adjusted to below 1, and reactant mixture is heated to 85-95 ℃.This separates acetyl group.
3) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with step 2) the product diazotization that obtains, and add in 1 mole of resorcinol aqueous solution.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
4) 1 mole of 5-nitro-2-amino-phenol is suspended in the frozen water, down with excessive nitrite sodium and hydrochloric acid diazotization, and adds in the reactant mixture that step 3) obtains pH＜1 and 0-5 ℃.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction is finished, in reactant mixture, add 0.40-0.60 mol sulfuric acid iron (III) and stirred 1 hour.Adding NaCl makes dye precipitated and leaches by suction.
Embodiment 43a:
React according to the method for describing among the embodiment 42a, different is does not exist subsequently reaction with molysite.
Embodiment 44:
1) 1 mole of Cleve's acid 7 is dissolved in 25 weight % sodium hydrate aqueous solutions.Simultaneously, 1 mole of MSP is suspended in the frozen water,, adds to then in the solution of Cleve's acid 7, keep the pH value to be lower than 2 simultaneously in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.
2) in pH＜1 and 0-5 ℃ of product diazotization that with excessive nitrite sodium and hydrochloric acid step 1) is obtained down.Reactant mixture is added in 1 mole of resorcinol aqueous solution then.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) 1 mole of 5-nitro-2-amino-phenol is suspended in the frozen water, pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization, and add step 2 to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction is finished, in reactant mixture, add 0.40-0.60 mol sulfuric acid iron (III) and stirred 1 hour.Adding NaCl makes dye precipitated and leaches by suction.
Embodiment 45:
React according to the method for describing among the embodiment 44, different is does not exist subsequently reaction with molysite.
Embodiment 46a:
Figure A20048003210601062
Method A:
1) 1 mole of MSP is suspended in the frozen water, in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions.With this solution with mix at the diazotization MSP that in 30 minutes, dropwise adds below 10 ℃, add 10 weight % sodium hydrate aqueous solutions simultaneously the pH value remained between 6 to 8.
2) 1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid diazotization and add in the reactant mixture of step 1) acquisition.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) 1 mole of 5-nitro-2-amino-phenol is suspended in the frozen water, after this pH＜1 and 0-5 ℃ down with excessive nitrite sodium diazotization, add step 2 then to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction is finished, in reactant mixture, add 0.40-0.60 mol sulfuric acid iron (III) and stirred 1 hour.Adding NaCl makes dye precipitated and leaches by suction.
Method B:
1) 1 mole of MSP is suspended in the frozen water, in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions.With this solution with mix at the diazotization MSP that in 30 minutes, dropwise adds below 10 ℃, add 10 weight % sodium hydrate aqueous solutions simultaneously the pH value remained between 6 to 8.
2) 1 mole of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, and with the acetylation of 1.1-1.5 mole of acetic anhydride.
3) 1 mole of 5-nitro-2-amino-phenol is suspended in the frozen water, and pH＜1 and 0-5 ℃ down with excessive nitrite sodium diazotization, and add step 2 to) in the reactant mixture that obtains.Adding sodium carbonate remains between 4 to 7 the pH value.After coupling is finished, add 21 weight % hydrochloric acid the pH value is adjusted to below 1, and reactant mixture is heated to 85-95 ℃.This separates acetyl group.
4) in pH＜1 and 0-5 ℃ of product diazotization that with excessive nitrite sodium and hydrochloric acid step 3) is obtained down, and add in the reactant mixture of the step 1) acquisition between the 3-8, add 10 weight % sodium hydrate aqueous solutions then.After reaction is finished, in reactant mixture, add 0.40-0.60 mol sulfuric acid iron (III) and stirred 1 hour.Adding NaCl makes dye precipitated and leaches by suction.
Embodiment 47a:
React according to the method for describing among the embodiment 46a, different is does not exist subsequently reaction with molysite.
Embodiment 48:
1) 1 mole of MSP is suspended in the frozen water, in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions.With this solution with mix at the diazotizing MSP that in 30 minutes, dropwise adds below 10 ℃, add 10 weight % sodium hydrate aqueous solutions simultaneously the pH value remained between 6 to 8.
2) 1 mole of 5-nitro-2-amino-phenol is suspended in the frozen water, and pH＜1 and 0-5 ℃ down with excessive nitrite sodium diazotization, and add in the 25 weight % sodium hydrate aqueous solutions with 1 mole of Cleve's acid 7, keep the pH value to be lower than 2 simultaneously.
3) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with step 2) the product diazotization that obtains, add to then in the reactant mixture that step 1) obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between the 3-8 pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to embodiment 42a, 44 and the similar mode of 46a, can obtain general formula D k 1-N=N-Napht-N=N-Kk-N=N-Dk 2The metal complex of dyestuff (dyestuff of general formula I when being P=Napht, p=1 and m=1), Dk wherein 1And Dk 2Represent the group that is derived from diazo component DK1 to DK9, DK13, DK14, DK26, DK27, DK39 to DK41 or DK58 or is derived from A1 to A12, Dk separately 1Or Dk 2In at least one represents the group of formula A, Kk representative is derived from the divalent group of Kk2 or Kk3, and Napht is the divalent group of formula II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 or II-16.Its example is listed in the table 12.
Table 12
Embodiment number Dk 1 Napht Kk Dk 2 Metal
42a A1 DK44 Kk3 DK1 Fe
42b A1 DK44 Kk3 DK4 Cu
42c A1 DK44 Kk3 DK5 Fe
42d A7 DK44 Kk3 DK5 Fe
42e A1 DK44 Kk3 DK40 Fe
42f A1 DK44 Kk3 DK58 Cr
42g A1 DK57 Kk3 DK5 Fe
42h DK1 DK44 Kk3 A1 Fe
42i DK2 DK44 Kk3 A1 Fe
42j DK4 DK44 Kk3 A1 Fe
42k DK5 DK44 Kk3 A1 Fe
42l DK27 DK44 Kk3 A1 Fe
42m DK41 DK44 Kk3 A1 Fe
42n A3 DK44 Kk3 DK5 Fe
42o A9 DK44 Kk3 DK40 Fe
46a DK1 DK44 Kk3 A1 Fe
46b DK2 DK44 Kk3 A1 Fe
46c DK4 DK44 Kk3 A1 Fe
46d DK5 DK44 Kk3 A1 Fe
46e DK27 DK44 Kk3 A1 Fe
46f DK41 DK44 Kk3 A1 Fe
46g A1 DK44 Kk3 DK1 Fe
46h A1 DK44 Kk3 DK4 Cu
46i A1 DK44 Kk3 DK5 Fe
46j A7 DK44 Kk3 DK5 Fe
46k A1 DK44 Kk3 DK40 Fe
46l A1 DK44 Kk3 DK58 Cr
46m A1 DK57 Kk3 DK5 Fe
According to embodiment 43a, 45,47a and 48 similar modes, can obtain general formula D k 1-N=N-Napht-N=N-Kk-N=N-Dk 2Dyestuff (dyestuff of general formula I when being P=Napht, p=1 and m=1), Dk wherein 1And Dk 2Represent the group that is derived from diazo component DK1 to DK83 or is derived from A1 to A12, Dk separately 1Or Dk 2In at least one represents the group of formula A, Kk representative is derived from the divalent group of Kk2, Kk3, Kk5, Kk49 or Kk50, and Napht is the divalent group of formula II-1, II-3, II-5, II-7, II-9, II-11, II-13, II-15 or II-16.Its example is listed in the table 13.
Table 13
Embodiment number Dk 1 Napht Kk Dk 2
43a A1 DK44 Kk3 DK1
43b A1 DK44 Kk3 DK4
43c A1 DK44 Kk3 DK5
43d A7 DK44 Kk3 DK5
43e A1 DK44 Kk3 DK9
43f A1 DK44 Kk3 DK10
43g A1 DK44 Kk3 DK12
43h A1 DK44 Kk3 DK28
43i A1 DK44 Kk3 DK32
43j A1 DK44 Kk3 DK37
43k A1 DK44 Kk3 DK40
43l A1 DK44 Kk3 DK46
43m A1 DK44 Kk3 DK58
43n A1 DK57 Kk3 DK5
43o DK1 DK44 Kk3 A1
43p DK2 DK44 Kk3 A1
43q DK4 DK44 Kk3 A1
43r DK5 DK44 Kk3 A1
43s DK8 DK44 Kk3 A1
43t DK10 DK44 Kk3 A1
43u DK12 DK44 Kk3 A1
43v DK17 DK44 Kk3 A1
43z DK27 DK44 Kk3 A1
43aa DK28 DK44 Kk3 A1
43ab DK32 DK44 Kk3 A1
43ac DK41 DK44 Kk3 A1
43ad DK46 DK44 Kk3 A1
43ae DK47 DK44 Kk3 A1
Embodiment number Dk 1 Napht Kk Dk 2
43af DK28 DK44 Kk3 A3
43ag DK32 DK45 Kk3 A7
43ah DK41 DK45 Kk3 A8
43ai DK46 DK45 Kk3 A11
47a DK1 DK44 Kk3 A1
47b A1 DK44 Kk3 DK4
47c A1 DK44 Kk3 DK5
47d A7 DK44 Kk3 DK5
47e A1 DK44 Kk3 DK9
47f A1 DK44 Kk3 DK10
47g A1 DK44 Kk3 DK12
47h A1 DK44 Kk3 DK28
47i A1 DK44 Kk3 DK32
47j A1 DK44 Kk3 DK37
47k A1 DK44 Kk3 DK40
47l A1 DK44 Kk3 DK46
47m A1 DK44 Kk3 DK58
47n A1 DK57 Kk3 DK5
47o A1 DK44 Kk3 DK1
47p DK2 DK44 Kk3 A1
47q DK4 DK44 Kk3 A1
47r DK5 DK44 Kk3 A1
47s DK8 DK44 Kk3 A1
47t DK10 DK44 Kk3 A1
47u DK12 DK44 Kk3 A1
47v DK17 DK44 Kk3 A1
47z DK27 DK44 Kk3 A1
47aa DK28 DK44 Kk3 A1
47ab DK32 DK44 Kk3 A1
47ac DK41 DK44 Kk3 A1
47ad DK46 DK44 Kk3 A1
47ae DK47 DK44 Kk3 A1
47af DK28 DK44 Kk3 A2
47ag DK32 DK45 Kk3 A6
47ah DK41 DK45 Kk3 A9
47ai DK46 DK45 Kk3 A10
Embodiment 49a:
Figure A20048003210601121
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4 '-benzidine base-3,3 '-dicarboxylic acids double couple gallium, and under 5 to 11 pH value with 1 mole of salicylism reaction.
2) time 1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions in pH＞12.This solution is mixed with the product that obtains in the step 1) that dropwise added in 30 minutes below 10 ℃, add 10 weight % sodium hydrate aqueous solutions during this period the pH value is remained on more than 9.
3) 1 mole of MSP is suspended in the frozen water, in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.Subsequently, MSP adds step 2 to this diazotization) in the reactant mixture that obtains, add 10 weight % sodium hydrate aqueous solutions simultaneously the pH value is remained between 5 to 8.After reaction is finished, in reactant mixture, add 1 mol sulfuric acid copper (II) and stirred 1 hour at 70 ℃.Adding NaCl makes dye precipitated and leaches by suction.
Embodiment 50a:
React according to the method for describing among the embodiment 49a, different is does not exist subsequently reaction with mantoquita.
Embodiment 51:
1) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with 1 mole 4,4 '-diaminobenzene formailide double couple gallium, and under pH5-11 with 1 mole of salicylism reaction.
2) 1 mole of MSP is suspended in the frozen water, in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.1 mole of resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions.In 30 minutes, diazotization MSP is dropwise being added wherein below 10 ℃, adding 10 weight % sodium hydrate aqueous solutions simultaneously the pH value is remained between the 6-8.
3) with step 2) product that obtains adds in the reactant mixture that step 1) obtains, adds 10 weight % sodium hydrate aqueous solutions simultaneously the pH value is remained between 5 to 8.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to embodiment 49a, 50a and 51 similar modes, can obtain general formula Kk 3-N=N-Tk-N=N-Kk 1The dyestuff of-N=N-A and their metal complex (being the dyestuff of general formula X IV), wherein the Kk3 representative is derived from the group of diazo component Kk1 to Kk48 or Kk51 to Kk67, or represents Dk42 to Dk83, and the Tk representative is derived from the divalent group of TK1 to TK20, Kk 1Representative is derived from the divalent group of Kk2, Kk3, Kk5, Kk49 or Kk50, and A represents one of group A1 to A12.Its example is listed in the table 14.
Table 14:
Embodiment number Kk 3 Tk Kk 1 A Metal
49a Kk1 Tk11 Kk3 A1 Cu
49b Kk40 Tk11 Kk3 A1 Cu
49c Dk46 Tk8 Kk3 A1 Cu
50a DK44 Tk16 Kk3 A1
50b DK44 Tk18 Kk3 A1
50c Kk39 Tk18 Kk3 A1
Embodiment 52a:
Figure A20048003210601141
1) 2 moles of H acid is dissolved in 25 weight % sodium hydrate aqueous solutions, down with excessive nitrite sodium and hydrochloric acid diazotization, and adds 1 mole 3 to pH＜1 and 0-5 ℃, in the aqueous solution of 3 '-dihydroxy diphenylamine.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 10 the pH value.
2) 2 moles of MSP are suspended in the frozen water, down with excessive nitrite sodium and hydrochloric acid diazotization, and add in the reactant mixture that step 1) obtains pH＜1 and 0-5 ℃.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to the similar mode of embodiment 52a, can obtain general formula D k 1-N=N-P-N=N-Kk 1-N=N-R-N=N-Dk 2Dyestuff and their metal complex (dyestuff of general formula X V), Dk wherein 1And Dk 2Representative is derived from diazo component DK1 to DK83 or is derived from the group of A1 to A12, Dk 1Or Dk 2In at least one represents the group of formula A, Kk representative is derived from the divalent group of Kk2, Kk3, Kk5, Kk49 or Kk50, and P and R represent the divalent group of formula II-1, II-3, II-5, II-7, II-9, II-11 and II-13 separately.Its example is listed in the table 15.
Table 15:
Embodiment number Dk 1 P Kk 1 R Dk 2 Metal
52a A1 DK44 Kk50 DK44 A1
52b A1 DK44 Kk50 DK44 A1 Cu
52c A1 DK44 Kk50 DK44 A1 Co
52d A1 DK44 Kk49 DK44 A1 Cu
52e A1 DK44 Kk49 DK44 A1 Co
Embodiment 53a:
1) 1 mole of MSP is suspended in the frozen water, down with excessive nitrite sodium and hydrochloric acid diazotization, and adds in the alkaline solution of 1 mole of Cleve's acid 7 pH＜1 and 0-5 ℃.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
2) 1 mole of MSP is suspended in the frozen water, down with excessive nitrite sodium and hydrochloric acid diazotization, and adds in the alkaline solution of 1 mole of 8-amino naphthalenes-1-sulfonic acid (Dk56) pH＜1 and 0-5 ℃.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
3) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with the product diazotization of step 1) acquisition and in 30 minutes, add 1 mole 3 to, in the alkaline solution of 3 '-dihydroxy diphenylamine.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.
4) pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with step 2) in the product diazotization that obtains and the reactant mixture that adds the step 3) acquisition to, add 10 weight % sodium hydrate aqueous solutions simultaneously the pH value remained between 5 to 8.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to the similar mode of embodiment 53a, can obtain general formula D k 1-N=N-P-N=N-Kk 1-N=N-R-N=N-Dk 2Dyestuff and their metal complex (dyestuff of general formula X V), Dk wherein 1And Dk 2Representative is derived from diazo component DK1 to DK83 or is derived from the group of A1 to A12, Dk 1Or Dk 2In at least one represents the group of formula A, Kk representative is derived from the divalent group of Kk2, Kk3, Kk5, Kk49 or Kk50, and P and R represent the divalent group of formula II-15 or II-16 separately or be derived from the divalent group of diazo component DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK22 to DK27, DK29, DK30, DK33, DK36, DK38 or DK39.Its example is listed in the table 16.
Table 16:
Embodiment number Dk 1 P Kk 1 R Dk 2 Metal
53a A1 DK46 Kk50 DK56 A1
53b A1 DK4 Kk49 DK46 A1 Cu
53c A1 DK4 K49 DK46 A1 Co
53d A1 DK4 Kk50 DK46 A1 Cu
Embodiment 54:
1) 70-80 ℃ with 2 moles of ortho-aminobenzoic acid vitriolizations (96%), and react with the 0.5-0.6 moles of formaldehyde.At 70-80 ℃ after 2 hours, add ice reactant mixture be cooled to about 0 ℃, and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with the products therefrom double couple gallium.Time 1.8-2.2 mole resorcinol is dissolved in 50 weight % sodium hydrate aqueous solutions in pH＞12, and, add 10 weight % sodium hydrate aqueous solutions during this period the pH value is remained on more than 8 with this solution and in the double couple gallium compound that in 30 minutes, dropwise adds below 5 ℃.
2) 2 moles of MSP are suspended in the frozen water, down with excessive nitrite sodium and hydrochloric acid diazotization, and add in the reactant mixture that step 1) obtains pH＜1 and 0-5 ℃.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction is finished, reaction solution is heated to 80 ℃, and adds 2 moles of CuSO 4Then the gained reactant mixture is evaporated to obtain complex dye.
Embodiment 55:
React according to the method for describing among the embodiment 54, different is does not exist subsequently reaction with mantoquita.
Embodiment 56:
1) 70-80 ℃ with 2 moles of ortho-aminobenzoic acid vitriolizations (96%), and react with the 0.5-0.6 moles of formaldehyde.At 70-80 ℃ after 2 hours, add ice reactant mixture be cooled to about 0 ℃, and pH＜1 and 0-5 ℃ down with excessive nitrite sodium and hydrochloric acid with the products therefrom double couple gallium.
2) 2 moles of MSP are suspended in the frozen water, in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.2 moles of resorcinols are dissolved in 50 weight % sodium hydrate aqueous solutions.In 30 minutes, diazotizing MSP is dropwise being added wherein below 10 ℃, adding 10 weight % sodium hydrate aqueous solutions during this period the pH value is remained between 6 to 8.
3) product that step 1) is obtained is added step 2 to) in the reactant mixture that obtains.Adding 10 weight % sodium hydrate aqueous solutions remains between 3 to 8 the pH value.After reaction is finished, reaction solution is heated to 80 ℃, and adds 2 moles of CuSO 4Then with gained reactant mixture evaporation as for to obtain complex dye.
Embodiment 57:
React according to the method for describing among the embodiment 56a, different is does not exist subsequently reaction with mantoquita.
According to embodiment 54 and 56 similar modes, can obtain general formula D k 1-N=N-Kk 1-N=N-Tk 1-N=N-Kk 2-N=N-Dk 2The metal complex of dyestuff (dyestuff of general formula I V), Dk wherein 1And Dk 2Representative is derived from diazo component DK1 to DK83 or is derived from the group of A1 to A12, group Dk 1Or Dk 2In at least one represents the group of formula A, Tk 1Representative is derived from the divalent group of Tk3, Tk4, Tk8 to Tk11, Tk14, Tk16 or Tk19, and Kk 1And Kk represents the divalent group that is derived from Kk2, Kk3, Kk5, Kk49 or Kk50 or the divalent group of formula II-2, II-4, II-6, II-8, II-10, II-12 or II-14 independently.
According to embodiment 55 and 57 similar modes, can obtain general formula D k 1-N=N-Kk 1-N=N-Tk 1-N=N-Kk 2-N=N-Dk 2Dyestuff (dyestuff of general formula I V), Dk wherein 1And Dk 2Representative is derived from diazo component DK1 to DK83 or is derived from the group of A1 to A12, group Dk 1Or Dk 2In at least one represents the group of formula A, Tk 1Representative is derived from the divalent group of Tk1 to Tk20, and Kk 1And Kk 2Representative is derived from the divalent group of Kk2, Kk3, Kk5, Kk49 or Kk50 or the divalent group of formula II-2, II-4, II-6, II-8, II-10, II-12 or II-14 independently.
Embodiment 58:
Figure A20048003210601181
1) 1 mole of Cleve's acid 7 is dissolved in 25 weight % sodium hydrate aqueous solutions.Simultaneously, 1 mole of MSP is suspended in the frozen water, and, adds to then in the solution of Cleve's acid 7, keep the pH value to be lower than 2 simultaneously in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.
2) in pH＜1 and 0-5 ℃ of product diazotization that with excessive nitrite sodium and hydrochloric acid step 1) is obtained down.Under pH 3-8, react then with 1 mole of methylamine Fei Taming.After reaction was finished, adding NaCl made dye precipitated and leaches by suction.
According to embodiment 58 similar modes, can obtain the dyestuff (dyestuff of general formula I when being P=Naptht, p=1 and m=0) of general formula A-N=N-Napht-N=N-Kk, wherein the Napht representative is derived from the group of DK42 to DK59, the Kk representative is derived from the group of Kk1 to Kk48 or Kk51 to Kk67, and A represents one of group A1 to A12.Its example is listed in the table 17.
Table 17:
Embodiment number A Napht Kk
58a A1 Dk46 Kk5
58b A1 Dk46 Kk27
58c A1 Dk44 Kk27
Embodiment 59a:
Figure A20048003210601191
1 mole of Cleve's acid 7 is dissolved in 25 weight % sodium hydrate aqueous solutions.Simultaneously, 1 mole of MSP is suspended in the frozen water, and, adds to then in the solution of Cleve's acid 7, keep the pH value to be lower than 2 simultaneously in pH＜1 and 0-5 ℃ of following excessive nitrite sodium and the hydrochloric acid diazotization used.After reaction is finished, with the dye solution spray drying.
According to the similar mode of embodiment 59a, can obtain the dyestuff (dyestuff of general formula I when being P=m=0) of general formula A-N=N-Kk, wherein Kk represents the group that is derived from the group of Kk1 to Kk48 or Kk51 to Kk67 or is derived from Dk3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 to DK27, DK29, DK30, DK33, DK36, DK38, DK39 or Dk42 to Dk83, and A represents one of group A1 to A12.According to reaction pH value, the coupling of group A-N=N-not only Dk42 to Dk57 and in Dk59 the ortho position of hydroxyl carry out, also carry out at the ortho position of amino.Its example is listed in the table 18.
Table 18:
Embodiment number A Napht
59a A1 DK47
59b A1 Kk32
59c A1 DK44
59d A1 Kk15
59e A1 DK42
59f A7 DK42
59g A7 DK47
59h A7 Kk46
59i A7 DK52
59j A4 DK52
59k A4 DK47
Dyeing recipe (prescription):
Umber by weight.About all data of tanning material, water-repelling agent, fatting agent and auxiliary agent all based on the commercially available prod.About the data of dyestuff is based on coloured organic chemistry composition, owing to the total amount of synthesis condition any salt (synthetic salt) that exists and any standard agent that exists.
Degree of fixation is analyzed qualitative determination and is passed through the quantitative assay of UV-VIS spectroscopic methodology by the HPLC of dyeing bath.For this reason, after dyeing (pH＜7), fixation after 60 minutes, 120 minutes, 180 minutes (pH＞7) get 5 ml samples of every kind of washing lotion body lotion, and be adjusted to pH 3-4 with 1 milliliter of formic acid solution.Dyestuff and hydrolysate thereof by the HPLC analytic sample.Used HPLC post is Nucleodur C18Gravity 3 μ from Macherey-Nagel, CC70/2 and Hypersil 120-5ODS, CC100/2.Used eluant, eluent is acetonitrile/buffer (1.6 gram hydrogen sulfate tetrabutylammoniums, 6 grams, three hypophosphite monohydrate hydrogen dipotassiums are in 1 premium on currency).
According to following internationally recognized standard test fastness:
Perspiration fastness: according to Veslic C4260
Fastness to washing: according to DIN EN ISO 15703
Ooze and move fastness: according to DIN EN ISO 15701 and with DIN EN ISO 15701 similar conditions under under 85 ℃ and 95% humidity, store 16 hours
The degree of anti-wiping the: according to DIN EN ISO 105-X12 (Crockmeter rubs with spun cotton) and according to DIN EN ISO 11640 (Veslic rubs with felt)
Maeser: according to ASTM D 2099
Penetrometer: according to DIN EN ISO 5403
Water vapour permeability: according to DIN EN ISO 14268
Stiffness: according to DIN EN ISO 5402
Test is pulled out in stitching: according to DIN 5331
Tear strength: according to DIN EN ISO 3377
TENSILE STRENGTH: according to DIN EN ISO 3376
Dyeing recipe 1:
A) under 30 ℃, with shaving thickness 1.1 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 150 parts of water, 2 parts of dispersants and 5 parts from the dyestuff of embodiment 2d in pH 4.4 and 30 ℃ dyeing 60 minutes down.In 60 minutes rotary drum process, add 100 part of 15% sodium carbonate liquor so that the pH value remains between 10.0 to 10.2 at 40 ℃ by part, thus fixed dye.Then 6 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.7 pH value.
B) leather that will dye thus in the new system body lotion that constitutes by 100 parts of water, 2 parts of polymerization tanning materials and 2 parts of natural basic fatting agents 35 ℃ of retannings 30 minutes.Then body lotion is mixed also rotary drum processing 20 minutes with 15 parts of liquid synthetic tanning materials, 6 parts of polymerization tanning materials, 10 parts of Tara vegetable tanning materials.In identical body lotion, process 2 hours with leather greasing by rotary drum at 35 ℃ then with 8 parts of fish oil base fatting agents and 2 parts of lecithin base fatting agents.At last, with 2 parts of dense formic acid leather is acidified to pH 3.6, and rotary drum processed twice 10 minutes, rotary drum processing is one time 30 minutes again.Leather that will dye again, retanning and stuffing 15 ℃ with cold rinse 10 minutes, stretch then, the dried overnight that at room temperature suspends, repair, scrape soft tension.
The gained leather has bright-coloured peony, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 2:
A) under 30 ℃, with shaving thickness 1.1 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 150 parts of water, 2 parts of dispersants and 5 parts from the dyestuff of embodiment 2a in pH 4.4 and 30 ℃ dyeing 60 minutes down.In 60 minutes rotary drum process, add 15 parts of solid sodium carbonates so that the pH value keeps 10.0 at 40 ℃ by part, thus fixed dye.Then 4 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.7 pH value.Then as the part b of dyeing recipe 1) described in handle.
The gained leather has bright-coloured peony, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 3:
A) under 30 ℃, with shaving thickness 1.1 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 150 parts of water, 2 parts of dispersants and 5 parts from the dyestuff of embodiment 24 in pH 4.4 and 30 ℃ dyeing 60 minutes down.In 60 minutes rotary drum process, add 100 part of 15% sodium carbonate liquor so that the pH value keeps 10.0 at 50 ℃ by part, thus fixed dye.Then 4 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.7 pH value.Then as the part b of dyeing recipe 1) described in handle.
The gained leather has bright-coloured peony, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 4:
Under 30 ℃, with shaving thickness 1.1 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 150 parts of water, 2 parts of dispersants and 5 parts from the dyestuff of embodiment 58a in pH 4.4 and 30 ℃ dyeing 60 minutes down.In 90 minutes rotary drum process, add 100 part of 15% sodium carbonate liquor so that the pH value keeps 10.0 at 40 ℃ by part, thus fixed dye.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.7 pH value.Then as the part b of dyeing recipe 1) described in handle.
The gained leather has bright-coloured peony, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 5:
Under 30 ℃, with shaving thickness 1.1 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 150 parts of water, 2 parts of dispersants and 5 parts from the dyestuff of embodiment 58b in pH 4.4 and 30 ℃ dyeing 60 minutes down.In 60 minutes rotary drum process, add 100 part of 15% sodium carbonate liquor so that the pH value keeps 10.0 at 40 ℃ by part, thus fixed dye.When adding sodium carbonate liquor, divide to add 15 parts of saltcake altogether for 3 times.Then 5 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.7 pH value.Then as the part b of dyeing recipe 1) described in handle.
The gained leather has bright-coloured peony, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 6:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 150 parts of water, 2 parts of dispersants and 5 parts from the dyestuff of embodiment 59a in pH 4.1 and 30 ℃ dyeing 60 minutes down.In 180 minutes rotary drum process, add 100 parts of borax buffers so that the pH value remains between 7.9 to 9.0 at 40 ℃ by part, thus fixed dye.Then 5 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.6 part of formic acid to reach 4.3 pH value.Then as the part b of dyeing recipe 1) described in handle.
The gained leather has bright-coloured peony, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 7:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 150 parts of water, 2 parts of dispersants and 5 parts from the dyestuff of embodiment 59e in pH 4.1 and 30 ℃ dyeing 60 minutes down.In 180 minutes rotary drum process, 30 part of 15% sodium carbonate liquor of disposable interpolation so that the pH value remain between the 9.4-9.9 at 40 ℃, thereby fixed dye.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.5 pH value.Then as the part b of dyeing recipe 1) described in handle.
The gained leather has bright-coloured peony, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 8:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 150 parts of water, 2 parts of dispersants and 5 parts from the dyestuff of embodiment 2b in pH 4.1 and 30 ℃ dyeing 60 minutes down.In 180 minutes rotary drum process, add 100 parts of borax buffers so that the pH value remains between 8.0 to 9.0 at 40 ℃ by part, thus fixed dye.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.5 pH value.Then as the part b of dyeing recipe 1) described in handle.
The gained leather has navy blue, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 9:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 150 parts of water, 2 parts of dispersants and 5 parts from the dyestuff of embodiment 2k in pH4.2 and 30 ℃ dyeing 60 minutes down.In 180 minutes rotary drum process, 30 part of 15% sodium carbonate liquor of disposable interpolation so that the pH value remain between the 9.4-9.9 at 40 ℃, thereby fixed dye.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.8 pH value.Then as the part b of dyeing recipe 1) described in handle.
The gained leather has navy blue, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 10:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 100 parts of water, 2 parts of dispersants and 5 parts from the dyestuff of embodiment 11a in pH 4.2 and 30 ℃ dyeing 30 minutes down.In 180 minutes rotary drum process, add 20 part of 15% sodium carbonate liquor so that the pH value remains between the 8.6-9.3 at 40 ℃ by part, thus fixed dye.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.8 pH value.Then as the part b of dyeing recipe 1) described in handle.
The gained leather has dark purplish red, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 11:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 150 parts of water, 2 parts of dispersants and 5 parts from the dyestuff of embodiment 12ae in pH 4.3 and 30 ℃ dyeing 45 minutes down.In 240 minutes rotary drum process, add 40 part of 7% sodium bicarbonate solution so that the pH value remains between the 7.3-8.2 at 40 ℃ by part, thus fixed dye.Then 6 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 1.2 parts of formic acid to reach 3.9 pH value.Then as the part b of dyeing recipe 1) described in handle.
The gained leather has bright-coloured navy blue, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 12:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 150 parts of water, 2 parts of dispersants and 5 parts from the dyestuff of embodiment 13c in pH 4.1 and 30 ℃ dyeing 30 minutes down.By part adding 40 part of 7% sodium bicarbonate solution so that pH value is adjusted to 7.9-8.1, thereby fixed dye and carry out 60 minutes rotary drum processing divides 3 times then and adds 15 parts of saltcake, and rotary drum is processed continued under pH 8.1-9.0 120 minutes again.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 1.0 parts of formic acid to reach 3.8 pH value.Then as the part b of dyeing recipe 1) described in handle.
The gained leather has bottle green, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 13:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 150 parts of water, 2 parts of dispersants and 5 parts from the dyestuff of embodiment 12n in pH 4.2 and 30 ℃ dyeing 45 minutes down.By part adding 20 part of 15% sodium carbonate liquor so that pH value is adjusted to 8.4-9.2, thereby fixed dye and the rotary drum that carried out 120 minutes are processed.Then 2 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 1.1 parts of formic acid to reach 3.9 pH value.Then as the part b of dyeing recipe 1) described in handle.
The gained leather has black, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 14:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 150 parts of water, 2 parts of dispersants and 5 parts from the dyestuff of embodiment 13i in pH 4.2 and 30 ℃ dyeing 60 minutes down.By part adding 21 part of 15% sodium carbonate liquor so that pH value is adjusted to 8.8-9.3, thereby fixed dye and the rotary drum that carried out 180 minutes are processed.Then 6 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.5 pH value.Then as the part b of dyeing recipe 1) described in handle.
The gained leather has bottle green, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 15:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 150 parts of water and 5 parts from the dyestuff of embodiment 59e in pH 4.1 and 30 ℃ dyeing 60 minutes down.By part adding 21 part of 15% sodium carbonate liquor so that pH value is adjusted to 8.8-9.3, thereby fixed dye and the rotary drum that carried out 180 minutes are processed.Then 6 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.5 pH value.Then as the part b of dyeing recipe 1) described in handle.
The gained leather has bright-coloured peony, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 16:
Under 35 ℃, the traditional chrome-tanned bovine leather that with shaving thickness is 1.8 millimeters 1 100 weight portion washed 10 minutes in the rotary drum that 200 parts of water and 0.1 part of formic acid are housed, then in the body lotion that constitutes by 100 parts of water, 2 parts of sodium formates, 1 part of sodium acetate, 0.5 part of sodium bicarbonate and 1 part of dispersant in 35 ℃ and 120 minutes.Thereby the depickling body lotion has 5.0 pH.Then with leather at 35 ℃ with 200 parts of water washings 10 minutes.With the leather of neutralization thus in the new system body lotion that constitutes by 30 parts of water and 2 parts of polymerization tanning materials 30 ℃ of retannings 30 minutes.Then body lotion is mixed with 2 parts of hydrophobic fatting agents.Carry out 30 minutes rotary drum processing again, add 5 parts of sulfone type tanning materials and 4 parts of resin type tanning materials then, and then rotary drum was processed 60 minutes.At last, with 0.5% formic acid leather is acidified to pH 4.0, and rotary drum processing 10 minutes once, 30 minutes once.
Under pH 4.8 and 35 ℃, with leather dyeing 90 minutes in the new system body lotion that constitutes from the dyestuff of 59f and 0.2 part of sodium bicarbonate by 150 parts of water, 2 parts of dispersants, 5 parts.By part adding 40 part of 15% sodium carbonate liquor so that pH value is adjusted between 9.0 to 9.3, thus fixed dye, and process at 40 ℃ of rotary drums that carried out 180 minutes.Then 6 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.5 pH value.
At 55 ℃, rotary drum processing is 40 minutes in the new body lotion that is made of 100 parts of water, 4.5 parts of mixing fatting agents based on sulfited fish oil and artificial oil, 0.5 part of lanolin base fatting agent, thereby with leather greasing.Be acidified to pH 3.5 and rotary drum processing 40 minutes with 1.5 parts of dense formic acid then.To dye again and the leather of stuffing with 15 ℃ cold rinse 10 minutes, soft tension is repaired, scraped to stretching, extension then, at the dried overnight that at room temperature suspends.
The gained leather has bright-coloured peony, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 17:
Under 35 ℃, the traditional chrome-tanned bovine leather that with shaving thickness is 1.8 millimeters 1 100 weight portion washed 10 minutes in the rotary drum that 200 parts of water and 0.1 part of formic acid are housed, then in the body lotion that constitutes by 100 parts of water, 2 parts of sodium formates, 1 part of sodium acetate, 1.5 parts of sodium bicarbonates and 1 part of dispersant in 35 ℃ and 120 minutes.The depickling body lotion has 6.3 pH value.Then with leather at 35 ℃ with 200 parts of water washings 10 minutes.
Under pH 5.6 and 30 ℃, with leather dyeing 60 minutes in by 150 parts of water and 5 parts of new system body lotions that constitute from the dyestuff of embodiment 35g.Be adjusted between the 8.5-9.1 with pH value by part 13 part of 15% sodium carbonate liquor of interpolation, then 40 ℃ of rotary drums processing 180 minutes body lotion.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 1.5 parts of formic acid to reach 4.8 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 30 parts of water and 2 parts of polymerization tanning materials 30 ℃ of retannings 30 minutes.Then body lotion is mixed with 2 parts of hydrophobic fatting agents.Add 5 parts of sulfone type tanning materials and 4 parts of resin type tanning materials at 30 minutes rotary drum again after process time, and then rotary drum processing 60 minutes.At last, with 0.5 part of formic acid leather is acidified to pH 4.4, and rotary drum processing 10 minutes once, 30 minutes once.With 100 parts of water washings after 10 minutes, in the new body lotion that constitutes by 100 parts of water, 4.5 parts of mixing fatting agents, 0.5 part of lanolin base fatting agent based on sulfited fish oil and artificial oil by 55 ℃ of rotary drums processing 40 minutes with leather greasing.Be acidified to pH 3.5 and rotary drum processing 40 minutes with 1.5 parts of dense formic acid then.To dye again and the leather of stuffing with 15 ℃ cold rinse 10 minutes, soft tension is repaired, scraped to stretching, extension then, at the dried overnight that at room temperature suspends.
The gained leather has bright-coloured peony, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 18:
Under 35 ℃, the traditional chrome-tanned bovine leather that with shaving thickness is 1.8 millimeters 1 100 weight portion washed 10 minutes in the rotary drum that 200 parts of water and 0.1 part of formic acid are housed, then in the body lotion that constitutes by 100 parts of water, 2 parts of sodium formates, 1 part of sodium acetate, 1.5 parts of sodium bicarbonates and 1 part of dispersant in 35 ℃ and 120 minutes.Thereby this depickling body lotion has 6.5 pH value.Then with leather at 35 ℃ with 200 parts of water washings 10 minutes.
Under pH 5.9 and 30 ℃, with leather dyeing 45 minutes in by 150 parts of water and 5 parts of new system body lotions that constitute from the dyestuff of embodiment 35h.Be adjusted between the 8.8-9.6 with pH value by part 15 part of 15% sodium carbonate liquor of interpolation, then 50 ℃ of rotary drums processing 120 minutes body lotion.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.5 part of formic acid to reach 5.1 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 30 parts of water and 2 parts of polymerization tanning materials 30 ℃ of retannings 30 minutes.Then body lotion is mixed with 2 parts of hydrophobic fatting agents.Add 5 parts of sulfone type tanning materials and 4 parts of resin type tanning materials at 30 minutes rotary drum again after process time, and then rotary drum processing 60 minutes.At last, with 1.0 parts of formic acid leather is acidified to pH 4.1, and rotary drum processing 10 minutes once, 30 minutes once.With 100 parts of water washings after 10 minutes, in the new body lotion that constitutes by 100 parts of water, 4.5 parts of mixing fatting agents, 0.5 part of lanolin base fatting agent based on sulfited fish oil and artificial oil by 55 ℃ of rotary drums processing 40 minutes with leather greasing.Be acidified to pH 3.5 and rotary drum processing 40 minutes with 1.5 parts of dense formic acid then.To dye again and the leather of stuffing with 15 ℃ cold rinse 10 minutes, soft tension is repaired, scraped to stretching, extension then, at the dried overnight that at room temperature suspends.
The gained leather has dark-brown, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 19:
Under 35 ℃, the traditional chrome-tanned bovine leather that with shaving thickness is 1.8 millimeters 1 100 weight portion washed 10 minutes in the rotary drum that 200 parts of water and 0.1 part of formic acid are housed, then in the body lotion that constitutes by 100 parts of water, 2 parts of sodium formates, 1 part of sodium acetate, 1.5 parts of sodium bicarbonates and 1 part of dispersant in 35 ℃ and 120 minutes.Thereby this depickling body lotion has 6.6 pH value.Then with leather at 35 ℃ with 200 parts of water washings 10 minutes.
Under pH 6.0 and 30 ℃, with leather dyeing 60 minutes in by 150 parts of water and 5 parts of new system body lotions that constitute from the dyestuff of embodiment 12a.Be adjusted between the 8.8-9.8 with pH value by part 18 part of 15% sodium carbonate liquor of interpolation, then 50 ℃ of rotary drums processing 120 minutes body lotion.Then 2 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.5 part of formic acid to reach 5.0 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 30 parts of water and 2 parts of polymerization tanning materials 30 ℃ of retannings 30 minutes.Then body lotion is mixed with 2 parts of hydrophobic fatting agents.Add 5 parts of sulfone type tanning materials and 4 parts of resin type tanning materials at 30 minutes rotary drum again after process time, and then rotary drum processing 60 minutes.At last, with 1.0 parts of formic acid leather is acidified to pH 4.1, and rotary drum processing 10 minutes once, 30 minutes once, 20 minutes twice.With 200 parts of water washings after 10 minutes, in the new body lotion that constitutes by 100 parts of water, 4.5 parts of mixing fatting agents, 0.5 part of lanolin base fatting agent based on sulfited fish oil and artificial oil by 55 ℃ of rotary drums processing 40 minutes with leather greasing.Be acidified to pH 3.4 and rotary drum processing 40 minutes with 1.5 parts of dense formic acid then.To dye again and the leather of stuffing with 15 ℃ cold rinse 10 minutes, soft tension is repaired, scraped to stretching, extension then, at the dried overnight that at room temperature suspends.
The gained leather has black, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.Dyeing recipe 20:
Under 35 ℃, the traditional chrome-tanned bovine leather that with shaving thickness is 1.8 millimeters 1 100 weight portion washed 10 minutes in the rotary drum that 200 parts of water and 0.1 part of formic acid are housed, then in the body lotion that constitutes by 100 parts of water, 2 parts of sodium formates, 1 part of sodium acetate, 1.5 parts of sodium bicarbonates and 1 part of dispersant in 35 ℃ and 120 minutes.This depickling body lotion thereby have 6.4 pH value.Then with leather at 35 ℃ with 200 parts of water washings 10 minutes.
Under pH 5.7 and 30 ℃, with leather dyeing 90 minutes in by 150 parts of water and 4.25 parts of new system body lotions that constitute from the dyestuff of embodiment 17h.Be adjusted between the 8.6-9.3 with pH value by part 16 part of 15% sodium carbonate liquor of interpolation, then 50 ℃ of rotary drums processing 180 minutes body lotion.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.7 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 30 parts of water and 2 parts of polymerization tanning materials 30 ℃ of retannings 30 minutes.Then body lotion is mixed with 2 parts of hydrophobic fatting agents.Add 5 parts of sulfone type tanning materials and 4 parts of resin type tanning materials at 30 minutes rotary drum again after process time, and then rotary drum processing 60 minutes.At last, with 0.5 part of formic acid leather is acidified to pH 4.7, and rotary drum processing 10 minutes once, 30 minutes once.With 200 parts of water 40 ℃ of washings after 10 minutes, in the new body lotion that constitutes by 100 parts of water, 4.5 parts of mixing fatting agents, 0.5 part of lanolin base fatting agent based on sulfited fish oil and artificial oil by 55 ℃ of rotary drums processing 40 minutes with leather greasing.Be acidified to pH 3.7 and rotary drum processing 40 minutes with 1.5 parts of dense formic acid then.To dye again and the leather of stuffing with 15 ℃ cold rinse 10 minutes, soft tension is repaired, scraped to stretching, extension then, at the dried overnight that at room temperature suspends.
The gained leather has black, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 21:
Under 35 ℃, the traditional chrome-tanned bovine leather that with shaving thickness is 1.8 millimeters 1 100 weight portion washed 10 minutes in the rotary drum that 200 parts of water and 0.1 part of formic acid are housed, then in the body lotion that constitutes by 100 parts of water, 2 parts of sodium formates, 1 part of sodium acetate, 1.5 parts of sodium bicarbonates and 1 part of dispersant in 35 ℃ and 120 minutes.Thereby this depickling body lotion has 6.4 pH value.Then with leather at 35 ℃ with 200 parts of water washings 10 minutes.
Under pH 5.4 and 30 ℃, with leather dyeing 45 minutes in by 150 parts of water and 10 parts of new system body lotions that constitute from the dyestuff of embodiment 25.Be adjusted between the 8.4-9.1 with pH value by part 20 part of 15% sodium carbonate liquor of interpolation, then 50 ℃ of rotary drums processing 120 minutes body lotion.Then 2 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.6 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 30 parts of water and 2 parts of polymerization tanning materials 30 ℃ of retannings 30 minutes.Then body lotion is mixed with 2 parts of hydrophobic fatting agents.Add 5 parts of sulfone type tanning materials and 4 parts of resin type tanning materials at 30 minutes rotary drum again after process time, and then rotary drum processing 60 minutes.At last, with 0.5 part of formic acid leather is acidified to pH 4.7, and rotary drum processing 10 minutes once, 30 minutes once.With 200 parts of water 40 ℃ of washings after 10 minutes, in the new body lotion that constitutes by 100 parts of water, 4.5 parts of mixing fatting agents, 0.5 part of lanolin base fatting agent based on sulfited fish oil and artificial oil by 55 ℃ of rotary drums processing 40 minutes with leather greasing.Be acidified to pH 3.7 and rotary drum processing 40 minutes with 1.5 parts of dense formic acid then.To dye again and the leather of stuffing 15 ℃ with cold rinse 15 minutes, stretch then, the dried overnight that at room temperature suspends, repair, scrape soft tension.
The gained leather has aterrimus, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 22:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then by 150 parts of water, 2 parts of dispersants and 10 parts of body lotions that constitute from the dyestuff of embodiment 32 pH 4.3 and 30 ℃ of following dyeing 60 minutes.Add 27 part of 15% sodium carbonate liquor by part then so that the pH value of body lotion reaches between 8.7 to 9.3 and this pH value of maintenance in the rotary drum process at 180 minutes at 40 ℃.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.2 pH value.Part b as dyeing recipe 1) carries out retanning/stuffing/mechanically actuated described in.
The gained leather has aterrimus, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 23:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use the body lotions that constitute from the dyestuff of embodiment 40b by 150 parts of water and 10 parts in pH 4.3 and 30 ℃ dyeing 60 minutes down then.Add 27 part of 15% sodium carbonate liquor by part then so that the pH value of body lotion reaches between 8.7 to 9.3 and this pH value of maintenance in the rotary drum process at 180 minutes at 40 ℃.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 0.7 part of formic acid to reach 4.3 pH value.Part b as dyeing recipe 1) carries out retanning/stuffing/mechanically actuated described in.
The gained leather has dark-brown, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 24:
Under 35 ℃, the traditional chrome-tanned bovine leather that with shaving thickness is 1.8 millimeters 1 100 weight portion washed 10 minutes in the rotary drum that 200 parts of water and 0.1 part of formic acid are housed, then in the body lotion that constitutes by 100 parts of water, 2 parts of sodium formates, 1 part of sodium acetate, 1.5 parts of sodium bicarbonates and 1 part of dispersant in 35 ℃ and 120 minutes.Thereby this depickling body lotion has 6.4 pH value.Then with leather at 35 ℃ with 200 parts of water washings 10 minutes.
Under pH6.1 and 30 ℃, with leather dyeing 60 minutes in by 150 parts of water and 4.25 parts of new system body lotions that constitute from the dyestuff of embodiment 42g.Be adjusted between the 8.5-9.1 with pH value by part 3 part of 15% sodium carbonate liquor of interpolation, then 50 ℃ of rotary drums processing 180 minutes body lotion.Then 4 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 1.5 parts of formic acid to reach 4.3 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 30 parts of water and 2 parts of polymerization tanning materials 30 ℃ of retannings 30 minutes.Then body lotion is mixed with 2 parts of hydrophobic fatting agents.Add 5 parts of sulfone type tanning materials and 4 parts of resin type tanning materials at 30 minutes rotary drum again after process time, and then rotary drum processing 60 minutes.At last, leather is acidified to pH 3.8, and rotary drum is processed 10 minutes once, 30 minutes three times with 2.0 parts of formic acid.With 200 parts of water 40 ℃ of washings after 10 minutes, in the new body lotion that constitutes by 100 parts of water, 4.5 parts of mixing fatting agents, 0.5 part of lanolin base fatting agent based on sulfited fish oil and artificial oil by 55 ℃ of rotary drums processing 40 minutes with leather greasing.Be acidified to pH 3.3 and rotary drum processing 40 minutes with 1.5 parts of dense formic acid then.To dye again and the leather of stuffing with 15 ℃ cold rinse 15 minutes, stretch then, reduce pressure, the dried overnight that at room temperature suspends, repair, scrape soft tension.
The gained leather has dark-brown, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 25:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use the body lotions that constitute from the dyestuff of embodiment 43a by 150 parts of water and 4.25 parts in pH 4.2 and 30 ℃ dyeing 60 minutes down then.Add 30 part of 15% sodium carbonate liquor so that the pH value of body lotion reaches between 8.5 to 9.4 and this pH value of maintenance in the rotary drum process at 180 minutes at 40 ℃ by part.Then 2 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 1.4 parts of formic acid to reach 4.0 pH value.Part b as dyeing recipe 1) carries out retanning/stuffing/mechanically actuated described in.
The gained leather has brown, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 26:
Under 35 ℃, the traditional chrome-tanned bovine leather that with shaving thickness is 1.8 millimeters 1 100 weight portion washed 10 minutes in the rotary drum that 200 parts of water and 0.1 part of formic acid are housed, then in the body lotion that constitutes by 100 parts of water, 2 parts of sodium formates, 1 part of sodium acetate, 1.5 parts of sodium bicarbonates and 1 part of dispersant in 35 ℃ and 120 minutes.Thereby this depickling body lotion has 6.2 pH value.Then with leather at 35 ℃ with 200 parts of water washings 10 minutes.
Under pH5.3 and 30 ℃, with leather dyeing 60 minutes in by 150 parts of water and 11.5 parts of new system body lotions that constitute from the dyestuff of embodiment 1c.Be adjusted between the 8.8-9.3 with pH value by part 28 part of 15% sodium carbonate liquor of interpolation, then 50 ℃ of rotary drums processing 180 minutes body lotion.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 1.0 parts of formic acid to reach 4.5 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 30 parts of water and 2 parts of polymerization tanning materials 30 ℃ of retannings 30 minutes.Then body lotion is mixed with 2 parts of hydrophobic fatting agents.Add 5 parts of sulfone type tanning materials and 4 parts of resin type tanning materials at 30 minutes rotary drum again after process time, and then rotary drum processing 60 minutes.At last, leather is acidified to pH 3.8, and rotary drum is processed 10 minutes once, 30 minutes three times with 2.0 parts of formic acid.With 200 parts of water 40 ℃ of washings after 10 minutes, in the new body lotion that constitutes by 100 parts of water, 4.5 parts of mixing fatting agents, 0.5 part of lanolin base fatting agent based on sulfited fish oil and artificial oil by 55 ℃ of rotary drums processing 40 minutes with leather greasing.Be acidified to pH 4.0 and rotary drum processing 40 minutes with 1.5 parts of dense formic acid then.To dye again and the leather of stuffing with 15 ℃ cold rinse 15 minutes, stretch then, reduce pressure, the dried overnight that at room temperature suspends, repair, scrape soft tension.
The gained leather has aterrimus, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 27:
Under 35 ℃, the traditional chrome-tanned bovine leather that with shaving thickness is 1.8 millimeters 1 100 weight portion washed 10 minutes in the rotary drum that 200 parts of water and 0.1 part of formic acid are housed, then in the body lotion that constitutes by 100 parts of water, 2 parts of sodium formates, 1 part of sodium acetate, 1.5 parts of sodium bicarbonates and 1 part of dispersant in 35 ℃ and 120 minutes.Thereby this depickling body lotion has 6.2 pH value.Then with leather at 35 ℃ with 200 parts of water washings 10 minutes.
Under pH 5.3 and 30 ℃, with leather dyeing 60 minutes in by 150 parts of water and 14.3 parts of new system body lotions that constitute from the dyestuff of embodiment 6c.Be adjusted between the 8.7-9.3 with pH value by part 28 part of 15% sodium carbonate liquor of interpolation, then 50 ℃ of rotary drums processing 180 minutes body lotion.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 1.0 parts of formic acid to reach 4.6 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 30 parts of water and 2 parts of polymerization tanning materials 30 ℃ of retannings 30 minutes.Then body lotion is mixed with 2 parts of hydrophobic fatting agents.Add 5 parts of sulfone type tanning materials and 4 parts of resin type tanning materials at 30 minutes rotary drum again after process time, and then rotary drum processing 60 minutes.At last, leather is acidified to pH 4.0, and rotary drum is processed 10 minutes once, 30 minutes three times with 1.8 parts of formic acid.With 200 parts of water 40 ℃ of washings after 10 minutes, in the new body lotion that constitutes by 100 parts of water, 4.5 parts of mixing fatting agents, 0.5 part of lanolin base fatting agent based on sulfited fish oil and artificial oil by 55 ℃ of rotary drums processing 40 minutes with leather greasing.Be acidified to pH 3.3 and rotary drum processing 40 minutes with 1.5 parts of dense formic acid then.To dye again and the leather of stuffing with 15 ℃ cold rinse 15 minutes, stretch then, reduce pressure, the dried overnight that at room temperature suspends, repair, scrape soft tension.
The gained leather has aterrimus, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 28:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then by 150 parts of water, 2 parts of dispersants and 11.5 parts of body lotions that constitute from the dyestuff of embodiment 6d pH 4.3 and 30 ℃ of following dyeing 60 minutes.Add 30 part of 15% sodium carbonate liquor in 180 minutes rotary drum process, the pH value is remained between 8.8 to 9.2 by part at 40 ℃.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 1.0 parts of formic acid to reach 4.4 pH value.Part b as dyeing recipe 1) carries out retanning/stuffing/mechanically actuated described in.
The gained leather has aterrimus, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 29:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then 150 parts of water, 2 parts of dispersants and 14.3 parts from the dyestuff of embodiment 9f in pH 4.3 and 30 ℃ dyeing 60 minutes down.Keep between 8.7 to 9.2 at 40 ℃ with the pH value that in 180 minutes rotary drum process, makes body lotion by part 30 part of 15% sodium carbonate liquor of interpolation.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 1.0 parts of formic acid to reach 4.5 pH value.Part b as dyeing recipe 1) carries out retanning/stuffing/mechanically actuated described in.
The gained leather has aterrimus, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 30:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use the body lotions that constitute from the dyestuff of embodiment 1f by 150 parts of water and 11.5 parts in pH 4.3 and 30 ℃ dyeing 60 minutes down then.In 180 minutes rotary drum process, add 30 part of 15% sodium carbonate liquor so that the pH value of body lotion remains between 8.8 to 9.4 at 40 ℃ by part, thus fixed dye.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 1.0 parts of formic acid to reach 4.6 pH value.Part b as dyeing recipe 1) carries out retanning/stuffing/mechanically actuated described in.
The gained leather has aterrimus, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 31:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use the body lotions that constitute from the dyestuff of embodiment 12q by 150 parts of water and 14.3 parts in pH 4.3 and 30 ℃ dyeing 60 minutes down then.In 180 minutes rotary drum process, add 30 part of 15% sodium carbonate liquor so that the pH value of body lotion remains between 8.6 to 9.3 at 40 ℃ by part, thus fixed dye.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 1.0 parts of formic acid to reach 4.6 pH value.Part b as dyeing recipe 1) carries out retanning/stuffing/mechanically actuated described in.
The gained leather has aterrimus, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 32:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Then by the pH value of part adding the new body lotion that 30 part of 15% sodium carbonate liquor will be made of from the dyestuff of embodiment 12s 150 parts of water, 2 parts of dispersants and 8 parts be adjusted to immediately＞8.5, and in 220 minutes rotary drum process 40 ℃ the pH value remained on 8.7 to 9.2 between with fixed dye.Then 3 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 1.0 parts of formic acid to reach 4.5 pH value.
Part b as dyeing recipe 1) carries out retanning/stuffing/mechanically actuated described in.
The gained leather has aterrimus, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 33:
Under 35 ℃, the traditional chrome-tanned bovine leather that with shaving thickness is 1.8 millimeters 1 100 weight portion washed 10 minutes in the rotary drum that 200 parts of water and 0.1 part of formic acid are housed, then in the body lotion that constitutes by 100 parts of water, 2 parts of sodium formates, 1 part of sodium acetate, 1.5 parts of sodium bicarbonates and 1 part of dispersant in 35 ℃ and 120 minutes.Thereby this depickling body lotion has 6.4 pH value.Then with leather at 35 ℃ with 200 parts of water washings 10 minutes.
To be adjusted to immediately by the pH value that 150 parts of water and 8 parts of dyestuffs from embodiment 12 constitute the new system body lotion by part adding 23 part of 15% sodium carbonate liquor＞8.5, and in 240 minutes rotary drum process 50 ℃ remain on 8.7 to 9.5 between with fixed dye.Then 4 times 40 ℃ in 200 parts of water the washing 10 minutes.Add 200 parts of water and 1.1 parts of formic acid to reach 4.2 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 30 parts of water and 2 parts of polymerization tanning materials 30 ℃ of retannings 30 minutes.Then body lotion is mixed with 2 parts of hydrophobic fatting agents.Add 5 parts of sulfone type tanning materials and 4 parts of resin type tanning materials at 30 minutes rotary drum again after process time, and then rotary drum processing 60 minutes.At last, leather is acidified to pH 3.8, and rotary drum is processed 10 minutes once, 30 minutes three times with 2.0 parts of formic acid.With 200 parts of water 40 ℃ of washings after 10 minutes, in the new body lotion that constitutes by 100 parts of water, 4.5 parts of mixing fatting agents, 0.5 part of lanolin base fatting agent based on sulfited fish oil and artificial oil by 55 ℃ of rotary drums processing 40 minutes with leather greasing.Be acidified to pH 3.3 and rotary drum processing 40 minutes with 1.5 parts of dense formic acid then.To dye again and the leather of stuffing with 15 ℃ cold rinse 15 minutes, stretch then, reduce pressure, the dried overnight that at room temperature suspends, repair, scrape soft tension.
The gained leather has aterrimus, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 34:
Under 30 ℃, with shaving thickness 1.0 millimeters 1 100 weight portion the traditional organic ox-hide leather washing 20 minutes in the rotary drum that 200 parts of water are housed of tanning.Use then by 150 parts of water, 2 parts of dispersants and 7 parts of body lotions that constitute from the dyestuff of embodiment 12u pH 4.3 and 30 ℃ of following dyeing 60 minutes.In 200 minutes rotary drum process, add 30 part of 15% sodium carbonate liquor so that the pH value of body lotion remains between 8.6 to 9.3 at 40 ℃ by part, thus fixed dye.After changing body lotion, add 200 parts of water and 1.0 parts of formic acid so that the pH value is made as 4.5.Part b as dyeing recipe 1) carries out retanning/stuffing/mechanically actuated described in.
The gained leather has aterrimus, and has excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Dyeing recipe 35:
Under 35 ℃, the traditional chrome-tanned bovine leather that with shaving thickness is 1.8 millimeters 1 100 weight portion washed 10 minutes in the rotary drum that 200 parts of water and 0.1 part of formic acid are housed, then in the body lotion that constitutes by 100 parts of water, 2 parts of sodium formates, 1 part of sodium acetate, 1.5 parts of sodium bicarbonates and 1 part of dispersant in 35 ℃ and 120 minutes.Thereby this depickling body lotion has 6.4 pH value.Then with leather at 35 ℃ with 200 parts of water washings 10 minutes.
Under pH 6.3 and 30 ℃, with leather dyeing 60 minutes in by 150 parts of water and 7 parts of new system body lotions that constitute from the dyestuff of embodiment 13n.Be adjusted between the 8.7-9.5 with pH value by part 23 part of 15% sodium carbonate liquor of interpolation body lotion, thus fixed dye, then 50 ℃ of rotary drums processing 210 minutes.Body lotion adds 200 parts of water and 1.0 parts of formic acid the pH value is made as 4.3 after changing.
With the leather of dyeing thus in the new system body lotion that constitutes by 30 parts of water and 2 parts of polymerization tanning materials 30 ℃ of retannings 30 minutes.Then body lotion is mixed with 2 parts of hydrophobic fatting agents.Add 5 parts of sulfone type tanning materials and 4 parts of resin type tanning materials at 30 minutes rotary drum again after process time, and then rotary drum processing 60 minutes.At last, leather is acidified to pH 3.8, and rotary drum is processed 10 minutes once, 30 minutes three times with 2.0 parts of formic acid.With 200 parts of water 40 ℃ of washings after 10 minutes, in the new body lotion that constitutes by 100 parts of water, 4.5 parts of mixing fatting agents, 0.5 part of lanolin base fatting agent based on sulfited fish oil and artificial oil by 55 ℃ of rotary drums processing 40 minutes with leather greasing.Be acidified to pH 3.3 and rotary drum processing 40 minutes with 1.5 parts of dense formic acid then.To dye again and the leather of stuffing with 15 ℃ cold rinse 15 minutes, stretch then, reduce pressure, the dried overnight that at room temperature suspends, repair, scrape soft tension.
Dyeing recipe 36:
Under 35 ℃, the traditional chrome-tanned bovine leather that with shaving thickness is 1.8 millimeters 1 100 weight portion washed 10 minutes in the rotary drum that 300 parts of water are housed, then in the body lotion that constitutes by 100 parts of water, 2 parts of sodium formates, 1 part of sodium acetate and 2.2 parts of sodium bicarbonates in 40 ℃ and 120 minutes.Thereby this depickling body lotion has 7.2 pH value.This depickling body lotion and 10.5 parts of dyestuff 12bj are mixed be incorporated in pH6.9 and 40 ℃ dyeing 30 minutes down.Be adjusted between the 9.2-9.7 with pH value by part 8 parts of sodium carbonate of interpolation, then 40 ℃ of rotary drums processing 75 minutes body lotion.Twice at 40 ℃ of washing operations that carry out 20 minutes in 300 parts of water then.Add 200 parts of water and 1.2 parts of formic acid to reach 3.9 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 100 parts of water and 2 parts of polymerization tanning materials 30 ℃ of retannings 30 minutes.Then body lotion is mixed with 2 parts of hydrophobic fatting agents.Add 5 parts of sulfone type tanning materials and 4 parts of resin type tanning materials at 30 minutes rotary drum again after process time, and then rotary drum processing 60 minutes.With the retanning body lotion with 4.5 parts based on sulfited fish oil and artificial oil mix fatting agent and 0.5 part of lanolin base fatting agent mixes, and by 55 ℃ of rotary drums processing 40 minutes with leather greasing.Be acidified to pH 3.6 and rotary drum processing 45 minutes with 1.6 parts of dense formic acid then.To dye again and the leather of stuffing with 300 parts 20 ℃ cold water washing 10 minutes, soft tension is repaired, scraped to stretching, extension then 70 ℃ of decompressions, the dried overnight that at room temperature suspends.
The gained leather be sooty black and have excellent washable, sweat proof, anti-wiping and anti-oozing and move fastness.
Carry out the described dyeing of table 19 in a comparable manner.
Table 19
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
1a 4 5 Black
1b 11 7 Black
1b 26 14.1 Black
1c 4 6.7 Black
1d 19 11.3 Black
1e 30 6.4 Black
1f 19 9.5 Black
2a 35 7.9 Red
2b 5 4.7 Blue
2c 6 5.8 Blue
2d 9 18.6 Red
2e 25 14.6 Blue
2f 12 12.4 Blue
2g 34 12.0 Purple
2h 35 7.9 Blue
2i 26 18.6 Blue
2j 4 14.6 Blue
2k 19 12.4 Blue
3 30 12.0 Purple
4a 31 6.3 Dark-brown
5a 34 7.8 Brown
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
6a 9 17.4 Blue
6b 1 5.2 Black
6b 16 8.3 Black
6c 15 8.8 Black
6d 13 8.9 Black
6d 17 12.0 Black
6e 9 17.4 Blue
6f 9 17.4 Blue
6g 9 17.4 Blue
6h 9 17.4 Red
7 18 6.7 Blue
8 21 9.2 Blue
9a 2 17.1 Red
9b 17 11.4 Red
9c 14 9.5 Black
9c 22 16.7 Black
9d 33 15.4 Brown
9e 33 15.4 Black
9f 34 4.9 Black
9g 2 17.1 Red
9h 14 9.5 Black
10 24 7.9 Blue
11a 27 12.0 Purplish red
11b 21 10.2 Purplish red
12a 3 28 34 21 2.3 8.4 17.9 10.0 Black black black black
12b 5 23 32 18 27 33 2.4 8.4 16.9 4.7 10.5 18.7 Black black black black black black
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
12c 6 16 9.8 9.8 The bottle green bottle green
12d 1 29 18.1 4.6 The bottle green bottle green
12e 20 3.3 Bottle green
12f 35 11.7 Bottle green
12g 7 15.4 Bottle green
12h 8 24 5.0 5.2 Green
12i 7 7 17 2.7 15.4 5.1 Bottle green bottle green bottle green
12j 4 10 31 2.7 15.4 5.1 Black black black
12k 12 19 10.0 10.0 Black black
12l 15 15.1 Green
12m 26 8.8 Black
12n 15 15.1 Black
12o 26 8.8 Bottle green
12p 13 6.5 Black
12q 14 8.3 Black
12r 22 15.1 Black
12s 1 8.3 Black
12t 3 12.0 Black
12u 11 3.8 Black
12v 22 4.7 Black
12z 33 9.0 Bottle green
12aa 13 7.6 Navy blue
12ab 6 6.2 Navy blue
12ac 2 7.9 Navy blue
12ad 7 5.3 Navy blue
12ae 9 8.8 Blue
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
12af 8 7.4 Black
12ag 4 7.9 Black
12ah 14 8.8 Black
12ai 5 10.1 Black
12aj 23 5.9 Black
12ak 17 14.3 Black
12al 31 13.2 Black
12am 1 19.3 Black
12an 4 1.8 Black
12ao 11 5.7 Green
12ap 28 3.8 Green
12aq 20 6.4 Green
12ar 13 12.5 Black
12as 26 10.5 Black
12at 35 7 19 36 7.7 10.2 14.3 3.5 Black black black black
12au 15 4.6 Black
12av 16 2.3 Black
12aw 6 3.1 Green
12ax 34 8.6 Black
12ay 18 17.3 Black
12az 31 2.8 Black
12ba 8 5.1 Black
12bb 10 6.2 Black
12bc 33 11.3 Black
12bd 1 7.1 Bottle green
12be 25 13.7 Bottle green
12bf 29 18.1 Bottle green
12bg 21 4.4 Bottle green
12bh 12 3.5 Bottle green
12bi 17 6.2 Green
12bj 2 2.1 Black
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
12bk 23 3.6 Green
12bl 30 5.2 Black
12bm 27 8.9 Black
12bn 14 5.6 Green
12bo 32 3.1 Green
12bp 22 14.5 Green
12bq 24 9.6 Black
12br 9 5.4 Black
12bs 7 7.5 Black
12bt 5 2.9 Black
12bu 3 9.8 Black
12bv 19 4.9 Black
12bw 8 1.8 Black
12bx 10 5.7 Black
12by 33 3.8 Blue
12bz 1 6.4 Blue
12ca 25 12.5 Blue
12cb 29 10.5 Blue
12cc 21 7.7 Blue
12cd 12 4.6 Blue
12ce 17 2.3 Blue
12cf 2 3.1 Blue
12cg 23 8.6 Blue
12ch 30 17.3 Blue
12ci 27 2.8 Blue
12cj 14 5.1 Blue
12ck 32 6.2 Blue
12cl 22 12.5 Blue
12cm 24 10.5 Blue
12cn 9 7.7 Blue
12co 7 4.6 Blue
12cp 5 2.3 Blue
12cq 3 3.1 Blue
12cr 19 8.6 Blue
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
12cs 35 17.3 Blue
12ct 15 2.8 Blue
12cu 16 5.1 Blue
12cv 6 6.2 Blue
12cw 34 11.3 Blue
12cx 18 7.1 Blue
12cy 31 13.7 Blue
12cz 4 18.1 Blue
12da 11 4.4 Blue
12db 28 3.5 Blue
12dc 20 6.2 Blue
12dd 13 2.1 Blue
12de 26 3.6 Green
12df 35 5.2 Green
12dg 15 8.9 Black
12dh 16 5.6 Black
12di 6 3.1 Black
12dj 25 14.5 Black
12dk 29 9.6 Black
12dl 21 5.4 Green
12dm 12 7.5 Green
12dn 17 2.9 Green
12do 2 9.8 Black
12dp 23 4.9 Black
12dq 30 1.8 Black
12dr 27 5.7 Black
12ds 14 3.8 Black
12dt 32 6.4 Black
12du 22 12.5 Black
12dv 24 10.5 Black
12dw 9 7.7 Blue
12dx 7 4.6 Blue
12dy 5 2.3 Blue
12dz 3 3.1 Blue
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
12ea 19 8.6 Blue
12eb 35 17.3 Blue
12ec 15 2.8 Blue
12ed 16 5.1 Blue
12ee 6 6.2 Blue
12ef 14 5.6 Blue
12eg 32 3.1 Blue
12eh 22 14.5 Blue
12ei 24 9.6 Blue
12ej 9 5.4 Blue
12ek 7 7.5 Blue
12el 5 2.9 Blue
12em 3 1.8 Blue
12en 19 5.7 Blue
12eo 35 3.8 Blue
12ep 15 6.4 Blue
12eq 16 12.5 Blue
12er 6 10.5 Blue
12es 34 7.7 Blue
12et 18 4.6 Blue
12eu 31 2.3 Blue
12ev 4 3.1 Blue
12ew 11 8.6 Blue
12ex 28 17.3 Blue
12ey 20 2.8 Blue
12ez 13 5.1 Blue
12fa 15 6.2 Blue
12fb 16 11.3 Blue
12fc 6 7.1 Blue
12fd 14 13.7 Blue
12fe 32 18.1 Blue
12ff 22 7.7 Blue
12fg 24 4.6 Green
12fh 9 2.3 Green
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
12fi 7 3.1 Black
12fj 5 8.6 Black
12fk 3 17.3 Black
12fl 19 2.8 Black
12fm 34 5.1 Black
12fn 18 6.2 Green
12fo 31 5.6 Green
12fp 4 3.1 Green
12fq 11 14.5 Black
12fr 28 9.6 Black
12fs 20 5.4 Black
12ft 13 8.2 Black
12fu 15 1.9 Black
12fv 16 2.6 Black
12fw 6 14.3 Black
12fx 5 6.7 Black
12fy 1 5.9 Blue
12fz 14 3.2 Blue
12ga 36 4.6 Blue
12gb 15 17.9 Blue
12gc 27 6.8 Blue
12gd 4 2.4 Blue
12ge 20 10.1 Black
12gf 9 6.6 Black
12gg 3 7.5 Black
12gh 33 3.5 Black
12gi 15 11.2 Black
12gj 7 8.6 Black
12gk 11 3.6 Blue
12gl 2 19 Blue
12gm 4 10.9 Blue
12gn 8 5.6 Blue
12go 15 6.1 Blue
12gp 16 4.8 Blue
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
12gq 7 3.1 Black
12gr 13 9.9 Black
12gs 21 12.6 Black
12gt 30 13.5 Black
12gu 36 14.8 Black
12gv 25 2.8 Black
12gw 15 29 15.1 4.8 Black black
12gz 26 8.8 Black
12ha 15 8 15.1 5.5 Black black
12hb 26 11 8.8 6.1 Black black
12hc 13 24 6.5 11.2 Black black
12hd 14 35 8.3 4.1 Black black
12he 22 16 15.1 7.5 Black black
12hf 1 33 8.3 4.6 Black black
12hh 3 27 12.0 6.1 Black black
12hi 11 3.8 Black
12hj 22 4.7 Black
12hk 33 9.0 Black
12hl 13 7.6 Black
12hm 6 6.2 Black
12hn 2 7.9 Black
12ho 7 5.3 Black
12hp 9 8.8 Black
12hq 8 7.4 Black
12hr 4 7.9 Black
12hs 14 8.8 Black
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
12ht 5 10.1 Blue
12hu 23 5.9 Blue
12bv 17 14.3 Blue
12hw 31 13.2 Black
13a 2 6 11 17 2.3 8.4 17.9 10.0 Black black black black
13b 9 25 21 21 21 2.4 8.4 4.7 10.5 18.7 Black black black black black
13c 25 11.0 Bottle green
13d 17 10.8 Bottle green
13e 30 17.0 Bottle green
13f 34 11.5 Bottle green
13g 7 11.2 Bottle green
13h 3 24 8.4 8.4 Black black
13i 16 8.4 Bottle green
13j 27 11.4 Black
13k 10 10 6.6 13.2 Black black
13l 12 15.1 Green
13m 15 8.8 Black
13n 15 8.8 Black
13o 1 8.2 Bottle green
13p 19 2.9 Black
13q 21 4.5 Black
13r 4 6.7 Black
13s 20 15.0 Black
13t 5 4.6 Black
13u 17 6.7 Black
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
13v 19 8.2 Black
13z 8 2.9 Bottle green
13aa 9 4.5 Navy blue
13ab 10 6.7 Navy blue
13ac 11 7.7 Navy blue
13ad 18 9.1 Navy blue
13ae 16 8.3 Blue
13af 14 5.9 Black
13ag 15 11.0 Black
13ah 14 8.8 Black
13ai 6 10.9 Black
13aj 7 11.1 Navy blue
13ak 15 9.7 Navy blue
13al 12 8.4 Bottle green
13am 13 7.6 Black
13an 23 5.9 Black
13ao 17 14.3 Black
13ap 31 13.2 Black
13aq 1 19.3 Black
13ar 4 1.8 Black
13as 11 5.7 Green
13at 28 3.8 Green
13au 20 6.4 Green
13av 13 12.5 Black
13aw 26 10.5 Black
13ax 35 7.7 Black
13ay 15 4.6 Black
13az 16 2.3 Black
13ba 6 3.1 Black
13bb 34 8.6 Black
13bc 18 17.3 Black
13bd 31 2.8 Black
13be 8 5.1 Black
13bf 10 6.2 Black
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
13bg 33 11.3 Black
13bh 1 7.1 Bottle green
13bi 25 13.7 Bottle green
13bj 29 18.1 Bottle green
13bk 21 4.4 Bottle green
13bl 12 3.5 Bottle green
13bm 17 6.2 Bottle green
13bn 2 2.1 Black
13bo 23 3.6 Bottle green
13bp 30 5.2 Green
13bq 27 8.9 Black
13br 14 5.6 Green
13bs 32 3.1 Green
13bt 22 14.5 Green
13bu 24 9.6 Black
13bv 9 5.4 Black
13bw 7 7.5 Black
13bx 5 2.9 Black
13by 3 9.8 Black
13bz 19 4.9 Black
13ca 8 1.8 Black
13cb 10 5.7 Black
13cc 33 3.8 Blue
13cd 1 6.4 Blue
13ce 25 12.5 Blue
13cf 29 10.5 Blue
13cg 21 7.7 Blue
13ch 12 4.6 Blue
13ci 17 2.3 Blue
13cj 2 3.1 Blue
13ck 23 8.6 Blue
13cl 30 17.3 Blue
13cm 27 2.8 Blue
13cn 14 5.1 Blue
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
13co 32 6.2 Blue
13cp 22 12.5 Blue
13cq 24 10.5 Blue
13cr 9 7.7 Blue
13cs 7 4.6 Blue
13ct 5 2.3 Blue
13cu 3 3.1 Blue
13cv 19 8.6 Blue
13cw 35 17.3 Blue
13cx 15 2.8 Blue
13cy 16 5.1 Blue
13cz 6 6.2 Blue
13da 34 11.3 Blue
13db 18 7.1 Blue
13dc 31 13.7 Blue
13dd 4 18.1 Blue
13de 11 4.4 Blue
13df 28 3.5 Blue
13dg 20 6.2 Blue
13dh 13 2.1 Green
13di 26 3.6 Green
13dj 35 5.2 Black
13dk 15 8.9 Black
13dl 16 5.6 Black
13dm 6 3.1 Black
13dn 25 14.5 Black
13do 29 9.6 Green
13dp 21 5.4 Green
13dq 12 7.5 Green
13dr 17 2.9 Black
13ds 2 9.8 Black
13dt 23 4.9 Black
13du 30 1.8 Black
13dv 27 5.7 Black
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
13dw 14 3.8 Black
13dx 32 6.4 Black
13dy 22 12.5 Black
13dz 24 10.5 Blue
13ea 9 7.7 Blue
13eb 7 4.6 Blue
13ec 5 2.3 Blue
13ed 3 3.1 Blue
13ee 19 8.6 Blue
13ef 35 17.3 Blue
13eg 15 2.8 Blue
13eh 16 5.1 Blue
13ei 6 6.2 Blue
13ej 14 5.6 Blue
13ek 32 3.1 Blue
13el 22 14.5 Blue
13em 24 9.6 Blue
13en 9 5.4 Blue
13eo 7 7.5 Blue
13ep 5 2.9 Blue
13eq 3 1.8 Blue
13er 19 5.7 Blue
13es 35 3.8 Blue
13et 15 6.4 Blue
13eu 16 12.5 Blue
13ev 6 10.5 Blue
13ew 34 7.7 Blue
13ex 18 4.6 Blue
13ey 31 2.3 Blue
13ez 4 3.1 Blue
13fa 11 8.6 Blue
13fb 28 17.3 Blue
13fc 20 2.8 Blue
13fd 13 5.1 Blue
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
13fe 15 6.2 Blue
13ff 16 11.3 Blue
13fg 6 7.1 Blue
13fh 14 13.7 Blue
13fi 32 18.1 Blue
13fj 22 7.7 Green
13fk 24 4.6 Green
13fl 9 2.3 Black
13fm 7 3.1 Black
13fn 5 8.6 Black
13fo 3 17.3 Black
13fp 19 2.8 Black
13fq 34 5.1 Green
13fr 18 6.2 Green
13fs 31 5.6 Green
13ft 4 3.1 Black
13fu 11 14.5 Black
13fv 28 9.6 Black
13fw 20 5.4 Black
13fx 13 8.2 Black
13fy 11 8.6 Black
13fz 28 17.3 Black
13ga 20 2.8 Black
13gb 1 5.9 Blue
13gc 14 3.2 Blue
13gd 36 4.6 Blue
13ge 15 17.9 Blue
13gf 27 6.8 Blue
13gg 4 2.4 Blue
13gh 20 10.1 Black
13gi 9 6.6 Black
13gj 3 7.5 Black
13gk 33 3.5 Black
13gl 15 11.2 Black
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
13gm 7 8.6 Black
13gn 11 3.6 Blue
13go 2 19 Blue
13gp 4 10.9 Blue
13gq 8 5.6 Blue
13gr 15 6.1 Blue
13gs 16 4.8 Blue
13gt 7 3.1 Black
13gr 13 9.9 Black
13gs 21 12.6 Black
13gt 30 13.5 Black
13gu 36 14.8 Black
13gv 25 2.8 Black
13gw 15 29 15.1 4.8 Black black
13gz 26 8.8 Black
13ha 15 8 15.1 5.5 Black black
13hb 26 11 8.8 6.1 Black black
13hc 13 24 6.5 11.2 Black black
13hd 14 35 8.3 4.1 Black black
13he 22 16 15.1 7.5 Black black
13hf 1 33 8.3 4.6 Black black
13hh 3 27 12.0 6.1 Black black
13hi 11 3.8 Black
13hj 22 4.7 Black
13hk 33 9.0 Black
13hl 13 7.6 Black
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
13hm 6 6.2 Black
13hn 2 7.9 Black
13ho 7 5.3 Black
13hp 9 8.8 Black
13hq 8 7.4 Black
13hr 4 7.9 Black
13hs 14 8.8 Black
13ht 5 10.1 Blue
13hu 23 5.9 Blue
13hv 17 14.3 Blue
13hw 31 13.2 Black
14 2 6.9 Black
15 3 3.9 Black
16a 8 10.0 Green
16b 22 7.3 Black
16c 16 10.0 Black
16d 24 10.9 Bottle green
16e 30 11.1 Bottle green
16f 28 11.1 Green
16g 23 12.4 Black
16h 31 12.4 Black
16i 26 12.4 Black
16j 15 3.6 Navy blue
16k 27 12.3 Navy blue
17a 13 8.4 Green
17b 28 14.4 Black
17c 32 14.4 Black
17d 35 12.4 Bottle green
17e 34 8.4 Bottle green
17f 33 14.4 Green
17g 4 4 19 19 3.4 13.6 3.4 13.6 Black black black black
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
17h 18 5.8 Black
17i 35 19.8 Black
17j 17 9.7 Green
17k 14 7.6 Navy blue
171 26 17.3 Navy blue
18 16 8.6 Bottle green
19 15 6.8 Bottle green
20 31 5.9 Bottle green
21 29 3.9 Bottle green
22 30 10.0 Bottle green
23 22 7.3 Blue
24 21 10.0 Red
25 18 7.3 Black
26 13 8.2 Brown
27 34 11.1 Brown
28a 33 8.4 Brown
28b 32 7.6 Brown
29a 11 6.9 Brown
29b 2 10.9 Brown
30 1 11.1 Blue
31 5 8.8 Blue
32 4 10.4 Black
33 12 11.2 Red
34a 28 28 28 4.2 8.4 16.8 Brown brown
34b 21 21 21 4.2 8.4 16.8 Dark-brown dark-brown dark-brown
34c 5 8.8 Brown
34d 4 10.4 Brown
34e 12 11.2 Brown
34f 9 18 10.2 10.2 Brown
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
34g 5 7 24 14.4 7.7 14.4 Brown brown
34h 7 5.5 Brown
34i 13 7.7 Dark-brown
34j 29 7.7 Dark-brown
34k 11 9.2 Brown
34l 15 4.9 Brown
34m 9 7.0 Brown
34n 8 6.3 Brown
34o 32 11.1 Brown
34p 14 13.1 Dark-brown
34q 12 12.5 Dark-brown
34r 13 7.8 Brown
34s 27 8.4 Brown
34t 11 7.7 Dark-brown
34u 18 9.1 Light brown
34v 16 8.3 Dark-brown
34z 7 4.6 Brown
34aa 14 5.7 Brown
34ab 21 18.6 Brown
34ac 28 12.2 Brown
35a 14 5.9 Brown
35b 1 1 1 4.2 8.4 16.8 Dark-brown dark-brown dark-brown
35c 6 8.1 Dark-brown
35d 19 5.4 Light brown
35e 2 2 2 27 27 27 7.2 14.4 20 7.2 14.4 20 Rufous rufous rufous rufous rufous rufous
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
35f 33 14.4 Brown
35g 26 12.4 Brown
35h 31 9.4 Dark-brown
35i 34 7.9 Brown
35j 15 8.8 Brown
35k 27 6.3 Brown
35l 22 8.8 Brown
35m 18 8.9 Brown
35n 12 5.7 Light brown
35o 26 8.2 Brown
35p 24 3.9 Brown
35q 29 6.4 Brown
35r 18 5.7 Brown
35s 30 30 26 26 4.1 17.6 4.1 17.6 Brown
35t 28 7.4 Brown
35u 25 8.9 Dark-brown
35v 24 4.7 Light brown
35z 11 4.7 Light brown
35aa 23 8.8 Dark-brown
35ab 11 16.6 Light brown
35ac 12 6.8 Brown
35ad 14 6.8 Brown
35ae 20 7.4 Brown
35af 34 4.8 Brown
35ag 33 4.8 Brown
35ah 18 4.2 Brown
35ai 29 17.9 Brown
36 10 7.4 Brown
37 16 7.4 Brown
38a 20 7.4 Brown
38b 3 8.8 Brown
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
38c 9 16.6 Brown
38d 7 15.4 Brown
38e 6 5.6 Yellowish-brown
38f 4 5.2 Light brown
38g 12 13.3 Dark-brown
38h 10 35 5.6 5.6 Brown
38i 25 16.6 Brown
38j 33 15.4 Brown
38k 34 4.9 Brown
38l 24 7.9 Brown
38m 27 12.0 Brown
38n 31 10.0 Brown
38o 26 7.7 Brown
38p 31 9.2 Brown
38q 34 4.9 Brown
38r 15 7.0 Brown
38s 27 12.4 Brown
38t 22 9.4 Brown
38u 18 7.9 Brown
38v 17 11.3 Brown
38z 3 18.2 Brown
39a 12 8.8 Brown
39b 26 6.3 Brown
39c 23 5.6 Brown
39d 3 8.8 Brown
39e 34 6.4 Brown
39f 12 6.4 Brown
39g 4 5.6 Brown
39h 7 4.4 Brown
39i 8 13.3 Brown
39j 5 20 10.6 10.6 Brown
39k 14 10.2 Brown
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
39l 17 10.2 Brown
39m 34 14.6 Brown
39n 15 7.3 Brown
39o 19 7.3 Brown
39p 17 11.0 Brown
39q 11 9.2 Brown
39r 15 4.9 Brown
39s 9 7.0 Brown
39t 8 6.3 Brown
39u 32 11.1 Brown
39v 18 7.4 Brown
39z 16 11.0 Brown
40a 10 7.4 Brown
40b 20 7.4 Brown
40c 13 8.8 Brown
40d 16 8.4 Brown
40e 17 8.0 Yellowish-brown
40f 21 8.8 Light brown
40g 25 8.9 Dark-brown
40h 24 4.7 Brown
40i 11 7.3 Brown
40j 12 4.7 Brown
40k 24 24 24 4.2 8.4 16.8 Brown brown
40l 29 16.8 Brown
40m 25 12.4 Brown
40n 16 14.1 Brown
40o 34 8.6 Brown
40p 1 12.0 Brown
40q 28 4.2 Brown
40r 22 8.6 Brown
40s 24 9.0 Brown
40t 27 9.0 Brown
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
40u 11 5.9 Brown
40v 2 12.7 Brown
40z 21 4.5 Brown
41a 13 8.8 Brown
41b 9 8.6 Brown
41c 21 9.0 Brown
41d 32 8.8 Brown
41e 30 6.2 Brown
41f 33 8.6 Brown
41g 24 9.0 Brown
41h 29 7.4 Brown
41i 9 9 9 4.2 8.4 16.8 Brown brown
41j 30 16.8 Brown
41k 15 12.4 Brown
41l 14 12.4 Brown
41m 17 14.0 Brown
41n 18 9.8 Brown
410 27 4.2 Brown
41p 24 12.1 Brown
41q 27 12.4 Brown
41r 11 12.4 Brown
41s 13 11.8 Brown
41t 9 14.2 Brown
41u 10 14.0 Brown
42a 12 2.4 Brown
42b 25 4.6 Brown
42c 16 6.8 Dark-brown
42d 31 8.7 Brown
42e 17 19 8.8 8.8 Brown
42f 32 8.6 Dark-brown
42g 25 9.0 Brown
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
42h 14 11.0 Brown
42i 33 8.6 Brown
42j 24 9.0 Brown
42k 16 16 8.8 16.8 Brown
42l 10 14.0 Brown
42m 12 2.4 Brown
42n 4 15.0 Brown
42o 23 18.6 Brown
43a 25 4.6 Brown
43b 16 6.8 Brown
43c 31 8.7 Brown
43d 8 4.4 Brown
43e 5 4.6 Brown
43f 29 5.4 Brown
43g 32 10.8 Brown
43h 11 33 14.1 14.4 Brown
43i 17 12.2 Brown
43j 19 12.2 Brown
43k 7 11.0 Brown
43l 9 12.2 Brown
43m 5 11.0 Brown
43n 22 22 8.8 16.8 Brown
43o 28 2.4 Green
43p 34 4.6 Green
43q 21 4.8 Green
43r 20 8.7 Green
43s 18 18 6.9 15.1 Green
43t 15 12.2 Breen
43u 25 8.7 Green
43v 1 11.0 Brown
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
43z 26 5.4 Green
43aa 14 5.4 Green
43ab 2 11.1 Green
43ac 13 10.0 Green
43ad 27 12.7 Brown
43ae 30 16.8 Brown
43af 11 5.4 Green
43ag 24 11.9 Green
43ah 23 10.5 Green
43ai 29 2.7 Brown
44 15 12.4 Brown
45 14 12.4 Brown
46a 17 14.0 Olive green
46b 18 9.8 Green
46c 10 8.8 Green
46d 21 7.4 Green
46e 32 7.4 Green
46f 13 8.2 Green
46g 4 7.4 Brown
46h 15 5.6 Light brown
46i 21 7.4 Brown
46j 32 7.4 Brown
46k 26 5.6 Brown
46l 23 12.1 Dark-brown
46m 12 14.6 Brown
47a 6 6.8 Green
47b 24 8.7 Brown
47c 11 8.7 Brown
47d 28 2.4 Brown
47e 34 4.6 Brown
47f 16 10.6 Brown
47g 24 10.6 Brown
47h 34 4.8 Brown
47i 33 4.8 Brown
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
47j 18 4.2 Brown
47k 29 17.9 Brown
47l 1 11.0 Brown
47m 10 8.8 Brown
47n 1 11.0 Brown
47o 16 10.6 Brown
47p 24 10.6 Green
47q 2 11.1 Green
47r 19 10.1 Green
47s 10 8.8 Green
47t 20 8.8 Green
47u 16 10.6 Green
47v 24 10.6 Green
47z 10 8.8 Green
47aa 28 2.4 Green
47ab 34 4.6 Green
47ac 10 8.8 Green
47ad 28 2.4 Green
47ae 34 4.6 Green
47af 9 4.8 Green
47ag 32 12.6 Green
47ah 7 11.6 Green
47ai 20 7.8 Green
48 23 12.0 Brown
49a 16 10.6 Brown
49b 24 10.6 Brown
49c 28 10.4 Brown
50a 33 4.8 Rufous
50b 31 16.4 Rust red
50c 29 17.9 Rufous
51 30 12.0 Yellowish-brown
52a 23 7.8 Brown
52b 23 7.8 Brown
52c 30 14.4 Brown
Dyestuff embodiment number Dyeing recipe Parts by weight (%) The leather color
52d 19 7.8 Brown
52e 22 7.8 Brown
53a 27 7.8 Brown
53b 9 6.6 Brown
53c 21 6.6 Brown
53d 14 10.2 Brown
54 17 10.2 Brown
55 34 14.6 Brown
56 15 7.3 Brown
57 19 7.3 Brown
58a 17 11.0 Red
58b 11 9.2 Red
58c 15 4.9 Red
59a 9 7.0 Red
59b 8 6.3 Purplish red
59c 32 11.1 Red
59d 10 7.4 Yellow
59e 20 7.4 Red
59f 13 8.8 Red
59g 16 8.4 Red
59h 17 8.0 Yellowish-brown
59i 21 8.8 Red
59j 25 8.9 Red
59k 24 8.8 Ecru
Goods prescription now with reference to the colouring leather that is used to make most important goods parts (footwear, clothes, automobile, gloves and furniture) illustrates method of the present invention in more detail.Yet method of the present invention is not limited to this 5 kinds of leather parts; For example, the present invention also can make the reptile leather that accessory was removed from office and be used for to suitcase.
In following goods prescription, umber is by weight.All information that provide all relate to commercial materials.About all data of tanning material, water-repelling agent, fatting agent and auxiliary agent all based on the commercially available prod.About the data of dyestuff is based on coloured organic chemistry composition, owing to the total amount of synthesis condition any salt (synthetic salt) that exists and any standard agent that exists.In goods prescriptions, use following abbreviation for the chemicals of wet end method.
The main component of commercial fatting agent (F):
F1: the aqueous emulsion of vegetable oil and sulfited fish oil.
F2: based on the sodium salt of anionic vinyl polymer and the aqueous compositions of non-ionic surface active agent (oleic acid of ethoxylation).
F3: based on the aqueous compositions of the aliphatic acid of modification.
F4: based on the aqueous compositions of the phosphate (comprising fatty alcohol sulphonic acid ester and butyldiglycol) of artificial oil and ethoxylized fatty alcohol.
F5: based on the hydrolysate of bisulfite-reacted fish oil (sodium salt) and chlorosulfonation paraffin oil, the aqueous compositions of the different tridecane of ethoxylation.
F6: based on the sodium salt of sulfonated vegetable oil and the aqueous compositions of modification artificial oil and polymer.
F7: based on the aqueous compositions of sulfated fatty acid ester.
F8: based on the aqueous compositions of non-ionic surface active agent, sulfited oil (sodium salt).
F9: with the surfactant mixture based on paraffin sulphonic acid ester, alkylphosphonate and sulfuric acid mono alkyl ester of the ammonium salt dosage form in solvent/water.
The main component of commercial water-repelling agent (H):
H1: based on the aqueous compositions of paraffin, functional polysiloxanes, N-oleoyl sarcosine sodium salt.
H2: based on the aqueous compositions of paraffin, modified siloxane, N-oleoyl sarcosine sodium salt.
H3: based on the aqueous compositions of paraffin and anion surfactant.
H4: based on the aqueous compositions of functional polysiloxanes and emulsifier system.
H5: based on aqueous compositions with the siloxanes of the salt modification of polyvinyl.
H6: based on aqueous compositions with the functionalized polysiloxanes of anion surfactant.
H7: based on the aqueous compositions of functional polysiloxanes.
H8: based on the aqueous compositions of paraffin and anion surfactant sodium salt.
Hereinafter " mixture " of Shi Yonging be at the mixture that not only refers to aspect tanning material and the auxiliary agent be mixed and made under room temperature and atmospheric pressure by with each component, also comprises by at following short time of temperature and pressure that raises or the mixture that is mixed and made into for a long time.
The main component of commercial retanning agent (G):
G1: the condensation product of the sodium-salt form of phenolsulfonic acid, formaldehyde and aniline.
G2: the aqueous compositions of the sodium salt of the condensation product of phenolsulfonic acid, formaldehyde and aniline.
G3: the sodium-ammonium salt of the condensation product of phenolsulfonic acid, formaldehyde, melamine, urea and aniline and aqueous compositions based on the mixture of the both sexes addition copolymer of acrylic acid and alkaline monomer.
G4: the aqueous compositions of the ammonium salt of the condensation product of phenol, phenolsulfonic acid and formaldehyde.
G5: based on the sodium salt of the condensation product of dihydroxy-diphenyl sulfone, phenolsulfonic acid, urea and formaldehyde.
G6: based on the aqueous solution of the sodium-ammonium salt of the condensation product of dihydroxy-diphenyl sulfone, phenolsulfonic acid, urea and formaldehyde.
G7: the high molecular condensation product based on dihydroxy-diphenyl sulfone, phenolsulfonic acid, urea and formaldehyde of sodium-salt form.
G8: based on the aqueous compositions of the mixture of the low molecular weight condensation product of the sodium-ammonium salt of dihydroxy-diphenyl sulfone, urea and formaldehyde low molecular weight condensation product and diphenyl sulfone and formaldehyde.
G9: based on modified paraffin (C 16-C 34-alkyl sulfonyl chloride) fatty tanning material.
G10: based on the aqueous compositions of the copolymer of acrylic acid and acrylonitrile and amine.
G11: the mixture of naphthalene sulfonic acids-melamine condensation product and hydroxyl methane sulfonates and urea.
G12: the 24 weight % solution of glutaraldehyde in water.
G13: the 50 weight % solution of glutaraldehyde in water.
G14: based on the preparation that contains aqueous solvent (condensation product of formaldehyde and glutaraldehyde) of aldehyde radical polymerization tanning agent.
G15: based on the aqueous compositions of the copolymer of acrylic acid and acrylonitrile.
G16: based on the aqueous compositions of low-molecular-weight polypropylene acid (Mn＜8000, number average).
G17: based on the aqueous compositions of high molecular weight polypropylene acid (Mn＞40000, number average).
G18: based on the aqueous compositions of polymethylacrylic acid.
G19: the aqueous compositions of maleic acid and cinnamic copolymer.
G20: chrome syntans (based on the condensation product mixture of low polysulfones of aromatics and Chroma-Pak).
G21：Tara。
G22: sensitive plant.
G23: chestnut.
G24: Cr with 24 weight % 2O 3Content and 40% basicity gently shelter the chrome tanning material.
G25: the four (liquid preparations of methylol) Phosphonium chloride and sulfate.
G26:4,4-dimethyl-1,3-oxazolidine.
G27:1-azepine-3,7-dioxy two ring-5-ethyl [3.3.0] octanes.
G28: based on the polycondensation product of urea and formaldehyde and mixture based on the polycondensation product of phenol and formaldehyde.
G29: the 30 weight % aqueous solution of formaldehyde.
G30: based on the aluminium hydroxide of 14 weight % (with Al 2O 3Calculate) and the chromic salts of 3 weight % (with Cr 2O 3Calculating) mineral tanning agent mixture.
The main component of commercial auxiliary agent (HM):
HM1: the mixture of hydroxyl methane sulfonates and the sodium salt of the condensation product that forms by naphthalene sulfonic acids, urea and formaldehyde.
HM2: ethoxylated alkylamine (C 16-C 18) mixture.
HM3: the aqueous compositions of the poly-N-vinyl formamide of partial hydrolysis slightly is cationic.
HM4: the aqueous compositions of anion-modified addition copolymer.
HM5: methylolated urea.
HM6: based on the mixture of aromatic sulfonic acid, phenol, formaldehyde and the urea of sodium-salt form.
HM7: the cationic aqueous compositions that contains amino condensation polymer.
According to following internationally recognized standard test fastness:
Perspiration fastness: according to Veslic C4260
Fastness to washing: according to DIN EN ISO 15703
Ooze and move fastness: according to DIN EN ISO 15701 and with DIN EN ISO 15701 classes
Like under 85 ℃ and 95% humidity, store 16 hours under the condition
The degree of anti-wiping the: according to DIN EN ISO 105-X12 (Crockmeter rubs with spun cotton)
And according to DIN EN ISO 11640 (Veslic rubs with felt)
Maeser: according to ASTM D 2099
Penetrometer: according to DIN EN ISO 5403
Water vapour permeability: according to DIN EN ISO 14268
Stiffness: according to DIN EN ISO 5402
Test is pulled out in stitching: according to DIN 5331
Tear strength: according to DIN EN ISO 3377
TENSILE STRENGTH: according to DIN EN ISO 3376
A upper leather prescription
Upper leather prescription 1:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 2.0 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 150 parts of water, 2 parts of sodium formates and 1 part of sodium acetate, mix being incorporated in 40 ℃ and 10 minutes then with 2 parts of sodium bicarbonates.Thereby this depickling body lotion has 7.3 pH value.This depickling body lotion and 4.6 parts of dyestuff 1e are mixed be incorporated in pH 6.8 and 40 ℃ dyeing 30 minutes down.Each a little ground adds altogether 6 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, and leather is added 60 minutes at 40 ℃ of rotary drums.Body lotion uses 300 parts of water with the leather washed twice after changing at every turn, washs altogether 30 minutes.In 30 minutes process, in the body lotion of 300 parts of water by part adding altogether 0.5 part of formic acid to reach 6.5 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 200 parts of water and 5 parts of stuffings and tanning water-repelling agent H5 40 ℃ of retannings 20 minutes.In 20 minutes process, add 0.5 part of formic acid to reach 5.0 pH value.Use 3 parts of polymerization tanning material G15, carried out retanning 30 minutes at 40 ℃.Then the mixture of body lotion with 5 parts of water-repelling agent H2 and 0.3 part of auxiliary agent HM4 mixed.At 60 minutes rotary drum again after process time, each a little ground adds altogether 2.5 parts of formic acid so that the pH value is acidified to 3.7 in 60 minutes process.Then in the new system body lotion that constitutes by 150 parts of water and 0.5 part of formic acid 30 ℃ of rotary drums processing 10 minutes.Add 5 parts of chrome tanning material G24 then with chrome tanning once more 90 minutes.Obtain 3.6 pH value.At last, leather was washed 10 minutes at 30 ℃ in 300 parts of water, this washing is carried out twice.
Dyeing thus, retanning and hydrophobic leather are taken horse (horse up) spend the night, stretch then, in 60 ℃ of reduced pressure treatment 3 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-hydrophobic upper leather that moves with anti-wiping fastness that oozes.The upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 2:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 2.0 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 150 parts of water, 2 parts of sodium formates and 1 part of sodium acetate, mix being incorporated in 40 ℃ and 10 minutes then with 2 parts of sodium bicarbonates.Thereby this depickling body lotion has 7.3 pH value.This depickling body lotion and 7.5 parts of dyestuff 2f are mixed be incorporated in pH 6.8 and 40 ℃ dyeing 30 minutes down.Each a little ground adds altogether 8 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, and leather was processed 60 minutes at 40 ℃ of rotary drums.Body lotion uses 300 parts of water with the leather washed twice after changing at every turn, washs altogether 30 minutes.In 30 minutes process, in the body lotion of 300 parts of water by part adding altogether 0.5 part of formic acid to reach 6.5 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 200 parts of water and 5 parts of stuffings and tanning water-repelling agent H5 40 ℃ of retannings 20 minutes.In 20 minutes process, add 0.5 part of formic acid to reach 5.0 pH value.Use 3 parts of polymerization tanning material G15, carried out retanning 20 minutes at 40 ℃.Then, in body lotion, add 5 parts of retanning material G1, and then carry out rotary drum processing in 30 minutes.Then the mixture of body lotion with 6 parts of water-repelling agent H2 and 0.3 part of auxiliary agent HM4 mixed.At 60 minutes rotary drum again after process time, each a little ground adds altogether 2.5 parts of formic acid so that the pH value is acidified to 3.6 in 60 minutes process.Then in the new system body lotion that constitutes by 150 parts of water and 0.5 part of formic acid 30 ℃ of rotary drums processing 10 minutes.Add 5 parts of chrome tanning material G24 then with chrome tanning once more 90 minutes.Obtain 3.6 pH value.At last, leather was washed 10 minutes at 30 ℃ in 300 parts of water, this washing is carried out twice.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, in 60 ℃ of reduced pressure treatment 3 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-hydrophobic upper leather that moves with anti-wiping fastness that oozes.The upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 3:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 2.0 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 150 parts of water, 2 parts of sodium formates and 1 part of sodium acetate, mix being incorporated in 40 ℃ and 10 minutes then with 2 parts of sodium bicarbonates.Thereby this depickling body lotion has 7.3 pH value.This depickling body lotion and 5.1 parts of dyestuffs 3 are mixed be incorporated in pH 6.8 and 40 ℃ dyeing 30 minutes down.Each a little ground adds altogether 6 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, and leather was processed 60 minutes at 40 ℃ of rotary drums.Body lotion uses 300 parts of water with the leather washed twice after changing at every turn, washs altogether 30 minutes.In 30 minutes process, in the body lotion of 300 parts of water by part adding altogether 0.5 part of formic acid to reach 6.5 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 200 parts of water and 5 parts of stuffings and tanning water-repelling agent H5 40 ℃ of retannings 20 minutes.In 20 minutes process, add 0.5 part of formic acid to reach 5.0 pH value.Use 3 parts of polymerization tanning material G15, carried out retanning 20 minutes at 40 ℃.Then, in this liquid, add 5 parts of retanning material G11 with rotary drum processing again 30 minutes.Then the mixture of body lotion with 6 parts of water-repelling agent H2 and 0.3 part of auxiliary agent HM4 mixed.At 60 minutes rotary drum again after process time, each a little ground adds altogether 2.5 parts of formic acid so that the pH value is acidified to 3.6 in 60 minutes process.Then in the new system body lotion that constitutes by 150 parts of water and 0.5 part of formic acid 30 ℃ of rotary drums processing 10 minutes.Add 5 parts of chrome tanning material G24 then with chrome tanning once more 90 minutes.Obtain 3.7 pH value.At last, leather was washed 10 minutes at 30 ℃ in 300 parts of water, this washing is carried out twice.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, in 60 ℃ of reduced pressure treatment 3 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-hydrophobic upper leather that moves with anti-wiping fastness that oozes.The upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 4:
Be that 1 100 weight portion traditional organic of 1.3-1.4 millimeter tans the ox-hide leather 30 ℃ of washings 15 minutes in the body lotion that is made of 300 parts of water with shaving thickness, then 35 ℃ of rotary drum processing 10 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates.This body lotion has the pH value of 4.2-4.6.This body lotion is mixed with 8.5 parts of dyestuff 4d, then pH 5.5 and 35 ℃ of following dyeing 60 minutes.In 20 minutes process, a little ground adds altogether 3 parts of sodium bicarbonates to reach the pH value of 7.3-7.8 at every turn.For fixation, by part adding altogether 8 parts of sodium carbonate and, thereby the pH value of body lotion is reached between the 9.2-9.6 35 ℃ of rotary drums processing 60 minutes.After body lotion changes, use at every turn 300 parts of water and 1.5 parts of HM3 40 ℃ with the leather washed twice, washed altogether 50 minutes.In 70 minutes process, in the body lotion of 200 parts of water, add the pH value of 2 parts of formic acid to keep 4.3-4.6 altogether at 40 ℃ by part.
With the leather of dyeing thus in the new system body lotion that constitutes by 100 parts of water, 6 parts of polymerization tanning material G18 and 1.5 parts of fatting agent F6 35 ℃ of retannings 30 minutes.Adding the processing of 10 parts of retanning material G18 and rotary drum after 60 minutes, by add 10 parts of vegetable tanning material G22 and 10 parts of retanning material G4 and 35 ℃ of rotary drums processing 60 minutes to finish tanning.Body lotion mixed with 5.5 parts of fatting agent F6 and with leather 35 ℃ of stuffings 90 minutes.For fixing fatting agent, add 100 parts 40 ℃ hot water and rotary drum processing 20 minutes, added formic acid then through 50 minutes to reach 3.5 pH value.Rinsing is 15 minutes then.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, in 45 ℃ of reduced pressure treatment 4 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and vacuumize.
This generation has excellent washable, sweat proof, anti-white wet (wet-white) upper leather that moves with anti-wiping fastness that oozes.The white wet upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 5:
Be that 1 100 weight portion traditional organic of 1.3-1.4 millimeter tans the ox-hide leather 30 ℃ of washings 15 minutes in the body lotion that is made of 300 parts of water with shaving thickness, then 35 ℃ of rotary drum processing 10 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates.This body lotion has the pH value of 4.2-4.6.This body lotion is mixed with 10 parts of dyestuff 5b, then pH 5.5 and 35 ℃ of following dyeing 60 minutes.In 20 minutes process, a little ground adds altogether 3 parts of sodium bicarbonates to reach the pH value of 7.3-7.8 at every turn.For fixation, by part adding altogether 9 parts of sodium carbonate and, thereby the pH value of body lotion is reached between the 9.2-9.6 35 ℃ of rotary drums processing 60 minutes.After body lotion changes, leather is washed three times at 40 ℃ with 300 parts of water at every turn, washed altogether 60 minutes.In 70 minutes process, in the body lotion of 200 parts of water, add the pH value of 2 parts of formic acid to keep 4.3-4.6 altogether at 40 ℃ by part.
With the leather of dyeing thus in the new system body lotion that constitutes by 100 parts of water, 6 parts of polymerization tanning material G18 and 1.5 parts of fatting agent F6 35 ℃ of retannings 30 minutes.Adding the processing of 10 parts of retanning material G18 and rotary drum after 60 minutes, by add 10 parts of vegetable tanning material G22 and 10 parts of retanning material G4 and 35 ℃ of rotary drums processing 60 minutes to finish tanning.Body lotion mixed with 5.5 parts of fatting agent F6 and with leather 35 ℃ of stuffings 90 minutes.For fixing fatting agent, add 100 parts 40 ℃ hot water and rotary drum processing 20 minutes, added formic acid then through 50 minutes to reach 3.5 pH value.Rinsing is 15 minutes then.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, in 45 ℃ of reduced pressure treatment 4 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and vacuumize.
This generation has excellent washable, sweat proof, the anti-white wet upper leather that moves with anti-wiping fastness that oozes.The white wet upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 6:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.8 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 150 parts of water and 1.5 parts of sodium formates, mix being incorporated in 40 ℃ and 10 minutes then with 1.5 parts of sodium bicarbonates.Further add 1.5 parts of sodium bicarbonates and 3 parts of HM4, further rotary drum was processed 15 minutes then.Thereby this depickling body lotion has 7.6 pH value.This depickling body lotion and 9 parts of dyestuff 6c are mixed be incorporated in pH 7.2 and 40 ℃ dyeing 90 minutes down.Each a little ground adds altogether 8 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.3-9.9 with fixation, and leather was processed 60 minutes at 40 ℃ of rotary drums.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.In 60 minutes process, in the body lotion of 200 parts of water by part adding altogether 2 parts of formic acid to reach 4.5 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water and 4 parts of polymerization tanning material G15 45 ℃ of retannings 30 minutes.After adding 5 parts of vegetable tanning material G22 and 3 parts of resin tanning material G11, rotary drum processing is proceeded 40 minutes again.For stuffing, then the mixture of this body lotion with 6 parts of water-repelling agent H1 and 0.4 part of auxiliary agent HM4 mixed.Add 70 parts 60 ℃ hot water at 90 minutes rotary drum again after process time, rotary drum processing 10 minutes, then in 60 minutes process by part adding altogether 5 parts of formic acid so that the pH value is acidified to 3.4.With 200 parts of water 30 ℃ of washings after 10 minutes, with leather in the new system body lotion that constitutes by 200 parts of water, 1 part of water-repelling agent H6 and 0.2 part of auxiliary agent H4 30 ℃ of rotary drums processing 20 minutes.Add then 4 parts of chrome tanning material G24 with leather once more chrome tanning spend the night.The pH value of body lotion is 3.4.At last, leather was washed 10 minutes at 30 ℃ in 200 parts of water, this washing is carried out twice.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, in 50 ℃ of reduced pressure treatment 6 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 50 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-hydrophobic upper leather that moves with anti-wiping fastness that oozes.The hydrophobic upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 7:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.8 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 150 parts of water and 1.5 parts of sodium formates, mix being incorporated in 40 ℃ and 10 minutes then with 1.5 parts of sodium bicarbonates.Further add 1.5 parts of sodium bicarbonates and 3 parts of HM4, further rotary drum was processed 15 minutes then.Thereby this depickling body lotion has 7.6 pH value.This depickling body lotion and 11.5 parts of dyestuffs 7 are mixed be incorporated in pH 7.2 and 40 ℃ dyeing 90 minutes down.Each a little ground adds altogether 10 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.3-9.9 with fixation, and leather was processed 60 minutes at 40 ℃ of rotary drums.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.In 60 minutes process, in the body lotion of 200 parts of water by part adding altogether 2 parts of formic acid to reach 4.6 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water and 4 parts of polymerization tanning material G15 45 ℃ of retannings 30 minutes.After adding 5 parts of vegetable tanning material G22 and 3 parts of resin tanning material G11, rotary drum processing is proceeded 40 minutes again.For stuffing, then the mixture of this body lotion with 6 parts of water-repelling agent H1 and 0.4 part of auxiliary agent HM4 mixed.Add 70 parts 60 ℃ hot water at 90 minutes rotary drum again after process time, rotary drum processing 10 minutes, then in 60 minutes process by part adding altogether 5 parts of formic acid so that the pH value is acidified to 3.3.After 10 minutes, leather is spent the night 30 ℃ of rotary drums processing in the new system body lotion that is made of 100 parts of water and 3 parts of auxiliary agent G24 30 ℃ of washings with 200 parts of water.With 200 parts of water 30 ℃ of washings after 10 minutes, in the new system body lotion that constitutes by 10 parts of water and 2 parts of water-repelling agent H6 30 ℃ of rotary drums processing 20 minutes.Add 3 parts of chrome tanning material G24 then with leather chrome tanning 90 minutes once more.The pH value of body lotion is 3.4.At last, leather was washed 10 minutes at 30 ℃ in 200 parts of water, this washing is carried out twice.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, in 50 ℃ of reduced pressure treatment 6 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 50 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-hydrophobic upper leather that moves with anti-wiping fastness that oozes.The hydrophobic upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 8:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.8 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 20 minutes each a little ground, neutralization is 7.7 pH value.After adding 1.5 parts of HM2, leather 40 ℃ of rotary drums processing 5 minutes, is added 6.5 parts of dyestuffs 8 then in acidifying liquid, then in pH 7.5 and 40 ℃ dyeing 40 minutes down.Each a little ground adds altogether 7.1 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 90 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.In 90 minutes process, each a little ground adds altogether 2 parts of formic acid to reach 4.3 pH value in the body lotion of 200 parts of water.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water and 3 parts of polymerization tanning material G15 45 ℃ of retannings 40 minutes.Add 3 parts of retanning material G1,3 parts of vegetable tanning material G22 and 3 parts of resin tanning material G11 with leather 45 ℃ of retannings 60 minutes.After adding 70 parts 60 ℃ hot water, with leather 60 ℃ of rotary drums processing 20 minutes, and after adding 2.5 parts of fatting agent F7 and 2.5 parts of fatting agent F4 with leather 60 ℃ of stuffings 60 minutes.Each a little ground adds altogether 4 parts of formic acid so that leather is acidified to 3.5 pH value in 60 minutes process.Rinsing is 15 minutes then.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, in 60 ℃ of reduced pressure treatment 2 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-upper leather that moves with anti-wiping fastness that oozes.The upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 9:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.8 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 20 minutes each a little ground, and neutralization is 7.7 pH value.After adding 1.5 parts of HM2, leather 40 ℃ of rotary drums processing 5 minutes, is added 4 parts of dyestuff 9b then in the acidifying body lotion, then in pH 7.5 and 40 ℃ dyeing 40 minutes down.Each a little ground adds altogether 5 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 90 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 90 minutes in the body lotion of 200 parts of water each a little ground add altogether 2 parts of formic acid to reach 4.3 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water and 3 parts of polymerization tanning material G17 45 ℃ of retannings 40 minutes.Add 3 parts of retanning material G7,2 parts of vegetable tanning material G22,2 parts of vegetable tanning material G23 and 3 parts of resin tanning material G11 with leather 45 ℃ of retannings 60 minutes.After adding 70 parts 60 ℃ hot water, with leather 60 ℃ of rotary drums processing 20 minutes, and after adding 2.5 parts of fatting agent F7 and 2.5 parts of fatting agent F4 with leather 60 ℃ of stuffings 60 minutes.Each a little ground adds altogether 4 parts of formic acid so that leather is acidified to 3.5 pH value in 60 minutes process.Rinsing is 15 minutes then.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, in 60 ℃ of reduced pressure treatment 2 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-upper leather that moves with anti-wiping fastness that oozes.The upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 10:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.8 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 20 minutes each a little ground, and neutralization is 7.7 pH value.After adding 1.5 parts of HM2, leather 40 ℃ of rotary drums processing 5 minutes, is added 6.9 parts of dyestuffs 10 then in the acidifying body lotion, then in pH 7.5 and 40 ℃ dyeing 40 minutes down.Each a little ground adds altogether 7.2 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 90 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 90 minutes in the body lotion of 200 parts of water each a little ground add altogether 2 parts of formic acid to reach 4.3 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water and 5 parts of polymerization tanning material G18 45 ℃ of retannings 40 minutes.Add 3 parts of retanning material G1,2 parts of vegetable tanning material G22 and 4 parts of polymerization tanning material G10 with leather 45 ℃ of retannings 60 minutes.After adding 70 parts 60 ℃ hot water, with leather 60 ℃ of rotary drums processing 20 minutes, and after adding 4.5 parts of fatting agent F5 and 0.5 part of fatting agent F8 with leather 60 ℃ of stuffings 60 minutes.Each a little ground adds altogether 4 parts of formic acid so that leather is acidified to 3.5 pH value in 60 minutes process.Rinsing is 15 minutes then.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, in 60 ℃ of reduced pressure treatment 2 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-upper leather that moves with anti-wiping fastness that oozes.The upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 11:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.8 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 20 minutes each a little ground, and neutralization is 7.7 pH value.After adding 1.5 parts of HM2, leather 40 ℃ of rotary drums processing 5 minutes, is added 9 parts of dyestuff 11b then in the depickling body lotion, then in pH 7.5 and 40 ℃ dyeing 40 minutes down.Each a little ground adds altogether 9.5 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 90 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 90 minutes in the body lotion of 200 parts of water each a little ground add altogether 2 parts of formic acid to reach 4.3 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water, 1.5 parts of retanning material G13 and 2.5 parts of polymerization tanning material G16 45 ℃ of retannings 40 minutes.Add 3 parts of retanning material G1,3 parts of vegetable tanning material G22 and 3 parts of resin tanning material G11 with leather 45 ℃ of retannings 60 minutes.After adding 70 parts 60 ℃ hot water, with leather 60 ℃ of rotary drums processing 20 minutes, and after adding 4.5 parts of fatting agent F5 and 0.5 part of fatting agent F8 with leather 60 ℃ of stuffings 60 minutes.Each a little ground adds altogether 4 parts of formic acid so that leather is acidified to 3.5 pH value in 60 minutes process.Cold then rinsing 15 minutes.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, in 60 ℃ of reduced pressure treatment 2 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-upper leather that moves with anti-wiping fastness that oozes.The upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 12:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.8 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 20 minutes each a little ground, and neutralization is 7.7 pH value.After adding 1.5 parts of HM2, leather 40 ℃ of rotary drums processing 5 minutes, is added 8.5 parts of dyestuff 12d then in the depickling body lotion, then in pH 7.5 and 40 ℃ dyeing 40 minutes down.Each a little ground adds altogether 9 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 90 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 90 minutes in the body lotion of 200 parts of water each a little ground add altogether 2 parts of formic acid to reach 4.3 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water, 1.5 parts of retanning material G13 and 2.5 parts of polymerization tanning material G16 45 ℃ of retannings 40 minutes.Add 8 parts of retanning material G2,3 parts of polymerization tanning material G19 and 3 parts of resin tanning material G11 with leather 45 ℃ of retannings 60 minutes.After adding 70 parts 60 ℃ hot water, with leather 60 ℃ of rotary drums processing 20 minutes, and after adding 4.5 parts of fatting agent F5 and 0.5 part of fatting agent F8 with leather 60 ℃ of stuffings 60 minutes.Each a little ground adds altogether 4 parts of formic acid so that leather is acidified to 3.5 pH value in 60 minutes process.Cold then rinsing 15 minutes.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, in 60 ℃ of reduced pressure treatment 2 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-upper leather that moves with anti-wiping fastness that oozes.The upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 12:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.8 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 20 minutes each a little ground, and neutralization is 7.7 pH value.After adding 1.5 parts of HM2, leather 40 ℃ of rotary drums processing 5 minutes, is added 8 parts of dyestuff 12at then in the depickling body lotion, then in pH 7.5 and 40 ℃ dyeing 40 minutes down.Each a little ground adds altogether 9 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 90 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 90 minutes in the body lotion of 200 parts of water each a little ground add altogether 2 parts of formic acid to reach 4.3 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water, 1 part of retanning material G13 and 3 parts of polymerization tanning material G16 45 ℃ of retannings 40 minutes.Add 1.5 parts of auxiliary agent HM4,3 parts of polymerization tanning material G19 and 3 parts of polymerization tanning material G10 with leather 45 ℃ of retannings 60 minutes.After adding 70 parts 60 ℃ hot water, with leather 60 ℃ of rotary drums processing 20 minutes, and after adding 1.5 parts of fatting agent F2 and 3.5 parts of water-repelling agent H3 with leather 60 ℃ of stuffings 60 minutes.Each a little ground adds altogether 4 parts of formic acid so that leather is acidified to 3.5 pH value in 60 minutes process.Cold then rinsing 10 minutes.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, in 60 ℃ of reduced pressure treatment 2 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-upper leather that moves with anti-wiping fastness that oozes.The upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 14:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.3 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 20 minutes each a little ground, and neutralization is 7.7 pH value.After adding 1.5 parts of HM2, leather 40 ℃ of rotary drums processing 5 minutes, is added 8 parts of dyestuff 12bx then in the depickling body lotion, then in pH 7.5 and 40 ℃ dyeing 40 minutes down.Each a little ground adds altogether 8.5 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 90 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 90 minutes in the body lotion of 200 parts of water each a little ground add altogether 2 parts of formic acid to reach 4.3 pH value.
With the retanning 10 minutes in the new system body lotion that constitutes by 80 parts of water and 1 part of retanning material G13 of the leather of dyeing thus.Add 4 parts of chrome tanning material G24,2 parts of retanning material G1,1 part of fatting agent F1 with leather 35 ℃ of retannings 40 minutes.Add 1 part of sodium formate and rotary drum processing 20 minutes.After adding 0.3 part of sodium bicarbonate, again with leather retanning 90 minutes.In 300 parts of water 35 ℃ of washings after 10 minutes, with leather in the new system body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates in 35 ℃ and 10 minutes.Mix with 0.5 part of sodium bicarbonate with body lotion in inciting somebody to action, rotary drum processing is 30 minutes then.After 30 minutes, adding 5 parts of retanning material G5 and 3 parts of retanning material G1 with 5 parts of polymerization tanning material G18 retanning to finish the tanning of leather.,, processed 10 minutes at 60 ℃ of rotary drums then after process time at 40 minutes rotary drums the hot water dilution of body lotion with 100 parts 60 ℃.After adding 3.5 parts of fatting agent F1 and 3.5 parts of water-repelling agent H3 with leather 60 ℃ of stuffings 60 minutes.Add altogether 4 parts of formic acid to be acidified to 3.5 pH value through 60 minutes each a little ground.Cold then rinsing 10 minutes.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, in 60 ℃ of reduced pressure treatment 2 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-soft upper leather that moves with anti-wiping fastness that oozes.The soft upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 15:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.3 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 20 minutes each a little ground, and neutralization is 7.7 pH value.After adding 1.5 parts of HM2, leather 40 ℃ of rotary drums processing 5 minutes, is added 8 parts of dye mixture 12gz then in the depickling body lotion, then in pH 7.5 and 40 ℃ dyeing 40 minutes down.Each a little ground adds altogether 8.5 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 90 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 90 minutes in the body lotion of 200 parts of water each a little ground add altogether 2 parts of formic acid to reach 4.3 pH value.
With the retanning 10 minutes in the new system body lotion that constitutes by 80 parts of water and 1.5 parts of retanning material G14 of the leather of dyeing thus.Add 6 parts of chrome syntans G20 and 1 part of fatting agent F1 with leather 35 ℃ of retannings 40 minutes.Add 1 part of sodium formate and rotary drum processing 20 minutes.After adding 0.3 part of sodium bicarbonate, again with leather retanning 90 minutes.In 300 parts of water 35 ℃ of washings after 10 minutes, with leather in the new system body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates in 35 ℃ and 10 minutes.Mix with 0.5 part of sodium bicarbonate with body lotion in inciting somebody to action, rotary drum processing is 30 minutes then.After 30 minutes, adding 6 parts of retanning material G5 and 6 parts of retanning material G3 with 6 parts of polymerization tanning material G18 retanning to finish the tanning of leather.,, processed 10 minutes at 60 ℃ of rotary drums then after process time at 40 minutes rotary drums the hot water dilution of body lotion with 100 parts 60 ℃.After adding 3.5 parts of fatting agent F1 and 3.5 parts of water-repelling agent H3 with leather 60 ℃ of stuffings 60 minutes.Add altogether 4 parts of formic acid to be acidified to 3.5 pH value through 60 minutes each a little ground.Cold then rinsing 10 minutes.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, in 60 ℃ of reduced pressure treatment 2 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-soft upper leather that moves with anti-wiping fastness that oozes.The soft upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 16:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.8 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 20 minutes each a little ground, and neutralization is 7.4 pH value.After adding 1.5 parts of HM2, leather 40 ℃ of rotary drums processing 5 minutes, is added 7 parts of dye mixture 12hf then in the depickling body lotion, then in pH 7.5 and 40 ℃ dyeing 40 minutes down.Each a little ground adds altogether 8 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 90 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 90 minutes in the body lotion of 200 parts of water each a little ground add altogether 4 parts of formic acid to reach 3.7 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water, 1.5 parts of aldehyde tannage material G13 and 6 parts of polymerization tanning material G18 45 ℃ of retannings 40 minutes.Add 8 parts of retanning material G2,2 parts of polymerization tanning material G19 and 3 parts of resin tanning material G11 then, in 60 minutes, finish tanning at 45 ℃ again.Then with the hot water dilution of body lotion and 70 parts 60 ℃, then 60 ℃ of rotary drums processing 20 minutes.After adding 6.5 parts of fatting agent F1 and 3.5 parts of fatting agent F3 with leather 60 ℃ of stuffings 60 minutes.Add altogether 4 parts of formic acid to be acidified to pH 3.5 through 60 minutes each a little ground.Cold then rinsing 10 minutes.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, in 60 ℃ of reduced pressure treatment 2 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-soft upper leather that moves with anti-wiping fastness that oozes.The soft upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.Upper leather prescription 17:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.5 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 25 minutes each a little ground, and neutralization is 7.6 pH value.In the depickling body lotion, add 9 parts of dye mixture 12hr, then pH 7.5 and 40 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 9 parts of solid sodium carbonates so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 90 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 90 minutes in the body lotion of 200 parts of water each a little ground add altogether 4 parts of formic acid to reach 3.5 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 100 parts of water and 4 parts of aldehyde tannage material G12 35 ℃ of rotary drums processing 10 minutes.After this add 6 parts of chrome tanning material G24 and 2 parts of retanning material G1, again 35 ℃ of retannings 50 minutes.Then body lotion is mixed with 1 part of sodium formate, rotary drum processing is 10 minutes again.After adding 1.5 parts of fatting agent F1, leather was processed 90 minutes at 35 ℃ of rotary drums.Body lotion is oozed and with leather with 300 parts of water 45 ℃ the washing 10 minutes.
Then, with leather in the new system body lotion that constitutes by 70 parts of water and 2 parts of water-repelling agent H3 45 ℃ of pre-stuffings 15 minutes.Add 2 parts of sodium formates, 1 part of sodium bicarbonate and 3 parts of auxiliary agent HM4 then, rotary drum processing is 30 minutes again.Should in and body lotion mix with 12 parts of retanning material G6,, add 2 parts of polymerization tanning material G19, and then in 50 minutes process, finish tanning after process time at 10 minutes rotary drum then.The retanning body lotion is mixed with 4 parts of fatting agent F4,4 parts of fatting agent F1 and 2 parts of fatting agent F6, again 45 ℃ of stuffings 60 minutes.Each a little ground adds altogether 4 parts of formic acid to be acidified to pH 3.5 in 60 minutes process.Body lotion is oozed and with the cold rinsing of leather 5 minutes.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, in 55 ℃ of reduced pressure treatment 1 minute, the dried overnight that at room temperature suspends, finishing is scraped that soft, dried rotary drum processing is spent the night and is removed from office the frame drying with stretching tight.
This generation has the grain of drying drum drying (dry-drumming) and excellent washable, sweat proof, the anti-soft upper leather that moves with anti-wiping fastness that oozes.Can make in a similar way and have the dry grain of drying drum and with the soft upper leather of one of the dyestuff of embodiment 1a to 59k dyeing.
Upper leather prescription 18:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 2.1 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 25 minutes each a little ground, and neutralization is 7.6 pH value.In the depickling body lotion, add 7.5 parts of dye mixture 13b, then pH 7.5 and 40 ℃ of following dyeing 30 minutes.Each a little ground adds altogether 8 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 75 minutes at 40 ℃ of rotary drums then.Body lotion uses 300 parts of water with the leather washed twice after changing at every turn, washs altogether 60 minutes.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water and 3 parts of aldehyde tannage material G12 45 ℃ of rotary drums processing 30 minutes.After this add 5 parts of retanning material G5 and with leather 45 ℃ of retannings 30 minutes.Then with body lotion and 1 part of fatting agent F1 and 1 part of fatting agent F4 mixes and with leather 45 ℃ of pre-stuffings 40 minutes.Add 70 parts 55 ℃ hot water then and 55 ℃ of rotary drums processing 20 minutes.In 55 minutes process, by part adding 1.5 parts of formic acid to reach 5.0 pH value.Body lotion is oozed and with leather with 300 parts of water 45 ℃ the washing 10 minutes.
Then, with leather in the new system body lotion that constitutes by 100 parts of water and 2 parts of water-repelling agent H3 45 ℃ of rotary drums processing 15 minutes.After this add 2 parts of polymerization tanning material G19., add 2 parts of polymerization tanning material G15, and in 30 minutes process, finish tanning again after process time at 15 minutes rotary drums.The retanning body lotion is mixed with 2.5 parts of fatting agent F1,4 parts of fatting agent F4,1 part of fatting agent F3 and 1 part of fatting agent F2, again 45 ℃ of stuffings 60 minutes.Each a little ground adds altogether 4 parts of formic acid to be acidified to pH 3.5 in 60 minutes process.Body lotion is oozed and with the cold rinsing of leather 5 minutes.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, dry 40 ℃ of wet tensions, finishing is scraped that soft, dried rotary drum processing is spent the night and is removed from office the frame drying with stretching tight.
This generation has excellent washable, sweat proof, the anti-tan vat upper leather that moves with anti-wiping fastness that oozes.The tan vat upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 19:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 2.1 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 20 minutes each a little ground, and neutralization is 7.7 pH value.In the depickling body lotion, add 5.9 parts of dyestuff 13ae, then pH 7.5 and 40 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 6.5 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 90 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 200 parts of water each a little ground add altogether 4 parts of formic acid to reach 3.6 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water and 1 part of aldehyde tannage material G13 and 3 parts of polymerization tanning material G16 45 ℃ of rotary drums processing 60 minutes.After this add 0.5 part of sodium bicarbonate, after process time, add 5 parts of polymerization tanning material G18 at 30 minutes rotary drums then, again 45 ℃ of retannings 30 minutes.Then this body lotion is mixed with 0.8 part of auxiliary agent HM5,3 parts of polymerization tanning material G17 and 2 parts of polymerization tanning material G19, and finished tanning 60 minutes at 45 ℃.Add 70 parts of water then, again 60 ℃ of rotary drum processing 10 minutes.The retanning body lotion is mixed with 2.5 parts of fatting agent F6,1.5 parts of water-repelling agent H3 and 1.5 parts of fatting agent F2, again 45 ℃ of stuffings 60 minutes.Each a little ground adds altogether 4 parts of formic acid to reach 3.5 pH value in 60 minutes process then.Body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, 60 ℃ of reduced pressure treatment 2 minutes, it was dry at room temperature to suspend, and finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-simple polymerisation base upper leather that moves with anti-wiping fastness that oozes.The simple polymerisation base upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 20:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 2.0 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 20 minutes each a little ground, and neutralization is 7.8 pH value.After in the depickling body lotion, adding 4.8 parts of dyestuff 13dt, with leather in pH 7.6 and 40 ℃ dyeing 35 minutes down.Each a little ground adds altogether 6 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.4-9.9 with fixation, processed 60 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 200 parts of water each a little ground add altogether 2 parts of formic acid to reach 4.3 pH value.
With the rotary drum processing 20 minutes in the new system body lotion that constitutes by 80 parts of water and 1.5 parts of water-repelling agent H3 of the leather of dyeing thus.Add 5 parts of polymerization tanning material G18 then, after process time, add 1 part of auxiliary agent HM5 and 5 parts of polymerization tanning material G18 at 40 minutes rotary drum again.45 ℃ of rotary drum processing 30 minutes, add 3 parts of polymerization tanning material G19 then, more again 45 ℃ of retannings 60 minutes.Add 70 parts of water then, again 60 ℃ of rotary drum processing 10 minutes.The retanning body lotion is mixed with 2.5 parts of fatting agent F6,0.5 part of water-repelling agent H3 and 1.5 parts of fatting agent F2, again 60 ℃ of stuffings 60 minutes.Each a little ground adds altogether 4 parts of formic acid to reach 3.4 pH value in 60 minutes process then.Body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, 60 ℃ of reduced pressure treatment 2 minutes, it was dry at room temperature to suspend, and finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-simple polymerisation base upper leather that moves with anti-wiping fastness that oozes.The simple polymerisation base upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 21:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 2.2 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 20 minutes each a little ground, and neutralization is 7.8 pH value.In the depickling body lotion, add 7.7 parts of dye mixture 13hb, then pH 7.6 and 40 ℃ of following dyeing 35 minutes.Each a little ground adds altogether 8 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.5-10.0 with fixation, processed 55 minutes at 40 ℃ of rotary drums then.Body lotion uses 300 parts of water with the leather washed twice after changing at every turn, washs altogether 60 minutes.Through 60 minutes in the body lotion of 200 parts of water each a little ground add altogether 2 parts of formic acid to reach 4.4 pH value.
With the rotary drum processing 15 minutes in the new system body lotion that constitutes by 80 parts of water and 1.5 parts of water-repelling agent H3 of the leather of dyeing thus.Add 5 parts of polymerization tanning material G18 then, after process time, add 1 part of auxiliary agent HM5,3 parts of polymerization tanning material G17,3 parts of vegetable tanning material G23 and 2 parts of tanning material G11 at 40 minutes rotary drum again.45 ℃ of rotary drum processing 30 minutes, add 3 parts of polymerization tanning material G19 then, more again 45 ℃ of retannings 60 minutes.Add 70 parts of water then, again 60 ℃ of rotary drum processing 10 minutes.The retanning body lotion is mixed with 2.5 parts of fatting agent F7 and 2 parts of fatting agent F4, again 60 ℃ of stuffings 60 minutes.Each a little ground adds altogether 4 parts of formic acid to reach 3.5 pH value in 60 minutes process then.Body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, 60 ℃ of reduced pressure treatment 2 minutes, it was dry at room temperature to suspend, and finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-upper leather that moves with anti-wiping fastness that oozes.The upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 22:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.9 millimeters is 35 ℃ of washings 10 minutes in the body lotion that is made of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this in 20 minutes process by part add altogether 3 parts of sodium bicarbonates with reach 7.8 in and the pH value.This depickling body lotion is mixed with 10.5 parts of dye mixture 13hp, then pH 7.6 and 40 ℃ of following dyeing 20 minutes.Each a little ground adds altogether 9 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.5-10.0 with fixation, processed 70 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 200 parts of water by part adding 2 parts of formic acid to reach 4.3 pH value.
With the rotary drum processing 5 minutes in the new system body lotion that constitutes by 80 parts of water and 3 parts of polymerization tanning material G19 of the leather of dyeing thus.Add 6 parts of retanning material G2 then, after process time, add 5 parts of polymerization tanning material G18,3 parts of polymerization tanning material G19 and 4 parts of retanning material G2 at 30 minutes rotary drum again.45 ℃ of rotary drum processing 60 minutes, add 70 parts of water then again, and 65 ℃ of rotary drum processing 20 minutes.The retanning body lotion is mixed with 3 parts of fatting agent F1 and 2 parts of fatting agent F2, again 65 ℃ of stuffings 60 minutes.Each a little ground adds altogether 4 parts of formic acid to reach 3.6 pH value in 60 minutes process then.Body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse to be spent the night, stretches then, 55 ℃ of reduced pressure treatment 4 minutes, it is dry at room temperature to suspend, finishing, scrape soft and 55 ℃ of vacuumizes 3 minutes, emery paper with 220 specifications carries out nubuck processing (nubucked), and dedusting is also with the leather frame drying that stretches tight.
This generation has excellent washable, sweat proof, anti-oozing moved and the positive matte upper leather of straight burr (direct-route) of anti-wiping fastness.The positive matte upper leather of straight burr that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 23:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 2.0 millimeters is 35 ℃ of washings 10 minutes in the body lotion that is made of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this in 20 minutes process by part add altogether 3 parts of sodium bicarbonates with reach 7.6 in and the pH value.This depickling body lotion is mixed with 6.1 parts of dye mixture 13hw, then pH 7.5 and 40 ℃ of following dyeing 15 minutes.Each a little ground adds altogether 8 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 90 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.In 60 minutes process in the body lotion of 200 parts of water by part adding 2 parts of formic acid to reach 4.2 pH value.
With the rotary drum processing 3 minutes in the new system body lotion that constitutes by 80 parts of water and 1 part of aldehyde tannage material G13 of the leather of dyeing thus.After adding 3 parts of polymerization tanning material G19, with leather rotary drum processing 30 minutes again.Add 0.8 part of sodium bicarbonate then.Rotary drum processing 30 minutes, then before rotary drum processing again 30 minutes, add 3 parts of water-repelling agent H5 afterwards, with 5 parts of polymerization tanning material G18 retanning 30 minutes.The retanning body lotion is mixed with 5 parts of water-repelling agent H1 and 0.5 part of auxiliary agent HM4, then 45 ℃ of stuffings 60 minutes.Add 70 parts of water then, again 65 ℃ of rotary drum processing 20 minutes.Then in 60 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed.With leather in the new system body lotion that constitutes by 150 parts of water and 0.5 part of formic acid 30 ℃ of rotary drums processing 10 minutes.Add 5 parts of chrome tanning material G24 hydrophobization is fixed 90 minutes at 30 ℃.Use 300 parts of water washings 10 minutes once then, after this with leather rotary drum processing 10 minutes in the body lotion that constitutes by 300 parts of water and 0.2 part of formic acid.Leather drained and with the leather brief cold rinse.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, 55 ℃ of reduced pressure treatment 4 minutes, it was dry at room temperature to suspend, finishing, scrape soft and 55 ℃ of vacuumizes 3 minutes, carry out nubuck with the emery paper of 220 specifications and handle, dedusting is also removed from office the frame drying with stretching tight.
This generation has excellent washable, sweat proof, anti-oozing moved and the positive matte upper leather of the hydrophobic straight burr of anti-wiping fastness.The positive matte upper leather of hydrophobic straight burr that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 24:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.8 millimeters is 35 ℃ of washings 10 minutes in the body lotion that is made of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this in 20 minutes process by part add altogether 3 parts of sodium bicarbonates with reach 7.5 in and the pH value.This depickling body lotion is mixed with 9.2 parts of dyestuffs 14, then pH 7.5 and 40 ℃ of following dyeing 25 minutes.Each a little ground adds altogether 9 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 50 minutes at 40 ℃ of rotary drums then.Body lotion uses 300 parts of water with the leather washed twice after changing at every turn, washs altogether 60 minutes.In 60 minutes process in the body lotion of 200 parts of water by part adding 2 parts of formic acid to reach 4.3 pH value.
With the rotary drum processing 15 minutes in the new system body lotion that constitutes by 80 parts of water and 3 parts of polymerization tanning material G19 of the leather of dyeing thus.After this, add 2 parts of water-repelling agent H1.Rotary drum processing 15 minutes adds 5 parts of polymerization tanning material G18,3 parts of retanning material G1 and 1 part of polymerization tanning material G19 then, and retanning is 30 minutes then.The retanning body lotion is mixed with 4 parts of water-repelling agent H1 and 0.3 part of auxiliary agent HM4, then 45 ℃ of stuffings 60 minutes.Add 70 parts of water then, again 65 ℃ of rotary drum processing 20 minutes.Then in 60 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed.With leather in the new system body lotion that constitutes by 150 parts of water and 0.5 part of formic acid 30 ℃ of rotary drums processing 10 minutes.Add 5 parts of chrome tanning material G24 hydrophobization is fixed 90 minutes at 30 ℃.Use 300 parts of water washings 10 minutes once then, after this with leather rotary drum processing 10 minutes in the body lotion that constitutes by 300 parts of water and 0.2 part of formic acid.Leather drained and with the leather brief cold rinse.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, 55 ℃ of reduced pressure treatment 4 minutes, it was dry at room temperature to suspend, finishing, scrape soft and 55 ℃ of vacuumizes 3 minutes, carry out nubuck with the emery paper of 220 specifications and handle, dedusting is also removed from office the frame drying with stretching tight.
This generation has excellent washable, sweat proof, anti-oozing moved and the positive matte upper leather of the hydrophobic straight burr of anti-wiping fastness.The positive matte upper leather of hydrophobic straight burr that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 25:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.8 millimeters is 35 ℃ of washings 10 minutes in the body lotion that is made of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this in 20 minutes process by part add altogether 3 parts of sodium bicarbonates with reach 7.5 in and the pH value.This depickling body lotion is mixed with 6.8 parts of dyestuffs 15, then pH 7.5 and 40 ℃ of following dyeing 30 minutes.Each a little ground adds altogether 8 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 90 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.In 90 minutes process in the body lotion of 200 parts of water by part adding 5 parts of formic acid to reach 3.0 pH value.
With the rotary drum processing 10 minutes in the new system body lotion that constitutes by 80 parts of water and 0.4 part of formic acid of the leather of dyeing thus.Add 1 part of retanning material G14 then, rotary drum processing is 30 minutes again.Add 4 parts of chrome tanning material G24 and 2 parts of retanning material G28 then.After process time, add 0.5 part of sodium formate at 30 minutes rotary drums, again chrome tanning 60 minutes again.This body lotion is mixed with 100 parts of water, and rotary drum processing is spent the night again.Body lotion is oozed.
With leather in the new system body lotion that constitutes by 80 parts of water, 1.5 parts of sodium formates and 0.5 part of sodium bicarbonate 30 ℃ of rotary drums processing 30 minutes.Add 2 parts of polymerization tanning material G19 then.After process time, add 2 parts of water-repelling agent H1 at 15 minutes rotary drums, rotary drum processing is 15 minutes again.Add 5 parts of polymerization tanning material G18, and rotary drum processing 30 minutes,, add 4 parts of retanning material G28 and 3 parts of retanning material G11 then for finishing tanning, and then retanning 30 minutes.The retanning body lotion is mixed with 4 parts of water-repelling agent H1 and 0.3 part of auxiliary agent HM4, and stuffing is 60 minutes then.In this body lotion, add 70 parts of water then, again 65 ℃ of rotary drum processing 20 minutes.Then in 45 minutes process by part adding altogether 3.5 parts of formic acid to reach 3.5 pH value.With leather in the new system body lotion that constitutes by 150 parts of water and 0.5 part of formic acid 30 ℃ of rotary drums processing 10 minutes.Add 5 parts of chrome tanning material G24 hydrophobization is fixed 90 minutes at 30 ℃.Use 300 parts of water washings 10 minutes once then, after this with leather rotary drum processing 10 minutes in the body lotion that constitutes by 300 parts of water and 0.2 part of formic acid.Leather drained and with the leather brief cold rinse.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, 55 ℃ of reduced pressure treatment 4 minutes, it was dry at room temperature to suspend, finishing, scrape soft and 55 ℃ of vacuumizes 3 minutes, carry out nubuck with the emery paper of 220 specifications and handle, dedusting is also removed from office the frame drying with stretching tight.
This generation has excellent washable, sweat proof, anti-oozing moved and the positive matte upper leather of the hydrophobic straight burr of anti-wiping fastness.The positive matte upper leather of hydrophobic straight burr that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 26:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.9 millimeters is 35 ℃ of washings 10 minutes in the body lotion that is made of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this in 20 minutes process by part add altogether 3 parts of sodium bicarbonates with reach 7.6 in and the pH value.This depickling body lotion is mixed with 8.8 parts of dyestuff 16j, then pH 7.5 and 40 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 8 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.1-9.7 with fixation, processed 60 minutes at 40 ℃ of rotary drums then.Body lotion uses 300 parts of water with the leather washed twice after changing at every turn, washs altogether 60 minutes.In 60 minutes process in the body lotion of 200 parts of water by part adding 2 parts of formic acid to reach 4.2 pH value.
With the rotary drum processing 5 minutes in the new system body lotion that constitutes by 80 parts of water and 1 part of retanning material G14 of the leather of dyeing thus.Add 2 parts of polymerization tanning material G19 then, after process time, add 5 parts of polymerization tanning material G18 at 15 minutes rotary drum again.45 ℃ of rotary drum processing 40 minutes, add 3 parts of vegetable tanning material G22 and 3 parts of retanning material G28 then, more again 45 ℃ of retannings 60 minutes.Add 70 parts of water then, again 60 ℃ of rotary drum processing 10 minutes.With retanning body lotion and 2.5 parts of fatting agent F1 and 2.5 parts of mixed 50 ℃ of stuffings 60 minutes that are incorporated in of water-repelling agent H3.Then in 60 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, 55 ℃ of reduced pressure treatment 4 minutes, it was dry at room temperature to suspend, finishing, scrape soft and 55 ℃ of vacuumizes 3 minutes, carry out nubuck with the emery paper of 220 specifications and handle, dedusting is also removed from office the frame drying with stretching tight.
This generation has excellent washable, sweat proof, anti-oozing moved and the positive matte upper leather of the straight burr of anti-wiping fastness.The positive matte upper leather of straight burr that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 27:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.9 millimeters is 35 ℃ of washings 10 minutes in the body lotion that is made of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this in 20 minutes process by part add altogether 3 parts of sodium bicarbonates with reach 7.6 in and the pH value.This depickling body lotion is mixed with 9 parts of dyestuff 17b, then pH 7.5 and 40 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 9.5 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.8 with fixation, processed 60 minutes at 40 ℃ of rotary drums then.Body lotion uses 300 parts of water with the leather washed twice after changing at every turn, washs altogether 60 minutes.In 60 minutes process in the body lotion of 200 parts of water by part adding 2 parts of formic acid to reach 4.3 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water and 1 part of retanning material G14 45 ℃ of rotary drums processing 5 minutes.Add 2 parts of polymerization tanning material G19 then, after process time, add 5 parts of polymerization tanning material G18 at 15 minutes rotary drum again.45 ℃ of rotary drum processing 40 minutes, add 4 parts of resin tanning material G28 and 4 parts of resin tanning material G11 then, more again 45 ℃ of retannings 60 minutes.Add 70 parts of water then, again 60 ℃ of rotary drum processing 10 minutes.With retanning body lotion and 2.5 parts of fatting agent F1 and 2.5 parts of mixed 55 ℃ of stuffings 60 minutes that are incorporated in of water-repelling agent H3.Then in 60 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, 55 ℃ of reduced pressure treatment 4 minutes, it was dry at room temperature to suspend, finishing, scrape soft and 55 ℃ of vacuumizes 3 minutes, carry out nubuck with the emery paper of 220 specifications and handle, dedusting is also removed from office the frame drying with stretching tight.
This generation has excellent washable, sweat proof, anti-oozing moved and the positive matte upper leather of the straight burr of anti-wiping fastness.The positive matte upper leather of straight burr that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 28:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.9 millimeters is 35 ℃ of washings 10 minutes in the body lotion that is made of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this in 20 minutes process by part add altogether 3 parts of sodium bicarbonates with reach 7.6 in and the pH value.This depickling body lotion is mixed with 5 parts of dyestuffs 19, then pH 7.5 and 40 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 6.5 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.8 with fixation, processed 65 minutes at 40 ℃ of rotary drums then.Body lotion uses 300 parts of water with the leather washed twice after changing at every turn, washs altogether 60 minutes.In 60 minutes process in the body lotion of 200 parts of water by part adding altogether 2 parts of formic acid to reach 4.3 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water and 1 part of retanning material G14 45 ℃ of rotary drums processing 5 minutes.Add 2 parts of polymerization tanning material G19 then, after process time, add 5 parts of polymerization tanning material G18 at 15 minutes rotary drum again.45 ℃ of rotary drum processing 40 minutes, add 2 parts of vegetable tanning material G22 and 4 parts of resin tanning material G28 then, more again 45 ℃ of retannings 60 minutes.Add 70 parts of water then, again 60 ℃ of rotary drum processing 10 minutes.With retanning body lotion and 2.5 parts of fatting agent F1 and 2.5 parts of mixed 60 ℃ of stuffings 60 minutes that are incorporated in of water-repelling agent H3.Then in 50 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, 55 ℃ of reduced pressure treatment 4 minutes, it was dry at room temperature to suspend, finishing, scrape soft and 55 ℃ of vacuumizes 3 minutes, carry out nubuck with the emery paper of 220 specifications and handle, dedusting is also removed from office the frame drying with stretching tight.
This generation has excellent washable, sweat proof, anti-oozing moved and the positive matte upper leather of the straight burr of anti-wiping fastness.The positive matte upper leather of straight burr that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 29:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.9 millimeters is 35 ℃ of washings 10 minutes in the body lotion that is made of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this in 20 minutes process by part add altogether 3 parts of sodium bicarbonates with reach 7.6 in and the pH value.This depickling body lotion is mixed with 7.1 parts of dyestuffs 22, then pH 7.5 and 40 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 8 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.8 with fixation, processed 60 minutes at 40 ℃ of rotary drums then.Body lotion uses 300 parts of water with the leather washed twice after changing at every turn, washs altogether 60 minutes.In 60 minutes process in the body lotion of 200 parts of water by part adding 3 parts of formic acid to reach 3.9 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water and 2 parts of retanning material G29 45 ℃ of rotary drums processing 20 minutes.Add 2 parts of polymerization tanning material G19 then, after process time, add 5 parts of polymerization tanning material G18 at 15 minutes rotary drum again.45 ℃ of rotary drum processing 40 minutes, add 4 parts of resin tanning material G28 and 4 parts of resin tanning material G11 then, more again 45 ℃ of retannings 60 minutes.Add 70 parts of water then, again 60 ℃ of rotary drum processing 10 minutes.With retanning body lotion and 2.5 parts of fatting agent F1 and 2.5 parts of mixed 55 ℃ of stuffings 60 minutes that are incorporated in of water-repelling agent H3.Then in 60 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, 55 ℃ of reduced pressure treatment 4 minutes, it was dry at room temperature to suspend, finishing, scrape soft and 55 ℃ of vacuumizes 3 minutes, carry out nubuck with the emery paper of 220 specifications and handle, dedusting is also removed from office the frame drying with stretching tight.
This generation has excellent washable, sweat proof, anti-oozing moved and the positive matte upper leather of the straight burr of anti-wiping fastness.The positive matte upper leather of straight burr that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 30:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 2.0 millimeters is 35 ℃ of washings 10 minutes in the body lotion that is made of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this in 20 minutes process by part add altogether 3 parts of sodium bicarbonates with reach 7.6 in and the pH value.This depickling body lotion is mixed with 7.2 parts of dyestuffs 24, then pH 7.5 and 40 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 8 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.8 with fixation, processed 60 minutes at 40 ℃ of rotary drums then.Body lotion uses 300 parts of water with the leather washed twice after changing at every turn, washs altogether 60 minutes.In 60 minutes process in the body lotion of 200 parts of water by part adding 4 parts of formic acid to reach 4.0 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water and 3 parts of retanning material G25 45 ℃ of rotary drums processing 5 minutes.Add 2 parts of polymerization tanning material G19 then, after process time, add 5 parts of polymerization tanning material G18 at 15 minutes rotary drum again.45 ℃ of rotary drum processing 40 minutes, add 4 parts of resin tanning material G28 and 4 parts of resin tanning material G11 then, more again 45 ℃ of retannings 60 minutes.Add 70 parts of water then, again 60 ℃ of rotary drum processing 10 minutes.With retanning body lotion and 2.5 parts of fatting agent F1 and 2.5 parts of mixed 55 ℃ of stuffings 60 minutes that are incorporated in of water-repelling agent H3.Then in 60 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, 55 ℃ of reduced pressure treatment 4 minutes, it was dry at room temperature to suspend, finishing, scrape soft and 55 ℃ of vacuumizes 3 minutes, carry out nubuck with the emery paper of 220 specifications and handle, dedusting is also removed from office the frame drying with stretching tight.
This generation has excellent washable, sweat proof, anti-oozing moved and the positive matte upper leather of the straight burr of anti-wiping fastness.The positive matte upper leather of straight burr that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 31:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 2.0 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, then in 25 minutes process each a little ground add altogether 3 parts of sodium bicarbonates with reach 7.7 in and the pH value.This depickling body lotion is mixed with 4.9 parts of dyestuff 28a, then pH 7.5 and 40 ℃ of following dyeing 30 minutes.Each a little ground adds altogether 6.8 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.5-10.0 with fixation, processed 60 minutes at 40 ℃ of rotary drums then.Body lotion uses 300 parts of water with the leather washed twice after changing at every turn, washs altogether 60 minutes.In 50 minutes process in the body lotion of 200 parts of water by part adding altogether 1.5 parts of formic acid to reach 5.5 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water and 5 parts of water-repelling agent H5 45 ℃ of rotary drums processing 20 minutes.Add 5 parts of polymerization tanning material G18 then, after process time, add 5 parts of water-repelling agent H1 and 0.3 part of auxiliary agent HM4 at 40 minutes rotary drum again.After 60 minutes, add 70 parts of water 45 ℃ of stuffings, again 60 ℃ of rotary drum processing 10 minutes.In 60 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed and with leather rotary drum processing 5 minutes in the new system body lotion that constitutes by 150 parts of water and 0.5 part of formic acid.Add 5 parts of chrome tanning material G24, fixation is 90 minutes then.At last, with leather 30 ℃ with 300 parts of water rinses 10 minutes, this rinsing is carried out twice.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, in 55 ℃ of reduced pressure treatment 4 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 55 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-hydrophobic upper leather that moves with anti-wiping fastness that oozes.The hydrophobic upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 32:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.9 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, then in 25 minutes process each a little ground add 3 parts of sodium bicarbonates altogether and reach 7.7 in and the pH value.In this depickling body lotion, add 9.1 parts of dyestuffs 30, then pH 7.6 and 40 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 9.2 parts of solid sodium carbonates so that the pH value of body lotion reaches between the 9.3-9.8 with fixation, processed 60 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 50 minutes in the body lotion of 150 parts of water each a little ground add altogether 2 parts of formic acid to reach 4.3 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water, 1.5 parts of retanning material G13 and 2 parts of polymerization tanning material G19 45 ℃ of rotary drums processing 40 minutes.Add 0.7 part of sodium bicarbonate then and obtain 5.5 pH value after process time with rotary drum at 20 minutes.Add 3 parts of water-repelling agent H1 and 0.2 part of auxiliary agent HM4 then, rotary drum processing after this 20 minutes.After adding 6 parts of polymerization tanning material G18, retanning is 30 minutes again.For with leather greasing, add 5 parts of water-repelling agent H1 and 0.3 part of auxiliary agent HM4, and rotary drum was processed 60 minutes.Add 70 parts of water then.In the processing of 60 ℃ of rotary drums after 10 minutes, in 60 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed and with leather rotary drum processing 5 minutes in the new system body lotion that constitutes by 150 parts of water and 0.5 part of formic acid.Add 5 parts of chrome tanning material G24, fixation is 90 minutes then.At last, with leather 30 ℃ with 300 parts of water rinses 10 minutes, this rinsing is carried out twice.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, in 55 ℃ of reduced pressure treatment 4 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 55 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-hydrophobic soft upper leather that moves with anti-wiping fastness that oozes.The hydrophobic soft upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 33:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 2.0 millimeters is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, then in 25 minutes process each a little ground add altogether 3 parts of sodium bicarbonates with reach 7.7 in and the pH value.This depickling body lotion is mixed with 9.9 parts of dyestuffs 32, then pH 7.6 and 40 ℃ of following dyeing 40 minutes., so that reaching between the 9.2-9.7 with fixation, the pH value of body lotion processed 60 minutes at 40 ℃ of rotary drums then by part adding altogether 10.0 parts of sodium carbonate.After body lotion changed, use altogether 300 parts of water washed the leather washed twice altogether 60 minutes at every turn.In 50 minutes process in the body lotion of 200 parts of water by part adding altogether 1.5 parts of formic acid to reach 5.4 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water and 3 parts of polymerization tanning material G19 45 ℃ of rotary drums processing 15 minutes.Add 1.5 parts of water-repelling agent H1 then, rotary drum processing is 15 minutes then.Add 5 parts of polymerization tanning material G18, and then retanning 30 minutes.Add 2 parts of vegetable tanning material G22,2 parts of retanning material G1,2 parts of resin tanning material G28 and 3 parts of retanning material G11 then, rotary drum processing is 30 minutes again.For with leather greasing, add 4.5 parts of water-repelling agent H1 and 0.3 part of auxiliary agent HM4, and rotary drum was processed 60 minutes.Add 70 parts of water then.In the processing of 60 ℃ of rotary drums after 10 minutes, in 50 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed and with leather rotary drum processing 10 minutes in the new system body lotion that constitutes by 150 parts of water and 0.5 part of formic acid.Add 5 parts of chrome tanning material G24, fixation is 90 minutes then.After this 30 ℃ of washings 10 minutes once, and use the body lotion washing that constitutes by 300 parts of water and 0.2 part of formic acid once with 300 parts of water.At last, with the simple rinsing of leather.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, 55 ℃ of reduced pressure treatment 4 minutes, it was dry at room temperature to suspend, and finishing is scraped soft and 55 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-hydrophobic upper leather that moves with anti-wiping fastness that oozes.The hydrophobic upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 34:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is the 1.8-2.0 millimeter is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, then in 25 minutes process each a little ground add altogether 3 parts of sodium bicarbonates with reach 7.7 in and the pH value.This depickling body lotion is mixed with 6.8 parts of dyestuff 34p, then pH 7.6 and 40 ℃ of following dyeing 40 minutes., so that reaching between the 9.2-9.6 with fixation, the pH value of body lotion and processed 90 minutes by part adding altogether 7.5 parts of sodium carbonate at 40 ℃ of rotary drums.After body lotion changed, use altogether 300 parts of water washed leather washing three times altogether 60 minutes at every turn.In 60 minutes process in the body lotion of 200 parts of water by part adding altogether 2 parts of formic acid to reach 4.3 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water, 1 part of retanning material G14 and 2 parts of polymerization tanning material G19 45 ℃ of rotary drums processing 40 minutes.Add 0.8 part of sodium bicarbonate then to obtain 5.6 pH value.Add 3 parts of water-repelling agent H5 and 0.15 part of HM4 then, and rotary drum was processed 20 minutes.Add 5 parts of polymerization tanning material G18, and then retanning 30 minutes.Add 2 parts of retanning material G1,2 parts of vegetable tanning material G22 and 2 parts of resin tanning material G28 then, and rotary drum was processed 30 minutes.For with leather greasing, add 5 parts of water-repelling agent H1 and 0.15 part of auxiliary agent HM4, and rotary drum was processed 60 minutes.Add 70 parts of water then.In the processing of 60 ℃ of rotary drums after 10 minutes, in 40 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed and with leather rotary drum processing 10 minutes in the new system body lotion that constitutes by 150 parts of water and 0.5 part of formic acid.Add 5 parts of chrome tanning material G24, fixation is 90 minutes then.After this 30 ℃ of washings 10 minutes once, and use the body lotion washing that constitutes by 300 parts of water and 0.2 part of formic acid once with 300 parts of water.At last, with the simple rinsing of leather.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, 55 ℃ of reduced pressure treatment 4 minutes, it was dry at room temperature to suspend, and finishing is scraped soft and 55 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-hydrophobic upper leather that moves with anti-wiping fastness that oozes.The hydrophobic upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 35:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.8 millimeters is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 25 minutes each a little ground, and reach 7.7 in and the pH value.After in the depickling body lotion, adding 8.1 parts of dyestuffs 36, with leather in pH 7.6 and 40 ℃ dyeing 50 minutes down.Each a little ground adds altogether 8.7 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 60 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 150 parts of water each a little ground add altogether 1.5 parts of formic acid to reach 5.3 pH value.
With the pre-stuffing 20 minutes in the new system body lotion that constitutes by 100 parts of water and 3 parts of water-repelling agent H5 of the leather of dyeing thus.Add 5 parts of polymerization tanning material G18 then, rotary drum processing after this 40 minutes.After adding 3 parts of polymerization tanning material G16, retanning is 30 minutes again.After this, add 2 parts of polymerization tanning material G19, and through finishing tanning in 30 minutes.The retanning body lotion is mixed with 5 parts of water-repelling agent H1 and 0.5 part of auxiliary agent HM4, and stuffing is 60 minutes then.Add 100 parts of water then.In the processing of 60 ℃ of rotary drums after 10 minutes, through 55 minutes by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed and with leather rotary drum processing 10 minutes in the new system body lotion that constitutes by 120 parts of water and 0.5 part of formic acid.Add 5 parts of chrome tanning material G24, fixation is 90 minutes then.Then with leather 30 ℃ with 300 parts of water washings 10 minutes, this washing is carried out twice.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, 55 ℃ of reduced pressure treatment 4 minutes, it was dry at room temperature to suspend, and finishing is scraped soft and 55 ℃ of vacuumizes 3 minutes.
This generation has excellent washable, sweat proof, the anti-hydrophobic upper leather of simple polymerisation base that moves with anti-wiping fastness that oozes.The hydrophobic upper leather of simple polymerisation base that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 36:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.8 millimeters is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 25 minutes each a little ground, and reach 7.7 in and the pH value.After in the depickling body lotion, adding 5.7 parts of dyestuff 35v, leather was processed 50 minutes at pH 7.6 and 40 ℃ of following rotary drums.Each a little ground adds altogether 6.5 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 60 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 150 parts of water each a little ground add altogether 1.5 parts of formic acid to reach 5.3 pH value.
With the pre-stuffing 20 minutes in the new system body lotion that constitutes by 100 parts of water and 2 parts of water-repelling agent H5 of the leather of dyeing thus.Add 5 parts of polymerization tanning material G18 then, rotary drum processing after this 40 minutes.After adding 3 parts of polymerization tanning material G1, retanning is 30 minutes again.After this, add 2 parts of polymerization tanning material G22, and through finishing tanning in 30 minutes.The retanning body lotion is mixed with 5 parts of water-repelling agent H1 and 0.5 part of auxiliary agent HM4, and stuffing is 60 minutes then.Add 100 parts of water then.In the processing of 60 ℃ of rotary drums after 10 minutes, through 55 minutes by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed and with leather rotary drum processing 10 minutes in the new system body lotion that constitutes by 120 parts of water and 0.5 part of formic acid.Add 5 parts of chrome tanning material G24, fixation is 90 minutes then.Then with leather 30 ℃ with 300 parts of water washings 10 minutes, this washing is carried out twice.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, 55 ℃ of reduced pressure treatment 4 minutes, it was dry at room temperature to suspend, and finishing is scraped soft and 55 ℃ of vacuumizes 3 minutes.
This generation has excellent washable, sweat proof, the anti-hydrophobic upper leather that moves with anti-wiping fastness that oozes.The hydrophobic upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 37:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.8 millimeters is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 25 minutes each a little ground, and reach 7.7 in and the pH value.After in the depickling body lotion, adding 7.8 parts of dyestuff 38o, leather was processed 50 minutes at pH 7.6 and 40 ℃ of following rotary drums.Each a little ground adds altogether 8.1 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 60 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 150 parts of water each a little ground add altogether 2 parts of formic acid to reach 4.5 pH value.
With the rotary drum processing 40 minutes in the new system body lotion that constitutes by 100 parts of water, 1.5 parts of retanning material G14,1.5 parts of polymerization tanning material G16 and 1.5 parts of retanning material G19 of the leather of dyeing thus.Add 2 parts of vegetable tanning material G22 and 3 parts of vegetable tanning material G28, tanning 60 minutes is to finish tanning then.The retanning body lotion is mixed with 6 parts of water-repelling agent H1 and 0.5 part of auxiliary agent HM4, and stuffing is 90 minutes then.Add 100 parts of water then.In the processing of 60 ℃ of rotary drums after 10 minutes, through 50 minutes by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed and with leather rotary drum processing 5 minutes in the new system body lotion that constitutes by 120 parts of water and 0.5 part of formic acid.Add 5 parts of chrome tanning material G24, fixation is 90 minutes then.Then with leather 30 ℃ with 300 parts of water washings 10 minutes, this washing is carried out twice.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, 55 ℃ of reduced pressure treatment 4 minutes, it was dry at room temperature to suspend, and finishing is scraped soft and 55 ℃ of vacuumizes 3 minutes.
This generation has excellent washable, sweat proof, the anti-hydrophobic upper leather that moves with anti-wiping fastness that oozes.The hydrophobic upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 38:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 2.0 millimeters is 35 ℃ of washings 10 minutes in the body lotion that is made of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this in 20 minutes process by part add altogether 3 parts of sodium bicarbonates with reach 7.6 in and the pH value.This depickling body lotion is mixed with 9.2 parts of dyestuff 40d, then pH 7.5 and 40 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 9.3 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.8 with fixation, processed 60 minutes at 40 ℃ of rotary drums then.Body lotion uses 300 parts of water with the leather washed twice after changing at every turn, washs altogether 60 minutes.In 60 minutes process in the body lotion of 200 parts of water by part adding altogether 3.5 parts of formic acid to reach 3.8 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water and 3 parts of retanning material G26 45 ℃ of rotary drums processing 60 minutes.Add 2 parts of polymerization tanning material G19 then, after process time, add 5 parts of polymerization tanning material G18 at 15 minutes rotary drum again.45 ℃ of rotary drum processing 40 minutes, add 4 parts of resin tanning material G28 and 4 parts of resin tanning material G11 then again, again 45 ℃ of rotary drum processing 60 minutes.Add 70 parts of water then, again 60 ℃ of rotary drum processing 10 minutes.The retanning body lotion is mixed with 2.5 parts of fatting agent F1 and 2.5 parts of water-repelling agent H3, then 55 ℃ of stuffings 60 minutes.Then in 60 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, 55 ℃ of reduced pressure treatment 4 minutes, it was dry at room temperature to suspend, finishing, scrape soft and 55 ℃ of vacuumizes 3 minutes, carry out nubuck with the emery paper of 220 specifications and handle, dedusting is also removed from office the frame drying with stretching tight.
This generation has excellent washable, sweat proof, anti-oozing moved and the positive matte upper leather of the straight burr of anti-wiping fastness.The positive matte upper leather of straight burr that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 39:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 2.1 millimeters is 35 ℃ of washings 10 minutes in the body lotion that is made of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this in 20 minutes process by part add altogether 3 parts of sodium bicarbonates with reach 7.6 in and the pH value.This depickling body lotion is mixed with 8 parts of dyestuff 39I, then pH 7.5 and 40 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 8.6 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.8 with fixation, processed 60 minutes at 40 ℃ of rotary drums then.Body lotion uses 300 parts of water with the leather washed twice after changing at every turn, washs altogether 60 minutes.In 60 minutes process in the body lotion of 200 parts of water by part adding altogether 3.5 parts of formic acid to reach 3.8 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water and 3.5 parts of retanning material G27 45 ℃ of rotary drums processing 50 minutes.Add 2 parts of polymerization tanning material G19 then, after process time, add 5 parts of polymerization tanning material G18 at 15 minutes rotary drum again.45 ℃ of rotary drum processing 40 minutes, add 4 parts of resin tanning material G28 and 4 parts of resin tanning material G11 then again, again 45 ℃ of rotary drum processing 60 minutes.Add 70 parts of water then, again 60 ℃ of rotary drum processing 10 minutes.The retanning body lotion is mixed with 2.5 parts of fatting agent F1 and 2.5 parts of water-repelling agent H3, then 55 ℃ of stuffings 60 minutes.Then in 60 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.Body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, 55 ℃ of reduced pressure treatment 4 minutes, it was dry at room temperature to suspend, finishing, scrape soft and 55 ℃ of vacuumizes 3 minutes, carry out nubuck with the emery paper of 220 specifications and handle, dedusting is also removed from office the frame drying with stretching tight.
This generation has excellent washable, sweat proof, anti-oozing moved and the positive matte upper leather of the straight burr of anti-wiping fastness.The positive matte upper leather of straight burr that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Upper leather prescription 40:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.8 millimeters is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 40 ℃ of rotary drum processing 60 minutes in the body lotion that is made of 100 parts of water, 1.5 parts of tanning material G1 and 1 part of auxiliary agent HM7.Then body lotion is mixed with 1.5 parts of sodium formates, then 40 ℃ of rotary drum processing 30 minutes.After this add 3 parts of sodium bicarbonates altogether through 25 minutes each a little ground, and reach 7.6 in and the pH value.In the depickling body lotion, add 8.0 parts of dyestuff 13ae, then pH 7.0 and 40 ℃ of following dyeing 45 minutes.Each a little ground adds altogether 7.5 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.5 with fixation, processed 60 minutes at 40 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 200 parts of water each a little ground add altogether 4 parts of formic acid to reach 3.6 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 80 parts of water, 1 part of aldehyde tannage material G13 and 3 parts of polymerization tanning material G16 45 ℃ of retannings 60 minutes.Add 0.5 part of sodium bicarbonate then, add 5 parts of polymerization tanning material G18 after process time at 30 minutes rotary drum again, and 45 ℃ of retannings 30 minutes again.Then body lotion is mixed with 0.8 part of auxiliary agent HM5,3 parts of polymerization tanning material G17 and 2 parts of polymerization tanning material G19, again 45 ℃ of tannings 60 minutes to finishing.Add 70 parts of water then, again 60 ℃ of rotary drum processing 10 minutes.The retanning body lotion is mixed with 2.5 parts of fatting agent F6,1.5 parts of water-repelling agent H3 and 1.5 parts of fatting agent F2, and 45 ℃ of stuffings 60 minutes.Each a little ground adds altogether 4 parts of formic acid to reach pH 3.5 in 60 minutes process.After this, body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, in 60 ℃ of reduced pressure treatment 2 minutes, the dried overnight that at room temperature suspends, finishing is scraped soft and 60 ℃ of vacuumizes 2 minutes.
This generation has excellent washable, sweat proof, the anti-upper leather that moves with anti-wiping fastness that oozes.The upper leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Furniture leather prescription 1:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.1 millimeters is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 35 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 25 minutes each a little ground, and reach 7.8 in and the pH value.After adding 1.5 parts of HM2, with leather rotary drum processing 5 minutes.In the depickling body lotion, add 10.5 parts of dyestuff 41c then, then pH 7.3 and 35 ℃ of following dyeing 30 minutes.Add 0.5 part of sodium bicarbonate and rotary drum processing 60 minutes then.Each a little ground adds altogether 9.5 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.3-9.5 with fixation, processed 60 minutes at 35 ℃ of rotary drums then.After body lotion changes, use at every turn 300 parts of water with leather 40 ℃ of washed twice, washed altogether 60 minutes.Through 60 minutes in the body lotion of 200 parts of water each a little ground add altogether 3 parts of formic acid to reach 3.7 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 150 parts of water and 2 parts of retanning material G13 45 ℃ of rotary drums processing 60 minutes.Add 2 parts of polymerization tanning material G18 then.After process time, add 1.5 parts of sodium bicarbonates at 60 minutes rotary drums.45 ℃ of rotary drum processing 20 minutes, add 2 parts of fatting agent F1 and 0.2 part of auxiliary agent HM4 then again, stuffing is 20 minutes again.Body lotion is mixed with 5 parts of retanning material G5,3 parts of vegetable tanning material G22 and 2 parts of resin tanning material G11, and retanning is 60 minutes then.The retanning body lotion is mixed with 7 parts of fatting agent F1 and 3 parts of fatting agent F6, then 45 ℃ of stuffings 60 minutes.Then in 45 minutes process by part adding 5 parts of formic acid to reach 3.5 pH value.After this, body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet and strain and, repair, scrape soft and dried rotary drum processing with the leather frame drying that stretches tight.
This generation has excellent washable, sweat proof, the anti-furniture leather that moves with anti-wiping fastness that oozes.The furniture leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Furniture leather prescription 2:
Be that 1 100 weight portion traditional organic of 1.0-1.1 millimeter tans the ox-hide leather 30 ℃ of washings 15 minutes in the body lotion of 300 parts of water with shaving thickness, then 35 ℃ of rotary drum processing 10 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates.This body lotion has the pH value of 4.2-4.6.This body lotion is mixed with 8.7 parts of dyestuff 42g, then pH 5.5 and 35 ℃ of following dyeing 40 minutes.Then in 20 minutes process by part adding altogether 3 parts of sodium bicarbonates to reach the pH value of 7.3-7.8.For fixation, so that reaching between the 9.2-9.6, the pH value of body lotion processed 60 minutes at 35 ℃ of rotary drums then by part adding altogether 9 parts of sodium carbonate.After body lotion changes, use at every turn 300 parts of water and 1.5 parts of auxiliary agent HM3 with leather 40 ℃ of washed twice, washed altogether 60 minutes.In 60 minutes process, in the body lotion of 200 parts of water, add the pH value of 2 parts of formic acid to keep 4.3-4.6 altogether at 40 ℃ by part.
With the leather of dyeing thus in the new system body lotion that constitutes by 100 parts of water, 3 parts of polymerization tanning material G18 and 1.5 parts of fatting agent F6 35 ℃ of retannings 30 minutes.Add 6 parts of polymerization tanning material G18 and 10 parts of retanning material G18 then, then 35 ℃ of rotary drum processing 60 minutes.Add the processing of 1.5 parts of fatting agent F6 and rotary drum after 30 minutes, add 6 parts of polymerization tanning material G18 and 10 parts of retanning material G8, and 35 ℃ of retannings 60 minutes.The retanning body lotion is mixed with 10 parts of fatting agent F6, then 35 ℃ of stuffings 60 minutes.For fixing fatting agent, add 100 parts 45 ℃ hot water, and at 20 minutes rotary drum after process time, in 50 minutes process, add formic acid to reach 3.5 pH value.After this use 300 parts of water washings 15 minutes.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet tension with the leather frame drying that stretches tight, finishing, is scraped softly, and dried rotary drum processing is also strained.
This generation has excellent washable, sweat proof, the anti-white wet furniture leather that moves with anti-wiping fastness that oozes.The white wet furniture leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Furniture leather prescription 3:
Be that 1 100 weight portion traditional organic of 1.0-1.1 millimeter tans the ox-hide leather 30 ℃ of washings 15 minutes in the body lotion of 300 parts of water with shaving thickness, then 35 ℃ of rotary drum processing 10 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates.This body lotion has 4.4 pH value.This body lotion is mixed with 7.5 parts of dyestuff 46e, then pH 5.3 and 35 ℃ of following dyeing 45 minutes.In 20 minutes process by part adding altogether 3 parts of sodium bicarbonates to reach the pH value of 7.3-7.8.For fixation, so that reaching between the 9.5-10.0, the pH value of body lotion processed 60 minutes at 35 ℃ of rotary drums then by part adding altogether 8 parts of sodium carbonate.After body lotion changes, use the body lotion that constitutes by 300 parts of water that leather is washed three times at 40 ℃ at every turn, washed altogether 60 minutes.In 60 minutes process, in the body lotion of 200 parts of water, add the pH value of 1.5 parts of formic acid to keep 4.7-5.0 altogether at 40 ℃ by part.
With the leather of dyeing thus in the new system body lotion that constitutes by 50 parts of water, 15 parts of water-repelling agent H5 and 15 parts of polymerization tanning material G18 35 ℃ of retannings 90 minutes.Add 8 parts of water-repelling agent H5 and 6 parts of fatting agent F6 then, again 35 ℃ of stuffings 150 minutes.The hot water that adds 100 parts 45 ℃ then, and rotary drum was processed 10 minutes.In 40 minutes process, add 3 parts of formic acid then to reach 3.5 pH value.At last, leather is used water rinse simply.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet tension with the leather frame drying that stretches tight, finishing, is scraped softly, and dried rotary drum is processed and spent the night and strain.
This generation has excellent washable, sweat proof, the anti-wet in vain furniture leather of straight polymer base that moves with anti-wiping fastness that oozes.The wet in vain furniture leather of the straight polymer base that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Furniture leather prescription 4:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.1 millimeters is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 35 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 4 parts of sodium bicarbonates altogether through 30 minutes each a little ground, and reach 7.7 in and the pH value.After adding 1.5 parts of HM2, with leather rotary drum processing 5 minutes.In the depickling body lotion, add 9 parts of dyestuff 43ag then, then pH 7.4 and 35 ℃ of following dyeing 30 minutes.Add 0.5 part of sodium bicarbonate then and 7.5 times rotary drums of pH processing 60 minutes.Each a little ground adds altogether 9.8 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.3-9.8 with fixation, processed 60 minutes at 35 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at 40 ℃ at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 200 parts of water each a little ground add altogether 1.8 parts of formic acid to reach 4.6 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 150 parts of water and 6 parts of retanning material G18 45 ℃ of rotary drums processing 40 minutes.The pH value of this body lotion is 5.0.Add 0.8 part of sodium bicarbonate and rotary drum processing 20 minutes, so that the pH value of body lotion reaches 6.9.The retanning body lotion is mixed with 2 parts of fatting agent F1 and 0.2 part of auxiliary agent HM4, then 45 ℃ of pre-stuffings 20 minutes.Body lotion is mixed with 3 parts of retanning material G5,3 parts of vegetable tanning material G22 and 2 parts of resin tanning material G11, and retanning is 60 minutes then.The retanning body lotion is mixed with 7 parts of fatting agent F1 and 3 parts of fatting agent F6, then 45 ℃ of stuffings 60 minutes.Then in 45 minutes process by part adding 5 parts of formic acid to reach 3.5 pH value.After this, body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet and strain and, repair, scrape soft and dried rotary drum processing with the leather frame drying that stretches tight.
This generation has excellent washable, sweat proof, the anti-furniture leather that moves with anti-wiping fastness that oozes.The furniture leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Furniture leather prescription 5:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.1 millimeters is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 35 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 4 parts of sodium bicarbonates altogether through 30 minutes each a little ground, and reach 7.7 in and the pH value.After adding 1.5 parts of HM2, with leather rotary drum processing 5 minutes.In the depickling body lotion, add 8 parts of dyestuff 47ac then, then pH 7.5 and 35 ℃ of following dyeing 30 minutes.Add 0.5 part of sodium bicarbonate then and 7.6 times rotary drums of pH processing 60 minutes.Each a little ground adds altogether 9 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.5-9.9 with fixation, processed 60 minutes at 35 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at 40 ℃ at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 200 parts of water each a little ground add altogether 3.0 parts of formic acid to reach 3.7 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 150 parts of water and 1 part of retanning material G13 45 ℃ of rotary drums processing 40 minutes.Add 6 parts of polymerization tanning material G18 then and 45 ℃ of retannings 40 minutes.The pH value of this body lotion is 4.2.Add 1.5 parts of sodium bicarbonates and rotary drum processing 20 minutes, so that the pH value of body lotion reaches 6.2.The retanning body lotion is mixed with 2 parts of fatting agent F1 and 0.2 part of auxiliary agent HM4, then 45 ℃ of pre-stuffings 20 minutes.Body lotion is mixed with 3 parts of retanning material G5,3 parts of vegetable tanning material G22 and 2 parts of resin tanning material G11, and retanning is 60 minutes then.The retanning body lotion is mixed with 7 parts of fatting agent F1 and 3 parts of fatting agent F6, then 45 ℃ of stuffings 60 minutes.The pH value of this body lotion is 5.6.Then in 45 minutes process by part adding 5 parts of formic acid to reach 3.5 pH value.After this, body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet and strain and, repair, scrape soft and dried rotary drum processing with the leather frame drying that stretches tight.
This generation has excellent washable, sweat proof, the anti-furniture leather that moves with anti-wiping fastness that oozes.The furniture leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Furniture leather prescription 6:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.1 millimeters is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 35 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 4 parts of sodium bicarbonates altogether through 30 minutes each a little ground, and reach 7.7 in and the pH value.After adding 1.5 parts of HM2, with leather rotary drum processing 5 minutes.In the depickling body lotion, add 7 parts of dyestuff 49b then, then pH 7.5 and 35 ℃ of following dyeing 30 minutes.Add 0.5 part of sodium bicarbonate then and 7.6 times rotary drums of pH processing 60 minutes.Each a little ground adds altogether 8 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.5-9.9 with fixation, processed 60 minutes at 35 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at 40 ℃ at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 200 parts of water each a little ground add altogether 3.0 parts of formic acid to reach 3.7 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 150 parts of water and 1 part of retanning material G13 45 ℃ of rotary drums processing 40 minutes.Add 6 parts of polymerization tanning material G18, and 45 ℃ of retannings 40 minutes.The pH value of this body lotion is 4.2.Add 1 part of sodium bicarbonate and rotary drum processing 20 minutes.The retanning body lotion is mixed with 2 parts of fatting agent F1, and 45 ℃ of stuffings 20 minutes.Body lotion is mixed with 10 parts of retanning material G3, and rotary drum processing is 90 minutes then.Carried out stuffing 60 minutes with 6 parts of fatting agent F1 and 2 parts of fatting agent F6 at 45 ℃ then.Then in 45 minutes process by part adding 5 parts of formic acid to reach 3.5 pH value.After this, body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet and strain and, repair, scrape soft and dried rotary drum processing with the leather frame drying that stretches tight.
This generation has excellent washable, sweat proof, the anti-furniture leather that moves with anti-wiping fastness that oozes.The furniture leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Furniture leather prescription 7:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.1 millimeters is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 35 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 30 minutes each a little ground, and reach 7.6 in and the pH value.In the depickling body lotion, add 5.5 parts of dyestuff 52e then, then pH 7.5 and 35 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 7 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.2-9.6 with fixation, processed 60 minutes at 35 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at 40 ℃ at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 150 parts of water each a little ground add altogether 2.0 parts of formic acid to reach 5.2 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 100 parts of water, 3 parts of polymerization tanning material G18 and 1.5 parts of polymerization tanning material G19 45 ℃ of rotary drums processing 20 minutes.This retanning body lotion is mixed with 1 part of fatting agent F6 and 0.5 part of fatting agent F2, then 45 ℃ of pre-stuffings 20 minutes.Body lotion is mixed with 3 parts of polymerization tanning material G18,6 parts of retanning material G8 and 2 parts of vegetable tanning material G22, and retanning is 60 minutes then.Use 6 parts of fatting agent F6,2 parts of fatting agent F2 and 1 part of fatting agent F3 45 ℃ of stuffings 60 minutes then.Then in 45 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value, add 100 parts of water and rotary drum then and processed 10 minutes.After this, body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet and strain and, repair, scrape soft and dried rotary drum processing with the leather frame drying that stretches tight.
This generation has excellent washable, sweat proof, the anti-furniture leather that moves with anti-wiping fastness that oozes.The furniture leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Furniture leather prescription 8:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.1 millimeters is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 35 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 25 minutes each a little ground, and reach 7.6 in and the pH value.In the depickling body lotion, add 6 parts of dyestuff 53b then, then pH 7.5 and 35 ℃ of following dyeing 50 minutes.Each a little ground adds altogether 7 parts of solid sodium carbonates so that the pH value of body lotion reaches between the 9.5-10.0 with fixation, processed 60 minutes at 35 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at 40 ℃ at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 150 parts of water and 2.2 parts of formic acid each a little ground reach 4.9 pH value.
With the rotary drum processing 30 minutes in the new system body lotion that constitutes by 100 parts of water and 2 parts of retanning material G14 of the leather of dyeing thus.Add 5 parts of polymerization tanning material G18 then, again 45 ℃ of retannings 40 minutes.The retanning body lotion is mixed with 2 parts of fatting agent F6 and 1 part of fatting agent F2, then 45 ℃ of pre-stuffings 20 minutes.Body lotion is mixed with 6 parts of retanning material G2,2 parts of vegetable tanning material G22 and 2 parts of resin tanning material G28, and retanning is 60 minutes then.Use 8 parts of fatting agent F6,2 parts of fatting agent F2 and 1 part of fatting agent F3 45 ℃ of stuffings 60 minutes then.In 45 minutes process,, after this add 100 parts of water and rotary drum and processed 10 minutes by part adding 4 parts of formic acid to reach 3.5 pH value.Then with the body lotion discharge and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet and strain and, repair, scrape soft and dried rotary drum processing with the leather frame drying that stretches tight.
This generation has excellent washable, sweat proof, the anti-furniture leather that moves with anti-wiping fastness that oozes.The furniture leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Furniture leather prescription 9:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is 1.1 millimeters is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 35 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 25 minutes each a little ground, and reach 7.8 in and the pH value.In the depickling body lotion, add 5.7 parts of dyestuff 58b then, then pH 7.7 and 35 ℃ of following dyeing 60 minutes.Each a little ground adds altogether 9 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.5-10.0 with fixation, processed 60 minutes at 35 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at 40 ℃ at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 150 parts of water each a little ground add altogether 2.3 parts of formic acid to reach 5.0 pH value.
With the rotary drum processing 30 minutes in the new system body lotion that constitutes by 100 parts of water and 2 parts of retanning material G14 of the leather of dyeing thus.Add 6 parts of polymerization tanning material G18 then, again 45 ℃ of retannings 40 minutes.The retanning body lotion is mixed with 2 parts of fatting agent F1, then 45 ℃ of pre-stuffings 20 minutes.Body lotion is mixed with 4 parts of retanning material G3 and 2 parts of vegetable tanning material G22, and rotary drum processing is 60 minutes then.Add 2 parts of polymerization tanning material G19, and then retanning 20 minutes.In the retanning body lotion, add 6 parts of fatting agent F1,4 parts of fatting agent F6 and 1 part of fatting agent F3, then 45 ℃ of stuffings 60 minutes.In 45 minutes process,, after this add 100 parts of water and rotary drum and processed 10 minutes by part adding 4 parts of formic acid to reach 3.5 pH value.Then with the body lotion discharge and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet and strain and, repair, scrape soft and dried rotary drum processing with the leather frame drying that stretches tight.
This generation has excellent washable, sweat proof, the anti-furniture leather that moves with anti-wiping fastness that oozes.The furniture leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Automobile leather prescription 1:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is the 1.2-1.3 millimeter is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 35 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3 parts of sodium bicarbonates altogether through 25 minutes each a little ground, and reach 7.8 in and the pH value.After adding 1.5 parts of HM2, with leather rotary drum processing 5 minutes.In the depickling body lotion, add 4.7 parts of dyestuff 59d then, then pH 7.3 and 35 ℃ of following dyeing 30 minutes.Add 0.5 part of sodium bicarbonate then and rotary drum processing 60 minutes under pH7.4.Each a little ground adds altogether 5 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.4-9.8 with fixation, processed 60 minutes at 35 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at 40 ℃ at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 200 parts of water by part adding altogether 3 parts of formic acid to reach 3.7 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 150 parts of water and 1.5 parts of retanning material G13 45 ℃ of rotary drums processing 60 minutes.Add 8 parts of polymerization tanning material G18 then, again 45 ℃ of retannings 40 minutes.Add 1.5 parts of sodium bicarbonates, and at 20 minutes rotary drum after process time, with 2 parts of fatting agent F1 and 0.2 part of auxiliary agent HM4 45 ℃ of pre-stuffings 20 minutes.Body lotion is mixed with 4 parts of retanning material G5,4 parts of vegetable tanning material G21 and 2 parts of resin tanning material G11, and retanning is 60 minutes then.The retanning body lotion is mixed with 7 parts of fatting agent F1 and 3 parts of fatting agent F6, again 45 ℃ of stuffings 60 minutes.Then in 45 minutes process by part adding 5 parts of formic acid to reach 3.5 pH value, body lotion is oozed and with the leather brief cold rinse.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet and strain and, repair, scrape soft and dried rotary drum processing with the leather frame drying that stretches tight.
This generation has excellent washable, sweat proof, the anti-automobile leather that moves with anti-wiping fastness that oozes.The automobile leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Automobile leather prescription 2:
Be that 1 100 weight portion traditional organic of 1.1-1.2 millimeter tans the ox-hide leather 30 ℃ of washings 15 minutes in the body lotion of 300 parts of water with shaving thickness, then 35 ℃ of rotary drum processing 10 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates.This body lotion has 4.4 pH value.This body lotion is mixed with 7.2 parts of dyestuffs 56, then pH 4.5 and 35 ℃ of following dyeing 60 minutes.In 20 minutes process by part adding altogether 3 parts of sodium bicarbonates to reach the pH value of 7.1-7.6.For fixation, so that reaching between the 9.6-9.7, the pH value of body lotion processed 90 minutes at 35 ℃ of rotary drums then by part adding altogether 8 parts of sodium carbonate.After body lotion changes, use the body lotion that constitutes by 300 parts of water that leather is washed three times at 40 ℃ at every turn, washed altogether 60 minutes.Through 60 minutes 40 ℃ in the body lotion of 300 parts of water by part adding altogether 2 parts of formic acid to reach 4.2 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 100 parts of water and 5 parts of polymerization tanning material G18 35 ℃ of retannings 10 minutes.Add 1 part of fatting agent F6 and 0.5 part of fatting agent F2 then so that 35 ℃ of pre-stuffings 20 minutes.Add 5 parts of polymerization tanning material G18 and 10 parts of retanning material G8 so that retanning 60 minutes.The retanning body lotion is mixed with 1 part of fatting agent F6 and 0.5 part of fatting agent F2, so that 35 ℃ of stuffings 30 minutes.With 5 parts of polymerization tanning material G18 and 10 parts of retanning material G18 and 10 parts of retanning material G8 tanning was finished through 90 minutes then.Then after adding fatting agent F6 and 2 parts of fatting agent F2,35 ℃ of stuffings 60 minutes.For fixing fatting agent, add 100 parts 45 ℃ hot water, and at 20 minutes rotary drum after process time, in 60 minutes process, add 3 parts of formic acid to reach 3.5 pH value.After this with leather with 300 parts of water washings 15 minutes.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet tension, the leather frame drying that stretches tight, soft, dried rotary drum processing and tension are scraped in finishing.
This generation has excellent washable, sweat proof, the anti-white wet steam car leather that moves with anti-wiping fastness that oozes.The white wet steam car leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Automobile leather prescription 3:
Be that 1 100 weight portion traditional organic of 1.1-1.2 millimeter tans the ox-hide leather 30 ℃ of washings 15 minutes in the body lotion of 300 parts of water with shaving thickness, then 35 ℃ of rotary drum processing 10 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates.This body lotion has 4.4 pH value.This body lotion is mixed with 3.5 parts of dyestuffs 54, then pH 4.5 and 35 ℃ of following dyeing 40 minutes.In 20 minutes process by part adding altogether 3 parts of sodium bicarbonates to reach 7.6 pH value.For fixation, so that reaching between the 9.6-9.7, the pH value of body lotion processed 90 minutes at 35 ℃ of rotary drums then by part adding altogether 5 parts of sodium carbonate.After body lotion changes, use by 300 parts of water at every turn leather is washed three times at 40 ℃, washed altogether 60 minutes.In 60 minutes process, in the body lotion of 200 parts of water by part adding altogether 1.5 parts of formic acid to keep 5.0 pH value at 40 ℃.
With the leather of dyeing thus in the new system body lotion that constitutes by 50 parts of water, 15 parts of water-repelling agent H5 and 15 parts of polymerization tanning material G18 35 ℃ of retannings 90 minutes.Add 4 parts of water-repelling agent H5,6 parts of fatting agent F6 and 4 parts of fatting agent F2 then, again 35 ℃ of stuffings 150 minutes.The hot water that adds 100 parts 45 ℃ then, and rotary drum was processed 10 minutes.Then in 60 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.At last, with leather with 300 parts of water washings 15 minutes.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet tension, the leather frame drying that stretches tight, finishing is scraped softly, and dried rotary drum processing is spent the night, and scrapes soft and removes from office the frame drying with stretching tight.
This generation has excellent washable, sweat proof, the anti-white wet steam car leather of straight polymer base that moves with anti-wiping fastness that oozes.The white wet steam car leather of the straight polymer base that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Automobile leather prescription 4:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is the 1.1-1.2 millimeter is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 35 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3.5 parts of sodium bicarbonates altogether through 30 minutes each a little ground, and reach 7.6 in and the pH value.In the depickling body lotion, add 5.2 parts of dyestuffs 51 then, then pH 7.5 and 35 ℃ of following dyeing 30 minutes.Add 0.5 part of sodium bicarbonate then and 7.6 times rotary drums of pH processing 60 minutes.Each a little ground adds altogether 7 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.3-9.9 with fixation, processed 60 minutes at 35 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at 40 ℃ at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 200 parts of water each a little ground add altogether 3.5 parts of formic acid to reach 3.5 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 150 parts of water and 3 parts of retanning material G12 45 ℃ of rotary drums processing 10 minutes.After adding 1.5 parts of fatting agent F1, with leather 45 ℃ of pre-stuffings 50 minutes.Add 0.5 part of sodium bicarbonate and rotary drum processing 30 minutes then.Body lotion is mixed with 5 parts of polymerization tanning material G18 and 1.5 parts of fatting agent F1, and rotary drum processing is 40 minutes then.The retanning body lotion is mixed with 1.5 parts of fatting agent F1 and 1.5 parts of fatting agent F2, then 45 ℃ of stuffings 20 minutes.Add 8 parts of retanning material G6,8 parts of retanning material G8 and 2 parts of polymerization tanning material G19 then.Add 3 parts of fatting agent F1,1.5 parts of fatting agent F6 and 1.5 parts of fatting agent F2, then 45 ℃ of stuffings 90 minutes at 60 minutes rotary drum again after process time.Then in 50 minutes process by part adding 3.5 parts of formic acid to reach 3.5 pH value.After this, body lotion is oozed and with leather with 300 parts of water washings 15 minutes.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet and strain and, repair, scrape soft and dried rotary drum processing with the leather frame drying that stretches tight.
This generation has excellent washable, sweat proof, the anti-automobile leather that moves with anti-wiping fastness that oozes.The automobile leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Automobile leather prescription 5:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is the 1.1-1.2 millimeter is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 35 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this add 3.5 parts of sodium bicarbonates altogether through 30 minutes each a little ground, and reach 7.5 in and the pH value.In the depickling body lotion, add 4.7 parts of dyestuffs 48, then pH 7.5 and 35 ℃ of following dyeing 30 minutes.Add 0.5 part of sodium bicarbonate then and 7.6 times rotary drums of pH processing 60 minutes.Each a little ground adds altogether 6 parts of solid sodium carbonates so that the pH value of body lotion reaches between the 9.3-9.9 with fixation, processed 60 minutes at 35 ℃ of rotary drums then.After body lotion changes, with 300 parts of water leather is washed three times at 40 ℃ at every turn, washed altogether 60 minutes.Through 60 minutes in the body lotion of 200 parts of water each a little ground add altogether 1.5 parts of formic acid to reach 5.5 pH value.
With the leather of dyeing thus in the new system body lotion that constitutes by 120 parts of water and 6 parts of polymerization tanning material G18 45 ℃ of rotary drums processing 5 minutes.Add 2 parts of polymerization tanning material G19 then.At 5 minutes rotary drum again after process time, add 1.5 parts of fatting agent F1 and 45 ℃ of rotary drums processing 30 minutes.Add 1.5 parts of fatting agent F1 and 1 part of fatting agent F2 then, pre-again stuffing 20 minutes.Body lotion is mixed with 4 parts of polymerization tanning material G18, and rotary drum processing is 20 minutes then.Add 8 parts of retanning material G6 and 8 parts of retanning material G8 then.After process time, add 1 part of polymerization tanning material G19 at 40 minutes rotary drums, tanning 20 minutes is to finishing then.The retanning body lotion is mixed with 6 parts of fatting agent F1 and 2 parts of fatting agent F2, then 45 ℃ of stuffings 90 minutes.Then in 45 minutes process by part adding 3.5 parts of formic acid to reach 3.5 pH value.After this, body lotion is oozed and with leather with 300 parts of water washings 15 minutes.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet and strain and, repair, scrape soft and dried rotary drum processing with the leather frame drying that stretches tight.
This generation has excellent washable, sweat proof, the anti-automobile leather that moves with anti-wiping fastness that oozes.The automobile leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Clothing leather prescription 1:
The traditional chrome tanning glace kid leather of 1 100 weight portion that with shaving thickness is 0.7 millimeter is 35 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 150 parts of water and 1.5 parts of sodium formates, after this through each a little ground interpolation in 20 minutes 3 parts of sodium bicarbonates altogether.Add 3 parts of auxiliary agent HM4 and rotary drum processing 10 minutes then.The pH value of this body lotion is 7.7.This depickling body lotion is mixed with 9 parts of dyestuffs 44, then pH 7.4 and 40 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 9 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.6-9.8 with fixation, and leather was processed 60 minutes at 40 ℃ of rotary drums.After body lotion changes, with 300 parts of water leather is washed three times at 40 ℃ at every turn, washed altogether 60 minutes.In 55 minutes process, each a little ground adds altogether 4 parts of formic acid to reach 3.6 pH value in the body lotion of 150 parts of water.
With the leather of dyeing thus in the new system body lotion that constitutes by 150 parts of water and 2 parts of retanning material G14 45 ℃ of rotary drums processing 40 minutes.Add 2 parts of sodium formates then.At 20 minutes rotary drum again after process time, add 2 parts of sodium bicarbonates and 45 ℃ of rotary drums processing 20 minutes.The pH value of this body lotion is 5.2.This body lotion is mixed with 8 parts of retanning material G3 and 2 parts of retanning material G11, and rotary drum processing is 40 minutes then.Add 6 parts of fatting agent F1,4 parts of fatting agent F3 and 1 part of water-repelling agent H7 then.After process time, add 4 parts of polymerization tanning material G10 and rotary drum processing 20 minutes at 20 minutes rotary drums.Add 6 parts of fatting agent F1,4 parts of fatting agent F3 and 1 part of water-repelling agent H7 then.After 40 minutes stuffing time, in 45 minutes process by part adding 5 parts of formic acid to reach 3.5 pH value.After this, body lotion is oozed and with leather with 300 parts of water washings 15 minutes.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, it is dry to suspend, and finishing is scraped softly, and dried rotary drum processing is also removed from office the frame drying with stretching tight.
This generation has excellent washable, sweat proof, the anti-clothing leather that moves with anti-wiping fastness that oozes.The clothing leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Clothing leather prescription 2:
The traditional chrome-tanned bovine leather of 1 100 weight portion that with shaving thickness is the 0.8-0.9 millimeter is 35 ℃ of washings 10 minutes in the body lotion of 200 parts of water, then 40 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 100 parts of water and 1.5 parts of sodium formates, after this through 25 minutes each a little ground add altogether 3.2 parts of sodium bicarbonates with reach 7.6 in the pH value.This depickling body lotion is mixed with 8 parts of dye mixture 12hu, then pH 7.5 and 40 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 8.7 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.6-9.8 with fixation, and leather was processed 90 minutes at 40 ℃ of rotary drums.After body lotion changes, with 300 parts of water leather is washed three times at every turn, washed altogether 60 minutes.In 60 minutes process, each a little ground adds altogether 5 parts of formic acid to reach 3.3 pH value in the body lotion of 200 parts of water.
With the leather of dyeing thus in the new system body lotion that constitutes by 100 parts of water and 3 parts of retanning material G12 30 ℃ of rotary drums processing 10 minutes.Add 4 parts of chrome tanning material G24 and 1.5 parts of auxiliary agent HM6, then at 30 ℃ of chrome tannings 50 minutes again.Add 1 part of sodium formate then, rotary drum processing is 90 minutes again.After adding 100 parts of water, leather chrome tanning is again spent the night.Then body lotion is drained and leather was washed 10 minutes at 45 ℃ with 300 parts of water.With leather rotary drum processing 20 minutes in the new system body lotion that constitutes by 100 parts of water and 1.5 parts of water-repelling agent H5.Add 5 parts of polymerization tanning material G18 then, after process time, add 2 parts of retanning material G5 at 5 minutes rotary drums.Retanning added 2 parts of polymerization tanning material G19 after 30 minutes again, with leather rotary drum processing 10 minutes, added 5 parts of retanning material G5 then.Retanning added 4 parts of water-repelling agent H8,6 parts of water-repelling agent H2,7 parts of water-repelling agent H7 and 0.8 part of auxiliary agent HM4, then 45 ℃ of stuffings 60 minutes after 60 minutes again.Add 100 parts of water then and 60 ℃ of rotary drums processing 10 minutes.Then in 45 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.After this, body lotion is drained and with leather washing 15 minutes in the new system body lotion that constitutes by 300 parts of water and 0.15 part of formic acid.With leather in the new system body lotion that constitutes by 150 parts of water, 2 parts of water-repelling agent H7 and 0.2 part of auxiliary agent HM4 30 ℃ of rotary drums processing 20 minutes.Add 5 parts of mineral tanning agent G30, fix 90 minutes then.At last, use the body lotion washing that constitutes by 300 parts of water and 0.2 part of formic acid once leather, and use the body lotion washing that constitutes by 300 parts of water and 0.1 part of formic acid once, at every turn all 30 ℃ of washings 10 minutes.
Dyeing thus, retanning and hydrophobic leather are taken horse spend the night, stretch then, wet tension and with the leather frame drying that stretches tight, finishing is scraped softly, and dried rotary drum processing is also removed from office the frame drying with stretching tight.
This generation has excellent washable, sweat proof, the anti-hydrophobic motorcycle clothes leather that moves with anti-wiping fastness that oozes.The motorcycle clothes leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Glove leather prescription 1:
The traditional chrome tanning saffian leather of 1 100 weight portion that with shaving thickness is the 0.5-0.7 millimeter is 35 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 35 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 120 parts of water and 1.5 parts of sodium formates, after this through each a little ground interpolation in 30 minutes 3.1 parts of sodium bicarbonates altogether.Add 3 parts of auxiliary agent HM2 and rotary drum processing 5 minutes then.The pH value of this body lotion is 7.8.This depickling body lotion is mixed with 10 parts of dye mixture 13hi, then pH 7.4 and 35 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 9 parts of sodium carbonate so that the pH value of body lotion reaches between the 9.6-9.8 with fixation, and leather was processed 90 minutes at 35 ℃ of rotary drums.After body lotion changes, use at every turn 300 parts of water and 1.5 parts of auxiliary agent HM3 with leather 40 ℃ of washed twice, washed altogether 50 minutes.In 60 minutes process, each a little ground adds altogether 3 parts of formic acid to reach 3.4 pH value in the body lotion of 200 parts of water.
With the leather of dyeing thus in the new system body lotion that constitutes by 150 parts of water and 1.5 parts of retanning material G13 40 ℃ of rotary drums processing 60 minutes.Add 1.5 parts of sodium formates then.At 20 minutes rotary drums after process time, add 1 part of sodium bicarbonate and 40 ℃ of rotary drums processing 30 minutes.This body lotion is mixed with 6 parts of polymerization tanning material G18, and rotary drum processing is 40 minutes then.After this add 6 parts of retanning material G3, retanning is 30 minutes again.Add 5 parts of water-repelling agent H3,2 parts of polymerization tanning material G19,10 parts of retanning material G9,4 parts of fatting agent F9 and 1 part of sodium carbonate then, retanning is 120 minutes then.In 45 minutes process by part adding 3.5 parts of formic acid to reach 3.5 pH value.After adding 3 parts of water-repelling agent H4 then, rotary drum processing 20 minutes.After this, body lotion is oozed and, all used the body lotion washing that constitutes by 300 parts of water and 0.2 part of formic acid 15 minutes at every turn the leather washed twice.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet-as to strain and, repair with the leather frame drying that stretches tight, scrape soft and dried rotary drum processing.
This generation has excellent washable, sweat proof, the anti-glove leather that moves with anti-wiping fastness that oozes.The glove leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Glove leather prescription 2:
The traditional chrome tanning saffian leather of 1 100 weight portion that with shaving thickness is the 0.5-0.7 millimeter is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 35 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 120 parts of water and 1.5 parts of sodium formates, after this through each a little ground interpolation in 30 minutes 3.1 parts of sodium bicarbonates altogether.Add 3 parts of auxiliary agent HM2 and rotary drum processing 5 minutes then.The pH value of this body lotion is 7.8.This depickling body lotion is mixed with 8 parts of dye mixture 13gz, then pH 7.4 and 35 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 8 parts of solid sodium carbonates so that the pH value of body lotion reaches between the 9.6-9.8 with fixation, and leather was processed 90 minutes at 35 ℃ of rotary drums.After body lotion changes, use at every turn 300 parts of water and 1.5 parts of auxiliary agent HM3 with leather 40 ℃ of washed twice, washed altogether 50 minutes.In 60 minutes process, each a little ground adds altogether 1.3 parts of formic acid to reach 5.8 pH value in the body lotion of 200 parts of water.
With the rotary drum processing 20 minutes in the new system body lotion that constitutes by 150 parts of water and 4 parts of water-repelling agent H3 of the leather of dyeing thus.Add 8 parts of polymerization tanning material G18 then, retanning is 40 minutes again, after this, adds 8 parts of retanning material G2, again 40 ℃ of rotary drum processing 30 minutes.Add 4 parts of water-repelling agent H3,0.5 part of auxiliary agent HM4,8 parts of retanning material G9,3 parts of fatting agent F9 and 0.8 part of sodium carbonate then, retanning is 120 minutes then.In 35 minutes process by part adding 3.5 parts of formic acid to reach 3.5 pH value.Add 3 parts of water-repelling agent H7 and 3 parts of auxiliary agent HM4 then, and rotary drum was processed 20 minutes.After this, body lotion is oozed and, all used the body lotion washing that constitutes by 300 parts of water and 0.2 part of formic acid 15 minutes at every turn the leather washed twice.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet-as to strain and, repair with the leather frame drying that stretches tight, scrape soft and dried rotary drum processing.
This generation has excellent washable, sweat proof, the anti-glove leather that moves with anti-wiping fastness that oozes.The glove leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.
Glove leather prescription 3:
The traditional chrome tanning saffian leather of 1 100 weight portion that with shaving thickness is the 0.5-0.7 millimeter is 30 ℃ of washings 10 minutes in the body lotion of 300 parts of water, then 35 ℃ of rotary drum processing 5 minutes in the body lotion that constitutes by 120 parts of water and 1.5 parts of sodium formates, after this through each a little ground interpolation in 30 minutes 3.1 parts of sodium bicarbonates altogether.Add 3 parts of auxiliary agent HM2 and rotary drum processing 5 minutes then.The pH value of this body lotion is 7.8.This depickling body lotion is mixed with 8.2 parts of dye mixture 12hb, then pH 7.4 and 35 ℃ of following dyeing 40 minutes.Each a little ground adds altogether 8 parts of solid sodium carbonates so that the pH value of body lotion reaches between the 9.6-9.8 with fixation, and leather was processed 90 minutes at 35 ℃ of rotary drums.After body lotion changes, use at every turn 300 parts of water with leather 40 ℃ of washed twice, washed altogether 60 minutes.In 60 minutes process, each a little ground adds altogether 1.2 parts of formic acid to reach 5.7 pH value in the body lotion of 200 parts of water.
With the rotary drum processing 20 minutes in the new system body lotion that constitutes by 100 parts of water, 1 part of water-repelling agent H1 and 0.2 part of auxiliary agent HM4 of the leather of dyeing thus.Add 10 parts of water-repelling agent H5 and rotary drum processing 5 minutes then.Add 10 parts of polymerization tanning material G18 and retanning 55 minutes then.The retanning body lotion is mixed with 5 parts of water-repelling agent H5,8 parts of water-repelling agent H1 and 0.8 part of auxiliary agent HM4, and stuffing is 120 minutes then.Add the processing of 100 parts of water and rotary drum after 20 minutes, in 50 minutes process by part adding 4 parts of formic acid to reach 3.5 pH value.After this, body lotion is oozed and, all used the body lotion washing that constitutes by 300 parts of water and 0.2 part of formic acid 15 minutes at every turn the leather washed twice.
The leather of dyeing thus, retanning and stuffing is taken horse spend the night, stretch then, wet-as to strain and, repair with the leather frame drying that stretches tight, scrape soft and dried rotary drum processing.
This generation has excellent washable, sweat proof, the anti-hydrophobic glove leather of straight polymer base that moves with anti-wiping fastness that oozes.The glove leather that one of the dyestuff that can make usefulness embodiment 1a to 59k in a similar way dyes.

Claims (20)

1. one kind with the method for at least a dyestuff F with leather coloring, and wherein dyestuff F contains the group that can be activated by alkali of at least one formula A:
Figure A2004800321060002C1
Wherein
The key that-----representative links to each other with dye molecule;
X is an electron withdraw group,
K is 1,2 or 3,
N be 0 or 1 and
B is CH=CH 2Group or CH 2-CH 2-Q group, wherein Q is the group that theobromine separates,
This method comprises that being not less than 7.5 the water bath shampoo that contains at least a dyestuff F with the pH value handles leather.
2. according to the process of claim 1 wherein that at least one radicals X is SO among the formula A 3The H group.
3. according to the method for claim 1 or 2, the B among its Chinese style A is CH=CH 2, CH 2-CH 2-O-SO 3H group or CH 2-CH 2-O-C (O) CH 3Group.
4. according to each method of aforementioned claim, wherein group A by-NH-or-the N=N-group links to each other with dye molecule.
5. according to the method for claim 4, wherein dyestuff F is selected from dyestuff, anthraquinone dye, azo dyes, first _ dyestuff, dioxazine dyestuff, actidine dyestuff, xanthene dye, poly-methine dyes, stilbene dyestuff, sulphur dyestuff and the triarylmethane dye of phthalocyanine series.
6. according to each method of aforementioned claim, wherein n=0.
7. according to the method for claim 6, wherein group A is selected from following groups A1 to A12:
Figure A2004800321060003C1
8. according to each method of aforementioned claim, wherein dyestuff F is selected from general formula I to the dyestuff of XV and the metal complex of these dyestuffs:
Dk 1-N＝N-[P-N＝N-] pKk 1[-N＝N-Dk 2] m (I)
Dk 1-N＝N-Napht 1[-N＝N-Tk 1] r[-N＝N-Kk 1] k[-N＝N-Dk 2] n (II)
Dk 1-N＝N-Napht 1-N＝N-Tk 1-N＝N-Kk 1-N＝N-Tk 2-N＝N-Napht 2-N＝N-Dk 2 (III)
Dk 1-N＝N-Kk 1-N＝N-Tk 1-N＝N-Kk 2-N＝N-Dk 2 (IV)
Dk 1-N＝N-[P-N＝N-] pNapht 1[-N＝N-R] r-NH-Tr 1-NH-Dk 2 (V)
Dk 1-N＝N-P-NH-Tr 1-NH-R-N＝N-Dk 2 (VI)
Dk 1-N＝N-Napht 1-N＝N-Tk 1-N＝N-P-NH-Tr 1-NH-Dk 2 (VII)
Dk 1-N＝N-Napht 1-NH-Tr 1-NH-P-NH-Tr 2-NH-Napht 2-N＝N-Dk 2 (VIII)
Dk 1-N＝N-Napht 1-NH-Tr 1-NH-Tk 1-NH-Tr 2-NH-Napht 2-N＝N-Dk 2 (IX)
Dk 1[-N＝N-L] k-NH-Tr 1-NH-M-N＝N-Napht 1-N＝N-P-NH-Tr 2-NH-[R-N＝N-] nDk 2 (X)
Dk 1-N＝N-Kk 1-N＝N-Tk 1-NH-Tr 1-NH-Dk 2 (XI)
Dk 1-N＝N-[P-N＝N-] pR-N＝N-Kk 1[-N＝N-Dk 2] n (XII)
Dk 1-N＝N-Pyr-A (XIII)
Kk 3-N＝N-Tk 1-N＝N-Kk 1-N＝N-A (XIV)
Dk 1-N＝N-P-N＝N-Kk 1-N＝N-R-N＝N-Dk 2 (XV)
Wherein:
K, n, p and r are 0 or 1 independently, and condition is the k+n+r=1,2 or 3 among the formula II;
M is 0,1 or 2;
Dk 1, Dk 2Represent the group that is derived from the group of arylamine or represents formula A independently, condition is in each formula of formula I-XII and XV, Dk 1And Dk 2At least one represents the group of formula A;
Kk 1, Kk 2Represent independently single-, two-or trivalent aryl, it is derived from benzene, naphthalene, pyrazoles, quinoline, diphenylamines, diphenyl methane, pyrimidine, pyridine or diphenyl ether, and it can be chosen wantonly and comprises one or more following groups as substituting group: SO 3H, COOH, CN, CONH 2, OH, NH 2, NO 2, halogen, C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, carboxyl-C 1-C 4Alkyl, C 1-C 4Alkoxyl, C 1-C 4Alkyl amino, C 1-C 4Dialkyl amido, C 1-C 4Alkyl amino-carbonyl, C 1-C 4Dialkyl amino carbonyl, C 1-C 4Alkyl-carbonyl-amino, N-(C 1-C 4Alkyl-carbonyl)-N-(C 1-C 4Alkyl-carbonyl) amino, C 1-C 4Alkyl amino carbonyl oxy, C 1-C 4Dialkyl amino carbonyl oxy, C 1-C 4Alkyl amino-carbonyl amino, C 1-C 4Dialkyl amino carbonyl amino, phenyl amino ketonic oxygen base, phenyl amino carbonylamino, C 1-C 4Alkoxycarbonyl amino, C 1-C 4Hydroxyl-C 1-C 4Alkyl amino, carboxyl-C 1-C 4Alkyl amino, phenylcarbonyl group amino, C 1-C 4Alkyl sulphonyl, hydroxyl-C 1-C 4Alkyl sulphonyl, C 1-C 4Alkyl amino sulfonyl, C 1-C 4Alkyl sulfonyl-amino, phenyl sulfonyl, phenyl sulfonyl amino, formamide, formula SO 2NR 56R 57Group, R wherein 56And R 57Represent hydrogen, C independently 1-C 4Alkyl, formoxyl, C 1-C 4Alkyl-carbonyl, C 1-C 4Alkoxy carbonyl, NH 2-CO or C 1-C 4Alkyl amino-carbonyl, C 1-C 4Alkyl amino sulfonyl amino, two-C 1-C 4Alkyl amino sulfonyl amino, phenyl sulfonyl amino---it can be selected from C by one or two on phenyl ring 1-C 4Alkyl, C 1-C 4The substituting group of alkoxy or halogen replaces or is optional by 1,2 or 3 following groups: OH, halogen, C 1-C 45-that alkyl or phenyl replaces or 6-unit heterocyclic radical, aromatic heterocyclic radical---it can be chosen wantonly and comprise one or two following groups: OH, SO to choose the 5-unit of containing phenyl or naphthyl on nitrogen wantonly 3H, C 1-C 4Alkyl and/or C 1-C 4Alkoxyl;
Kk 3Be the univalent perssad that is derived from benzene, pyrimidine, pyridine or naphthalene, it is chosen wantonly to comprise 1 or 2 hydroxyl sulfonyl and choose wantonly and comprises 1,2 or 3 other substituting group that is selected from following groups: SO 3H, COOH, CN, CONH 2, OH, NH 2, NO 2, halogen, C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, carboxyl-C 1-C 4Alkyl, C 1-C 4Alkoxyl, C 1-C 4Alkyl amino, C 1-C 4Dialkyl amido, C 1-C 4Alkyl amino-carbonyl, C 1-C 4Dialkyl amino carbonyl, C 1-C 4Alkyl-carbonyl-amino, N-(C 1-C 4Alkyl-carbonyl)-N-(C 1-C 4Alkyl-carbonyl) amino, C 1-C 4Alkyl amino carbonyl oxy, C 1-C 4Dialkyl amino carbonyl oxy, C 1-C 4Alkyl amino-carbonyl amino, C 1-C 4Dialkyl amino carbonyl amino, phenyl amino ketonic oxygen base, phenyl amino carbonylamino, C 1-C 4Alkoxycarbonyl amino, C 1-C 4Hydroxyl-C 1-C 4Alkyl amino, carboxyl-C 1-C 4Alkyl amino, phenylcarbonyl group amino, C 1-C 4Alkyl sulphonyl, hydroxyl-C 1-C 4Alkyl sulphonyl, C 1-C 4Alkyl amino sulfonyl, C 1-C 4Alkyl sulfonyl-amino, phenyl sulfonyl, phenyl sulfonyl amino, formamide, formula SO 2NR 56R 57Group, R wherein 56And R 57Represent hydrogen, C independently 1-C 4Alkyl, formoxyl, C 1-C 4Alkyl-carbonyl, C 1-C 4Alkoxy carbonyl, NH 2-CO or C 1-C 4Alkyl amino-carbonyl, C 1-C 4Alkyl amino sulfonyl amino, two-C 1-C 4Alkyl amino sulfonyl amino, phenyl sulfonyl amino---it can be selected from C by one or two on phenyl ring 1-C 4Alkyl, C 1-C 4The substituting group of alkoxy or halogen replaces or is optional by 1,2 or 3 following groups: OH, halogen, C 1-C 45-that alkyl or phenyl replaces or 6-unit heterocyclic radical, aromatic heterocyclic radical---it can be chosen wantonly and comprise one or two following groups: OH, SO to choose the 5-unit of containing phenyl or naphthyl on nitrogen wantonly 3H, C 1-C 4Alkyl and/or C 1-C 4Alkoxyl;
Tk 1, Tk 2Represent divalent aryl independently; it is derived from benzene, diphenylamines, biphenyl, diphenyl methane, 2-Phenylbenzimidazole, phenyl sulfonyl benzene, phenyl amino sulfonyl benzene, stilbene or phenyl amino carbonyl benzene, and they are chosen wantonly separately and comprise one or more following groups as substituting group: SO 3H, COOH, OH, NH 2, NO 2, halogen, C 1-C 4Alkyl;
L, M, P and R represent the divalent aryl that is derived from benzene or naphthalene independently, and they can be chosen wantonly separately and comprise one or morely, and for example, 1,2,3,4 or 5 following groups is as substituting group: SO 3H, COOH, CN, CONH 2, OH, NH 2, NO 2, halogen, C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, carboxyl-C 1-C 4Alkyl, C 1-C 4Alkoxyl, C 1-C 4Alkyl amino, C 1-C 4Dialkyl amido, C 1-C 4Alkyl amino-carbonyl, C 1-C 4Dialkyl amino carbonyl, C 1-C 4Alkyl-carbonyl-amino, N-(C 1-C 4Alkyl-carbonyl)-N-(C 1=C 4Alkyl-carbonyl) amino, C 1-C 4Alkyl amino carbonyl oxy, C 1-C 4Dialkyl amino carbonyl oxy, C 1-C 4Alkyl amino-carbonyl amino, C 1-C 4Dialkyl amino carbonyl amino, phenyl amino ketonic oxygen base, phenyl amino carbonylamino, C 1-C 4Alkoxycarbonyl amino, C 1-C 4Hydroxyl-C 1-C 4Alkyl amino, carboxyl-C 1-C 4Alkyl amino, phenylcarbonyl group amino, C 1-C 4Alkyl sulphonyl, hydroxyl-C 1-C 4Alkyl sulphonyl, C 1-C 4Alkyl amino sulfonyl, C 1-C 4Alkyl sulfonyl-amino, phenyl sulfonyl, phenyl sulfonyl amino, formamide, formula SO 2NR 56R 57Group, R wherein 56And R 57Represent hydrogen, C independently 1-C 4Alkyl, formoxyl, C 1-C 4Alkyl-carbonyl, C 1-C 4Alkoxy carbonyl, NH 2-CO or C 1-C 4Alkyl amino-carbonyl, C 1-C 4Alkyl amino sulfonyl amino, two-C 1-C 4Alkyl amino sulfonyl amino, phenyl sulfonyl amino---it can be selected from C by one or two on phenyl ring 1-C 4Alkyl, C 1-C 4The substituting group of alkoxy or halogen replaces or is optional by 1,2 or 3 following groups: OH, halogen, C 1=C 45-that alkyl or phenyl replaces or 6-unit heterocyclic radical, aromatic heterocyclic radical---it can be chosen wantonly and comprise one or two following groups: OH, SO to choose the 5-unit of containing phenyl or naphthyl on nitrogen wantonly 3H, C 1-C 4Alkyl and/or C 1-C 4Alkoxyl;
Napht 1, Napht 2Representative is derived from the divalent group of naphthalene independently, and it comprises 1 or 2 hydroxyl sulfonyl and can choose wantonly and comprises 1,2 or 3 other substituting group that is selected from following groups: OH, NH 2, C 1-C 4Alkyl amino, C 1-C 4Dialkyl amido, C 1-C 4Alkyl sulfonyl-amino, phenyl sulfonyl amino, 4-aminomethyl phenyl sulfuryl amino, C 1-C 4Alkyl amino sulfonyl, two-C 1-C 4Alkyl amino sulfonyl, phenyl amino sulfonyl, 4-aminomethyl phenyl amino-sulfonyl and NHC (O) R xGroup, wherein R xBe hydrogen, C 1-C 4Alkyl, maleoyl or phenyl;
Pyr represents pyrazoles-1,4-two bases, and it is connected on the A group by nitrogen-atoms, and optional comprise 1 or 2 and be selected from halogen, C 1-C 4Alkyl, hydroxyl or C 1-C 4The substituting group of alkoxyl;
Tr 1, Tr 2Represent 1,3,5-triazines-2 independently, 4-two bases, it is chosen wantonly and further contains halogen atom, methyl or methoxyl group as substituting group.
9. according to each method of aforementioned claim, be that 3 to 6.5 the water bath shampoo that contains at least a dyestuff F is handled leather at first wherein with the pH value, then the pH value in the body lotion is made as at least 7.5.
10. according to each method of claim 1 to 7, wherein dye and carry out as one-step method.
11., wherein dye and before retanning, carry out according to each method of aforementioned claim.
12., wherein dye and carry out 10 to 60 ℃ temperature according to each method of aforementioned claim.
13. contain at least one purposes of the dyestuff F and composition thereof of the group that can be activated by alkali of formula A according to claim 1, be used in pH 〉=7.5 o'clock with leather coloring.
14. the dyestuff F of general formula I Ia, IIIa or IVa
Dk 1-N＝N-Napht 1-N＝N-Tk 1-[N＝N-Kk 1] k-N＝N-Dk 2 (IIa)
Dk 1-N＝N-Napht 1-N＝N-Tk 1-N＝N-Kk 1-N＝N-Tk 2-N＝N-Napht 2-N＝N-Dk 2
(IIIa)
Dk 1-N＝N-Napht 1-N＝N-Tk 1-N＝N-Napht 2-N＝N-Dk 2 (IVa)
Dk wherein 1, Dk 2, Napht 1, Napht 2And Kk 1Each is as above self-defined, and k is 0 or 1, and TK wherein 1And Tk 2Representative is derived from the divalent group of biphenyl, diphenyl methane, 2-Phenylbenzimidazole, phenyl sulfonyl benzene, phenyl amino sulfonyl benzene, diphenylamines, stilbene or phenyl amino carbonyl benzene independently, and can choose wantonly and comprise one or more following groups as substituting group: SO 3H, COOH, OH, NH 2, NO 2, halogen, C 1-C 4Alkyl, but when k=0, the Tk among the formula IIa 1Do not represent the group that is derived from diphenylamine, and group Dk 1And/or Dk 2Represent the group of formula A as claimed in claim 1.
15. the dyestuff F of general formula I Ib
A-N＝N-Napht 1-N＝N-Tk 1-N＝N-Kk 1-[N＝N-Dk 2] n (IIb)
Wherein A, Dk 2, Napht 1And Kk 1Each is as above self-defined, and n is 0Or 1, and Tk wherein 1Representative is derived from the divalent group of biphenyl, diphenyl methane, 2-Phenylbenzimidazole, phenyl sulfonyl benzene, phenyl amino sulfonyl benzene, diphenylamines, stilbene or phenyl amino carbonyl benzene, and can choose wantonly and comprise one or more following groups as substituting group: SO 3H, COOH, OH, NH 2, NO 2, halogen, C 1-C 4Alkyl, wherein Tk when n=0 1Do not represent the group that is derived from diphenylamines, and Dk wherein 2Group can also be represented the group of formula A as claimed in claim 1.
16. according to the dyestuff of claim 14 or 15, wherein in formula IIa, IIb, IIIa or IVa, Tk 1And/or Tk 2Represent the group of following general formula:
Figure A2004800321060009C1
Wherein----represents the key that is connected with azo group.
17. according to each dyestuff of claim 14 to 16, wherein Napht 1And/or Napht 2Represent the divalent group of following general formula
Figure A2004800321060009C2
R wherein 1And R 2Be hydrogen, OH, NH independently 2Or NHC (O) R 3, R wherein 3Represent hydrogen, C 1-C 4Alkyl, maleoyl or phenyl, and R 1And R 2In at least one is not a hydrogen, the key that is connected with azo group of----representative, s and t represent 0 or 1, and s+t's and be 1 or 2.
18. according to each dyestuff of claim 14 to 17, wherein group Dk 1And/or Dk 2Represent one of A1 to A12 group as claimed in claim 7.
19. the colouring leather that can obtain by each colouring method of claim 1 to 12.
20. the leather that is used for gloves, footwear, automobile, clothes or furniture according to claim 19.
CN2004800321064A 2003-10-29 2004-10-28 Method for the reactive colouring of leather Active CN1875144B (en)

Applications Claiming Priority (5)

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DE10350368.4 2003-10-29
DE2003150368 DE10350368A1 (en) 2003-10-29 2003-10-29 Dyeing leather with dyes containing vinylsulfonyl, or precursor, reactive groups, useful e.g. for making gloves or clothing, by treatment with dye liquor at pH at least 7.5
DE102004041187.5 2004-08-25
DE200410041187 DE102004041187A1 (en) 2004-08-25 2004-08-25 Dyeing leather with dyes containing vinylsulfonyl, or precursor, reactive groups, useful e.g. for making gloves or clothing, by treatment with dye liquor at pH at least 7.5
PCT/EP2004/012231 WO2005040490A1 (en) 2003-10-29 2004-10-28 Method for the reactive colouring of leather

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DE3517547A1 (en) * 1985-05-15 1986-11-20 Hoechst Ag, 6230 Frankfurt WATER-SOLUBLE DISAZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES
JPH04363363A (en) * 1991-06-10 1992-12-16 Sumitomo Chem Co Ltd Trisazo compound, method for dyeing textile material, paper or leather using the same and ink containing the same
DE59409181D1 (en) * 1993-10-12 2000-04-13 Ciba Sc Holding Ag Reactive dyes, processes for their production and their use
ES2246002T3 (en) * 1997-06-24 2006-02-01 Ciba Specialty Chemicals Holding Inc. PROCEDURE FOR DYING OR PRINTING FIBER MATERIALS WITH CELLULOSE CONTENT, AND NEW REACTIVE COLORS.

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