CN102747171A

CN102747171A - Wet processing method of waterproof shoe upper leather

Info

Publication number: CN102747171A
Application number: CN201110107342XA
Authority: CN
Inventors: 刘四华; 金硕; 杨非
Original assignee: TANGPULE CHEMICAL DYE (JIAXING) CO Ltd
Current assignee: TANGPULE CHEMICAL DYE (JIAXING) CO Ltd
Priority date: 2011-04-20
Filing date: 2011-04-20
Publication date: 2012-10-24

Abstract

The invention discloses a method for processing waterproof shoe upper leather, comprising the following steps: conducting routine immersion, liming, splitting, deliming, softening, then pickling, tanning, finally washing at a normal temperature three times, stripping from a drum, stacking, and conventionally drying, wherein the Ph value of the step of pickling is between 3.0-3.2, ionic surfacetants are not used in the whole process, the tanning step comprises: 1, tanning; 2, conventionally wringing and shaving; 3, retanning and dying; and 4, retanning and fatliquoring. Experiments show that a hyperbranched polymer can be used for tanning of the leather, by combining with auxiliary chromium powder to tan, the absorption of chromium powder can be improved, and the fixation and combination of chromium (Cr3+) in leather fibers are enhanced by the synergism; the strength of the leather is raised, and the waterproof performance of the leather is raised by introducing waterproof groups; dynamic waterproof test shows that the waterproof leather processed by the method can be subject to more than 4000 times of dynamic waterproof MAESER tests, the water absorption is less than 15%, thereby meeting the standard of ASTM-D20099.

Description

A kind of wet working method of waterproof footwear upper leather

Technical field

What the present invention relates to is a kind ofly to tan as the associativity master with hyperbranched polymer and chromium powder, the wet process operation method that combines composite water-proof oil to produce the upper leather with water resistance in the retanning stage with hyperbranched polymer again.

Background technology

In the prior art, for the processing of Waterproof Leather, mainly existing the defectives such as Waterproof Leather water resistance difference after the processing, mainly is because there is imperfection in complete processing, and processing raw material of being adopted receives certain reasons such as use restriction.

Summary of the invention

The objective of the invention is to overcome the deficiency that prior art exists; And a kind of grease that special water resistance is arranged through adding is provided; In conjunction with the water-repellancy Polymer Tanning Agent that can significantly improve water resistance, reach the wet working method of the waterproof footwear upper leather of producing high water resistance.

The objective of the invention is to accomplish through following technical scheme, its adopts conventional immersion, and liming is cutd open layer, deliming, softening back and got into pickling, tanning stage, through normal temperature wash water behind retanning, the dyeing and fat-liquoring three times, goes out drum, takes horse, and the conventional drying processing gets final product; Described pickling PH is controlled between 3.0～3.2, and whole technological process is not used ionogenic surfactant, and the described tanning stage comprises: a tanning; Carry out according to the following steps: select for use 3% chromium powder (basicity 33) to change 120 minutes, adding 1% sodium formiate changeed 30 minutes, and adding 1% sodium bicarbonate changeed 240 minutes; Wherein sodium bicarbonate is with the dilution of 1: 10 water, and gradation adds with pan, target P H:3.9+; Adding 3% hyperbranched polymer A changeed 90 minutes, and the water that adds 150%, 38 degree changeed target P H:4.0 240 minutes; Go out drum then, take horse, left standstill 24 hours; Two according to after the above-mentioned operation tanning wet blue leather being carried out water squeezing, shaving (thickness 1.4mm); Three retannings, carry out according to the following steps: add 150%, 35 degree water, select for use 3% chromium powder (basicity 33) to change 60 minutes; Adding 2% sodium formiate changeed 20 minutes, and adding 0.5% sodium bicarbonate changeed 60 minutes, wherein used 1: 10 water dilution; Add target P H: 5.0 with pan; Four stuffings are carried out according to the following steps, add water 50%, 35 degree; Select 6% hyperbranched polymer A, 1% composite water-proof oil C and 10% hyperbranched polymer B for use, changeed 120 minutes, adding 2% dyestuff changeed 60 minutes; The water, adding 6% composite water-proof oil C and the 4% hyperbranched polymer A that add 45 degree after the inspection dyestuff full impregnated changeed 90 minutes; Divide 3% formic acid three times at last and added each 20 minutes, adding 2% chromium powder then changeed 60 minutes, and adding 2% chromium powder again changeed 60 minutes; Five, the normal temperature cold water with 300%, each 10 minutes, wash, going out drum after washing 3 times carries out the dry finishing operation.

The present invention finds that through experiment the master that hyperbranched polymer can be used for leather tans, again the tanning of secondary combined chromium powder; Except the absorption that can improve chromium powder; Also pass through synergy, strengthen chromium (Cr3+), not only improved the intensity of leather in the inner fixing and combination of leather fiber; Through the water-repellancy group of introducing, can improve the water resistance of leather simultaneously.

The present invention measures through dynamic water-proof, and with the waterproof leather of this method processing, dynamic water-proof MAESER measures and can reach more than 40000 times, and water-intake rate meets the ASTM-D20099 standard less than 15%.

Embodiment

To combine specific embodiment below, the present invention is done detailed introduction: the present invention adopts conventional immersion, and layer, deliming, the entering pickling of softening back, tanning stage are cutd open in liming, and last normal temperature wash water three times goes out drum, takes horse, and conventional drying is handled and got final product; Described pickling PH is controlled between 3.0～3.2, and whole technological process is not used ionogenic surfactant, and the described tanning stage comprises: a tanning, carry out according to the following steps: select for use 3% chromium powder (basicity 33) to change 120 minutes; Adding 1% sodium formiate changeed 30 minutes, and adding 1% sodium bicarbonate changeed 240 minutes, wherein used 1: 10 water dilution, and gradation adds with pan; PH:3.9+, adding 3% hyperbranched polymer A changeed 90 minutes, and the water that adds 150%, 38 degree changeed 240 minutes; PH4.0 goes out drum then, takes horse; Left standstill water squeezing, shaving 24 hours; Two according to after the above-mentioned operation tanning wet blue leather being carried out water squeezing, shaving (thickness 1.4mm); Three retannings, carry out according to the following steps: add 150%, 35 degree water, select for use 3% chromium powder (basicity 33) to change 60 minutes; Adding 2% sodium formiate changeed 20 minutes, and adding 0.5% sodium bicarbonate changeed 60 minutes, wherein used 1: 10 water dilution; Add target P H:5.0 with pan; Four stuffings are carried out according to the following steps, add water 50%, 35 degree; Select 6% hyperbranched polymer A, 1% composite water-proof oil C and 10% hyperbranched polymer B for use, changeed 120 minutes, adding 2% dyestuff changeed 60 minutes; The water, adding 6% composite water-proof oil C and the 4% hyperbranched polymer A that add 45 degree after the inspection dyestuff full impregnated changeed 90 minutes; Divide 3% formic acid three times at last and added each 20 minutes, adding 2% chromium powder then changeed 60 minutes, and adding 2% chromium powder again changeed 60 minutes; Five, the normal temperature cold water with 300%, each 10 minutes, wash, going out drum after washing 3 times carries out the dry finishing operation.

Advantage explanation of the present invention:

A. select for use hyperbranched polymer A stable under the different PH, B, and wherein a kind of polymkeric substance can be used under the chrome tanning condition; A large amount of end groups that hyperbranched polymer contains can with the leather fiber combine well, can form firm chemical bond, part has substituted chrome tanning agent; Also obviously reduced chrome tanning agent residual at body lotion; Experiment shows that residual Cr3+ can reduce to (when beginning according to chrome tanning, the content of Cr3+ is 100% calculation) below 10%.

B. the main stage of tanning uses 3% chromium powder and 3% hyperbranched polymer can make wet blue leather reach good rerum natura, and shrinkage temperature also can reach more than 98 degrees centigrade.Tear strength, draw high intensity physical strength etc. near the wet blue with 6% chromium powder tanning, error is less than 10%.

C. hyperbranched polymer A.B is used for the retanning stage, cooperates dubbin, can reach good waterproof effect; Make that simultaneously whole technological process consumption is less: the main tanning agent consumption is altogether: 6%; The retanning agent consumption is: 20%, and the consumption of dubbin is 7%, just can reach good waterproof effect.

Hyperbranched polymer A of the present invention; B is that end group is main with carboxyl, also contains hydroxyl simultaneously, and the hyperbranched polymer of the high degree of branching of end groups such as amino has been introduced vinyl and siloxane chain simultaneously, and certain auxiliary waterproof effect is arranged, and whole effective content all reaches more than 50%.

Composite water-proof of the present invention oil C is that to mix be the polymkeric substance waterproof system: the one, wherein contain the polyether-type silicone oil of highly water-soluble, and form by organosilicon raw material and natural fats and oils modification; The 2nd, introduced two keys and halogen isopolarity group therebetween, the fluorine-containing fatting agent that makes through modification; The 3rd, the complicated polymkeric substance that vinyl-type monomer and natural fats and oils copolymerization produce.

Claims

1. the working method of a waterproof footwear upper leather, its adopts conventional immersion, and liming is cutd open layer, deliming, softening back and is got into pickling, tanning stage, through normal temperature wash water behind retanning, the dyeing and fat-liquoring three times, goes out drum, takes horse, and the conventional drying processing gets final product; Described pickling PH is controlled between 3.0～3.2, and whole technological process is not used ionogenic surfactant, and the described tanning stage comprises: one, tanning; Carry out according to the following steps: select for use 3% chromium powder (basicity 33) to change 120 minutes, adding 1% sodium formiate changeed 30 minutes, and adding 1% sodium bicarbonate changeed 240 minutes; Wherein sodium bicarbonate is with the dilution of 1: 10 water, and gradation adds with pan, target P H:3.9+; Adding 3% hyperbranched polymer A changeed 90 minutes, and the water that adds 150%, 38 degree changeed target P H:4.0 240 minutes; Go out drum then, take horse, left standstill 24 hours; Two, according to after the above-mentioned operation tanning wet blue leather being carried out water squeezing, shaving (thickness 1.4mm); Three, retanning, carry out according to the following steps: add 150%, 35 degree water, select for use 3% chromium powder (basicity 33) to change 60 minutes; Adding 2% sodium formiate changeed 20 minutes, and adding 0.5% sodium bicarbonate changeed 60 minutes, wherein used 1: 10 water dilution; Add target P H:5.0 with pan; Four, stuffing is carried out according to the following steps, adds water 50%, 35 degree; Select 6% hyperbranched polymer A, 1% composite water-proof oil C and 10% hyperbranched polymer B for use, changeed 120 minutes, adding 2% dyestuff changeed 60 minutes; The water, adding 6% composite water-proof oil C and the 4% hyperbranched polymer A that add 45 degree after the inspection dyestuff full impregnated changeed 90 minutes; Divide 3% formic acid three times at last and added each 20 minutes, adding 2% chromium powder then changeed 60 minutes, and adding 2% chromium powder again changeed 60 minutes; Five, the normal temperature cold water with 300%, each 10 minutes, wash, going out drum after washing 3 times carries out the dry finishing operation.