Preparation method of ecological functional leather based on nano material

An ecological function and nano-material technology, applied in leather impregnation, leather surface treatment, small raw hide/big raw hide/leather/fur treatment, etc., to achieve the effect of improving softness, improving wear resistance and reducing dosage

Active Publication Date: 2021-03-16
XINGYE LEATHER TECH CO LTD
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Problems solved by technology

As a new type of material, nanomaterials have been involved in the research of innovative materials, but the existing nanotechnology mainly focuses on the modification of nanomaterials suc...
the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
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Abstract

The invention discloses a preparation method of ecological functional leather based on a nano material. The preparation method comprises a wet dyeing and finishing process. The technological process of the wet dyeing and finishing process is characterized by comprising the steps of obtaining crust leather through tanning of a cationic metal tanning agent, re-wetting, anionic surface dyeing 1, neutralizing 1, anionic filling, cationic re-tanning, neutralizing 2, anionic filling and dyeing, anionic fat liquoring, cationic fixing 1, anionic surface dyeing 2, cationic fixing 2 and cationic fat liquoring; wherein a nano titanium dioxide modifier is added into at least one of the anion filling process and the anion filling and dyeing process; according to the application, a nano titanium dioxidemodifier with a photocatalytic function is used in the leather wet dyeing and finishing section, formaldehyde in leather can be removed, the antibacterial and bacteriostatic effects can be achieved,and the application of the nano titanium dioxide modifier in the leather wet dyeing and finishing section is expanded.

Application Domain

Technology Topic

Examples

  • Experimental program(3)

Example Embodiment

[0052] Example 1:
[0053] A preparation method of ecological functional leather based on nanomaterials, comprising the following steps:
[0054] Step 1: Preparation of nano-titanium dioxide-polyurethane retanning agent
[0055] (1) Take 5 parts of nano titanium dioxide in the reaction vessel, add 0.4 part of aminosilane coupling agent, 0.1 part of epoxy silane coupling agent, 50 parts of water, 100 parts of ethanol, stir and disperse, adjust pH=10, then ultrasonically Disperse for 5min, react at 30°C for 5h, filter, wash and dry to obtain modified nano-titanium dioxide;
[0056] (2) Take 3 parts of polytetramethylene glycol, add it to the reactor after dehydration treatment, add 0.8 part of isophorone diisocyanate, and prepolymerize at 80°C for 2 hours. The temperature was lowered to 65°C, 0.4 part of acetone was added to dilute, 0.3 part of butanediol was added, and the reaction was carried out for 4h. 0.1 part of dimethylolpropionic acid was added, and the reaction was carried out for 2h. The temperature was lowered to 50° C., and 0.1 part of triethylamine was added for neutralization for 30 min. The temperature was controlled at 45° C., 0.2% of modified nano-titanium dioxide and 0.05 part of graphene oxide were added, and the reaction was stirred at a high speed for 60min. The temperature was controlled at 40°C, 60 parts of water were added while stirring at a high speed, and the mixture was emulsified and dispersed for 1 hour. 0.05 part of diethylenetriamine was added, the temperature was controlled at 30° C., the reaction was stirred for 30 minutes, and the acetone in the emulsion was removed to obtain a nano-titanium dioxide-polyurethane retanning agent.
[0057] Step 2: Preparation of Nano Graphene Finishing Agent
[0058] (1) Preparation of carboxylated graphene powder
[0059] Add 1 part of graphene oxide to 1000 parts of deionized water, ultrasonically disperse for 60 minutes, then add 10 parts of sodium hydroxide, ultrasonically disperse for 30 minutes, then add 20 parts of α-bromoacetic acid, ultrasonically disperse for 30 minutes, and finally adjust the reaction temperature To 30 ° C, react for 6 h to obtain a carboxylated graphene dispersion. The obtained product is washed alternately with acetic acid and deionized water for 6 times, and finally washed with anhydrous ethanol for 3 times, and the product is vacuum-dried to obtain carboxylated graphite. alkene powder;
[0060] (2) Preparation of chitosan solution
[0061] Dissolving 5 parts of acetic acid in 100 parts of deionized water, then adding 2.5 parts of chitosan, and adjusting the pH of the solution to 3.5 to obtain a chitosan solution;
[0062] (3) prepare carboxylated graphene solution:
[0063] Add 2.5 parts of carboxylated graphene powder to 100 parts of deionized water, ultrasonically disperse for 5 minutes, and adjust the pH of the solution to 4.5 to obtain a carboxylated graphene solution;
[0064] (4) Add 5 parts of carboxylated graphene solution to 1000 parts of chitosan solution, mix well, adjust the pH value of the solution to 3.5, react at 30 °C for 3 hours, then add 2.5 parts of pyruvic acid, and react at 35 °C for 3 hours, Then add 2.5 parts of triethylenetetramine, react at 40° C. for 3 hours, and finally add 1 part of nano-titanium dioxide and react at 40° C. for 1 hour to obtain the nano-graphene finishing agent.
[0065] Step 3: Preparation of functional leather
[0066] (1) Take the wet blue leather obtained by chrome tanning of Xingye Leather Technology Co., Ltd., squeeze water, shave it evenly, weigh (calculate the amount of subsequent materials based on the weighted mass) and add it to the drum.
[0067] (2) Rewetting: add 300% water to the drum, add 0.5% surfactant SAF (Derui Leather Technology Co., Ltd.), 0.3% oxalic acid, control the temperature to 40°C, rotate for 2 hours, and drain.
[0068] (3) Anionic surface dyeing 1: Add 300% water to the drum, add 0.8% anionic dye, control the temperature to 30°C, rotate for 20min, and drain.
[0069] (4) Neutralization 1: add 150% of water in the drum, add 1.5% of neutralized tannin PAK (LANXESS CHINA CO., LTD.), 1.5% of sodium formate, control the temperature to be 30°C, rotate for 10min; add 1% of baking soda, 1% of anionic fatliquor MIR90 (Yixiang Chemical Co., Ltd.), control pH to 4.8-5.2, rotate for 50min, and drain.
[0070] (5) Anion filling: add 50% water in the drum, add 1% polyurethane retanning agent CC-01 (Lanxess Chemical China Co., Ltd.), control the temperature to 30°C, and rotate for 10min. Add 2% acrylic resin retanning agent TP340 (ALPA Leather Chemical Co., Ltd.), 3% acrylic resin retanning agent CC (Xiamen Wantongli Chemical Materials Co., Ltd.), and rotate for 60 min. Add 0.5% anionic fatliquor OSL (Thompler), 2% synthetic tanning agent FO (BASF AG), 3% amino resin tanning agent HB (Thompler), 2% protein filler FB (Desaier Chemical Industry Co., Ltd.), rotate for 90min. Add 100% water, add 1% formic acid, control the temperature to 30°C, rotate for 20 minutes, add 1% formic acid, and rotate for 20 minutes.
[0071] (6) Cationic retanning: add 3% chrome tanning agent AB (Turkey Jinshan Group), 1.5% protein filler CCL (Huakai Trading Co., Ltd.), cationic fatliquor GS (Stal Leather Chemical Co., Ltd.) in the drum Co., Ltd.) 1%, the control temperature is 30 ° C, and the rotation is 60 min. Add 1% sodium formate, 1% baking soda, turn for 60min, drain.
[0072] (7) Neutralization 2: Add 150% water, 1.5% baking soda, 0.5% anionic fatliquor MIR90 (Yixiang Chemical Co., Ltd.) to the drum, control the temperature to 30°C, and pH 4.8-5 , rotate for 60min, drain.
[0073] (8) Anionic filling dyeing: add 50% water in the drum, add 4% nano-titanium dioxide-polyurethane retanning agent, control the temperature to 30°C, rotate for 20min, add 3% acrylic resin retanning agent TP340 (ALPA Leather Chemical Company), 3% acrylic resin retanning agent 1084 (Lanxess Chemical China Co., Ltd.), rotate for 40min, add 1% syntan T-M (BASF AG), 2% syntan OS (LANXESS) Chemical China Co., Ltd.), 3% amino resin tanning agent HB (Thompler Corporation), 2% amino resin tanning agent DCT (Stahl Leather Chemical Co., Ltd.), 3% vegetable tanning agent ME (Jinfeng Leather Chemical Co., Ltd.) Co., Ltd.), 1% of anionic fatliquor EY (Sima Chemical Co., Ltd.), 2% of dye, and rotated for 2h.
[0074] (9) Anionic fatliquor: add 70-300% water in the drum, add 3% polymer fatliquor GS-606 (Smit Leather Chemicals Co., Ltd.), 3% synthetic fatliquor SU (Xiamen Wantongli Chemical Materials Co., Ltd.), 1.5% lanolin fatliquor ZBN (Biokimica company), 2% phospholipid fatliquor BA (Sima Chemical Co., Ltd.), 0-2% vegetable oil fatliquor Agent BCA (Yide Leather Chemical Co., Ltd.), the control temperature is 50 ℃, rotate for 30min, add 1% acrylic resin retanning agent R83 (Thompler company), 2% polycarboxylate MAP (Sima Chemical Co., Ltd.) ), control the temperature to 40-60℃, and rotate for 40min.
[0075] (10) Cation fixation 1: Add 1% formic acid to the drum, control the temperature to 50°C, rotate for 10 minutes, add 1% formic acid, rotate for 10 minutes, add 1% formic acid, rotate for 40 minutes, add 1% chrome tanning Agent AB (Turkey Jinshan Group), rotate for 30min, drain.
[0076] (11) Anionic surface dyeing 2: add 300% water to the drum, add 1% dye, control the temperature to 55°C, and rotate for 15min.
[0077] (12) Cation fixation 2: Add 0.6% formic acid to the drum, control the temperature to 55° C., rotate for 15 minutes, add 1% aluminum tannin AL (Sichuan Desaier Chemical Industry Co., Ltd.), and rotate for 10 minutes.
[0078] (13) Cationic fatliquoring: add 0.5% cationic fatliquoring agent GS (Stal Leather Chemical Co., Ltd.) and 0.5% cattle hoof oil fatliquoring agent OPE (Shanghai Fengzheng Wanwei Leather Chemical Co., Ltd.) in the drum ), control the temperature to 55℃, rotate for 15min, and drain.
[0079] (14) Wash out the drum with water, and let it stand on a horse (8h).
[0080] (15) Squeeze water and stretch, vacuum drying (38°C, 4min), hanging drying (24h), drying tunnel (4h), backwater, standing (8h), shaking and softening (level 5) in sequence.
[0081] (16) Spot repair: Take 100 copies of repairing paste 8182 (Maiji Chemical Co., Ltd.), and scratch and repair the damaged part of the raw leather.
[0082] (17) Knurling roller (100℃, 50kg), grinding leather;
[0083] (18) Bottom coating: prepare bottom coating agent, spray 3 times;
[0084] Bottom finishing formula: 200 parts of water, 20 parts of polyurethane finishing agent RU3904 (Staer Leather Chemical Co., Ltd.), 100 parts of polyurethane finishing agent RU3989 (Staer Leather Chemical Co., Ltd.), surfactant PT4235 (Staer Leather Chemical Co., Ltd.) Limited company) 40 copies;
[0085] (19) Rolling (130℃, 30-40kg), trimming;
[0086] (20) Middle layer finishing: prepare middle layer finishing agent, spray 3 times;
[0087]Middle-layer finishing agent formula: 300 parts of water, 200 parts of polyurethane finishing agent RU3904 (Staer Leather Chemical Co., Ltd.), 150 parts of acrylic resin finishing agent RA-2 (Staer Leather Chemical Co., Ltd.), acrylic resin finishing agent SB- 300 (LANXESS Chemical China Co., Ltd.) 100 parts, filler S-C01 (LANXESS Chemical China Co., Ltd.) 60 parts, Casein 688/B (Derui Leather Technology Co., Ltd.) 40 parts, paint 120 parts;
[0088] (21) Embossing (100°C, 3 seconds);
[0089] (22) Oil return: prepare oil return agent and return oil on the back;
[0090] Oil return agent formula: 100 parts of water, 5 parts of synthetic fatliquor 94S (Sima Chemical Co., Ltd.).
[0091] (23) Falling soft (1h), shaking and pulling soft (level 6);
[0092] (24) Upper coating: prepare the upper coating and spray it once;
[0093] Upper layer finishing agent formula: 120 parts of water, 160 parts of polyurethane finishing agent LN.A (Stal Leather Chemical Co., Ltd.), 50 parts of polyurethane finishing agent 1418 (Derui Leather Technology Co., Ltd.), 100 parts of nano-graphene finishing agent, 5 parts of crosslinking agent, 5 parts of modified polysiloxane aqueous solution;
[0094] (25) Rolling (130℃, 30-40kg), softening (1h);
[0095] (26) Oil return: 100 parts of water, 5 parts of synthetic fatliquor 94S (Sima Chemical Co., Ltd.);
[0096] (27) Vibration to soften (grade 6), vacuum drying (70°C, 20 seconds);
[0097] (28) Top coating: prepare top coating, spray 1 time
[0098] Top finishing agent formula: 100 parts of water, 5 parts of modified polysiloxane solution 5230 (Staer Leather Chemical Co., Ltd.), 5 parts of hand feeling agent MA330 (Jinjiang Sanxingtai Trading Co., Ltd.);
[0099] (29) Rolling (100°C, 20-30kg).

Example Embodiment

[0100] Example 2
[0101] A preparation method of ecological functional leather based on nanomaterials, comprising the following steps:
[0102] The method of this embodiment 2 is the same as that of embodiment 1, and the difference is the anion filling process and the anion filling dyeing process, as follows:
[0103] (5) Anion filling: add 50% of water to the drum, add 3% of nano-titanium dioxide-polyurethane retanning agent, control the temperature to 30°C, and rotate for 10min. Add 2% acrylic resin retanning agent TP340 (ALPA Leather Chemical Co., Ltd.), 3% acrylic resin retanning agent CC (Xiamen Wantongli Chemical Materials Co., Ltd.), and rotate for 60 min. Add 0.5% anionic fatliquor OSL (Thompler), 2% synthetic tanning agent FO (BASF AG), 3% amino resin tanning agent HB (Thompler), 2% protein filler FB (Desaier Chemical Industry Co., Ltd.), rotate for 90min. Add 100% water, add 1% formic acid, control the temperature to 30°C, rotate for 20 minutes, add 1% formic acid, and rotate for 20 minutes.
[0104] (8) Anionic filling dyeing: add 50% water in the drum, add 1% polyurethane retanning agent CC-01 (Lanxess Chemical China Co., Ltd.), control the temperature to 30°C, rotate for 20min, add 3% Acrylic resin retanning agent TP340 (ALPA leather chemical company), 3% acrylic resin retanning agent 1084 (Lanxess Chemical China Co., Ltd.), rotate for 40min, add 1% synthetic tanning agent T-M (BASF Co., Ltd.), 2% The synthetic tanning agent OS (Lanxess Chemical China Co., Ltd.), 3% amino resin tanning agent HB (Thompler Corporation), 2% amino resin tanning agent DCT (Stahl Leather Chemical Co., Ltd.), 3% vegetable tanning agent Tanning agent ME (Jinfeng Leather Chemical Co., Ltd.), 1% anionic fatliquor EY (Sima Chemical Co., Ltd.), 2% dye, and rotating for 2h.

Example Embodiment

[0105] Example 3
[0106] A preparation method of ecological functional leather based on nanomaterials, comprising the following steps:
[0107] The method of this embodiment 3 is the same as that of embodiment 1, the difference is the anion filling process and the anion filling dyeing process, as follows:
[0108] (5) Anion filling: add 50% of water to the drum, add 2% of nano-titanium dioxide-polyurethane retanning agent, control the temperature to 30°C, and rotate for 10min. Add 2% acrylic resin retanning agent TP340 (ALPA Leather Chemical Co., Ltd.), 3% acrylic resin retanning agent CC (Xiamen Wantongli Chemical Materials Co., Ltd.), and rotate for 60 min. Add 0.5% anionic fatliquor OSL (Thompler), 2% synthetic tanning agent FO (BASF AG), 3% amino resin tanning agent HB (Thompler), 2% protein filler FB (Desaier Chemical Industry Co., Ltd.), rotate for 90min. Add 100% water, add 1% formic acid, control the temperature to 30°C, rotate for 20 minutes, add 1% formic acid, and rotate for 20 minutes.
[0109] (8) Anionic filling dyeing: add 50% water in the drum, add 3% nano-titanium dioxide-polyurethane retanning agent, control the temperature to 30°C, rotate for 20min, add 3% acrylic resin retanning agent TP340 (ALPA Leather Chemical Company), 3% acrylic resin retanning agent 1084 (Lanxess Chemical China Co., Ltd.), rotate for 40min, add 1% syntan T-M (BASF AG), 2% syntan OS (LANXESS) Chemical China Co., Ltd.), 3% amino resin tanning agent HB (Thompler Corporation), 2% amino resin tanning agent DCT (Stahl Leather Chemical Co., Ltd.), 3% vegetable tanning agent ME (Jinfeng Leather Chemical Co., Ltd.) Co., Ltd.), 1% of anionic fatliquor EY (Sima Chemical Co., Ltd.), 2% of dye, and rotated for 2h.
the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
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the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
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