CN111172332B - Negative oxygen ion chrome tanning agent and preparation method and application thereof - Google Patents
Negative oxygen ion chrome tanning agent and preparation method and application thereof Download PDFInfo
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- CN111172332B CN111172332B CN202010032141.7A CN202010032141A CN111172332B CN 111172332 B CN111172332 B CN 111172332B CN 202010032141 A CN202010032141 A CN 202010032141A CN 111172332 B CN111172332 B CN 111172332B
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- negative oxygen
- oxygen ion
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/04—Mineral tanning
- C14C3/06—Mineral tanning using chromium compounds
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/28—Multi-step processes
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a negative oxygen ion chrome tanning agent and a preparation method and application thereof, which comprises the steps of weighing 1-10 parts of chromium salt, 0.5-40 parts of cross-linking agent and 0.5-5 parts of negative oxygen ion material, adding into 5-200 parts of water, adjusting the pH value to 1-5, stirring and reacting at 5-80 ℃ for 0.5-24h, concentrating and drying; the prepared negative oxygen ion chromium tanning agent is applied to a process for preparing leather, and the negative oxygen ion chromium tanning agent can be added in at least one of the tanning, retanning and fixing processes; the invention solves the problem of poor binding property of negative oxygen ion materials and collagen fibers in the prior art, realizes that the leather releases negative oxygen ions from inside to outside, removes free formaldehyde in the leather, kills bacteria inside and outside the leather and ensures that the leather has long-acting formaldehyde-removing and antibacterial effects.
Description
Technical Field
The invention relates to the field of leather making, in particular to a negative oxygen ion chrome tanning agent and a preparation method and application thereof.
Background
The negative oxygen ions are called as 'air vitamins' and 'longevity elements' by human beings, have the effects of sterilizing, reducing dust, cleaning air, eliminating formaldehyde, improving immunity and regulating functional balance, have very important influence on the life activity and the service life of the human body, are very beneficial to the health of the human body and have important medical care function. The negative oxygen ion material is introduced into the leather, so that the produced leather has the function of releasing negative oxygen ions, and the purposes of improving the living environment quality, eliminating the formaldehyde of the leather, giving the leather an antibacterial function, improving the grade of the leather product and increasing the added value of the leather product are achieved.
The prior negative oxygen ion leather is mainly coated with negative oxygen ion powder dispersed in a coating process by a coating method, the binding property of a negative oxygen ion material and collagen fibers is poor, and if the negative oxygen ion leather is used in a leather-making water field, the negative oxygen ion leather needs to be combined with other materials so as to improve the stability and the binding capacity with the collagen fibers.
Disclosure of Invention
The embodiment of the application provides the negative oxygen ion chrome tanning agent and the preparation method and application thereof, solves the problem of poor binding property of a negative oxygen ion material and collagen fibers in the prior art, realizes that leather releases negative oxygen ions from inside to outside, removes free formaldehyde in the leather, kills bacteria inside and outside the leather, and ensures that the leather has long-acting formaldehyde-removing and antibacterial effects.
The embodiment of the application provides a negative oxygen ion chrome tanning agent, which comprises the following raw materials in parts by weight:
further, the chromium salt is selected from at least one of chromium chloride, chromium sulfate, basic chromium sulfate and chrome tanning agent.
Further, the crosslinking agent is at least one selected from the group consisting of saccharides, dicarboxylic acids, polycarboxylic acids, dialdehydes, aldehydic compounds, polyhydroxy compounds, dicarboxylic acid salts, polycarboxylic acid salts, aromatic sulfonic acid condensates, and neutralized tannins.
Further, the negative oxygen ion material is at least one of water-soluble negative oxygen ion powder and surface modified negative oxygen ion powder.
Further, the preparation method of the surface modified negative oxygen ion powder comprises the following steps:
adding 1-10 parts of water-insoluble negative oxygen ion powder, 0.1-5 parts of surface modifier and 1-30 parts of water into a ball mill for grinding modification.
Further, the water-insoluble negative oxygen ion powder is selected from one or more of superfine negative oxygen ion powder, nanometer negative oxygen ion powder, superfine tourmaline, nanometer tourmaline and superfine pearl powder.
Further, the surface modifier is any one or more of a silane coupling agent, a titanate coupling agent, waterborne polyurethane, polyvinyl alcohol, polycarboxylate and an acrylate compound.
A preparation method of a negative oxygen ion chrome tanning agent comprises the following steps: weighing 1-10 parts of chromium salt, 0.5-40 parts of cross-linking agent and 0.5-5 parts of negative oxygen ion material, adding into 5-200 parts of water, adjusting the pH to 1-5, stirring and reacting at 5-80 ℃ for 0.5-24h, concentrating and drying to obtain the negative oxygen ion chromium tanning agent.
A process for preparing leather includes such steps as tanning, retanning, neutralizing, filling, greasing and fixing, and adding the negative oxygen ion chrome tanning agent to at least one of tanning, retanning and fixing.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
1. when the negative oxygen ion material is mixed and modified, the negative oxygen ion material is combined with chromium salt in a crosslinking way through a crosslinking agent to form a larger complex, and the complex takes chromium as an active point, so that the complex is convenient to be combined with collagen fibers in leather subsequently.
2. The negative oxygen ion material and the chrome tanning agent are complexed through the cross-linking agent, so that the stability of the negative oxygen ion material can be improved, the negative oxygen ion material can be combined with the collagen fiber through the chromium salt, and the negative oxygen ion powder can be combined with the chromium salt through the cross-linking agent and then is subjected to multi-element net-shaped cross-linking with the collagen fiber, so that the negative oxygen ion powder is firmly combined on the fiber, and the effect of releasing the negative oxygen ion for a long time is achieved.
3. The negative oxygen ion powder and the chrome tanning agent enter the leather together and are combined with the collagen fiber of the leather, so that the negative oxygen ion powder and the chrome tanning agent are uniformly dispersed in the leather, the leather releases negative oxygen ions from inside to outside, free formaldehyde in the leather is removed, bacteria inside and outside the leather are killed, and the leather has long-acting formaldehyde removing and antibacterial effects.
4. The surface energy of the water-insoluble negative oxygen ions is large, the surface activity of the negative oxygen ion powder particles is very high, and single particles cannot exist stably and are often agglomerated through mutual attraction, so that the performance of the negative oxygen ion powder is deteriorated; the surface modification of the negative oxygen ion powder by using the surface modifier such as the silane coupling agent can improve the activation index of the surface of the negative oxygen ion powder and improve the stability of the negative oxygen ion powder in the solution.
Detailed Description
In order to better understand the technical solutions, the technical solutions will be described in detail with reference to the description and the specific embodiments.
Example 1:
weighing 5 parts of chrome tanning agent AB (Turkey Jinshan group), 2 parts of sodium citrate (one of polycarboxylate), 2 parts of water-soluble negative oxygen ion powder and 40 parts of water, adjusting the pH value to 3, stirring at the constant temperature of 30 ℃, reacting for 8 hours, and spray drying.
Example 2:
taking 2 parts of superfine negative oxygen ion powder, adding 8 parts of water to prepare an 80% mixture, adding 0.1 part of silane coupling agent KH-602, adding the mixture into a ball milling tank of a planetary ball mill, carrying out ball milling in the ball mill for 0.5h, and carrying out centrifugal dehydration, drying and grinding to obtain the surface modified negative oxygen ion powder.
Weighing 5 parts of basic chromium sulfate, 10 parts of glyoxylic acid, 1 part of surface modified negative oxygen ion powder and 20 parts of water, adjusting the pH value to be 2.5, stirring at the constant temperature of 50 ℃ for reacting for 4 hours, and spray drying.
Example 3:
taking the split leatheroid, weighing, and sequentially washing, deliming, softening, washing, pickling and tanning according to the mass of the leatheroid;
the method comprises the following specific steps:
washing with water: adding ash into a rotary drum, adding 300% water and 0.5% ammonia-free deashing agent TM (Sichuan Desaier chemical industry Co., Ltd.), controlling the temperature in the drum at 30 deg.C, rotating for 20min, and draining.
Deashing, 80% of water, 1.5% of ammonia-free deashing agent TM (Sichuan Desair chemical industry Co., Ltd.), 0.1% of sodium metabisulfite are added into a rotary drum, and the rotary drum is rotated for 30min at 30 ℃.
Softening: adding 2% ammonia-free softening enzyme U5 (Sichuan Desaier chemical industry Co., Ltd.), rotating at 30 deg.C for 30min, and draining.
Washing with water: adding 300% ice water into the rotary drum, controlling the temperature in the drum at 18 ℃, rotating for 10min, and draining; adding 300% ice water into the rotary drum, controlling the temperature in the drum at 18 ℃, rotating for 10min, and draining;
pickling: adding 30% ice water and 5% sodium chloride into the rotary drum, rotating at 18 deg.C for 10min, controlling Baume degree of bath liquid to 7.5-8.0, adding 1% formic acid, rotating for 30min, adding 1% sulfuric acid, and rotating for 90 min.
Tanning: adding 0.5% of sodium formate into a rotary drum, rotating for 30min, adding 3% of negative oxygen ion chrome tanning agent, rotating for 60min, adding 3% of negative oxygen ion chrome tanning agent, rotating for 120min, adding 5% of automatic alkali extraction agent BF, rotating for 6h, adding 100% of water, controlling the temperature to be 40 ℃, rotating for 120min, draining, discharging from the drum, setting aside and standing for 24 h.
Example 4:
taking tanned wet blue leather, wringing, shaving, weighing, and sequentially softening, retanning, neutralizing, filling, dyeing, fatliquoring, fixing and topping according to the mass of the shaved wet blue leather. The method comprises the following specific steps:
softening: putting wet blue leather into a rotary drum, adding 200% of water, 0.8% of surfactant SAF (Delui leather chemical Co., Ltd.), 0.3% of oxalic acid into the rotary drum, controlling the temperature at 40 ℃, rotating for 60min, and draining.
Retanning: adding 100% water and 1% fatty aldehyde tanning agent PF (German Sema chemical Co., Ltd.), rotating at 30 deg.C for 30min, adding 3% negative oxygen ion chrome tanning agent, rotating at 30 deg.C for 60min, adding 1.5% sodium formate, rotating at 30 deg.C for 60min, and draining.
Neutralizing: adding 100% water, 2% neutralized tannin NG (Deri leather chemical Co., Ltd.), 1.5% sodium formate into a rotary drum, controlling the temperature at 30 deg.C, rotating for 30min, adding 0.5% sodium bicarbonate, rotating for 60min at 30 deg.C, and draining.
Filling and dyeing: adding 50% of water into a rotary drum, adding 2% of synthetic fatting agent BQ (Kyoho chemical Co., Ltd., Pengzhou), 5% of acrylic resin retanning agent R83 (Thompler, Germany), controlling the temperature to be 30 ℃ and rotating for 40min, adding 1% of dispersed tannin JOM (New Material Co., Ltd., Sichuan Tingjiang), 3% of wattle bark tannin extract ME (Jinfeng leather chemical Co., Ltd.), 3% of synthetic tanning agent FO (Pasteur Co., Ltd.), 2% of melamine resin retanning agent DLF (Pasteur Co., Ltd.), 3% of synthetic tanning agent BN (Lansheng, Germany), rotating for 60min at 30 ℃, adding 2% of dye, and rotating for 60min at 30 ℃.
Fat liquoring: 150% of warm water is added into the rotary drum, 1% of fatty aldehyde tanning agent PF (German Semak chemical Co., Ltd.), 3% of mixed fatting agent DB (German Toepller Co., Ltd.), 3% of synthetic fatting agent 94S and 3% of lecithin fatting agent NLM (Steal leather chemical Co., Ltd.) are added, the temperature is controlled at 50 ℃, and the rotary drum is rotated for 60 min.
Fixing: adding 1% formic acid into the rotary drum, rotating at 50 deg.C for 20min, adding 1% formic acid, rotating for 20min, adding 1% negative oxygen ion chrome tanning agent, rotating for 30min, and draining.
Color register: adding 200% warm water into the drum, adding 1% dye, controlling the temperature at 50 deg.C, rotating for 15min, adding 0.5% formic acid, rotating for 15min at 50 deg.C, adding 0.5% cationic fatliquoring agent GS (Craine chemical Co., Ltd.), rotating for 10min at 50 deg.C, and washing with water.
Standing the crust leather for 8h, squeezing water and stretching, vacuum drying, hanging and drying, drying in a drying tunnel, returning water, standing for 8h, vibrating and softening, and coating.
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (7)
1. The negative oxygen ion chrome tanning agent is characterized by comprising the following raw materials in parts by weight:
the chromium salt is selected from at least one of chromium chloride, chromium sulfate, basic chromium sulfate and chrome tanning agent;
the cross-linking agent is at least one selected from saccharides, dicarboxylic acids, polycarboxylic acids, dialdehydes, aldehydic compounds, polyhydroxy compounds, dicarboxylic acid salts, polycarboxylic acid salts, aromatic sulfonic acid condensates and neutralized tannins.
2. The negative oxygen ion chromium tanning agent according to claim 1, wherein the negative oxygen ion material is at least one of water-soluble negative oxygen ion powder and surface modified negative oxygen ion powder.
3. The negative oxygen ion chrome tanning agent of claim 2, wherein the surface modified negative oxygen ion powder is prepared by the following steps:
adding 1-10 parts of water-insoluble negative oxygen ion powder, 0.1-5 parts of surface modifier and 1-30 parts of water into a ball mill for grinding modification.
4. The negative oxygen ion chromium tanning agent according to claim 3, wherein the water-insoluble negative oxygen ion powder is selected from one or more of ultrafine negative oxygen ion powder, nano negative oxygen ion powder, ultrafine tourmaline, nano tourmaline and ultrafine pearl powder.
5. The negative oxygen ion chrome tanning agent of claim 3, wherein the surface modifier is any one or more of a silane coupling agent, a titanate coupling agent, water-based polyurethane, polyvinyl alcohol, polycarboxylate and an acrylate compound.
6. The preparation method of the negative oxygen ion chrome tanning agent is characterized by comprising the following steps: weighing 1-10 parts of chromium salt, 0.5-50 parts of cross-linking agent and 0.5-5 parts of negative oxygen ion material, adding into 5-500 parts of water, adjusting the pH to 1-5, stirring and reacting at 5-80 ℃ for 0.5-24h, concentrating and drying to obtain the negative oxygen ion chromium tanning agent.
7. A method for preparing leather at least comprises the procedures of tanning, retanning, neutralizing, filling, greasing and fixing, and is characterized in that an oxygen anion chromium tanning agent is added in at least one of the procedures of tanning, retanning and fixing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010032141.7A CN111172332B (en) | 2020-01-13 | 2020-01-13 | Negative oxygen ion chrome tanning agent and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010032141.7A CN111172332B (en) | 2020-01-13 | 2020-01-13 | Negative oxygen ion chrome tanning agent and preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN111172332A CN111172332A (en) | 2020-05-19 |
| CN111172332B true CN111172332B (en) | 2022-05-20 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004217880A (en) * | 2003-01-17 | 2004-08-05 | Haruta Seika Kk | Leather material |
| CN1664113A (en) * | 2005-03-23 | 2005-09-07 | 李上辉 | Anion materials, modified leather materials thereby, and use thereof |
| CN108276935A (en) * | 2018-01-18 | 2018-07-13 | 中国科学院理化技术研究所 | A kind of negative ion pollutionless emulsion and preparation method thereof based on acrylic resin |
| CN108411049A (en) * | 2018-04-10 | 2018-08-17 | 中国皮革和制鞋工业研究院（晋江）有限公司 | Negative oxygen ion filler and preparation method thereof |
-
2020
- 2020-01-13 CN CN202010032141.7A patent/CN111172332B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004217880A (en) * | 2003-01-17 | 2004-08-05 | Haruta Seika Kk | Leather material |
| CN1664113A (en) * | 2005-03-23 | 2005-09-07 | 李上辉 | Anion materials, modified leather materials thereby, and use thereof |
| CN108276935A (en) * | 2018-01-18 | 2018-07-13 | 中国科学院理化技术研究所 | A kind of negative ion pollutionless emulsion and preparation method thereof based on acrylic resin |
| CN108411049A (en) * | 2018-04-10 | 2018-08-17 | 中国皮革和制鞋工业研究院（晋江）有限公司 | Negative oxygen ion filler and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 超细负离子粉在有机单体中分散性能的研究;邓爱民等;《沈阳理工大学学报》;20150630;第34卷(第3期);第37-40页 * |
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| CN111172332A (en) | 2020-05-19 |
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