CN103374634A - Accessory ingredient capable of removing and avoiding generating hexavalent chromium in leather and preparation method of accessory ingredient - Google Patents
Accessory ingredient capable of removing and avoiding generating hexavalent chromium in leather and preparation method of accessory ingredient Download PDFInfo
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Abstract
The invention relates to an accessory ingredient capable of removing and avoiding generating hexavalent chromium in leather and a preparation method of the accessory ingredient, belonging to the technical field of chemical product manufacture. The accessory ingredient is mainly and technologically characterized by being prepared from raw materials including a reducing agent, an antioxidant, a dispersing agent, a masking agent and a pH value regulator. The reducing agent mainly comprises the following components: sodium sulfite, sodium hydrogen sulfite, sodium hyposulfate, sodium pyrosulfite and glucose; the antioxidant comprises the following components: sulfonated tannin extract, sulfited tannin extract, tea polyphenol, gallic acid, ellagic acid, vitamin C and vitamin E; the dispersing agent comprises the following components: an auxiliary naphthalene sulfonic acid synthetic tanning agent and an auxiliary phenolsulfonic acid synthetic tanning agent; the masking agent mainly comprises the following components: sodium formate, sodium acetate and sodium citrate; and the pH value regulator comprises the following components: citric acid and oxalic acid. The accessory ingredient is prepared through grinding, crushing and uniformly mixing. The accessory ingredient is few in raw material component, simpler in preparation method, free of pollution and capable of thoroughly removing and avoiding generating hexavalent chromium in leather.
Description
One, technical field
The present invention relates to the preparation of fine chemistry product and the production of Ecology Leather, remove the chromic auxiliary agent in the leather, particularly relate to and a kind ofly can remove and prevent to generate chromic auxiliary agent and preparation method in the leather, belong to Chemicals manufacturing technology field.
Two, background technology
Chromium exists with positive trivalent and positive two kinds of forms of sexavalence usually, and its valence state is different, and is also different with biological effect on the impact of environment.It is believed that trivalent chromium is human body and biological essential a kind of micro-metals, and be carcinogens than the sexavalent chrome that trivalent chromium easily is absorbed by the body, large more than 100 times than trivalent chromium of chromic toxicity.
In the leather industry production process, do not use now sexavalent chrome, the chromium that exists in leather all is considered to only have trivalent always, thereby before German Government proposed sexavalent chrome in the leather, worldwide nobody discussed the sexavalent chrome problem in the leather.German Government at first proposes the sexavalent chrome problem in the leather, then in European Union in 1994 chromic the limiting the quantity of in the glove leather is 2mg/Kg, some countries and other many countries in the European Union will be suggestive standard originally, become the standard to the imported product check, and as examination criteria, the leading exporter European Union of Chinese leather product and the U.S. are all with the examination criteria of sexavalent chrome as the exotic leather product with chromic index in increasing country.How to prevent the sexavalent chrome in the leather, the internal authority magazine just from the origin cause of formation study more, for the problem of used additives control, each state has no open report all under study for action.
Chromic problem in the leather, when just proposing, scientific worker worldwide focuses on sight following aspect: unreduced sexavalent chrome is arranged in employed material such as the chromium powder during leather processing, in the pigment paste with sexavalent chrome; The processing conditions of leather as in and the time pH high, temperature height etc. during buffing; Verified at present external world's sexavalent chrome that bring and that misoperation causes and all can have been solved by stringent regulations, control condition, yet these are not the key of problem.Chromic generation has its source in to exist by trivalent chromium in the leather and changes chromic chemical reaction in the leather.This reaction is caused by unsaturated fatting agent in the leather, is subjected to the metal ion institute catalysis that exists in the leather.Can be expressed as follows:
Unsaturated fatty acids, the hydrogen atom on the methylene radical of its pair key next door easily comes off after namely α-H is attacked by oxygen and becomes R (radical), has namely begun its autoxidation.Concrete reaction formula is illustrated as: chain causes:
That is: RH → R
Chain development: R+O
2→ ROO
ROO·+RH→ROOH+R·
2ROOH→ROO·+RO·+H
2O
RH+·OH→R·+H
2O
RO·+RH→ROH+R·
The resultant that contains peroxy-radical that wherein generates has very strong oxidisability, Cr3+ can be oxidized to Cr6+, in the peroxidation of α-H that two keys occur, the oxidizing reaction with the two keys that add the characteristics of becoming has occured also.Theoretical according to traditional unsaturated oil lipid oxidation, oxygen is as follows with the addition reaction reaction formula that two keys occur:
The same cyclic peroxide that generates also has high oxidisability, also Cr3+ can be oxidized to Cr6+.Reason is in the existence of above-mentioned reaction, chromic amount in the leather and the iodine number of fatting agent have great dependency, because some transition metal ions have katalysis to the peroxidation of two keys, thus the Cr3+ in the leather be oxidized person also be the promoter of this reaction.This reaction Once you begin, will be carried out as not interrupting continuously for free chain reaction.So, for chromic existence in the leather, has following feature: one, the sexavalent chrome that this reason produces has disguise, some suppress the existence of factor in the leather, and such as the existence of phenolic compound, the conditions such as the high humidity of storage all can suppress above-mentioned reaction or reduction of hexavalent chromium, make this reaction be issued to balance at content of 6-valence Cr ions in lower level, thereby can not detect; Its two, chromic generation has persistence, as long as the two keys in the leather exist, reacts and carries out all the time, Cr6+ will produce; They are three years old, chromic generation has subtle property and since leather and leather products place and use procedure in, chemical equilibrium is broken because of the variation of condition, can carry out towards generating more chromic direction, thereby originally not have chromic leather to become chromic leather is arranged.So, can or can not produce on earth sexavalent chrome in the leather and depend on that above-mentioned reaction carries out and downtrod degree.
Based on above technical background, the present invention can thoroughly remove the sexavalent chrome in the leather and prevent from the leather generating chromic auxiliary agent, and it is a kind of high-performance, environmentally friendly Ecology Leather with crucial fine chemistry industry material.The application of this material can solve sexavalent chrome in the leather problem that exceeds standard, can guarantee finished product leather heating under 80 ℃ the condition after 24 hours chromic content less than 2ppm, can reach the limitation standard of China's Ecology Leather, also can reach the maximum limit standard of the developed countries such as leather products outlet European Union.
Three, summary of the invention
The objective of the invention is to change sexavalent chrome into for the auxiliary agent that solves existing leather work in-process use produces to exist by trivalent chromium in sexavalent chrome or the leather easily, contain chromic leather human body is harmful to, thereby a kind of new technical scheme is provided.
For achieving the above object, the present invention is achieved through the following technical solutions:
A kind ofly can remove and prevent in the leather to generate chromic auxiliary agent, the auxiliary agent that it is made by mass parts by following raw materials according:
3～5 parts of reductive agents, 2～4 parts of antioxidants, 2～4 parts of dispersion agents, 1～3 part of masking agent, 2～4 parts of pH value conditioning agents:
Described reductive agent feed composition by mass parts is: 1～5 part of S-WAT, 2～4 parts of sodium bisulfites, 3～5 parts of sodium hyposulfates, 2～5 parts of Sodium Pyrosulfites, 2～4 parts of glucose;
Described antioxidant feed composition by mass parts is: 2～5 parts of sulfonation tannin extracts, 1～4 part of sulphiting tannin extract, 1～5 part of tea-polyphenol, 3～5 parts of gallic acids, 2～5 parts of ellagic acids, Catergen～5 part, vitamin E2～5 part;
Described dispersion agent feed composition by mass parts is: 2～5 parts of naphthene sulfonic acid class accessory syntans, 3～6 parts of naphthene sulfonic acid class accessory syntans;
Described masking agent feed composition by mass parts is: 2～5 parts of sodium formiates, 3～6 parts of sodium acetates, 1～5 part of Trisodium Citrate;
Described pH value conditioning agent feed composition by mass parts is: 2～5 parts of citric acids, 1～5 part of oxalic acid.
A kind of can remove and prevent in the leather generates chromic auxiliary agent, and it is the auxiliary agent of being made by mass parts by following raw materials according:
4 parts of reductive agents, 3 parts of antioxidants, 3 parts of dispersion agents, 2 parts of masking agents, 3 parts of pH value conditioning agents:
Described reductive agent feed composition by mass parts is: 3 parts of S-WATs, 3 parts of sodium bisulfites, 4 parts of sodium hyposulfates, 3 parts of Sodium Pyrosulfites, 3 parts of glucose;
Described antioxidant feed composition by mass parts is: 3 parts of sulfonation tannin extracts, 2 parts of sulphiting tannin extracts, 3 parts of tea-polyphenol, 4 parts of gallic acids, 3 parts of ellagic acids, 3 parts of vitamins Cs, 3 parts of vitamin-Es;
Described dispersion agent feed composition by mass parts is: 3 parts of naphthene sulfonic acid class accessory syntans, 4 parts of naphthene sulfonic acid class accessory syntans;
Described masking agent feed composition by mass parts is: 3 parts of sodium formiates, 4 parts of sodium acetates, 3 parts of Trisodium Citrates;
Described pH value conditioning agent feed composition by mass parts is: 3 parts of citric acids, 2 parts of oxalic acid.
A kind of preparation method that can remove and prevent to generate in the leather chromic auxiliary agent the steps include:
(1) grinds: with 1～5 part of raw material S-WAT, 2～4 parts of sodium bisulfites, 3～5 parts of sodium hyposulfates, 2～5 parts of Sodium Pyrosulfites, 2～4 parts of glucose; 2～5 parts of sulfonation tannin extracts, 1～4 part of sulphiting tannin extract, 1～5 part of tea-polyphenol, 3～5 parts of gallic acids, 2～5 parts of ellagic acids, Catergen～5 part, vitamin E2～5 part; 2～5 parts of naphthene sulfonic acid class accessory syntans, 3～6 parts of naphthene sulfonic acid class accessory syntans; 2～5 parts of sodium formiates, 3～6 parts of sodium acetates, 1～5 part of Trisodium Citrate; 1～5 part of 2～5 parts of citric acid, oxalic acid at room temperature grind respectively to 200 orders;
(2) evenly mix: pack was for subsequent use after the various powder stocks in the step (1) were evenly mixed.
The advantage that the present invention compared with prior art has is: material component is few, the preparation method is fairly simple, experimental results show that: the present invention a kind ofly can thoroughly remove the sexavalent chrome in the leather and prevent from the leather generating chromic auxiliary agent, and it is a kind of high-performance, environmentally friendly Ecology Leather with crucial fine chemistry industry material.The application of this material can solve sexavalent chrome in the leather problem that exceeds standard, can guarantee finished product leather heating under 80 ℃ the condition after 24 hours chromic content less than 2ppm, can reach the limitation standard of China's Ecology Leather, also can reach the maximum limit standard of the developed countries such as leather products outlet European Union.
Four, embodiment
The present invention is described in further detail below by embodiment, but the present invention has more than and is limited to these examples.
A kind of can remove and prevent in the leather generates chromic auxiliary agent, and used feedstock composition and proportion by weight are:
4 parts of reductive agents, 3 parts of antioxidants, 3 parts of dispersion agents, 2 parts of masking agents, 3 parts of pH value conditioning agents:
Described reductive agent feed composition by mass parts is: 3 parts of S-WATs, 3 parts of sodium bisulfites, 4 parts of sodium hyposulfates, 3 parts of Sodium Pyrosulfites, 3 parts of glucose.
Described antioxidant feed composition by mass parts is: 3 parts of sulfonation tannin extracts, 2 parts of sulphiting tannin extracts, 3 parts of tea-polyphenol, 4 parts of gallic acids, 3 parts of ellagic acids, 3 parts of vitamins Cs, 3 parts of vitamin-Es.
Described dispersion agent feed composition by mass parts is: 3 parts of naphthene sulfonic acid class accessory syntans, 4 parts of naphthene sulfonic acid class accessory syntans.
Described masking agent feed composition by mass parts is: 3 parts of sodium formiates, 4 parts of sodium acetates, 3 parts of Trisodium Citrates.
Described pH value conditioning agent feed composition by mass parts is: 3 parts of citric acids, 2 parts of oxalic acid.
A kind of preparation method that can remove and prevent to generate in the leather chromic auxiliary agent the steps include:
(1) grinds: the various raw materials of above-mentioned composition and proportion by weight are ground respectively to 200 orders, at room temperature carry out when grinding;
(2) evenly mix: pack was for subsequent use after the various powder stocks in the step (1) were evenly mixed according to the above ratio.
The name of product that the present invention produces is: sexavalent chrome control auxiliary agent.
Below by the qualitative experiment data advantage that the present invention compared with prior art has is described:
The present invention is a kind of high-performance, environmentally friendly Ecology Leather with crucial fine chemistry industry material.Experimental results show that: the promoter material that the present invention produces is in being applied to the production process of leather, can solve sexavalent chrome in the leather problem that exceeds standard, can guarantee finished product leather heating under 80 ℃ the condition after 24 hours chromic content less than 2ppm, can reach the limitation standard of China's Ecology Leather, chromic content also can reach the maximum limit standard (chromic content is less than 2ppm) of the developed countries such as leather products outlet European Union less than 5ppm.The qualitative experiment gained: use behind the present invention leather sample to deliver to national leatherware quality supervision and test center and test, its result is that the gained leather sample does not detect sexavalent chrome.One, the auxiliary agent that the present invention manufactures comprise reductive agent, antioxidant, dispersion agent, masking agent and pH value conditioning agent five class main ingredients.Its two, the reductive agent component can be effectively be trivalent chromium with the hexavalent chrome reduction of trace in the leather, the reductive agent component comprises S-WAT, sodium bisulfite, sodium hyposulfate, Sodium Pyrosulfite and five kinds of components of glucose; They are three years old, antioxidant ingredients can be caught free radical, blocking-up originates in the chain reaction of α-H activity, thereby prevented that the trivalent chromium in the leather is oxidized to sexavalent chrome, antioxidant ingredients comprises sulfonation tannin extract component, sulphiting tannin extract, tea-polyphenol, gallic acid, ellagic acid, vitamins C and seven kinds of components of vitamin-E; They are four years old, the dispersion agent component can be good at disperseing antioxidant and reductive agent, make in its micro-fiber structure that is distributed in leather, thereby play comprehensively thoroughly preventive and therapeutic effect, dispersion agent comprises naphthene sulfonic acid class accessory syntan and two kinds of components of phenol sulphonic acids accessory syntan; Its five, the masking agent component can the complexing leather in free trivalent chromic ion, prevent that the free trivalent chromium in the leather is oxidized to sexavalent chrome, the masking agent component comprises sodium formiate, sodium acetate and three kinds of components of Trisodium Citrate; Its six, pH value conditioning agent component can make first three plant component to be in the best pH value sphere of action, to bring into play the maximum efficiency of these three kinds of components, pH value conditioning agent comprises citric acid and two kinds of components of oxalic acid.Why this auxiliary agent can bring into play very high usefulness, and be not only each component and can bring into play separately effect, and, have good synergistic function between each component.
Claims (3)
1. can remove and prevent to generate chromic auxiliary agent in the leather for one kind, it is characterized in that the auxiliary agent of being made by mass parts by following raw materials according:
3～5 parts of reductive agents, 2～4 parts of antioxidants, 2～4 parts of dispersion agents, 1～3 part of masking agent, 2～4 parts of pH value conditioning agents:
Described reductive agent feed composition by mass parts is: 1～5 part of S-WAT, 2～4 parts of sodium bisulfites, 3～5 parts of sodium hyposulfates, 2～5 parts of Sodium Pyrosulfites, 2～4 parts of glucose;
Described antioxidant feed composition by mass parts is: 2～5 parts of sulfonation tannin extracts, 1～4 part of sulphiting tannin extract, 1～5 part of tea-polyphenol, 3～5 parts of gallic acids, 2～5 parts of ellagic acids, Catergen～5 part, vitamin E2～5 part;
Described dispersion agent feed composition by mass parts is: 2～5 parts of naphthene sulfonic acid class accessory syntans, 3～6 parts of naphthene sulfonic acid class accessory syntans;
Described masking agent feed composition by mass parts is: 2～5 parts of sodium formiates, 3～6 parts of sodium acetates, 1～5 part of Trisodium Citrate;
Described pH value conditioning agent feed composition by mass parts is: 2～5 parts of citric acids, 1～5 part of oxalic acid.
2. a kind of can remove and prevent in the leather according to claim 1 generates chromic auxiliary agent, it is characterized in that the auxiliary agent of being made by mass parts by following raw materials according:
4 parts of reductive agents, 3 parts of antioxidants, 3 parts of dispersion agents, 2 parts of masking agents, 3 parts of pH value conditioning agents:
Described reductive agent feed composition by mass parts is: 3 parts of S-WATs, 3 parts of sodium bisulfites, 4 parts of sodium hyposulfates, 3 parts of Sodium Pyrosulfites, 3 parts of glucose;
Described antioxidant feed composition by mass parts is: 3 parts of sulfonation tannin extracts, 2 parts of sulphiting tannin extracts, 3 parts of tea-polyphenol, 4 parts of gallic acids, 3 parts of ellagic acids, 3 parts of vitamins Cs, 3 parts of vitamin-Es;
Described dispersion agent feed composition by mass parts is: 3 parts of naphthene sulfonic acid class accessory syntans, 4 parts of naphthene sulfonic acid class accessory syntans;
Described masking agent feed composition by mass parts is: 3 parts of sodium formiates, 4 parts of sodium acetates, 3 parts of Trisodium Citrates;
Described pH value conditioning agent feed composition by mass parts is: 3 parts of citric acids, 2 parts of oxalic acid.
3. the manufacturing right economic rights are asked 1 or 2 described a kind of preparation methods that can remove and prevent to generate in the leather chromic auxiliary agent, the steps include:
(1) grinds: with 1～5 part of raw material S-WAT, 2～4 parts of sodium bisulfites, 3～5 parts of sodium hyposulfates, 2～5 parts of Sodium Pyrosulfites, 2～4 parts of glucose; 2～5 parts of sulfonation tannin extracts, 1～4 part of sulphiting tannin extract, 1～5 part of tea-polyphenol, 3～5 parts of gallic acids, 2～5 parts of ellagic acids, Catergen～5 part, vitamin E2～5 part; 2～5 parts of naphthene sulfonic acid class accessory syntans, 3～6 parts of naphthene sulfonic acid class accessory syntans; 2～5 parts of sodium formiates, 3～6 parts of sodium acetates, 1～5 part of Trisodium Citrate; 1～5 part of 2～5 parts of citric acid, oxalic acid at room temperature grind respectively to 200 orders;
(2) evenly mix: pack was for subsequent use after the various powder stocks in the step (1) were evenly mixed.
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Cited By (7)
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| CN104450996A (en) * | 2014-09-22 | 2015-03-25 | 王晓锦 | Effective method for preventing hexavalent chromium in leather materials and leather products |
| WO2017131138A1 (en) * | 2016-01-29 | 2017-08-03 | シチズン時計株式会社 | Inspection liquid for inspecting whether leather has been treated using hexavalent chromium reducing compound |
| WO2017131140A1 (en) * | 2016-01-29 | 2017-08-03 | シチズン時計株式会社 | Method for producing reptile leather or leather product using hexavalent chromium treatment agent, and reptile leather or leather product using hexavalent chromium treatment agent |
| CN108267412A (en) * | 2018-03-20 | 2018-07-10 | 东北大学 | The quick repeatable hexavalent chromium detecting system and method utilized |
| CN109162124A (en) * | 2018-09-14 | 2019-01-08 | 桐乡市濮院毛针织技术服务中心 | Dispersing agent is used in a kind of rose dyeing of dacron |
| CN109294245A (en) * | 2018-09-18 | 2019-02-01 | 四川大学 | A method of protein plastic is prepared using chromed residues |
| CN111593147A (en) * | 2020-06-02 | 2020-08-28 | 四川达威科技股份有限公司 | Hexavalent chromium scavenger, preparation method and application thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108267412B (en) * | 2018-03-20 | 2020-09-29 | 东北大学 | Rapid and reusable hexavalent chromium ion detection system and method |
| CN109162124A (en) * | 2018-09-14 | 2019-01-08 | 桐乡市濮院毛针织技术服务中心 | Dispersing agent is used in a kind of rose dyeing of dacron |
| CN109294245A (en) * | 2018-09-18 | 2019-02-01 | 四川大学 | A method of protein plastic is prepared using chromed residues |
| CN109294245B (en) * | 2018-09-18 | 2021-07-23 | 四川大学 | Method for preparing protein plastic by using chromium-containing waste leather scraps |
| CN111593147A (en) * | 2020-06-02 | 2020-08-28 | 四川达威科技股份有限公司 | Hexavalent chromium scavenger, preparation method and application thereof |
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Application publication date: 20131030 |