CN105039611B - Antistatic cattle vamp leather and preparation method thereof - Google Patents
Antistatic cattle vamp leather and preparation method thereof Download PDFInfo
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Abstract
Hair brushThe invention discloses antistatic cattle vamp leather and a preparation method thereof, the invention adopts a method of combining wet dyeing and finishing antistatic treatment and dry finishing antistatic treatment, 6.0 percent of antistatic agent is added after a dyeing and greasing process in a wet dyeing and finishing section to carry out antistatic treatment, and the leather is stopped to be blown overnight; in the coating process of dry finishing, conductive filler is doped in a coating material to carry out antistatic treatment on the coating. The physical and chemical properties of the antistatic cattle shoe upper leather manufactured according to the patent technology can reach the national standard, and the volume resistivity is 103Omega · m, the number of the paper sheets absorbed by the meat surface is 4, and the antistatic grade is 4.
Description
Technical Field
The invention belongs to the technical field of functional leather.
Background
The antistatic leather is also called antistatic leather, and refers to leather with an antistatic function. Static electricity is an electric energy existing on the surface of an object, and is a phenomenon generated after positive and negative charges are locally unbalanced. Static electricity can bring certain harm to human bodies and also can affect the performance and quality of products which generate the static electricity, for example, the static electricity in high-grade cars and airplanes and in computer rooms can not only cause operators to suffer electric shock, but also cause the failure of instruments, remote controllers and the like in the cars or airplanes, and a computer command system is out of control. In production and life, leather and products thereof are widely used, and static hazard is inevitably generated in the using process of the leather and the products, so that the production of antistatic leather has very important significance.
Generally, the method of antistatic is to suppress generation of static charge by increasing lubricity of the surface of a material; secondly, the static charge generated is dredged and leaked as soon as possible by a certain means. The method for leaking static electricity mainly comprises the following steps: increasing the humidity of the surrounding environment and increasing the electrical conductivity of the material. Increasing the conductivity of a material is the most effective and fundamental method to prevent static electricity, and the conductivity of the material can be increased by surface modification or addition of conductive materials. Zhang Fanghui, etc. is used to plate aluminium film or silver film with thickness of 200-400nm on the leather after vacuum drying by vacuum evaporation, then the silver or aluminium ion is injected into the leather from the leather flesh side in a certain vacuum, finally polyaniline conductive coating with thickness of micrometer order of magnitude is coated, so as to obtain an antistatic leather (Zhang Fanghui, Wang Xiufeng, Sunlihong, etc.. an antistatic leather and its preparation method [ P ] Chinese patent, 200610104967. X). Research on the influence of suniting and the like on the conductivity of pigskin finished leather prepared by three tanning methods, namely chrome tanning, iron tanning and aldehyde tanning shows that the conductivity of aldehyde-tanned leather is the largest, the conductivity of iron-tanned leather is the next to the conductivity of chrome-tanned leather is the smallest, and the pigskin finished leather tanned by the three tanning methods belongs to organic semiconductor materials (suniting, li institute, octobo. the influence of the tanning method on the conductivity of leather [ J ]. Chinese leather, 2008(3): 14-15.). So far, the research of national and even world antistatic leather is still in the beginning stage, and no relevant antistatic leather product standard exists, and the antistatic standard of textiles is generally used, for example, the main detection items of the antistatic leather are electrostatic voltage half-life period, surface charge density, charge quantity and the like. According to the invention, according to an electrostatic generation mechanism and an electrostatic elimination method, the influence of common retanning and greasing materials in leather making on the antistatic property of leather is researched, and the blue wet leather is subjected to antistatic treatment by adopting a method combining wet dyeing and finishing antistatic treatment and dry finishing antistatic treatment, so that the cattle vamp leather with excellent antistatic property is obtained.
Disclosure of Invention
The invention adopts a method combining wet dyeing and finishing antistatic treatment with dry dyeing and finishing antistatic treatment, wherein the wet dyeing and finishing can be carried out antistatic treatment in the filling process and stop the drum for overnight or 6.0 percent of antistatic agent is added after dyeing and greasing for antistatic treatment and stop the drum for overnight; in the coating process of dry finishing, conductive filler is doped in the coating material to carry out antistatic treatment on the coating.
The preparation method of the antistatic cattle vamp leather comprises the following steps:
wet dyeing and finishing antistatic treatment:
squeezing wet blue leather, shaving, washing, softening, retanning, washing, filling, washing, neutralizing, dyeing, greasing, washing, antistatic treatment, stopping the drum for over night, discharging, squeezing water, stretching, vacuum drying, dampening and softening;
wherein the antistatic treatment is performed by: the liquid ratio is 1.5, the temperature is 32 ℃, the antistatic agent is 6.0 percent, and the rotation time is 30 min. The other processes are the same as the conventional processes;
dry finishing antistatic treatment: the coating is treated by doping conductive filler in a coating material, and the specific operations are as follows: wet dyeing and finishing antistatic treated crust leather, spraying primer, spraying bottom antistatic slurry, ironing, spraying middle antistatic slurry, spraying top antistatic slurry, ironing and finishing.
3. The antistatic treatment agent in the step (I) is as follows: betaine, ethoxylated fatty alkylamine, cationic quaternary ammonium salt, sulfate, phosphate, polyethylene glycol derivative or amido polyoxyethylene ether.
4. The step II comprises the following steps:
the capping agent comprises the following raw materials in parts by weight: 120 parts of polyurethane resin, 100 parts of water and 80 parts of ethyl glycol;
the bottom layer spraying agent consists of the following raw materials in parts by weight: 100 parts of pigment paste, 30 parts of plate-separating wax, 50 parts of synthetic resin, 130 parts of medium-soft acrylic resin, 100 parts of medium-soft polyurethane, 5 parts of cross-linking agent for leather, 200 parts of water and 120 parts of antistatic agent;
the middle layer spraying agent consists of the following raw materials in parts by weight: 100 parts of pigment paste, 30 parts of wax, 70 parts of medium-hard acrylic resin, 50 parts of soft acrylic resin, 80 parts of medium-soft acrylic resin, 140 parts of medium-soft polyurethane, 5 parts of cross-linking agent for leather, 300 parts of water and 120 parts of antistatic agent;
the top layer spraying agent consists of the following raw materials in parts by weight: 100 parts of nitrocotton brightener and 100 parts of water;
the conductive materials added in the coating formula are as follows: at least one of Polyaniline (PAN), conductive carbon black, and nano-silver.
5. The preparation method of the antistatic cattle vamp leather comprises the following specific operation steps:
(1) sampling and weighing, wherein the weight is 120% of that of the wet blue leather;
(2) washing with water: the liquid ratio is 3.0, the temperature is normal temperature, the washing is carried out for 2 times in a closed water way, each time is 5min, the rotating speed is 8-10rpm, and the liquid is controlled;
(3) softening: the liquid ratio is 2.0, the internal temperature is set at 32 ℃, the rotating speed is 8-10rpm, formic acid is added, the rotation is carried out for 40min, the pH value is measured, and then the liquid control is carried out;
(4) washing with water: the liquid ratio is 3.0, the temperature is normal temperature, the washing is carried out for 2 times in a closed water way, each time is 5min, the rotating speed is 8-10rpm, and the liquid is controlled;
(5) retanning: the liquid ratio is 1.5, the internal temperature is 32 ℃, 3.0 percent of neutralization retanning agent is added, the reaction is carried out for 30min, the pH value is required to be more than 4.6, 6.0 percent of anionic acrylic resin is carried out, the reaction is carried out for 40min, 6.0 percent of amino resin is carried out, and the reaction is carried out for 40 min;
(6) washing with water: the liquid ratio is 3.0, the temperature is normal temperature, the washing is carried out for 2 times in a closed water way, each time is 5min, the rotating speed is 8-10rpm, and the liquid is controlled;
(7) filling: the liquid ratio is 1.5, the internal temperature is 32 ℃, the synthetic retanning agent is added for 10 percent, and the operation is carried out for 30 min; adding tannin extract 15%, rotating for 60min, adding formic acid, rotating for 30min, and controlling liquid;
(8) neutralizing: the liquid ratio is 1.5, the internal temperature is 32 ℃, 0.8 percent of sodium formate is added, and the mixture is rotated for 20 min; adding sodium bicarbonate 0.6%, transferring for 40min, measuring pH 5.2-5.4, neutralizing completely, and controlling liquid;
(9) dyeing and fat liquoring: the liquid ratio is 1.5, the internal temperature is 52-55 ℃, 2.5 percent of black dye and 5.0 percent of permeable grease are added, the operation is carried out for 60min, the dyeing condition is checked, and the operation is carried out for 40min continuously when the dyeing condition is not penetrated; adding synthetic oil 4.0%, and rotating for 60 min; adding formic acid for 2 times, rotating for 20min every time, measuring the pH value, wherein the end point pH value is required to be about 4.0, and then controlling the liquid;
(10) washing with water: the liquid ratio is 3.0, the temperature is normal temperature, the washing is carried out for 2 times in a closed water way, each time is 5min, the rotating speed is 8-10rpm, and the liquid is controlled;
(11) antistatic treatment: the liquid ratio is 1.5, the temperature is 32 ℃, the antistatic agent is 6.0 percent, the mixing time is 30min, and the drum is stopped for overnight;
(12) the next day, out of the drum → setting aside overnight → squeezing and stretching → vacuum drying (temperature: 65 ℃, pressure: 0.99Mpa, time 2min) → hanging and drying → picking the skin and turning → shaking and softening → flat drying → trimming → semi-finished product;
(13) spraying a bottom sealing agent: 120 parts of polyurethane resin, 100 parts of water and 80 parts of ethyl glycol; spraying the cross for one time;
(14) priming coating: the bottom layer spraying agent consists of the following raw materials in parts by weight: 100 percent of pigment paste, 30 percent of board-separated wax, 200 percent of acrylic resin, 100 percent of medium-soft polyurethane, 10 percent of cross-linking agent for leather, 200 percent of water and 2.5 percent of antistatic agent, wherein the amount of the antistatic agent is multiplied by the total weight of the coating material; spraying the cross for one time;
(14) ironing: the temperature is 100 ℃, and the pressure is 80Kg/cm2；
(15) Middle coating: the middle layer spraying agent consists of the following raw materials in parts by weight: 80 percent of pigment paste, 20 percent of wax, 200 percent of acrylic resin, 140 percent of medium-soft polyurethane, 5 percent of cross-linking agent for leather, 300 percent of water and 2.5 percent of antistatic agent, wherein the amount of the antistatic agent is multiplied by the total weight of the coating material; spraying the cross for one time;
(16) ironing: the temperature is 100 ℃, and the pressure is 50Kg/cm2；
(17) Top coating: the top layer spraying agent consists of the following raw materials in parts by weight: 100 parts of nitrocotton brightener and 100 parts of water; spraying the cross for one time;
(18) ironing: the temperature is 100 ℃, and the pressure is 40Kg/cm2；
(19) And (5) finishing.
The invention also provides the antistatic cattle shoe upper leather prepared by the method, which is characterized by meeting the following indexes:
firstly, the shrinkage temperature is more than or equal to 95 ℃, and the tanning is not carried out after long-term storage;
② volume resistivity of 103Omega.m, the number of the paper sheets adsorbed on the meat surface is 4, and the antistatic grade is 4 grade;
③ conductivity 10-6S/cm；
Fourthly, the elongation at break is more than or equal to 70 percent;
specifying the load elongation rate to be less than or equal to 35 percent;
⑥ tear strength is more than or equal to 40N/mm2；
The cracking height is more than or equal to 9 mm;
the tensile strength is larger than or equal to 15 Mpa;
ninthly, the fracture resistance of the coating is positive for 20000 times without cracks;
⑩pH4.0-6.0。
Detailed Description
While the invention has been described in detail in the following for the purpose of illustration, it is to be understood that this invention is not limited thereto but is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention as defined by the appended claims.
Example 1
Taking wet blue leather obtained by a conventional process as a raw material;
(1) sampling and weighing, wherein the weight is 120% of that of the wet blue leather;
(2) washing with water: the liquid ratio is 3.0, the temperature is normal temperature, the washing is carried out for 2 times in a closed water way, each time is 5min, the rotating speed is 8-10rpm, and the liquid is controlled;
(3) softening: the liquid ratio is 2.0, the internal temperature is set at 32 ℃, the rotating speed is 8-10rpm, formic acid is added, the rotation is carried out for 40min, the pH value is measured, and then the liquid control is carried out;
(4) washing with water: the liquid ratio is 3.0, the temperature is normal temperature, the washing is carried out for 2 times in a closed water way, each time is 5min, the rotating speed is 8-10rpm, and the liquid is controlled;
(5) retanning: the liquid ratio is 1.5, the internal temperature is 32 ℃, NL20 (Sichuan Dawei science and technology limited, neutralization retanning agent) is added, 30min is carried out, the pH is required to be more than 4.6, A18 (Sichuan Dawei science and technology limited, micromolecular acrylic acid) and A33 (Sichuan Dawei science and technology limited, macromolecule acrylic acid) are added, 40min is carried out, DD42 (Sichuan Dawei science and technology limited, amino resin) and MM51 (Sichuan Dawei science and technology limited, dispersion type synthetic tanning agent) are added, and 40min is carried out;
(6) washing with water: the liquid ratio is 3.0, the temperature is normal temperature, the washing is carried out for 2 times in a closed water way, each time is 5min, the rotating speed is 8-10rpm, and the liquid is controlled;
(7) filling: adding R7 (Langshen, synthetic tannin) and OH (Langshen, synthetic tannin) at an internal temperature of 32 deg.C and a liquid ratio of 1.5, and turning for 30 min; adding valonia extract 5.0%, bayberry extract 5.0%, and wattle bark 5.0%, transferring for 60min, adding formic acid, transferring for 30min, and controlling liquid;
(8) neutralizing: the liquid ratio is 1.5, the internal temperature is 32 ℃, 0.8 percent of sodium formate is added, and the mixture is rotated for 20 min; adding sodium bicarbonate 0.6%, transferring for 40min, measuring pH 5.2-5.4, neutralizing completely, and controlling liquid;
(9) dyeing and fat liquoring: the liquid ratio is 1.5, the internal temperature is 52-55 ℃, 2.5 percent of black dye, 2.0 percent of JM (sulfonated fatliquor, Sichuan Dawei technology Co., Ltd.), 2.0 percent of DF (sulfited neat foot oil fatliquor, Sichuan Dawei technology Co., Ltd.) and 1.0 percent of FS-90 (lecithin fatliquor, Sichuan Dawei technology Co., Ltd.) are added, the dyeing condition is checked, and the dyeing condition is checked and the dyeing condition is not completely transferred for 40 min; adding JM (sulfonated fatting agent of Sichuan Dawei science and technology limited) 2.0% and DF (sulfited neat's foot oil fatting agent of Sichuan Dawei science and technology limited) 3.0%, and rotating for 60 min; adding formic acid for 2 times, rotating for 20min every time, measuring pH, and controlling the pH at the end point to be about 4.0;
(10) washing with water: the liquid ratio is 3.0, the temperature is normal temperature, the washing is carried out for 2 times in a closed water way, each time is 5min, the rotating speed is 8-10rpm, and the liquid is controlled;
(11) antistatic treatment: the liquid ratio is 1.5, the temperature is 32 ℃, the antistatic agent betaine is 6.0 percent, the mixing time is 30min, and the drum is stopped for overnight;
(12) the next day, out of the drum → setting aside overnight → squeezing and stretching → vacuum drying (temperature 65 ℃, pressure 0.99Mpa, time 2min) → hanging and drying → picking skin and turning → vibration and softening → flat drying → trimming → semi-finished product;
(13) the coating specific scheme is shown in table 1;
(14) the dried sample is tested for the physical and chemical properties of the finished leather according to standard QB/T1873-2004. The antistatic simple detection method is independently established according to the principle of national standard GB/T12703.2-2009 charge surface density detection, and a sampled sample is regulated under a specified test condition and then detected. The rubbed sample attracts preset paper sheets, because in daily use, the contact friction between the flesh side of the leather and other materials or a human body is more, the antistatic effect of the sample is judged according to the amount of the paper sheets adsorbed on the flesh side, so that the antistatic performance is represented by measuring the amount of the sample attracting paper sheets, and the smaller the amount of the attracting paper sheets is, the better the antistatic performance is represented. The volume resistance Rv of the sample was measured using a 6487 volume resistance measuring instrument by KEITHLEY, and the volume resistivity of the sample was calculated using the formula ρ v (Ω · m) ═ Rv × width × thickness/length. The performance parameters of the obtained antistatic cattle upper leather are shown in table 2.
TABLE 1 anti-static cattle shoe upper leather finishing scheme
TABLE 2 Performance parameters of finished leather
Claims (3)
1. Antistatic cattle instep leather is characterized in that:
(1) sampling and weighing, wherein the weight is 120% of that of the wet blue leather;
(2) washing with water: the liquid ratio is 3.0, the temperature is normal temperature, the washing is carried out for 2 times in a closed water way, each time is 5min, the rotating speed is 8-10rpm, and the liquid is controlled;
(3) softening: the liquid ratio is 2.0, the internal temperature is set at 32 ℃, the rotating speed is 8-10rpm, formic acid is added, the rotation is carried out for 40min, the pH value is measured, and then the liquid control is carried out;
(4) washing with water: the liquid ratio is 3.0, the temperature is normal temperature, the washing is carried out for 2 times in a closed water way, each time is 5min, the rotating speed is 8-10rpm, and the liquid is controlled;
(5) retanning: the liquid ratio is 1.5, the internal temperature is 32 ℃, 3.0 percent of neutralization retanning agent is added, the reaction is carried out for 30min, the pH value is required to be more than 4.6, 6.0 percent of anionic acrylic resin is carried out, the reaction is carried out for 40min, 6.0 percent of amino resin is carried out, and the reaction is carried out for 40 min;
(6) washing with water: the liquid ratio is 3.0, the temperature is normal temperature, the washing is carried out for 2 times in a closed water way, each time is 5min, the rotating speed is 8-10rpm, and the liquid is controlled;
(7) filling: the liquid ratio is 1.5, the internal temperature is 32 ℃, the synthetic retanning agent is added for 10 percent, and the operation is carried out for 30 min; adding tannin extract 15%, rotating for 60min, adding formic acid, rotating for 30min, and controlling liquid;
(8) neutralizing: the liquid ratio is 1.5, the internal temperature is 32 ℃, 0.8 percent of sodium formate is added, and the mixture is rotated for 20 min; adding sodium bicarbonate 0.6%, rotating for 40min, measuring pH, requiring pH =5.2-5.4, neutralizing completely, and controlling liquid;
(9) dyeing and fat liquoring: the liquid ratio is 1.5, the internal temperature is 52-55 ℃, 2.5 percent of black dye and 5.0 percent of permeable grease are added, the operation is carried out for 60min, the dyeing condition is checked, and the operation is carried out for 40min continuously when the dyeing condition is not penetrated; adding synthetic oil 4.0%, and rotating for 60 min; adding formic acid for 2 times, rotating for 20min every time, measuring pH, and controlling the pH at the end point to be 4.0;
(10) washing with water: the liquid ratio is 3.0, the temperature is normal temperature, the washing is carried out for 2 times in a closed manner, each time is 5min, the rotating speed is 8-10r/min, and the liquid is controlled;
(11) antistatic treatment: the liquid ratio is 1.5, the temperature is 32 ℃, the antistatic agent is 6.0 percent, the mixing time is 30min, and the drum is stopped for overnight;
(12) the next day, out of the drum → setting aside overnight → squeezing and stretching → vacuum drying → hanging and drying → picking the skin and turning → shaking and softening → flat drying → trimming → semi-finished product;
(13) spraying a bottom sealing agent: the bottom sealing agent is prepared from the following raw materials in parts by weight: 120 parts of polyurethane resin, 100 parts of water and 80 parts of ethyl glycol; spraying the cross for one time;
(14) priming coating: the bottom layer spraying agent consists of the following raw materials in parts by weight: 100 parts of pigment paste, 30 parts of wax, 200 parts of acrylic resin, 100 parts of medium-soft polyurethane, 10 parts of a cross-linking agent for leather, 200 parts of water and 2.5 parts of an antistatic agent, wherein the amount of the antistatic agent is 2.5 percent of the total weight of the coating material; spraying the cross for one time;
(15) ironing: the temperature is 100 ℃, and the pressure is 80kg/cm2；
(16) Middle coating: the middle layer spraying agent consists of the following raw materials in parts by weight: 80 parts of pigment paste, 20 parts of wax, 200 parts of acrylic resin, 140 parts of medium-soft polyurethane, 5 parts of a leather cross-linking agent, 300 parts of water and 2.5 parts of an antistatic agent, wherein the amount of the antistatic agent is 2.5 percent of the total weight of the coating material; spraying the cross for one time;
(17) ironing: the temperature is 100 ℃ and the pressure is 50kg/cm2；
(18) Top coating: the top layer spraying agent consists of the following raw materials in parts by weight: 100 parts of nitrocotton brightener and 100 parts of water;
spraying the cross for one time;
(19) ironing: the temperature is 100 ℃, and the pressure is 40kg/cm2；
(20) And (5) finishing.
2. The antistatic cattle shoe upper leather according to claim 1, characterized in that: the antistatic agent in the step (11) is: betaine, ethoxylated fatty alkylamine, cationic quaternary ammonium salt, sulfate, phosphate, polyethylene glycol derivative or amido polyoxyethylene ether.
3. The antistatic cattle shoe upper leather according to claim 1, characterized in that: and (3) in the step (14) and the step (16), the antistatic agent is at least one of polyaniline, conductive carbon black and nano silver.
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| CN105867073B (en) * | 2016-06-04 | 2019-03-19 | 深圳市柯士达光电有限公司 | A kind of antistatic exposure machine system and its manufacturing method |
| CN108559807B (en) * | 2018-04-04 | 2019-06-25 | 钱秀英 | A kind of leather care products and preparation method thereof |
| CN109593452B (en) * | 2018-11-22 | 2021-01-29 | 温州东泰树脂有限责任公司 | Water-based matte finishing agent and preparation method thereof |
| CN111286219A (en) * | 2020-03-19 | 2020-06-16 | 福建华峰运动用品科技有限公司 | Method for recovering carbon black from shoe material and application |
| CN114561498A (en) * | 2022-02-24 | 2022-05-31 | 上海金狮化工有限公司 | Antistatic fatting agent, preparation method and production method of antistatic leather |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1978670A (en) * | 2006-11-24 | 2007-06-13 | 陕西科技大学 | Antistatic leather and its preparing method |
| CN101993962A (en) * | 2009-08-27 | 2011-03-30 | 际华三五一五皮革皮鞋有限公司 | Method for manufacturing waterproof soft-surface leather |
| CN102586508A (en) * | 2011-12-26 | 2012-07-18 | 河北东明牛皮制革有限公司 | Production method of leather for cow leather clothes |
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| CN1978670A (en) * | 2006-11-24 | 2007-06-13 | 陕西科技大学 | Antistatic leather and its preparing method |
| CN101993962A (en) * | 2009-08-27 | 2011-03-30 | 际华三五一五皮革皮鞋有限公司 | Method for manufacturing waterproof soft-surface leather |
| CN102586508A (en) * | 2011-12-26 | 2012-07-18 | 河北东明牛皮制革有限公司 | Production method of leather for cow leather clothes |
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