CN105694649A - Preparation method of antibacterial bottom sealing type cation modified casein leather finishing agent - Google Patents
Preparation method of antibacterial bottom sealing type cation modified casein leather finishing agent Download PDFInfo
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- CN105694649A CN105694649A CN201610176201.6A CN201610176201A CN105694649A CN 105694649 A CN105694649 A CN 105694649A CN 201610176201 A CN201610176201 A CN 201610176201A CN 105694649 A CN105694649 A CN 105694649A
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- cation
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- modified casein
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- caprolactam
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
- C14C11/00—Surface finishing of leather
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Plant Pathology (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention relates to a preparation method of an antibacterial bottom sealing type cation modified casein leather finishing agent. In the present leather production field, casein, which is most widely applied, is relatively crispy when being used for forming a film and has poor bending resistance, water resistance and antibacterial performance; almost traditional leather finishing materials in actual production are anion or non-ionic products, and covering is realized by using a lot of film forming materials. According to the preparation method, caprolactam and de-ionized water are stirred uniformly at the mass part ratio of 1:10 to obtain a caprolactam water solution; then dry casein, triethanolamine and the de-ionized water are weighed at the mass part ratio of 4:1:15 and are put into a three-mouth flask; after the temperature is raised and the materials are stirred, the temperature is continually raised and the caprolactam solution is dropwise added at a constant speed; after all the caprolactam solution is dropwise added and a thermal reaction is performed, butyl acrylate, ammonium persulfate and a cation monomer are dropwise added at the mass part ratio of 1:0.06:0.1 at the same time; after a thermal reaction, a product is cooled at a room temperature to obtain cation modified casein emulsion. With the adoption of the method, leather can be effectively finished and has the antibacterial property.
Description
Technical field
The preparation method that the present invention relates to a kind of antibacterial back cover cationic leather finishing agent, the preparation method being specifically related to the cation-modified Casein Leather finishing agent of a kind of antibacterial back cover。
Background technology
Covering with paint is the important procedure that light leather produces, and the presentation quality of Leather Finishing, sanitation performance, weatherability, ruggedness and solvent resistance etc. are played conclusive effect by it。Casein is one of coating material most widely used in leather finish, and since nineteen twenty is employed, casein and modified product thereof occupy important position always in tanning production。The film forming of casein own is more crisp, flexible resistance, resistance to water and antibiotic property poor, being modified so tackling it, (wearing red changing its kind serviceability, Zhang Zongcai, Lin Bo, etc. the performance [J] of the modified and modified product of casein. leather science and engineering, 1998,8(3): 18-20)。In leather sector, it is widely accepted and is applied to the conventional leather coating material in actual production mostly for anion or nonionic product。Tradition is covered with paint, lacquer, colour wash, etc. by means of using substantial amounts of coating and filler to realize hiding, and depends on and uses substantial amounts of filmogen (resin) to realize covering with paint, lacquer, colour wash, etc. and the combination of filler and leather, to obtain leather physical property in use and durability。Compared with covering with paint, lacquer, colour wash, etc. with traditional anion, Cationic Finish has a characteristic that 1. cationic materials can hide disability, filling and uniform surface effectively, it is not necessary to use too many coating can obtain excellent covering, thus decreasing coating consumption；2. cation product is close with the isoelectric point, IP of leather, and chrome tanning, vegetable tanning and synthesis tan skin base are all had good permeability and adhesion, it is not necessary to complete the bonding with leather by penetrating agent and the substantial amounts of filmogen of use；3. more similar anionic product, cation product is more easily imparted leather softness, smooth careful feel。Therefore, the anion that Cationic Finish is more traditional is covered with paint, lacquer, colour wash, etc. and more can be kept the natural characteristic that leather is soft, naturally comfortable, and meanwhile, the use of cationic materials is conducive to giving the antibiotic property that base material is certain。(Hu Xinhua, Shao Shuanxi. Cationic Finish System [J]. Chinese leather, 1997,26(3): 15-17；Chen Hualin, Liu Bailing. cationic coating agent application [J] in the leather. western leather, 2002,19(6): 6-9.) but, so far, be rarely reported with the research that casein prepares antibacterial back cover leather finishing agent for matrix。
Summary of the invention
It is an object of the invention to the shortcoming overcoming above-mentioned prior art, it is provided that the preparation method of the cation-modified Casein Leather finishing agent of a kind of antibacterial back cover, the emulsion applications according to said method prepared can improve the added value of leather goods to a certain extent in leather finish。
For reaching above-mentioned purpose, the technical solution used in the present invention is:
The preparation method of the cation-modified Casein Leather finishing agent of a kind of antibacterial back cover, is prepared by following steps:
Step one: the preparation of caprolactam water solution:
Weigh caprolactam 0.4～1.6 mass parts to be dissolved in 4.0～16.0 mass parts deionized waters, stir, obtain the caprolactam water solution that mass percent is 10%；
Step 2: weigh casein 2.0～8.0 mass parts, triethanolamine 0.5～2.0 mass parts, deionized water 30～80 mass parts are placed in there-necked flask, are warming up to 65～70 DEG C, stir 90～120 minutes；Being continuously heating to 75 DEG C～80 DEG C, at the uniform velocity caprolactam water solution in dropping step one, dropwises, insulation reaction 30～60 minutes；
Step 3: the preparation of cation-modified casein emulsion:
Weigh butyl acrylate 1.0～1.5 mass parts, Ammonium persulfate. 0.06～0.24 mass parts, cationic monomer 0.1～0.2 mass parts instill in step 2 in gained solution simultaneously, dropwise, insulation reaction 120～180 minutes, room temperature cools down, and obtains cation-modified casein emulsion。
In step 3, described cationic monomer includes one or more in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (DMC), dimethyl diallyl ammonium chloride (DMDAAC), N dimethylaminoethyl methacrylate (DMAEMA) etc.。
In step 3, cation-modified casein emulsion pH value is 5.5 ± 0.5。
The cation-modified Casein Leather finishing agent of antibacterial back cover that preparation method according to a kind of antibacterial back cover cation-modified Casein Leather finishing agent prepares。
Preparation in accordance with the present invention not only improves the shortcomings such as casein material filming hard, inextensibility, easy fracture, and its display cationic, after forming coating as leather finishing agent, and affinity is better between the leather surface of display anionic property, therefore coating is stronger with the bonding force of leather surface, difficult drop-off, without influence on the coating quality of leather。
Accompanying drawing illustrates:
Fig. 1 is latex film antibiotic property result (a: without cationic monomer, b: cation monomer)；
Fig. 2 is the emulsion back cover result to leather: state (a: cation monomer, b: without cationic monomer) that emulsion has just dropped on skin and emulsion all permeate after state (c: cation monomer, d: without cationic monomer)
Detailed description of the invention:
Below in conjunction with specific embodiment, the present invention will be described in detail:
Embodiment 1:
Take the casein that mass fraction is 2.0 parts, 0.5 part of triethanolamine and 30 parts of deionized waters and add in there-necked flask, controlling temperature is 65 DEG C, it is kept stirring for 90 minutes, take the caprolactam that mass fraction is 0.4 part, add in the deionized water of 4.0 parts, be stirring uniformly to obtain the caprolactam water solution that mass percent is 10%；Regulate temperature and reach 75 DEG C, drip caprolactam water solution, wait to dropwise, continue insulation reaction 30 minutes。Drip the butyl acrylate of 1.0 parts, the Ammonium persulfate. of 0.06 part and the cationic monomer DMC of 0.1 part, after dropwising, insulation reaction 120 minutes；It is down to room temperature, obtains cation-modified casein emulsion。
Embodiment 2:
Take the casein that mass fraction is 3.0 parts, 1.0 parts of triethanolamine and 40 parts of deionized waters and add in there-necked flask, controlling temperature is 65 DEG C, it is kept stirring for 100 minutes, take the caprolactam that mass fraction is 0.6 part, add in the deionized water of 6.0 parts, be stirring uniformly to obtain the caprolactam water solution that mass percent is 10%；Regulate temperature and reach 80 DEG C, drip caprolactam water solution, wait to dropwise, continue insulation reaction 30 minutes。Drip the butyl acrylate of 1.2 parts, the Ammonium persulfate. of 0.14 part and the cationic monomer DMDAAC of 0.2 part, after dropwising, insulation reaction 160 minutes；It is down to room temperature, obtains cation-modified casein emulsion。
Embodiment 3:
Take the casein that mass fraction is 5.0 parts, 1.5 parts of triethanolamine and 60 parts of deionized waters and add in there-necked flask, controlling temperature is 68 DEG C, it is kept stirring for 120 minutes, take the caprolactam that mass fraction is 0.8 part, add in the deionized water of 8.0 parts, be stirring uniformly to obtain the caprolactam water solution that mass percent is 10%；Regulate temperature and reach 78 DEG C, drip caprolactam water solution, wait to dropwise, continue insulation reaction 50 minutes。Drip the butyl acrylate of 1.3 parts, the Ammonium persulfate. of 0.16 part and the cationic monomer DMAEMA of 0.1 part, after dropwising, insulation reaction 140 minutes；It is down to room temperature, obtains cation-modified casein emulsion。
Embodiment 4:
Take the casein that mass fraction is 8.0 parts, 2.0 parts of triethanolamine and 80 parts of deionized waters and add in there-necked flask, controlling temperature is 70 DEG C, it is kept stirring for 120 minutes, take the caprolactam that mass fraction is 1.6 parts, add in the deionized water of 16.0 parts, be stirring uniformly to obtain the caprolactam water solution that mass percent is 10%；Regulate temperature and reach 80 DEG C, drip caprolactam water solution, wait to dropwise, continue insulation reaction 60 minutes。Drip the butyl acrylate of 1.5 parts, the Ammonium persulfate. of 0.24 part and the cationic monomer DMDAAC of 0.2 part, after dropwising, insulation reaction 180 minutes；It is down to room temperature, obtains cation-modified casein emulsion。
The cation-modified casein emulsion casting film-forming in the plastic culture dish that diameter is 90mm that will prepare in above-described embodiment, after drying at room temperature 12h, puts to 50 DEG C of vacuum drying ovens dry 4h, obtains cation-modified casein latex film。Adopt inhibition zone method that latex film carries out aspergillus flavus-resistance mycete performance test。Back cover was characterized by the emulsion infiltration skin bit time, and infiltration time more long explanation back cover is more good, otherwise, then more poor。
With reference to Fig. 1 it can be seen that scheme latex film antibiotic property in (b) to be better than (a), illustrate that the introducing of cationic monomer can give coating obvious antibiotic property；
With reference to Fig. 2 it can be seen that with compared with the emulsion of cationic monomer, cation emulsion substantially reduces in the seepage velocity of leather surface, illustrate that the introducing of cationic monomer can give the back cover that coating is certain。
Present disclosure is not limited to cited by embodiment, and the conversion of any equivalence that technical solution of the present invention is taked by those of ordinary skill in the art by reading description of the present invention, the claim being the present invention is contained。
Claims (4)
1. the preparation method of the cation-modified Casein Leather finishing agent of antibacterial back cover, it is characterised in that prepared by following steps:
Step one: the preparation of caprolactam water solution:
Weigh caprolactam 0.4～1.6 mass parts to be dissolved in 4.0～16.0 mass parts deionized waters, stir, obtain the caprolactam water solution that mass percent is 10%；
Step 2: weigh casein 2.0～8.0 mass parts, triethanolamine 0.5～2.0 mass parts, deionized water 30～80 mass parts are placed in there-necked flask, are warming up to 65～70 DEG C, stir 90～120 minutes；Being continuously heating to 75 DEG C～80 DEG C, at the uniform velocity caprolactam water solution in dropping step one, dropwises, insulation reaction 30～60 minutes；
Step 3: the preparation of cation-modified casein emulsion:
Weigh butyl acrylate 1.0～1.5 mass parts, Ammonium persulfate. 0.06～0.24 mass parts, cationic monomer 0.1～0.2 mass parts instill in step 2 in gained solution simultaneously, dropwise, insulation reaction 120～180 minutes, room temperature cools down, and obtains cation-modified casein emulsion。
2. the preparation method of the cation-modified Casein Leather finishing agent of a kind of antibacterial back cover according to claim 1, it is characterized in that: in step 3, described cationic monomer includes one or more in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, dimethyl diallyl ammonium chloride, N dimethylaminoethyl methacrylate etc.。
3. the preparation method of the cation-modified Casein Leather finishing agent of a kind of antibacterial back cover according to claim 1, it is characterised in that: in step 3, cation-modified casein emulsion pH value is 5.5 ± 0.5。
4. the cation-modified Casein Leather finishing agent of antibacterial back cover prepared according to the preparation method of a kind of antibacterial back cover cation-modified Casein Leather finishing agent。
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| CN201610176201.6A CN105694649A (en) | 2016-03-25 | 2016-03-25 | Preparation method of antibacterial bottom sealing type cation modified casein leather finishing agent |
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| CN201610176201.6A CN105694649A (en) | 2016-03-25 | 2016-03-25 | Preparation method of antibacterial bottom sealing type cation modified casein leather finishing agent |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106221558A (en) * | 2016-08-22 | 2016-12-14 | 中国皮革和制鞋工业研究院（晋江）有限公司 | A kind of preparation method of leather casein class gloss oil |
| CN106519257A (en) * | 2016-10-25 | 2017-03-22 | 齐鲁工业大学 | Antibacterial type casein and preparing method thereof |
| CN106632907A (en) * | 2016-11-18 | 2017-05-10 | 陕西科技大学 | Modified casein/thymol/nano-ZnO composite antibacterial film prepared based on in-situ emulsion polymerization, and preparation method of composite antibacterial film |
| CN106634327A (en) * | 2016-10-25 | 2017-05-10 | 齐鲁工业大学 | Antibacterial leather finishing agent and preparation method thereof |
| CN108997942A (en) * | 2018-07-26 | 2018-12-14 | 苏州华龙化工有限公司 | A kind of preparation method of sericin grape pip polysaccharide composite leather gloss agent |
| US11157640B2 (en) | 2014-02-28 | 2021-10-26 | International Business Machines Corporation | Protecting sensitive data in software products and in generating core dumps |
| CN117701787A (en) * | 2024-02-02 | 2024-03-15 | 德州兴隆皮革制品有限公司 | Manufacturing method of antibacterial and bacteriostatic sofa leather |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11157640B2 (en) | 2014-02-28 | 2021-10-26 | International Business Machines Corporation | Protecting sensitive data in software products and in generating core dumps |
| CN106221558A (en) * | 2016-08-22 | 2016-12-14 | 中国皮革和制鞋工业研究院（晋江）有限公司 | A kind of preparation method of leather casein class gloss oil |
| CN106519257A (en) * | 2016-10-25 | 2017-03-22 | 齐鲁工业大学 | Antibacterial type casein and preparing method thereof |
| CN106634327A (en) * | 2016-10-25 | 2017-05-10 | 齐鲁工业大学 | Antibacterial leather finishing agent and preparation method thereof |
| CN106634327B (en) * | 2016-10-25 | 2018-08-07 | 齐鲁工业大学 | A kind of antimicrobial form leather finishing agent and preparation method thereof |
| CN106519257B (en) * | 2016-10-25 | 2020-01-14 | 齐鲁工业大学 | Antibacterial casein and preparation method thereof |
| CN106632907A (en) * | 2016-11-18 | 2017-05-10 | 陕西科技大学 | Modified casein/thymol/nano-ZnO composite antibacterial film prepared based on in-situ emulsion polymerization, and preparation method of composite antibacterial film |
| CN108997942A (en) * | 2018-07-26 | 2018-12-14 | 苏州华龙化工有限公司 | A kind of preparation method of sericin grape pip polysaccharide composite leather gloss agent |
| CN117701787A (en) * | 2024-02-02 | 2024-03-15 | 德州兴隆皮革制品有限公司 | Manufacturing method of antibacterial and bacteriostatic sofa leather |
| CN117701787B (en) * | 2024-02-02 | 2024-05-03 | 德州兴隆皮革制品有限公司 | Manufacturing method of antibacterial and bacteriostatic sofa leather |
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Application publication date: 20160622 |