CN115701464B - Super-hydrophobic finishing agent and preparation method and application thereof - Google Patents
Super-hydrophobic finishing agent and preparation method and application thereof Download PDFInfo
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- CN115701464B CN115701464B CN202110879654.6A CN202110879654A CN115701464B CN 115701464 B CN115701464 B CN 115701464B CN 202110879654 A CN202110879654 A CN 202110879654A CN 115701464 B CN115701464 B CN 115701464B
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- 238000002360 preparation method Methods 0.000 title abstract description 11
- 101710091977 Hydrophobin Proteins 0.000 claims abstract description 76
- 239000004744 fabric Substances 0.000 claims abstract description 65
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000004088 foaming agent Substances 0.000 claims abstract description 13
- 229910052604 silicate mineral Inorganic materials 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 17
- 238000007493 shaping process Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 10
- 241000499912 Trichoderma reesei Species 0.000 claims description 9
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 8
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- MSYHGYDAVLDKCE-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluoro-1-imidazol-1-ylbutan-1-one Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(=O)N1C=CN=C1 MSYHGYDAVLDKCE-UHFFFAOYSA-N 0.000 claims description 6
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- -1 alkyl glycoside Chemical class 0.000 claims description 6
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
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- AOMUHOFOVNGZAN-UHFFFAOYSA-N N,N-bis(2-hydroxyethyl)dodecanamide Chemical compound CCCCCCCCCCCC(=O)N(CCO)CCO AOMUHOFOVNGZAN-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
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- 238000005096 rolling process Methods 0.000 claims description 3
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- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 2
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- DJUKOJWSBZPKGB-UHFFFAOYSA-N C(CCCCCCC(O)=N)(O)=N.C(CCC(=O)O)(=O)O Chemical compound C(CCCCCCC(O)=N)(O)=N.C(CCC(=O)O)(=O)O DJUKOJWSBZPKGB-UHFFFAOYSA-N 0.000 claims description 2
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- 125000000217 alkyl group Chemical group 0.000 claims description 2
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052622 kaolinite Inorganic materials 0.000 claims description 2
- ONHFWHCMZAJCFB-UHFFFAOYSA-N myristamine oxide Chemical compound CCCCCCCCCCCCCC[N+](C)(C)[O-] ONHFWHCMZAJCFB-UHFFFAOYSA-N 0.000 claims description 2
- ZHALDANPYXAMJF-UHFFFAOYSA-N octadecanoate;tris(2-hydroxyethyl)azanium Chemical compound OCC[NH+](CCO)CCO.CCCCCCCCCCCCCCCCCC([O-])=O ZHALDANPYXAMJF-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
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- WDQLRUYAYXDIFW-RWKIJVEZSA-N (2r,3r,4s,5r,6r)-4-[(2s,3r,4s,5r,6r)-3,5-dihydroxy-4-[(2r,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-6-[[(2r,3r,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxymethyl]oxan-2-yl]oxy-6-(hydroxymethyl)oxane-2,3,5-triol Chemical compound O[C@@H]1[C@@H](CO)O[C@@H](O)[C@H](O)[C@H]1O[C@H]1[C@H](O)[C@@H](O[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@@H](CO[C@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)O1 WDQLRUYAYXDIFW-RWKIJVEZSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
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- 125000001165 hydrophobic group Chemical group 0.000 description 2
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- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241001286670 Ulmus x hollandica Species 0.000 description 1
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- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a super-hydrophobic finishing agent, a preparation method and application thereof, wherein the super-hydrophobic finishing agent is prepared from the following raw materials in parts by weight: hydrophobin type I, hydrophobin type II, foaming agent, nano silicate mineral, accelerator, coupling agent and water. The super-hydrophobic finishing agent is formed by self-assembly of the type I hydrophobin, a foaming agent forms a large amount of water-air interfaces on the surface of the fabric, and the nano silicate mineral has a large specific surface area and the stable dispersion effect of the type II hydrophobin, so that the static water contact angle of the hydrophilic fabric is improved to be more than 150 degrees, and the hand feeling and the chromatic light of the fabric are not influenced; the invention has the advantages of convenient and easily obtained raw materials, simple equipment, simple process, environmental protection and no three wastes, and is suitable for industrialized application; the fabric obtained by the invention has super-strong hydrophobic capacity and keeps original hand feeling and luster.
Description
Technical Field
The invention relates to a fabric finishing agent and a preparation method and application thereof, in particular to a super-hydrophobic finishing agent and a preparation method and application thereof, and belongs to the field of textiles.
Background
The super-hydrophobic textile has waterproof, antifouling and self-cleaning capabilities, and is one of the research hot spots of functional textiles. The preparation method of the super-hydrophobic textile comprises a sol-gel method, a chemical vapor deposition method, a dip coating method, a self-assembly method and the like. The eight-carbon waterproof agent in the low-surface-energy material has good chemical stability, water repellency and oleophobic property, and incomparable superiority in three-proofing finishing of textiles. However, octacarbon waterproofing agents containing perfluorooctane sulfonate PFOS, perfluorooctanoic acid PFOA and other compounds are extremely difficult to degrade, have high bioaccumulation and various toxicities, and have been gradually limited in use. Some substitutes such as novel fluoroalkyl compounds, novel short fluorocarbon chain fabric finishing agents, novel fluorine-free durable water-repellent finishing agents, novel fluorine-containing silicon water-repellent oil-repellent finishing agents, nano hybrid fluorine-containing water-repellent oil-repellent finishing agents and the like are continuously developed, but along with the deep research, the novel harmfulness of perfluoro or polyfluoroalkyl compounds to human health and ecological environment is continuously exposed, and development of a novel safe and environment-friendly textile water-repellent finishing agent is urgently needed.
Disclosure of Invention
The invention aims to: the invention aims to provide a safe, environment-friendly, stable and efficient hydrophobic finishing agent which does not influence the hand feel and luster of fabric, and a preparation method and application thereof.
The technical scheme is as follows: the super-hydrophobic finishing agent disclosed by the invention is prepared from the following raw materials in parts by weight: hydrophobin type I, hydrophobin type II, foaming agent, nano silicate mineral, accelerator, coupling agent and water.
Hydrophobin is a small-molecule ampholytic protein with special physicochemical properties secreted by higher filamentous fungi, has a hydrophobic and hydrophilic structure, is amphiphilic, and can form a nanoscale protein film at a two-phase interface through self-assembly, and the characteristic enables the hydrophobin to be applied to various fields such as biosensors, cell immobilization, fine chemical engineering, medicine and health and the like.
The inventors therefore propose the assumption that: the hydrophobin is used for textile finishing to obtain a hydrophobic or hydrophilic fabric, and if the fabric is hydrophilic cellulose, the hydrophobic fabric is obtained after finishing; if the fabric is water-repellent chemical fiber, the hydrophilic fabric is obtained after finishing, and the invention mainly aims at the hydrophobic finishing of the natural fabric. Through a large number of experiments, it is unexpectedly found that the self-assembly of the type I hydrophobin to form a stable rod-shaped film needs to depend on a large amount of water-air interfaces, the process is an irreversible and non-spontaneous process which needs energy, and the formation of the rod-shaped film can be promoted by adding a certain amount of foaming agent, so that the hydrophobicity of the cloth cover is improved; the II-type hydrophobin stably disperses the nano silicate mineral, forms evenly distributed concave-convex points on the surface of the fabric, and can improve the roughness of the fabric surface, so that the contact angle of water, oil and other liquid on the surface of the material is further increased; and then a large number of stable rod-shaped film structures can be obtained by reasonably setting parameters such as pH of working solution, roller pressure, setting speed, setting temperature and the like.
0.5-2 Parts of type I hydrophobin, 0.05-0.1 part of type II hydrophobin, 0.1-0.5 part of foaming agent, 0.5-2 parts of nano silicate mineral, 0.1-0.5 part of accelerator, 1-2 parts of coupling agent and 90-100 parts of water.
Preferably, the foaming agent is any one of dodecyl dimethyl amine oxide, tetradecyl dimethyl amine oxide, coco diethanol amide, triethanolamine stearate, coco isopropanolamine, alkyl glycoside APG1214 and alkyl glycoside APG 0816.
The hydrophobin adopted by the invention widely exists in edible fungi, and researches show that the fungal hydrophobin has no cytotoxicity, strong immunogenicity and extremely high safety. The hydrophobin type I forms an ordered rod-like film structure after self-assembly on the surface of a fabric (e.g. natural and regenerated cellulose), which can significantly reduce the surface tension, and which is very stable and can only be dissolved in a few organic solvents. The II type hydrophobin has stronger effect of reducing surface tension, is commonly used for dispersion and emulsification, and forms a film which is easy to dissolve by anionic surfactant. Preferably, the type I hydrophobin is any one of schizophyllan SC, agaricus bisporus hydrophobin ABHI, neurospora crassa hydrophobin EAS and Grifola frondosa hydrophobin HGFI. Preferably, the type II hydrophobin is any one of Trichoderma reesei hydrophobin HFBI, trichoderma reesei hydrophobin HFBII and Ulmus hollandii hydrophobin CU.
The nano silicate mineral adopted by the invention has large specific surface area, the II-type hydrophobin is utilized to stably disperse the nano silicate mineral, evenly distributed concave-convex points are formed on the surface of the fabric, the roughness of the fabric surface can be improved, so that the contact angle of water, oil and other liquids on the surface of the material can be further increased, and the nano silicate can be firmly attached to the fabric surface by matching with the corresponding coupling agent. Preferably, the nano silicate mineral is any one of hydrotalcite, halloysite, montmorillonite and kaolinite.
The accelerator adopted by the invention can perform crosslinking with the type I hydrophobin to open hydrophobic groups in protein molecules, and simultaneously retain the secondary structure of the molecules, so that the hydrophobicity is further improved. Preferably, the accelerator is any one of maleimide, transglutaminase, dimethyl imidoester, and suberic acid diimine succinate.
The coupling agent adopted by the invention is any one of a silane coupling agent, a phthalate coupling agent, a phosphate coupling agent, a borate coupling agent and a bimetallic coupling agent.
The preparation method of the super-hydrophobic finishing agent comprises the following steps:
(1) Mixing the type I hydrophobin, the accelerator, the foaming agent and water to obtain a component A, and preferably mixing the components, stirring, standing and then defoaming;
(2) Mixing II-type hydrophobin, nano silicate mineral, coupling agent and water, filtering to obtain a component B, preferably, mixing the components, performing ultrasonic dispersion, standing and filtering;
(3) And mixing the component A and the component B to obtain the super-hydrophobic finishing agent.
The application of the super-hydrophobic finishing agent in fabric finishing comprises the following steps: preparing a super-hydrophobic finishing agent into a finishing liquid, padding, rolling and drying the fabric in the finishing liquid for shaping, wherein the drying temperature is controlled at 110-180 ℃.
Preferably, 10-30 parts of the super-hydrophobic finishing agent is dissolved in 100 parts of water to obtain finishing liquid, and the pH is regulated to 4-7. The fabric is soaked in the finishing liquid and rolled once, and the roll pressure is 2.0-2.5kg. The shaping temperature of the front part (for example, the front half section, further the front four sections) of the oven is controlled to be 150-180 ℃, the shaping temperature of the rear part (for example, the rear half section, further the rear four sections) of the oven is controlled to be 110-130 ℃, and the speed of the vehicle is kept to be 35-55 m/min.
The fabric suitable for the super-hydrophobic finishing agent is natural and regenerated cellulose fabrics, and further is one of all-cotton fabrics, viscose fabrics, tencel fabrics and modal fabrics.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages: the super-hydrophobic finishing agent forms a film by means of self-assembly of the type I hydrophobin, a foaming agent forms a large amount of water-air interfaces on the surface of the fabric, and the nano silicate mineral has a large specific surface area and stable dispersion effect of the type II hydrophobin, so that the static water contact angle of the hydrophilic fabric is improved to be more than 150 degrees, and the hand feeling and the chromatic light of the fabric are not influenced; the invention has the advantages of convenient and easily obtained raw materials, simple equipment, simple process, environmental protection and no three wastes, and is suitable for industrialized application; the fabric obtained by the invention has super-strong hydrophobic capacity and keeps original hand feeling and luster.
Detailed Description
Example 1
The preparation method of the super-hydrophobic finishing agent comprises the following steps:
(1) Mixing 0.5 part of schizophyllum commune hydrophobin SC, 0.1 part of maleimide, 0.1 part of dodecyl dimethyl amine oxide and 45 parts of deionized water, stirring, standing and defoaming to obtain a component A;
(2) Mixing 0.05 part of trichoderma reesei hydrophobin HFBI, 0.5 part of hydrotalcite, 1 part of silane coupling agent and 45 parts of deionized water, performing ultrasonic dispersion, standing and filtering to obtain a component B;
(3) And mixing the component A and the component B according to the mass ratio, and stirring to obtain the super-hydrophobic finishing agent.
The application method of the super-hydrophobic finishing agent comprises the following steps:
(1) Dissolving 30 parts of super-hydrophobic finishing agent in 100 parts of water, and regulating the pH to 4;
(2) The cotton fabric is soaked and rolled once, the roller pressure is 2.5kg, the shaping temperature of the first four sections of baking boxes is controlled to be 150 ℃, the shaping temperature of the second four sections of baking boxes is controlled to be 110 ℃, and the speed of the machine is kept to be 35 m/min.
Example 2
The preparation method of the super-hydrophobic finishing agent comprises the following steps:
(1) Mixing 2 parts of agaricus bisporus hydrophobin ABHI, 0.5 part of transglutaminase, 0.5 part of coco diethanolamide and 50 parts of deionized water, stirring, standing and defoaming to obtain a component A;
(2) Mixing 0.1 part of trichoderma reesei hydrophobin HFBII, 2 parts of halloysite, 2 parts of phthalate coupling agent and 50 parts of deionized water, performing ultrasonic dispersion, standing and filtering to obtain a component B;
(3) And mixing the component A and the component B according to the mass ratio, and stirring to obtain the super-hydrophobic finishing agent.
The application method of the super-hydrophobic finishing agent comprises the following steps:
(1) Dissolving 10 parts of super-hydrophobic finishing agent in 100 parts of water, and regulating the pH to 7;
(2) The tencel fabric is soaked and rolled once, the roller pressure is 2kg, the shaping temperature of the first four sections of baking boxes is controlled to be 180 ℃, the shaping temperature of the second four sections of baking boxes is controlled to be 130 ℃, and the speed of the machine is kept 55 meters/min.
Example 3
The preparation method of the super-hydrophobic finishing agent comprises the following steps:
(1) Mixing 1 part of a pulse-width bacterium hydrophobin EAS, 0.3 part of dimethyl iminoester, 0.3 part of alkyl glycoside APG1214 and 48 parts of deionized water, stirring, standing and defoaming to obtain a component A;
(2) Mixing 0.08 part of Ulmus hollandica hydrophobin CU, 0.1 part of montmorillonite, 1.5 parts of bimetal coupling agent and 48 parts of deionized water, performing ultrasonic dispersion, standing and filtering to obtain a component B;
(3) And mixing the component A and the component B according to the mass ratio, and stirring to obtain the super-hydrophobic finishing agent.
The application method of the super-hydrophobic finishing agent comprises the following steps:
(1) Dissolving 20 parts of super-hydrophobic finishing agent in 100 parts of water, and regulating the pH to 5.5;
(2) The modal fabric is immersed and rolled once, the roller pressure is 2.3kg, the shaping temperature of the first four sections of baking boxes is controlled at 165 ℃, the shaping temperature of the second four sections of baking boxes is controlled at 120 ℃, and the speed of the vehicle is kept at 55 m/min.
Comparative example 1
In comparison with example 1, the number of parts of schizophyllum commune hydrophobin SC was 0.3 part. The concentration of the type I hydrophobin is too low, not enough hydrophobin molecules are aggregated at a water-air interface, the number of hydrophobins which cannot self-assemble on the surface of the fabric or are self-assembled is small, the surface tension of the fabric is still large, and the fabric still presents hydrophilicity.
Comparative example 2
In comparison with example 1, the number of parts of schizophyllum commune hydrophobin SC is 2.4 parts. The concentration of the type I hydrophobin is too high, hydrophobin molecules which are self-assembled on the surface of the fabric reach a saturated state, and the surface tension only fluctuates within a small range and is not obviously reduced.
Comparative example 3
Compared to example 1, the fraction of trichoderma reesei hydrophobin HFBI is 0.04 parts. The concentration of the II type hydrophobin is too low, the content of hydrophobin molecules is insufficient, and nano silicate particles cannot be stably dispersed.
Comparative example 4
Compared to example 1, the fraction of trichoderma reesei hydrophobin HFBI is 0.12. Too high a concentration of type II hydrophobin, the excess hydrophobin molecules can act as cross-linking agents to adsorb onto the dispersed nano silicate particles, so that these particles are again aggregated and settled, and too high a concentration of type II hydrophobin can affect the hand feel. Therefore, the concentration of the II type hydrophobin is too high or too low, nano silicate particles cannot be stably dispersed, the nano silicate particles cannot be synergistically enhanced with the I type hydrophobin, and the cloth cover has certain hydrophobicity but does not reach the superhydrophobic level.
Comparative example 5
The fraction of hydrotalcite was 0.4 part compared to example 1. The hydrotalcite content is low, the cloth surface roughness is not obviously improved, and the synergistic effect with the type I hydrophobin is not achieved.
Comparative example 6
The fraction of hydrotalcite was 2.2 parts compared to example 1. The hydrotalcite content is high, the surface tension of the fabric is not reduced any more, and the hand feeling of the fabric is also affected.
Comparative example 7
The part of maleimide was 0.08 part as compared to example 1. The content of the accelerator is too low, the crosslinking modification degree of the type I hydrophobin is low, hydrophobic groups in the molecule are not fully opened, and the hydrophobicity after the cloth cover self-assembly is limited.
Comparative example 8
The part of maleimide was 0.55 part as compared with example 1. The content of the accelerator is too high, the degree of crosslinking is too high, so that protein molecules are denatured, and the hydrophobic property of the molecules is greatly reduced.
Comparative example 9
In comparison with example 1, the pH was 3. The pH of the working solution is far away from the isoelectric point of the type I hydrophobin, the critical concentration required by self-assembly of the type I hydrophobin is large, the rod-shaped film structure formed by the cloth cover is less, and the hydrophobicity is general.
Comparative example 10
In comparison with example 1, the pH was 8. The pH of the working solution is too large to cause protein denaturation, a rod-shaped film structure cannot be formed by self-assembly, and the cloth surface has poor hydrophobicity.
Comparative example 11
The fraction of dodecyldimethylamine oxide was 0.08 part compared to example 1. Because of the insufficient foaming agent content, the fabric has less foam on the fabric surface after passing through the roller, and does not have sufficient water-air interface to participate in the self-assembly of the type I hydrophobin molecules. The fabric surface tension is still relatively high and the hydrophobicity is generally.
Comparative example 12
In comparison with example 1, the fraction of dodecyldimethylamine oxide was 0.53 part. The foaming agent content is too high, the fabric is more foamed after passing through a roller, and the excessive water-air interface causes the I-type hydrophobin to aggregate into assembly particles, so that a stable rod-shaped film cannot be formed.
Comparative example 13
The roll pressure was 1.8kg compared to example 1. The pressure of the roller is smaller, the fabric has enough foam after passing through the roller, but the cloth cover is too wet, and the subsequent shaping cannot be completely dried.
Comparative example 14
The roll pressure was 2.8kg compared to example 1. The roller pressure is larger, the fabric has less foam after passing through the roller, and the water-air interface is not enough to participate in the self-assembly of the type I hydrophobin molecules. The fabric surface tension is still relatively high and the hydrophobicity is generally.
Comparative example 15
The vehicle speed was 30 m/min as compared with example 1. The speed of the vehicle is too slow, the fabric is less foamed through the grooves, and there is not enough water-air interface to support the self-assembly of type I hydrophobin molecules.
Comparative example 16
The vehicle speed was 60 m/min as compared with example 1. The speed of the vehicle is too high, and a large number of bubbles continuously enter the liquid to bring enough air/water interface, but the setting time is short, the supplied energy is insufficient, and part of the type I hydrophobin cannot form a stable rod-shaped structure.
Comparative example 17
Compared with example 1, the setting temperature of the first four sections of ovens is controlled at 185 ℃. The shaping temperature of the first four sections of ovens is too high, so that a large amount of bubbles on the cloth cover are rapidly discharged due to molecular thermal motion, the water-air interface formed by the supporting rod-shaped structure is rapidly reduced, the type I hydrophobin cannot self-assemble on the cloth cover, and the cloth cover still presents hydrophilicity.
Comparative example 18
Compared with example 1, the shaping temperature of the first four sections of ovens is controlled at 145 ℃. The shaping temperature of the first four sections of ovens is too low, the energy in the early stage is insufficient, the formation rate of a rod-shaped structure is slower, and the quantity of I-type hydrophobins self-assembled on the cloth cover is smaller.
Comparative example 19
The final four-section oven set temperature was controlled at 135 c as compared to example 1. The shaping temperature of the last four sections of ovens is too high, and the content of external air secondarily introduced into the cloth cover is insufficient.
Comparative example 20
The final four-section oven set temperature was controlled at 105c as compared to example 1. The latter four-section oven set temperature is too low, although there is a large amount of air entering the surface, too low a temperature is not sufficient to allow self-assembly of the type I hydrophobin at the secondarily formed water-air interface. The fabric surface tension is still relatively high and the hydrophobicity is generally.
Unlike conventional constant temperature setting process, the present invention needs to ensure that the setting temperature of the back part is lower than that of the front part. In this way, in the cooling process, the internal air pressure of the liquid is reduced, a large amount of air is gathered on the cloth surface, and the formation of the rod-shaped film is further promoted. In addition, the hydrophobin finishing agent is adopted in comparative examples 1 to 20, and although the waterproof performance is not ideal, the hand gloss of the fabric is not affected, and the details are not repeated in the table.
Comparative example 21
30 Parts of a conventional waterproof agent (six-carbon fluorine-containing acrylic resin) is taken and dissolved in 100 parts of water, the fabric is soaked and rolled once, the setting temperature is controlled at 150 ℃, and the speed of the vehicle is kept at 50 m/min. Compared with the conventional waterproof agent, the fabric obtained by the invention can obtain the same-level hydrophobic effect on the premise of keeping the original hand feeling and color light.
Comparative example 22
Compared with the example 1, if any one of the components of schizophyllan SC, trichoderma reesei hydrophobin HFBI, maleimide, dodecyl dimethyl amine oxide or hydrotalcite is absent in the system, the static contact angle and the waterproof grade of the cloth cover are obviously reduced, the super-hydrophobic grade is not reached, and the table is not repeated.
The performance characterization method comprises the following steps:
1. Reference DB 44/T1872-2016 "determination of wettability of textile surface-contact Angle method" test sample Water contact Angle (static);
2. The water-proof grade before and after washing is tested by referring to GB/T4745-2012 test sample of textile water-proof Performance detection and evaluation-Water-soaking method;
3. hand feel and color difference
Table 1 results of measurements of the wettability of the surfaces of the textiles of examples and comparative examples
Table 2 results of testing and evaluating the waterproof properties of the textiles of examples and comparative examples
| Sequence number | Waterproof grade | Sequence number | Waterproof grade | Sequence number | Waterproof grade |
| Example 1 | Grade 5 | Example 2 | Grade 5 | Example 3 | Grade 5 |
| Comparative example 1 | Level 1 | Comparative example 2 | Grade 5 | Comparative example 3 | 3-4 Grade |
| Comparative example 4 | 3-4 Grade | Comparative example 5 | 3-4 Grade | Comparative example 6 | Grade 5 |
| Comparative example 7 | 3 Grade | Comparative example 8 | 1-2 Grade | Comparative example 9 | 2-3 Stages |
| Comparative example 10 | 1-2 Grade | Comparative example 11 | 3 Grade | Comparative example 12 | 2-3 Stages |
| Comparative example 13 | Level 0 | Comparative example 14 | 3 Grade | Comparative example 15 | 3 Grade |
| Comparative example 16 | 3 Grade | Comparative example 17 | 1-2 Grade | Comparative example 18 | 2-3 Stages |
| Comparative example 19 | 3 Grade | Comparative example 20 | 3 Grade | Comparative example 21 | Grade 5 |
Table 3 examples and comparative textile feel and color difference results
| Sequence number | Hand feel | Chromatic aberration |
| Example 1 | Has no influence on | 4-5 Grade |
| Example 2 | Has no influence on | 4-5 Grade |
| Example 3 | Has no influence on | 4-5 Grade |
| Comparative example 21 | Rough hand feeling | 3 Grade |
Claims (7)
1. The super-hydrophobic finishing agent is characterized by comprising the following raw materials in parts by weight: 0.5-2 parts of type I hydrophobin, 0.05-0.1 part of type II hydrophobin, 0.1-0.5 part of foaming agent, 0.5-2 parts of nano silicate mineral, 0.1-0.5 part of accelerator, 1-2 parts of coupling agent and 90-100 parts of water; the type I hydrophobin is any one of schizophyllum commune hydrophobin SC, agaricus bisporus hydrophobin ABHI, neurospora crassa hydrophobin EAS and grifola frondosa hydrophobin HGFI; the II type hydrophobin is any one of trichoderma reesei hydrophobin HFBI, trichoderma reesei hydrophobin HFBII and Ulmus hollandii hydrophobin CU.
2. The superhydrophobic finish of claim 1, wherein: the foaming agent is any one of dodecyl dimethyl amine oxide, tetradecyl dimethyl amine oxide, coco diethanol amide, triethanolamine stearate, coco isopropanolamine, alkyl glycoside APG1214 and alkyl glycoside APG 0816.
3. The superhydrophobic finish of claim 1, wherein: the nano silicate mineral is any one of hydrotalcite, halloysite, montmorillonite and kaolinite.
4. The superhydrophobic finish of claim 1, wherein: the promoter is any one of maleimide, transglutaminase, dimethyl imidoester and succinic acid suberic acid diimine.
5. The superhydrophobic finish of claim 1, wherein: the coupling agent is any one of a silane coupling agent, a phthalate coupling agent, a phosphate coupling agent, a borate coupling agent and a bimetallic coupling agent.
6. The method for preparing the super-hydrophobic finishing agent according to claim 1, which is characterized by comprising the following steps:
(1) Mixing the type I hydrophobin, the accelerator, the foaming agent and water, and defoaming to obtain a component A;
(2) Mixing II-type hydrophobin, nano silicate mineral, coupling agent and water, and filtering to obtain a component B;
(3) And mixing the component A and the component B to obtain the super-hydrophobic finishing agent.
7. Use of the superhydrophobic finish of claim 1 in fabric finishing comprising the steps of: preparing a super-hydrophobic finishing agent into a finishing liquid, regulating the pH value to 4-7, padding, rolling and drying the fabric in the finishing liquid, wherein the pressure of the rolling roller is controlled to be 2.0-2.5kg, the shaping temperature of the first four sections of baking boxes is controlled to be 150-180 ℃, the shaping temperature of the last four sections of baking boxes is controlled to be 110-130 ℃, and the speed of the vehicle is kept to be 35-55 m/min.
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