CN109054476B - Waterproof coating for zipper and preparation method thereof - Google Patents
Waterproof coating for zipper and preparation method thereof Download PDFInfo
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- CN109054476B CN109054476B CN201810778115.1A CN201810778115A CN109054476B CN 109054476 B CN109054476 B CN 109054476B CN 201810778115 A CN201810778115 A CN 201810778115A CN 109054476 B CN109054476 B CN 109054476B
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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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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Abstract
The invention relates to the technical field of zipper coatings, in particular to a waterproof coating for a zipper and a preparation method thereof. The waterproof coating for the zipper is a polyurethane coating taking water as a dispersion medium, has the advantages of environmental protection and safety, and also has good water resistance, and a micro-nano uneven plane can be formed on a formed coating by adding hydrophobic nano silicon dioxide into the waterproof coating, so that the waterproof coating has super-hydrophobic performance, the surface contact angle is 157.2 +/-1.5 degrees, the rolling angle is less than 8 degrees, and the waterproof coating can effectively block water vapor when being used for the zipper, thereby meeting the requirements of waterproof zipper clothes.
Description
Technical Field
The invention relates to the technical field of zipper coatings, in particular to a waterproof coating for a zipper and a preparation method thereof.
Background
Zippers (zippers), which are connectors for uniting or separating articles by means of a continuous arrangement of zipper teeth, are now widely used in clothing, bags, tents, etc. The existing zippers are various in types, and waterproof effect is required on some functional clothes, such as outdoor jacket. The existing zipper clothes are easy to permeate water from a zipper cloth belt due to the water absorption of fibers, so that the application of the zipper on waterproof clothes is limited.
One of the methods for improving the water resistance of the fastener tape is to coat a waterproof coating material on the fastener tape to form a waterproof layer. However, the existing waterproof paint has the following problems: 1. the formed coating has poor performances on stretchability and toughness, and the coating is easy to crack in the repeated bending process of the zipper cloth belt, so that the texture of the clothes is influenced; 2. the existing waterproof coating is more solvent-based coating, the water-based coating is few and less, and the water-based coating generally has poor water resistance, so that the zipper does not have water washing resistance.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the present invention aims to provide a waterproof coating for slide fasteners, which has superhydrophobic property and also has good bending resistance and water resistance; the invention also aims to provide a preparation method of the waterproof coating, which is simple and efficient and is beneficial to industrial production.
The purpose of the invention is realized by the following technical scheme:
a waterproof coating for a zipper comprises the following raw materials in parts by weight:
the waterproof coating for the zipper is a polyurethane coating taking water as a dispersion medium, has the advantages of environmental protection and safety, and also has good water resistance, and a micro-nano uneven plane can be formed on a formed coating by adding hydrophobic nano silicon dioxide into the waterproof coating, so that the waterproof coating has super-hydrophobic performance, the surface contact angle is 157.2 +/-1.5 degrees, the rolling angle is less than 8 degrees, and the waterproof coating can effectively block water vapor when being used for the zipper, thereby meeting the requirements of waterproof zipper clothes.
Wherein the diluent monomer consists of 2-hydroxyethyl acrylate, 4-hydroxy-n-butyl (methyl) acrylate and vinyltrimethoxysilane in a weight ratio of 1-3:1-2: 1-2. 4-hydroxy-n-butyl (methyl) acrylate is an acrylate monomer with hydroxy, can be subjected to cross-linking reaction with-NCO in a polyurethane prepolymer to realize polymerization, methyl methacrylate and vinyl trimethoxy silane can be subjected to polymerization with 4-hydroxy-n-butyl (methyl) acrylate through free radical polymerization, and a finally formed coating has compactness, and in addition, the vinyl trimethoxy silane can enhance the hydrophobicity of the coating, so that the super-hydrophobicity of the coating is more excellent.
The hydrophobic nano silicon dioxide is nano silicon dioxide modified by dodecyl triethoxy silane, and the average particle size of the hydrophobic nano silicon dioxide is 30-50 nm. The invention preferably adopts dodecyl triethoxy silane for modification, can effectively reduce the number of hydroxyl groups of the nano silicon dioxide, can improve the dispersibility of the nano silicon dioxide in the waterproof coating by controlling the particle size of the hydrophobic nano silicon dioxide, and is beneficial to the improvement of the mechanical property and the hydrophobicity of the waterproof coating.
The preparation method of the polyurethane prepolymer comprises the following steps:
A. adding 1-5 parts by weight of nano anion powder into 18-28 parts by weight of ethanol water solution with volume concentration of 92% -98% for ultrasonic dispersion to obtain dispersion liquid;
B. adding 23-33 parts by weight of ethyl orthosilicate into the dispersion liquid, and adjusting the pH to 9-10 by using ammonia water to hydrolyze the ethyl orthosilicate to obtain nano composite microspheres;
C. mixing polyester polyol, a catalyst and isocyanate, heating to 50-70 ℃ to obtain a mixed solution, adding nano composite microspheres into the mixed solution, heating to 66-80 ℃, and reacting for 3.5-7 hours to obtain a polyurethane curing agent, wherein the molar ratio of the polyester polyol to the isocyanate is 0.12-0.14:1, the amount of the catalyst is 0.1-1 wt% of the mixed solution, and the mass ratio of the nano composite microspheres to the mixed solution is 2-5: 10;
D. mixing the polyurethane curing agent with hydroxyl acrylic resin, and reacting at 70-90 ℃ for 4-8h to obtain a polyurethane prepolymer, wherein the molar ratio of-NCO of the polyurethane curing agent to-OH of the hydroxyl resin is 1.0-1.2: 1.
The negative ion powder has pyroelectricity and piezoelectricity, so that under the condition of temperature and pressure change (even small change), the potential difference between component crystals can be caused, the static electricity is up to 100 ten thousand electron volts, so that the air is ionized, the hit electrons are attached to adjacent water and oxygen molecules and are converted into air negative ions, namely negative oxygen ions, and the function of health care can be given to clothes by adding the negative ion powder into the zipper coating.
However, the nano negative ion powder has the characteristic of easy agglomeration, so the nano negative ion powder is easy to settle and difficult to disperse in an aqueous formula, and a waterproof coating formed by directly adding the nano negative ion powder into an aqueous coating is easy to generate the phenomenon of stress concentration, so the bending resistance of the waterproof coating is greatly reduced.
According to the invention, tetraethoxysilane is used for generating mesoporous nano silicon dioxide, namely nano composite microspheres, which coats nano anion powder, so that the problem of nano anion powder agglomeration can be effectively solved; the characteristic that the hydroxyl on the surface of the mesoporous nano silicon dioxide is reacted and anchored with the isocyanate group of diisocyanate is utilized, so that the nano composite microspheres are stably dispersed in the polyurethane prepolymer and participate in the subsequent crosslinking reaction for generating a crosslinking structure; in addition, hydroxyl on the surface of the mesoporous nano silicon dioxide is consumed by diisocyanate, so that the nano composite microspheres have hydrophobicity, namely the specific gravity of a nano hydrophobic inorganic substance in the hydrophobic coating is increased, the hydrophobicity of the hydrophobic coating is increased, the phenomenon of stress concentration is avoided, and the waterproof coating still has good bending resistance.
Wherein the particle size of the nanometer anion powder is 6-17nm, the particle size of the nanometer composite microsphere is 51.6-96.4nm, and the BET specific surface area is 210.5-352.3m2(ii) in terms of/g. The particle size of the nanometer anion powder can influence the size and the shape of the composite microspheres, the particle size and the specific surface area of the nanometer composite microspheres have great influence on the stability of the nanometer composite microspheres in a cross-linked structure, when the particle size of the nanometer anion powder is 6-17nm, the particle size of the composite microspheres is 51.6-96.4nm, and the BET specific surface area of the nanometer composite microspheres is 210.5-352.3m2When the coating is used for coating, the three-dimensional cross-linked structure formed in the polyurethane prepolymer is stable, and the elasticity, flexibility and impact resistance of the coating are improved to a large extent.
Wherein the polyester polyol has an average functionality of 2-2.5, a hydroxyl value of 200-260mgKOH/g and an acid value of 0.1-1mgKOH/g, the isocyanate is isophorone diisocyanate, and the-NCO content of the isophorone diisocyanate is 41% -48%. The polyester polyol and the isophorone diisocyanate selected by the invention have mild reaction rate and are beneficial to generation of a linear crosslinking structure.
Wherein the catalyst is at least one of triethylamine, triethylene diamine and dibutyltin dilaurate. The catalyst can promote the reaction of the isocyanate curing agent and hydroxyl, and is further preferably composed of triethylene diamine and dibutyltin dilaurate according to the weight ratio of 2:1, so that the reaction activity of isocyanate and water can be reduced, the isocyanate curing agent and the polyol have a relatively proper reaction rate, the generated waterproof coating is more stable, and the mechanical property of the prepared waterproof coating is better.
Wherein the photoinitiator is at least one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide. 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide are efficient photoinitiators and can effectively promote the cross-linking polymerization of polymers and monomers; further preferably, the photoinitiator is composed of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide in a weight ratio of 1-2:1-3:1, and by utilizing the excitation principle of different photoinitiators, the rapid crosslinking and curing of polymers and monomers can be realized to form a coating with stable performance.
Wherein the leveling agent is at least one of CAB381-0.1, CAB552-0.2, CAB551-0.01 and CAB 381-20. CAB381-0.1, CAB552-0.2, CAB551-0.01 and CAB381-20 refer to different types of cellulose acetate butyrate products produced by Istman, which have excellent weather resistance and ultraviolet irradiation resistance, and can promote the directional distribution of composite fibers and improve the mechanical properties of coatings. Further preferably, the leveling agent consists of CAB381-0.1 and CAB381-20 according to the weight ratio of 1:1, so that the leveling performance of the coating can be improved, the generation of a compact coating is facilitated, the water resistance of the coating is improved, and the adhesion of the coating to a zipper cloth tape can also be improved.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the waterproof coating for the zipper comprises the following steps: adding the polyurethane prepolymer, the hydrophobic nano-silica, the diluent monomer and the photoinitiator into deionized water according to the weight parts, stirring at the rotating speed of 1200-1400rpm for 10-20min, adding the leveling agent and the defoaming agent, and stirring the mixture at the rotating speed of 400-600rpm for 10-16min to obtain the waterproof coating for the zipper.
The invention has the beneficial effects that: the waterproof coating for the zipper is a polyurethane coating taking water as a dispersion medium, has the advantages of environmental protection and safety, and also has good water resistance, and a micro-nano uneven plane can be formed on a formed coating by adding hydrophobic nano silicon dioxide into the waterproof coating, so that the waterproof coating has super-hydrophobic performance, the surface contact angle is 157.2 +/-1.5 degrees, the rolling angle is less than 8 degrees, and the waterproof coating can effectively block water vapor when being used for the zipper, thereby meeting the requirements of waterproof zipper clothes.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A waterproof coating for a zipper comprises the following raw materials in parts by weight:
wherein the diluent monomer consists of 2-hydroxyethyl acrylate, 4-hydroxy-n-butyl (methyl) acrylate and vinyl trimethoxy silane according to the weight ratio of 2:1.5:1.5
The hydrophobic nano silicon dioxide is nano silicon dioxide modified by dodecyl triethoxy silane, and the average particle size of the hydrophobic nano silicon dioxide is 40 nm.
The preparation method of the polyurethane prepolymer comprises the following steps:
A. adding 3 parts by weight of nano anion powder into 23 parts by weight of ethanol water solution with volume concentration of 95% for ultrasonic dispersion to obtain dispersion liquid;
B. adding 28 parts by weight of ethyl orthosilicate into the dispersion liquid, and adjusting the pH to 9.5 by using ammonia water to hydrolyze the ethyl orthosilicate to obtain nano composite microspheres;
C. mixing polyester polyol, a catalyst and isocyanate, heating to 60 ℃ to obtain a mixed solution, adding nano composite microspheres into the mixed solution, heating to 73 ℃, and reacting for 5.2 hours to obtain a polyurethane curing agent, wherein the molar ratio of the polyester polyol to the isocyanate is 0.13:1, the dosage of the catalyst is 0.5 wt% of the mixed solution, and the mass ratio of the nano composite microspheres to the mixed solution is 3.5: 10;
D. and mixing the polyurethane curing agent with hydroxyl acrylic resin, and reacting at 80 ℃ for 4-8h to obtain a polyurethane prepolymer, wherein the molar ratio of-NCO of the polyurethane curing agent to-OH of the hydroxyl resin is 1.1: 1.
Wherein the particle size of the nano anion powder is 1.7nm, the particle size of the nano composite microsphere is 75.8nm, and the BET specific surface area is 376.2m2/g。
Wherein the polyester polyol has an average functionality of 2.2, a hydroxyl value of 230mgKOH/g, an acid value of 0.5mgKOH/g, the isocyanate is isophorone diisocyanate, and the-NCO content of isophorone diisocyanate is 44%.
The catalyst consists of triethylene diamine and dibutyltin dilaurate according to the weight ratio of 2:1.
Wherein the photoinitiator consists of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide in a weight ratio of 1.5:2: 1.
Wherein the leveling agent consists of CAB381-0.1 and CAB381-20 according to the weight ratio of 1: 1.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the waterproof coating for the zipper comprises the following steps: adding the polyurethane prepolymer, the hydrophobic nano-silica, the diluent monomer and the photoinitiator into deionized water according to the weight parts, stirring at the rotating speed of 1300rpm for 5min, adding the leveling agent and the defoaming agent, and stirring the mixture at the rotating speed of 500rpm for 13min to obtain the waterproof coating for the zipper.
Example 2
A waterproof coating for a zipper comprises the following raw materials in parts by weight:
wherein the diluent monomer consists of 2-hydroxyethyl acrylate, 4-hydroxy-n-butyl (methyl) acrylate and vinyl trimethoxy silane according to the weight ratio of 1:1:1
The hydrophobic nano silicon dioxide is nano silicon dioxide modified by dodecyl triethoxy silane, and the average particle size of the hydrophobic nano silicon dioxide is 30 nm.
The preparation method of the polyurethane prepolymer comprises the following steps:
A. adding 1 part by weight of nano anion powder into 18 parts by weight of ethanol water solution with volume concentration of 92% for ultrasonic dispersion to obtain dispersion liquid;
B. adding 23 parts by weight of ethyl orthosilicate into the dispersion liquid, and adjusting the pH to 9 by using ammonia water to hydrolyze the ethyl orthosilicate to obtain nano composite microspheres;
C. mixing polyester polyol, a catalyst and isocyanate, heating to 50 ℃ to obtain a mixed solution, adding nano composite microspheres into the mixed solution, heating to 66 ℃, and reacting for 3.5 hours to obtain a polyurethane curing agent, wherein the molar ratio of the polyester polyol to the isocyanate is 0.12:1, the dosage of the catalyst is 0.1 wt% of the mixed solution, and the mass ratio of the nano composite microspheres to the mixed solution is 2: 10;
D. and mixing the polyurethane curing agent with hydroxyl acrylic resin, and reacting at 70 ℃ for 4 hours to obtain a polyurethane prepolymer, wherein the molar ratio of-NCO of the polyurethane curing agent to-OH of the hydroxyl resin is 1.0: 1.
Wherein the particle size of the nanometer anion powder is 6nm, the particle size of the nanometer composite microsphere is 51.6nm, and the BET specific surface area is 210.5m2/g。
Wherein the polyester polyol has an average functionality of 2, a hydroxyl value of 200mgKOH/g and an acid value of 0.1mgKOH/g, the isocyanate is isophorone diisocyanate, and the-NCO content of the isophorone diisocyanate is 41%.
The catalyst consists of triethylene diamine and dibutyltin dilaurate according to the weight ratio of 1: 1.
Wherein the photoinitiator consists of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide according to the weight ratio of 1:1: 1.
Wherein the leveling agent consists of CAB381-0.1 and CAB381-20 according to the weight ratio of 1: 2.
The preparation method of the waterproof coating for the zipper comprises the following steps: adding the polyurethane prepolymer, the hydrophobic nano-silica, the diluent monomer and the photoinitiator into deionized water according to the weight parts, stirring at the rotating speed of 1200-1400rpm for 10-20min, adding the leveling agent and the defoaming agent, and stirring the mixture at the rotating speed of 400-600rpm for 10-16min to obtain the waterproof coating for the zipper.
Example 3
A waterproof coating for a zipper comprises the following raw materials in parts by weight:
wherein the diluent monomer consists of 2-hydroxyethyl acrylate, 4-hydroxy-n-butyl (methyl) acrylate and vinyl trimethoxy silane according to the weight ratio of 3:2:2
The hydrophobic nano silicon dioxide is nano silicon dioxide modified by dodecyl triethoxy silane, and the average particle size of the hydrophobic nano silicon dioxide is 50 nm.
The preparation method of the polyurethane prepolymer comprises the following steps:
A. adding 5 parts by weight of nano anion powder into 28 parts by weight of ethanol water solution with the volume concentration of 98% for ultrasonic dispersion to obtain dispersion liquid;
B. adding 33 parts by weight of ethyl orthosilicate into the dispersion liquid, and adjusting the pH to 10 by using ammonia water to hydrolyze the ethyl orthosilicate to obtain nano composite microspheres;
C. mixing polyester polyol, a catalyst and isocyanate, heating to 70 ℃ to obtain a mixed solution, adding nano composite microspheres into the mixed solution, heating to 80 ℃, and reacting for 7 hours to obtain a polyurethane curing agent, wherein the molar ratio of the polyester polyol to the isocyanate is 0.14:1, the dosage of the catalyst is 1 wt% of the mixed solution, and the mass ratio of the nano composite microspheres to the mixed solution is 5: 10;
D. and mixing the polyurethane curing agent with hydroxyl acrylic resin, and reacting at 90 ℃ for 8 hours to obtain a polyurethane prepolymer, wherein the molar ratio of-NCO of the polyurethane curing agent to-OH of the hydroxyl resin is 1.2: 1.
Wherein the particle size of the nanometer anion powder is 17nm, the particle size of the nanometer composite microsphere is 96.4nm, and the BET specific surface area is 352.3m2/g。
Wherein the polyester polyol has an average functionality of 2.5, a hydroxyl value of 260mgKOH/g and an acid value of 1mgKOH/g, the isocyanate is isophorone diisocyanate, and the-NCO content of the isophorone diisocyanate is 48%.
The catalyst is composed of triethylene diamine and dibutyltin dilaurate according to the weight ratio of 3: 1.
Wherein the photoinitiator consists of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide in a weight ratio of 2:3: 1.
Wherein the leveling agent consists of CAB381-0.1 and CAB381-20 according to the weight ratio of 2:1.
The preparation method of the waterproof coating for the zipper comprises the following steps: adding the polyurethane prepolymer, the hydrophobic nano-silica, the diluent monomer and the photoinitiator into deionized water according to the parts by weight, stirring at the rotating speed of 1400rpm for 20min, adding the leveling agent and the defoaming agent, and stirring the mixture at the rotating speed of 600rpm for 16min to obtain the waterproof coating for the zipper.
Example 4
A waterproof coating for a zipper comprises the following raw materials in parts by weight:
wherein the diluent monomer consists of 2-hydroxyethyl acrylate, 4-hydroxy-n-butyl (methyl) acrylate and vinyl trimethoxy silane according to the weight ratio of 1:2:1
The hydrophobic nano silicon dioxide is nano silicon dioxide modified by dodecyl triethoxy silane, and the average particle size of the hydrophobic nano silicon dioxide is 35 nm.
The preparation method of the polyurethane prepolymer comprises the following steps:
A. adding 2 parts by weight of nano anion powder into 21 parts by weight of ethanol water solution with volume concentration of 94% for ultrasonic dispersion to obtain dispersion liquid;
B. adding 25 parts by weight of ethyl orthosilicate into the dispersion liquid, and adjusting the pH to 9.3 by using ammonia water to hydrolyze the ethyl orthosilicate to obtain nano composite microspheres;
C. mixing polyester polyol, a catalyst and isocyanate, heating to 55 ℃ to obtain a mixed solution, adding nano composite microspheres into the mixed solution, heating to 72 ℃, and reacting for 5 hours to obtain a polyurethane curing agent, wherein the molar ratio of the polyester polyol to the isocyanate is 0.13:1, the dosage of the catalyst is 0.3 wt% of the mixed solution, and the mass ratio of the nano composite microspheres to the mixed solution is 3: 10;
D. and mixing the polyurethane curing agent with hydroxyl acrylic resin, and reacting for 5 hours at 75 ℃ to obtain a polyurethane prepolymer, wherein the molar ratio of-NCO of the polyurethane curing agent to-OH of the hydroxyl resin is 1.1: 1.
Wherein the particle size of the nanometer anion powder is 8nm, and the nanometer anion powderThe particle size of the composite microsphere is 63.4nm, and the BET specific surface area is 248.5m2/g。
Wherein the polyester polyol has an average functionality of 2.1, a hydroxyl value of 210mgKOH/g and an acid value of 0.0mgKOH/g, the isocyanate is isophorone diisocyanate, and the-NCO content of isophorone diisocyanate is 42%.
Wherein the catalyst is triethylamine.
Wherein the photoinitiator is 2-hydroxy-2-methyl-1-phenyl acetone.
Wherein the flatting agent is CAB 551-0.01.
The preparation method of the waterproof coating for the zipper comprises the following steps: adding the polyurethane prepolymer, the hydrophobic nano-silica, the diluent monomer and the photoinitiator into deionized water according to the weight parts, stirring at the rotating speed of 1250rpm for 12min, adding the leveling agent and the defoaming agent, and stirring the mixture at 450rpm for 12min to obtain the waterproof coating for the zipper.
Example 5
A waterproof coating for a zipper comprises the following raw materials in parts by weight:
wherein the diluent monomer consists of 2-hydroxyethyl acrylate, 4-hydroxy-n-butyl (methyl) acrylate and vinyl trimethoxy silane according to the weight ratio of 3:1:1
The hydrophobic nano silicon dioxide is nano silicon dioxide modified by dodecyl triethoxy silane, and the average particle size of the hydrophobic nano silicon dioxide is 45 nm.
The preparation method of the polyurethane prepolymer comprises the following steps:
A. adding 4 parts by weight of nano anion powder into 25 parts by weight of ethanol water solution with volume concentration of 96% for ultrasonic dispersion to obtain dispersion liquid;
B. adding 30 parts by weight of ethyl orthosilicate into the dispersion liquid, and adjusting the pH to 9.7 by using ammonia water to hydrolyze the ethyl orthosilicate to obtain nano composite microspheres;
C. mixing polyester polyol, a catalyst and isocyanate, heating to 65 ℃ to obtain a mixed solution, adding nano composite microspheres into the mixed solution, heating to 76 ℃ and reacting for 6 hours to obtain a polyurethane curing agent, wherein the molar ratio of the polyester polyol to the isocyanate is 0.13:1, the dosage of the catalyst is 0.8 wt% of the mixed solution, and the mass ratio of the nano composite microspheres to the mixed solution is 4: 10;
D. and mixing the polyurethane curing agent with hydroxyl acrylic resin, and reacting at 85 ℃ for 7 hours to obtain a polyurethane prepolymer, wherein the molar ratio of-NCO of the polyurethane curing agent to-OH of the hydroxyl resin is 1.1: 1.
Wherein the particle size of the nano anion powder is 15.4nm, the particle size of the nano composite microsphere is 87.4nm, and the BET specific surface area is 307.3m2/g。
Wherein the polyester polyol has an average functionality of 2.4, a hydroxyl value of 250mgKOH/g, an acid value of 0.7mgKOH/g, the isocyanate is isophorone diisocyanate, and the-NCO content of isophorone diisocyanate is 46%.
Wherein the catalyst is dibutyltin dilaurate.
Wherein the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide.
Wherein the leveling agent consists of CAB552-0.2 and CAB551-0.01 according to the weight ratio of 1: 1.
The preparation method of the waterproof coating for the zipper comprises the following steps: adding the polyurethane prepolymer, the hydrophobic nano-silica, the diluent monomer and the photoinitiator into deionized water according to the weight parts, stirring at the rotating speed of 1350rpm for 18min, adding the leveling agent and the defoaming agent, and stirring the mixture at the rotating speed of 550rpm for 15min to obtain the waterproof coating for the zipper.
Comparative example 1
This comparative example differs from example 1 in that: hydrophobic nanosilica is not included in the coating.
The coatings of examples 1 to 5 and comparative example were applied to a zipper tape, leveled for 1 to 2min, and then cured to form a film under irradiation of a UV lamp to form a coating layer. The coating is subjected to an adhesion test, a hardness test, a water resistance test, a bending property test, a water contact angle, a rolling angle measurement and a negative ion content test respectively, wherein the adhesion test is carried out according to GB/T1720-1979, the hardness test is carried out according to GB/T6739-2006, the water resistance test is carried out according to GB/T1733-1993, and the bending property test method is as follows: folding the zipper cloth belt in 2-3 seconds, reversely folding in 2-3 seconds, recording as the bending times once, and recording the bending times when reticulate patterns or cracks appear; the method for testing the content of the negative ions comprises the following steps: and (3) after the zipper cloth tape coated with the coating is placed in a closed space of 1cm3 for 24h, then an air negative ion tester is used for detecting the content of negative ions in the gas in the closed space, and the test results are as follows:
as can be seen from the comparison of example 1 and comparative example 1, the waterproof coating material formed a coating layer without super-hydrophobicity and having lower hardness but better bending resistance before the hydrophobic nano silica was not added. After the hydrophobic nano silicon dioxide is added into the coating, the bending resistance times are slightly lower, but the coating can have super-hydrophobic performance and better hardness and adhesion. In addition, the composite microspheres are added into the polyurethane prepolymer in advance for modification, so that the coating has a good negative ion emission function, the zipper is endowed with health-care effects of promoting blood circulation and the like, and the zipper has a wider application prospect.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (7)
1. A waterproof coating material for slide fasteners, which is characterized in that: the feed comprises the following raw materials in parts by weight:
the diluting monomer consists of 2-hydroxyethyl acrylate, 4-hydroxy-n-butyl (methyl) acrylate and vinyl trimethoxy silane in a weight ratio of 1-3:1-2: 1-2;
the hydrophobic nano silicon dioxide is nano silicon dioxide modified by dodecyl triethoxysilane, and the average particle size of the hydrophobic nano silicon dioxide is 30-50 nm;
the preparation method of the polyurethane prepolymer comprises the following steps:
A. adding 1-5 parts by weight of nano anion powder into 18-28 parts by weight of ethanol water solution with volume concentration of 92% -98% for ultrasonic dispersion to obtain dispersion liquid;
B. adding 23-33 parts by weight of ethyl orthosilicate into the dispersion liquid, and adjusting the pH to 9-10 by using ammonia water to hydrolyze the ethyl orthosilicate to obtain nano composite microspheres;
C. mixing polyester polyol, a catalyst and isocyanate, heating to 50-70 ℃ to obtain a mixed solution, adding nano composite microspheres into the mixed solution, heating to 66-80 ℃, and reacting for 3.5-7 hours to obtain a polyurethane curing agent, wherein the molar ratio of the polyester polyol to the isocyanate is 0.12-0.14:1, the amount of the catalyst is 0.1-1 wt% of the mixed solution, and the mass ratio of the nano composite microspheres to the mixed solution is 2-5: 10;
D. mixing the polyurethane curing agent with hydroxyl acrylic resin, and reacting at 70-90 ℃ for 4-8h to obtain a polyurethane prepolymer, wherein the molar ratio of-NCO of the polyurethane curing agent to-OH of the hydroxyl resin is 1.0-1.2: 1.
2. The waterproof paint for slide fasteners as claimed in claim 1, wherein: the particle size of the nanometer anion powder is 6-17nm, the particle size of the nanometer composite microsphere is 51.6-96.4nm, and the BET specific surface area is 210.5-352.3m2/g。
3. The waterproof paint for slide fasteners as claimed in claim 1, wherein: the polyester polyol has the average functionality of 2-2.5, the hydroxyl value of 200-260mgKOH/g and the acid value of 0.1-1mgKOH/g, the isocyanate is isophorone diisocyanate, and the-NCO content of the isophorone diisocyanate is 41% -48%.
4. The waterproof paint for slide fasteners as claimed in claim 1, wherein: the catalyst is at least one of triethylamine, triethylene diamine and dibutyltin dilaurate.
5. The waterproof paint for slide fasteners as claimed in claim 1, wherein: the photoinitiator is 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and 2,4, 6-trimethyl benzoyl-diphenyl phosphine oxide.
6. The waterproof paint for slide fasteners as claimed in claim 1, wherein: the leveling agent is at least one of CAB381-0.1, CAB552-0.2, CAB551-0.01 and CAB 381-20.
7. The method for producing a waterproof coating material for slide fasteners as claimed in any one of claims 1 to 6, wherein: adding the polyurethane prepolymer, the hydrophobic nano-silica, the diluent monomer and the photoinitiator into deionized water according to the weight parts, stirring at the rotating speed of 1200-1400rpm for 10-20min, adding the leveling agent and the defoaming agent, and stirring the mixture at the rotating speed of 400-600rpm for 10-16min to obtain the waterproof coating for the zipper.
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| CN109924593A (en) * | 2019-01-31 | 2019-06-25 | 广东科技学院 | A kind of clothes and its template type production technology |
| CN109881481B (en) * | 2019-01-31 | 2021-07-27 | 东莞职业技术学院 | Waterproof fabric |
| CN110623376B (en) * | 2019-09-29 | 2022-06-03 | 东莞市瑞翔新型材料科技有限公司 | Waterproof metal zipper and manufacturing process thereof |
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