CN118291031B - A coating composition with sunscreen and water repellent function - Google Patents

A coating composition with sunscreen and water repellent function Download PDF

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CN118291031B
CN118291031B CN202410582605.XA CN202410582605A CN118291031B CN 118291031 B CN118291031 B CN 118291031B CN 202410582605 A CN202410582605 A CN 202410582605A CN 118291031 B CN118291031 B CN 118291031B
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reaction
parts
coating composition
acrylate emulsion
temperature
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CN118291031A (en
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李婷婷
甘瑞霞
申双凤
秦枫
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Guangdong Mingnuo Textile Industry Co ltd
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Guangdong Mingnuo Textile Industry Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/14Polyurethanes having carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • C09D7/62Additives non-macromolecular inorganic modified by treatment with other compounds
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5285Polyurethanes; Polyurea; Polyguanides
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06PDYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/673Inorganic compounds
    • D06P1/67391Salts or oxidising-compounds mixtures
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The application discloses a coating composition with sun-proof and water-repellent functions, and relates to the technical field of coating compositions. The coating composition comprises the following raw materials in parts by weight: 50-80 parts of organosilicon modified aqueous polyurethane acrylate emulsion, 10-25 parts of ultraviolet-proof auxiliary agent, 8 parts of auxiliary agent and 1-3 parts of thickener PTF; the preparation method of the organosilicon modified aqueous polyurethane acrylate emulsion comprises the following steps: polyether glycol and isophorone diisocyanate are catalyzed by dibutyl tin dilaurate to prepare polyurethane prepolymer, and acrylic acid monomers are added to prepare aqueous polyurethane acrylate emulsion; and finally, blending the aqueous polyurethane acrylate emulsion and the silicon dioxide modified sol to obtain the organosilicon modified aqueous polyurethane acrylate emulsion. The coating composition prepared by the application is applied to fabrics to endow the fabrics with excellent water repellency and ultraviolet resistance.

Description

Coating composition with sun-proof water-repellent function
Technical Field
The invention relates to the technical field of coating compositions, in particular to a novel coating composition with sun-proof and water-repellent functions.
Background
With the gradual improvement of the living standard of substances, the requirements of people on textiles are correspondingly higher and higher. Textiles have gradually shifted from traditional warm-in-winter and cool-in-summer demands to sanitary, healthy, comfortable functional demands. Textiles are also required to have a variety of functions such as water and oil repellency, antistatic, launderable, antibacterial, flame retardant, and the like. Functional fabrics have been widely used in the fields of household textiles, environmental and health textiles, decorative and industrial textiles, national defense construction and sophisticated science. The development of functional fabrics not only relates to the textile, dyeing and finishing industries, but also relates to the chemical fiber and fine chemical industry, however, the basis is to develop materials with the functions, the development approaches mainly comprise two ways, namely, developing functional fibers, and then preparing functional textiles from the fibers; the other is to functionally finish the common textile to make it have functionality. In the textile printing industry, the functionalization of textiles is generally achieved by means of functional finishing, i.e. by means of functional finishing agents. The water-repellent finishing is to apply a water-repellent film which cannot be infiltrated by water on the fabric, but does not seal the pores of the fabric, so that the fabric has the characteristics of water repellency and air permeability. The ultraviolet ray resistant finishing can make the fabric absorb or reflect ultraviolet rays, thereby having protective effect on skin.
The fluorine-containing finishing agent for the three-proofing finishing of textiles is difficult to degrade, easy to accumulate in a human body and also has adverse environmental effects due to the release of fluorine compounds after finishing and neutralization. These non-environmentally friendly functional finishes are being challenged by environmental regulations as the awareness of human environmental protection increases. It has therefore been a great trend to find a safe and environmentally friendly finishing process to impart functionality to textiles.
Disclosure of Invention
The invention aims to provide a novel coating composition with sun-proof and water-repellent functions, which solves the following technical problems:
the existing coating composition imparts water repellency to fabrics by adding fluorine-containing compounds, and has adverse effects on human bodies and the environment.
The aim of the invention can be achieved by the following technical scheme:
A novel coating composition with sun-proof and water-repellent functions comprises the following raw materials in parts by weight: 50-80 parts of organosilicon modified aqueous polyurethane acrylate emulsion, 10-25 parts of ultraviolet-proof auxiliary agent, 8 parts of auxiliary agent and 1-3 parts of thickener PTF;
The preparation method of the organosilicon modified aqueous polyurethane acrylate emulsion comprises the following steps:
a1: in nitrogen atmosphere, polyether glycol (average molecular weight 1000), isophorone diisocyanate and dibutyltin dilaurate are added into a reaction kettle, the temperature is controlled to be 80-90 ℃, the reaction is carried out for 1-3 hours in a heat preservation mode, dimethylolpropionic acid and acetone are added, the reaction is carried out for 1-3 hours in a heat preservation mode, the temperature is controlled to be 60-70 ℃, hydroxyethyl methacrylate is added, the reaction is carried out for 1-3 hours in a heat preservation mode, the temperature is controlled to be 65-75 ℃, the reaction is carried out for 1-3 hours in a heat preservation mode, the temperature is controlled to be 35-45 ℃, triethylamine is added, the reaction is carried out for 0.5-1 hour in a heat preservation mode, deionized water is added, the reaction is carried out for 1-3 hours in a heat preservation mode, and acetone is removed by rotary evaporation, so that the aqueous polyurethane acrylate emulsion is obtained;
A2: and (3) blending the aqueous polyurethane acrylate emulsion and the silicon dioxide modified sol to obtain the organosilicon modified aqueous polyurethane acrylate emulsion.
As a further aspect of the invention: the addition ratio of the polyether glycol, the isophorone diisocyanate, the dibutyltin dilaurate, the dimethylolpropionic acid, the acetone, the hydroxyethyl methacrylate, the triethylamine and the deionized water in the A1 is 10g:5-8g:0.3-0.4g:1-2g:25-50mL:5-8g:1.1-1.5g:30-60mL.
As a further aspect of the invention: the mass ratio of the aqueous polyurethane acrylate emulsion to the silicon dioxide modified sol in the A2 is 20-30:20-50.
As a further aspect of the invention: the preparation method of the silica modified sol comprises the following steps:
S1: adding nano titanium dioxide, 2, 4-toluene diisocyanate and toluene into a reaction kettle in a nitrogen atmosphere, uniformly dispersing, controlling the temperature to be 80-90 ℃, carrying out heat preservation and stirring for 6-12h, washing with absolute ethyl alcohol, and drying to obtain a component I;
s2: adding the component I, gamma-aminopropyl triethoxysilane and ethyl acetate into a reaction kettle, controlling the temperature to be 50-60 ℃, carrying out heat preservation reaction for 3-6 hours, adding absolute ethyl alcohol, uniformly dispersing, carrying out heat preservation reaction for 1-3 hours, filtering, and drying to obtain a component II;
S3: adding absolute ethyl alcohol, a second component and tetraethoxysilane into a reaction kettle, dispersing uniformly, dripping acetic acid solution, controlling the temperature to be 25-35 ℃, and carrying out heat preservation reaction for 6-12 hours to obtain a third component;
S4: adding the three components, tripropylene glycol diacrylate into a reaction kettle, dispersing uniformly, and distilling under reduced pressure to remove the solvent to obtain the silica modified sol.
As a further aspect of the invention: the addition ratio of the nano titanium dioxide to the 2, 4-toluene diisocyanate to the toluene in the S1 is 10g:10-15g:100-300mL.
As a further aspect of the invention: the addition ratio of the component I, the gamma-aminopropyl triethoxysilane, the ethyl acetate and the absolute ethyl alcohol in the S2 is 10g:15-20g:100-300mL:2-20mL.
As a further aspect of the invention: the acetic acid solution in the S3 is 0.2-0.3 mol/L acetic acid solution, and the adding ratio of absolute ethyl alcohol, component II, tetraethoxysilane and acetic acid solution is 15-25mL:10g:4-12.5g:10-25mL.
As a further aspect of the invention: and in S4, the mass ratio of the component three to the tripropylene glycol diacrylate is 1:0.3-0.6.
As a further aspect of the invention: the ultraviolet-proof auxiliary agent is benzotriazole ultraviolet absorber.
As a further aspect of the invention: the auxiliary agent comprises 0.2-0.5 part of dispersing agent, 0.5-1 part of defoaming agent, 2-4 parts of humectant, 5-8 parts of aqueous wax emulsion handfeel agent and 0.3-0.5 part of pH regulator
As a further aspect of the invention: a method of preparing a coating composition comprising the steps of:
a1: cleaning a dispersion cylinder, adding the organosilicon modified aqueous polyurethane acrylate emulsion and the ultraviolet-proof auxiliary agent into the cylinder, and uniformly dispersing to form a premix;
a2: adding an auxiliary agent into the premix while stirring to uniformly disperse;
a3: adding a thickener PTF, and uniformly dispersing to obtain the coating composition.
The novel coating composition with sun-proof and water-repellent functions prepared by any one of the above is applied to textile printing.
As a further aspect of the application: the fabric material suitable for the coating composition prepared by the application comprises wind cloth, pure cotton, spandex and polyester fabric.
As a further aspect of the invention: sun protection and water repellency effects the preparation method of the fabric comprises the following steps: the novel coating composition with sun-proof and water-repellent functions prepared by any one of the above steps is used as printing paste; 100% printing paste is directly printed (recommended mesh: 800-1000 meshes), dried by hot air, and baked for 2-3min at 150-160 ℃ to obtain the fabric with sun-proof and water-repellent effects.
The invention has the beneficial effects that:
(1) The application utilizes excessive 2, 4-toluene diisocyanate to modify the surface of titanium dioxide nano particles to synthesize functional titanium dioxide with-NCO groups on the surface as a component I; the isocyanate group on the component one reacts with the amino group of gamma-aminopropyl triethoxysilane to obtain nano titanium dioxide modified by a silane coupling agent as a component two; the component II and the tetraethoxysilane are used as precursors to synthesize titanium dioxide modified silica sol; and finally, performing secondary modification by using tripropylene glycol diacrylate to obtain the silica modified sol. The application prepares polyurethane prepolymer by using polyether glycol and isophorone diisocyanate under the catalysis of dibutyltin dilaurate, and prepares aqueous polyurethane acrylate emulsion by adding acrylic acid monomer; and finally, blending the aqueous polyurethane acrylate emulsion and the silicon dioxide modified sol to obtain the organosilicon modified aqueous polyurethane acrylate emulsion. The organosilicon modified aqueous polyurethane acrylate emulsion prepared by the application is used as a finishing agent and is assisted with other functional additives to prepare a coating composition, and the coating composition prepared by the application is used for finishing fabrics, so that the fabrics are endowed with excellent water repellency, moisture permeability, ultraviolet resistance and high washing fastness.
The application takes titanium dioxide as an initial material, carries out organosilicon treatment through isocyanate and silane coupling agent, introduces special molecular composition and molecular structure of organosiloxane on the surface of the titanium dioxide, integrates the characteristics of the organic matters and the functions of the inorganic matters, and has excellent water resistance and low surface tension; the long-chain aliphatic hydrocarbon siloxane is used as a water repellent agent to replace fluorine-containing compound to be grafted on the surface of titanium dioxide, and the silicon dioxide hydrosol prepared based on tetraethoxysilane is modified by utilizing the hydrolysis end of a silane coupling agent, so that the coating composition achieves similar water repellent effect after the fluorine-containing finishing agent is finished, the finishing process is economical and safe, the environment is good, and the requirements of green chemistry are met.
The application utilizes the silicon dioxide modified sol to modify the polyurethane-acrylic ester, is favorable for reducing the surface energy of the material, improves the water resistance of the material, ensures that the silicon dioxide is uniformly dispersed in the polyurethane-acrylic ester matrix and is tightly combined with a high molecular chain segment, fills the pores among the chain segments, ensures that water molecules are difficult to enter, reduces the degree of affinity with water, ensures that water drops can not moisten fabrics, and ensures that a large number of pores are still maintained among fibers and yarns in the fabrics, so that the fabrics have good water repellency and air and moisture permeability.
(2) The application takes organosilicon modified titanium dioxide and tetraethoxysilane as precursors, takes water as solvent to prepare titanium dioxide modified silicon dioxide hydrosol, and uses tripropylene glycol diacrylate to carry out secondary modification to obtain silicon dioxide modified sol; the silica modified sol and polyurethane-acrylic ester have stronger intermolecular force, the silica plays a role similar to a crosslinking point in a matrix, inorganic particles and polymers are connected into a crosslinking network through chemical bonds, the resistance of bending, rotating and moving molecular chains is increased, the thermal decomposition of the molecular chains is blocked, and the thermal stability of the coating is improved. The application organically modified titanium dioxide and silicon dioxide effectively solves the problem that the direct addition of titanium dioxide and silicon dioxide as inorganic matters has no binding force with fabric fibers and extremely poor washability. Titanium dioxide is filled in sol-gel of organic modified silane, which not only endows the fabric with ultraviolet resistance, but also improves the combination fastness with the fabric, enhances the durability, improves the washing fastness of a functional layer on the surface of the fabric, and can obtain good air permeability and soft hand feeling.
Detailed Description
The following description will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The preparation method of the organosilicon modified aqueous polyurethane acrylate emulsion of the embodiment 1 comprises the following steps:
A1: in a nitrogen atmosphere, adding 10g of polyether glycol (average molecular weight 1000), 5g of isophorone diisocyanate and 0.3g of dibutyltin dilaurate into a reaction kettle, controlling the temperature to be 80 ℃, carrying out heat preservation reaction for 1h, adding 1g of dimethylolpropionic acid and 25mL of acetone, carrying out heat preservation reaction for 1h, controlling the temperature to be 60 ℃, adding 5g of hydroxyethyl methacrylate, carrying out heat preservation reaction for 1h, controlling the temperature to be 65 ℃, carrying out heat preservation reaction for 1h, controlling the temperature to be 35 ℃, adding 1.1g of triethylamine, carrying out heat preservation reaction for 0.5h, adding 30mL of deionized water, carrying out heat preservation for 1h, and carrying out rotary evaporation to remove the acetone to obtain aqueous polyurethane acrylate emulsion;
a2: adding 10g of nano titanium dioxide, 10g of 2, 4-toluene diisocyanate and 100mL of toluene into a reaction kettle in a nitrogen atmosphere, uniformly dispersing, controlling the temperature to 80 ℃, preserving heat, stirring for 6 hours, washing with absolute ethyl alcohol, and drying to obtain a component I;
A3: adding 10g of the component I, 15g of gamma-aminopropyl triethoxysilane and 100mL of ethyl acetate into a reaction kettle, controlling the temperature to be 50 ℃, carrying out heat preservation reaction for 3 hours, adding 2mL of absolute ethyl alcohol, uniformly dispersing, carrying out heat preservation reaction for 1-hour, filtering, and drying to obtain a component II;
a4: adding 15mL of absolute ethyl alcohol, 10g of component II and 12.5g of tetraethoxysilane into a reaction kettle, uniformly dispersing, dropwise adding 25mL of 0.2 mL/L acetic acid solution, controlling the temperature to be 25 ℃, and carrying out heat preservation reaction for 6 hours to obtain a component III;
A5: adding 1g of component III and 0.6g of tripropylene glycol diacrylate into a reaction kettle, uniformly dispersing, and distilling under reduced pressure to remove a solvent to obtain silica modified sol;
A6: 30g of aqueous polyurethane acrylate emulsion and 50g of silica modified sol are blended to obtain organosilicon modified aqueous polyurethane acrylate emulsion.
The preparation method of the organosilicon modified aqueous polyurethane acrylate emulsion comprises the following steps:
A1: in a nitrogen atmosphere, adding 10g of polyether glycol (average molecular weight 1000), 5g of isophorone diisocyanate and 0.3g of dibutyltin dilaurate into a reaction kettle, controlling the temperature to be 80 ℃, carrying out heat preservation reaction for 1h, adding 1g of dimethylolpropionic acid and 25mL of acetone, carrying out heat preservation reaction for 1h, controlling the temperature to be 60 ℃, adding 5g of hydroxyethyl methacrylate, carrying out heat preservation reaction for 1h, controlling the temperature to be 65 ℃, carrying out heat preservation reaction for 1h, controlling the temperature to be 35 ℃, adding 1.1g of triethylamine, carrying out heat preservation reaction for 0.5h, adding 30mL of deionized water, carrying out heat preservation for 1h, and carrying out rotary evaporation to remove the acetone to obtain aqueous polyurethane acrylate emulsion;
a2: adding 10g of nano titanium dioxide, 12g of 2, 4-toluene diisocyanate and 200mL of toluene into a reaction kettle in a nitrogen atmosphere, uniformly dispersing, controlling the temperature to be 85 ℃, preserving heat, stirring for 9 hours, washing with absolute ethyl alcohol, and drying to obtain a component I;
a3: adding 10g of the component I, 18g of gamma-aminopropyl triethoxysilane and 200mL of ethyl acetate into a reaction kettle, controlling the temperature to be 55 ℃, carrying out heat preservation reaction for 3 hours, adding 10mL of absolute ethyl alcohol, uniformly dispersing, carrying out heat preservation reaction for 2 hours, filtering, and drying to obtain a component II;
a4: adding 20mL of absolute ethyl alcohol, 10g of component II and 12.5g of tetraethoxysilane into a reaction kettle, uniformly dispersing, dropwise adding 20mL of 0.2 mL/L acetic acid solution, controlling the temperature to be 30 ℃, and carrying out heat preservation reaction for 9 hours to obtain a component III;
A5: adding 1g of component III and 0.6g of tripropylene glycol diacrylate into a reaction kettle, uniformly dispersing, and distilling under reduced pressure to remove a solvent to obtain silica modified sol;
A6: 30g of aqueous polyurethane acrylate emulsion and 50g of silica modified sol are blended to obtain organosilicon modified aqueous polyurethane acrylate emulsion.
Example 3 the preparation method of the organosilicon modified aqueous polyurethane acrylate emulsion comprises the following steps:
A1: in a nitrogen atmosphere, adding 10g of polyether glycol (average molecular weight 1000), 5g of isophorone diisocyanate and 0.3g of dibutyltin dilaurate into a reaction kettle, controlling the temperature to be 80 ℃, carrying out heat preservation reaction for 1h, adding 1g of dimethylolpropionic acid and 25mL of acetone, carrying out heat preservation reaction for 1h, controlling the temperature to be 60 ℃, adding 5g of hydroxyethyl methacrylate, carrying out heat preservation reaction for 1h, controlling the temperature to be 65 ℃, carrying out heat preservation reaction for 1h, controlling the temperature to be 35 ℃, adding 1.1g of triethylamine, carrying out heat preservation reaction for 0.5h, adding 30mL of deionized water, carrying out heat preservation for 1h, and carrying out rotary evaporation to remove the acetone to obtain aqueous polyurethane acrylate emulsion;
A2: in a nitrogen atmosphere, adding 10g of nano titanium dioxide, 15g of 2, 4-toluene diisocyanate and 300mL of toluene into a reaction kettle, uniformly dispersing, controlling the temperature to 90 ℃, preserving heat, stirring for 12 hours, washing with absolute ethyl alcohol, and drying to obtain a component I;
A3: adding 10g of the component I, 20g of gamma-aminopropyl triethoxysilane and 300mL of ethyl acetate into a reaction kettle, controlling the temperature to be 60 ℃, carrying out heat preservation reaction for 6 hours, adding 20mL of absolute ethyl alcohol, uniformly dispersing, carrying out heat preservation reaction for 3 hours, filtering, and drying to obtain a component II;
A4: adding 25mL of absolute ethyl alcohol, 10g of component II and 12.5g of tetraethoxysilane into a reaction kettle, uniformly dispersing, dropwise adding 25mL of 0.2 mL/L acetic acid solution, controlling the temperature to be 35 ℃, and carrying out heat preservation reaction for 12 hours to obtain a component III;
a5: adding 1g of component III and 0.6g of tripropylene glycol diacrylate into a reaction kettle for uniform dispersion, and removing the solvent by reduced pressure distillation to obtain the silica modified sol.
A6: 30g of aqueous polyurethane acrylate emulsion and 50g of silica modified sol are blended to obtain organosilicon modified aqueous polyurethane acrylate emulsion.
Example 4a method of preparing a coating composition comprising the steps of:
A1: cleaning a dispersing cylinder, adding 80 parts by weight of the organosilicon modified aqueous polyurethane acrylate emulsion prepared in the embodiment 1 and 10 parts by weight of an ultraviolet-proof auxiliary agent (Henschel model UV-FAST N2) into the cylinder, stirring at 200-300rpm for 10min, mixing and dispersing uniformly to form a premix;
A2: adding 0.2 weight parts of dispersing agent (model BG554 manufactured by Dongguan high chemical industry Co., ltd. Of sodium polyacrylate), 0.5 weight parts of defoaming agent (model LLT-DF-723 manufactured by Long Li chemical industry preparation Co., ltd., xinxiang Co., ltd.), 2 weight parts of humectant (propylene glycol), 5 weight parts of aqueous wax emulsion handfeel agent (model ENCOR7605 manufactured by Jining Hua Kai resin Co., ltd.) and 0.3 weight parts of ammonia pH regulator into the premix while stirring, and stirring at 400rpm for 20min;
a3: 3 parts by weight of a thickener PTF was added and dispersed at 600rpm for 20 minutes to obtain a coating composition.
Example 5 in comparison with example 4, example 5 replaced only the silicone-modified aqueous urethane acrylate emulsion prepared in example 1 added in example 4 by an equivalent amount of the silicone-modified aqueous urethane acrylate emulsion prepared in example 2, which was completely identical in composition and preparation method to example 4.
Example 6 in comparison with example 4, example 6 replaced the silicone-modified aqueous urethane acrylate emulsion prepared in example 1 added in example 4 by an equivalent amount of the silicone-modified aqueous urethane acrylate emulsion prepared in example 3, which was completely identical in composition and preparation method to example 4.
The preparation method of the organosilicon modified aqueous polyurethane acrylate emulsion of comparative example 1 comprises the following steps:
A1: in a nitrogen atmosphere, adding 10g of polyether glycol (average molecular weight 1000), 5g of isophorone diisocyanate and 0.3g of dibutyltin dilaurate into a reaction kettle, controlling the temperature to be 80 ℃, carrying out heat preservation reaction for 1h, adding 1g of dimethylolpropionic acid and 25mL of acetone, carrying out heat preservation reaction for 1h, controlling the temperature to be 60 ℃, adding 5g of hydroxyethyl methacrylate, carrying out heat preservation reaction for 1h, controlling the temperature to be 65 ℃, carrying out heat preservation reaction for 1h, controlling the temperature to be 35 ℃, adding 1.1g of triethylamine, carrying out heat preservation reaction for 0.5h, adding 30mL of deionized water, carrying out heat preservation for 1h, and carrying out rotary evaporation to remove the acetone to obtain aqueous polyurethane acrylate emulsion;
a2: adding 10g of nano titanium dioxide, 10g of 2, 4-toluene diisocyanate and 100mL of toluene into a reaction kettle in a nitrogen atmosphere, uniformly dispersing, controlling the temperature to 80 ℃, preserving heat, stirring for 6 hours, washing with absolute ethyl alcohol, and drying to obtain a component I;
A3: adding 10g of the component I, 15g of gamma-aminopropyl triethoxysilane and 100mL of ethyl acetate into a reaction kettle, controlling the temperature to be 50 ℃, carrying out heat preservation reaction for 3 hours, adding 2mL of absolute ethyl alcohol, uniformly dispersing, carrying out heat preservation reaction for 1-hour, filtering, and drying to obtain a component II;
A4: adding 15mL of absolute ethyl alcohol and 12.5g of ethyl orthosilicate into a reaction kettle, dispersing uniformly, dripping 25mL of 0.2 mL/L acetic acid solution, controlling the temperature to 25 ℃, carrying out heat preservation reaction for 6 hours, filtering, drying, and adding 10g of component II to obtain a component III;
a5: adding 1g of component III and 0.6g of tripropylene glycol diacrylate into a reaction kettle for uniform dispersion, and removing the solvent by reduced pressure distillation to obtain the silica modified sol.
A6: 30g of aqueous polyurethane acrylate emulsion and 50g of silica modified sol are blended to obtain organosilicon modified aqueous polyurethane acrylate emulsion.
The preparation method of the organosilicon modified aqueous polyurethane acrylate emulsion of comparative example 2 comprises the following steps:
A1: in a nitrogen atmosphere, adding 10g of polyether glycol (average molecular weight 1000), 5g of isophorone diisocyanate and 0.3g of dibutyltin dilaurate into a reaction kettle, controlling the temperature to be 80 ℃, carrying out heat preservation reaction for 1h, adding 1g of dimethylolpropionic acid and 25mL of acetone, carrying out heat preservation reaction for 1h, controlling the temperature to be 60 ℃, adding 5g of hydroxyethyl methacrylate, carrying out heat preservation reaction for 1h, controlling the temperature to be 65 ℃, carrying out heat preservation reaction for 1h, controlling the temperature to be 35 ℃, adding 1.1g of triethylamine, carrying out heat preservation reaction for 0.5h, adding 30mL of deionized water, carrying out heat preservation for 1h, and carrying out rotary evaporation to remove the acetone to obtain aqueous polyurethane acrylate emulsion;
a2: adding 10g of nano titanium dioxide, 10g of 2, 4-toluene diisocyanate and 100mL of toluene into a reaction kettle in a nitrogen atmosphere, uniformly dispersing, controlling the temperature to 80 ℃, preserving heat, stirring for 6 hours, washing with absolute ethyl alcohol, and drying to obtain a component I;
A3: adding 10g of the component I, 15g of gamma-aminopropyl triethoxysilane and 100mL of ethyl acetate into a reaction kettle, controlling the temperature to be 50 ℃, carrying out heat preservation reaction for 3 hours, adding 2mL of absolute ethyl alcohol, uniformly dispersing, carrying out heat preservation reaction for 1-hour, filtering, and drying to obtain a component II;
A4: adding 15mL of absolute ethyl alcohol and 12.5g of ethyl orthosilicate into a reaction kettle, dispersing uniformly, dripping 25mL of 0.2 mL/L acetic acid solution, controlling the temperature to 25 ℃, carrying out heat preservation reaction for 6 hours, filtering, drying, and adding 10g of component II to obtain silica modified sol;
A5: 30g of aqueous polyurethane acrylate emulsion and 50g of silica modified sol are blended to obtain organosilicon modified aqueous polyurethane acrylate emulsion.
The preparation method of the organosilicon modified aqueous polyurethane acrylate emulsion of comparative example 3 comprises the following steps:
A1: in a nitrogen atmosphere, adding 10g of polyether glycol (average molecular weight 1000), 5g of isophorone diisocyanate and 0.3g of dibutyltin dilaurate into a reaction kettle, controlling the temperature to be 80 ℃, carrying out heat preservation reaction for 1h, adding 1g of dimethylolpropionic acid and 25mL of acetone, carrying out heat preservation reaction for 1h, controlling the temperature to be 60 ℃, adding 5g of hydroxyethyl methacrylate, carrying out heat preservation reaction for 1h, controlling the temperature to be 65 ℃, carrying out heat preservation reaction for 1h, controlling the temperature to be 35 ℃, adding 1.1g of triethylamine, carrying out heat preservation reaction for 0.5h, adding 30mL of deionized water, carrying out heat preservation for 1h, and carrying out rotary evaporation to remove the acetone to obtain aqueous polyurethane acrylate emulsion;
a2: adding 10g of nano titanium dioxide, 10g of 2, 4-toluene diisocyanate and 100mL of toluene into a reaction kettle in a nitrogen atmosphere, uniformly dispersing, controlling the temperature to 80 ℃, preserving heat, stirring for 6 hours, washing with absolute ethyl alcohol, and drying to obtain a component I;
a3: adding 15mL of absolute ethyl alcohol and 12.5g of ethyl orthosilicate into a reaction kettle, dispersing uniformly, dripping 25mL of 0.2 mL/L acetic acid solution, controlling the temperature to 25 ℃, carrying out heat preservation reaction for 6 hours, filtering, drying, and adding 10g of component one to obtain a component three;
A4: adding 1g of component III and 0.6g of tripropylene glycol diacrylate into a reaction kettle for uniform dispersion, and removing the solvent by reduced pressure distillation to obtain the silica modified sol.
A5: 30g of aqueous polyurethane acrylate emulsion and 50g of silica modified sol are blended to obtain organosilicon modified aqueous polyurethane acrylate emulsion.
Comparative example 4 in comparison with example 4, comparative example 4 merely replaced the silicone-modified aqueous urethane acrylate emulsion prepared in example 1 added in example 4 by the same amount as the silicone-modified aqueous urethane acrylate emulsion prepared in comparative example 1, which was completely identical in composition and preparation method to example 4.
Comparative example 5 in comparison with example 4, comparative example 5 merely replaced the silicone-modified aqueous urethane acrylate emulsion prepared in example 1 added in example 4 by an equivalent amount of the silicone-modified aqueous urethane acrylate emulsion prepared in comparative example 2, which was completely identical in composition and preparation method to example 4.
Comparative example 6 in comparison with example 4, comparative example 6 replaced the silicone-modified aqueous urethane acrylate emulsion prepared in example 1 added in example 4 by an equivalent amount of the silicone-modified aqueous urethane acrylate emulsion prepared in comparative example 3, which was completely identical in composition and preparation method to example 4.
Performance detection
Preparing a sample: the printing process comprises the following steps: the coating compositions prepared in examples 4 to 6 and comparative examples 4 to 6 were used as printing pastes; 100% printing paste is directly printed (recommended mesh: 800 meshes), dried by hot air, and baked for 3min at a high temperature of 150 ℃ to obtain a fabric with sun-proof and water-repellent effects;
(1) Ultraviolet protection coefficient: detection is carried out according to GB/T18830-2009 evaluation of ultraviolet resistance of textiles, and the detection results are shown in Table 2;
(2) Water repellency (water resistance) performance, namely, water repellency grades of samples are distinguished according to the water repellency grade standard of the table 1 according to detection according to GB/T4745-2012 water repellency test for determination of surface moisture resistance of textile fabrics, and the detection results are shown in table 2;
table 1: waterproof grade standard
Level 1 Full wetting of the showered surface
Level 2 Half of the affected surface is wet
3 Grade The showered surface is only wetted by unconnected and small area
Grade 4 The showered surface is not wetted, but the surface is stained with small water drops.
Grade 5 The showered surface is not wetted, and the surface is not stained with small water drops
(3) Fastness to washing: detection is carried out according to GB/T3921.1-2008 washing fastness of textile color fastness test, and the detection result is shown in Table 2;
(4) Moisture permeability: according to GB/T12704-1991 method for testing moisture permeability of fabrics, moisture permeability cup method: the method A is used for measurement, the detection result is shown in table 3, and the detection result is shown in table 2;
table 2: statistical table of performance test data for examples 4-6 and comparative examples 4-6
As is clear from Table 2, the coating composition prepared by the present application was used as a finishing agent to impart excellent water repellency and UV resistance to fabrics, and the water repellency was still 4 or more after multiple water washes, and the UPF level was still maintained at 50 +. The coating composition prepared by the application is applied to fabrics, and does not influence the moisture permeability of the fabrics while endowing the fabrics with excellent water repellency and ultraviolet resistance.
The foregoing describes one embodiment of the present invention in detail, but the description is only a preferred embodiment of the present invention and should not be construed as limiting the scope of the invention. All equivalent changes and modifications within the scope of the present invention are intended to be covered by the present invention.

Claims (9)

1.一种具有防晒拒水功能的涂料组合物,其特征在于,包括如下重量份的原料:50-80份有机硅改性水性聚氨酯丙烯酸酯乳液、10-25份防紫外线助剂、8份助剂、1-3份增稠剂PTF;1. A coating composition with sunscreen and water repellent function, characterized in that it comprises the following raw materials in parts by weight: 50-80 parts of silicone-modified waterborne polyurethane acrylate emulsion, 10-25 parts of UV protection additive, 8 parts of additive, and 1-3 parts of thickener PTF; 所述有机硅改性水性聚氨酯丙烯酸酯乳液的制备方法包括如下步骤:The preparation method of the silicone-modified waterborne polyurethane acrylate emulsion comprises the following steps: A1:氮气氛围中,将聚醚二元醇、异氟尔酮二异氰酸酯、二月桂酸二丁基锡加入反应釜中,控制温度80-90℃,保温反应1-3h,加入二羟甲基丙酸、丙酮,保温反应1-3h,控制温度60-70℃,加入甲基丙烯酸羟乙酯,保温反应1-3h,控制温度65-75℃,保温反应1-3h,控制温度35-45℃,加入三乙胺,保温反应0.5-1h,加入去离子水,保温1-3h,旋蒸除去丙酮,得到水性聚氨酯丙烯酸酯乳液;A1: In a nitrogen atmosphere, polyether diol, isophorone diisocyanate and dibutyltin dilaurate are added to a reaction kettle, the temperature is controlled at 80-90°C, and the reaction is kept warm for 1-3h. Dimethylolpropionic acid and acetone are added, and the reaction is kept warm for 1-3h. The temperature is controlled at 60-70°C. Hydroxyethyl methacrylate is added, and the reaction is kept warm for 1-3h. The temperature is controlled at 65-75°C, and the reaction is kept warm for 1-3h. The temperature is controlled at 35-45°C, triethylamine is added, and the reaction is kept warm for 0.5-1h. Deionized water is added, and the reaction is kept warm for 1-3h. Acetone is removed by rotary evaporation to obtain an aqueous polyurethane acrylate emulsion; A2:将水性聚氨酯丙烯酸酯乳液、二氧化硅改性溶胶共混,得到有机硅改性水性聚氨酯丙烯酸酯乳液;A2: blending an aqueous polyurethane acrylate emulsion and a silica-modified sol to obtain an organosilicon-modified aqueous polyurethane acrylate emulsion; 二氧化硅改性溶胶的制备方法包括如下步骤:The preparation method of the silica modified sol comprises the following steps: S1:氮气氛围中,将纳米二氧化钛、2,4-甲苯二异氰酸酯、甲苯加入反应釜中分散均匀,控制温度80-90℃,保温搅拌6-12h,无水乙醇洗涤、干燥,得到组分一;S1: In a nitrogen atmosphere, nano titanium dioxide, 2,4-toluene diisocyanate and toluene are added into a reaction kettle and dispersed evenly, the temperature is controlled at 80-90°C, the mixture is stirred for 6-12 hours, washed with anhydrous ethanol and dried to obtain component 1; S2:将组分一、γ-氨基丙基三乙氧基硅烷、乙酸乙酯加入反应釜中,控制温度50-60℃,保温反应3-6h,加入无水乙醇分散均匀,保温反应1-3h,过滤、干燥,得到组分二;S2: Add component 1, γ-aminopropyltriethoxysilane and ethyl acetate into a reaction kettle, control the temperature at 50-60°C, keep the temperature for reaction for 3-6 hours, add anhydrous ethanol to disperse evenly, keep the temperature for reaction for 1-3 hours, filter and dry to obtain component 2; S3:将无水乙醇、组分二、正硅酸乙酯加入反应釜中分散均匀,滴加醋酸溶液,控制温度25-35℃,保温反应6-12h,得到组分三;S3: Add anhydrous ethanol, component 2, and tetraethyl orthosilicate into a reaction kettle and disperse them evenly, dropwise add acetic acid solution, control the temperature at 25-35°C, and keep the reaction warm for 6-12 hours to obtain component 3; S4:将组分三、三丙二醇二丙烯酸酯加入反应釜中分散均匀,减压蒸馏除去溶剂,得到二氧化硅改性溶胶。S4: Add components three and tripropylene glycol diacrylate into a reaction kettle and disperse them evenly, and remove the solvent by distillation under reduced pressure to obtain a silica-modified sol. 2.根据权利要求1所述的一种具有防晒拒水功能的涂料组合物,其特征在于,A1中聚醚二元醇、异氟尔酮二异氰酸酯、二月桂酸二丁基锡、二羟甲基丙酸、丙酮、甲基丙烯酸羟乙酯、三乙胺、去离子水的添加比为10g:5-8g:0.3-0.4g:1-2g:25-50mL:5-8g:1.1-1.5g:30-60mL。2. A coating composition with sunscreen and water repellent function according to claim 1, characterized in that the addition ratio of polyether diol, isophorone diisocyanate, dibutyltin dilaurate, dihydroxymethylpropionic acid, acetone, hydroxyethyl methacrylate, triethylamine, and deionized water in A1 is 10g: 5-8g: 0.3-0.4g: 1-2g: 25-50mL: 5-8g: 1.1-1.5g: 30-60mL. 3.根据权利要求1所述的一种具有防晒拒水功能的涂料组合物,其特征在于,A2中水性聚氨酯丙烯酸酯乳液、二氧化硅改性溶胶的质量比为20-30:20-50。3. A coating composition with sunscreen and water repellent function according to claim 1, characterized in that the mass ratio of the aqueous polyurethane acrylate emulsion and the silica-modified sol in A2 is 20-30:20-50. 4.根据权利要求1所述的一种具有防晒拒水功能的涂料组合物,其特征在于,S1中纳米二氧化钛、2,4-甲苯二异氰酸酯、甲苯的添加比为10g:10-15g:100-300mL。4. A coating composition with sunscreen and water repellent function according to claim 1, characterized in that the addition ratio of nano titanium dioxide, 2,4-toluene diisocyanate and toluene in S1 is 10g:10-15g:100-300mL. 5.根据权利要求1所述的一种具有防晒拒水功能的涂料组合物,其特征在于,S2中组分一、γ-氨基丙基三乙氧基硅烷、乙酸乙酯、无水乙醇的添加比为10g:15-20g:100-300mL:2-20mL。5. A coating composition with sunscreen and water repellent function according to claim 1, characterized in that the addition ratio of component 1, γ-aminopropyltriethoxysilane, ethyl acetate and anhydrous ethanol in S2 is 10g:15-20g:100-300mL:2-20mL. 6.根据权利要求1所述的一种具有防晒拒水功能的涂料组合物,其特征在于,S3中醋酸溶液为0.2-0.3mo l/L醋酸溶液,无水乙醇、组分二、正硅酸乙酯、醋酸溶液的添加比为15-25mL:10g:4-12.5g:10-25mL。6. A coating composition with sunscreen and water repellent function according to claim 1, characterized in that the acetic acid solution in S3 is 0.2-0.3 mol/L acetic acid solution, and the addition ratio of anhydrous ethanol, component two, tetraethyl orthosilicate, and acetic acid solution is 15-25 mL: 10 g: 4-12.5 g: 10-25 mL. 7.根据权利要求1所述的一种具有防晒拒水功能的涂料组合物,其特征在于,S4中组分三、三丙二醇二丙烯酸酯的质量比为1:0.3-0.6。7. A coating composition with sunscreen and water repellent function according to claim 1, characterized in that the mass ratio of component tripropylene glycol diacrylate in S4 is 1:0.3-0.6. 8.根据权利要求1所述的一种具有防晒拒水功能的涂料组合物,其特征在于,防紫外线助剂为苯并三唑类紫外线吸收剂。8. A coating composition with sunscreen and water repellent function according to claim 1, characterized in that the anti-ultraviolet auxiliary agent is a benzotriazole ultraviolet absorber. 9.根据权利要求1所述的一种具有防晒拒水功能的涂料组合物,其特征在于,助剂包括0.2-0.5份分散剂、0.5-1份消泡剂、2-4份保湿剂、5-8份水性蜡乳液手感剂、0.3-0.5份pH调节剂。9. A coating composition with sunscreen and water repellent function according to claim 1, characterized in that the auxiliary agent includes 0.2-0.5 parts of dispersant, 0.5-1 parts of defoaming agent, 2-4 parts of moisturizing agent, 5-8 parts of water-based wax emulsion feel agent, and 0.3-0.5 parts of pH regulator.
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