CN117089277B - Matte water-based ultraviolet light curing coating with odor removing function and preparation method thereof - Google Patents

Matte water-based ultraviolet light curing coating with odor removing function and preparation method thereof Download PDF

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CN117089277B
CN117089277B CN202311063170.XA CN202311063170A CN117089277B CN 117089277 B CN117089277 B CN 117089277B CN 202311063170 A CN202311063170 A CN 202311063170A CN 117089277 B CN117089277 B CN 117089277B
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CN117089277A (en
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周阳
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Tongjou Chemical Industrial Kunshan 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

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Abstract

The invention provides a water-based ultraviolet light curing coating with a smell removing and matte function, which comprises the following components in parts by weight: 100-200 parts of aqueous polyurethane acrylic ester; 2-5 parts of photoinitiator; 10-20 parts of filler; 0.5-3 parts of auxiliary agent; 10-20 parts of composite deodorant; 20-50 parts of water; wherein the composite odor removing agent contains a nano photocatalyst and a micropore-medium Kong Dianfen-based carbon sphere composite material. The water-based ultraviolet light curing coating disclosed by the invention has the performance of purifying air and absorbing TVOC harmful gases such as formaldehyde which is not generally possessed by conventional coatings, does not need to be added with an organic solvent, is environment-friendly, and has good adhesive force, high toughness, weather resistance and chemical stability.

Description

Matte water-based ultraviolet light curing coating with odor removing function and preparation method thereof
Technical Field
The invention relates to the field of surface protection of floors, wallboards and wood floors, in particular to a preparation method of a matte water-based ultraviolet light curing coating with a smell removing function.
Background
The ultraviolet curing coating has the advantages of no pollution, high curing efficiency and the like, and is rapidly developed and is mainly applied to different fields of wood coating, building materials, electronic communication, automobile parts and the like. Meanwhile, the water-based ultraviolet light curing coating has the advantages of no Volatile Organic Compound (VOC), little environmental pollution, high curing speed, energy conservation, better curing product performance than high-speed automatic production and the like. The traditional paint is easy to volatilize and has low curing speed, which is not beneficial to environmental protection. Therefore, the aqueous ultraviolet light curing coating is a main substitute for the traditional coating. Meanwhile, environmental protection products are uneven in modern furniture decoration, common furniture consumers containing formaldehyde and other TVOC harmful gases are difficult to distinguish, and the harm to the health of the consumers is possibly caused, so that the development of the water-based ultraviolet curing paint with the odor removing function has great practical value and wide market prospect.
Disclosure of Invention
The technical problems to be solved are as follows: the invention aims to solve the problem of odor removal, formaldehyde and other TVOC gas adsorption and decomposition performance which are not generally possessed by conventional coatings, and provides a preparation method of a water-based ultraviolet light curing coating with an odor removal function.
The technical scheme is as follows: the water-based ultraviolet light curing coating with the odor removing and matte functions is characterized by comprising the following components in parts by weight:
100-200 parts of aqueous polyurethane acrylic ester
2-5 Parts of photoinitiator
10-20 Parts of filler
0.5-3 Parts of auxiliary agent
10-20 Parts of composite deodorant
20-50 Parts of water;
Wherein the composite odor removing agent contains a nano photocatalyst and a micropore-medium Kong Dianfen-based carbon sphere composite material.
Preferably, the aqueous polyurethane acrylate is polyether aqueous polyurethane acrylate, polyester aqueous polyurethane acrylate or a combination of any one or two or more than two of the aqueous polyurethane acrylate and the polyester aqueous polyurethane acrylate;
The photoinitiator is any one or more than one mixture of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyclohexyl phenyl ketone, 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide, benzoin diethyl ether or benzoin dimethyl ether;
The filler is any one or more than one mixture or two or more than two compounds of silicon dioxide, aluminum stearate or calcium stearate with the particle size grade of micro powder or nano grade;
The auxiliary agent comprises any one or two or more of superfine synthetic silicon dioxide, ceramic powder, a water-based thickener, a defoaming agent, a formaldehyde removal additive, an antibacterial additive, an anti-sedimentation agent, a matting agent, a handfeel wax and a dispersing agent.
Preferably, the preparation method of the nano photocatalyst and microporous-medium Kong Dianfen-based carbon sphere composite material comprises the following steps:
S11, preparing microporous starch-based particles: mixing starch with phosphate buffer solution containing amylase, fully mixing and stirring at 50-60 ℃ to obtain a serous product, collecting the product, washing with deionized water to obtain a white intermediate product, adding sodium bicarbonate into the white intermediate product, uniformly mixing, and drying to obtain microporous starch-based particles;
S12, preparing a micropore-medium Kong Dianfen base carbon sphere: pre-oxidizing the microporous starch-based particles prepared in the step S11 for 12-20 hours at 180-200 ℃, naturally cooling, then placing the particles in a tube furnace for carbonization treatment, heating the particles from room temperature to 600 ℃ by using N 2 as a protective gas, and preserving heat for 1: 1 h at a heating rate of 2 ℃/min, and naturally cooling to room temperature after heating is completed to obtain microporous-medium Kong Dianfen-based carbon spheres;
s13, preparing a composite material: and (3) mixing the nano photocatalyst and the micropore-medium Kong Dianfen base carbon sphere according to the mass ratio of 1-3:1, and putting the mixture into a planetary ball mill for ball milling for 2 hours to obtain the nano photocatalyst and micropore-medium Kong Dianfen base carbon sphere composite material.
Preferably, the preparation method of the compound deodorant comprises the following steps: pouring 20g of deionized water and 5g of dispersing agent into a stirring device, stirring and mixing for 30 minutes at a stirring speed of 1500r/min, adding 50g of sodium acetate, 20g of sodium chloride, 20g of ammonium chloride, 100g of nano photocatalyst and microporous-mesoporous Kong Dianfen-base carbon sphere composite material, continuing stirring for 60 minutes at a stirring speed of 1200r/min until the mixture is completely mixed to form a stable solution, and filtering to obtain the composite odor removing agent.
Preferably, the weight average molecular weight of the aqueous urethane acrylate ranges from 400 to 40000g/mol.
The preparation method of the odor-free matte water-based ultraviolet curing coating comprises the following steps: firstly adding the aqueous polyurethane acrylic ester into a container, then sequentially adding a photoinitiator, a filler, an auxiliary agent, a composite odor removing agent and water, after each reaction raw material is added, uniformly stirring, adding the next raw material until the addition is completed, and uniformly mixing and stirring to obtain the aqueous ultraviolet light curing coating.
The application method of the odor-free matte water-based ultraviolet light curing coating is characterized by comprising the following steps of:
S1, coating ultraviolet light curing paint on a substrate, wherein the coating amount is 60-200g/m 2, and the number of coating channels is not limited;
s2, after coating is finished, adjusting the paint film effect through infrared treatment in each path;
And S3, finally curing the coating composition through ultraviolet irradiation.
Preferably, the substrate comprises: wood board, stone-plastic composite floor;
Wherein, the plank includes: a, a solid wood floor, b, a solid wood multilayer composite floor; c, a finger joint plate; d: a solid wood particle board; e: any other core material and substrate, but the surface of which is made of the above materials; the stone-plastic composite floor comprises the following components: the stone powder is adopted to form a solid base layer with a high-density and high-fiber net structure, and the surface of the solid base layer is covered with a super-strong wear-resistant polymer PVC wear-resistant layer.
The beneficial effects are that: the preparation method of the invention has the following advantages:
the water-based ultraviolet light curing coating disclosed by the invention has the performance of purifying air, absorbing TVOC harmful gases such as formaldehyde and the like which are not generally possessed by conventional coatings, does not need to add an organic solvent, is environment-friendly, and has good adhesive force, high toughness, weather resistance and chemical stability;
the raw material composite deodorant adopted by the invention has simple synthesis, extremely large specific surface area and strong adsorption capacity, and the paint can fully absorb and decompose harmful gases in the air through the nanoscale photocatalyst and the micropore-medium Kong Dianfen-based carbon sphere, so that the effect of deodorizing is achieved;
According to the invention, starch particles with a micropore structure are prepared, sodium bicarbonate is added into the starch particles, and the sodium bicarbonate can be decomposed under the action of heat to generate mesopores, so that the carbonized starch particles contain mesopores and micropores at the same time, and the adsorption capacity of the coating can be improved;
The coating disclosed by the invention has various application modes, can be coated on a base material in a conventional spraying mode, can be directly coated on the base material in a roller coating mode, widens the application range of the coating, reduces the equipment limit, and can be applied to wood boards and stone-plastic composite floors, thereby expanding the application range.
Detailed Description
The invention is further described below with reference to the following examples, which are illustrative of the invention and are not intended to limit the invention thereto:
Example 1
The preparation method of the compound deodorant comprises the following steps: pouring 20g of deionized water and 5g of dispersing agent into a stirring device for stirring and mixing, wherein the mixing time is 30 minutes, the stirring speed is 1500r/min, then 50g of sodium acetate, 20g of sodium chloride, 20g of ammonium chloride, 100g of nano photocatalyst and microporous-mesoporous Kong Dianfen-based carbon sphere composite material are added into the mixture, stirring is continued, the mixing time is 60 minutes, the stirring speed is 1200r/min until the mixture is completely mixed, a stable solution is formed, and the composite odor removing agent can be obtained after filtering;
The preparation method of the nano photocatalyst and microporous-medium Kong Dianfen-based carbon sphere composite material comprises the following steps:
S11, preparing microporous starch-based particles: mixing starch with phosphate buffer solution containing amylase, fully mixing and stirring for 2 hours at 60 ℃ to obtain a serous product, collecting the product, washing with deionized water to obtain a white intermediate product, adding sodium bicarbonate into the white intermediate product, wherein the mass ratio of the sodium bicarbonate to the starch is 1:20, uniformly mixing, and drying to obtain microporous starch-based particles;
s12, preparing a micropore-medium Kong Dianfen base carbon sphere: pre-oxidizing the microporous starch-based particles prepared in the step S11 for 20 hours at 180 ℃, naturally cooling, then placing the particles in a tube furnace for carbonization treatment, heating the particles from room temperature to 600 ℃ by taking N 2 as a protective gas, preserving heat for 1h at a heating rate of 2 ℃/min, and naturally cooling to room temperature after heating is completed, thus obtaining microporous-mesoporous Kong Dianfen-based carbon spheres;
S13, preparing a composite material: and (3) mixing the nano photocatalyst and the micropore-medium Kong Dianfen base carbon sphere according to the mass ratio of 1:1, and putting the mixture into a planetary ball mill for ball milling for 2 hours to obtain the nano photocatalyst and micropore-medium Kong Dianfen base carbon sphere composite material.
Example 2
The preparation method of the compound deodorant comprises the following steps: pouring 20g of deionized water and 5g of dispersing agent into a stirring device for stirring and mixing, wherein the mixing time is 30 minutes, the stirring speed is 1500r/min, then 50g of sodium acetate, 20g of sodium chloride, 20g of ammonium chloride, 100g of nano photocatalyst and microporous-mesoporous Kong Dianfen-based carbon sphere composite material are added into the mixture, stirring is continued, the mixing time is 60 minutes, the stirring speed is 1200r/min until the mixture is completely mixed, a stable solution is formed, and the composite odor removing agent can be obtained after filtering;
The preparation method of the nano photocatalyst and microporous-medium Kong Dianfen-based carbon sphere composite material comprises the following steps:
S11, preparing microporous starch-based particles: mixing starch with phosphate buffer solution containing amylase, fully mixing and stirring for 4 hours at 50 ℃ to obtain a serous product, collecting the product, washing with deionized water to obtain a white intermediate product, adding sodium bicarbonate into the white intermediate product, wherein the mass ratio of the sodium bicarbonate to the starch is 1:30, uniformly mixing, and drying to obtain microporous starch-based particles;
s12, preparing a micropore-medium Kong Dianfen base carbon sphere: pre-oxidizing the microporous starch-based particles prepared in the step S11 for 12 hours at 200 ℃, naturally cooling, then placing the particles in a tubular furnace for carbonization treatment, heating the particles from room temperature to 600 ℃ by taking N 2 as a protective gas, preserving heat for 1 hour at a heating rate of 2 ℃/min, and naturally cooling to room temperature after heating is completed, thus obtaining microporous-mesoporous Kong Dianfen-based carbon spheres;
S13, preparing a composite material: and (3) mixing the nano photocatalyst and the micropore-medium Kong Dianfen-based carbon sphere according to the mass ratio of 3:1, and putting the mixture into a planetary ball mill for ball milling for 2 hours to obtain the nano photocatalyst and micropore-medium Kong Dianfen-based carbon sphere composite material.
Example 3
The preparation method of the matte water-based ultraviolet light curing coating with the odor removing function comprises the following steps:
S1, adding 60g of polyether polyol and 60g of hydroxyethyl methacrylate, heating to 50 ℃, adding 1g of dibutyltin and 30g of IPDI, and reacting for 1h at 80 ℃;
S2, slowly adding 3g of DMPA, stirring for 20min, adding 3g of triethylamine, and preserving heat for 30min;
S3, cooling to 60 ℃, adding 50g of water for emulsification, stirring vigorously, adding 10g of hydrazine hydrate after the temperature is unchanged, stirring for 30-60min, and discharging to obtain the aqueous polyurethane acrylate.
S4, adding 100g of aqueous polyurethane acrylate, adding 10g of aqueous thickener under stirring, continuously adding 20g of superfine synthetic silicon dioxide, continuously adding 3g of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2g of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, further adding 1g of defoamer and 40g of composite deodorant prepared in example 1, finally adding 30g of deionized water, and stirring and dispersing for 30min at 1500 rpm to obtain the aqueous ultraviolet light curing coating.
Example 4
The preparation method of the matte water-based ultraviolet light curing coating with the odor removing function comprises the following steps:
s1, adding 40g of polyether polyol, 20g of polyester polyol and 60g of hydroxyethyl methacrylate, heating to 50 ℃, adding 1g of dibutyltin and 30g of IPDI, and reacting for 1h at 80 ℃;
S2, slowly adding 3g of DMPA, stirring for 20min, adding 3g of triethylamine, and preserving heat for 30min;
S3, cooling to 60 ℃, adding 50g of water for emulsification, stirring vigorously, adding 10g of hydrazine hydrate after the temperature is unchanged, stirring for 30-60min, and discharging to obtain the aqueous polyurethane acrylate.
S4, adding 100g of aqueous polyurethane acrylate, adding 20g of aqueous thickener under stirring, continuously adding 20g of superfine synthetic silicon dioxide, 10g of ceramic powder, continuously adding 3g of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2g of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, further adding 1g of defoamer, 3g of handfeel aid and 40g of composite deodorant prepared in example 1, finally adding 30g of deionized water, and stirring and dispersing for 30min at 1500 rpm to obtain the aqueous ultraviolet light curing coating.
Example 5
The preparation method of the matte water-based ultraviolet light curing coating with the odor removing function comprises the following steps:
s1, adding 60g of polyester polyol and 60g of hydroxypropyl acrylate, heating to 50 ℃, adding 1g of dibutyltin and 30gTDI, and reacting for 1h at 80 ℃;
s2, slowly adding 4g of DMPA, stirring for 20min, adding 4g of triethylamine, and preserving heat for 30min;
S3, cooling to 60 ℃, adding 50g of water for emulsification, stirring vigorously, adding 8g of hydrazine hydrate after the temperature is unchanged, stirring for 30-60min, and discharging to obtain the aqueous polyurethane acrylate.
S4, adding 100g of aqueous polyurethane acrylate, adding 10g of aqueous thickener under stirring, continuously adding 20g of superfine synthetic silicon dioxide, continuously adding 3g of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2g of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, further adding 1g of defoamer and 40g of composite deodorant prepared in example 2, finally adding 30g of deionized water, and stirring and dispersing for 30min at 1500 rpm to obtain the aqueous ultraviolet light curing coating.
Example 6
The preparation method of the matte water-based ultraviolet light curing coating with the odor removing function comprises the following steps:
S1, adding 60g of polyester polyol and 60g of hydroxypropyl acrylate, heating to 50 ℃, adding 1.5g of dibutyltin and 20g of IPDI, and reacting 10g of HDI at 80 ℃ for 1h;
s2, slowly adding 4g of DMPA, stirring for 20min, adding 4g of triethylamine and 2g of ethylenediamine, and preserving heat for 30min;
S3, cooling to 60 ℃, adding 50g of water for emulsification, stirring vigorously, adding 8g of hydrazine hydrate after the temperature is unchanged, stirring for 30-60min, and discharging to obtain the aqueous polyurethane acrylate.
S4, adding 100g of aqueous polyurethane acrylate, adding 30g of aqueous thickener under stirring, continuously adding 20g of superfine synthetic silicon dioxide, continuously adding 3g of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2g of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, further adding 1g of defoamer and 40g of composite deodorant prepared in example 1, finally adding 30g of deionized water, and stirring and dispersing for 30min at 1500 rpm to obtain the aqueous ultraviolet light curing coating.
Example 7
The preparation method of the matte water-based ultraviolet light curing coating with the odor removing function comprises the following steps:
S1, adding 60g of polyether polyol and 60g of hydroxyethyl acrylate, heating to 50 ℃, adding 1g of dibutyltin and 30gTDI, and reacting for 1h at 80 ℃;
s2, slowly adding 4g of DMPA, stirring for 20min, adding 4g of triethylamine and 2g of ethylenediamine, and preserving heat for 30min;
S3, cooling to 60 ℃, adding 50g of water for emulsification, stirring vigorously, adding 8g of hydrazine hydrate after the temperature is unchanged, stirring for 30-60min, and discharging to obtain the aqueous polyurethane acrylate.
S4, adding 100g of aqueous polyurethane acrylate, adding 30g of aqueous thickener under stirring, continuously adding 20g of superfine synthetic silicon dioxide, continuously adding 3g of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2g of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, further adding 1g of defoamer and 40g of composite deodorant prepared in example 2, and finally adding 30g of deionized water, stirring and dispersing for 30min at 1500 rpm to obtain the aqueous ultraviolet light curing coating.
Comparative example 1
The preparation method of the epoxy methacrylic acid ultraviolet light curing coating is characterized by comprising the following steps:
50 parts by weight of triglycol dimethacrylate is added into 100 parts by weight of epoxy acrylic resin under stirring, 3 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-acetone is continuously added, 10 parts by weight of superfine silica is added, 1 part by weight of defoamer is added, and stirring and dispersing are carried out for 60 minutes at 1500 revolutions per minute, so that the ultraviolet curing coating is obtained.
Comparative example 2
The preparation method of the epoxy methacrylic acid ultraviolet light curing coating is characterized by comprising the following steps:
Adding 50 parts by weight of pentaerythritol trimethacrylate into 100 parts by weight of epoxy acrylic resin under stirring, continuously adding 5 parts by weight of 1-hydroxy-cyclohexyl phenyl ketone, adding 10 parts by weight of talcum powder, adding 1 part by weight of defoamer, and stirring and dispersing for 60min at 1500 rpm to obtain the ultraviolet light curing coating.
Comparative example 3
The preparation method of the matte water-based ultraviolet light curing coating with the odor removing function comprises the following steps:
S1, adding 60g of polyester polyol and 60g of hydroxypropyl acrylate, heating to 50 ℃, adding 1.5g of dibutyltin and 20g of IPDI, and reacting 10g of HDI at 80 ℃ for 1h;
s2, slowly adding 4g of DMPA, stirring for 20min, adding 4g of triethylamine and 2g of ethylenediamine, and preserving heat for 30min;
S3, cooling to 60 ℃, adding 50g of water for emulsification, stirring vigorously, adding 8g of hydrazine hydrate after the temperature is unchanged, stirring for 30-60min, and discharging to obtain the aqueous polyurethane acrylate.
S4, adding 100g of aqueous polyurethane acrylic ester, adding 30g of aqueous thickener under stirring, continuously adding 20g of superfine synthetic silicon dioxide, continuously adding 3g of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2g of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, further adding 1g of defoamer and 40g of composite deodorant, finally adding 30g of deionized water, and stirring and dispersing for 30min at 1500 rpm to obtain the aqueous ultraviolet light curing coating;
The preparation method of the compound deodorant comprises the following steps: pouring 20g of deionized water and 5g of dispersing agent into a stirring device for stirring and mixing for 30 minutes at a stirring speed of 1500r/min, adding 50g of sodium acetate, 20g of sodium chloride, 20g of ammonium chloride and 100g of nano photocatalyst into the mixture, continuously stirring for 60 minutes at a stirring speed of 1200r/min until the mixture is completely mixed to form a stable solution, and filtering to obtain the composite odor removing agent.
Comparative example 4
The preparation method of the matte water-based ultraviolet light curing coating with the odor removing function comprises the following steps:
s1, adding 60g of polyether polyol and 60g of hydroxyethyl acrylate, heating to 50 ℃, adding 1g of dibutyltin and 30gTDI, and reacting for 1h at 80 ℃;
s2, slowly adding 4g of DMPA, stirring for 20min, adding 4g of triethylamine and 2g of ethylenediamine, and preserving heat for 30min;
S3, cooling to 60 ℃, adding 50g of water for emulsification, stirring vigorously, adding 8g of hydrazine hydrate after the temperature is unchanged, stirring for 30-60min, and discharging to obtain the aqueous polyurethane acrylate.
S4, adding 100g of aqueous polyurethane acrylate, adding 30g of aqueous thickener under stirring, continuously adding 20g of superfine synthetic silicon dioxide, continuously adding 3g of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2g of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, further adding 1g of defoamer and 40g of composite deodorant, finally adding 30g of deionized water, and stirring and dispersing for 30min at 1500 rpm to obtain the aqueous ultraviolet light curing coating;
The preparation method of the composite deodorant comprises the following steps: pouring 20g of deionized water and 5g of dispersing agent into a stirring device for stirring and mixing, wherein the mixing time is 30 minutes, the stirring speed is 1500r/min, then 50g of sodium acetate, 20g of sodium chloride, 20g of ammonium chloride, 100g of nano photocatalyst and microporous starch-based carbon sphere composite material are added into the stirring device, stirring is continued, the mixing time is 60 minutes, the stirring speed is 1200r/min, until the stable solution is formed, and the composite deodorant can be obtained after filtering;
the preparation method of the nano photocatalyst and microporous starch-based carbon sphere composite material comprises the following steps:
S11, preparing microporous starch-based particles: mixing starch with phosphate buffer solution containing amylase, fully mixing and stirring for 2 hours at 60 ℃ to obtain a serous product, collecting the product, washing with deionized water, and drying to obtain microporous starch-based particles;
S12, preparing microporous starch-based carbon spheres: pre-oxidizing the microporous starch-based particles prepared in the step S11 for 20 hours at 180 ℃, naturally cooling, then placing the particles in a tube furnace for carbonization treatment, heating the particles from room temperature to 600 ℃ by taking N 2 as a protective gas, preserving heat for 1 hour at a heating rate of 2 ℃/min, and naturally cooling to room temperature after heating is completed, thus obtaining microporous starch-based carbon spheres;
S13, preparing a composite material: and (3) mixing the nano photocatalyst and the microporous starch-based carbon sphere according to the mass ratio of 1:1, and putting the mixture into a planetary ball mill for ball milling for 2 hours to obtain the nano photocatalyst and microporous-medium Kong Dianfen-based carbon sphere composite material.
Examples 3-5 were sprayed on oak boards, examples 6-7 and comparative examples were each coated on oak boards by roll coating, and the examples were cured after uv irradiation to give coating films, and the appearance, impact resistance, adhesion, odor removal effect and other test properties were respectively tested as shown in table 1.
TABLE 1 Performance of the odor-free matte waterborne UV-curable coating of the invention
Sequence number Gloss/° Hardness of Adhesion/MPa Impact/cm resistance
Example 3 3.3 6H 6.89 45
Example 4 2.3 6H 6.78 45
Example 5 2.5 6H 6.57 45
Example 6 3.8 7H 6.69 50
Example 7 3.2 7H 6.58 50
Comparative example 1 20.06 3H 5.42 25
Comparative example 2 23.43 4H 4.86 25
Comparative example 3 3.3 6H 6.54 45
Comparative example 4 2.9 6H 6.61 45
The parameters tested above were obtained by testing the following methods: film gloss: measured according to ISO 2813-2014; impact resistance of the coating film: measured according to GB/T1732-2020; film adhesion: measured according to GB/T5210-2006 and 1720-1979 (2020).
Odor removal effect test:
Test 1: and (3) testing formaldehyde absorption and benzene absorption: preparing a coating according to a construction standard, spraying the coating on 4 oak boards with the density of 20cmx and 30cm, then placing the boards into a closed glass box with the volume of 60L, and introducing formaldehyde gas with the density of about 10mg/L into the glass box; after a period of time according to the detection requirements, the formaldehyde concentration change is measured. The experimental results are shown in Table 2.
TABLE 2
Sequence number Initial concentration mg/L 24H concentration mg/L
Example 3 9.6 0.53
Example 4 9.6 0.58
Example 5 9.6 0.56
Example 6 9.6 0.48
Example 7 9.6 0.69
Comparative example 1 9.6 8.52
Comparative example 2 9.6 8.26
Comparative example 3 9.6 2.56
Comparative example 4 9.6 1.89
In comparison of the performance of the odor-free matte waterborne uv curable coatings of the present invention provided by table 1, examples 3-7 and comparative examples 1-4, comparative examples 1 and 2 used conventional epoxy acrylic resins with higher gloss, poorer hardness, general adhesion, impact resistance, and comparative examples 3 and 4 used conventional nano-photocatalyst and only microporous starch-based carbon spheres. In examples 3-7, the aqueous polyurethane acrylate is used, and the performances of gloss, hardness, adhesive force, impact resistance and the like of the coating film are greatly improved. As can be seen from Table 2, the addition of the compound odor removing agent in examples 3-7 and comparative examples 1-4 can produce an obvious adsorption effect on TVOC, thereby achieving the effects of odor removal and air purification. Examples 3-5 are compared with examples 6-7, and it can be seen from the results that near uniform results can be achieved with different coating processes.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or modifications as equivalent embodiments using the methods and technical contents disclosed above without departing from the spirit and technical solution of the present invention. Therefore, any simple modification, equivalent substitution, equivalent variation and modification of the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention, unless departing from the technical solution of the present invention.

Claims (6)

1. The water-based ultraviolet light curing coating with the odor removing and matte functions is characterized by comprising the following components in parts by weight:
100-200 parts of waterborne polyurethane acrylic ester
2-5 Parts of photoinitiator
10-20 Parts of filler
0.5-3 Parts of auxiliary agent
10-20 Parts of composite odor removing agent
20-50 Parts of water;
wherein the composite odor removing agent contains a nano photocatalyst and a micropore-medium Kong Dianfen-based carbon sphere composite material;
the filler is any one or more than one mixture of silicon dioxide, aluminum stearate or calcium stearate with the particle size of micron or nanometer grade;
the preparation method of the nano photocatalyst and microporous-medium Kong Dianfen-based carbon sphere composite material comprises the following steps:
S11, preparing microporous starch-based particles: mixing starch with phosphate buffer solution containing amylase, fully mixing and stirring at 50-60 ℃ to obtain a serous product, collecting the product, washing with deionized water to obtain a white intermediate product, adding sodium bicarbonate into the white intermediate product, uniformly mixing, and drying to obtain microporous starch-based particles;
S12, preparing a micropore-medium Kong Dianfen base carbon sphere: pre-oxidizing the microporous starch-based particles prepared in the step S11 for 12-20 hours at 180-200 ℃, naturally cooling, then placing the particles in a tube furnace for carbonization treatment, heating the particles from room temperature to 600 ℃ and preserving heat for 1 h by taking N2 as a protective gas, heating the particles at a heating rate of 2 ℃/min, and naturally cooling the particles to room temperature after heating is completed, thus obtaining microporous-mesoporous Kong Dianfen-based carbon spheres;
S13, preparing a composite material: mixing the nano photocatalyst and the micropore-medium Kong Dianfen-based carbon sphere according to the mass ratio of 1-3:1, and putting the mixture into a planetary ball mill for ball milling for 2 hours to obtain a nano photocatalyst and micropore-medium Kong Dianfen-based carbon sphere composite material;
The preparation method of the compound deodorant comprises the following steps: pouring 20g of deionized water and 5g of dispersing agent into a stirring device, stirring and mixing for 30 minutes at a stirring speed of 1500r/min, adding 50g of sodium acetate, 20g of sodium chloride, 20g of ammonium chloride, 100g of nano photocatalyst and microporous-mesoporous Kong Dianfen-base carbon sphere composite material, continuing stirring for 60 minutes at a stirring speed of 1200r/min until the mixture is completely mixed to form a stable solution, and filtering to obtain the composite odor removing agent.
2. The aqueous ultraviolet light curing coating with the odor removal matte function according to claim 1, which is characterized in that: the aqueous polyurethane acrylic ester is any one or two of polyether aqueous polyurethane acrylic ester and polyester aqueous polyurethane acrylic ester;
The photoinitiator is any one or more than one mixture of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy-cyclohexyl phenyl ketone, 2,4, 6-trimethyl benzoyl diphenyl phosphine oxide, benzoin diethyl ether or benzoin dimethyl ether;
the auxiliary agent comprises any one or more than one of superfine synthetic silicon dioxide, ceramic powder, a water-based thickener, a defoaming agent, a formaldehyde removal additive, an antibacterial additive, an anti-sedimentation agent, a matting agent, hand feeling wax and a dispersing agent.
3. The aqueous ultraviolet light curing coating with the odor removal matte function according to claim 2, which is characterized in that: the weight average molecular weight of the aqueous polyurethane acrylate ranges from 400 g/mol to 40000g/mol.
4. A method for preparing a odor-free matte aqueous uv curable coating according to any one of claims 1-3, comprising the steps of: firstly adding the aqueous polyurethane acrylic ester into a container, then sequentially adding a photoinitiator, a filler, an auxiliary agent, a composite odor removing agent and water, after each reaction raw material is added, uniformly stirring, adding the next raw material until the addition is completed, and uniformly mixing and stirring to obtain the aqueous ultraviolet light curing coating.
5. A method of using the odor-free matte aqueous uv curable coating as defined in any one of claims 1-3, comprising the steps of:
S1, coating ultraviolet light curing paint on a substrate, wherein the coating amount is 60-200g/m 2, and the number of coating channels is not limited;
s2, after coating is finished, adjusting the paint film effect through infrared treatment in each path;
And S3, finally curing the coating composition through ultraviolet irradiation.
6. The application method of the odor-free matte water-based ultraviolet light curing coating according to claim 5, which is characterized in that: the substrate comprises: wood board, stone-plastic composite floor;
wherein, the plank includes: b any other core materials and substrates, wherein the surface of the product takes the solid wood floor as a surface layer; the stone-plastic composite floor comprises the following components: the stone powder is adopted to form a solid base layer with a high-density and high-fiber net structure, and the surface of the solid base layer is covered with a super-strong wear-resistant polymer PVC wear-resistant layer.
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