CN111849330A

CN111849330A - Ultralow VOC aqueous polyurethaneNano ATO/Tio of ester/acrylic acid transparent building glass2Transparent heat-insulating coating

Info

Publication number: CN111849330A
Application number: CN202010703833.XA
Authority: CN
Inventors: 曾国屏; 戴国太; 王刚; 王玲玲; 张军
Original assignee: Jiangsu Chunzhisheng Decoration Materials Co Ltd; Institute of Applied Chemistry Jiangxi Academy of Sciences
Current assignee: Jiangsu Chunzhisheng Decoration Materials Co Ltd; Institute of Applied Chemistry Jiangxi Academy of Sciences
Priority date: 2020-07-21
Filing date: 2020-07-21
Publication date: 2020-10-30

Abstract

The invention discloses a nanometer ATO/Tio of ultralow VOC waterborne polyurethane/acrylic acid transparent building glass₂The transparent heat-insulating paint consists of nanometer water-thinned polyurethane/acrylic acid, ATO dispersion and Tio₂Nano dispersion, organic silicon cross-linking agent, dispersant, wetting agent, defoaming agent, environment-friendly film-forming assistant and flatting agent. The invention adopts rutile reflective insulation Tio₂The one-component waterborne polyurethane/acrylic acid transparent heat-insulation coating compounded with the radiation heat-insulation ATO is green and environment-friendly, meets the national environmental protection quality standard, has excellent heat-insulation performance and transparency, has excellent paint film mechanical property, water resistance and weather resistance, can be widely applied to transparent heat insulation and energy conservation of automobile glass and building glass, and has wide market prospect.

Description

Nanometer ATO/Tio of ultralow VOC waterborne polyurethane/acrylic acid transparent building glass2Transparent heat-insulating coating

Technical Field

The invention relates to the technical field of single-component waterborne polyurethane/acrylic acid nano transparent heat-insulating coating, in particular to nano ATO/Tio of ultralow-VOC waterborne polyurethane/acrylic acid transparent building glass ₂Transparent heat insulation coating.

Background

Most of Chinese buildings are high-energy-consumption non-energy-saving buildings, and the buildings consume a large amount of energy, which accounts for 30% -40% of the total energy consumption of human beings. The total terminal energy consumption of China is second in the world, the average utilization rate of energy is only about 30%, the energy utilization rate of developed countries of the world industry can reach more than 70%, and the difference of the numbers with great disparity is caused by poor heat insulation or heat preservation effect of buildings. China has wide breadth, great climate difference in each region, and different building energy-saving design requirements in different regions. Generally, the energy consumption required for reducing the temperature once is 4 times of the energy consumption required for increasing the temperature once, the refrigeration in summer is very expensive, and the heat insulation problem in summer in the warm areas in summer and the warm areas in winter has great significance for building energy conservation.

In order to maintain the internal temperature of a building, save energy, reduce the use and consumption of disposable energy sources such as petroleum, coal, natural gas and the like, respond to the requirements on energy conservation and environmental protection of buildings in recent years, researchers have conducted extensive exploration and research to successively develop low-emissivity coated glass, sunlight-control coated glass, glass film, heat-absorbing glass, hollow glass, vacuum glass and other glass energy-saving products, but the products are often limited in popularization and application due to the reasons of low transmittance of a visible light region, complex process conditions, high price and the like. The newly developed nano transparent heat insulation coating is a glass energy-saving coating which can realize good near infrared light blocking and simultaneously can keep higher visible light transmittance, has the factors of environmental friendliness, good heat insulation effect, simple preparation process, lower cost and the like, provides a new direction for solving the glass heat insulation problem, and has wide energy-saving application prospect in the fields of building glass, automobile glass and the like.

At present, the invention patents of nano tin bismuth oxide (ATO) transparent heat-insulating coating for building glass exist in China. The Chinese patent with application number 200910105561.7 'a tin oxide bismuth water-based spectral selectivity nano-coating and a preparation method thereof', not only has lower cost, but also has the advantages of high visible light transmittance, high infrared and ultraviolet blocking rate, high hardness, strong adhesive force, weather resistance, environmental protection and the like. The application number of Chinese patent No. 201110140592.X, "a pass modified water-based transparent heat insulation coating and a preparation method thereof", discloses that the hardness of a coating of the water-based transparent heat insulation coating prepared by pass modified silicone-acrylic emulsion composite ATO reaches 4H, and the coating has the characteristics of high ultraviolet blocking rate, visible light transmittance, ultraviolet resistance, aging resistance, weather resistance and the like. The former of these inventions has insufficient water resistance, and the latter is relatively expensive to produce. Although the ATO/Tio2 phase is compounded to prepare the glass transparent heat-insulating coating, the coating has good visible light transmittance and heat-insulating property, but the coating is added into the heat-insulating coating as the heat-insulating filler, lacks systematic experimental research and is less in application value and difficult to apply because the coating is not added into the heat-insulating coating. Therefore, the research and development of green and environment-friendly products meeting the national environmental protection quality standard are urgently needed in the market, and the products not only have excellent heat-insulating property and transparency, but also have excellent mechanical property, water resistance and weather resistance of paint films, and are beneficial to the popularization and application in the fields of transparent heat insulation and energy conservation of automobile glass and building glass.

Disclosure of Invention

The invention aims to provide a nano ATO/Tio2 transparent heat-insulating coating for ultralow-VOC aqueous polyurethane/acrylic building glass. The coating product is green and environment-friendly, meets the national environmental protection quality standard, has excellent heat-insulating property and transparency, has excellent paint film mechanical property, water resistance and weather resistance, and is beneficial to promoting the heat preservation and energy conservation of the transparent heat-insulating coating for the building glass.

The technical scheme of the invention is as follows: nanometer ATO/Tio of ultralow VOC waterborne polyurethane/acrylic acid transparent building glass₂A transparent heat-insulating paint is prepared from Tio₂Preparation of slurry, preparation of ATO slurry and nano ATO/Tio₂Preparing a filler waterborne polyurethane/acrylic acid transparent heat-insulating coating; the preparation method comprises the following steps:

(1)Tio₂preparation of slurry: 100-500mg Tio₂Adding the nano particles into 10-30mL of deionized water, sequentially adding 20-70mg of silane coupling agent, 10-30mg of wetting agent and 20-100mg of dispersing agent, stirring at a high speed for 1-2 hours, and performing ultrasonic treatment for 10-50 minutes until the nano particles are uniformly dispersed;

(2) preparation of ATO slurry: adding 100-500mg of ATO nano particles into 10-30mL of deionized water, sequentially adding 20-70mg of silane coupling agent, 10-30mg of wetting agent and 20-100mg of dispersing agent, stirring at a high speed for 1-2 hours, and performing ultrasonic treatment for 10-50 minutes until the particles are uniformly dispersed;

(3)ATO/Tio₂Preparing the nano particle heat insulation coating: mixing ATO slurry, Tio₂The slurry and the polyurethane resin are mixed together with high speed agitation, wherein ATO/Tio₂The volume fraction of the slurry is 10:1, and the mass ratio of ATO to Tio is calculated by mass₂The mixed slurry is 15-25%, and the polyurethane/acrylic resin dispersion is 56.1-66%; sequentially adding 0.1-1% of thickening agent, 1-7.3% of non-VOC film forming additive, 0.05-03% of multifunctional PH regulator, 0.05-03% of organosilicon crosslinking agent, 0.1-3% of defoaming agent, 0.1-1% of flatting agent, 0.1-3% of wetting agent and 0.5-2% of dispersing agent; adjusting the pH value of the system to 7-9, adding deionized water, then carrying out ultrasonic dispersion for 10-30 minutes, and stirring at a high speed of 3000r/min for 1 hour to disperse uniformly.

The wetting agent is an LH308 aqueous wetting and leveling agent, and mainly comprises an organic silicon copolymer; the leveling agent is BYK-333, and mainly comprises polyether modified polydimethylsiloxane copolymer; the thickening agent is an LH360 polyurethane thickening agent, and mainly comprises nonionic polyether polyurethane; the silane coupling agent is a silane coupling agent KH-570, and mainly comprises gamma-methacryloxypropyltrimethoxysilane or 3- (methacryloyloxy) propyltrimethoxysilane; the non-VOC film forming auxiliary agent adopts YT-291 odorless non-VOC efficient film forming auxiliary agent or YT-300 odorless non-VOC efficient film forming auxiliary agent; YT-291 odorless non-VOC high-efficiency film-forming aid, mainly comprising dicarboxylic acid dimethyl propylene glycol ester; YT-300 odorless non-VOC efficient film-forming aid, and the main component molecular formula is C ₁₆H₃₀O₄(ii) a The multifunctional PH regulator is one or two of N, N-dimethylethanolamine and AMP-95. The dispersant is a BYK190 aqueous system wetting dispersant, and mainly comprises a high molecular weight block copolymer solution containing pigment affinity groups; the defoaming agent is a BYK022 defoaming agent and mainly comprises a mixture of hydrophobic solid and foam breaking polysiloxane in polyethylene glycol; the organosilicon cross-linking agent is WACKERSLM69800 organosilicon cross-linking agent, and mainly comprises organosilicon oligomer; the particle size of the nanometer ATO nanometer particles is 6-8 nm; the nano Tio₂The particle diameter of the particles is less than or equal to 15 nm.

Nanometer ATO/Tio of ultralow VOC waterborne polyurethane/acrylic acid transparent building glass₂The preparation method of the film-coated glass of the transparent heat-insulating coating comprises the following steps: respectively scrubbing the flat glass sheets by adopting 5 percent of NaOH and 10 percent of HCl in mass fraction, washing the flat glass sheets by using clean water,Drying for later use; coating the heat insulation coating on a 200mm multiplied by 160mm multiplied by 3mm flat glass sheet and a 75mm multiplied by 25mm multiplied by 1mm glass slide respectively by using different thickness surfaces of an SZQ type four-surface preparation device, and airing for about 5min at room temperature; and (3) continuously drying in an oven at 40 ℃ for 1-3 hours in an electric heating blowing constant-temperature drying oven to obtain coating film samples with the coating film thicknesses of 25, 50, 75 and 100 micrometers respectively.

The invention has the advantages that: (1) the adopted waterborne polyurethane has the advantages of good physical and mechanical properties, excellent cold resistance, small change of elasticity and hardness with temperature and the like, the acrylic resin has the advantages of quick drying, good transparency, good gloss and color retention and the like, and the acrylic resin has good adhesive force, luster, hardness and weather resistance, and the combination of the acrylic resin and the acrylic resin is environment-friendly, healthy, high in cost performance and better in performance. (2) Adopts nano rutile TiO₂The coating is compounded with ATO slurry, so that the coating has excellent transparency and heat-insulating property. The organic silicon cross-linking agent is adopted, the cross-linking reaction is carried out on the silane oxygen group and the base material, the ATO and the TiO2 filler and the hydroxyl group on the base material, and the cross-linking reaction is carried out on the epoxy group and the carboxyl group and the amino group on the polymer base material, so that the adhesive force and the cross-linking density of the coating can be improved, the water sensitivity is reduced, and the excellent mechanical property, the water resistance and the weather resistance of the coating are ensured. (3) Adopts the most advanced dispersing agent, defoaming agent, wetting agent, thickening agent, film-forming assistant, leveling agent and multifunctional assistant in the world to meet the requirement of the nano ATO/Tio of the waterborne polyurethane transparent building glass₂The production and construction requirements of the transparent heat-insulating coating. (4) The product is green, odorless, environment-friendly and healthy, the VOC content is not detected, the free formaldehyde content is low, the contents of benzene, toluene, ethylbenzene, xylene and soluble heavy metals are not detected, and the limit of harmful substances is far higher than the GB18582 industrial standard.

Drawings

FIG. 1 is a block diagram of a preparation method of the present invention;

FIG. 2 is a diagram of nano ATO/Tio₂And (3) a heat insulation test chart of the filler waterborne polyurethane/acrylic acid transparent heat insulation coating.

Detailed Description

The specific embodiment of the invention is shown in fig. 1, and is implemented as follows:

example 1: this practical example is a nanometer ATO/Tio for ultra-low VOC waterborne polyurethane/acrylic acid building glass₂The transparent heat-insulating coating is prepared by a general paint preparation process, and comprises the following specific components in percentage by mass:

respectively adding ATO and TiO according to the formula under the condition of magnetic stirring₂Adding the nano slurry into a polyurethane solution, sequentially adding a wetting agent, a dispersing agent, a thickening agent, a film forming aid and a flatting agent, mixing for 15min at a rotating speed of 1500r/min, dispersing for 25min at a rotating speed of 3000r/min, then ultrasonically dispersing for 20min, and adjusting the pH value to 7-9 by using ammonia water; adding deionized water to adjust viscosity.

Example 2: this practical example is a nanometer ATO/Tio for ultra-low VOC waterborne polyurethane/acrylic acid building glass₂The transparent heat-insulating coating is prepared by a general paint preparation process, and comprises the following specific components in percentage by mass:

Example 3: this practical example is a nanometer ATO/Tio for ultra-low VOC waterborne polyurethane/acrylic acid building glass₂The transparent heat-insulating coating is prepared by a general paint preparation process, and comprises the following specific components in percentage by mass:

Example 4: the actual nano ATO/Tio for the ultralow VOC waterborne polyurethane/acrylic acid building glass₂The transparent heat-insulating coating is prepared by a general paint preparation process, and comprises the following specific components in percentage by mass:

respectively adding ATO and TiO according to the formula under the condition of magnetic stirring₂Adding the nano slurry into a polyurethane/acrylic acid solution, sequentially adding a wetting agent, a dispersing agent, a thickening agent, a film forming aid and a flatting agent, mixing at a rotating speed of 1500r/min for 15min, dispersing at a rotating speed of 3000r/min for 25min, then ultrasonically dispersing for 20min, and adjusting the pH value to 7-9 by using ammonia water; adding deionized water to adjust viscosity.

The performance indexes of the water-based transparent heat-insulating nano coating for the single-component building glass are as follows:

Claims

1. nanometer ATO/Tio of ultralow VOC waterborne polyurethane/acrylic acid transparent building glass₂A transparent heat-insulating paint is prepared from Tio₂Preparation of slurry, preparation of ATO slurry and nano ATO/Tio₂Transparent heat insulation of filler waterborne polyurethane/acrylic acidPreparing a coating; the preparation method comprises the following steps:

（1）Tio₂preparation of slurry: 100-500 mg Tio₂Adding the nano particles into 10-30 mL of deionized water, sequentially adding 20-70 mg of silane coupling agent, 10-30 mg of wetting agent and 20-100 mg of dispersing agent, stirring at a high speed for 1-2 hours, and performing ultrasonic treatment for 10-50 minutes until the nano particles are uniformly dispersed;

(2) preparation of ATO slurry: adding 100-500 mg of ATO nano particles into 10-30 mL of deionized water, sequentially adding 20-70 mg of silane coupling agent, 10-30 mg of wetting agent and 20-100 mg of dispersing agent, stirring at a high speed for 1-2 hours, and performing ultrasonic treatment for 10-50 minutes until the particles are uniformly dispersed;

（3）ATO/ Tio₂preparing the nano particle heat insulation coating: mixing ATO slurry, Tio₂The slurry and the polyurethane resin are mixed together with high speed agitation, wherein ATO/Tio₂The volume fraction of the slurry is 10:1, and the mass ratio of ATO to Tio is calculated by mass ₂The mixed slurry is 15-25%, and the polyurethane/acrylic resin dispersion is 56.1-66%; sequentially adding 0.1-1% of thickening agent, 1-7.3% of non-VOC film forming additive, 0.05-03% of multifunctional PH regulator, 0.05-03% of organosilicon crosslinking agent, 0.1-3% of defoaming agent, 0.1-1% of flatting agent, 0.1-3% of wetting agent and 0.5-2% of dispersing agent; adjusting the pH value of the system to 7-9, adding deionized water, then carrying out ultrasonic dispersion for 10-30 minutes, and stirring at a high speed of 3000r/min for 1 hour to disperse uniformly.

2. Nanometer ATO/Tio of the ultralow VOC aqueous polyurethane/acrylic transparent architectural glass of claim 1₂The transparent heat-insulating coating is characterized in that: the wetting agent is an LH308 aqueous wetting and leveling agent, and mainly comprises an organic silicon copolymer; the leveling agent is BYK-333, and mainly comprises polyether modified polydimethylsiloxane copolymer; the thickening agent is an LH360 polyurethane thickening agent, and mainly comprises nonionic polyether polyurethane; the silane coupling agent is a silane coupling agent KH-570, and mainly comprises gamma-methacryloxypropyltrimethoxysilane or 3- (methacryloyloxy) propyltrimethoxysilane; the non-VOC film forming auxiliary agent adopts YT-291 odorless non-VOC efficient film forming auxiliary agent or YT-3 00 odorless non-VOC high-efficiency film-forming auxiliary agent; YT-291 odorless non-VOC high-efficiency film-forming aid, mainly comprising dicarboxylic acid dimethyl propylene glycol ester; YT-300 odorless non-VOC efficient film-forming aid, and the main component molecular formula is C₁₆H₃₀O₄(ii) a The multifunctional PH regulator is one or two of N, N-dimethylethanolamine and AMP-95; the dispersant is a BYK190 aqueous system wetting dispersant, and mainly comprises a high molecular weight block copolymer solution containing pigment affinity groups; the defoaming agent is a BYK022 defoaming agent and mainly comprises a mixture of hydrophobic solid and foam breaking polysiloxane in polyethylene glycol; the organosilicon cross-linking agent is WACKERSLM69800 organosilicon cross-linking agent, and mainly comprises organosilicon oligomer; the particle size of the nanometer ATO nanometer particles is 6-8 nm; the nano Tio₂The particle diameter of the particles is less than or equal to 15 nm.

3. Nanometer ATO/Tio of the ultralow VOC aqueous polyurethane/acrylic transparent architectural glass of claim 1₂The transparent heat-insulating coating is characterized in that: the preparation method of the coated glass of the coating comprises the following steps:

respectively scrubbing flat glass sheets by adopting 5% of NaOH and 10% of HCl, and cleaning and drying the flat glass sheets by using clear water for later use; the heat insulation coating is respectively coated on the surfaces with different thicknesses of an SZQ type four-side preparation device on a flat glass sheet with the thickness of 200 mm multiplied by 160 mm multiplied by 3 mm and a glass slide with the thickness of 75 mm multiplied by 25 mm multiplied by 1 mm, the glass slide is dried for about 5 min at room temperature, and the glass slide is placed in an electric heating blast constant temperature drying oven to be continuously dried for 1-3 hours at the temperature of 40 ℃ to prepare coating film samples with the thickness of 25, 50, 75 and 100 mu m respectively.