CN111410730A - Polyurethane emulsion and anti-reflection coating liquid prepared from same - Google Patents

Polyurethane emulsion and anti-reflection coating liquid prepared from same Download PDF

Info

Publication number
CN111410730A
CN111410730A CN202010347526.2A CN202010347526A CN111410730A CN 111410730 A CN111410730 A CN 111410730A CN 202010347526 A CN202010347526 A CN 202010347526A CN 111410730 A CN111410730 A CN 111410730A
Authority
CN
China
Prior art keywords
polyurethane emulsion
optionally
coating liquid
polyol
polyurethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010347526.2A
Other languages
Chinese (zh)
Other versions
CN111410730B (en
Inventor
吴后胜
严国杭
肖立铃
刘世基
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen Winlight Optical Coating Technology Co ltd
Original Assignee
Xiamen Winlight Optical Coating Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiamen Winlight Optical Coating Technology Co ltd filed Critical Xiamen Winlight Optical Coating Technology Co ltd
Priority to CN202010347526.2A priority Critical patent/CN111410730B/en
Publication of CN111410730A publication Critical patent/CN111410730A/en
Application granted granted Critical
Publication of CN111410730B publication Critical patent/CN111410730B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C03C17/322—Polyurethanes or polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/004—Reflecting paints; Signal paints

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to a polyurethane emulsion and an antireflection coating liquid prepared from the same, wherein the particle size range of the polyurethane emulsion in the polyurethane emulsion is 20-150 nm, and the polyurethane emulsion is prepared from the following raw materials: the polyurethane foaming agent comprises polyol, isocyanate, a catalyst, a chain extender, a first solvent, a neutralizer and deionized water. The antireflection coating liquid is prepared from the following raw materials: the polyurethane emulsion comprises alkoxy silane, deionized water, a hydrolysis catalyst, the polyurethane emulsion, a second solvent and an auxiliary agent. The polyurethane emulsion is used as a pore-forming agent, has good compatibility with other components in an anti-reflection film liquid, and an anti-reflection film prepared from the anti-reflection coating liquid prepared from the emulsion has the advantages of high anti-reflection, good wear resistance, good weather resistance and the like.

Description

Polyurethane emulsion and anti-reflection coating liquid prepared from same
Technical Field
The invention relates to a preparation technology of a pore-forming agent, in particular to polyurethane emulsion and antireflection coating liquid prepared from the same.
Background
Solar energy is a clean renewable energy source, and with the shortage of energy sources such as coal, petroleum and the like, the development of solar energy is more and more important. Generally, the material with a large refractive index has a large reflectivity, the average light transmittance of the solar photovoltaic glass for protecting the monocrystalline silicon cell is about 91.5%, and about 8% of sunlight is reflected. In order to increase the light transmittance of the solar photovoltaic glass, the current mainstream method is to prepare a low-refractive-index film layer, namely an antireflection film, on the surface of the photovoltaic glass. The method for forming an antireflection film, which is commonly used in the industry at present, is achieved by forming a silica coating layer containing pores. Among them, a typical method is a method of forming hollow silica particles, in which organic or inorganic particles are used as core particles, a silica precursor is used as a shell, and then the core particles are removed to form hollow silica particles having a low refractive index.
Patent CN101512387A discloses a method for preparing hollow silica particles by using a polymer as a core and a silica precursor as a shell, and removing the core particles by centrifugation or other processes, and performing secondary dispersion to obtain hollow silica particles. The production process is complicated, and the particle size distribution of the hollow silica particles is not uniform.
Patent CN107082868B uses cationic polyurethane as core particles and ethyl orthosilicate as shell to prepare the anti-reflective coating. Tetraethoxysilane is hydrolyzed under acidic condition, the hydrolysis rate is higher than the polycondensation rate, a linear structure is formed, a coating structure is easily formed on the surface of cationic polyurethane, the polycondensation rate of tetraethoxysilane is higher than the hydrolysis rate under alkaline condition, and a spherical structure is easily formed by self-polymerization, so that tetraethoxysilane and polyurethane are co-hydrolyzed to form a core-shell structure, which can only be carried out under acidic condition, thus limiting the use type of polyurethane and only adopting cationic polyurethane.
The spherical particles with the core-shell structure obtained by the tetraethoxysilane route in the 2 patents are coated and filmed, and a large number of gaps are generated due to the stacking among the spherical particles, so that the gaps cannot be eliminated in the toughening process, and the defects of poor wear resistance and weather resistance and the like can be brought to a coating.
Disclosure of Invention
The solar photovoltaic glass comprises photovoltaic glass and an antireflection film covering the surface of the photovoltaic glass, wherein the antireflection film is coated on the surface of the photovoltaic glass by adopting the antireflection coating liquid and is prepared by curing and toughening. The inventor finds that the specific alkoxy silane is taken as a film forming substance, prehydrolysis copolymerization is adopted to form the organic silicon resin with a continuous cross-linked net-shaped structure, then the anionic polyurethane is added to be taken as a pore forming agent, and through a toughening process, gas decomposed and volatilized by the anionic polyurethane forms hollow holes in the organic silicon resin film layer, so that the pore forming effect is good. By controlling the thermal decomposition residual rate of the anionic polyurethane and the particle size of particles, an ideal low-refractive-index film layer can be obtained, the solar reflectivity is reduced, and the light transmittance of the photovoltaic glass is improved.
According to the invention concept, the invention provides a novel pore-forming mechanism, namely, the pore-forming is carried out after thermal decomposition into gas, compared with the traditional silicon dioxide deposition method for forming a shell layer, the scheme can be suitable for various organic silicon raw materials and is not limited to tetraethoxysilane. Meanwhile, since the pores are generated by thermal decomposition, it is necessary to control the thermal decomposition residue rate and particle size of the polyurethane emulsion in order to obtain suitable pores.
The inventor finds that the particle size of the polyurethane emulsion is an important means for directly influencing the control conditions, the particle size of the polyurethane is 20-150 nm, and if the particle size of the emulsion is less than 20nm, holes formed by tempering are too small, so that the permeability is not high. If the particle diameter is more than 150nm and exceeds the thickness of the antireflection coating, the formed holes have an open pore structure. The suitable particle size range of the polyurethane in the emulsion is preferably 50-120 nm.
The polyurethane emulsion has a suitable thermal decomposition residual ratio, and the lower the thermal decomposition residual ratio, the more complete the decomposition. If the thermal decomposition residual rate is too high, polyurethane is not fully decomposed in the glass toughening process, so that an ideal hollow hole cannot be formed, the porosity is low, and the refractive index cannot reach the design target.
Furthermore, in order to obtain an anti-reflection film layer with good wear resistance and weather resistance, a unique organic silicon resin formula is designed, so that a product with a specific chemical structure is formed after film formation, and the film layer has excellent wear resistance and weather resistance.
The polyurethane of the invention comprises the following components: the polyurethane foaming agent comprises polyol, isocyanate, a catalyst, a chain extender (Ex), a first solvent, a neutralizing agent and deionized water.
The polyol refers to one or the combination of polyester polyol and polyether polyol, and the structural formula is HO-R' (OH)xWherein x is 1 or 2, R' is generally long-chain polyester or polyether, and can also be small-molecule alkyl, polybutadiene and the like. The ability of polyurethane nano particles to keep the particle shape can be adjusted, and the emulsion particle shape can be kept in the processes of drying and toughening of the antireflection coating liquid. In order to reduce volume change caused by swelling of the polyurethane emulsion nanoparticles in a system by a solvent, a mixture of difunctional groups and trifunctional groups or trifunctional or even higher-functional polyester polyol or polyether polyol can be adopted as the polyester polyol or polyether polyol. Polyether polyols are preferred because they are more stable in emulsion and have better hydrolysis resistance than polyester polyols. Suitable polyolsThe molecular weight Mn of (A) is preferably 500 to 6000.
The isocyanate compound is OCN-R-NCO, wherein R represents isocyanate nuclear group and is aromatic group or alkyl group, and can be one or more of isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), trimethyl hexamethylene diisocyanate (TMDI), dicyclohexylmethane diisocyanate (HMDI), Xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), methylstyrene isocyanate (TMI) and hexahydrotoluene diisocyanate (HTDI).
In the polyurethane component, the catalyst is used for promoting the reaction of isocyanate and hydroxyl compound in the polyol to generate a linear polyurethane prepolymer compound, and the optional catalyst is usually an organic tin compound, such as tin octoate, dibutyltin diacetate, dibutyltin dilaurate, diethyltin dilaurate and the like.
The chain extender is used for reacting with isocyanate groups in the polyurethane prepolymer, the residual free cyanate ester is grafted and supported on the polyurethane prepolymer under the action of a catalyst, and hydrophilic groups are introduced while chain extension is carried out. As an alternative chain extender for the preparation of anionic polyurethanes dimethylolpropionic acid or dimethylolbutyric acid is commonly used.
The first solvent can reduce the viscosity of the expected body in the reaction process, so that the reaction is fully carried out, and the polyurethane reaches a certain molecular weight. The optional solvent is one of ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, methyl isobutyl ketone, methyl amyl ketone, cyclohexane, diacetone alcohol, acetone, N-methyl pyrrolidone, butanone, ethylene glycol methyl ether, propylene glycol butyl ether, N-dimethylformamide and a combination thereof. The addition amount of the solvent is preferably 7-11% of the total amount of the polyurethane emulsion.
The neutralizing agent is also called as a salt forming agent and is a reagent which can react carboxyl, sulfonic acid group and other groups to form polymer salt or generate ionic groups, thereby improving the hydrophilic performance of the polyurethane. The neutralizing agent for preparing the anionic polyurethane mainly comprises triethylamine, ammonia water, sodium hydroxide and the like.
The deionized water can emulsify the polyurethane prepolymer in the polyurethane prepolymer and can react with excessive NCO ends in the polyurethane prepolymer, and the obtained urea bond can improve the decomposition temperature of polyurethane particles. The addition amount of the deionized water is 65-81% of the weight of the polyurethane emulsion.
The molar ratio of the hydroxyl group in the polyol, the isocyanate group in the isocyanate, the hydroxyl group in the chain extender and the neutralizing agent in the preparation of the polyurethane emulsion is preferably as follows:
wherein, the molar weight of hydroxyl groups (-OH) in the polyhydric alcohol: molar amount of isocyanate group in isocyanate (-NCO): the molar weight (-OH) of hydroxyl groups in the chain extender is 0.5-2: 2-20: 5-10, wherein the molar ratio of the neutralizing agent to the chain extender is 0.5-1: 1;
the preparation method of the polyurethane emulsion comprises the following steps:
1) adding isocyanate and a catalyst into the polyol subjected to vacuum pumping and dewatering, and stirring and reacting for 2-6 hours at 50-70 ℃;
2) uniformly mixing a chain extender and a first solvent, adding the mixture into the reaction solution, and continuously reacting for 2-6 hours;
3) adding a neutralizer into the solution, and uniformly stirring;
4) pouring into deionized water, stirring and emulsifying to form the polyurethane emulsion.
The invention also provides a preparation method of the antireflection coating solution. The main components of the antireflection coating solution comprise alkoxy silane and a hydrolysis condensation product thereof, the polyurethane emulsion, a second solvent and an auxiliary agent.
The above-mentioned alkoxysilane and its hydrolysis-condensation product are main film-forming substances, which are mainly obtained by hydrolysis-condensation of alkoxysilane in an acidic alcohol-water solution. The alkoxysilane has the general formula:
R1 aSi(OR2)4-a(I)
wherein R is1Independently selected from substituted or unsubstituted monovalent hydrocarbon radicals, R2Is C1-C3 alkyl, and a is 0, 1, 2.
In the formula (I), R1Selected from substituted or unsubstituted monovalent hydrocarbon groups, such as alkyl groups: such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and octyl; cycloalkyl radicals such as cyclopentyl and cyclohexyl; alkenyl: such as vinyl and allyl; (meth) acryloyloxy, epoxy, mercapto and amino substituted hydrocarbon groups: such as gamma-methacryloxypropyl, gamma-glycidoxypropyl, 3, 4-epoxycyclohexylethyl, gamma-mercaptopropyl, and gamma-aminopropyl, and the like.
R2Selected from C1 to C3 alkyl groups, such as methyl, ethyl, propyl. From the viewpoint of the hydrolysis reaction rate, methyl and ethyl groups are preferred.
The alkoxysilane of the formula (I) (I-1) in which a ═ 0 is a tetrafunctional alkoxysilane: si (OR)2)4Examples of tetraalkoxysilane or its partial hydrolysis condensate satisfying the conditions include tetramethoxysilane and tetraethoxysilane.
The alkoxysilane of the formula (I) (I-2) in which a ═ 1 is a trifunctional alkoxysilane: r1Si(OR2) Examples of the trialkoxysilane and its partial hydrolytic condensate satisfying the conditions include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, γ -methacryloxypropyltrimethylsilane, γ -methacryloxypropyltriethoxysilane, γ -acryloxypropyltrimethoxysilane, γ -glycidoxypropyltrimethoxysilane, γ -glycidoxypropyltriethoxysilane, γ -aminopropyltrimethoxysilane, γ -aminopropyltriethoxysilane and the like.
The alkoxysilane of the formula (I) (I-3) in which a ═ 2 is a difunctional alkoxysilane: (R)1)2Si(OR2)2，R1The dialkoxysilanes and partial hydrolytic condensates which may be the same or different, satisfy the conditions include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, diethyldimethoxysilane, methylpropaneMethyldimethoxysilane, methylpropyldiethoxysilane, diisopropyldimethoxysilane, vinylmethyldimethoxysilane, γ -glycidoxypropylmethyldimethoxysilane, γ -glycidoxypropylmethyldiethoxysilane, γ -methacryloxypropylmethyldimethoxysilane, γ -methacryloxypropylmethyldiethoxysilane, γ -mercaptopropylmethyldimethoxysilane, γ -aminopropylmethyldiethoxysilane and the like.
The alkoxysilane and its hydrolysis condensate may be prepared from a mixture of the above-mentioned components (I-1), (I-2) and (I-3) in any desired ratio. Specifically, the components (I-1), (I-2) and (I-3) are first (co) hydrolyzed with water at a pH of from 2 to 6. To adjust to the desired pH range and promote hydrolysis, hydrolysis catalysts organic or inorganic acids such as hydrochloric acid, nitric acid, acetic acid, propionic acid, oxalic acid, maleic acid, benzoic acid, malonic acid, glutaric acid, glycolic acid, p-toluenesulfonic acid and the like can be used. For hydrolysis, the amount of water used is based on the water and the hydrolyzable groups of the Siloxane (SiOR) in the composition2) The molar ratio of (A) to (B) is determined, the amount of water added being the ratio of hydroxyl groups to Siloxane (SiOR)2) The molar ratio of (A) to (B) is preferably 1 to 2: 1.
Examples of the second solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, ethylene glycol and the like; ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, and propylene glycol monomethyl ether; and esters such as ethyl acetate, propyl acetate, butyl acetate, and the like. These solvents may be used alone or in combination of two or more. The solvent is used in an amount such that the solid concentration of the antireflective coating solution composition is 2 to 5%, preferably 3 to 4.5%.
The auxiliary agent is one or more than two of a flatting agent, a defoaming agent and a wetting agent, and the addition amount of the auxiliary agent is 0.01-0.1% of the total liquid amount.
The preparation method of the antireflection film solution with polyurethane as the pore-forming agent comprises the following steps:
(1) adding alkoxy silane, deionized water and a hydrolysis catalyst into a reactor, and carrying out hydrolysis reaction for 1-5 hours at a certain temperature;
(2) and adding the polyurethane emulsion, a second solvent and an auxiliary agent into the hydrolyzed alkoxy silane solution, and uniformly stirring to obtain the antireflection solution containing polyurethane.
The specific scheme is as follows:
the polyurethane emulsion is characterized in that the particle size of polyurethane in the polyurethane emulsion is 20-150 nm, and the polyurethane emulsion is prepared from the following raw materials: the preparation method comprises the following steps of (1) polyol, isocyanate, a catalyst, a chain extender, a first solvent, a neutralizer and deionized water;
wherein the polyol has the chemical formula of HO-R' (OH)xX is 1 or 2, R' is long-chain polyester, polyether, micromolecular alkyl or polybutadiene;
the chemical formula of the isocyanate is OCN-RNCO, wherein R represents an aromatic group or an alkyl group.
Further, in the polyurethane emulsion, the particle size range of polyurethane is 50-120 nm;
optionally, the polyol is polyester polyol or polyether polyol with the molecular weight of 500-6000, the polyester polyol or polyether polyol is trifunctional polyester polyol or polyether polyol, or a mixture of the trifunctional polyester polyol or polyether polyol and polyester polyol or polyether polyol with the number of functional groups being more than or equal to 2;
optionally, the isocyanate is one or a combination of isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), trimethyl hexamethylene diisocyanate (TMDI), dicyclohexylmethane diisocyanate (HMDI), Xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), methylstyrene isocyanate (TMI), hexahydrotoluene diisocyanate (HTDI);
optionally, the catalyst is at least one of tin octoate, dibutyltin diacetate, dibutyltin dilaurate and diethyltin dilaurate;
optionally, the chain extender is at least one of diethylene glycol, trihydroxy methyl propane, dihydroxy half ester, ethylene diamino sodium ethanesulfonate, diethylenetriamine, dimethylol propionic acid, dimethylol butyric acid, methyl diethanol amine, isophorone diamine and the combination thereof;
optionally, the first solvent is at least one of ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, methyl isobutyl ketone, methyl amyl ketone, cyclohexane, diacetone alcohol, acetone, N-methyl pyrrolidone, butanone, ethylene glycol methyl ether, propylene glycol butyl ether and N, N-dimethylformamide;
optionally, the neutralizing agent is triethylamine, ammonia water, sodium hydroxide, acetic acid, CH3I or epichlorohydrin.
Further, the molar amount of hydroxyl groups (-OH) in the polyol: molar amount of isocyanate group (-NCO) in the isocyanate: the molar weight (-OH) of hydroxyl groups in the chain extender is 0.5-2: 2-20: 5-10;
optionally, the molar ratio of the chain extender to the neutralizer is 1: 0.5-1;
optionally, the mass of the catalyst is 0.01-0.06% of the total weight of the isocyanate and the polyol;
optionally, the mass of the first solvent accounts for 7-11% of the total weight of the polyurethane emulsion;
optionally, the mass of the deionized water accounts for 65-81% of the total weight of the polyurethane emulsion.
The invention also provides a preparation method of the polyurethane emulsion, which comprises the following steps:
step 1: adding the polyol, the isocyanate and the catalyst which are subjected to vacuum pumping and water removal into a reactor, and stirring and reacting for 2-6 hours at 50-70 ℃;
step 2: uniformly mixing the chain extender and the first solvent, adding the mixture into the reaction system in the step 1, and continuously reacting for 2-6 hours;
and step 3: adding a neutralizer into the solution obtained in the step 2, and uniformly stirring;
and 4, step 4: and (3) pouring deionized water into the solution obtained in the step (3), and stirring and emulsifying to form the polyurethane emulsion.
The invention also protects the application of the polyurethane emulsion as a pore-forming agent.
The invention also providesThe anti-reflection coating liquid is prepared from the following raw materials: the catalyst comprises alkoxysilane, deionized water, a hydrolysis catalyst, a pore-forming agent, a second solvent and an auxiliary agent, wherein the alkoxysilane has a chemical formula of R1 aSi(OR2)4-aWherein R is1Independently is a monovalent hydrocarbon group, R2Is alkyl with 1-3 carbon atoms, a is 0, 1 or 2; the pore-forming agent is the polyurethane emulsion.
Further, the alkoxysilane R1 aSi(OR2)4-aIn, R1Is any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, cycloalkyl, alkenyl, (methyl) acryloyloxy or epoxy or mercapto or amino substituted hydrocarbyl;
optionally, the hydrolysis catalyst is an organic acid or an inorganic acid;
optionally, the second solvent is any one of alcohol, ether or ester;
optionally, the auxiliary agent is one or more of a leveling agent, a defoaming agent and a wetting agent.
Further, hydroxyl groups in the deionized water and siloxane groups (SiOR) in the alkoxysilane2) The molar ratio of (A) to (B) is 1-2: 1;
optionally, the amount of the pore-forming agent is 10.71-25.93% of the total solid mass;
optionally, the addition amount of the auxiliary agent is 0.01-0.1% of the total mass of the liquid;
optionally, the addition amount of the second solvent is calculated according to the solid mass concentration of the antireflection coating liquid being 2-5%.
The invention also provides a preparation method of the antireflection coating liquid, which comprises the following steps: adding alkoxy silane, deionized water and a hydrolysis catalyst into a reactor, and carrying out hydrolysis reaction for 1-5 hours; and then adding a pore-forming agent, a second solvent and an auxiliary agent into the hydrolyzed alkoxy silane solution, and uniformly stirring to obtain the antireflection coating liquid.
The invention also provides solar photovoltaic glass which comprises photovoltaic glass and an antireflection film covered on the surface of the photovoltaic glass, wherein the antireflection film is prepared by coating the antireflection coating liquid on the surface of the photovoltaic glass, and curing and toughening the antireflection film.
Has the advantages that:
the polyurethane emulsion disclosed by the invention is nano-scale, has good compatibility with an anti-reflection film liquid as a pore-forming agent, and can be uniformly dispersed in the anti-reflection film coating liquid. The nanoscale polyurethane in the polyurethane emulsion forms a closed cell structure in the antireflection film, as shown in the cross-sectional SEM image of the antireflection film in figure 3.
The antireflection coating formed on the surface of the solar photovoltaic glass by the antireflection coating liquid has high light transmittance and good wear resistance, forms a closed pore structure, can isolate moisture and pollutants in the air, and has excellent weather resistance.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1 is a graph showing the thermogravimetric decomposition of a product provided in example 1 of the present invention;
FIG. 2 is a graph showing the thermogravimetric decomposition of a product according to comparative example 1 of the present invention;
FIG. 3 is an SEM image of a film provided by an embodiment of the invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
The test methods used below included:
1. the method for testing the particle size of the polyurethane emulsion comprises the following steps:
the particle size was measured using a nanometer laser particle sizer (pearl-sea physical optical instruments ltd, Nanolink S900).
2. The method for testing the residual rate of the polyurethane emulsion comprises the following steps:
the thermal decomposition residual rate of the polyurethane emulsion is tested by using a Mettlerlitosan TGA/SDTA8510 type thermogravimetric synchronous thermal analyzer, and the residual rate is determined according to
Figure BDA0002470691140000111
And (4) formula calculation. (the heating rate is 3 ℃/min, the air flow rate is 20ml/min, and the temperature of the thermal analyzer is calibrated by adopting standard metals In and Al.)
3. The performance test method of the antireflection coating comprises the following steps:
the antireflection coating solution is coated on photovoltaic glass with the thickness of 3.2mm in a rolling way, after the photovoltaic glass is solidified at the temperature of 200 ℃, the photovoltaic glass is tempered for 2min at the temperature of 700 +/-20 ℃, and then the performance of the antireflection coating is tested according to the following method.
(1) The light transmittance is improved by a gain evaluation method, the light transmittance is measured by using a Fimea sure2100 of an air floatation table type spectral transmittance measurement system of Beijing Ohbotte technology, Inc., the gain is △ T (after tau is coated and before tau is coated, wherein tau is the effective transmittance of the sunlight of the photovoltaic glass.
The light transmittance and the light transmittance in the embodiments are average values of 380-1100 nm sunlight effective transmittance.
(2) The wear resistance test method comprises the following steps: reference JC/T2170-2013(2017)/6.7 standard.
(3) The hardness test method comprises the following steps: refer to GB/T6739-2006 standard.
(4) The weather resistance test method comprises the following steps: referring to JC/T2170-2013(2017) standard, the weather resistance involved comprises acid resistance, neutral salt spray resistance, resistance to humidity and freezing, super ultraviolet test and resistance to humidity and heat test.
Example 1
The polyurethane emulsion was prepared by the following steps:
1) 89.47g of PPG6000(2 functional group) (Dow chemical, hydroxyl content 0.03mol), 33.6g of isophorone diisocyanate (Van. Waals chemical, NCO content 0.3mol) and 0.020g of dibutyltin dilaurate as a catalyst were added to a reactor, and mixed and stirred at 50 ℃ for 2 hours.
2) 18.52g of chain extender 2, 2-dimethylolbutanoic acid (hydroxyl content 0.25mol) was dissolved in 92.83g of solvent N-methylpyrrolidone, and then slowly added to the above solution, and the reaction was continued at a temperature of 50 ℃ for 2 hours.
3) 17.52g (25% concentration) of ammonia water serving as a neutralizing agent is added into the solution, and after the solution is uniformly stirred, the solution is added into 1074.14g of deionized water to be emulsified to obtain the nano polyurethane emulsion with the solid content of 12%.
The particle size was tested to be 100 nm. The thermal decomposition residue rate of the polyurethane emulsion is tested by adopting thermal weight loss analysis equipment, and the calculated residue rate is 0.008 percent.
Preparing an antireflection coating liquid, comprising the following steps:
1) 27g of tetraethoxysilane (Nanjing Needed new material technology Co., Ltd.), 50g of gamma-glycidoxypropyltrimethoxysilane (Nanjing Needed new material technology Co., Ltd.), 24.91g of deionized water and 1g of acetic acid are added into a reactor, and hydrolysis reaction is carried out for 2 hours at the temperature of 50 ℃;
2) 43.13g of the prepared polyurethane emulsion is added, 116.80g of ethylene glycol and 1.208g of a flatting agent (BYK 333), then 944.7g of isopropanol is added and stirred uniformly, and the solid content of the solution is adjusted to 4 percent, so that the antireflection coating liquid is obtained.
Example 2
The polyurethane emulsion was prepared by the following steps:
1) 14.83g of the polyether polyol PPG-600(2 functional group) (Dow chemical, hydroxyl content 0.05mol), 25.07g of diphenylmethane diisocyanate (Basff M20S, NCO content 0.2mol) and 0.024g of dibutyltin diacetate as a catalyst were charged into a reactor and mixed and stirred at 50 ℃ for 4 hours.
2) 55.56g of chain extender 2, 2-dimethylolbutyric acid (hydroxyl content 0.75mol) was dissolved in 78.51g of propylene glycol butyl ether as a solvent, and then slowly added to the above solution, and the reaction was continued at a temperature of 50 ℃ for 2 hours.
3) Adding 105.16g of ammonia water (with the concentration of 25%) into the solution, stirring uniformly, adding 593.21g of deionized water, and emulsifying to obtain the nano polyurethane emulsion with the solid content of 23%. The particle size was tested to be 50 nm. The thermal decomposition residue rate was measured by thermogravimetric analysis equipment and was 1.66%.
Preparing an antireflection coating liquid, comprising the following steps:
1) adding 35g of ethyl orthosilicate (Nanjing Needed new material technology Co., Ltd.), 45g of gamma-methacryloxypropyltrimethoxysilane (Nanjing Needed new material technology Co., Ltd.), 43.57g of deionized water and 2g of hydrochloric acid into a reactor, and carrying out hydrolysis reaction at 70 ℃ for 5 hours;
2) 42.58g of the prepared polyurethane emulsion is added, then 150g of ethylene glycol and 1.309g of a flatting agent (Tego 270) are added, 991.19g of ethanol is added and stirred uniformly, and the solid content of the solution is adjusted to 4% so as to obtain the antireflection coating liquid.
Example 3
1) 124.12g of polyether polyol PPG-2000(2 functional groups) (Dow chemical, hydroxyl content 0.125mol), 428.57g of hexamethylene diisocyanate based polyisocyanate (Wanhua chemical HT-90B, NCO content 2mol) and 0.1934g of catalyst tin octoate are added into a reactor and mixed and stirred for 2 hours at 50 ℃.
2) 37.04g of chain extender 2, 2-dimethylolbutyric acid (hydroxyl content: 0.5mol) was dissolved in 377.09g of ethyl acetate solvent, and then slowly added to the above solution, and the reaction was continued at 50 ℃ for 2 hours.
3) 10g of neutralizing agent sodium hydroxide is added into the solution, stirred evenly and then added into 2452.12g of deionized water for emulsification, so as to obtain the nano polyurethane emulsion with the solid content of 17.5 percent.
The particle size was tested to be 80 nm. And testing the thermal decomposition residual rate by adopting thermal weight loss analysis equipment, wherein the residual rate is 3.8013%.
Preparing an antireflection coating liquid, comprising the following steps:
1) adding 20g of methyltrimethoxysilane (Nanjing Needt new material Co., Ltd.), 50g of tetraethoxysilane (Nanjing Needt new material Co., Ltd.), 37.8g of deionized water and 1g of nitric acid into a reactor, and carrying out hydrolysis reaction for 2 hours at the temperature of 50 ℃;
2) adding 24.27g of the prepared polyurethane emulsion, then adding 100g of propylene glycol monomethyl ether and 0.713g of a flatting agent (BYK 346), then adding 479.86g of n-butyl alcohol, uniformly stirring, and adjusting the solid content of the solution to 4% so as to obtain the antireflection coating liquid.
Example 4
The polyurethane emulsion was prepared by the following steps:
1) 80.11g of polyether polyol PPG-330N (3 functional groups) (Shanghai Bieyu chemical Co., Ltd., hydroxyl content 0.05mol), 25.07g of diphenylmethane diisocyanate (basf M20S, NCO content 0.2mol) and 0.0105g of dibutyltin diacetate as a catalyst were added to a reactor, and the mixture was mixed and stirred at 60 ℃ for 3 hours.
2) 37.04g of chain extender 2, 2-dimethylolbutyric acid (hydroxyl content 0.5mol) was dissolved in 97.77g of solvent butyl acetate, and then slowly added to the above solution, and the reaction was continued at 60 ℃ for 3 hours.
3) Adding 25.30g of neutralizing agent triethylamine into the solution, stirring uniformly, adding the solution into 1131.30g of deionized water, and emulsifying to obtain the nano polyurethane emulsion with the solid content of 12%.
The particle size was tested to be 80 nm. The thermal weight loss residual rate is tested by adopting thermal weight loss analysis equipment, and the residual rate is 1.535%.
Preparing an antireflection coating liquid, comprising the following steps:
1) adding 45g of dimethyldiethoxysilane (Nanjing Needt new material Co., Ltd.), 20g of vinyl triethoxysilane (Nanjing Needt new material Co., Ltd.), 16.60g of deionized water and 1g of hydrochloric acid into a reactor, and carrying out hydrolysis reaction for 2 hours at 50 ℃;
2) 30.85g of the prepared polyurethane emulsion is added, 172.77g of propylene glycol monobutyl ether and 0.1152g of a flatting agent (BYK 346) are added, 865.55g of ethylene glycol is added and stirred uniformly, and the solid content of the solution is adjusted to 3 percent, so that the antireflection coating liquid is obtained.
Example 5
The polyurethane emulsion was prepared by the following steps:
1) 18.40g of polyester polyol PC L305 (3-functional group) (0.1 mol in hydroxyl group content, manufactured by Nippon Daiishi chemical Co., Ltd.), 24.93g of polyester polyol PCD L500 (2-functional group) (0.1 mol in hydroxyl group content, manufactured by Asahi Kasei chemical Co., Ltd.), 116.67g of toluene diisocyanate (basf, 0.5mol in NCO content) and 0.096g of tin octylate as a catalyst were charged into a reactor, and mixed and stirred at 70 ℃ for 4 hours.
2) 67.06g of the chain extender 2, 2-dimethylolpropionic acid (hydroxyl content 1mol) were dissolved in 226.56g of acetone as a solvent, and then slowly added to the above solution, and the reaction was continued at 70 ℃ for 4 hours.
3) And adding 20g of neutralizing agent sodium hydroxide into the solution, stirring uniformly, adding the solution into 1585.91g of deionized water, and emulsifying to obtain the nano polyurethane emulsion with the solid content of 12%.
The particle size was tested to be 120 nm. And (3) testing the thermal weight loss residual rate by adopting thermal weight loss analysis equipment, wherein the residual rate is 0.1008%.
Preparing an antireflection coating liquid, comprising the following steps:
1) adding 35g of gamma-glycidoxypropylmethyldimethoxysilane (Nanjing Yopu chemical Co., Ltd.), 20g of gamma-methacryloxypropyltrimethoxysilane (Nanjing Needt new material Co., Ltd.), 20.16g of deionized water and 3g of acetic acid into a reactor, and carrying out hydrolysis reaction for 2 hours at 50 ℃;
2) 122.86g of the prepared polyurethane emulsion is added, 67.39g of ethylene glycol butyl ether and 1.137g of a flatting agent (BYK 346) are added, 868.85g of ethylene glycol is added and stirred uniformly, and the solid content of the solution is adjusted to 5 percent, so that the antireflection coating liquid is obtained.
Example 6
The polyurethane emulsion was prepared by the following steps:
1) 18.40g of polyester polyol PC L305 (3 functional group) (0.1 mol in hydroxyl group content, manufactured by JASCO XO CHEMICAL CO., LTD.), 64.29g of hexamethylene diisocyanate (Basf, NCO content 0.3mol) and 0.025g of dibutyltin dilaurate as a catalyst were charged in a reactor, and mixed and stirred at 65 ℃ for 2 hours.
2) 46.94g of the chain extender 2, 2-dimethylolpropionic acid (hydroxyl content 0.7mol) were dissolved in 173.47g of propylene glycol monomethyl ether acetate as solvent and then slowly added to the above solution and the reaction was continued at a temperature of 65 ℃ for 2 hours.
3) 78.512g (25% concentration) of neutralizing agent ammonia water is added into the solution, stirred evenly and then added into 1353.093g of deionized water for emulsification, and the nano polyurethane emulsion with the solid content of 12% is obtained.
The particle size was tested to be 150 nm. And (3) testing the thermal weight loss residual rate by adopting thermal weight loss analysis equipment, wherein the residual rate is 2.235%.
Preparing an antireflection coating liquid, comprising the following steps:
1)50g of tetraethoxysilane (Nanjing Ender new materials Co., Ltd.), 25g of dimethyldiethoxysilane (Nanjing Ender new materials Co., Ltd.), 35.03g of deionized water and 1g of hydrochloric acid are added into a reactor, and hydrolysis reaction is carried out for 2 hours at the temperature of 50 ℃;
2) adding 44.88g of the prepared polyurethane emulsion, then adding 134.65g of n-butyl alcohol, 0.808g of a flatting agent (BYK 333), then adding 1325.24g of isopropanol, uniformly stirring, and adjusting the solid content of the solution to 2% so as to obtain the antireflection coating liquid.
Comparative example 1
An antireflection coating solution was prepared in the same manner as in example 1, except that a commercially available PU77 polyurethane emulsion (Guangzhou Huiyu chemical Co., Ltd.) having a particle size of 30nm was used. The thermal weight loss curve is shown in figure 2, and the thermal weight loss residual rate is 12.22%.
The same solid content was diluted instead of the polyurethane emulsion in example 1, and the other conditions were the same as in example 1.
Comparative example 2
The polyurethane emulsion was prepared by the following steps:
1) 208.77g of polyether polyol PPG-6000(2 functional group) (Dow chemical, hydroxyl content 0.07mol), 60.66g of toluene diisocyanate (Basf, NCO content 0.26mol) and 0.0808g of catalyst tin octoate were added to the reactor, and mixed and stirred at 50 ℃ for 2 hours.
2) 1.341g of chain extender 2, 2-dimethylolpropionic acid (hydroxyl content 0.02mol) was dissolved in 158.33g of butyl acetate as a solvent, and then slowly added to the above solution, and the reaction was continued at a temperature of 65 ℃ for 2 hours.
3) 0.56g of neutralizing agent sodium hydroxide is added into the solution, evenly stirred and then added into 1832.10g of deionized water for emulsification, thus obtaining the nano polyurethane emulsion with 12 percent of solid content.
The particle size was tested to be 200 nm. The thermal weight loss residual rate is tested by adopting thermal weight loss analysis equipment, and the residual rate is 15.21%.
Preparing an antireflection coating liquid, comprising the following steps:
1) 27g of tetraethoxysilane (Nanjing Needed new material technology Co., Ltd.), 50g of gamma-glycidoxypropyltrimethoxysilane (Nanjing Needed new material technology Co., Ltd.), 26.5g of deionized water and 1g of acetic acid are added into a reactor, and hydrolysis reaction is carried out for 2 hours at the temperature of 50 ℃;
2) 43.13g of the prepared polyurethane emulsion is added, 116.80g of ethylene glycol and 1.208g of a flatting agent (BYK 333), then 944.694g of isopropanol is added and stirred uniformly, and the solid content of the solution is adjusted to 4 percent, so that the antireflection coating liquid is obtained.
Performance detection
An antireflection coating was obtained on photovoltaic glass using the antireflection coating solutions prepared in examples and comparative examples 1 and 2.
The performance of the antireflective coating was tested and the results are shown in table 1.
Table 1 table of performance test results
Figure BDA0002470691140000191
As can be seen from Table 1, the antireflection coating solution prepared by the invention has high wear resistance and excellent weather resistance.
The result of SEM examination of the antireflection film prepared in example 1 is shown in fig. 3, and it can be seen from fig. 3 that the antireflection film has a closed cell structure, no gaps are formed by stacking between particles, and the surface of the coating is smooth.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. A polyurethane emulsion characterized by: in the polyurethane emulsion, the particle size range of polyurethane is 20-150 nm, and the polyurethane emulsion is prepared from the following raw materials: the preparation method comprises the following steps of (1) polyol, isocyanate, a catalyst, a chain extender, a first solvent, a neutralizer and deionized water;
wherein the polyol has the chemical formula of HO-R' (OH)xX is 1 or 2, R' is long-chain polyester, polyether, micromolecular alkyl or polybutadiene;
the chemical formula of the isocyanate is OCN-RNCO, wherein R represents an aromatic group or an alkyl group.
2. The polyurethane emulsion of claim 1, wherein: in the polyurethane emulsion, the particle size range of polyurethane is 50-120 nm;
optionally, the polyol is polyester polyol or polyether polyol with the molecular weight of 500-6000, the polyester polyol or polyether polyol is trifunctional polyester polyol or polyether polyol, or a mixture of the trifunctional polyester polyol or polyether polyol and polyester polyol or polyether polyol with the number of functional groups being more than or equal to 2;
optionally, the isocyanate is one or a combination of isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), trimethyl hexamethylene diisocyanate (TMDI), dicyclohexylmethane diisocyanate (HMDI), Xylylene Diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), methylstyrene isocyanate (TMI), hexahydrotoluene diisocyanate (HTDI);
optionally, the catalyst is at least one of tin octoate, dibutyltin diacetate, dibutyltin dilaurate and diethyltin dilaurate;
optionally, the chain extender is at least one of diethylene glycol, trihydroxy methyl propane, dihydroxy half ester, ethylene diamino sodium ethanesulfonate, diethylenetriamine, dimethylol propionic acid, dimethylol butyric acid, methyl diethanol amine, isophorone diamine and the combination thereof;
optionally, the first solvent is at least one of ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, methyl isobutyl ketone, methyl amyl ketone, cyclohexane, diacetone alcohol, acetone, N-methyl pyrrolidone, butanone, ethylene glycol methyl ether, propylene glycol butyl ether and N, N-dimethylformamide;
optionally, the neutralizing agent is triethylamine, ammonia water, sodium hydroxide, acetic acid, CH3I or epichlorohydrin.
3. The polyurethane emulsion according to claim 1 or 2, characterized in that: molar amount of hydroxyl groups (-OH) in the polyol: molar amount of isocyanate group (-NCO) in the isocyanate: the molar weight (-OH) of hydroxyl groups in the chain extender is 0.5-2: 2-20: 5-10;
optionally, the molar ratio of the chain extender to the neutralizer is 1: 0.5-1;
optionally, the mass of the catalyst is 0.01-0.06% of the total weight of the isocyanate and the polyol;
optionally, the mass of the first solvent accounts for 7-11% of the total weight of the polyurethane emulsion;
optionally, the mass of the deionized water accounts for 65-81% of the total weight of the polyurethane emulsion.
4. A method for preparing the polyurethane emulsion according to any one of claims 1 to 3, characterized in that: the method comprises the following steps:
step 1: adding the polyol, the isocyanate and the catalyst which are subjected to vacuum pumping and water removal into a reactor, and stirring and reacting for 2-6 hours at 50-70 ℃;
step 2: uniformly mixing the chain extender and the first solvent, adding the mixture into the reaction system in the step 1, and continuously reacting for 2-6 hours;
and step 3: adding a neutralizer into the solution obtained in the step 2, and uniformly stirring;
and 4, step 4: and (3) pouring deionized water into the solution obtained in the step (3), and stirring and emulsifying to form the polyurethane emulsion.
5. Use of a polyurethane emulsion according to any one of claims 1 to 3, characterized in that: used as a pore former.
6. An antireflection coating liquid is characterized in that: the antireflection coating liquid is prepared from the following raw materials: alkoxy silane, deionized water, a hydrolysis catalyst, a pore-forming agent, a second solvent and an auxiliary agent; wherein the alkoxysilane has the formula R1 aSi(OR2)4-aWherein R is1Independently is a monovalent hydrocarbon group, R2Is alkyl with 1-3 carbon atoms, a is 0, 1 or 2; the pore-forming agent is the polyurethane emulsion of any one of claims 1 to 3.
7. The anti-reflective coating solution of claim 6, wherein: the alkoxysilane R1 aSi(OR2)4-aIn, R1Is methyl, ethyl, propyl, butyl, pentyl,any one of hexyl, heptyl, octyl, cycloalkyl, alkenyl, (methyl) acryloyloxy or epoxy or mercapto or amino substituted hydrocarbyl;
optionally, the hydrolysis catalyst is an organic acid or an inorganic acid;
optionally, the second solvent is any one of alcohol, ether or ester;
optionally, the auxiliary agent is one or more of a leveling agent, a defoaming agent and a wetting agent.
8. The antireflective coating liquid according to claim 6 or 7, wherein: siloxane groups (SiOR) in the deionized water and the alkoxysilane2) The molar ratio of (A) to (B) is 1-2: 1;
optionally, the amount of the pore-forming agent is 10.71-25.93% of the total solid mass;
optionally, the addition amount of the auxiliary agent is 0.01-0.1% of the total mass of the liquid;
optionally, the addition amount of the second solvent is calculated according to the solid mass concentration of the antireflection coating liquid being 2-5%.
9. A method for preparing the anti-reflection coating liquid of any one of claims 6 to 8, which is characterized in that: the method comprises the following steps: adding alkoxy silane, deionized water and a hydrolysis catalyst into a reactor, and carrying out hydrolysis reaction for 1-5 hours; and then adding a pore-forming agent, a second solvent and an auxiliary agent into the hydrolyzed alkoxy silane solution, and uniformly stirring to obtain the antireflection coating liquid.
10. The solar photovoltaic glass comprises photovoltaic glass and an antireflection film covering the surface of the photovoltaic glass, and is characterized in that: the antireflection film is prepared by coating the antireflection coating liquid of any one of claims 6 to 8 on the surface of the photovoltaic glass, and curing and toughening the coating liquid.
CN202010347526.2A 2020-04-28 2020-04-28 Polyurethane emulsion and anti-reflection coating liquid prepared from same Active CN111410730B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010347526.2A CN111410730B (en) 2020-04-28 2020-04-28 Polyurethane emulsion and anti-reflection coating liquid prepared from same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010347526.2A CN111410730B (en) 2020-04-28 2020-04-28 Polyurethane emulsion and anti-reflection coating liquid prepared from same

Publications (2)

Publication Number Publication Date
CN111410730A true CN111410730A (en) 2020-07-14
CN111410730B CN111410730B (en) 2022-03-29

Family

ID=71488502

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010347526.2A Active CN111410730B (en) 2020-04-28 2020-04-28 Polyurethane emulsion and anti-reflection coating liquid prepared from same

Country Status (1)

Country Link
CN (1) CN111410730B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112795299A (en) * 2020-12-30 2021-05-14 中建材（合肥）新能源有限公司 Antireflection coating liquid, preparation method thereof and solar cell module
CN114621639A (en) * 2022-03-11 2022-06-14 东莞南玻太阳能玻璃有限公司 Coating liquid capable of reducing chromatic aberration, preparation method and application of coating liquid in photovoltaic glass
CN115140947A (en) * 2022-09-05 2022-10-04 鼎钰玻璃(扬州)有限公司 Coated photovoltaic glass and preparation method thereof
CN115584203A (en) * 2022-10-20 2023-01-10 上海达巧康新材料科技有限公司 Aqueous high-transmittance antireflection coating liquid for photovoltaic glass and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10147749A (en) * 1996-11-20 1998-06-02 Jsr Corp Composition for forming film
US20070020557A1 (en) * 2005-07-19 2007-01-25 Huirong Yao New organic bottom antireflective polymer compositions
CN102924990A (en) * 2012-10-16 2013-02-13 上海瑞冕新材料科技有限公司 Transparent antireflection coating liquid and preparation method and application thereof
CN107082868A (en) * 2017-04-26 2017-08-22 运研材料科技（上海）有限公司 A kind of nuclear shell structure nano hybrid particle, its preparation method and its anti-reflective coating compositions
CN107163207A (en) * 2017-06-08 2017-09-15 华南理工大学 A kind of heat-resisting high solid content aqueous polyurethane emulsion and its preparation method and application
CN107286781A (en) * 2017-08-01 2017-10-24 苏州朗迪纳米科技有限公司 The preparation method and application process of a kind of aqueous antireflective coating liquid of hole-closing structure

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10147749A (en) * 1996-11-20 1998-06-02 Jsr Corp Composition for forming film
US20070020557A1 (en) * 2005-07-19 2007-01-25 Huirong Yao New organic bottom antireflective polymer compositions
CN102924990A (en) * 2012-10-16 2013-02-13 上海瑞冕新材料科技有限公司 Transparent antireflection coating liquid and preparation method and application thereof
CN107082868A (en) * 2017-04-26 2017-08-22 运研材料科技（上海）有限公司 A kind of nuclear shell structure nano hybrid particle, its preparation method and its anti-reflective coating compositions
CN107163207A (en) * 2017-06-08 2017-09-15 华南理工大学 A kind of heat-resisting high solid content aqueous polyurethane emulsion and its preparation method and application
CN107286781A (en) * 2017-08-01 2017-10-24 苏州朗迪纳米科技有限公司 The preparation method and application process of a kind of aqueous antireflective coating liquid of hole-closing structure

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112795299A (en) * 2020-12-30 2021-05-14 中建材（合肥）新能源有限公司 Antireflection coating liquid, preparation method thereof and solar cell module
CN114621639A (en) * 2022-03-11 2022-06-14 东莞南玻太阳能玻璃有限公司 Coating liquid capable of reducing chromatic aberration, preparation method and application of coating liquid in photovoltaic glass
CN115140947A (en) * 2022-09-05 2022-10-04 鼎钰玻璃(扬州)有限公司 Coated photovoltaic glass and preparation method thereof
CN115140947B (en) * 2022-09-05 2022-11-08 鼎钰玻璃(扬州)有限公司 Coated photovoltaic glass and preparation method thereof
CN115584203A (en) * 2022-10-20 2023-01-10 上海达巧康新材料科技有限公司 Aqueous high-transmittance antireflection coating liquid for photovoltaic glass and preparation method thereof

Also Published As

Publication number Publication date
CN111410730B (en) 2022-03-29

Similar Documents

Publication Publication Date Title
CN111410730B (en) Polyurethane emulsion and anti-reflection coating liquid prepared from same
Cheng et al. Design and synthesis of novel aminosiloxane crosslinked linseed oil-based waterborne polyurethane composites and its physicochemical properties
CN111995943B (en) Organic silicon modified waterborne polyurethane waterproof coating and preparation method thereof
CN101497687B (en) Anti-scratch aqueous polyurethane disperse system with high hygrometric state adhesive force and use thereof
CN109135530B (en) DAPBI modified waterborne polyurethane coating and preparation method thereof
CN111423775B (en) Single-component water-based finishing varnish and preparation method thereof
US20120219802A1 (en) Copolycarbonates, Their Derivatives and the Use Thereof in Silicone Hardcoat Compositions
EP0924232B1 (en) Aqueous dispersions of polyurethane/ureas containing alkoxysilane groups and colloidal silica
KR102324995B1 (en) Primer composition having excellent water proof and adhesion property and water-proof construction method for concrete constructions
CN113831829B (en) Polyurethane anti-icing paint and preparation method and application thereof
EP3812411B1 (en) Polyisocyanate composition, coating composition and coated substrate
CN108129974B (en) Polysiloxane finish paint for rolling stock and preparation method thereof
CN112358593B (en) Two-component waterborne polyurethane and preparation method and application thereof
CN111647306B (en) In situ generation of organized SiO 2 Environment-friendly enhanced waterborne polyurethane ink and preparation method thereof
CN104844778B (en) The dual modified polyester-type aqueous polyurethane dispersion of a kind of organosilicon and four-needle-like zinc oxide and preparation and application
JP4099726B2 (en) Water-based coating composition, organic-inorganic composite coating film and method for producing the same
CN113278128B (en) Waterborne polyurethane/polyurea with fluorine-containing side chain and preparation method thereof
JP2010138274A (en) Aqueous coating agent
CN108499826B (en) Spraying and curing process of water-based UV (ultraviolet) coating
CN116463056B (en) Composite varnish with self-cleaning function and preparation method thereof
CN114231155B (en) Hydroxyalkyl aqueous organosilicon modified polyurethane aqueous dispersion composition and preparation method thereof
CN117701065B (en) Water-based polyurethane ink binder and preparation method and application thereof
CN116769396A (en) Super-hydrophobic wind power blade surface protective coating and preparation method thereof
CN113999599B (en) Waterborne polyurethane-silica sol antifogging coating and preparation method and application thereof
TW202300547A (en) Method for producing liquid carbamate compound using heat-resistant, low-hygroscopic reactive aminosilane to react with liquid aliphatic urethane prepolymer to form a copolymer composition and improve the temperature and humidity resistance of polyurethane materials

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant