CN114773943A - Coating film forming material resistant to bowl washing machine and preparation method and application thereof - Google Patents
Coating film forming material resistant to bowl washing machine and preparation method and application thereof Download PDFInfo
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- CN114773943A CN114773943A CN202210321472.1A CN202210321472A CN114773943A CN 114773943 A CN114773943 A CN 114773943A CN 202210321472 A CN202210321472 A CN 202210321472A CN 114773943 A CN114773943 A CN 114773943A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a coating film forming material for a washable bowl machine, which comprises the following components in parts by mass: 45-55 parts of prepolymer, 0.5-2 parts of fluorine-containing acrylic monomer, 0.5-2 parts of epoxy group-containing acrylic monomer, 0.5-2 parts of tertiary carboxylic acid structure-containing monomer, 4-10 parts of hydroxyl group-containing acrylic monomer, 2-5 parts of carboxyl group-containing acrylic monomer, 15-20 parts of other acrylic monomers, 8-15 parts of butyl cellosolve and 2-5 parts of initiator; the prepolymer comprises the following components in parts by mass: 5-10 parts of nano silicon dioxide, 0.5-2 parts of nano titanium dioxide, 0.5-2 parts of functional monomer, 0.2-0.8 part of epoxy silane coupling agent, 0.5-2 parts of silicon-containing monomer, 2-8 parts of epoxy active diluent, 10-20 parts of bisphenol F type epoxy resin, 1-3 parts of furan resin, 20-25 parts of ethylene glycol butyl ether, 2-6 parts of n-butyl alcohol and 0.1-1 part of dispersing agent. The coating film forming material for the washable bowl machine provided by the invention can obviously improve the performance of the coating for the washable bowl machine. The invention also discloses a preparation method of the coating film-forming material for washing bowl machines and application of the coating film-forming material in water-based coatings.
Description
Technical Field
The invention relates to the technical field of water-based paint, in particular to a paint film forming matter for washing bowls and a preparation method and application thereof.
Background
In recent years, waterborne coatings are popular in the market because of environmental protection and safety due to the fact that the waterborne coatings do not contain toxic solvents such as benzene and the like and are not inflammable and explosive. When the existing water-based paint product is applied to glass ceramics and vessels thereof, the aim of decoration of the glass ceramics and the vessels thereof is more. However, for the export products, the water-based paint on the product not only needs to have a decorative effect, but also needs to meet certain functional requirements, such as: is not easy to fall off, and has the functions of acid and alkali resistance, baking resistance and the like. The products exported to foreign areas, especially to the European and American areas, are required to have the requirement of bowl washing resistance, namely the water-based paint coated on the daily utensils can be washed and baked for more than 100 times by the dish washing machine. However, the number of times of washing and baking the best water-based paint coated on the product in China through a dish-washing machine can only reach about 50 times, and the water-based paint can not meet the requirements of European and American areas on the water-based paint coated on the product, so that enterprises in the field in China are difficult to develop foreign markets, and the development of the enterprises is limited to a certain extent. At present, domestic daily utensils coated with water-based paint capable of being washed and baked for more than 200 times by a dishwasher only depend on import, but the purchase cost of imported products is higher, and the daily utensils influence the life of people to a certain extent.
In view of the above, it is necessary to provide a new coating film forming material for washing bowl machine to solve the above technical problems.
Disclosure of Invention
The invention aims to provide a coating film forming material for a washable bowl machine, which is applied to a water-based coating system, can obviously improve the adhesive force between a coating and a ceramic material, and obviously improve the performance of the coating for the washable bowl machine.
In order to solve the problems, the technical scheme of the invention is as follows:
the coating film forming material for the washable bowl machine comprises the following components in parts by weight:
45-55 parts of prepolymer, 0.5-2 parts of fluorine-containing acrylic monomer, 0.5-2 parts of epoxy group-containing acrylic monomer, 0.5-2 parts of tertiary carboxylic acid structure-containing monomer, 4-10 parts of hydroxyl group-containing acrylic monomer, 2-5 parts of carboxyl group-containing acrylic monomer, 15-20 parts of other acrylic monomers, 8-15 parts of butyl cellosolve and 2-5 parts of initiator;
the prepolymer comprises the following components in parts by mass:
5-10 parts of nano silicon dioxide, 0.5-2 parts of nano titanium dioxide, 0.5-2 parts of functional monomer, 0.2-0.8 part of epoxy silane coupling agent, 0.5-2 parts of silicon-containing monomer, 2-8 parts of epoxy active diluent, 10-20 parts of bisphenol F type epoxy resin, 1-3 parts of furan resin, 20-25 parts of ethylene glycol butyl ether, 2-6 parts of n-butyl alcohol and 0.1-1 part of dispersing agent.
Further, the fluorine-containing acrylic monomer is dodecafluoroheptyl methacrylate;
the hydroxyl-containing acrylic monomer is at least one of hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate;
the monomer containing the tertiary carbonic acid structure is at least one of tertiary carbonic acid glycidyl ester and tertiary carbonic acid ethylene ester;
the carboxyl-containing acrylic monomer is at least one of acrylic acid and methacrylic acid;
the other acrylic monomer is at least one of styrene, butyl (meth) acrylate, isobornyl (meth) acrylate, methyl (meth) acrylate, isooctyl (meth) acrylate and (meth) acrylamide;
the acrylic monomer containing epoxy groups is glycidyl methacrylate.
Further, the initiator is at least one of benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, di-tert-butyl peroxide, di-tert-amyl peroxide, cumyl peroxide, tert-butyl peroxy (2-ethylhexanoate), dicumyl peroxide, tert-butyl peroxy 3,5, 5-trimethylhexanoate and tert-butyl peroxy-2-ethylhexanoate.
Further, the functional monomer is zinc methacrylate;
the epoxy silane coupling agent is at least one of Dow Corning Z-6040, Nanjing eosin KH-560, Japan Xinyue KBM-403 and Zhejiang boiling point FD-560;
the silicon-containing monomer is at least one of vinyl trimethoxy silane and vinyl triethoxy silane;
the epoxy reactive diluent is an alkyl glycidyl ether type epoxy reactive diluent containing epoxy groups, double bonds and benzene rings. Further, the bisphenol F type epoxy resin has an epoxy equivalent of 150-200.
Further, the preparation method of the coating film-forming material for the washable bowl machine comprises the following steps:
step S1, preparing a prepolymer:
step S11, firstly, adding ethylene glycol monobutyl ether, n-butyl alcohol and a dispersant into an ultrasonic reactor in sequence, and then ultrasonically stirring for 5-15 min;
step S12, adding nano silicon dioxide, nano titanium dioxide and functional monomers, and ultrasonically stirring for 20-40min after the addition is finished;
step S13, adding epoxy silane coupling agent and silicon-containing monomer, and stirring for 5-15min with ultrasound after adding;
step S14, finally adding an epoxy active diluent, bisphenol F type epoxy resin and furan resin, and after the addition, ultrasonically stirring for 4-6 hours to obtain a prepolymer;
step S2, preparing a coating film-forming material by grafting, polymerizing and modifying the prepolymer:
step S21, adding a prepolymer into an ultrasonic reactor, and heating to 100-120 ℃ under the action of ultrasonic stirring;
step S22, uniformly dripping the fluorine-containing acrylic monomer, the epoxy group-containing acrylic monomer, the tertiary carbonic acid structure-containing monomer, the hydroxyl group-containing acrylic monomer, other acrylic monomers, a proper amount of ethylene glycol butyl ether and a proper amount of initiator into a reaction kettle after fully mixing and dissolving;
step S23, uniformly dripping carboxyl-containing acrylic acid monomer, hydroxyl-containing acrylic acid monomer, other acrylic acid monomers, a proper amount of ethylene glycol butyl ether and a proper amount of initiator into a reaction kettle after fully mixing and dissolving;
step S24, keeping the temperature for 0.5-2h, and dropwise adding the mixture into a reaction kettle after sufficiently mixing and dissolving a proper amount of initiator and a proper amount of ethylene glycol monobutyl ether;
step S25, preserving heat for 0.5-2h, and dropwise adding the mixture into a reaction kettle after fully mixing and dissolving the residual initiator and ethylene glycol butyl ether;
and step S26, preserving heat for 2-4h, and filtering to obtain the coating film-forming material for the dish washing machine.
Further, in step S22, the reactant is added dropwise for 1.5-2.5 h;
in the step S23, the reactant is dripped for 1.5 to 2.5 hours;
in step S24, the reactant is dripped for 5-15 min;
in step S25, the reactant is added dropwise for 5-15 min.
The invention also provides a preparation method of the coating film-forming material for the washable bowl machine, which comprises the following steps:
step S1, preparing a prepolymer:
step S11, firstly, adding ethylene glycol monobutyl ether, n-butanol and a dispersing agent into an ultrasonic reactor in sequence, and then carrying out ultrasonic stirring for 5-15 min;
step S12, adding nano silicon dioxide, nano titanium dioxide and functional monomers, and ultrasonically stirring for 20-40min after the addition;
step S13, adding epoxy silane coupling agent and silicon-containing monomer, and stirring for 5-15min with ultrasound after adding;
step S14, finally adding an epoxy active diluent, bisphenol F type epoxy resin and furan resin, and after the addition, ultrasonically stirring for 4-6 hours to obtain a prepolymer;
step S2, preparing a coating film-forming material by prepolymer grafting polymerization modification:
step S21, adding a prepolymer into an ultrasonic reactor, and heating to 100-120 ℃ under the action of ultrasonic stirring;
step S22, uniformly dripping the fluorine-containing acrylic monomer, the epoxy group-containing acrylic monomer, the tertiary carbonic acid structure-containing monomer, the hydroxyl group-containing acrylic monomer, other acrylic monomers, a proper amount of ethylene glycol butyl ether and a proper amount of initiator into a reaction kettle after fully mixing and dissolving;
step S23, uniformly dripping carboxyl-containing acrylic acid monomer, hydroxyl-containing acrylic acid monomer, other acrylic acid monomer, a proper amount of ethylene glycol monobutyl ether and a proper amount of initiator into a reaction kettle after fully mixing and dissolving;
step S24, keeping the temperature for 0.5-2h, and dropwise adding the mixture into a reaction kettle after sufficiently mixing and dissolving a proper amount of initiator and a proper amount of ethylene glycol monobutyl ether;
step S25, preserving heat for 0.5-2h, and dropwise adding the mixture into a reaction kettle after fully mixing and dissolving the residual initiator and ethylene glycol butyl ether;
and step S26, preserving heat for 2-4h, and filtering to obtain the coating film-forming material for the dish washing machine.
Further, in step S22, the reactant is added dropwise for 1.5-2.5 h;
in the step S23, the dropping time of the reactant is 1.5-2.5 h;
in step S24, the reactant is dripped for 5-15 min;
in step S25, the dropping time of the reactant is 5-15 min.
The invention also provides application of the coating film forming material of the washable bowl machine in water-based coatings.
Compared with the prior art, the coating film forming material for the washable bowl machine, and the preparation method and the application thereof provided by the invention have the beneficial effects that:
the invention provides a washable bowl machine coating film forming material, which adopts nano silicon dioxide and nano titanium dioxide as inorganic functional materials, adopts epoxy silane coupling agents, silicon-containing monomers and zinc methacrylate for modification, and introduces epoxy reactive diluents, low molecular weight bisphenol F epoxy resin and furan resin under the vibration and dispersion effects of ultrasonic waves to realize surface coating modification of nanoparticles and form a prepolymer with a core-shell structure; the prepolymer is grafted and modified by acrylic monomers, so that the weather resistance, corrosion resistance and baking resistance of the material are enhanced.
Secondly, aiming at the problem that secondary agglomeration is easy to occur to nano powder (silicon dioxide, titanium dioxide and the like), in the aspect of the preparation process, ultrasonic equipment is adopted from preparation of the prepolymer to subsequent polymerization and modification of the acrylic monomer, and the uniform stability of an inorganic/organic hybrid system of the coating film-forming material is realized through continuous ultrasonic dispersion in the whole process. In the acrylic monomer polymerization modification stage, two stages of special designs are also carried out on the aspect of the high molecular structure, namely the step S22 and the step S23, and the monomers in the step S22 mainly play a role in enhancing the functional indexes of a paint film such as bowl washing resistance, boiling resistance, wear resistance, salt mist resistance, acid resistance, alkali resistance and the like, and are properly polymerized at the inner position of the high molecular structure; the monomers in step S23 are mainly used to provide the film-forming material with good compatibility with aqueous coating systems, and also provide groups for toner compatibility, crosslinking reaction, etc., so that the film-forming material is polymerized properly at the outer position of the polymer structure.
The coating film forming material for the washable bowl machine is applied to a water-based coating system, can obviously improve the adhesive force between a coating and a ceramic material, and obviously improves the bowl machine washing resistance of the coating for more than or equal to 1000 times, the boiling resistance for more than or equal to 100 hours, the wear resistance (more than or equal to 1000 revolutions, GB/T1768-2SO4) The time is more than or equal to 200 hours, and the alkali resistance (10 percent NaOH) is more than or equal to 100 hours.
Detailed Description
The following description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
It should be noted that the description of the embodiments is provided to help understanding of the present invention, and is not intended to limit the present invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The coating film forming material for the washable bowl machine comprises the following components in parts by weight:
45-55 parts of prepolymer, 0.5-2 parts of fluorine-containing acrylic monomer, 0.5-2 parts of epoxy group-containing acrylic monomer, 0.5-2 parts of tertiary carboxylic acid structure-containing monomer, 4-10 parts of hydroxyl group-containing acrylic monomer, 2-5 parts of carboxyl group-containing acrylic monomer, 15-20 parts of other acrylic monomers, 8-15 parts of butyl cellosolve and 2-5 parts of initiator;
the prepolymer comprises the following components in parts by mass:
5-10 parts of nano silicon dioxide, 0.5-2 parts of nano titanium dioxide, 0.5-2 parts of functional monomer, 0.2-0.8 part of epoxy silane coupling agent, 0.5-2 parts of silicon-containing monomer, 2-8 parts of epoxy active diluent, 10-20 parts of bisphenol F type epoxy resin, 1-3 parts of furan resin, 20-25 parts of ethylene glycol butyl ether, 2-6 parts of n-butyl alcohol and 0.1-1 part of dispersing agent.
In the prepolymer, the particle size of the nano-silicon dioxide is less than or equal to 100nm, and the particle size of the nano-titanium dioxide is less than or equal to 10 nm; the functional monomer is zinc methacrylate; the main structure of the epoxy silane coupling agent contains silane and epoxy group, such as at least one of Dow Corning Z-6040, Nanjing eosin KH-560, Japan Xinyue KBM-403 or Zhejiang boiling point FD-560; the silicon-containing monomer is a silane monomer containing double bonds, such as at least one of vinyltrimethoxysilane and vinyltriethoxysilane; the epoxy reactive diluent is an alkyl glycidyl ether type epoxy reactive diluent containing epoxy groups, double bonds and benzene rings; the epoxy equivalent of the bisphenol F type epoxy resin is 150-200; the dispersant was BYK 192. Wherein the functional monomer improves the acid resistance, alkali resistance and salt resistance, and simultaneously contains double bonds which can provide active sites for subsequent acrylic acid medium modification; the epoxy silane coupling agent has a silane structure, so that the epoxy silane coupling agent has a good infiltration and dispersion effect on inorganic powder materials such as nano silicon dioxide, titanium dioxide and the like, contains an epoxy group, is favorable for being compatible with organic systems such as epoxy resin and the like, and forms a coupling synergistic effect on an organic/inorganic hybrid system; the silicon-containing monomer can form chemical grafting on the active sites of epoxy resin and acrylic monomer under the action of an initiator due to the double bond structure of the silicon-containing monomer, and meanwhile, the silane structure of the silicon-containing monomer has better compatibility with inorganic powder such as nano silicon dioxide, titanium dioxide and the like, and forms a coupling synergistic effect on an organic/inorganic hybrid system in the invention; the epoxy reactive diluent can better reduce the viscosity of bisphenol F type epoxy resin on one hand, and can provide an active site for subsequent acrylic acid grafting modification because of the double bond; the low molecular weight bisphenol F epoxy resin can provide good adhesive force and improve the acid-base salt resistance; the furan resin has stronger alkali resistance and can resist the corrosion damage of an alkaline cleaning solution in the washing of a dish washing machine. In the coating film forming material, a fluorine-containing acrylic monomer is dodecafluoroheptyl methacrylate; the hydroxyl-containing acrylic monomer is at least one of hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; the monomer containing the tertiary carbonic acid structure is at least one of tertiary carbonic acid glycidyl ester and tertiary carbonic acid ethylene ester; the carboxyl-containing acrylic monomer is at least one of acrylic acid and methacrylic acid; the other acrylic monomer is at least one of styrene, butyl (meth) acrylate, isobornyl (meth) acrylate, methyl (meth) acrylate, isooctyl (meth) acrylate, and (meth) acrylamide; the acrylic monomer containing epoxy group is glycidyl methacrylate. The initiator is at least one of benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, di-tert-butyl peroxide, di-tert-amyl peroxide, cumyl peroxide, tert-butyl peroxy (2-ethylhexanoate), dicumyl peroxide, tert-butyl peroxy 3,5, 5-trimethylhexanoate and tert-butyl peroxy-2-ethylhexanoate.
The fluorine-containing acrylic monomer can enhance corrosion resistance, and can optimize the function of easy cleaning of the coating due to the characteristic of low surface energy; the epoxy group-containing acrylic monomer realizes better fusion of an epoxy system and an acrylic system; ester groups on a side chain of a polymer are difficult to hydrolyze due to the steric effect of alkyl groups on alpha-carbon atoms of the monomer containing the tertiary carbonic acid structure, so that the alkali resistance of a coating can be remarkably improved; the carboxyl-containing acrylic monomer provides good pigment compatibility and provides crosslinking points for subsequent thermosetting; the hydroxyl-containing acrylic monomer has good compatibility with hydroxyl of the nano silicon dioxide and the nano titanium dioxide, and provides a crosslinking point for subsequent thermal curing; other acrylic monomers provide suitable degrees of softness, improved corrosion resistance, gloss, and the like.
The invention relates to a coating film forming material for washing bowl machines, which comprises the following steps:
step S1, preparing a prepolymer:
step S11, firstly, adding ethylene glycol monobutyl ether, n-butyl alcohol and a dispersant into an ultrasonic reactor in sequence, and then ultrasonically stirring for 5-15 min;
step S12, adding nano silicon dioxide, nano titanium dioxide and functional monomers, and ultrasonically stirring for 20-40min after the addition;
step S13, adding epoxy silane coupling agent and silicon-containing monomer, and stirring for 5-15min with ultrasound after adding;
step S14, finally adding an epoxy active diluent, bisphenol F type epoxy resin and furan resin, and after the addition, ultrasonically stirring for 4-6 hours to obtain a prepolymer;
step S2, preparing a coating film-forming material by prepolymer grafting polymerization modification:
step S21, adding a prepolymer into an ultrasonic reactor, and heating to 100-120 ℃ under the action of ultrasonic stirring;
step S22, uniformly dripping a fluorine-containing acrylic monomer, an epoxy group-containing acrylic monomer, a tertiary carbonic acid structure-containing monomer, a hydroxyl group-containing acrylic monomer, other acrylic monomers, a proper amount of ethylene glycol butyl ether and a proper amount of initiator into a reaction kettle after fully mixing and dissolving; preferably, the dripping time is 1.5-2.5 h;
step S23, uniformly dripping carboxyl-containing acrylic acid monomer, hydroxyl-containing acrylic acid monomer, other acrylic acid monomers, a proper amount of ethylene glycol butyl ether and a proper amount of initiator into a reaction kettle after fully mixing and dissolving; preferably, the dropping time is 1.5-2.5 h;
step S24, preserving heat for 0.5-2h, fully mixing and dissolving a proper amount of initiator and a proper amount of ethylene glycol butyl ether, and then dropwise adding into a reaction kettle; preferably, the dripping time is 5-15 min;
step S25, preserving heat for 0.5-2h, and dropwise adding the mixture into a reaction kettle after fully mixing and dissolving the residual initiator and ethylene glycol butyl ether; preferably, the dropping time is 5-15 min;
and step S26, preserving the heat for 2-4h, and filtering to obtain the dish washing machine-resistant paint film forming matter.
The invention provides a washing-resistant dish washer coating film-forming material which is explained in detail by specific embodiments.
Example 1
The coating film forming material for the washable bowl machine comprises the following components in parts by weight:
50 parts of prepolymer, 1 part of fluorine-containing acrylic monomer, 1 part of epoxy group-containing acrylic monomer, 1 part of tertiary carbonic acid structure-containing monomer, 6 parts of hydroxyl group-containing acrylic monomer, 3 parts of carboxyl group-containing acrylic monomer, 17 parts of other acrylic monomers, 10 parts of butyl cellosolve and 3 parts of initiator;
the prepolymer comprises the following components in parts by mass:
7 parts of nano silicon dioxide, 1 part of nano titanium dioxide, 1 part of functional monomer, 0.5 part of epoxy silane coupling agent, 1 part of silicon-containing monomer, 5 parts of epoxy active diluent, 15 parts of bisphenol F epoxy resin, 2 parts of furan resin, 22 parts of butyl cellosolve, 3 parts of n-butyl alcohol and 0.3 part of dispersing agent.
The preparation method of the coating film-forming material for washing bowl machines comprises the following steps:
1. preparing a prepolymer:
sequentially adding 22 parts of ethylene glycol butyl ether, 3 parts of n-butanol and 0.3 part of dispersant (BYK192) into an ultrasonic reactor, and after the addition is finished, ultrasonically stirring for 10 min;
slowly adding 7 parts of nano silicon dioxide (the particle size is less than or equal to 100nm) and 1 part of nano titanium dioxide (anatase type, the particle size is less than or equal to 10nm) and 1 part of functional monomer (zinc methacrylate), and after the addition is finished, ultrasonically stirring for 30 min;
then slowly adding 0.5 part of epoxy silane coupling agent FD560 (Zhejiang boiling point chemical Co., Ltd.) and 1 part of silicon-containing monomer (such as vinyl trimethoxy silane), and after adding, ultrasonically stirring for 10 min;
then slowly adding 5 parts of epoxy active diluent (alkyl glycidyl ether type epoxy active diluent containing epoxy group, double bond and benzene ring, such as Kadela Ultra LITE 513), 15 parts of bisphenol F type epoxy resin (epoxy equivalent is 150-200) and 2 parts of furan resin (molecular weight is less than 400), and after the addition, ultrasonically stirring for 5h to obtain the prepolymer.
2. Modification by grafting polymerization of a prepolymer:
starting ultrasound and stirring in an ultrasonic reactor, and heating 50 parts of prepolymer to 110 ℃;
1 part of fluorine-containing acrylic monomer (such as dodecafluoroheptyl methacrylate), 1 part of epoxy group-containing acrylic monomer (glycidyl methacrylate), 1 part of versatic acid structure-containing monomer (glycidyl versatate and ethylene versatate), 3 parts of hydroxyl-containing acrylic monomer, 7 parts of other acrylic monomers, 2 parts of butyl cellosolve and 1 part of initiator are uniformly dripped into a reaction kettle after being fully mixed and dissolved, and the time is 2 hours;
after fully mixing and dissolving 3 parts of carboxyl-containing acrylic monomer, 3 parts of hydroxyl-containing acrylic monomer, 10 parts of other acrylic monomer, 4 parts of butyl cellosolve and 1.5 parts of initiator, uniformly dropwise adding the mixture into a reaction kettle, and taking 2 hours;
after the mixture is dripped, keeping the temperature for 1h, and dripping the mixture into a reaction kettle after 0.3 part of initiator and 2 parts of butyl cellosolve are fully mixed and dissolved for 5-15 min;
keeping the temperature for 1 hour, fully mixing and dissolving 0.3 part of initiator and 2 parts of butyl cellosolve, and dripping into the reaction kettle for 5-15 min;
then preserving the heat for 2-4 h; finally filtering with 400 meshes to obtain the film forming material which is washable to bowls and machines.
Example 2
A coating film forming material for a washable bowl machine comprises the following components in parts by weight:
45 parts of prepolymer, 0.5 part of fluorine-containing acrylic monomer, 0.5 part of epoxy group-containing acrylic monomer, 0.5 part of tertiary carbonic acid-containing structural monomer, 4 parts of hydroxyl-containing acrylic monomer, 2 parts of carboxyl-containing acrylic monomer, 15 parts of other acrylic monomers, 8 parts of butyl cellosolve and 2 parts of initiator;
the prepolymer comprises the following components in parts by mass:
5 parts of nano silicon dioxide, 0.5 part of nano titanium dioxide, 0.5 part of functional monomer, 0.2 part of epoxy silane coupling agent, 0.5 part of silicon-containing monomer, 2 parts of epoxy active diluent, 10 parts of bisphenol F type epoxy resin, 1 part of furan resin, 20 parts of butyl cellosolve, 2 parts of n-butyl alcohol and 0.1 part of dispersing agent.
The preparation method of the dish washer-resistant coating film-forming material of the embodiment is the same as that of the embodiment 1.
Example 3
The coating film forming material for the washable bowl machine comprises the following components in parts by weight:
55 parts of prepolymer, 2 parts of fluorine-containing acrylic monomer, 2 parts of epoxy group-containing acrylic monomer, 2 parts of tertiary carbonic acid structure-containing monomer, 10 parts of hydroxyl group-containing acrylic monomer, 5 parts of carboxyl group-containing acrylic monomer, 20 parts of other acrylic monomers, 15 parts of butyl cellosolve and 5 parts of initiator;
the prepolymer comprises the following components in parts by mass:
10 parts of nano silicon dioxide, 2 parts of nano titanium dioxide, 2 parts of a functional monomer, 0.8 part of an epoxy silane coupling agent, 2 parts of a silicon-containing monomer, 8 parts of an epoxy active diluent, 20 parts of bisphenol F epoxy resin, 3 parts of furan resin, 25 parts of ethylene glycol butyl ether, 6 parts of n-butyl alcohol and 1 part of a dispersing agent.
The preparation method of the dish washing resistant coating film forming material is the same as that of the example 1.
Example 4
A coating film forming material for a washable bowl machine comprises the following components in parts by weight:
48 parts of prepolymer, 1.5 parts of fluorine-containing acrylic monomer, 1.5 parts of epoxy group-containing acrylic monomer, 1.5 parts of tertiary carboxylic acid structure-containing monomer, 8 parts of hydroxyl-containing acrylic monomer, 4 parts of carboxyl-containing acrylic monomer, 18 parts of other acrylic monomers, 12 parts of butyl cellosolve and 4 parts of initiator;
the prepolymer comprises the following components in parts by mass:
8 parts of nano silicon dioxide, 1.5 parts of nano titanium dioxide, 1.5 parts of functional monomer, 0.6 part of epoxy silane coupling agent, 1.5 parts of silicon-containing monomer, 6 parts of epoxy active diluent, 12 parts of bisphenol F type epoxy resin, 1.8 parts of furan resin, 23 parts of ethylene glycol butyl ether, 5 parts of n-butyl alcohol and 0.7 part of dispersing agent.
The preparation method of the dish washing resistant coating film forming material is the same as that of the example 1.
The properties of the coating film-forming materials of the invention are illustrated below by their application in aqueous coatings.
Example 5
The water-based paint is prepared by adopting the paint film-forming material of the embodiment 1, and the specific process is as follows:
(1) and (3) varnish blending: 48 parts of film forming material of example 1, 3 parts of NN dimethyl ethanolamine, 12 parts of high imino methylated amino resin (such as cyanot 325), 2 parts of methylated phenylamine resin (such as Mei screw 85), 5 parts of ethylene glycol butyl ether, 5 parts of propylene glycol methyl ether, 12 parts of ethanol, 15 parts of water, 0.5 part of leveling wetting agent and 0.05 part of defoaming agent are added.
(2) Color paste blending: 35 parts of film forming material of example 1, 2 parts of NN dimethyl ethanolamine, 12 parts of ethylene glycol butyl ether, 5 parts of propylene glycol methyl ether, 25 parts of water, 3 parts of BYK190 dispersant, 0.05 part of defoaming agent and 18 parts of toner, and grinding the mixture until the particle size is less than or equal to 15 mu m.
(3) Blending the colored paint: 54 parts of varnish, 21 parts of color paste, 20 parts of water, 3 parts of adhesion promoting material (ZTC-088, New materials for Hunan Zhi coating Co., Ltd.), and 2 parts of FD560 silane coupling agent, and stirring uniformly.
Examples 6 to 8
Waterborne coatings were formulated using the coating film-forming compositions of examples 2-4 using the same procedure as in example 5 to provide examples 6-8. The blending process of the water-based paint is not described herein.
The water-based paints of examples 5 to 8 were respectively sprayed on a ceramic pan, baked at 180 ℃ for 30min, and then the formed coating films were subjected to the performance test, the test results are shown in table 1:
table 1: water-based paint test results
As can be seen from Table 1, the coating film forming material for the washable bowl machine, provided by the invention, has excellent adhesive force when applied to a water-based coating, and can remarkably improve the acid and alkali resistance, the bowl machine test resistance, the boiling resistance and other performances of the coating.
Compared with the prior art, the coating film forming material for the washable bowl machine, and the preparation method and the application thereof provided by the invention have the beneficial effects that:
the invention provides a coating film forming material for a washable bowl machine, which adopts nano silicon dioxide and nano titanium dioxide as inorganic functional materials, adopts epoxy silane coupling agents, silicon-containing monomers and zinc methacrylate for modification, and introduces epoxy active diluents, low-molecular-weight bisphenol F epoxy resin and furan resin under the vibration dispersion effect of ultrasonic waves to realize the surface coating modification of nanoparticles and form a prepolymer with a core-shell structure; the prepolymer is modified by acrylic monomer grafting, so that the weather resistance, corrosion resistance and baking resistance of the material are enhanced.
Secondly, aiming at the problem that secondary agglomeration is easy to occur to nano powder (silicon dioxide, titanium dioxide and the like), in the aspect of the preparation process, ultrasonic equipment is adopted from preparation of the prepolymer to subsequent polymerization and modification of the acrylic monomer, and the uniform stability of an inorganic/organic hybrid system of the coating film-forming material is realized through continuous ultrasonic dispersion in the whole process. In the acrylic monomer polymerization modification stage, two stages of special design are also carried out on the aspect of a high molecular structure, namely step S22 and step S23, and the monomers in the step S22 mainly play a role in enhancing the functional indexes of a paint film such as bowl washing resistance, water boiling resistance, wear resistance, salt mist resistance, acid resistance, alkali resistance and the like, and are properly polymerized at the inner position of the high molecular structure; the monomers in step S23 are mainly used to provide the film-forming material with a better compatibility with aqueous paint systems, and also provide groups for toner compatibility, crosslinking reaction, etc., so that the film-forming material is properly polymerized at the outer position of the polymer structure.
Thirdly, the paint film forming matter capable of washing the bowl machine is applied to a water-based paint system, can obviously improve the adhesive force between the coating and the ceramic material, and obviously improve the bowl machine washing resistance of the coating for more than or equal to 1000 times, the boiling resistance for more than or equal to 100 hours, the wear resistance (more than or equal to 1000 revolutions, GB/T1768-2SO4) The time is more than or equal to 200 hours, and the alkali resistance (10 percent NaOH) is more than or equal to 100 hours.
The embodiments in the present specification are described in a progressive manner, and the same and similar parts among the embodiments are referred to each other, and each embodiment focuses on the differences from the other embodiments.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. Various changes, modifications, substitutions and alterations to these embodiments will occur to those skilled in the art without departing from the spirit and scope of the present invention.
Claims (10)
1. The coating film forming material for the washable bowl machine is characterized by comprising the following components in parts by mass:
45-55 parts of prepolymer, 0.5-2 parts of fluorine-containing acrylic monomer, 0.5-2 parts of epoxy group-containing acrylic monomer, 0.5-2 parts of tertiary carboxylic acid structure-containing monomer, 4-10 parts of hydroxyl group-containing acrylic monomer, 2-5 parts of carboxyl group-containing acrylic monomer, 15-20 parts of other acrylic monomers, 8-15 parts of butyl cellosolve and 2-5 parts of initiator;
the prepolymer comprises the following components in parts by mass:
5-10 parts of nano silicon dioxide, 0.5-2 parts of nano titanium dioxide, 0.5-2 parts of functional monomer, 0.2-0.8 part of epoxy silane coupling agent, 0.5-2 parts of silicon-containing monomer, 2-8 parts of epoxy active diluent, 10-20 parts of bisphenol F type epoxy resin, 1-3 parts of furan resin, 20-25 parts of ethylene glycol butyl ether, 2-6 parts of n-butyl alcohol and 0.1-1 part of dispersing agent.
2. The dish wash resistant coating film former as claimed in claim 1, wherein said fluorine-containing acrylic monomer is dodecafluoroheptyl methacrylate;
the hydroxyl-containing acrylic monomer is at least one of hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate;
the monomer containing the tertiary carbonic acid structure is at least one of tertiary carbonic acid glycidyl ester and tertiary carbonic acid ethylene ester;
the carboxyl-containing acrylic monomer is at least one of acrylic acid and methacrylic acid;
the other acrylic monomer is at least one of styrene, butyl (meth) acrylate, isobornyl (meth) acrylate, methyl (meth) acrylate, isooctyl (meth) acrylate, and (meth) acrylamide;
the epoxy group-containing acrylic monomer is glycidyl methacrylate.
3. The dish wash resistant paint film former of claim 1, wherein the initiator is at least one of benzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl hydroperoxide, di-tert-butyl peroxide, di-tert-amyl peroxide, cumyl peroxide, tert-butyl peroxy (2-ethylhexanoate), dicumyl peroxide, tert-butyl peroxy 3,5, 5-trimethylhexanoate, tert-butyl peroxy-2-ethylhexanoate.
4. The dish washer resistant coating film forming material according to claim 1, wherein the functional monomer is zinc methacrylate;
the epoxy silane coupling agent is at least one of Dow Corning Z-6040, Nanjing eosin KH-560, Ningyue KBM-403 and Zhejiang boiling point FD-560;
the silicon-containing monomer is at least one of vinyl trimethoxy silane and vinyl triethoxy silane;
the epoxy reactive diluent is an alkyl glycidyl ether type epoxy reactive diluent containing epoxy groups, double bonds and benzene rings.
5. The dishwasher-resistant paint film-forming material as claimed in claim 1, wherein the bisphenol F type epoxy resin has an epoxy equivalent of 150-200.
6. The dishwasher-resistant paint film-forming article according to any one of claims 1 to 5, characterized in that the method for preparing the dishwasher-resistant paint film-forming article comprises the following steps:
step S1, preparing a prepolymer:
step S11, firstly, adding ethylene glycol monobutyl ether, n-butanol and a dispersing agent into an ultrasonic reactor in sequence, and then carrying out ultrasonic stirring for 5-15 min;
step S12, adding nano silicon dioxide, nano titanium dioxide and functional monomers, and ultrasonically stirring for 20-40min after the addition;
step S13, adding epoxy silane coupling agent and silicon-containing monomer, and ultrasonically stirring for 5-15min after the addition;
step S14, finally adding an epoxy active diluent, bisphenol F type epoxy resin and furan resin, and carrying out ultrasonic stirring for 4-6h after the addition to obtain a prepolymer;
step S2, preparing a coating film-forming material by grafting, polymerizing and modifying the prepolymer:
step S21, adding a prepolymer into an ultrasonic reactor, and heating to 100-120 ℃ under the action of ultrasonic stirring;
step S22, uniformly dripping the fluorine-containing acrylic monomer, the epoxy group-containing acrylic monomer, the tertiary carbonic acid structure-containing monomer, the hydroxyl group-containing acrylic monomer, other acrylic monomers, a proper amount of ethylene glycol butyl ether and a proper amount of initiator into a reaction kettle after fully mixing and dissolving;
step S23, uniformly dripping carboxyl-containing acrylic acid monomer, hydroxyl-containing acrylic acid monomer, other acrylic acid monomer, a proper amount of ethylene glycol monobutyl ether and a proper amount of initiator into a reaction kettle after fully mixing and dissolving;
step S24, preserving heat for 0.5-2h, fully mixing and dissolving a proper amount of initiator and a proper amount of ethylene glycol butyl ether, and then dropwise adding into a reaction kettle;
step S25, keeping the temperature for 0.5-2h, and dropwise adding the mixture into a reaction kettle after the residual initiator and the ethylene glycol butyl ether are fully mixed and dissolved;
and step S26, preserving heat for 2-4h, and filtering to obtain the coating film-forming material for the dish washing machine.
7. The dish washing resistant paint film forming material according to claim 6, wherein in the step S22, the dropping time of the reactant is 1.5-2.5 h;
in the step S23, the dropping time of the reactant is 1.5-2.5 h;
in step S24, the reactant is dripped for 5-15 min;
in step S25, the reactant is added dropwise for 5-15 min.
8. A method for preparing a dish washing resistant coating film forming material according to claim 1, comprising the steps of:
step S1, preparing a prepolymer:
step S11, firstly, adding ethylene glycol monobutyl ether, n-butyl alcohol and a dispersant into an ultrasonic reactor in sequence, and then ultrasonically stirring for 5-15 min;
step S12, adding nano silicon dioxide, nano titanium dioxide and functional monomers, and ultrasonically stirring for 20-40min after the addition;
step S13, adding epoxy silane coupling agent and silicon-containing monomer, and ultrasonically stirring for 5-15min after the addition;
step S14, finally adding an epoxy active diluent, bisphenol F type epoxy resin and furan resin, and carrying out ultrasonic stirring for 4-6h after the addition to obtain a prepolymer;
step S2, preparing a coating film-forming material by grafting, polymerizing and modifying the prepolymer:
step S21, adding a prepolymer into an ultrasonic reactor, and heating to 100-120 ℃ under the action of ultrasonic stirring;
step S22, uniformly dripping a fluorine-containing acrylic monomer, an epoxy group-containing acrylic monomer, a tertiary carbonic acid structure-containing monomer, a hydroxyl group-containing acrylic monomer, other acrylic monomers, a proper amount of ethylene glycol butyl ether and a proper amount of initiator into a reaction kettle after fully mixing and dissolving;
step S23, uniformly dripping carboxyl-containing acrylic acid monomer, hydroxyl-containing acrylic acid monomer, other acrylic acid monomer, a proper amount of ethylene glycol monobutyl ether and a proper amount of initiator into a reaction kettle after fully mixing and dissolving;
step S24, preserving heat for 0.5-2h, fully mixing and dissolving a proper amount of initiator and a proper amount of ethylene glycol butyl ether, and then dropwise adding into a reaction kettle;
step S25, keeping the temperature for 0.5-2h, and dropwise adding the mixture into a reaction kettle after the residual initiator and the ethylene glycol butyl ether are fully mixed and dissolved;
and step S26, preserving heat for 2-4h, and filtering to obtain the coating film-forming material for the dish washing machine.
9. The method for preparing a dishwasher-resistant coating film-forming material according to claim 8,
in the step S22, the dropping time of the reactant is 1.5-2.5 h;
in the step S23, the dropping time of the reactant is 1.5-2.5 h;
in step S24, the reactant is dripped for 5-15 min;
in step S25, the dropping time of the reactant is 5-15 min.
10. Use of a dishwasher-resistant coating film-forming composition according to claim 1 in aqueous coatings.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031516A (en) * | 2014-05-27 | 2014-09-10 | 安徽菱湖漆股份有限公司 | Water-based glass winebottle baking varnish and preparation method thereof |
| CN104231147A (en) * | 2014-09-26 | 2014-12-24 | 江苏日出化工有限公司 | Preparation method of acrylate-fluorinated acrylate and silica sol hybrid latex |
| CN105061700A (en) * | 2015-08-14 | 2015-11-18 | 华南理工大学 | Nano-silica/polyacrylate organic and inorganic hybrid water-dispersible resin and preparation method thereof |
| CN105153847A (en) * | 2015-10-14 | 2015-12-16 | 芜湖春风新材料有限公司 | Water-based glass high-temperature baking varnish and preparation method thereof |
| US20180371286A1 (en) * | 2015-12-31 | 2018-12-27 | 3M Innovative Properties Company | Anti-fog coating composition including functionalized silica nanoparticles and multifunctional (meth)acrylate monomers |
| CN112029030A (en) * | 2020-09-09 | 2020-12-04 | 江苏三木化工股份有限公司 | Water-based acrylic resin for organic silicon modified glass paint and preparation method and application thereof |
-
2022
- 2022-03-30 CN CN202210321472.1A patent/CN114773943A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031516A (en) * | 2014-05-27 | 2014-09-10 | 安徽菱湖漆股份有限公司 | Water-based glass winebottle baking varnish and preparation method thereof |
| CN104231147A (en) * | 2014-09-26 | 2014-12-24 | 江苏日出化工有限公司 | Preparation method of acrylate-fluorinated acrylate and silica sol hybrid latex |
| CN105061700A (en) * | 2015-08-14 | 2015-11-18 | 华南理工大学 | Nano-silica/polyacrylate organic and inorganic hybrid water-dispersible resin and preparation method thereof |
| CN105153847A (en) * | 2015-10-14 | 2015-12-16 | 芜湖春风新材料有限公司 | Water-based glass high-temperature baking varnish and preparation method thereof |
| US20180371286A1 (en) * | 2015-12-31 | 2018-12-27 | 3M Innovative Properties Company | Anti-fog coating composition including functionalized silica nanoparticles and multifunctional (meth)acrylate monomers |
| CN112029030A (en) * | 2020-09-09 | 2020-12-04 | 江苏三木化工股份有限公司 | Water-based acrylic resin for organic silicon modified glass paint and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 霍丽霞等: "原位聚合制备纳米SiO2／聚丙烯酸酯复合树脂及其氨基烤漆性能的研究", 《涂料工业》 * |
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