CN116355145A - Epoxy acrylate hybrid dispersion and preparation method and application thereof - Google Patents
Epoxy acrylate hybrid dispersion and preparation method and application thereof Download PDFInfo
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- CN116355145A CN116355145A CN202310327045.9A CN202310327045A CN116355145A CN 116355145 A CN116355145 A CN 116355145A CN 202310327045 A CN202310327045 A CN 202310327045A CN 116355145 A CN116355145 A CN 116355145A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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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
Abstract
The invention relates to an acrylic acid epoxy ester hybrid dispersion, a preparation method and application thereof, and belongs to the technical field of functional coatings. The invention provides an acrylic acid epoxy ester hybrid dispersion, which comprises the following raw materials: the preparation method comprises the steps of (1) a nonionic epoxy resin prepolymer, a first mixed monomer, a catalyst, a second mixed monomer, an organic solvent, deionized water and a free radical initiator; the nonionic epoxy resin prepolymer is prepared by ring-opening reaction of polyether amine and epoxy resin. The epoxy acrylate hybrid dispersion provided by the invention has excellent oxidative crosslinking capability, shows the characteristics of quick drying, high gloss, good fullness, high hardness and the like at room temperature, is suitable for preparing water-based paint, and can greatly improve the storage stability and hydrolysis resistance of the paint, so that the paint coating has better adhesive force, water resistance, chemical corrosion resistance and other properties.
Description
Technical Field
The invention relates to the technical field of functional coatings, in particular to an epoxy acrylate hybrid dispersion, a preparation method and application thereof.
Background
Alkyd resin has the advantages of high gloss, good fullness, good adhesive force, good pigment wettability and the like, raw materials are cheap and easy to obtain, vegetable oil which is one of main raw materials is a renewable resource, is not limited by petrochemical industry, and occupies a considerable proportion in the field of traditional coatings. With the enhancement of environmental awareness and the strictness of environmental regulations, water-based paint is gradually replacing solvent-based paint due to safety and environmental protection, and the water-based of alkyd resin becomes one of the main development trends in the current industry.
The aqueous alkyd resin has the characteristic of air drying, and a network with extremely high molecular weight is formed through oxidative crosslinking in the air drying process. In general, an aqueous alkyd resin is prepared by adding a raw material containing a carboxylic acid group, and the remaining carboxylic acid is neutralized with aqueous ammonia or an organic amine, thereby achieving the aqueous property of the aqueous alkyd resin. A large amount of water and a hydrophilic organic solvent are required to be added for dispersing, so that the solid content of the aqueous alkyd resin dispersion is low, the drying speed is low, the hardness is low, and the water resistance is poor; the alkyd resin has a large amount of ester bonds in the main chain, and the ester bonds are hydrolyzed due to the increase of hydrophilicity, so that the performances of paint such as storage stability and hydrolysis resistance are greatly reduced. The invention disclosed in publication No. CN115322302A provides a preparation method and application of an acrylic acid alkyd hybrid emulsion, wherein the acrylic acid hybrid alkyd resin is used for improving the resin performance, and the emulsifier is added to disperse the resin by an emulsion polymerization method without pretreatment of the hybrid alkyd to change the hybrid alkyd into a dispersion; however, small molecule emulsifiers (e.g., octylphenol polyoxyethylene ether, etc.) tend to migrate to the coating surface, affecting the water resistance and gloss of the coating. The invention patent with publication number of CN104086712A discloses an epoxy acrylate modified water-based alkyd resin, a preparation method and application thereof, wherein the epoxy acrylate modified water-based alkyd resin is modified by adding epoxy resin and then by adding acrylic ester for grafting modification, but because the grafting rate of acrylic ester is low, organic amine is required to be added to neutralize acrylic ester which does not participate in grafting reaction, so that a water-based acrylic acid modified epoxy ester dispersoid with excellent performance can be obtained, unpleasant odor can be emitted in the neutralization reaction process, and pollution is caused to a construction site.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an epoxy acrylate hybrid dispersion, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides an epoxy acrylate hybrid dispersion, which comprises the following raw materials in parts by weight: 100-150 parts of nonionic epoxy resin prepolymer, 310-480 parts of first mixed monomer, 0.1-1 part of catalyst, 125-200 parts of second mixed monomer, 70-90 parts of organic solvent, 680-800 parts of deionized water and 10-16 parts of free radical initiator; the nonionic epoxy resin prepolymer is formed by ring-opening reaction of polyether amine and epoxy resin; the first mixed monomer comprises the following raw materials in parts by weight: 180-250 parts of unsaturated oleic acid, 65-120 parts of polyol, 60-90 parts of polybasic acid and 5-20 parts of polybasic acid anhydride; the second mixed monomer comprises the following raw materials in parts by weight: 50-150 parts of acrylate monomer and 50-75 parts of vinyl monomer.
The epoxy acrylate hybrid dispersion provided by the invention has excellent oxidative crosslinking capability, and has the characteristics of quick drying, high gloss, good fullness, high hardness and the like at room temperature; the epoxy acrylate hybrid dispersion provided by the invention is suitable for preparing water-based paint, can greatly improve the storage stability and hydrolysis resistance of the paint, and enables the paint coating to have better adhesive force, water resistance, chemical corrosion resistance and other performances.
As a preferred embodiment of the present invention, the epoxy acrylate hybrid dispersion comprises the following raw materials in parts by weight: 120 parts of nonionic epoxy resin prepolymer, 400 parts of first mixed monomer, 0.3-0.5 part of catalyst, 155-180 parts of second mixed monomer, 75-80 parts of organic solvent, 700-750 parts of deionized water and 12-14 parts of free radical initiator; the first mixed monomer comprises the following raw materials in parts by weight: 200-230 parts of unsaturated oleic acid, 75-100 parts of polyol, 65-86 parts of polybasic acid and 10-19 parts of polybasic acid anhydride; the second mixed monomer comprises the following raw materials in parts by weight: 100-110 parts of acrylate monomer and 55-70 parts of vinyl monomer. When the raw material components of the epoxy acrylate hybrid dispersion meet the condition, the epoxy acrylate dispersion with moderate particle size and uniform dispersion can be prepared, the storage stability of the coating can be greatly improved, the coating has the characteristics of quick drying, high gloss, good fullness, high hardness and the like at room temperature, and also has good water resistance, acid and alkali resistance and salt resistance.
As a preferred embodiment of the present invention, the nonionic epoxy resin prepolymer is prepared by the following method: and (3) uniformly mixing polyether amine and epoxy resin, heating to 120-150 ℃, and reacting for 3-5 hours at a temperature maintaining condition to obtain the nonionic epoxy resin prepolymer.
As a preferred embodiment of the present invention, the nonionic epoxy resin prepolymer comprises the following raw materials in parts by weight: 300-750 parts of polyether amine and 750-1200 parts of epoxy resin.
Further preferably, the nonionic epoxy resin prepolymer comprises the following raw materials in parts by weight: 480-560 parts of polyether amine and 940-1020 parts of epoxy resin.
As a preferred embodiment of the present invention, the polyetheramine comprises at least one of polyetheramine D-240, polyetheramine D-400, polyetheramine D-2000, polyetheramine M-600, polyetheramine M-1000, polyetheramine M-2070 and polyetheramine M-3085.
Further preferably, the polyetheramine is a mixture of polyetheramine M-2070 and polyetheramine M-1000.
As a preferred embodiment of the present invention, the epoxy resin includes at least one of epoxy resin E-51, epoxy resin E-44, epoxy resin E-20, epoxy resin E-12 and epoxy resin E-03.
Further preferably, the epoxy resin is epoxy resin E-20 or epoxy resin E-12.
As a preferred embodiment of the present invention, the radical initiator comprises an oxidizing agent solution and a reducing agent solution, wherein the oxidizing agent in the oxidizing agent solution comprises at least one of ammonium persulfate, potassium persulfate and tert-butyl hydroperoxide, and the reducing agent in the reducing agent solution comprises at least one of sodium bisulfite, ferrous sulfate, sodium formaldehyde sulfoxylate, sodium dithionite, ascorbic acid and isoascorbic acid; in the raw materials of the epoxy acrylate hybrid dispersion, the weight part of the oxidant is 0.5-0.8 part, and the weight part of the reducer is 0.5-0.8 part.
As a preferred embodiment of the present invention, the unsaturated oleic acid includes at least one of linoleic acid, soybean oleic acid, dehydrated ricinoleic acid, tall oil acid, eleostearic acid and ricinoleic acid.
Further preferably, the unsaturated oleic acid is linoleic acid.
As a preferred embodiment of the present invention, the polyhydric alcohol includes at least one of neopentyl glycol, ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, methyl-1, 2-propanediol, 1, 2-cyclohexanedimethanol, 1, 3-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, and glycerol.
Further preferably, the polyhydric alcohol includes any two of neopentyl glycol, ethylene glycol, 1, 4-butanediol, trimethylolpropane, pentaerythritol, and diethylene glycol.
Still more preferably, the polyol is a mixture of pentaerythritol and diethylene glycol, and in the first mixed monomer, the pentaerythritol is 61 to 67 parts by weight and the diethylene glycol is 28 to 33 parts by weight.
As a preferred embodiment of the present invention, the polybasic acid includes phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, oxalic acid, glutaric acid, adipic acid, sebacic acid, azelaic acid, 1, 3-cyclohexanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid.
Further preferably, the polybasic acid is any one of phthalic acid and isophthalic acid.
As a preferred embodiment of the present invention, the polybasic acid anhydride includes at least one of maleic anhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride.
Further preferably, the polybasic acid anhydride is tetrahydrophthalic anhydride.
As a preferred embodiment of the present invention, the acrylate monomer comprises C 1 -C 18 The acrylic acid ester of C 1 -C 18 The acrylic acid ester of (C) comprises at least one of ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate and n-butyl methacrylate.
Further preferably, the acrylate monomer consists of methyl methacrylate and n-butyl methacrylate; in the acrylic ester monomer, the weight part of the methyl methacrylate is 67-80 parts, and the weight part of the n-butyl methacrylate is 30-33 parts.
As a preferred embodiment of the present invention, the vinyl monomer includes at least one of styrene and α -methylstyrene.
Further preferably, the vinyl monomer is styrene.
As a preferred embodiment of the present invention, the catalyst includes at least one of an organotin catalyst and an organotin catalyst; the organotin catalyst comprises at least one of monobutyl tin oxide and dibutyl tin oxide; the organic titanium catalyst comprises at least one of titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetra-n-butoxide and titanium butyl isopropoxide.
As a preferred embodiment of the present invention, the organic solvent includes at least one of xylene, toluene, ethanol, methanol, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, dipropylene glycol butyl ether.
Further preferably, the organic solvent is ethylene glycol butyl ether.
As a preferred embodiment of the present invention, the solid content of the epoxy acrylate hybrid dispersion is not less than 41.2%.
In a second aspect, the present invention provides a method for preparing an epoxy acrylate hybrid dispersion according to the first aspect, comprising the steps of:
(1) Mixing the nonionic epoxy resin prepolymer, the first mixed monomer and the catalyst, performing esterification reaction, and then adding an organic solvent and deionized water for mixing and diluting;
(2) Adding a second mixed monomer into the product obtained in the step (1) to perform pre-emulsification dispersion;
(3) And (3) adding a free radical initiator into the product obtained in the step (2), and carrying out in-situ emulsion polymerization to obtain the epoxy acrylate hybrid dispersion.
Under the action of a catalyst, unsaturated oleic acid, polybasic acid and polybasic acid anhydride are subjected to esterification reaction with polyhydric alcohol to generate alkyd resin; meanwhile, the nonionic epoxy resin prepolymer reacts with unsaturated oleic acid and the like to produce nonionic epoxy ester, the nonionic epoxy ester is introduced onto an alkyd molecular chain, the hydrophilic end of the nonionic epoxy ester is outwards, the hydrophobic end of the alkyd is inwards, and the nonionic epoxy ester modified alkyd resin emulsion is formed after mixing and diluting with deionized water and an organic solvent; after the second mixed monomer is added, the nonionic epoxy ester modified alkyd resin emulsion can play a role of an emulsifier, and the second mixed monomer is fully emulsified through pre-emulsification and dispersion; after emulsification, under the action of a free radical initiator, acrylic resin is formed by polymerizing acrylate monomers and vinyl monomers in emulsion to form polymer microspheres with a core-shell structure, the polymer microspheres are uniformly distributed to form a dispersion, the polymer microspheres with the core-shell structure take nonionic epoxy ester modified alkyd resin as a shell layer, and the acrylic resin is a core layer; the inward alkyd hydrophobic end contains double bonds and conjugated double bonds, and is subjected to free radical polymerization with acrylate monomers, so that a certain interpenetrating network structure is formed, the core-shell performance is complementary, the stability of the polymer microsphere structure in the dispersion is further improved, and the storage stability and hydrolysis resistance are improved.
According to the invention, the waterborne epoxy ester is modified by the nonionic epoxy ester, amine neutralization is not needed in the preparation process, the generated smell is small, and the epoxy ester acrylate dispersion is more friendly to human and environment, so that the epoxy ester acrylate dispersion can be applied to the waterborne coating, and the hydrolysis resistance of the coating is improved. The hydrophilic end of the nonionic epoxy ester is outwards, the hydrophobic end of the alkyd is inwards, a hydrophobic space is provided for an ester bond, and the storage stability and the hydrolysis resistance of the water-based paint can be effectively improved; in the coating film forming process, the interpenetrating network structure promotes the complementation of core-shell performance, the nonionic epoxy ester of the shell layer improves the good film forming performance, and the coating can be quickly dried and the hardness of the coating layer is improved through the introduction of the acrylate monomer and the vinyl monomer.
As a preferred embodiment of the present invention, the step (1) specifically includes: mixing the first mixed monomer with the nonionic epoxy resin prepolymer, reflux esterification reaction at 200-230 ℃ by taking dimethylbenzene as a solvent until the acid value of the system reaches 3-5 mgKOH/g, then decompressing to remove dimethylbenzene, cooling to 65-85 ℃, and adding an organic solvent and deionized water for mixing and diluting.
As a preferred embodiment of the present invention, the time of pre-emulsification and dispersion in the step (2) is 20 to 40 minutes.
As a preferred embodiment of the present invention, the conditions for the in-situ emulsion polymerization in step (3) are: the temperature is 45-65 ℃ and the time is 2-4 h.
In a third aspect, the present invention provides the use of an epoxy acrylate hybrid dispersion according to the first aspect for the preparation of an aqueous coating.
In a fourth aspect, the invention provides an aqueous single-component metal anticorrosive paint, which comprises the following raw materials: pigment filler, co-solvent, adjuvant, deionized water, and epoxy acrylate hybrid dispersion as described in the first aspect.
As a preferred embodiment of the invention, the aqueous single-component metal anticorrosive paint comprises the following raw materials in parts by weight: 20-35 parts of pigment filler, 3-5 parts of cosolvent, 1-3 parts of auxiliary agent, 5-15 parts of deionized water and 35-65 parts of epoxy acrylate hybrid dispersion.
As a preferred embodiment of the present invention, the cosolvent includes an alcohol ether solvent including at least one of ethanol, n-butanol, isobutanol, isopropanol, ethylene glycol butyl ether, propylene glycol methyl ether, diethylene glycol butyl ether, and dipropylene glycol butyl ether.
As a preferred embodiment of the present invention, the auxiliary agent includes at least one of a pH adjustor, a dispersing agent, a leveling agent, a wetting agent, a defoaming agent, a drier, an anti-flash rust agent, and a thickener.
Further preferably, the leveling agent includes at least one of a fluorosurfactant and a polyacrylic acid copolymer.
Further preferably, the wetting agent comprises an organosiloxane copolymer, which may be at least one of Tego270, tego 4100.
Further preferably, the defoamer comprises at least one of mineral oil, polyether, and silicone defoamer; still more preferred is a silicone defoamer which may be at least one of silicone defoamer Tego810, silicone defoamer Tego 902W.
Further preferably, the drier includes at least one of cobalt naphthenate, zirconium naphthenate and zinc naphthenate. For example, the drier is an aqueous drier OMG123.
Further preferably, the thickener comprises a nonionic polyurethane thickener, which may be Hamming 299.
As a preferred embodiment of the present invention, the pigment filler includes at least one of an inorganic pigment, an organic pigment, a metal complex pigment and a filler.
Further preferably, the inorganic pigment includes at least one of carbon black, graphite, titanium dioxide, iron oxide red, iron oxide yellow, silver powder, aluminum powder, zinc phosphate, aluminum tripolyphosphate, strontium chrome yellow, and zinc chrome yellow.
Further preferably, the organic pigment includes azo-based pigments and non-azo-based pigments; the azo-based pigment includes at least one of a monoazo pigment, a disazo pigment, a condensed azo-based pigment, and an azo condensed-based pigment; the non-azo pigment includes at least one of phthalocyanine blue, phthalocyanine green, thioindigo pigment, anthraquinone pigment, dioxazine pigment, and triarylmethane pigment. The anthraquinone pigment may be at least one of anthrapyrimidine pigment, indanthrone pigment, pyrene anthrone pigment, and dibenzopyrene dione pigment.
Further preferably, the filler includes at least one of precipitated barium sulfate, light calcium carbonate, heavy calcium carbonate, kaolin, talc, sericite, and bentonite.
As a preferred embodiment of the present invention, the aqueous one-component metal anticorrosive paint further comprises an additional resin including at least one of an acrylic resin, a polyurethane resin, a polyester resin, an alkyl resin, and an epoxy ester resin.
As a preferred embodiment of the invention, the auxiliary agent comprises a pH regulator, a dispersing agent, a wetting agent, a defoaming agent, a drier, a flash rust inhibitor and a thickening agent, and the aqueous single-component metal anticorrosive paint is prepared by adopting the following method:
s1, mixing deionized water, a pH regulator, a dispersing agent, a part of wetting agent, a part of defoaming agent and pigment and filler, and grinding until the fineness is less than 20 mu m to obtain aqueous slurry;
s2, adding the epoxy acrylate hybrid dispersion, the cosolvent, the drier, the flash rust inhibitor, the thickener, the residual wetting agent and the residual defoaming agent into the aqueous slurry obtained in the step S1, and uniformly stirring and mixing to obtain the aqueous single-component metal anticorrosive paint.
Compared with the prior art, the invention has the beneficial effects that:
(1) The epoxy acrylate hybrid dispersion provided by the invention takes nonionic epoxy ester modified alkyd resin as a shell and acrylic resin as a core to form a special core-shell structure, has excellent oxidative crosslinking capability, and has the characteristics of quick drying, high gloss, good fullness, high hardness and the like at room temperature;
(2) The epoxy acrylate hybrid dispersion provided by the invention is suitable for preparing water-based paint, can greatly improve the storage stability and hydrolysis resistance of the paint, and enables the paint coating to have better adhesive force, water resistance, chemical corrosion resistance and other performances; the water-based paint is prepared by taking water as a main medium, has low organic solvent content, low VOC content and little environmental pollution, has no fire and potential safety hazard, and can be widely applied to the fields of rail transit, automobiles and ships, bridges, steel structures, storage tanks and the like.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Examples 1 to 7
Examples 1 to 7 provide epoxy acrylate hybrid dispersions, which are prepared by:
(1) Adding polyether amine and epoxy resin into a reaction container with the capacity of 2L, wherein the reaction container is provided with a stirring mechanism, a condenser and a heater, and carrying out ring-opening reaction for 4 hours under the conditions of stirring and 130 ℃ to obtain a nonionic epoxy resin prepolymer;
(2) Adding a certain amount of the nonionic epoxy resin prepolymer obtained in the step (1), a first mixed monomer and dimethylbenzene into a reaction container with the capacity of 2L, wherein the reaction container is provided with a stirring mechanism, a condenser and a heater, refluxing the dimethylbenzene under stirring and 220 ℃, reacting until the acid value of a reaction system reaches 3-5 mgKOH/g, decompressing and extracting the dimethylbenzene, cooling to 80 ℃, adding ethylene glycol butyl ether and deionized water, mixing and diluting;
(3) Adding a second mixed monomer into the product obtained in the step (2), and stirring for 30min;
(4) And (3) simultaneously dropwise adding an aqueous solution of tert-butyl hydroperoxide and an aqueous solution of isoascorbic acid into the product obtained in the step (3), and carrying out in-situ emulsion polymerization at 60 ℃ for 3 hours to obtain the epoxy acrylate hybrid dispersion.
Examples 1 to 7 were different in that the raw material formulations of the nonionic epoxy resin prepolymers used in examples 1 to 7 are shown in Table 1.
Examples 1 to 7 the amounts of raw materials used in step (2) to step (4) were the same as shown in example 5 in table 2.
Examples 8 to 15
The preparation methods of the epoxy acrylate hybrid dispersions provided in examples 8 to 15 are different from example 5 in that the raw materials of steps (2) to (4) in examples 8 to 15 are shown in table 2.
Example 16
The preparation method of the epoxy acrylate hybrid dispersion provided by the embodiment comprises the following steps:
(1) Adding polyether amine and epoxy resin into a reaction container with the capacity of 2L, wherein the reaction container is provided with a stirring mechanism, a condenser and a heater, and carrying out ring-opening reaction for 3 hours under the conditions of stirring and 120 ℃ to obtain a nonionic epoxy resin prepolymer;
(2) Adding a certain amount of the nonionic epoxy resin prepolymer obtained in the step (1), a first mixed monomer and dimethylbenzene into a reaction container with the capacity of 2L, wherein the reaction container is provided with a stirring mechanism, a condenser and a heater, refluxing the dimethylbenzene under stirring and 200 ℃, reacting until the acid value of a reaction system reaches 3-5 mgKOH/g, decompressing and extracting the dimethylbenzene, cooling to 65 ℃, adding ethylene glycol butyl ether and deionized water, mixing and diluting;
(3) Adding a second mixed monomer into the product obtained in the step (2), and stirring for 40min;
(4) And (3) simultaneously dropwise adding an aqueous solution of tert-butyl hydroperoxide and an aqueous solution of isoascorbic acid into the product obtained in the step (3), and carrying out in-situ emulsion polymerization at 45 ℃ for 2 hours to obtain the epoxy acrylate hybrid dispersion.
The composition of the raw materials used in step (1) of this example was the same as that used in step (1) of example 5, and the raw materials used in steps (2) to (4) of this example are shown in Table 2.
Example 17
The preparation method of the epoxy acrylate hybrid dispersion provided by the embodiment comprises the following steps:
(1) Adding polyether amine and epoxy resin into a reaction container with the capacity of 2L, wherein the reaction container is provided with a stirring mechanism, a condenser and a heater, and carrying out ring-opening reaction for 5 hours under the conditions of stirring and 150 ℃ to obtain a nonionic epoxy resin prepolymer;
(2) Adding a certain amount of the nonionic epoxy resin prepolymer obtained in the step (1), a first mixed monomer and dimethylbenzene into a reaction container with the capacity of 2L, wherein the reaction container is provided with a stirring mechanism, a condenser and a heater, refluxing the dimethylbenzene under the conditions of stirring and 230 ℃, reacting until the acid value of a reaction system reaches 3-5 mgKOH/g, decompressing and extracting the dimethylbenzene, cooling to 85 ℃, adding ethylene glycol butyl ether and deionized water, mixing and diluting;
(3) Adding a second mixed monomer into the product obtained in the step (2), and stirring for 20min;
(4) And (3) simultaneously dropwise adding an aqueous solution of tert-butyl hydroperoxide and an aqueous solution of isoascorbic acid into the product obtained in the step (3), and carrying out in-situ emulsion polymerization at 65 ℃ for 4 hours to obtain the epoxy acrylate hybrid dispersion.
The composition of the raw materials used in step (1) of this example was the same as that used in step (1) of example 5, and the raw materials used in steps (2) to (4) of this example are shown in Table 2.
TABLE 1
TABLE 2
Comparative example 1
The comparative example provides a method for preparing an epoxy acrylate hybrid dispersion, comprising the following steps:
(1) 120g of epoxy resin E-20, 200g of linoleic acid, 65g of pentaerythritol, 30g of diethylene glycol, 86g of isophthalic acid, 19g of tetrahydrophthalic anhydride, 10g of dimethylbenzene and 0.5g of monobutyl tin oxide are added into a reaction vessel with the capacity of 2L, the reaction vessel is provided with a stirring mechanism, a condenser and a heater, the dimethylbenzene is refluxed under the temperature of 220 ℃ and is reacted until the acid value of the reaction system reaches 3-5 mgKOH/g, the dimethylbenzene is pumped out under reduced pressure, the temperature is reduced to 80 ℃, and 80g of ethylene glycol butyl ether is added for mixing and dilution;
(2) Dripping the second mixed monomer into the product obtained in the step (1), wherein the temperature in the reaction container is maintained at 125 ℃ in the dripping process; after the dripping is finished, stirring is continued for 2 hours at 125 ℃, then cooling is carried out to 60 ℃, and stirring is continued for 30 minutes; the raw material composition of the second mixed monomer in this comparative example was the same as that of the second mixed monomer in example 5;
(3) And (3) adding the product obtained in the step (2) into 750g of deionized water, and stirring and dispersing for 30min to obtain the epoxy acrylate hybrid dispersion.
Comparative example 2
The comparative example provides a method for producing an epoxy acrylate hybrid dispersion, which is different from comparative example 1 in that the epoxy resin used in step (1) of the comparative example is epoxy resin E-12.
Comparative example 3
The preparation method of the epoxy acrylate hybrid dispersion provided by the comparative example comprises the following steps:
(1) Adding polyetheramine M-2070, epoxy resin E-20, a first mixed monomer and dimethylbenzene into a reaction vessel with the capacity of 2L, wherein the reaction vessel is provided with a stirring mechanism, a condenser and a heater, refluxing the dimethylbenzene under the conditions of stirring and 220 ℃, reacting until the acid value of a reaction system reaches 3-5 mgKOH/g, decompressing and extracting the dimethylbenzene, cooling to 80 ℃, adding ethylene glycol butyl ether and deionized water, mixing and diluting;
(2) Adding a second mixed monomer into the product obtained in the step (2), and stirring for 30min;
(3) And (3) simultaneously dropwise adding an aqueous solution of tert-butyl hydroperoxide and an aqueous solution of isoascorbic acid into the product obtained in the step (2), and carrying out in-situ emulsion polymerization at 60 ℃ for 3 hours to obtain the epoxy acrylate hybrid dispersion.
The weight of the polyether amine M-2070 and the weight of the epoxy resin E-20 were respectively 96g, the weight of the first mixed monomer, the xylene, the ethylene glycol butyl ether, the deionized water, the second mixed monomer, the aqueous solution of tert-butyl hydroperoxide and the aqueous solution of isoascorbic acid were the same as those of the corresponding raw materials in the steps (2) to (4) of the example 5.
Comparative example 4
The preparation method of the epoxy acrylate hybrid dispersion provided by the comparative example comprises the following steps:
(1) 200g of polyether amine M-2070, 360g of polyether amine M-1000 and 940g of epoxy resin E-12 are added into a reaction vessel with the capacity of 2L, the reaction vessel is provided with a stirring mechanism, a condenser and a heater, and the non-ionic epoxy resin prepolymer is obtained through ring-opening reaction for 4 hours under the conditions of stirring and 130 ℃;
(2) 120g of the nonionic epoxy resin prepolymer obtained in the step (1) was taken, and a first mixed monomer composed of the following raw materials was prepared: 220 g of soybean oleic acid, 67g of trimethylolpropane, 33g of neopentyl glycol, 65g of phthalic acid, 15g of tetrahydrophthalic anhydride and 0.5g of monobutyl tin oxide, and taking 10g of xylene;
adding the obtained nonionic epoxy resin prepolymer, a first mixed monomer and dimethylbenzene into a reaction container with the capacity of 2L, wherein the reaction container is provided with a stirring mechanism, a condenser and a heater, refluxing the dimethylbenzene under stirring and 220 ℃ until the acid value of a reaction system reaches 3-5 mgKOH/g, decompressing and extracting the dimethylbenzene, cooling to 80 ℃, adding 80g of ethylene glycol butyl ether, mixing and diluting;
(3) Preparing a second mixed monomer consisting of the following raw materials: 80g of methyl methacrylate, 30g of n-butyl methacrylate, 70g of styrene, 5g of tert-butyl peroxy-2-ethylhexyl acid;
dropwise adding a second mixed monomer and tert-butyl peroxy-2-ethylhexyl acid into the product obtained in the step (2), wherein the temperature in the reaction vessel is maintained at 125 ℃ in the dropwise adding process; after the dripping is finished, stirring is continued for 2 hours at 125 ℃, and then cooling is carried out to 65 ℃;
(4) And (3) adding 750g of deionized water into the product obtained in the step (3), and stirring and dispersing for 30min to obtain the epoxy acrylate hybrid dispersion.
Effect example 1
The products obtained in the above examples and comparative examples were subjected to characterization tests, as follows:
(1) Placing the samples in transparent glass containers, and visually observing the appearance of each sample;
(2) Taking 1g of sample, drying at 125 ℃ for 1h, detecting the weight of the dried sample, and calculating the content of non-volatile matters in the sample;
(3) Testing the viscosity of each sample using a rotational viscometer in an environment at 25 ℃;
(4) Detecting the acid value of the sample by adopting a titration method, and further testing the OH content relative to 100% of solid;
(5) Detecting the average particle size of the polymer in the sample by using a laser particle sizer;
(6) Diluting a sample with deionized water according to a mass ratio of 1:4, and detecting the pH value of the diluted sample by using a pH meter;
(7) The samples were placed in a 50 ℃ dry box and after 30 days of storage, the appearance of the samples was observed.
The test results are shown in Table 3.
TABLE 3 Table 3
In contrast to example 5, comparative examples 1 to 2 did not use polyetheramine, did not carry out ring-opening reaction of polyetheramine with epoxy resin, but directly mixed the epoxy resin, raw materials of the first mixed monomer, xylene and catalyst, resulting in excessive viscosity of the dispersion.
In comparison with example 5, in comparative example 3, the polyether amine and the epoxy resin were not subjected to the ring-opening reaction in advance, but the polyether amine, the epoxy resin, the first mixed monomer and the catalyst were directly mixed, resulting in uneven hydrophilic distribution, insufficient emulsification of the second mixed monomer, and thus larger particle size of the polymer particles in the dispersion and poor storage stability.
The average particle diameter of comparative example 4 is significantly larger and the storage stability is inferior to that of example 14. This is probably because the product obtained in step (1) of comparative example 4 was not diluted with deionized water, and was not pre-emulsified and dispersed, and the second mixed monomer and the initiator t-butyl peroxy-2-ethylhexyl acrylate were directly added dropwise to the product obtained in step (1) at the same time, so that the grafting rate of the acrylic resin was not high, and a part of the acrylic acid ester was not wrapped in the shell layer of the nonionic epoxy ester modified alkyd resin, resulting in a large particle size of the polymer in the dispersion and poor storage stability.
Application example 1
A preparation method of an aqueous single-component metal anti-corrosion coating comprises the following steps:
(1) Weighing the following raw materials in parts by weight: 9.4 parts of deionized water, 0.2 part of N, N-Dimethylethanolamine (DMEA), 0.5 part of dispersing agent (BYK 190), 0.1 part of wetting agent (Tego 270), 0.3 part of defoamer (Tego 810), 2 parts of carbon black (MA-100), 20 parts of 1250-mesh precipitated barium sulfate, 5 parts of zinc phosphate and 0.5 part of bentonite (EW); after the raw materials are uniformly mixed and stirred, adding the mixture into a sand mill, and grinding the mixture until the fineness is less than 20 mu m to obtain aqueous slurry;
(2) The following raw materials in parts by weight are sequentially added into color paste: 55 parts of epoxy acrylate hybrid dispersion, 0.8 part of waterborne drier (OMG 123), 5 parts of ethylene glycol butyl ether (BCS), 0.2 part of wetting agent (Tego 4100), 0.1 part of defoamer (Tego 902W), 0.5 part of anti-flash rust agent (T730) and 0.4 part of thickener (Haimines 299) are uniformly dispersed to obtain waterborne single-component metal anti-corrosive paint; the epoxy acrylate hybrid dispersion was prepared by the preparation method of example 1.
Application examples 2 to 17 and application comparative examples 1 to 4
Application examples 2 to 17 and comparative examples application examples 1 to 4 respectively provide a preparation method of an aqueous single-component metal anticorrosive paint, which is different from application example 1 in that:
the epoxy acrylate hybrid dispersion employed in application example 2 was prepared by the preparation method of example 2;
the epoxy acrylate hybrid dispersion employed in application example 3 was prepared by the preparation method of example 3;
the epoxy acrylate hybrid dispersion employed in application example 4 was prepared by the preparation method of example 4;
the epoxy acrylate hybrid dispersion employed in application example 5 was prepared by the preparation method of example 5;
the epoxy acrylate hybrid dispersion employed in application example 6 was prepared by the preparation method of example 6;
the epoxy acrylate hybrid dispersion employed in application example 7 was prepared by the preparation method of example 7;
the epoxy acrylate hybrid dispersion employed in application example 8 was prepared by the preparation method of example 8;
the epoxy acrylate hybrid dispersion employed in application example 9 was prepared by the preparation method of example 9;
the epoxy acrylate hybrid dispersion employed in application example 10 was prepared by the preparation method of example 10;
the epoxy acrylate hybrid dispersion employed in application example 11 was prepared by the preparation method of example 11;
the epoxy acrylate hybrid dispersion employed in application example 12 was prepared by the preparation method of example 12;
the epoxy acrylate hybrid dispersion employed in application example 13 was prepared by the preparation method of example 13;
the epoxy acrylate hybrid dispersion employed in application example 14 was prepared by the preparation method of example 14;
the epoxy acrylate hybrid dispersion employed in application example 15 was prepared by the preparation method of example 15;
the epoxy acrylate hybrid dispersion employed in application example 16 was prepared by the preparation method of example 16;
the epoxy acrylate hybrid dispersion employed in application example 17 was prepared by the preparation method of example 17;
the epoxy acrylate hybrid dispersion used in comparative example 1 was prepared by the preparation method of comparative example 1;
the dispersion used in comparative example 2 was prepared by the preparation method of comparative example 2;
the dispersion used in comparative example 3 was prepared by the preparation method of comparative example 3;
the dispersion used in comparative example 4 was prepared by the preparation method of comparative example 4.
Effect example 2
And carrying out construction and performance characterization tests on the water-based single-component metal anticorrosive paint prepared in each application example and each application comparative example.
1. The construction method comprises the following steps: and (3) mixing the aqueous single-component metal anti-corrosion coating with deionized water, spraying the mixture on a tinplate, wherein the spraying viscosity is 23', the construction temperature is 25 ℃, the construction humidity is 55%, curing is carried out for 7 days at 25 ℃, and the dry film thickness is 35-45 mu m.
2. The method for performance characterization test is as follows:
(1) Viscosity test: the viscosity test was performed using a paint-4 cup manufactured by Guangzhou Birda limited, measured according to GB/T1723-1979.
(2) Non-volatile test: 1g of a coating sample is taken, the sample is dried at 125 ℃ for 1h, the weight of the dried sample is detected, and the content of non-volatile matters in the sample is calculated according to GB/T1725-2007.
(3) Surface drying time: the measurement is carried out according to GB/T1728-1979, a paint sample is coated on a glass plate, the thickness of the coating is about 100um, a absorbent cotton ball is lightly placed on the surface of the coating, the cotton ball is lightly blown along the horizontal direction by 10-15 cm from the mouth, if the cotton ball is blown away, no cotton thread is left on the surface of the coating, the surface is considered to be dry, and the time is recorded.
(4) Real drying time: the measurement was carried out according to GB/T1728-1979 by applying a sample of the coating to a glass plate, the thickness of the coating being about 100um, placing a piece of qualitative filter paper on the coating, placing a further drying tester gently on the filter paper, simultaneously starting the stopwatch, after 30 seconds, removing the drying tester, turning the template over (coating downwards), the filter paper being free to fall, or tapping the back with the index finger of the hand holding the plate down, the filter paper being free to fall without the filter paper fibre being stuck to the coating, i.e. the coating is considered to be actually dry, and the time is recorded.
(5) Gloss test: the measurement was carried out according to GB/T9754-1998, and the measurement was carried out by using a BGD 516/2 dual-angle gloss meter manufactured by Guangzhou Bidada Co.
(6) Adhesion test: the measurement was performed according to GB/T9286-1998, and BGD502 test produced by Guangzhou Bida Limited was used.
(7) Pencil hardness test: the measurement was performed according to GB/T6739-2006, and a BGD 505 combination pencil durometer test manufactured by Guangzhou Bidada Co., ltd.
(8) Impact resistance test: the measurement was performed according to GB/T1732-1993, and BGD 304 coating impactor test manufactured by Guangzhou Bida limited was used.
(9) And (3) water resistance test: the test was carried out according to GB/T1733-1993, the sample plate was sealed with a model 600 adhesive tape from 3M company at room temperature, then immersed in water at 25℃to observe the coating, and the foaming time was recorded.
(10) Acid resistance test: measured according to GB/T9274-1988, the sample plate is sealed by a model 600 adhesive tape of 3M company at room temperature and then soaked in H with the mass concentration of 0.1mol/L 2 SO 4 In solution, the coating was observed and the etching time was recorded.
(11) Alkali resistance test: the test was carried out according to GB/T9274-1988, the sample plate was sealed with a model 600 adhesive tape of 3M company at room temperature, then immersed in a NaOH solution with a mass concentration of 0.1mol/L, the coating was observed, and the etching time was recorded.
(12) Salt water resistance test: the test was carried out according to GT/9274-1988, and after the sample plate was sealed with a model 600 adhesive tape of 3M company at room temperature, the sample plate was immersed in a NaCL solution having a mass concentration of 5%, and the coating was observed and the foaming time was recorded.
(13) Salt spray resistance test: the test is carried out according to GB/T1771-2007, after the template is sealed by using a model 600 adhesive tape of 3M company at room temperature, two breaking lines with an angle of 60 DEG are crossed and cut by a blade in the middle of the template, the coating is observed based on the cutting of the coating, and the corrosion time is recorded.
(14) Storage stability test: and (3) measuring according to GB/T6753.3-1986, taking three samples, filling the three samples into a 0.4L standard gland type metal paint can, weighing the samples with the sample filling amount being about 15mm away from the top of the can, then placing the samples into a constant temperature drying oven at 50+/-2 ℃, and after storing the samples for 7 days, checking whether the samples have the phenomena of skinning, sedimentation, coarse agglomeration, viscosity change, corrosion or spoilage, and the like.
(15) Test of artificial aging resistance: the measurement is carried out according to GB/T23987-2009, and a QUV/se type ultraviolet accelerated aging tester of Q-Panel company in the United states is adopted for testing, UVA aging, a lamp tube of UVA-340nm, 4h ultraviolet irradiation and 4h condensation.
The test results are shown in Table 4.
TABLE 4 Table 4
From the test results of application examples 1 to 7, it is understood that the polyether amine used in application example 1 has too small a proportion in the nonionic epoxy resin prepolymer component, resulting in a decrease in the impact resistance of the paint coating; the polyether amine used in application example 4 had an excessively large ratio in the nonionic epoxy resin prepolymer component, resulting in a decrease in the hardness of the paint coating, with a hardness grade of HB; application example 6 and application example 7 are inferior in impact resistance or hardness to application example 3 and application example 5, and therefore, the polyether amine of the present invention is preferably polyether amine M-2070 or a mixture of polyether amine M-2070 and polyether amine M-1000, and the epoxy resin is preferably epoxy resin E-20 or epoxy resin E-12.
In application examples 5 and application examples 8 to 17, the products of application examples 8 to 10 and application example 15 were better in combination properties.
In comparison with application example 5, in application comparative examples 1 to 2, polyether amine was not used, the ring-opening reaction of polyether amine and epoxy resin was not performed, but the epoxy resin, the raw material of the first mixed monomer, xylene and the catalyst were directly mixed, which resulted in deterioration of the water resistance, acid and alkali resistance, salt resistance and other properties of the coating, deterioration of the impact resistance of the coating, excessive viscosity of the dispersion, and further a prolonged open time of the coating.
Compared with application example 5, application comparative example 3 does not carry out ring opening reaction on polyether amine and epoxy resin in advance, but directly mixes polyether amine and epoxy resin with the first mixed monomer and catalyst, so that the hydrophilicity distribution is uneven, the emulsification of the second mixed monomer is insufficient, the particle size of polymer particles in the dispersion is larger, the storage stability is poor, and the water resistance, acid and alkali resistance, salt resistance and other performances of the coating are poor.
Compared with application example 14, application comparative example 4 has significantly larger average particle diameter, poorer storage stability, low grafting ratio and incomplete encapsulation, resulting in poor water resistance, acid and alkali resistance, salt resistance and the like of the coating.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. The epoxy acrylate hybrid dispersion is characterized by comprising the following raw materials in parts by weight: 100-150 parts of nonionic epoxy resin prepolymer, 310-480 parts of first mixed monomer, 0.1-1 part of catalyst, 125-200 parts of second mixed monomer, 70-90 parts of organic solvent, 680-800 parts of deionized water and 10-16 parts of free radical initiator; the nonionic epoxy resin prepolymer is formed by ring-opening reaction of polyether amine and epoxy resin; the first mixed monomer comprises the following raw materials in parts by weight: 180-250 parts of unsaturated oleic acid, 65-120 parts of polyol, 60-90 parts of polybasic acid and 5-20 parts of polybasic acid anhydride; the second mixed monomer comprises the following raw materials in parts by weight: 50-150 parts of acrylate monomer and 50-75 parts of vinyl monomer.
2. The epoxy acrylate hybrid dispersion of claim 1, comprising the following raw materials in parts by weight: 120 parts of nonionic epoxy resin prepolymer, 400 parts of first mixed monomer, 0.3-0.5 part of catalyst, 155-180 parts of second mixed monomer, 75-80 parts of organic solvent, 700-750 parts of deionized water and 12-14 parts of free radical initiator; the nonionic epoxy resin prepolymer is formed by ring-opening reaction of polyether amine and epoxy resin; the first mixed monomer comprises the following raw materials in parts by weight: 200-230 parts of unsaturated oleic acid, 75-100 parts of polyol, 65-86 parts of polybasic acid and 10-19 parts of polybasic acid anhydride; the second mixed monomer comprises the following raw materials in parts by weight: 100-110 parts of acrylate monomer and 55-70 parts of vinyl monomer.
3. The epoxy acrylate hybrid dispersion of claim 1 wherein the nonionic epoxy resin prepolymer comprises the following raw materials in parts by weight: 300-750 parts of polyether amine and 750-1200 parts of epoxy resin; the polyether amine comprises at least one of polyether amine D-240, polyether amine D-400, polyether amine D-2000, polyether amine M-600, polyether amine M-1000, polyether amine M-2070 and polyether amine M-3085; the epoxy resin comprises at least one of epoxy resin E-51, epoxy resin E-44, epoxy resin E-20, epoxy resin E-12 and epoxy resin E-03.
4. A process for preparing the epoxy acrylate hybrid dispersion according to any one of claims 1 to 3, comprising the steps of:
(1) Mixing the nonionic epoxy resin prepolymer, the first mixed monomer and the catalyst, performing esterification reaction, and then adding an organic solvent and deionized water for mixing and diluting;
(2) Adding a second mixed monomer into the product obtained in the step (1) to perform pre-emulsification dispersion;
(3) And (3) adding a free radical initiator into the product obtained in the step (2), and carrying out in-situ emulsion polymerization to obtain the epoxy acrylate hybrid dispersion.
5. The method for preparing an epoxy acrylate hybrid dispersion according to claim 4, wherein the step (1) specifically comprises: mixing the nonionic epoxy resin prepolymer with the first mixed monomer, reflux-reacting with dimethylbenzene as a solvent at 200-230 ℃ until the acid value of the system reaches 3-5 mgKOH/g, removing dimethylbenzene under reduced pressure, cooling to 65-85 ℃, and adding an organic solvent and deionized water for mixing and diluting.
6. The method for preparing an epoxy acrylate hybrid dispersion according to claim 5, wherein the time of pre-emulsification and dispersion in the step (2) is 20 to 40min.
7. The method of preparing an epoxy acrylate hybrid dispersion according to claim 5 wherein the in-situ emulsion polymerization conditions in step (3) are: the temperature is 45-65 ℃ and the time is 2-4 h.
8. Use of an epoxy acrylate hybrid dispersion according to any one of claims 1 to 3 for the preparation of an aqueous coating.
9. An aqueous one-component metal anticorrosive coating comprising a pigment filler, a co-solvent, an auxiliary agent, deionized water, and the epoxy acrylate hybrid dispersion of any one of claims 1 to 3.
10. The aqueous one-component metallic anti-corrosive coating of claim 9, wherein said adjuvant comprises at least one of a pH adjuster, a dispersant, a leveling agent, a wetting agent, an antifoaming agent, a drier, an anti-flash rust agent, and a thickener; the pigment and filler comprises at least one of an inorganic pigment, an organic pigment, a metal complex pigment and a filler.
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