CN108192490B - Water-based composite resin composition, water-based plastic paint and preparation method thereof - Google Patents

Water-based composite resin composition, water-based plastic paint and preparation method thereof Download PDF

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CN108192490B
CN108192490B CN201711376460.4A CN201711376460A CN108192490B CN 108192490 B CN108192490 B CN 108192490B CN 201711376460 A CN201711376460 A CN 201711376460A CN 108192490 B CN108192490 B CN 108192490B
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aqueous
water
plastic paint
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ethylenediamine
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CN108192490A (en
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赵炳炎
邓俊英
张洁
耿丹丹
孙家宽
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
Wanhua Chemical Guangdong Co Ltd
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
Wanhua Chemical Guangdong Co Ltd
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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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6625—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/34
    • 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 belongs to the technical field of water-based plastic paint, and provides a water-based composite resin composition, a water-based plastic paint and a preparation method thereof, wherein the water-based composite resin composition is prepared from the following components in percentage by weight: 70-90 wt% of aqueous polyurethane resin with large particle size, the particle size of the aqueous polyurethane resin is 800-2000 nm, 6-25 wt% of aqueous acrylic resin and 2-8 wt% of auxiliary agent. The water-based plastic paint is prepared from the following raw materials in parts by weight: A. 100 parts by weight of the aqueous composite resin composition as described above; B. 2-6 parts of a water-based isocyanate curing agent. According to the invention, the waterborne polyurethane resin with large particle size and the waterborne acrylic resin are compounded, so that the plastic paint has excellent adhesive force, scratch resistance, wear resistance, chemical resistance and other properties.

Description

Water-based composite resin composition, water-based plastic paint and preparation method thereof
Technical Field
The invention belongs to the technical field of water-based plastic paint, and particularly relates to a water-based composite resin composition, water-based plastic paint and a preparation method thereof.
Background
The water-based environment-friendly polyurethane paint does not contain organic solvent, is nontoxic and convenient to use, and has physical and chemical properties reaching the effect of solvent-based paint, so that the application of the water-based environment-friendly polyurethane paint in the fields of textile coating, leather finishing, industrial paint and the like is more and more emphasized, and the water-based environment-friendly polyurethane paint is the trend of the development of the future industry.
In addition, products with matte surface material are more and more favored. At present, the direct addition of matting powder in the formulation for preparing matte materials is still the most widely used method. However, the organic or inorganic matting powder has rough or slippery hand feeling, poor compatibility with the main film-forming resin, poor abrasion resistance, poor scratch resistance and poor chemical resistance.
The pure aqueous large-particle-size self-extinction polyurethane resin has extremely low matt degree and excellent black haze, no dulling agent is required to be added in the system, and the product obtained by using the pure aqueous large-particle-size self-extinction polyurethane resin has good soft touch feeling and has a wide application prospect in plastic products.
On the basis of the existing products and technologies, if a water-based plastic paint can be developed, the plastic paint can maintain the matte degree, black transmittance and soft touch caused by the large-particle-size self-extinction polyurethane resin, and can remarkably improve the performances of adhesive force, wear resistance, scratch resistance, alcohol rub resistance, hand sweat resistance and the like of the plastic paint on a plastic base material, so that the water-based plastic paint has wide application prospect and market value.
Disclosure of Invention
The invention aims to provide a water-based composite resin composition, a water-based plastic paint and a preparation method thereof aiming at the problems in the prior art, and the prepared water-based plastic paint not only has better matte brightness and soft touch, but also has excellent adhesive force, scratch resistance, wear resistance, alcohol rub resistance and hand sweat resistance.
In order to achieve the above object, the present invention provides an aqueous composite resin composition, which is prepared from the following components, by weight, based on the total weight of the components being 100 wt%:
70-90 wt% of aqueous large-particle-size polyurethane resin, preferably 75-87 wt%, with the particle size of 800-2000 nm, preferably 1000-1800 nm;
6-25 wt% of water-based acrylic resin, preferably 9-20 wt%;
2-8 wt% of an auxiliary agent, preferably 2-5 wt%.
According to the aqueous composite resin composition provided by the invention, preferably, the aqueous large-particle-size polyurethane resin is prepared by a polymerization reaction of aliphatic diisocyanate, polyol, hydrophilic compound and chain extender.
Preferably, the weight ratio of the aliphatic diisocyanate to the polyol to the hydrophilic compound to the chain extender is 20-40: 60-80: 1-5: 1 to 10.
According to the aqueous composite resin composition provided by the invention, preferably, the aliphatic diisocyanate is selected from one or more of hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate.
In a preferred embodiment of the present invention, the aliphatic diisocyanate is selected from a composite of hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, wherein the weight ratio of the hexamethylene diisocyanate to the dicyclohexylmethane diisocyanate is 1 to 50: 1, more preferably 4 to 20: 1; or the aliphatic diisocyanate is selected from a compound of hexamethylene diisocyanate and isophorone diisocyanate, wherein the weight ratio of the hexamethylene diisocyanate to the isophorone diisocyanate is 1-50: 1, more preferably 4 to 20: 1. hexamethylene diisocyanate is slightly flexible, dicyclohexylmethane diisocyanate and isophorone diisocyanate are slightly rigid, and the aliphatic diisocyanate is compounded for the purpose of: the polyurethane resin with large particle size is added into the formula to prepare a paint film with a certain rigid hardness while the surface hand feeling of the paint film keeps more flexible and elastic, and the paint film is favorable for obtaining good wear-resistant, hand sweat-resistant and velvety soft touch effects.
According to the aqueous composite resin composition provided by the invention, preferably, the number average molecular weight of the polyol is 400-8000, and more preferably 1000-4000; one or more selected from the group consisting of polypropylene glycol ether glycol, polytetrahydrofuran ether glycol, 1, 4-butanediol adipate glycol, polyhexamethylene adipate glycol, neopentyl glycol adipate glycol, polycaprolactone glycol and polycarbonate glycol, and more preferably one or more selected from the group consisting of polytetrahydrofuran ether glycol, polycaprolactone glycol and polycarbonate glycol.
In a preferred embodiment of the present invention, the polyol is selected from a compound of polytetrahydrofuran ether glycol and polycaprolactone diol, wherein the weight ratio of polytetrahydrofuran ether glycol to polycaprolactone diol is 1-20: 1, more preferably 2 to 10: 1; or the polyol is selected from a compound of polytetrahydrofuran ether glycol and polycarbonate diol, wherein the weight ratio of polytetrahydrofuran ether glycol to polycarbonate diol is 1-20: 1, more preferably 2 to 10: 1. the polytetrahydrofuran ether glycol is flexible, the polycaprolactone diol and the polycarbonate diol are rigid, and the polyol is compounded to ensure that the large-particle-size polyurethane resin is uniformly distributed on the whole molecular chain in a flexible and rigid structure manner, so that the surface hand feeling of a paint film prepared by adding the large-particle-size polyurethane resin into the formula keeps more flexible and elastic, and the paint film has certain rigidity and hardness, and is favorable for obtaining good wear-resisting, hand sweat-resisting and skin-like soft touch effects.
According to the aqueous composite resin composition provided by the present invention, preferably, the hydrophilic compound is selected from a hydrophilic compound containing an ionic group or a hydrophilic compound containing a nonionic group.
Preferably, the hydrophilic compound containing ionic groups is selected from one or more of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolacetic acid, dihydroxysuccinic acid, N- (2-aminoethyl) -2-aminoethanesulfonate and N- (3-aminopropyl) -2-aminoethanesulfonic acid.
Preferably, the hydrophilic compound containing a nonionic group is selected from polyethoxy ethers having a number average molecular weight of 150 to 10000 and an ethylene oxide number of 5 to 200, and more preferably from bifunctional polyethoxy ethers having a number average molecular weight of 500 to 2000 and an ethylene oxide number of 10 to 80.
In a preferred embodiment of the invention, the hydrophilic compound is selected from one or more of dimethylolpropionic acid, N- (2-aminoethyl) -2-aminoethanesulfonate, Ymer (TM) 120 and MPEG 1200.
According to the aqueous composite resin composition provided by the invention, preferably, the chain extender is a small-molecular organic amine compound selected from one or more of isophorone diamine, N- (2-hydroxyethyl) ethylene diamine and ethylene diamine.
In a preferred embodiment of the invention, the chain extender is selected from a compound of N- (2-hydroxyethyl) ethylenediamine and isophorone diamine, wherein the molar ratio of N- (2-hydroxyethyl) ethylenediamine to isophorone diamine is 0.2-10: 1, more preferably 0.5 to 5: 1; or the chain extender is selected from a compound of N- (2-hydroxyethyl) ethylenediamine and ethylenediamine, wherein the molar ratio of the N- (2-hydroxyethyl) ethylenediamine to the ethylenediamine is 0.2-10: 1, more preferably 0.5 to 5: 1. the N- (2-hydroxyethyl) ethylenediamine contains redundant 2-hydroxyethyl groups, and can play a role in internal plasticization in a paint film made of the aqueous large-particle-size polyurethane resin, so that the aqueous large-particle-size polyurethane resin has certain film forming property, and the plastic paint is ensured to have uniform matte transparency, wear resistance and other properties.
In the invention, the preparation method of the aqueous large-particle-size polyurethane resin comprises the following steps of:
adding dehydrated polyol, aliphatic diisocyanate, hydrophilic compound and acetone into a reaction vessel filled with nitrogen to contact, and stirring the mixture at 70-90 ℃ to react; dissolving the obtained prepolymer in acetone and cooling until the NCO value in the system reaches 1.5-2.8 wt%, contacting the aqueous solution in which the chain extender is dissolved with the acetone solution in which the prepolymer is dissolved, stirring vigorously for 10-30 minutes, dispersing the mixture by adding water, and then adding an emulsifier; finally, after acetone is separated out by distillation, the aqueous polyurethane resin emulsion with large particle size is obtained. The solid content of the aqueous large-particle-size polyurethane resin emulsion is adjusted by adding water, and the particle size of the aqueous large-particle-size polyurethane resin in the emulsion is 800-2000 nm, so that the emulsion has self-extinction performance.
In a preferred embodiment of the present invention, in the method for preparing the aqueous large-particle-size polyurethane resin, the amount of polytetrahydrofuran ether glycol is 70 to 200 parts, the amount of polycaprolactone glycol or polycarbonate glycol is 50 to 100 parts, the amount of hexamethylene diisocyanate is 12 to 45 parts, the amount of dicyclohexylmethane diisocyanate or isophorone diisocyanate is 3 to 15 parts, the amount of acetone is 350 to 550 parts, the amount of hydrophilic compound is 1 to 6 parts, the amount of N- (2-hydroxyethyl) ethylenediamine is 1 to 15 parts, the amount of isophorone diamine or ethylene diamine is 0.5 to 5 parts, and the amount of emulsifier is 2 to 6 parts. In the preparation method, the components are used in parts by weight.
The emulsifier is a non-ionic emulsifier, preferably selected from LCN070, LCN407 and one or more of Tween20 and Tween60 of Craine, more preferably selected from LCN407 and/or Tween 20.
According to the aqueous composite resin composition provided by the invention, preferably, the polymerized monomer of the aqueous acrylic resin is selected from one or more mixed monomers of styrene, methyl methacrylate, acrylic acid, butyl methacrylate, methacrylic acid, butyl acrylate, ethyl methacrylate and vinyl acetate and one or two of tetrahydrofuran acrylate and tetrahydrofuran acrylate; the Tg value of the mixed monomer is 20-100 ℃.
In a preferred embodiment of the present invention, the polymerized monomer of the aqueous acrylic resin is selected from a mixed monomer consisting of one of styrene and methyl methacrylate and one of tetrahydrofuran acrylate and tetrahydrofuran acrylate; based on the total molar weight of the mixed monomers being 100%, the mole percentage of the styrene or the methyl methacrylate is 30-70%; the polymerization monomer of the aqueous acrylic resin necessarily contains tetrahydrofuran acrylate or tetrahydrofuran acrylate, and the mole percentage of the tetrahydrofuran acrylate or the tetrahydrofuran acrylate is 30-70%. In the polymerization process of the water-based acrylic resin, when the molar amount of tetrahydrofuran acrylate or tetrahydrofuran acrylate serving as a polymerization monomer is more than 30%, the prepared plastic paint prepared from the water-based acrylic resin can show excellent adhesive force when being coated on plastic substrates such as ABS and the like. The Tg of the tetrahydrofuran acrylate or the tetrahydrofuran acrylate is low, and the hardness and the resistance of a paint film prepared from the plastic paint are affected by the too soft acrylic resin, so that a high-Tg polymerization monomer (such as styrene and methyl methacrylate) is required to be introduced in the polymerization process of the water-based acrylic resin, so that the adhesion is satisfied, and the hardness and the other resistance of the paint film are ensured.
In a preferred embodiment of the present invention, the method for preparing the aqueous acrylic resin comprises the steps of:
under the protection of nitrogen, mixing 1-3 parts of sodium dodecyl sulfate, 1-3 parts of nonylphenyl polyoxyethylene ether, 0.2-1 part of ammonium persulfate and 50-70 parts of water, stirring to fully dissolve the sodium dodecyl sulfate, adding 60 parts of a tetrahydrofuran acrylate monomer or a tetrahydrofuran acrylate monomer and 40 parts of a styrene monomer or a methyl methacrylate monomer while stirring, gradually heating to 80-90 ℃, reacting at a constant temperature for 1-2 hours, cooling to 65-70 ℃, adding 8-15 parts of a prepared 1.5 wt% sodium bisulfite solution into a reaction container, adding ammonia water to adjust the pH value to 7-9, cooling to room temperature, and discharging. In the preparation method, the components are used in parts by weight.
According to the aqueous composite resin composition provided by the invention, preferably, the solid content of the aqueous large-particle-size polyurethane resin is 34-36 wt%, and the solid content of the aqueous acrylic resin is 39-41 wt%.
Preferably, the auxiliary agent is selected from one or more of an aqueous wetting agent, an aqueous leveling agent, an aqueous defoaming agent, an aqueous thickening agent, a pH regulator and a sterilization and mildew prevention agent.
The invention also aims to provide the water-based plastic paint which is prepared from the following raw materials in parts by weight:
A. 100 parts by weight of the aqueous composite resin composition as described above;
B. 2-6 parts of a water-based isocyanate curing agent.
The invention also provides a preparation method of the water-based plastic paint, which comprises the following steps:
1) preparation of component A: dispersing and mixing the aqueous large-particle-size polyurethane resin, the aqueous acrylic resin and the auxiliary agent, adjusting the viscosity of the mixture to 400-1000 cps, adjusting the pH value of the mixture to 8-9, and filtering to obtain a component A;
2) preparing paint: and uniformly stirring the component A and the component B to obtain the water-based plastic paint.
In the preparation method of the water-based plastic paint, the step 1) of dispersing and mixing is carried out at a rotating speed of 300-500 r/min. And 2) uniformly stirring the component A and the component B for 10min, wherein the obtained water-based plastic paint is recommended to be used within 4 h.
The inventors have selected from the usual auxiliaries for the preparation of varnishes or paints for the purpose of the invention, and have preferred the auxiliaries to be added to the formulation and the amounts thereof to be added in accordance with the effect of the test. Therefore, in the above formulation, in addition to the water-based large particle size polyurethane resin and the water-based acrylic resin, the auxiliary agents are those commonly used in the art and can be used in the present invention. The preferred scheme of each type of auxiliary agent is as follows:
the water-based wetting agent has the function of enabling the plastic paint to be uniformly spread on a plastic substrate without shrinkage cavity at a relatively low viscosity; the aqueous wetting agent is preferably a silicone-based wetting agent such as Silok8000 from Stokes or 104E from air chemistry.
The aqueous leveling agent has the effects that a paint film of the plastic paint is uniformly leveled in the construction process, the paint film is smooth, and the hand sweat resistance, scratch resistance and other performances are improved; the aqueous leveling agent is preferably a silicone-based leveling agent, such as Tego-410 of winning company or Silok8488 of Storocco company.
The water-based defoaming agent has the effects of solving the problems of bubbles generated in the plastic paint preparation process and avoiding shrinkage cavities during defoaming in the construction process; the aqueous antifoam agent may be selected from silicone antifoam agents, organic lipid antifoam agents or silicone antifoam agents, preferably silicone antifoam agents such as BYK024 from Pico or Deform W-0506 from Hamming Demodex.
The pH adjuster may be high purity industrial grade ammonia water of 30% effective mass content.
The water-based thickener has the functions of ensuring that the environment-friendly matte soft-feel plastic paint has excellent sagging resistance and leveling property in the construction process, and avoiding the sedimentation, water diversion or layering of the large-particle-size self-extinction polyurethane resin in the component A. As the thickener, an alkali-swelling acrylic thickener such as those available from Wanhua corporation can be used
Figure BDA0001514672360000071
And
Figure BDA0001514672360000073
and associative polyurethane thickeners, e.g. from Wanhua company
Figure BDA0001514672360000072
And AcrysolRW-8W and Acrysol RW-12W of Dow chemical.
The sterilization and mildew-proof agent has the function of ensuring that the component A of the plastic paint has a certain in-tank storage period, and the addition of the sterilization and mildew-proof agent is necessary because the plastic paint does not use a solvent; preferably, the broad-spectrum sterilization mildewcide Karthon of Dow chemical comprises the chemical components of CMIT/MIT, the mass ratio of the CMIT to the MIT is 3:1, and the effective component is 1.5 wt%.
The aqueous isocyanate curing agentThe isocyanate curing agent has the effects of assisting in improving important components of the adhesion, hardness, alcohol rub resistance, hand sweat resistance and other resistance of a paint film of the water-based environment-friendly high-adhesion matte soft-feel plastic paint, and improving the performances of the paint film such as hardness, alcohol rub resistance, hand sweat resistance, scratch resistance and the like by improving the crosslinking density of the paint film. The waterborne isocyanate curing agent adopts a HDI-based hydrophilic modified aliphatic isocyanate curing agent, such as products of Wanhua company
Figure BDA0001514672360000074
Or product of Corsia
Figure BDA0001514672360000075
In the research process, the inventor of the application finds that the waterborne composite resin composition is formed by compounding the waterborne polyurethane resin with large particle size and the waterborne acrylic resin, and can prepare the waterborne environment-friendly high-adhesion matte soft-feel plastic paint. The plastic paint film has better matt degree, substrate adhesive force, wear resistance and soft touch effect like velvety skin due to the compound use of the aqueous large-particle-size polyurethane resin and the aqueous acrylic resin. In the invention, no inorganic or organic matting powder is required to be added, the waterborne large-particle-size polyurethane resin provides extremely low matte brightness, black transmittance and soft touch effect like velvety skin, and the waterborne large-particle-size polyurethane resin is compounded with the waterborne acrylic resin and preferably selects a waterborne auxiliary agent, so that the plastic paint has excellent adhesive force, scratch resistance, wear resistance, chemical resistance and other properties. The invention uses water-based isocyanate as a curing agent, and has the advantages of safety, environmental protection, good crosslinking curing performance and excellent chemical resistance.
The technical scheme of the invention has the following beneficial effects:
1. the aqueous composite resin composition is used as the main resin of the aqueous plastic paint, provides matt, black and soft touch for the plastic paint, has simple formula, simple and convenient operation and high cost performance, and overcomes the defects of poor hand feeling, poor chemical resistance and the like caused by poor compatibility of the added matting powder and the resin;
2. according to the invention, the problem of poor adhesive force of the waterborne large-particle-size polyurethane resin on the plastic base material is solved by preferably selecting the waterborne acrylic resin and the waterborne auxiliary agent, rather than adding a solvent to corrode the base material, pretreating the plastic base material and the like, so that the method is simple and environment-friendly;
3. the requirements of different gloss and the like of the plastic paint are met by adjusting the proportion of the aqueous large-particle-size polyurethane resin and the aqueous acrylic resin, and the requirements of different levels of coating effects are met;
4. the water-based environment-friendly high-adhesion matte soft-feel plastic paint disclosed by the invention has the advantages of lower matte gloss, black transparency, excellent adhesion, scratch resistance, wear resistance and chemical resistance, no VOC (volatile organic compounds) in the process, uniform gloss and no defect white points, and solves the problem of application of large-particle-size self-extinction polyurethane resin in plastic substrates.
Detailed Description
In order that the technical features and contents of the present invention can be understood in detail, preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention have been described in the examples, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
Firstly, the source of raw materials
1. Aqueous large particle size polyurethane resin
Figure BDA0001514672360000081
Vanhua chemical group, Inc.;
Figure BDA0001514672360000082
vanhua chemical group, Inc.;
the aqueous large-particle-size polyurethane resin 1 is prepared by self;
the aqueous large-particle-size polyurethane resin 2 is prepared by self;
the aqueous large-particle-size polyurethane resin 3 is prepared by self;
2. water-based acrylic resin
Figure BDA0001514672360000083
Vanhua chemical group, Inc.;
the water-based acrylic resin 1 is prepared by self;
the waterborne acrylic resin 2 is prepared by self;
the waterborne acrylic resin 3 is prepared by self;
the waterborne acrylic resin 4 is prepared by self;
3. aqueous wetting agent
Silok8000, scoco;
104E, air chemistry;
4. aqueous defoaming agent
BYK024, Bike corporation;
deform W-0506, Hamming D.modest Inc.;
5. aqueous leveling agent
Silok8488, siloco;
tego-410, winning company;
6. aqueous thickener
Figure BDA0001514672360000091
Vanhua chemical group, Inc.;
Figure BDA0001514672360000092
vanhua chemical group, Inc.;
Figure BDA0001514672360000093
vanhua chemical group, Inc.;
acrysol RW-8W, Dow chemistry;
acrysol RW-12W, Dow chemistry;
7. bactericidal mildew inhibitor
Karthon, dow chemistry;
8. aqueous isocyanate curing agent
Figure BDA0001514672360000094
Vanhua chemical group, Inc.;
Figure BDA0001514672360000095
vanhua chemical group, Inc.;
Figure BDA0001514672360000096
scientific and creative company.
Example 1
The water-based plastic paint consists of a component A and a component B. Wherein the components A and B comprise the following components in parts by weight:
component A
Figure BDA0001514672360000101
Component B
Figure BDA0001514672360000102
5；
Wherein the content of the first and second substances,
Figure BDA0001514672360000103
the water-based large-particle-size polyurethane resin is mainly prepared from hexamethylene diisocyanate, 4' -dicyclohexylmethane diisocyanate, polytetrahydrofuran ether glycol, polycaprolactone glycol, MPEG1200, N- (2-aminoethyl) -2-aminoethane sulfonate, N- (2-hydroxyethyl) ethylenediamine and isophorone diamine.
Figure BDA0001514672360000104
The acrylic resin is water-based acrylic resin, and the main raw materials of the acrylic resin comprise styrene, methyl methacrylate and tetrahydrofuran acrylate.
The manufacturing method of the water-based plastic paint comprises the following steps:
the preparation method of the component A comprises the following steps: in the dispersing barrel, the dispersing machine is started, the rotating speed is adjusted to 300-500 r/min, and the components are added according to the formula amount
Figure BDA0001514672360000105
The water-based wetting agent, the water-based leveling agent, the water-based defoaming agent, the water-based thickening agent, the pH regulator and the sterilization mildew preventive are mixed, the viscosity is adjusted to be 800cps, the pH value is adjusted to be 8.5, and the mixture is filtered and packaged; and finishing the preparation of the component A. The component B is a waterborne isocyanate curing agent of Wanhua company
Figure BDA0001514672360000106
According to the formula, the component B is added into the component A, the mixture is uniformly stirred at a low speed for about 10min, a 150-micron wire rod is coated on a black ABS plate in a scraping manner to prepare a plastic sample plate, the plastic sample plate is cured for 2h at the temperature of 60 ℃, the plastic sample plate is placed at the normal temperature for 1 day, and the performance of a paint film is tested.
The test results are shown in table 1.
Example 2
The water-based plastic paint consists of a component A and a component B. Wherein the components A and B comprise the following components in parts by weight:
component A
Figure BDA0001514672360000111
Component B
Figure BDA0001514672360000112
6；
Wherein the content of the first and second substances,
Figure BDA0001514672360000113
the self-extinction polyurethane resin with large particle size is aqueous polyurethane resin with large particle size, and the main raw materials of the self-extinction polyurethane resin comprise hexamethylene diisocyanate, isophorone diisocyanate, polytetrahydrofuran ether glycol, polycarbonate diol, N120, N- (2-aminoethyl) -2-aminoethane sulfonate, N- (2-hydroxyethyl) ethylenediamine and isophorone diamine.
Wherein, the main raw materials of the water-based acrylic resin 1 comprise styrene, methyl methacrylate, tetrahydrofuran acrylate and tetrahydrofuran acrylate. The preparation method comprises the following steps:
under the protection of nitrogen, 2 parts of sodium dodecyl sulfate, 2 parts of nonylphenyl polyoxyethylene ether, 0.5 part of ammonium persulfate and 60 parts of water are mixed and stirred to be fully dissolved, 25 parts of tetrahydrofuran acrylate monomer, 20 parts of tetrahydrofuran acrylate monomer, 10 parts of styrene monomer and 15 parts of methyl methacrylate monomer are added while stirring, the temperature is gradually increased to 85 ℃, the mixture is cooled to 70 ℃ after reacting for 1.5h at a constant temperature, 10 parts of prepared 1.5 wt% sodium bisulfite solution is added into a reaction container, meanwhile, ammonia water is added to adjust the pH value to 8-8.5, then the mixture is cooled to room temperature, and the obtained waterborne acrylic resin is discharged, wherein the solid content of the waterborne acrylic resin is 40 wt%. In the preparation method, the components are used in parts by weight.
The manufacturing method and film forming method were the same as example 1.
The test results are shown in table 1.
Example 3
The water-based plastic paint consists of a component A and a component B. Wherein the components A and B comprise the following components in parts by weight:
component A
Figure BDA0001514672360000121
Component B
Figure BDA0001514672360000122
4；
The main raw materials of the aqueous large-particle-size polyurethane resin 1 comprise hexamethylene diisocyanate, isophorone diisocyanate, polytetrahydrofuran ether glycol, polycarbonate glycol, polycaprolactone glycol, MPEG1200, dimethylolpropionic acid, N- (2-aminoethyl) -2-aminoethane sodium sulfonate, N- (2-hydroxyethyl) ethylenediamine and ethylenediamine. Adding dehydrated polyol, aliphatic diisocyanate, hydrophilic compound and acetone into a reaction vessel filled with nitrogen to contact, and stirring the mixture at 80 ℃ to react; dissolving the obtained prepolymer in acetone and cooling until the NCO value in the system reaches 1.8 wt%, contacting the aqueous solution in which the chain extender is dissolved with the acetone solution in which the prepolymer is dissolved, stirring vigorously for 30 minutes, dispersing the mixture by adding water, and then adding an emulsifier; finally, after acetone is separated out by distillation, the aqueous polyurethane resin emulsion with large particle size is obtained. The solid content of the aqueous large-particle-size polyurethane resin emulsion is adjusted to be 35 wt% by adding water, and the particle size of the aqueous large-particle-size polyurethane resin in the emulsion is 1500nm, so that the aqueous large-particle-size polyurethane resin emulsion has self-extinction performance.
In the preparation method of the aqueous large-particle-size polyurethane resin, the using amount of polytetrahydrofuran ether glycol is 75 parts, the using amounts of polycaprolactone glycol and polycarbonate glycol are 15 parts, the using amount of hexamethylene diisocyanate is 30 parts, the using amount of isophorone diisocyanate is 10 parts, the using amount of acetone is 450 parts, the using amount of MPEG1200 is 0.5, the using amount of dimethylolpropionic acid is 0.5, the using amount of N- (2-aminoethyl) -2-aminoethane sodium sulfonate is 0.5, the using amount of N- (2-hydroxyethyl) ethylenediamine is 5 parts, the using amount of ethylenediamine is 2 parts, and the using amount of an emulsifier is 5 parts. In the preparation method, the components are used in parts by weight.
The main raw materials of the water-based acrylic resin 2 comprise styrene, acrylic acid, methyl methacrylate, tetrahydrofuran acrylate and tetrahydrofuran acrylate. The preparation method comprises the following steps:
under the protection of nitrogen, 2 parts of sodium dodecyl sulfate, 1 part of nonylphenyl polyoxyethylene ether, 0.5 part of ammonium persulfate and 60 parts of water are mixed and stirred to be fully dissolved, 15 parts of tetrahydrofuran acrylate monomer, 35 parts of tetrahydrofuran acrylate monomer, 5 parts of acrylic acid monomer, 10 parts of styrene monomer and 10 parts of methyl methacrylate monomer are added while stirring, the temperature is gradually increased to 90 ℃, the temperature is reduced to 70 ℃ after 1 hour of constant temperature reaction, prepared 8 parts of 1.5 wt% sodium bisulfite solution is added into a reaction container, meanwhile, ammonia water is added to adjust the pH value to 8-8.5, then the temperature is reduced to room temperature, and discharging is carried out, wherein the solid content of the obtained waterborne acrylic resin is 40 wt%. In the preparation method, the components are used in parts by weight.
The manufacturing method and film forming method were the same as example 1.
The test results are shown in table 1.
Example 4
The water-based plastic paint consists of a component A and a component B. Wherein the components A and B comprise the following components in parts by weight:
component A
Figure BDA0001514672360000131
Figure BDA0001514672360000141
B component
Figure BDA0001514672360000142
2；
The main raw materials of the aqueous large-particle-size polyurethane resin 2 comprise hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate, polytetrahydrofuran ether glycol, polycaprolactone glycol, MPEG1200, dimethylolpropionic acid, N- (2-hydroxyethyl) ethylenediamine and isophorone diamine. Adding dehydrated polyol, aliphatic diisocyanate, hydrophilic compound and acetone into a reaction vessel filled with nitrogen to contact, and stirring the mixture at 80 ℃ to react; dissolving the obtained prepolymer in acetone and cooling until the NCO value in the system reaches 1.8 wt%, contacting the aqueous solution in which the chain extender is dissolved with the acetone solution in which the prepolymer is dissolved, stirring vigorously for 30 minutes, dispersing the mixture by adding water, and then adding an emulsifier; finally, after acetone is separated out by distillation, the aqueous polyurethane resin emulsion with large particle size is obtained. The solid content of the aqueous large-particle-size polyurethane resin emulsion is adjusted to be 35 wt% by adding water, and the particle size of the aqueous large-particle-size polyurethane resin in the emulsion is 800nm, so that the aqueous large-particle-size polyurethane resin emulsion has self-extinction performance.
In the preparation method of the aqueous large-particle-size polyurethane resin, the using amount of polytetrahydrofuran ether glycol is 75 parts, the using amount of polycaprolactone glycol is 50 parts, the using amount of hexamethylene diisocyanate is 20 parts, the using amount of dicyclohexylmethane diisocyanate is 15 parts, the using amount of acetone is 550 parts, the using amount of MPEG1200 is 2 parts, the using amount of dimethylolpropionic acid is 3 parts, the using amount of N- (2-hydroxyethyl) ethylenediamine is 10 parts, the using amount of isophorone diamine is 5 parts, and the using amount of an emulsifier is 2 parts. In the preparation method, the components are used in parts by weight.
Wherein, the main raw materials of the water-based acrylic resin 3 comprise methyl methacrylate and tetrahydrofuran acrylate. The preparation method comprises the following steps:
under the protection of nitrogen, 3 parts of sodium dodecyl sulfate, 3 parts of nonylphenyl polyoxyethylene ether, 1 part of ammonium persulfate and 60 parts of water are mixed and stirred to be fully dissolved, 60 parts of tetrahydrofuran acrylate monomer and 40 parts of methyl methacrylate monomer are added while stirring, the temperature is gradually increased to 80 ℃, the temperature is reduced to 65 ℃ after 2 hours of constant temperature reaction, 8 parts of prepared 1.5 wt% sodium bisulfite solution is added into a reaction container, meanwhile, ammonia water is added to adjust the pH value to 8-8.5, then the temperature is reduced to room temperature, discharging is carried out, and the solid content of the obtained waterborne acrylic resin is 40 wt%. In the preparation method, the components are used in parts by weight.
The manufacturing method and film forming method were the same as example 1.
The test results are shown in table 1.
Comparative example 1
The preparation method, formulation components and film-making method are the same as example 1, except that aqueous large-particle-size polyurethane resin 3 is used instead of aqueous large-particle-size polyurethane resin
Figure BDA0001514672360000151
The main raw materials of the aqueous large-particle-size polyurethane resin 3 comprise hexamethylene diisocyanate, isophorone diisocyanate, polytetrahydrofuran ether glycol, polycarbonate glycol, polycaprolactone glycol, MPEG1200, dimethylolpropionic acid, N- (2-aminoethyl) -2-aminoethane sodium sulfonate, N- (2-hydroxyethyl) ethylenediamine and ethylenediamine. Adding dehydrated polyol, aliphatic diisocyanate, hydrophilic compound and acetone into a reaction vessel filled with nitrogen to contact, and stirring the mixture at 80 ℃ to react; dissolving the obtained prepolymer in acetone and cooling until the NCO value in the system reaches 1.8 wt%, contacting the aqueous solution in which the chain extender is dissolved with the acetone solution in which the prepolymer is dissolved, stirring vigorously for 30 minutes, dispersing the mixture by adding water, and then adding an emulsifier; finally, after acetone is separated out by distillation, the aqueous polyurethane resin emulsion with large particle size is obtained. The solid content of the aqueous large-particle-size polyurethane resin emulsion is adjusted to 35 wt% by adding water, and the particle size of the aqueous large-particle-size polyurethane resin in the emulsion is 500nm, so that the aqueous large-particle-size polyurethane resin emulsion has self-extinction performance.
In the preparation method of the aqueous large-particle-size polyurethane resin, the using amount of polytetrahydrofuran ether glycol is 75 parts, the using amounts of polycaprolactone glycol and polycarbonate glycol are 15 parts, the using amount of hexamethylene diisocyanate is 25 parts, the using amount of isophorone diisocyanate is 5 parts, the using amount of acetone is 450 parts, the using amount of MPEG1200 is 3 parts, the using amount of dimethylolpropionic acid is 5 parts, the using amount of N- (2-aminoethyl) -2-aminoethane sodium sulfonate is 1.5 parts, the using amount of N- (2-hydroxyethyl) ethylenediamine is 5 parts, the using amount of ethylenediamine is 2 parts, and the using amount of an emulsifier is 5 parts. In the preparation method, the components are used in parts by weight.
The test results are shown in table 2.
Comparative example 2
The preparation method, the formula components and the film preparation method are the same as example 1, except that the aqueous acrylic resin 4 is used for replacing the aqueous acrylic resin
Figure BDA0001514672360000161
Wherein, the main raw materials of the water-based acrylic resin 3 comprise methyl methacrylate, styrene, butyl methacrylate and ethyl methacrylate. The preparation method comprises the following steps:
under the protection of nitrogen, 3 parts of sodium dodecyl sulfate, 3 parts of nonylphenyl polyoxyethylene ether, 1 part of ammonium persulfate and 60 parts of water are mixed and stirred to be fully dissolved, 20 parts of methyl methacrylate monomer, 15 parts of styrene monomer, 25 parts of butyl methacrylate monomer and 45 parts of ethyl methacrylate monomer are added while stirring, the temperature is gradually increased to 80 ℃, the temperature is reduced to 65 ℃ after 2-hour constant-temperature reaction, 8 parts of prepared 1.5% sodium bisulfite solution is added into a reaction container, meanwhile, ammonia water is added to adjust the pH value to 8-8.5, then the mixture is cooled to room temperature to be discharged, and the solid content of the obtained waterborne acrylic resin is 40 wt%. In the preparation method, the components are used in parts by weight.
The test results are shown in table 2.
Comparative example 3:
the preparation method and the film preparation method are the same as the example 3, except that the dosage of the aqueous large-particle-size polyurethane resin and the aqueous acrylic resin is different from the example 3, and the specific formula is as follows:
Figure BDA0001514672360000162
component B
Figure BDA0001514672360000163
4；
The test results are shown in table 2.
Comparative example 4:
the preparation method and the film preparation method are the same as the example 3, except that the dosage of the aqueous large-particle-size polyurethane resin and the aqueous acrylate resin is different from the example 3, and the specific formula is as follows:
Figure BDA0001514672360000171
component B
Figure BDA0001514672360000172
4；
The test results are shown in table 2.
TABLE 1 results of the measurements of the basic properties of the paint films obtained in the examples
Figure BDA0001514672360000173
Figure BDA0001514672360000181
TABLE 2 results of the measurements of the basic properties of the paint films obtained in the examples
Figure BDA0001514672360000182
Figure BDA0001514672360000191
Remarking: the film transmittance in tables 1 and 2 was graded as 1-5, 5-for best, and 1-for worst, as judged by visual observation. In the wear resistance test, the smaller the weight loss is, the better the wear resistance is represented, and the stronger the scratch resistance is; in the adhesion test, a smaller number represents better adhesion.
Comparing the performance data of comparative example 1 and example 1 shows that:
the gloss value of comparative example 1 was very high and the paint film had no skin-feel tactile effect; mainly, in comparative example 1, the amount of dimethylolpropionic acid and N- (2-aminoethyl) -2-aminoethane sulfonic acid sodium added is increased, so that the hydrophilic groups of the prepared aqueous polyurethane resin with large particle size are too much, the particle size is too small, and a self-extinction effect cannot be formed when a paint film is dried to form a film, so that a matte touch effect cannot be obtained.
As can be seen by comparing the performance data of comparative example 2 and example 1:
the adhesive force of the comparative example 2 is poor, and the wear resistance of the paint film is poor; mainly, the polymerized monomer of the aqueous acrylic resin in the comparative example 2 does not contain tetrahydrofuran acrylate or tetrahydrofuran acrylate, and tests show that the polymerized monomer of the aqueous acrylic resin contains the two monomers, so that the prepared plastic paint can establish good adhesive force on the ABS substrate.
As can be seen by comparing the performance data of comparative example 3 and example 3:
the comparative example 3 has lower glossiness, poorer adhesion and poorer abrasion resistance of the paint film; the proportion of the aqueous acrylic resin in the component A in the comparative example 3 is too small, which affects the film forming property of the aqueous polyurethane resin with large particle size in the plastic paint, so that the adhesive force is obviously affected, and the abrasion resistance is affected.
As can be seen by comparing the performance data of comparative example 4 and example 3:
the gloss value of comparative example 4 was very high and the paint film had no skin-feel tactile effect; the main reason is that the proportion of the aqueous acrylic resin in the component A is too large, so that the self-extinction effect with large particle size cannot be displayed, and the skin-feeling touch effect required by the market cannot be obtained, although other indexes can meet the performance requirements of the plastic paint.
In conclusion, the water-based plastic paint disclosed by the invention has the advantages of lower matte degree, black transmittance, excellent adhesive force, scratch resistance, wear resistance, chemical resistance and the like, meanwhile, the process has no VOC (volatile organic compounds), the gloss is uniform, no flaws and white spots exist, and the problem of application of large-particle-size polyurethane resin in plastic substrates is solved. Therefore, the invention can provide a solution of a high-adhesion matte soft-feel plastic coating system with high cost performance, high performance and high environmental protection.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.

Claims (19)

1. The water-based plastic paint is characterized by being prepared from the following raw materials in parts by weight:
A. 100 parts by weight of an aqueous composite resin composition;
B. 2-6 parts of water-based isocyanate curing agent;
the aqueous composite resin composition is prepared from the following components in percentage by weight, wherein the total weight of the components is 100 wt%:
70-90 wt% of aqueous large-particle-size polyurethane resin, wherein the particle size of the aqueous large-particle-size polyurethane resin is 800-2000 nm;
6-25 wt% of water-based acrylic resin;
2-8 wt% of an auxiliary agent;
the polymerization monomer of the water-based acrylic resin is selected from one or more of styrene, methyl methacrylate, acrylic acid, butyl methacrylate, methacrylic acid, butyl acrylate, ethyl methacrylate and vinyl acetate and one or two of tetrahydrofuran acrylate and tetrahydrofuran acrylate to form a mixed monomer; the Tg value of the mixed monomer is 20-100 ℃;
the waterborne large-particle-size polyurethane resin is prepared by polymerization reaction of aliphatic diisocyanate, polyol, hydrophilic compound and chain extender;
the aliphatic diisocyanate is selected from a compound of hexamethylene diisocyanate and dicyclohexylmethane diisocyanate or a compound of hexamethylene diisocyanate and isophorone diisocyanate;
the polyalcohol is selected from a compound of polytetrahydrofuran ether glycol and polycaprolactone diol, or a compound of polytetrahydrofuran ether glycol and polycarbonate diol;
the chain extender is selected from a compound of N- (2-hydroxyethyl) ethylenediamine and isophorone diamine or a compound of N- (2-hydroxyethyl) ethylenediamine and ethylenediamine.
2. The water-based plastic paint according to claim 1, wherein the water-based composite resin composition is prepared from the following components in percentage by weight:
75-87 wt% of aqueous large-particle-size polyurethane resin;
9-20 wt% of water-based acrylic resin;
2-5 wt% of an auxiliary agent.
3. The water-based plastic paint according to claim 1, wherein the particle size of the water-based large-particle size polyurethane resin is 1000-1800 nm.
4. The aqueous plastic paint according to claim 1, wherein in the aqueous large-particle-size polyurethane resin,
the weight ratio of the aliphatic diisocyanate to the polyol to the hydrophilic compound to the chain extender is 20-40: 60-80: 1-5: 1 to 10.
5. The water-based plastic paint according to claim 1, wherein in the compound of hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, the weight ratio of hexamethylene diisocyanate to dicyclohexylmethane diisocyanate is 1-50: 1; or in the compound of hexamethylene diisocyanate and isophorone diisocyanate, the weight ratio of the hexamethylene diisocyanate to the isophorone diisocyanate is (1-50): 1.
6. the water-based plastic paint according to claim 5, wherein in the composite of hexamethylene diisocyanate and dicyclohexylmethane diisocyanate, the weight ratio of hexamethylene diisocyanate to dicyclohexylmethane diisocyanate is 4-20: 1; or in the compound of hexamethylene diisocyanate and isophorone diisocyanate, the weight ratio of hexamethylene diisocyanate to isophorone diisocyanate is 4-20: 1.
7. the aqueous plastic paint according to any one of claims 1 to 6, wherein the polyol has a number average molecular weight of 400 to 8000;
in the compound of the polytetrahydrofuran ether glycol and the polycaprolactone diol, the weight ratio of the polytetrahydrofuran ether glycol to the polycaprolactone diol is 1-20: 1; or in the compound of the polytetrahydrofuran ether glycol and the polycarbonate dihydric alcohol, the weight ratio of the polytetrahydrofuran ether glycol to the polycarbonate dihydric alcohol is 1-20: 1.
8. the water-based plastic paint according to claim 7, wherein the polyol has a number average molecular weight of 1000 to 4000.
9. The water-based plastic paint according to claim 7, wherein in the compound of polytetrahydrofuran ether glycol and polycaprolactone diol, the weight ratio of polytetrahydrofuran ether glycol to polycaprolactone diol is 2-10: 1; or in the compound of the polytetrahydrofuran ether glycol and the polycarbonate diol, the weight ratio of the polytetrahydrofuran ether glycol to the polycarbonate diol is 2-10: 1.
10. the aqueous plastic paint according to any one of claims 1 to 6 and 8 to 9, wherein the hydrophilic compound is selected from hydrophilic compounds containing ionic groups or hydrophilic compounds containing nonionic groups.
11. The aqueous plastic paint according to claim 10, wherein the hydrophilic compound containing ionic groups is selected from one or more of dimethylolpropionic acid, dimethylolbutyric acid, dimethylolacetic acid, dihydroxysuccinic acid, N- (2-aminoethyl) -2-aminoethanesulfonate and N- (3-aminopropyl) -2-aminoethanesulfonic acid;
the hydrophilic compound containing nonionic groups is selected from polyethoxy ether with the number average molecular weight of 150-10000 and the ethylene oxide number of 5-200.
12. The aqueous plastic paint according to claim 11, wherein the hydrophilic compound containing nonionic group is selected from bifunctional polyethoxyethers having number average molecular weight of 500 to 2000 and ethylene oxide number of 10 to 80.
13. The aqueous plastic paint of claim 11, wherein the hydrophilic compound is selected from one or more of dimethylolpropionic acid, N- (2-aminoethyl) -2-aminoethane sulfonate, ymer (tm) 120, and MPEG 1200.
14. The waterborne plastic paint of any one of claims 1-6, 8-9 and 11-13, wherein the molar ratio of the N- (2-hydroxyethyl) ethylenediamine to the isophorone diamine in the composite of N- (2-hydroxyethyl) ethylenediamine and isophorone diamine is 0.2-10: 1; or in the compound of the N- (2-hydroxyethyl) ethylenediamine and the ethylenediamine, the molar ratio of the N- (2-hydroxyethyl) ethylenediamine to the ethylenediamine is 0.2-10: 1.
15. the waterborne plastic paint of claim 14, wherein in the compound of N- (2-hydroxyethyl) ethylenediamine and isophorone diamine, the molar ratio of N- (2-hydroxyethyl) ethylenediamine to isophorone diamine is 0.5-5: 1; or in the compound of the N- (2-hydroxyethyl) ethylenediamine and the ethylenediamine, the molar ratio of the N- (2-hydroxyethyl) ethylenediamine to the ethylenediamine is 0.5-5: 1.
16. the aqueous plastic paint according to any one of claims 1 to 6, 8 to 9, 11 to 13 and 15, wherein the polymerized monomer of the aqueous acrylic resin is selected from a mixed monomer consisting of one of styrene and methyl methacrylate and one of tetrahydrofuran acrylate and tetrahydrofuran acrylate;
based on the total molar weight of the mixed monomers being 100%, the mole percentage of the styrene or the methyl methacrylate is 30-70%, and the mole percentage of the tetrahydrofuran acrylate or the tetrahydrofuran acrylate is 30-70%.
17. The water-based plastic paint as claimed in any one of claims 1 to 6, 8 to 9, 11 to 13 and 15, wherein the solid content of the water-based large-particle size polyurethane resin is 34 to 36 wt%, and the solid content of the water-based acrylic resin is 39 to 41 wt%.
18. The aqueous plastic paint according to any one of claims 1 to 6, 8 to 9, 11 to 13 and 15, wherein the auxiliary agent is one or more selected from the group consisting of an aqueous wetting agent, an aqueous leveling agent, an aqueous defoaming agent, an aqueous thickener, a PH regulator and a bactericidal and mildewproof agent.
19. A method for preparing the aqueous plastic paint according to any one of claims 1-18, characterized by comprising the steps of:
1) preparation of component A: dispersing and mixing the aqueous large-particle-size polyurethane resin, the aqueous acrylic resin and the auxiliary agent, adjusting the viscosity of the mixture to 400-1000 cps, adjusting the pH value of the mixture to 8-9, and filtering to obtain a component A;
2) preparing paint: and uniformly stirring the component A and the component B to obtain the water-based plastic paint.
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