CN115368768B - Water-based environment-friendly strippable protective coating and preparation method thereof - Google Patents
Water-based environment-friendly strippable protective coating and preparation method thereof Download PDFInfo
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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
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
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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
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a water-based environment-friendly strippable protective coating (IPC classification number: C09D 133/04), in particular to a water-based environment-friendly strippable protective coating and a use method thereof, wherein the water-based environment-friendly strippable protective coating comprises a component A and a component B: the component A comprises the following components in parts by mass: 15-25 parts of aqueous polyurethane resin, 13-26 parts of aqueous dispersion emulsion, 1-3 parts of fluoronatural rubber powder, 15-30 parts of filler, 0.3-1 part of defoamer, 1-2 parts of dispersant, 0.3-0.5 part of flash rust inhibitor, 0.1-1 part of flexibilizer, 5-8 parts of aluminum tripolyphosphate and 20-30 parts of water; the component B is isocyanate curing agent. The water-based environment-friendly strippable protective coating prepared by the invention can be embedded into emulsion when being mixed in a system by adding the natural rubber powder with the fluorine content of 5-8% and matching with the mutual synergistic effect between the modified polyurethane emulsion and the aqueous dispersion emulsion, so that the prepared protective coating has better adaptability.
Description
Technical Field
The invention relates to a water-based environment-friendly strippable protective coating (IPC class number: C09D), in particular to a water-based environment-friendly strippable protective coating and a preparation method thereof.
Background
In order to improve the construction and installation efficiency, more and more people adopt the mode of field assembly of prefabricated parts, namely workpieces are produced in factories and transported to the field for assembly, the prefabricated parts/finished products are transported to the field for a long distance after being taken off line from the factories, and the whole transportation process needs to be protected, so that the strippable paint with the protection effect is generated. The strippable paint is a special protective paint, is coated on the surface of a substrate to isolate external corrosion, avoids the influence of rust, scratch, aging, pollution, dust, greasy dirt, fingerprints and the like in the production, transportation or storage process, can provide temporary protection for the surfaces of various substrates, such as substrates of woodware, metal, glass, plastic, concrete and the like, can be conveniently stripped from the surfaces of the substrates after the protection is finished, and does not negatively influence the surfaces of the substrates.
Chinese patent No. CN107828322B provides an aqueous releasable coating prepared by film forming materials, pigments, fillers, thickeners, release agents, wetting agents, dispersants, leveling agents, defoamers and water as disclosed in the published patent. Because the film forming material is a mixture of polyurethane film forming material and polyvinyl alcohol film forming material, the film surface is not smooth easily in the specific experimental process, and the phenomenon of bubbles exists, particularly when the film forming material is used on the surface of a base material such as steel, the flash rust phenomenon easily occurs in the early stage, so that the strippable coating loses the anti-corrosion effect, and the application of the strippable coating is greatly limited.
Disclosure of Invention
In order to solve the problems, the first aspect of the invention provides an aqueous environment-friendly strippable protective coating, which comprises a component A and a component B:
the component A comprises the following components in parts by mass: 15-25 parts of aqueous polyurethane resin, 13-26 parts of aqueous dispersion emulsion, 1-3 parts of fluoronatural rubber powder, 15-30 parts of filler, 0.3-1 part of defoamer, 1-2 parts of dispersant, 0.3-0.5 part of flash rust inhibitor, 0.1-1 part of flexibilizer, 5-8 parts of aluminum tripolyphosphate and 20-30 parts of water;
the component B is isocyanate curing agent;
the mass ratio of the component A to the component B is (7-9): 1, a step of;
the aqueous dispersion emulsion at least comprises a strippable acrylic emulsion and a fluorine modified styrene-acrylic emulsion.
As a preferable scheme, the mass ratio of the strippable acrylic emulsion to the fluorine modified styrene-acrylic emulsion is (3-4): 1.
as a preferable scheme, the fluorine modified styrene-acrylic emulsion is self-made; the preparation method of the fluorine modified styrene-acrylic emulsion comprises the following steps:
1) Preparing a core pre-emulsion A;
2) Preparing a shell pre-emulsion B;
3) And (3) polymerizing the emulsion prepared in the steps 1) and 2) to obtain the polymer.
As a preferred scheme, the preparation raw materials of the nuclear pre-emulsion A comprise water, styrene and an emulsifier.
As a preferable scheme, the shell pre-emulsion B is prepared from water, butyl acrylate, acrylic acid, N-methylol acrylamide, a modifier and an emulsifier.
Further preferably, the preparation method of the fluorine modified styrene-acrylic emulsion specifically comprises the following steps:
1) Preparation of a core pre-emulsion A: weighing a certain amount of water, styrene and a mixed emulsifier (the mass mixing ratio of OP-10 to SDS is 1:3), and placing the mixture in a four-neck flask provided with a mechanical stirrer, a nitrogen inlet, a condenser and a pipette outlet for pre-emulsification;
2) Preparation of shell pre-emulsion B: weighing part of water, butyl acrylate, acrylic acid, N-methylolacrylamide, modifier (dodecafluoroheptyl methacrylate, GO 4) and the rest of mixed emulsifier, and placing into a flask for pre-emulsification.
3) Polymerization reaction: firstly, adding 1/3 core pre-emulsion A into a four-neck flask, heating to a reaction temperature, adding 4mL of initiator (ammonium persulfate), dripping the residual emulsion A after blue light is generated for 15min, finishing within 60min, and then preserving heat for 30min, wherein 1 drop of initiator (ammonium persulfate) is added every 15 min; after heat preservation, the emulsion B is dripped within 130min, and the initiator is dripped every 15 min; heating to 85 ℃ for curing for 30min, cooling to below 50 ℃, adopting ammonia water to adjust the pH value to 7-8, removing slag, and obtaining the fluorine modified styrene-acrylic emulsion.
As a preferred embodiment, the aqueous polyurethane resin is an aqueous aliphatic polyurethane dispersion.
Further preferably, the aqueous polyurethane resin is HT3630.
As a preferable scheme, the mass content of fluorine in the fluoronatural rubber is 5-8%.
As a preferable embodiment, the particle size of the fluoronatural rubber is 0.5-1. Mu.m.
As a preferred embodiment, the defoamer is a silicone defoamer, commercially available, such as Michaelson SAG638.
As a preferable scheme, the filler is one or more of kaolin, barium sulfate, talcum powder, water-washed kaolin, heavy calcium carbonate, silicon micropowder, silicon dioxide and diatomite.
As a preferred embodiment, the filler is a mixture of water-washed kaolin and ground calcium carbonate.
As a preferable scheme, the weight ratio of the water-washed kaolin to the heavy calcium carbonate is (10-25): (10-20).
As a preferable scheme, the weight ratio of the water-washed kaolin to the heavy calcium carbonate is (15-20): (14-16).
As a preferred embodiment, the dispersant is an ammonium acrylate dispersant, commercially available, such as the Dow chemical OROTAN1124.
As a preferable scheme, the toughening agent is a low-molecular amide substance; further preferably, the toughening agent is a carboxamide.
The flash rust inhibitor of the present invention is not particularly limited as long as it can achieve its flash rust inhibiting effect.
The second aspect of the invention provides a preparation method of an aqueous environment-friendly strippable protective coating, which comprises the following steps:
1) And (3) preparation of the component A: mixing the preparation raw materials according to the weight requirement, and reacting to obtain the product;
2) Mixing the component B and the component A according to the mass ratio.
The beneficial effects are that: compared with the prior art, the water-based environment-friendly strippable protective coating prepared by the invention has the following advantages:
the water-based environment-friendly strippable protective coating prepared by the invention has excellent anti-corrosion effect, particularly has better adhesive force when being used on the surface of steel, and avoids phenomena such as flashing and the like in the early stage; in addition, the water-based environment-friendly strippable protective coating prepared by the invention can be embedded into emulsion when being mixed in a system by adding the natural rubber powder with the fluorine content of 5-8% and matching with the mutual synergistic effect between the modified polyurethane emulsion and the aqueous dispersion emulsion, so that the prepared protective coating has better adaptability and better adhesive force, better ageing resistance and tensile strength are provided for the protective coating, and the protective effect of the protective coating when the protective coating is used on the surfaces of various substrates is ensured.
Detailed Description
Examples
Example 1
The embodiment 1 of the invention provides an aqueous environment-friendly strippable protective coating, which comprises a component A and a component B:
the component A comprises the following components in parts by mass: 20 parts of aqueous polyurethane resin, 25 parts of aqueous dispersion emulsion, 2 parts of fluorine natural rubber powder, 18 parts of filler, 0.5 part of defoamer, 1.5 parts of dispersant, 0.4 part of flash rust inhibitor, 0.6 part of flexibilizer, 6 parts of aluminum tripolyphosphate and 26 parts of water;
the component B is isocyanate curing agent;
the mass ratio of the component A to the component B is 8:1, a step of;
the strippable composite acrylic emulsion comprises the following raw materials in parts by weight: 10 parts of water, 60 parts of acrylic emulsion, 0.5 part of defoamer and 0.4 part of pH regulator.
The aqueous dispersion emulsion comprises a strippable acrylic emulsion and a fluorine modified styrene-acrylic emulsion, wherein the mass ratio of the strippable acrylic emulsion to the fluorine modified styrene-acrylic emulsion is 3.5:1, a step of;
among them, acrylic emulsion type Carboset PL3127 can be peeled off.
The fluorine modified styrene-acrylic emulsion is self-made, and the preparation method comprises the following steps:
1) Preparation of a core pre-emulsion A: weighing water, styrene and a mixed emulsifier (OP-10: SDS, wherein the mass mixing ratio is 1:3) with the mass ratio of 30:40:30, and placing the mixture in a four-neck flask provided with a mechanical stirrer, a nitrogen inlet, a condenser and a pipette outlet for pre-emulsification;
2) Preparation of shell pre-emulsion B: weighing the following components in percentage by mass: 45:15:5:20 water, butyl acrylate, acrylic acid, N-methylolacrylamide, modifier (dodecafluoroheptyl methacrylate, GO 4) and the remaining mixed emulsifier were placed in a flask for pre-emulsification.
3) Polymerization reaction: firstly, adding 1/3 core pre-emulsion A into a four-neck flask, heating to 65 ℃, adding 4mL of initiator (ammonium persulfate), dripping the residual emulsion A after blue light is generated for 15min, finishing within 60min, and then preserving heat for 30min, wherein 1 drop of initiator (ammonium persulfate) is added every 15 min; after heat preservation, the emulsion B is dripped within 130min, and the initiator is dripped every 15 min; heating to 85 ℃ for curing for 30min, cooling to below 50 ℃, adopting ammonia water to adjust the pH value to 7-8, removing slag, and obtaining the fluorine modified styrene-acrylic emulsion.
The aqueous polyurethane resin is purchased from Hefei Hengtian New Material science and technology Co.
The fluoronatural rubber powder has the brandPPA 2626；
The filler is a mixture of water-washed kaolin and heavy calcium carbonate; the weight ratio of the water-washed kaolin to the heavy calcium carbonate is 18:15.
the defoamer is a silicone defoamer, purchased from michaux SAG638.
The dispersant is an ammonium acrylate dispersant available from the dow chemical ortan 1124.
The toughening agent is carbonamide.
The second aspect of the invention provides a preparation method of an aqueous environment-friendly strippable protective coating, which comprises the following steps:
1) And (3) preparation of the component A: mixing the preparation raw materials according to the weight requirement, and reacting to obtain the product;
2) Mixing the component B and the component A according to the mass ratio.
Example 2
The specific implementation mode of the water-based environment-friendly strippable protective coating is the same as that of example 1, and the mass ratio of the strippable acrylic emulsion to the fluorine modified styrene-acrylic emulsion is 4:1.
example 3
The specific implementation mode of the water-based environment-friendly strippable protective coating is the same as that of the example 1, and the mass ratio of the strippable acrylic emulsion to the fluorine modified styrene-acrylic emulsion is 3:1.
comparative example 1
An aqueous environment-friendly strippable protective coating, the specific embodiment of which is the same as that of example 1, except that the fluorine-containing modified styrene-acrylic emulsion in comparative example 1 is not used.
Comparative example 2
An aqueous environmental-friendly strippable protective coating, the specific embodiment of which is the same as that of example 1, except that in comparative example 2, fluoronatural rubber powder is not present.
Performance test:
the basic properties of the aqueous environmental-friendly strippable protective coating obtained in example 1 are recorded in table 1.
After the aqueous environment-friendly strippable protective coating obtained in the example 1 was coated on the surfaces of different protective substrates, the protective coating was left to dry and solidify by itself, and then a protective top coating was coated, and the stripping grades on the different substrates were detected, and the stripping grade descriptions and the divisions are shown in table 2.
TABLE 2
Performance test results:
table 1 shows the basic performance test results of the aqueous environmental-friendly strippable protective coating obtained in example 1.
TABLE 1
Table 3 shows the peel level test results of examples 1-3 and comparative examples 1-2 to obtain coatings applied to different substrate surfaces as shown in Table 3.
TABLE 3 Table 3
| Glass plate | Cold-rolled steel sheet | ABS plate | Wood board | Irregular stone | |
| Thickness/m | 75 | 75 | 75 | 75 | 80 |
| Example 1 | 1 | 1 | 1 | 1 | 1 |
| Example 2 | 1 | 1 | 1 | 1 | 1 |
| Example 3 | 1 | 1 | 1 | 1 | 1 |
| Comparative example 1 | 2 | 2 | 2 | 3 | 2 |
| Comparative example 2 | 2 | 3 | 2 | 2 | 2 |
Note that: the protective coating needs to have proper stripping force and adhesive force, and meanwhile, the protective coating has the best performance when the stripping grade is 1 grade (complete and easy stripping, no damage to a paint film and no residue on a substrate).
Claims (5)
1. The water-based environment-friendly strippable protective coating is characterized by comprising a component A and a component B:
the component A comprises the following components in parts by mass: 15-25 parts of aqueous polyurethane resin, 13-26 parts of aqueous dispersion emulsion, 1-3 parts of fluoronatural rubber powder, 15-30 parts of filler, 0.3-1 part of defoamer, 1-2 parts of dispersant, 0.3-0.5 part of flash rust inhibitor, 0.1-1 part of flexibilizer, 5-8 parts of aluminum tripolyphosphate and 20-30 parts of water;
the component B is isocyanate curing agent;
the mass ratio of the component A to the component B is (7-9): 1, a step of;
the aqueous dispersion emulsion at least comprises a strippable acrylic emulsion and a fluorine modified styrene-acrylic emulsion;
the fluorine modified styrene-acrylic emulsion is self-made; the preparation method of the fluorine modified styrene-acrylic emulsion comprises the following steps:
1) Preparing a core pre-emulsion A;
2) Preparing a shell pre-emulsion B;
3) Polymerizing the emulsion prepared in the steps 1) and 2) to obtain the emulsion;
the preparation raw materials of the nuclear pre-emulsion A comprise water, styrene and an emulsifying agent;
the preparation raw materials of the shell pre-emulsion B comprise water, butyl acrylate, acrylic acid, N-methylolacrylamide, dodecafluoroheptyl methacrylate and an emulsifier;
the brand BL PPA 2626 of the fluorine natural rubber powder.
2. The aqueous environment-friendly strippable protective coating according to claim 1, wherein the weight ratio of the strippable acrylic emulsion to the fluorine modified styrene-acrylic emulsion is (3-4): 1.
3. the aqueous environmental protection peelable protective coating according to claim 1 or 2, wherein the peelable acrylic emulsion is at least one selected from Carboset PL3127 and Carboset PL-958.
4. The aqueous environmental protection strippable protective coating of claim 1, wherein the aqueous polyurethane resin is an aqueous aliphatic polyurethane dispersion.
5. A method of preparing an aqueous environmentally friendly strippable protective coating according to any one of claims 1 to 4, comprising the steps of:
1) And (3) preparation of the component A: mixing the preparation raw materials according to the weight requirement, and reacting to obtain the product;
2) Mixing the component B and the component A according to the mass ratio.
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| CN104164174A (en) * | 2014-05-16 | 2014-11-26 | 深圳市谷域材料研发有限公司 | Aqueous strippable coating |
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| CN113004758A (en) * | 2020-12-29 | 2021-06-22 | 东华大学 | Core-shell type acrylate strippable coating and preparation method thereof |
| CN114450359A (en) * | 2019-09-27 | 2022-05-06 | 日东电工株式会社 | Peelable coating film, coating composition, and coating material for forming hydrophilic coating film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4397386B2 (en) * | 2005-07-29 | 2010-01-13 | 株式会社ダスキン | Releasable floor coating and method for forming the coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5747572A (en) * | 1995-05-19 | 1998-05-05 | Kansai Paint Co., Ltd. | Releasable aqueous coating composition and method of temporarily protecting finished coating film on automobile body by use of the same |
| CN101768403A (en) * | 2009-12-22 | 2010-07-07 | 北京航材百慕新材料技术工程股份有限公司 | Aqueous transparent strippable protective coating |
| CN104164174A (en) * | 2014-05-16 | 2014-11-26 | 深圳市谷域材料研发有限公司 | Aqueous strippable coating |
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| CN109161264A (en) * | 2018-08-16 | 2019-01-08 | 华南理工大学 | A kind of water solubility Stripable paint and its preparation method and application |
| CN114450359A (en) * | 2019-09-27 | 2022-05-06 | 日东电工株式会社 | Peelable coating film, coating composition, and coating material for forming hydrophilic coating film |
| CN111534172A (en) * | 2020-05-12 | 2020-08-14 | 广州市首牵化工有限公司 | Composite strippable emulsion, strippable protective coating and application thereof |
| CN113004758A (en) * | 2020-12-29 | 2021-06-22 | 东华大学 | Core-shell type acrylate strippable coating and preparation method thereof |
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