CN113061390A - Anti-doodling and anti-sticking coating and preparation method thereof - Google Patents
Anti-doodling and anti-sticking coating and preparation method thereof Download PDFInfo
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- CN113061390A CN113061390A CN202110487531.8A CN202110487531A CN113061390A CN 113061390 A CN113061390 A CN 113061390A CN 202110487531 A CN202110487531 A CN 202110487531A CN 113061390 A CN113061390 A CN 113061390A
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Classifications
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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
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses an anti-doodling and anti-sticking coating and a preparation method thereof. The anti-doodling anti-sticking coating comprises the following raw materials in parts by weight: 20-30 parts of urethane acrylate, 5-8 parts of acrylate type perfluorinated polyurethane, 1-2 parts of fluorine modified oligomer, 2-3 parts of oxazoline-containing polymer, 1-1.5 parts of light curing agent, 10-15 parts of organic solvent, 1-2 parts of wetting agent and 1-2 parts of thickening agent. The paint film formed by the paint has good compactness and high hardness, and the acrylate type perfluorinated polyurethane and the fluorine modified oligomer which are reacted on a molecular chain can be more efficiently distributed on the surface of the paint film, so that the surface tension of the paint film can be durably reduced, and the anti-graffiti and anti-sticking effects are durable.
Description
Technical Field
The invention relates to the field of coatings, and particularly relates to an anti-doodling and anti-sticking coating and a preparation method thereof.
Background
In recent years, the loss caused by malicious graffiti is more and more concerned by people, the city appearance and the landscape are influenced, and the cost for removing the graffiti is huge in various countries. It is not possible to reduce the amount of graffiti and therefore the paint industry is faced with a significant challenge in developing paints with anti-graffiti properties. Aims to remove the scrawling by a simple cleaning method, if possible, only water is needed for removing.
CN106280946A discloses a transparent durable water-based anti-doodling coating and a coating method thereof, wherein low surface energy components including hydroxyl silicone oil, alkyl silicone oil, amino silicone oil, perfluoroalkyl alkoxy silane, perfluoroalkyl trichlorosilane, carboxyl fluorine ether and hydroxyl fluorine ether are added. Although the scheme obtains a certain anti-doodling effect, the introduction of the low surface energy component makes the high-surface-tension water-based pen difficult to spread on the surface layer of the pen, and the introduction of the low surface energy component greatly increases the difficulty of recoating, so that the application of the low-surface-energy component in a whiteboard is limited. In recent years, research on the use of perfluoropolyether type anti-graffiti coatings has been carried out, but the anti-graffiti effect is poor, the hardness of a paint film of the coating does not meet the requirement of hardness being more than or equal to 2H in JG/T304-2011 national standard, the weather resistance and the durability also need to be further tested in practical use, and in addition, the adhesion on plastics and PU films is not ideal, so that the application of the coating is greatly limited.
Disclosure of Invention
In view of the above, the invention provides a novel anti-graffiti anti-sticking coating and a preparation method thereof. The paint film formed by the paint has good compactness and high hardness, and the acrylate type perfluorinated polyurethane and the fluorine modified oligomer which are reacted on a molecular chain can be more efficiently distributed on the surface of the paint film, so that the surface tension of the paint film can be durably reduced, and the anti-graffiti and anti-sticking effects are durable.
The invention provides an anti-doodling and anti-sticking coating which comprises the following raw materials in parts by weight: 20-30 parts of urethane acrylate, 5-8 parts of acrylate type perfluorinated polyurethane, 1-2 parts of fluorine modified oligomer, 2-3 parts of oxazoline-containing polymer, 1-1.5 parts of light curing agent, 10-15 parts of organic solvent, 1-2 parts of wetting agent and 1-2 parts of thickening agent.
Preferably, the raw materials of the anti-doodling and anti-sticking coating comprise the following components in parts by weight: 20-30 parts of urethane acrylate, 5-8 parts of acrylate type perfluorinated polyurethane, 1-2 parts of fluorine modified oligomer, 2-3 parts of oxazoline-containing polymer, 1-1.5 parts of light curing agent, 10-15 parts of organic solvent, 1-2 parts of wetting agent and 1-2 parts of thickening agent.
Wherein the urethane acrylate is a urethane acrylate conventionally used in the field of coating, and the invention is not limited.
Among them, the oxazoline-containing polymer is preferably EPOCROS (Nippon Shokubai co., Ltd, Japan).
The fluorine modified oligomer is fluoroalkyl mercaptan modified hyperbranched polymer; wherein, the fluoroalkyl thiol is preferably pentafluoro pentanethiol; the hyperbranched polymer is preferably one or a mixture of hydroxyl-terminated hyperbranched polyester, hydroxyl-terminated hyperbranched polyether and hydroxyl-terminated hyperbranched polyamide. More preferred are the hyperbranched polyesters of the BoltornH30 series from the Pestorp company, the hyperbranched polyethers of the BoltornP500 series, and the hyperbranched polyamides of the HybraePS 2550 series from the DSMMHybrane B.V.
Wherein, the acrylic ester type perfluorinated polyurethane is preferably prepared by the following preparation method: and (2) reacting perfluoropolyether diol with diisocyanate, adding a mixture of acetone and hydroxypropyl methacrylate, and reacting to obtain the acrylate type perfluorinated polyurethane.
Wherein the structural formula of the perfluoropolyether diol is preferably HOCH2(CF2CF2O)p(CF2O)qCH2OH，p＝18～22，q＝18～22。
Among them, the diisocyanate is preferably isophorone diisocyanate or toluene diisocyanate.
Among them, the wetting agent is preferably an aqueous wetting agent. More preferably, the wetting agent is one or more of ByK-187, ByK-3400, and ByK-3410.
Among them, the thickener is preferably an aqueous thickener. More preferably, the thickener is one or more of modesty WT-105A, modesty WT-113, modesty WT-115 and modesty WT-120.
Wherein, the organic solvent is preferably one or more of isopropanol, propylene glycol methyl ether, propylene glycol butyl ether and dipropylene glycol butyl ether.
The light curing agent is preferably an alpha-aminoketone curing agent, and the alpha-aminoketone curing agent is preferably one or more of Irgacure 907, Irgacure 369 and Irgacure 1300.
The invention also provides a preparation method of the anti-doodling and anti-sticking coating, which comprises the following steps:
adding urethane acrylate, acrylic ester type perfluorinated polyurethane, fluorine modified oligomer, oxazoline-containing polymer and organic solvent into a stirrer, stirring, adding a light curing agent, a wetting agent and a thickening agent, and uniformly stirring.
In the invention, the fluorine modified oligomer is introduced into the coating component, so that the anti-doodling effect is further improved, and the adhesion of the coating can be improved due to the addition of the oxazoline-containing polymer, so that the coating can be applied to plastics and PU films, and the application range of the anti-doodling coating is greatly expanded.
The invention achieves the positive improvement effects that: the paint film formed by the paint disclosed by the invention is good in compactness and high in hardness, the acrylate type perfluorinated polyurethane and the fluorine modified oligomer which react on a molecular chain can be more efficiently distributed on the surface of the paint film, the surface tension of the paint film can be durably reduced, the anti-graffiti and anti-sticking effects are durable, the performance of the prepared anti-graffiti and anti-sticking paint meets the C-type requirement in national standard JG/T304-2011, the anti-sticking property (180-degree peeling strength) is less than or equal to 0.10N/mm, and the anti-graffiti property (oily marker pen) is less than or equal to level 3.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
The raw material formulation is shown in the following table:
| serial number | Name of Material | Parts by weight |
| 1 | Urethane acrylate | 20 |
| 2 | Acrylate type perfluorinated polyurethane | 6 |
| 3 | Fluorine modified oligomers | 1 |
| 4 | Oxazoline-containing polymers | 3 |
| 5 | Light curing agent | 1 |
| 6 | Organic solvent | 12 |
| 7 | Wetting agent | 1 |
| 8 | Thickening agent | 1 |
The acrylic ester type perfluorinated polyurethane is prepared by the following preparation method: adding perfluoropolyether diol, diisocyanate and a catalyst dibutyltin dilaurate into acetone, reacting for 12h at 50 ℃, adding a mixture of acetone and hydroxypropyl methacrylate, and reacting for 8h at 60 ℃ to obtain the acrylate type perfluorinated polyurethane. The structural formula of the perfluoropolyether diol is HOCH2(CF2CF2O)p(CF2O)qCH2OH, p is 18-22, q is 18-22; the diisocyanate is isophorone diisocyanate.
The fluorine modified oligomer is Pentafluoropentylthiol modified BoltornH30 hyperbranched polyester from Pestorp company; the oxazoline-containing polymer is EPOCROS (Nippon Shokubai co., Ltd, Japan); the wetting agent is bike BYK-187; the thickener is modesty WT-105A; the organic solvent is isopropanol; the light curing agent is Irgacure 907.
The preparation method comprises the following steps: adding urethane acrylate, acrylic ester type perfluorinated polyurethane, fluorine modified oligomer, oxazoline-containing polymer and organic solvent into a stirrer, stirring, adding a light curing agent, a wetting agent and a thickening agent, and uniformly stirring.
The coating of this example was brush coated on a PET plastic base film, UV light (40 mW/cm)2) And (5) irradiating and curing for 20s, and testing the effect performance of the coating film. According to the C-type requirement in the national standard JG/T304-. The test results are shown in the following table:
example 2
The raw material formulation is shown in the following table:
| serial number | Name of Material | Parts by weight |
| 1 | Urethane acrylate | 30 |
| 2 | Acrylate type perfluorinated polyurethane | 8 |
| 3 | Fluorine modified oligomers | 2 |
| 4 | Oxazoline-containing polymers | 2 |
| 5 | Light curing agent | 1.5 |
| 6 | Organic solvent | 14 |
| 7 | Wetting agent | 1 |
| 8 | Thickening agent | 2 |
The acrylic ester type perfluorinated polyurethane is prepared by the following preparation method: adding perfluoropolyether diol, diisocyanate and a catalyst dibutyltin dilaurate into acetone, reacting for 12h at 50 ℃, adding a mixture of acetone and hydroxypropyl methacrylate, and reacting for 8h at 60 ℃ to obtain the acrylate type perfluorinated polyurethane. The structural formula of the perfluoropolyether diol is HOCH2(CF2CF2O)p(CF2O)qCH2OH, p is 18-22, q is 18-22; diisocyanatoThe acid ester is toluene diisocyanate.
The fluorine modified oligomer is DSMHybranePS 2550 hyperbranched polyamide subjected to pentafluo-pentanethiol modification treatment; the oxazoline-containing polymer is EPOCROS (Nippon Shokubai co., Ltd, Japan); the wetting agent is bike BYK-3400; the thickener is modesty WT-120; the organic solvent is propylene glycol methyl ether; the light curing agent is Irgacure 369.
The preparation method comprises the following steps: adding urethane acrylate, acrylic ester type perfluorinated polyurethane, fluorine modified oligomer, oxazoline-containing polymer and organic solvent into a stirrer, stirring, adding a light curing agent, a wetting agent and a thickening agent, and uniformly stirring.
The coating of this example was brush coated on a PU base film with ultraviolet light (40 mW/cm)2) And (5) irradiating and curing for 30s, and testing the effect performance of the coating film. According to the C-type requirement in the national standard JG/T304-. The test results are shown in the following table:
it is obvious that the above description of the embodiments is only intended to facilitate the understanding of the products, methods and their core ideas of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (9)
1. The anti-doodling and anti-sticking coating comprises the following raw materials in parts by weight: 20-30 parts of urethane acrylate, 5-8 parts of acrylate type perfluorinated polyurethane, 1-2 parts of fluorine modified oligomer, 2-3 parts of oxazoline-containing polymer, 1-1.5 parts of light curing agent, 10-15 parts of organic solvent, 1-2 parts of wetting agent and 1-2 parts of thickening agent.
2. The anti-doodling and anti-sticking coating as claimed in claim 1, which is prepared from the following raw materials in parts by weight: 20-30 parts of urethane acrylate, 5-8 parts of acrylate type perfluorinated polyurethane, 1-2 parts of fluorine modified oligomer, 2-3 parts of oxazoline-containing polymer, 1-1.5 parts of light curing agent, 10-15 parts of organic solvent, 1-2 parts of wetting agent and 1-2 parts of thickening agent.
3. The anti-graffiti anti-stick coating of claim 1, wherein the fluorine-modified oligomer is a fluoroalkyl thiol-modified hyperbranched polymer; wherein, the fluoroalkyl thiol is preferably pentafluoro pentanethiol; the hyperbranched polymer is preferably one or a mixture of hydroxyl-terminated hyperbranched polyester, hydroxyl-terminated hyperbranched polyether and hydroxyl-terminated hyperbranched polyamide.
4. The anti-graffiti anti-stick coating of claim 1, wherein the acrylate-based perfluorinated polyurethane is prepared by the following method: and (2) reacting perfluoropolyether diol with diisocyanate, adding a mixture of acetone and hydroxypropyl methacrylate, and reacting to obtain the acrylate type perfluorinated polyurethane.
5. The anti-graffiti anti-stick coating of claim 4, wherein the perfluoropolyether diol has the formula HOCH2(CF2CF2O)p(CF2O)qCH2OH, p is 18-22, q is 18-22; the diisocyanate is isophorone diisocyanate or toluene diisocyanate.
6. The anti-graffiti anti-stick coating of claim 1, wherein the wetting agent is preferably an aqueous wetting agent; more preferably, the wetting agent is one or more of ByK-187, ByK-3400, and ByK-3410;
the thickener is preferably an aqueous thickener; more preferably, the thickener is one or more of modesty WT-105A, modesty WT-113, modesty WT-115 and modesty WT-120.
7. The anti-graffiti anti-stick coating of claim 1, wherein the organic solvent is one or more of isopropyl alcohol, propylene glycol methyl ether, propylene glycol butyl ether, and dipropylene glycol butyl ether.
8. The anti-graffiti anti-adhesive coating of claim 1, wherein the light curing agent is an α -aminoketone type curing agent, preferably one or more of Irgacure 907, Irgacure 369 and Irgacure 1300.
9. A method for preparing the anti-doodling and anti-sticking coating as claimed in any one of claims 1 to 8, which comprises the following steps: adding urethane acrylate, acrylic ester type perfluorinated polyurethane, fluorine modified oligomer, oxazoline-containing polymer and organic solvent into a stirrer, stirring, adding a light curing agent, a wetting agent and a thickening agent, and uniformly stirring.
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| CN202110487531.8A CN113061390A (en) | 2021-04-30 | 2021-04-30 | Anti-doodling and anti-sticking coating and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571314A (en) * | 2013-09-27 | 2014-02-12 | 上海维凯化学品有限公司 | Ultraviolet curing high-hardness anti-fingerprint coating composition for polyethylene glycol terephthalate (PET) base material |
| CN106752754A (en) * | 2017-03-14 | 2017-05-31 | 浙江世窗光学薄膜制造有限公司 | A kind of gum polyurethane protective film and preparation method thereof |
| US20170152333A1 (en) * | 2014-06-26 | 2017-06-01 | Basf Se | Copolymer comprising oxazoline monomers and use thereof as crosslinker |
| CN109679483A (en) * | 2018-12-10 | 2019-04-26 | 成都晨光博达橡塑有限公司 | A kind of UV photocureable coating of perfluoro-polyether modified additive and its preparation method and application |
| CN111511790A (en) * | 2017-12-26 | 2020-08-07 | 阿克佐诺贝尔国际涂料股份有限公司 | Fluorinated polyacrylate coating compositions, method for their preparation and their use |
-
2021
- 2021-04-30 CN CN202110487531.8A patent/CN113061390A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571314A (en) * | 2013-09-27 | 2014-02-12 | 上海维凯化学品有限公司 | Ultraviolet curing high-hardness anti-fingerprint coating composition for polyethylene glycol terephthalate (PET) base material |
| US20170152333A1 (en) * | 2014-06-26 | 2017-06-01 | Basf Se | Copolymer comprising oxazoline monomers and use thereof as crosslinker |
| CN106752754A (en) * | 2017-03-14 | 2017-05-31 | 浙江世窗光学薄膜制造有限公司 | A kind of gum polyurethane protective film and preparation method thereof |
| CN111511790A (en) * | 2017-12-26 | 2020-08-07 | 阿克佐诺贝尔国际涂料股份有限公司 | Fluorinated polyacrylate coating compositions, method for their preparation and their use |
| CN109679483A (en) * | 2018-12-10 | 2019-04-26 | 成都晨光博达橡塑有限公司 | A kind of UV photocureable coating of perfluoro-polyether modified additive and its preparation method and application |
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