CN113150677A - High-temperature-resistant injection-molding anti-fouling UV coating and preparation method and application thereof - Google Patents
High-temperature-resistant injection-molding anti-fouling UV coating and preparation method and application thereof Download PDFInfo
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- 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
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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Abstract
The invention provides a high-temperature-resistant injection-molding anti-fouling UV coating, and a preparation method and application thereof, wherein the UV coating comprises the following components in parts by weight: 25-40 parts of multifunctional polyurethane acrylate resin; 10-25 parts of organic fluorine modified UV resin; 3-5 parts of a UV photoinitiator; 1-3 parts of low oxygen resistance composite initiator; 1-3 parts of a hydrophobic and oleophobic auxiliary agent; 1-5 parts of nano filler; 30-50 parts of an organic solvent. By adopting the blending of the organic fluorine modified UV resin, the hydrophobic and oleophobic auxiliary agent and the nano filler, the coating has high anti-fouling capability and flexibility after high-temperature injection molding, and the R angle of the high-temperature injection molding is not cracked.
Description
Technical Field
The invention relates to the technical field of coatings, and particularly relates to a high-temperature-resistant injection-molding anti-fouling UV coating as well as a preparation method and application thereof.
Background
The anti-fouling UV coating has the advantages of hydrophobicity and oleophobicity, fingerprint resistance, high hardness, wear resistance and excellent chemical resistance, and is widely applied to the surface of plastic substrates in the fields of consumer electronics and small household appliances. The existing high-hardness anti-fouling UV coating generally adopts high-functional group resin, and is matched with a fluorine-containing material to achieve the effects of high hardness, wear resistance and anti-fouling. The product has good characteristics in the aspect of hardness and wear resistance and also has good anti-fouling effect, after the UV coating is prepared into a coating, the coating can be directly used if the coating is applied to a shell with a simple geometric shape, but if the coating is applied to the surface of a shell with a complex shape such as a household appliance, a mobile phone, a computer and the like, high-temperature injection molding treatment is needed, high-temperature deformation and stretching steps are carried out on a sample after injection molding, the injection molding R angle crack is easy to occur on the sample, the water contact angle is reduced after molding, and the anti-fouling performance is reduced.
Also, Chinese patent (CN109536001A) discloses a high-hardness high-wear-resistance fingerprint-resistant photocureable coating. The organic fluorine modified urethane acrylate oligomer and the 9-functionality nano hybrid organic silicon modified urethane acrylate oligomer are blended to ensure that the coating has high hardness and wear resistance, but the coating prepared by the scheme does not overcome the defects that R-angle cracking is easy to occur after high-temperature injection molding, the water contact angle is reduced after molding, and the stain resistance is reduced.
Therefore, how to improve the flexibility of the UV coating after high-temperature injection molding is still kept, and the high water contact angle has great significance.
Disclosure of Invention
The invention provides a high-temperature-resistant injection-molding anti-fouling UV coating, aiming at overcoming the defects that the R angle is cracked after high-temperature injection molding, and the anti-fouling performance and the flexibility are reduced after injection molding.
The invention also aims to provide a preparation method of the high-temperature-resistant injection-molding anti-fouling UV coating.
The invention also aims to provide application of the high-temperature-resistant injection molding anti-fouling UV coating.
In order to achieve the purpose, the invention adopts the technical scheme that:
the high-temperature-resistant injection-molding anti-fouling UV coating comprises the following components in parts by weight:
the high-temperature-resistant injection-molding anti-fouling UV coating disclosed by the invention adopts polyurethane acrylate resin as a main material, and the coating still has high anti-fouling performance after high-temperature injection molding and does not crack at an injection-molding R angle, wherein the high-temperature resistance is provided by the synergistic effect of multifunctional polyurethane acrylate resin, nano filler and organic fluorine modified UV resin; the anti-fouling performance is the combined action of the organic fluorine modified UV resin, the hydrophobic and oleophobic auxiliary agent and the nano filler.
The nano filler can be well dispersed in the cross-linked network body of the multifunctional polyurethane acrylic resin, and the network compactness, the uniformity and the temperature resistance of the system are further improved. The nanometer filler can improve the crosslinking density, reduce the strength of the coating, can provide a large extension space for the molecular chain segment of the coating, when external force reaches the surface of the coating, the impacted part can transmit force along the polymer according to a network through the motion of the high-molecular chain of the coating, reduce the damage caused by overlarge local stress, and simultaneously, the extension of the high-molecular chain segment can also be macroscopically expressed as the toughness of the coating, thereby playing a good impact-resistant protection effect, improving the flexibility, and preventing the R angle from cracking in the injection molding process.
On the other hand, the nano filler matched with the hydrophobic and oleophobic agent can improve the water contact angle after injection molding, probably because the hydrophobic and oleophobic auxiliary agent can provide very low surface energy and high water contact angle and has reactivity, the anchoring on the surface of the coating is enhanced, and the nano filler is uniformly dispersed on the surface of the coating, so that the nano filler can still keep high water contact angle and stain resistance after high temperature.
The multifunctional polyurethane acrylate resin provides a paint film with good crosslinking density, so that the paint film has good hardness, scratch resistance and chemical resistance, and the compact coating improves the surface smoothness; the organic fluorine modified UV resin can provide a system with lower surface energy and higher water contact angle, so that the stain resistance is provided, meanwhile, the organic fluorine structure provides good temperature resistance, and the stain resistance after high temperature is good in durability.
Preferably, the average particle size of the nano filler is 20-40 nm. When the average particle size of the nano filler is 20-40 nm, the nano filler has a better water contact angle after injection molding, and the anti-fouling effect is better. Too small a particle size or too large a particle size will affect.
Preferably, the nanofiller is one or more of nano alumina, nano zirconia or nano silica.
Preferably, the organic fluorine modified UV resin is a 6 functional group perfluoropolyether modified acrylic resin.
Preferably, the functionality of the multifunctional urethane acrylate resin is 6 or more.
Preferably, the hydrophobic and oleophobic auxiliary agent is one or more of a perfluoropolyether carboxylic ester methacrylate compound, a perfluoropolyether hydroxy acrylate compound, a perfluorooctyl ethyl methacrylate compound and a perfluorohexyl ethyl methacrylate compound.
Preferably, the low oxygen resistance composite initiator is one or two of 1,1' - (methylenedi-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone ] or modified alpha hydroxyalkyl ketone initiator.
Preferably, the organic solvent is one or more of ethyl acetate, butyl acetate or propylene glycol methyl ether.
The invention also provides a preparation method of the high-temperature-resistant injection-molding anti-fouling UV coating, which comprises the following steps:
and (2) uniformly mixing multifunctional polyurethane acrylate resin, organic fluorine modified UV resin, a UV photoinitiator, a low-oxygen-resistance composite initiator, a hydrophobic and oleophobic auxiliary agent, nano filler and an organic solvent to obtain the high-temperature-resistant and anti-fouling coating.
The high-temperature-resistant injection-molding anti-fouling UV coating prepared by the preparation method is obtained by injection molding, and the injection molding temperature is 180-200 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the high-temperature-resistant injection-molding anti-fouling UV coating adopts polyurethane acrylate resin as a main material, has high-temperature resistance and anti-fouling performance, and does not crack at an injection-molding R angle, wherein the high-temperature resistance is provided by the synergistic effect of the multifunctional polyurethane acrylate resin, the nano filler and the organic fluorine modified UV resin; the antifouling property is the combined action of the organic fluorine modified UV resin, the hydrophobic oil transportation auxiliary agent and the nano filler. The UV coating is temperature-resistant, and does not crack at an injection molding R angle, and a water contact angle after injection molding is more than 108 degrees.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The starting materials in the examples are all commercially available:
polyfunctional urethane acrylate resin: 6 functional urethane acrylate resin, bayer U400;
organic fluorine modified UV resin: jersda DSP-552F;
hydrophobic and oleophobic auxiliary agent: neutralized C1604;
nano filler A: nanometer alumina with average particle size of 10nm, crystal and VK-L10C;
nano filler B: nano alumina with the average grain diameter of 20nm and Jiupeng CY-L20C;
nano filler C: nano alumina with average grain size of 30nm and Deloka EA 440X;
nano filler D: nanometer alumina with average particle size of 40nm, TaD-N60;
nano filler E: nanometer alumina with average particle diameter of 50nm, Hennan HN-L50 CUV;
nano-filler F: nanometer silicon oxide with average particle diameter of 30nm, and MEK-ST-UP
Nano filler G: nano zirconia with average grain size of 30nm, crystal and VK-R30W
Photoinitiator (2): igarc 184;
organic solvent: acetic acid ethyl ester;
low oxygen resistance composite initiator: and the IGM 127.
The following examples and comparative examples were prepared as follows, and the formulations are shown in tables 1-3:
and uniformly mixing 6-functional polyurethane acrylate resin, organic fluorine modified UV resin, a UV photoinitiator, a low-oxygen-resistance composite initiator, a hydrophobic and oleophobic auxiliary agent, nano filler dispersion liquid and an organic solvent to obtain the high-temperature-resistant and anti-fouling coating.
Preparation ofCoating: diluting the high-temperature-resistant injection-molding high-water-contact-angle anti-fouling UV coating to 30% solid content by using butyl acetate, coating the coating on PET, baking the PET for 30-60 seconds in an IR furnace at 60 ℃, and then using 400mJ/cm2The UV energy is used for carrying out UV irradiation curing at the machine speed of 8m/min, and the thickness of the obtained dry film is 3-4 mu m. Wherein the light source used for curing is a high-pressure mercury lamp, and the central wavelength is 365 nm.
High-temperature injection molding: injection molding machines are offered by the strong intelligent companies; and (3) testing conditions are as follows: the membrane temperature is 180-200 ℃, the cavity temperature is 280 ℃, the injection molding time is 30 seconds, and the size of the injection molded sample plate membrane is 130um thick, 15cm long and 8cm wide.
Examples 1 to 5
TABLE 1 formulations of examples 1-5
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Multifunctional urethane acrylate resin | 30 | 30 | 30 | 30 | 30 |
| Organic fluorine modified UV resin | 15 | 15 | 15 | 15 | 15 |
| UV photoinitiators | 3 | 3 | 3 | 3 | 3 |
| Low oxygen resistance composite initiator | 1 | 1 | 1 | 1 | 1 |
| Hydrophobic and oleophobic auxiliary agent | 1.5 | 1 | 3 | 1.5 | 1.5 |
| Nano-filler C | 3 | 3 | 3 | 1 | 5 |
| Organic solvent | 50 | 50 | 50 | 50 | 50 |
Examples 6 to 11
TABLE 2 formulations of examples 6-11
Examples 12 to 15 and comparative examples 1 to 3
TABLE 3 formulations (parts) of examples 12 to 15 and comparative examples 1 to 3
The above examples and comparative examples were each tested for performance by the following test method:
viscosity: the viscosity was determined according to GB/T1723;
adhesion force: ASTM D3359 coating adhesion test method;
hardness: 750g force, 45 degrees, then the Mitsubishi pencil test, GB/T6739-;
water contact angle: adopting a water contact angle tester to test the static water contact angle of the surface of the coating before and after injection molding to test GB/T30693-;
flexibility: and (5) quickly folding the membrane by 10cm by 5cm, folding the membrane once, and checking whether the membrane is cracked.
High-temperature tensile property: the obtained coating film was softened at 180 ℃ and then subjected to an R angle of 25 ° to 60 °, and whether or not cracking occurred was examined.
TABLE 4 data for examples and comparative examples
From examples 1 to 5, the high-temperature-resistant injection-molded high-water-drop-angle antifouling UV coating has good adhesion to a substrate, a high water contact angle, good flexibility and no cracking of an R angle after injection molding, and the water contact angle can be kept at 98.2% after high-temperature-resistant injection molding.
From examples 2 and 6 to 9, the water contact angle of the nanofiller after injection molding was higher for particle sizes between 20 and 40nm than for other particle sizes.
From examples 12 to 15, the organic fluororesin and the water-repellent and oil-repellent auxiliary agent contribute to the improvement of the water contact angle, contribute to the heat resistance, and keep the water angle well after the high-temperature injection molding.
From comparative examples 1-3, the hydrophobic and oleophobic auxiliary agent has great influence on the lifting water contact angle, and from comparative example 1, the water contact angle before high-temperature injection molding is lower, and the water contact angle after high-temperature injection molding is lower; from comparative example 2, the nanofiller had an effect on toughness, the nanofiller was not added, cracks after injection molding, and the water contact angle after high temperature injection molding was also reduced because only the hydrophobic oil transportation aid was present; comparative example 3 no organic fluororesin was added and cracked after high temperature stretching.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The high-temperature-resistant injection-molding anti-fouling UV coating is characterized by comprising the following components in parts by weight:
2. the high-temperature-resistant injection-molded anti-fouling UV coating as claimed in claim 1, wherein the average particle size of the nano filler is 20-40 nm.
3. The high-temperature-resistant injection-molded anti-fouling UV coating material as claimed in claim 1, wherein the nano filler is one or more of nano aluminum oxide, nano zirconium oxide or nano silicon oxide.
4. The high-temperature-resistant injection-molded antifouling UV coating as claimed in claim 1, wherein the organic fluorine modified UV resin is 6-functional perfluoropolyether modified acrylic resin.
5. The high temperature resistant injection molding antifouling UV coating of claim 1, wherein the functionality of the multifunctional urethane acrylate resin is greater than or equal to 6.
6. The high-temperature-resistant injection-molded anti-fouling UV coating material as claimed in claim 1, wherein the hydrophobic and oleophobic auxiliary agent is one or more of a perfluoropolyether carboxylic ester methacrylate compound, a perfluoropolyether hydroxy acrylate compound, a perfluorooctylethyl methacrylate compound, or a perfluorohexylethyl methacrylate compound.
7. The high-temperature-resistant injection-molding antifouling UV coating as claimed in claim 1, wherein the low-oxygen-resistance composite initiator is one or two of 1,1' - (methylenedi-4, 1-phenylene) bis [ 2-hydroxy-2-methyl-1-acetone ] or modified alpha hydroxyalkyl ketone initiators.
8. The high-temperature-resistant injection-molded anti-fouling UV coating material as claimed in claim 1, wherein the organic solvent is one or more of ethyl acetate, butyl acetate or propylene glycol methyl ether.
9. The preparation method of the high-temperature-resistant injection-molding anti-fouling UV coating according to any one of claims 1 to 8, characterized by comprising the following steps:
and (2) uniformly mixing multifunctional polyurethane acrylate resin, organic fluorine modified UV resin, a UV photoinitiator, a low-oxygen-resistance composite initiator, a hydrophobic and oleophobic auxiliary agent, nano filler and an organic solvent to obtain the high-temperature-resistant and anti-fouling coating.
10. The high-temperature-resistant injection-molded anti-fouling UV coating prepared by the preparation method of claim 9 is obtained by injection molding, and the injection molding temperature is 180-200 ℃.
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Application publication date: 20210723 |