CN112708296A - Hardening and toughening type anti-doodling coating, anti-doodling composite film and preparation method of anti-doodling composite film - Google Patents
Hardening and toughening type anti-doodling coating, anti-doodling composite film and preparation method of anti-doodling composite film 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
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- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
The invention discloses a reinforced and toughened doodling-resistant coating, an anti-doodling composite film and a preparation method thereof, wherein the reinforced and toughened doodling-resistant coating is a UV LED ultraviolet light curing coating, and the coating comprises the following components in parts by weight: 60-78 parts of fluorine-silicon modified acrylate resin, 10-14 parts of ethoxylated tetrahydrofuran acrylate, 6-10 parts of dipentaerythritol hexaacrylate, 2.7-4.5 parts of photoinitiator and 0.5-1.5 parts of flatting agent; the reinforced and toughened anti-graffiti coating is coated on the surface of a plastic film, and a composite film with anti-graffiti performance can be obtained through ultraviolet light curing, and the composite film has higher hardness and toughness, can avoid a hard object from scratching the surface, can withstand secondary deformation, and does not crack or fall off.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a hardening and toughening type doodling-resistant coating, an anti-doodling composite film and a preparation method thereof.
Background
Plastic films, such as PET films, PVC films, PC films and PE films, are excellent in physical properties, chemical properties and dimensional stabilityThe film has the advantages of good transparency and recyclability, and can be widely applied to the fields of magnetic recording, photosensitive materials, electronics, electrical insulation, industrial films, packaging decoration, decorative plates, screen protection, optical mirror surface protection and the like. However, since the plastic film has low surface hardness, it is easily scratched by hard objects, has poor antifouling effect, easily penetrates stains, and leaves fingerprints, so that its application is limited. In the prior art, an antifouling coating film layer or a hardening coating layer is coated on the surface of a plastic film so as to improve the antifouling property or hardness of the plastic film. However, most anti-graffiti coatings on the market today are usually made by adding inorganic nanoparticles (TiO)2、SiO2ZnO, etc.) or a silicon fluorine-based assistant is added to improve the graffiti resistance of the coating, but since the inorganic nanoparticles lose their effect once they are coated with the coating, only the portion on the surface is effective, and the effect of the silicon fluorine-based additive is also reduced gradually due to migration, the stain-resistant effect is temporary. The two-component waterborne polyurethane is also used as a reinforcing and toughening type anti-graffiti coating, although the coating has a relatively durable anti-graffiti performance, the polyurethane coating has poor toughness, cannot be bent and is easy to crack although the hardness is relatively high, so that the secondary processability of the plastic film is reduced, and the application of the plastic film is limited. It is seen that improvements and enhancements to the prior art are needed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide the hardening and toughening type anti-graffiti coating, the anti-graffiti composite film and the preparation method thereof, and aims to overcome the technical defects of poor stain resistance, poor graffiti resistance, poor hardness and poor toughness of the surface of the plastic film in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
the hardening and toughening type anti-doodling coating is a UV LED ultraviolet light curing coating, and comprises the following components in parts by weight:
60-78 parts of fluorine-silicon modified acrylate resin;
10-14 parts of ethoxylated tetrahydrofuran acrylate;
6-10 parts of dipentaerythritol hexaacrylate;
2.7-4.5 parts of a photoinitiator;
0.5-1.5 parts of a leveling agent.
In the hardening and toughening type anti-graffiti coating, the fluorine-silicon modified acrylate comprises three-functionality fluorine-silicon modified acrylate and six-functionality fluorine-silicon modified acrylate.
In the hardening and toughening type anti-doodling coating, the weight ratio of the three-functionality fluorine-silicon modified acrylate to the six-functionality fluorine-silicon modified acrylate is 3-5: 1.
In the hardening and toughening type anti-graffiti coating, the photoinitiator comprises 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 1-hydroxy-cyclohexyl phenyl ketone.
In the hardening and toughening type anti-doodling coating, the weight ratio of the 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide to the 1-hydroxy-cyclohexyl phenyl ketone is 6-8: 1
In the hardening and toughening type anti-doodling coating, the coating comprises the following components in parts by weight:
75 parts of fluorine-silicon modified acrylate;
12 parts of ethoxylated tetrahydrofuran acrylate;
8 parts of dipentaerythritol hexaacrylate;
4 parts of a photoinitiator;
and 1 part of a leveling agent.
An anti-graffiti composite film, wherein the anti-graffiti composite film comprises a substrate layer and an anti-graffiti coating layer coated on the substrate layer, the substrate layer comprises one of a PET film, a PVC film, a PC film and a PE film, and the anti-graffiti coating layer is the reinforced and toughened anti-graffiti coating film layer as claimed in any one of claims 1-6.
In the anti-doodling composite film, the thickness of the anti-doodling coating is 10-12 microns.
A method for preparing an anti-graffiti composite film as described above, wherein the method comprises the steps of:
s1, preparing a reinforced and toughened anti-graffiti coating: taking the components according to the proportion, sequentially adding fluorine-silicon modified acrylate, ethoxylated tetrahydrofuran acrylate and dipentaerythritol hexaacrylate into a dispersion machine, mixing and dispersing for 5-10 min at the rotating speed of 700-1000 rpm, measuring the fineness after uniform mixing, adding a photoinitiator and a leveling agent after the fineness is qualified, and mixing and dispersing for 10-20 min at the rotating speed of 1200-1500 rpm to obtain the hardening and toughening type doodle-resistant coating;
s2, preparing an anti-doodling composite film: taking a substrate layer, firstly carrying out corona treatment on a PET or PE film substrate layer, then rolling a hardening and toughening type anti-graffiti coating on the surface of the substrate layer, then carrying out UV LED ultraviolet light curing for 3-5 s, and cooling to obtain the anti-graffiti composite film. In the case of PVC or PC film, the coating is applied directly to the film without corona treatment.
In the preparation method of the anti-graffiti composite film, in the step S1, the fineness is not more than 5 μm, and the anti-graffiti composite film is qualified.
Has the advantages that:
the invention provides a hardening and toughening type doodling-resistant paint, an anti-doodling composite film and a preparation method thereof, wherein the hardening and toughening type doodling-resistant paint can be used by matching fluorine-silicon modified acrylate resin, ethoxylated tetrahydrofuran acrylate and dipentaerythritol hexaacrylate, so that a paint with excellent stain resistance, doodling resistance and higher hardness and toughness can be obtained, the paint has better adhesive force on the surface of a plastic film, and the hardening and toughening type doodling-resistant paint is coated on the surface of the plastic film by a roller so as to obtain the anti-doodling composite film.
Detailed Description
The invention provides a hardening and toughening type anti-doodling coating, an anti-doodling composite film and a preparation method thereof, and the invention is further detailed by the following examples in order to make the purpose, the technical scheme and the effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The strengthening and toughening type anti-doodling coating is a UV LED ultraviolet light curing coating, and comprises the following components in parts by weight:
60-78 parts of fluorine-silicon modified acrylate resin;
10-14 parts of ethoxylated tetrahydrofuran acrylate;
6-10 parts of dipentaerythritol hexaacrylate;
2.7-4.5 parts of a photoinitiator;
0.5-1.5 parts of a leveling agent.
In the reinforced and toughened anti-graffiti coating with the composition ratio, the fluorine-silicon modified acrylate resin is modified acrylate resin with multiple functionality, the main chain of the coating is polyurethane, the side chain contains fluorine-silicon modified chain segments, and the end parts of the side chains have fluorine-silicon groups which naturally migrate to the surface of the coating due to factors such as specific gravity, compatibility and the like, so that a nano-synapse-shaped microstructure is formed on the surface of the coating, and the surface has better hydrophobic and oleophobic properties, and further has better anti-fouling and anti-graffiti properties; the ethoxylated tetrahydrofuran acrylate has low viscosity and good wettability, can improve the adhesive force and curing speed of the coating on a plastic film, and simultaneously enhances the boiling resistance of the coating; the dipentaerythritol hexaacrylate can improve the crosslinking density of the coating, so that the surface of a film layer is compact after the coating is formed into a film, and the wear resistance and the weather resistance of the coating are improved; the photoinitiator is a ketone hydrogen abstraction type liquid photoinitiator, can improve the curing speed of the coating, can enable the coating to be instantly cured under the irradiation of 385nm or 395nm ultraviolet light, and improves the curing speed of a paint film; the leveling agent can reduce the viscosity of the coating, improve the leveling speed of the coating on the surface of the substrate and improve the adhesive force of the coating. Preferably, the coating is a leveling agent provided by Bick Germany and having a BYK3505 mark, and has better leveling performance.
The coating with excellent anti-fouling and anti-doodling performances on the surface can be obtained by matching and using the components, the coating is coated on the surface of a plastic film and can be instantly cured through ultraviolet illumination, the cured coating has excellent anti-fouling performance and has hydrophobic and oleophobic performances, a contact angle with water is large, oil pen doodling is performed, pen marks have an obvious oil shrinkage phenomenon and can be easily erased, no trace residue is left on the surface after erasing, more importantly, the coating also has higher hardness and excellent flexibility, scratch resistance and bending resistance, the coating does not crack or fall off after being bent for many times, and the coating can be used as a surface protection film layer of each plastic film.
Preferably, in the reinforcing and toughening type anti-graffiti coating, the fluorine-silicon modified acrylate comprises three-functionality fluorine-silicon modified acrylate and six-functionality fluorine-silicon modified acrylate which are a mixture of the three-functionality fluorine-silicon modified acrylate and the six-functionality fluorine-silicon modified acrylate. The three-functionality fluorine-silicon modified acrylate and the six-functionality fluorine-silicon modified acrylate both have fluorine-silicon side chains, the fluorine-silicon side chains migrate to the surface of the coating in the preparation process, a rough nano synaptic microstructure is formed on the surface of the coating, and the synaptic microstructure can make polar and non-polar liquids difficult to wet the surface, so that the coating has hydrophobic and oleophobic properties, and antifouling and doodling-resistant performances are obtained. The tri-functionality fluorosilicone modified acrylate can provide excellent toughness and wear resistance for a system, and the hexa-functionality fluorosilicone modified acrylate has high crosslinking density, and can greatly improve the hardness of a film layer due to the high crosslinking density. This application is through using the fluorine silicon modified acrylate of high functionality and the fluorine silicon acrylate complex formulation of low functionality, the cross-linking mixes, produce the synergism, make the coating that obtains not only have better resistant dirty anti-graffiti nature, more importantly, increase cross-linking density, when improving the hardness of coating, improve the toughness of coating, even make the coating fold, the phenomenon that can not appear cracking or drop yet, furthermore, both complex formulation uses, because surface structure is more compact, make the weatherability of coating improve greatly, and its boiling water resistance also obtains showing and improves, can stand boiling water and boil the back, still have better antipollution, hardness and toughness.
More preferably, in the reinforced and toughened anti-graffiti coating, the anti-fouling property, hardness and toughness of the coating are in a better state by adjusting the proportion of the tri-functionality fluorosilicone modified acrylate to the hexa-functionality fluorosilicone modified acrylate, and when the weight ratio of the tri-functionality fluorosilicone modified acrylate to the hexa-functionality fluorosilicone modified acrylate is 3-5: 1, the coating has better anti-fouling property, hardness and toughness, and the reaction speed of the system is high, so that the coating can be instantly cured under the irradiation of ultraviolet light. More preferably, the weight ratio of the tri-functional fluorosilicone modified acrylate to the hexa-functional fluorosilicone modified acrylate is 4: 1.
Specifically, in the reinforced and toughened anti-graffiti coating, the photoinitiator comprises 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 1-hydroxy-cyclohexylphenyl ketone, and the 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 1-hydroxy-cyclohexylphenyl ketone are used in combination, so that on one hand, the system can initiate a reaction under ultraviolet irradiation with a wavelength of 385nm or 395nm, and on the other hand, the system can have a relatively high reaction speed. Preferably, when the weight ratio of the 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide to the 1-hydroxy-cyclohexyl-phenyl-ketone is 6-8: 1, the photoinitiation speed is high.
Preferably, the reinforced and toughened anti-graffiti coating has excellent stain resistance, graffiti resistance, hardness, toughness and weather resistance when comprising the following components in parts by weight:
75 parts of fluorine-silicon modified acrylate;
12 parts of ethoxylated tetrahydrofuran acrylate;
8 parts of dipentaerythritol hexaacrylate;
4 parts of a photoinitiator;
and 1 part of a leveling agent.
The application also discloses an anti graffiti complex film of toughening type that hardens, the anti graffiti complex film of toughening type that hardens includes the stratum basale and sets up the anti graffiti coating on the stratum basale, the stratum basale includes one in PET membrane, PVC membrane, PC membrane and the PE membrane, anti graffiti coating is as above the anti graffiti coating of toughening type that hardens, through coating the anti graffiti coating of toughening type that hardens on the stratum basale, the complex film that obtains has excellent antifouling anti graffiti performance to surface hardness is big, and scratch resistance is good, and toughness is good simultaneously, even if through folding many times, the phenomenon that the surface coating ftractures can not appear yet.
Preferably, in the anti-doodling composite film, the thickness of the anti-doodling coating is 10-12 μm, the anti-doodling composite film has good transparency, the color and the texture of the base layer can be well displayed, the surface hardness of the base layer can be greatly improved due to the thickness of the anti-doodling coating, and the coating is guaranteed to have good scratch resistance.
The application also discloses a preparation method of the anti-doodling composite film, which comprises the following steps:
s1, preparing a reinforced and toughened anti-graffiti coating: taking the components according to the proportion, sequentially adding fluorine-silicon modified acrylate, ethoxylated tetrahydrofuran acrylate and dipentaerythritol hexaacrylate into a dispersion machine, mixing and dispersing for 5-10 min at the rotating speed of 700-1000 rpm, measuring the fineness after uniform mixing, adding a photoinitiator and a leveling agent after the fineness is less than or equal to 5 microns, and mixing and dispersing for 10-20 min at the rotating speed of 1200-1500 rpm to obtain the UV LED ultraviolet photocuring reinforced toughened anti-graffiti coating;
s2, preparing an anti-doodling composite film: taking a PET or PE substrate layer, carrying out corona treatment, roller-coating a reinforced and toughened anti-doodling coating on the surface, wherein the thickness of the coating is 10-12 microns, carrying out photocuring for 3-5 s by UV LED ultraviolet rays with the wavelength of 385nm or 395nm, and cooling to obtain the anti-doodling composite film comprising the substrate layer and the anti-doodling layer. In the case of PVC or PC film, the coating is applied directly to the film without corona treatment.
To further illustrate the reinforced and toughened anti-graffiti coating, the anti-graffiti composite film and the preparation method of the anti-graffiti composite film provided by the present invention, the following examples are provided.
Example 1
The reinforced and toughened anti-doodling coating comprises the following components in parts by weight:
60 parts of trifunctional fluorine-silicon modified acrylate resin;
15 parts of six-functionality fluorosilicone modified acrylate resin;
12 parts of ethoxylated tetrahydrofuran acrylate;
8 parts of dipentaerythritol hexaacrylate;
3.5 parts of 2.4.6-trimethylbenzoyl-diphenylphosphine oxide photoinitiator;
0.5 part of 1-hydroxy-cyclohexyl phenyl ketone photoinitiator
And 1.0 part of a leveling agent.
The anti-doodling composite film prepared from the reinforced and toughened anti-doodling coating comprises a PET film and an anti-doodling coating, wherein the thickness of the anti-doodling coating is 10 micrometers.
The preparation method of the reinforced and toughened anti-doodling composite film comprises the following steps:
s1, preparing a reinforced and toughened anti-graffiti coating: taking the components in the reinforced toughened anti-doodling coating according to the proportion, sequentially adding three-functionality fluorine-silicon modified acrylate, six-functionality fluorine-silicon modified acrylate, ethoxylated tetrahydrofuran acrylate and dipentaerythritol hexaacrylate into a dispersion machine, mixing and dispersing for 8min at the rotating speed of 800rpm, measuring the fineness, adding a photoinitiator and a leveling agent after the fineness is less than or equal to 5 mu m, mixing and dispersing for 15min at the rotating speed of 1300rpm, and obtaining the UV LED ultraviolet photocuring reinforced toughened anti-doodling coating;
s2, preparing an anti-doodling composite film: taking a PET film, carrying out corona treatment, roll-coating a reinforcing and toughening type anti-graffiti coating on the surface of a substrate layer, wherein the thickness of the coating is 10 microns, then carrying out ultraviolet curing for 4s through a UV LED (ultraviolet light emitting diode) with the wavelength of 395nm, and cooling to obtain the anti-graffiti composite film comprising the PET film layer and the anti-graffiti layer.
Example 2
The reinforced and toughened anti-doodling coating comprises the following components in parts by weight:
45 parts of trifunctional fluorosilicone modified acrylate resin;
15 parts of six-functionality fluorosilicone modified acrylate resin;
10 parts of ethoxylated tetrahydrofuran acrylate;
6 parts of dipentaerythritol hexaacrylate;
2.4 parts of 2.4.6-trimethylbenzoyl-diphenylphosphine oxide photoinitiator;
0.3 part of 1-hydroxy-cyclohexyl phenyl ketone photoinitiator
0.5 part of leveling agent.
The anti-doodling composite film prepared from the reinforced and toughened anti-doodling coating comprises a PET film and an anti-doodling coating, wherein the thickness of the anti-doodling coating is 11 microns.
The preparation method of the anti-doodling composite film comprises the following steps:
s1, preparing a reinforced and toughened anti-graffiti coating: taking the components in the reinforced toughened anti-doodling coating according to the proportion, sequentially adding three-functionality fluorine-silicon modified acrylate, six-functionality fluorine-silicon modified acrylate, ethoxylated tetrahydrofuran acrylate and dipentaerythritol hexaacrylate into a dispersion machine, mixing and dispersing for 10min at the rotating speed of 700rpm, measuring the fineness after uniformly mixing, adding a photoinitiator and a flatting agent after the fineness is less than or equal to 5 mu m, and mixing and dispersing for 20min at the rotating speed of 1200rpm to obtain the UV LED ultraviolet photocuring reinforced toughened anti-doodling coating;
s2, preparing an anti-doodling composite film: taking a PET film, carrying out corona treatment, roll-coating a reinforcing and toughening type anti-doodling coating on the surface of the PET film, wherein the thickness of the coating is 10 microns, then carrying out ultraviolet curing for 3s through a UV LED (ultraviolet light emitting diode) with the wavelength of 385nm, and cooling to obtain the anti-doodling composite film comprising the PET film and the anti-doodling layer.
Example 3
The reinforced and toughened anti-doodling coating comprises the following components in parts by weight:
65 parts of trifunctional fluorine-silicon modified acrylate resin;
13 parts of six-functionality fluorosilicone modified acrylate resin;
14 parts of ethoxylated tetrahydrofuran acrylate;
10 parts of dipentaerythritol hexaacrylate;
4.0 parts of 2.4.6-trimethylbenzoyl-diphenylphosphine oxide photoinitiator;
0.5 part of 1-hydroxy-cyclohexyl phenyl ketone photoinitiator
And 1.5 parts of a leveling agent.
The anti-doodling composite film prepared from the reinforced and toughened anti-doodling coating comprises a PET film and an anti-doodling coating, wherein the thickness of the anti-doodling coating is 12 micrometers.
The preparation method of the anti-doodling composite film comprises the following steps:
s1, preparing a reinforced and toughened anti-graffiti coating: taking the components in the reinforced toughened anti-doodling coating according to the proportion, sequentially adding three-functionality fluorine-silicon modified acrylate, six-functionality fluorine-silicon modified acrylate, ethoxylated tetrahydrofuran acrylate and dipentaerythritol hexaacrylate into a dispersion machine, mixing and dispersing for 5min at the rotating speed of 1000rpm, measuring the fineness after uniformly mixing, adding a photoinitiator and a flatting agent after the fineness is less than or equal to 5 mu m, and mixing and dispersing for 10min at the rotating speed of 1500rpm to obtain the UV LED ultraviolet photocuring reinforced toughened anti-doodling coating;
s2, preparing an anti-doodling composite film: taking a PET film, carrying out corona treatment, roll-coating a reinforcing and toughening type anti-doodling coating on the surface of the PET film, wherein the thickness of the coating is 12 microns, then carrying out ultraviolet curing for 5 seconds through a UV LED (light emitting diode) with the wavelength of 395nm, and cooling to obtain the anti-doodling composite film comprising a base layer and an anti-doodling layer.
Example 4
An anti-doodling composite film comprises a PVC film and an anti-doodling coating, wherein the anti-doodling coating adopts the reinforced and toughened anti-doodling paint as described in example 1, the thickness of the anti-doodling coating is 12 microns, the preparation method is the same as that of example 1, and only a PET film is replaced by the PVC film.
Example 5
An anti-doodling composite film comprises a PC film and an anti-doodling coating, wherein the anti-doodling coating adopts the reinforced and toughened anti-doodling coating as described in example 1, the thickness of the anti-doodling coating is 12 microns, the preparation method is the same as that of example 1, and only the PET film is replaced by the PC film.
Example 6
An anti-doodling composite film comprises a PE film and an anti-doodling coating, wherein the anti-doodling coating adopts the reinforced and toughened anti-doodling coating as described in example 1, the thickness of the anti-doodling coating is 12 microns, the preparation method is the same as that of example 1, and only the PET film is replaced by the PE film.
Comparative example 1
The reinforced and toughened anti-doodling coating comprises the following components in parts by weight:
75 parts of trifunctional fluorine-silicon modified acrylate resin;
12 parts of ethoxylated tetrahydrofuran acrylate;
8 parts of dipentaerythritol hexaacrylate;
3.5 parts of 2.4.6-trimethylbenzoyl-diphenylphosphine oxide photoinitiator;
0.5 part of 1-hydroxy-cyclohexyl phenyl ketone photoinitiator
And 1.0 part of a leveling agent.
The anti-doodling composite film prepared from the reinforced and toughened anti-doodling coating comprises a PET film and an anti-doodling coating, wherein the thickness of the anti-doodling coating is 10 micrometers.
Comparative example 1 a graffiti resistant composite film was prepared in the same manner as in example 1.
Comparative example 2
The reinforced and toughened anti-doodling coating comprises the following components in parts by weight:
75 parts of six-functionality fluorosilicone modified acrylate resin;
12 parts of ethoxylated tetrahydrofuran acrylate;
8 parts of dipentaerythritol hexaacrylate;
3.5 parts of 2.4.6-trimethylbenzoyl-diphenylphosphine oxide photoinitiator;
0.5 part of 1-hydroxy-cyclohexyl phenyl ketone photoinitiator
And 1.0 part of a leveling agent.
The anti-doodling composite film prepared from the reinforced and toughened anti-doodling coating comprises a PET film and an anti-doodling coating, wherein the thickness of the anti-doodling coating is 10 micrometers.
Comparative example 2 the anti-graffiti composite film was prepared in the same manner as in example 1.
The anti-doodling composite films of examples 1 to 6 and the anti-doodling composite films of comparative examples 1 and 2 are subjected to performance tests, meanwhile, the waterborne polyurethane reinforced and toughened anti-doodling paint purchased in the market is used as comparative example 3, and the performance test results are shown in table 1. In addition, the anti-graffiti composite films described in the embodiments 1 to 6 are subjected to an anti-graffiti performance test, oil pens, water-based pens, inks and soy sauce are respectively adopted to randomly paint on the surfaces of the composite films, the surfaces of the composite films described in the embodiments 1 to 6 are not easy to leave marks, and the phenomenon of sink marks is obviously caused, the marks can be removed by lightly wiping the surfaces with a rag, and the surfaces of the composite films after removal have no residual marks.
TABLE 1 test results of various performance indexes
As can be seen from table 1, the curing time of each anti-doodling composite film in examples 1 to 6 is fast, and can be completed within only a few seconds, the anti-sticking phenomenon does not occur after curing, the adhesive force is strong, and the surface hardness, flexibility, wear resistance and water resistance are excellent, while comparative examples 1 and 2 do not adopt the complex use of the fluorosilicone modified acrylate resin with the three-functionality degree and the six-functionality degree, so that the hardness, flexibility, wear resistance and adhesive force cannot be improved in a balanced manner, and thus, the complex use of the fluorosilicone modified acrylate resin with multiple functionality degrees can better improve various performances of the anti-doodling composite film.
It should be understood that equivalents and modifications of the technical solution and inventive concept thereof may occur to those skilled in the art, and all such modifications and alterations should fall within the scope of the appended claims.
Claims (10)
1. The hardening and toughening type anti-doodling coating is characterized by being a UV LED ultraviolet light curing coating, and comprising the following components in parts by weight:
60-78 parts of fluorine-silicon modified acrylate resin;
10-14 parts of ethoxylated tetrahydrofuran acrylate;
6-10 parts of dipentaerythritol hexaacrylate;
2.7-4.5 parts of a photoinitiator;
0.5-1.5 parts of a leveling agent.
2. The paint of claim 1, wherein the fluorosilicone modified acrylate comprises trifunctional fluorosilicone modified acrylate and hexafunctional fluorosilicone modified acrylate.
3. The hardening and toughening type anti-graffiti coating according to claim 2, wherein the weight ratio of the tri-functional fluorosilicone modified acrylate to the hexafunctional fluorosilicone modified acrylate is 3-5: 1.
4. The paint of claim 1, wherein the photoinitiator comprises 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide and 1-hydroxy-cyclohexylphenyl ketone.
5. The paint of claim 1, wherein the weight ratio of 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide to 1-hydroxy-cyclohexyl phenyl ketone is 6-8: 1.
6. The paint of claim 1, wherein the paint comprises the following components in parts by weight:
75 parts of fluorine-silicon modified acrylate;
12 parts of ethoxylated tetrahydrofuran acrylate;
8 parts of dipentaerythritol hexaacrylate;
4 parts of a photoinitiator;
and 1 part of a leveling agent.
7. An anti-graffiti composite film, wherein the anti-graffiti composite film comprises a substrate layer and an anti-graffiti coating layer coated on the substrate layer, the substrate layer comprises one of a PET film, a PVC film, a PC film and a PE film, and the anti-graffiti coating layer is the reinforced and toughened anti-graffiti coating film layer as claimed in any one of claims 1-6.
8. The anti-graffiti composite film according to claim 7, wherein the thickness of the anti-graffiti coating layer is 10-12 μm.
9. A process for the preparation of a composite anti-graffiti film according to any one of claims 7 to 8, characterized in that it comprises the steps of:
s1, preparing a reinforced and toughened anti-graffiti coating: taking the components according to the proportion, sequentially adding the fluorine-silicon modified acrylate, the ethoxylated tetrahydrofuran acrylate and the dipentaerythritol hexaacrylate into a dispersion machine, mixing and dispersing for 5-10 min at the rotating speed of 700-1000 rpm, measuring the fineness after uniformly mixing, and determining the fineness after the fineness is qualified; adding a photoinitiator and a leveling agent, and mixing and dispersing at the rotating speed of 1200-1500 rpm for 10-20 min to obtain the hardening and toughening type anti-graffiti coating;
s2, preparing an anti-doodling composite film: taking a PET or PE substrate layer, firstly carrying out corona treatment on the substrate layer, then rolling a hardening and toughening type anti-graffiti coating on the surface of the substrate layer, then carrying out UV LED ultraviolet light curing for 3-5 s, and cooling to obtain the anti-graffiti composite film. In the case of PVC or PC film, the coating is applied directly to the film without corona treatment.
10. The method for preparing the anti-graffiti composite film according to claim 9, wherein the fineness of the composite film is not more than 5 μm in step S1.
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