CN113912893B

CN113912893B - Colorful film and preparation method thereof

Info

Publication number: CN113912893B
Application number: CN202111527209.XA
Authority: CN
Inventors: 曹丽军; 张丛见; 任月璋
Original assignee: Suzhou Omay Optical Materials Co ltd
Current assignee: Suzhou Omay Optical Materials Co ltd
Priority date: 2021-12-15
Filing date: 2021-12-15
Publication date: 2022-03-08
Anticipated expiration: 2041-12-15
Also published as: CN113912893A

Abstract

The invention discloses a colorful film and a preparation method thereof. The preparation method of the colorful film comprises the following steps: 1) coating the coating composition on a base material by utilizing a fluid shear induction force generated by a coating means to form a microstructure in which nanospheres are periodically arranged, and drying the nanospheres to form a nanosphere coating surface by regularly and periodically arranging the nanospheres on the surface of the base material; 2) carrying out ultraviolet curing on the base material containing the nanosphere coating layer surface obtained in the step 1) to obtain the colorful film. The preparation method disclosed by the invention is simple in preparation process, and the prepared film has a colorful effect, and meanwhile, has excellent mechanical properties and outstanding adhesive force.

Description

Colorful film and preparation method thereof

Technical Field

The invention relates to the technical field of colorful films, in particular to a colorful film and a preparation method thereof.

Background

The colorful film is also called as a colorful film, a rainbow film and the like, and refers to a film which shows different colors along with the change of the visual observation angle. Tracing the development history of the color-changing plate, going through different stages, the principle is realized at first by utilizing the light interference phenomenon generated by stacking multilayer structures with different refractive indexes, the gradual change of the color can be seen under the observation of naked eyes, and simultaneously, different vivid color changing effects can be generated along with the change of angles. The technology is typically represented as a 3M multilayer coextrusion technology, namely, multilayer structures with different refractive indexes and even hundreds of thin films are coextruded through multiple layers, the technology has obvious colorful effect, but the technology is complex, the equipment cost is high, and the production efficiency is low; later, a multilayer structure is developed by using a magnetron coating technology, a plurality of metals or oxides thereof with different refractive indexes are sputtered on a substrate in a vacuum environment to form a multilayer structure thin film so as to generate multilayer light refraction, and the technology is complex, equipment and raw materials are expensive, and the production efficiency is low.

With the advent of the scientific era, nanomaterials can produce nano-effects such as melting point, magnetic, optical, thermal, electrical conductivity, etc. that are distinguished from macroscopic physical materials due to their nanoscale. On the basis, people realize the purpose of dazzling the phenomenon with the help of nano materials: the periodic structure nano material with different dielectric constants and refractive indexes can prevent light from transmitting at specific wavelength due to the regular arrangement periodicity of the periodic structure nano material, and vivid rainbow colors can be observed within the range of human naked eyes.

In the current development technology of nano materials, in order to realize the periodic arrangement of nano structures, the current preparation technology generally comprises a micro-nano preparation technology or a self-assembly method: the former micro-nano preparation technology is to form a periodic microstructure on a nano material by a preset periodic structure die by means of yellow light etching, laser etching or silk screen etching and the like, and has the defects of time and labor consumption, high cost and low efficiency; the self-assembly method of the nanometer crystal has the advantages that the cost is low, the process is simple, namely, the ideal periodic regular arrangement growth of the nanometer crystal nanometer is completed in the field action environment by utilizing the field action environments of capillary action, gravity action, electric field force and the like, but the obvious disadvantages of the method are that the production efficiency is extremely low, the defect is more, the yield is low, the large-scale production is limited, meanwhile, the mechanical property is poor, and the method does not have practical application performance.

In the face of the above problems, some preliminary solutions have been made. For example, Changchun Wang et al (Journal of Colloid and Interface Science 584 (2021)145-153) first proposed that the core-shell structure nano material is obtained by repeated purification through emulsion polymerization, and then the core-shell nano color and the polymer film are formed into the sandwich composite colorful film by multiple high-temperature extrusion, and meanwhile, the method greatly improves the mechanical strength of the film. However, the preparation steps for preparing the core-shell nano-color material are repeated centrifugal purification, and the process is complicated, time-consuming and labor-consuming; meanwhile, the film forming process needs to be carried out for many times of high-temperature extrusion, so that the efficiency is low, the energy consumption is high, and the application range of the method is greatly limited.

CN110058330A discloses a dazzle various optical film and preparation method and application structure thereof, should dazzle various optical film, includes: a substrate; the coating group is arranged on the surface of the substrate and comprises N inorganic thin film layers and M organic thin film layers, and the inorganic thin film layers and the organic thin film layers are alternately arranged; m and N are integers greater than or equal to 1; the refractive index of the organic thin film layer is smaller than that of the inorganic thin film layer. Because the refracting index of organic thin layer can be done littleer to organic thin layer and inorganic thin layer have bigger refracting index difference, thereby make dazzle various optical film and can realize good dazzle various effect and glossiness with the inorganic thin layer of less and the number of piles of organic thin layer, and because the rete number of coating the rete is less, be favorable to promoting the preparation efficiency of dazzling various optical film, reduce the whole preparation degree of difficulty and the preparation cost of dazzling various optical film. But the process is complex and the production efficiency is low.

In summary, there is an urgent need to find a process for producing a colorful film with high efficiency, rapidness, low cost, and excellent practical performance.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide the colorful film and the preparation method thereof.

One of the purposes of the invention is to provide a preparation method of a colorful film, and in order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of a colorful film comprises the following steps:

step 1) coating the coating composition on a base material by utilizing a fluid shear induction force generated by a coating means to form a microstructure in which nanospheres are periodically arranged, and drying the nanospheres to form a nanosphere coating layer surface in which the nanospheres are regularly and periodically arranged on the surface of the base material;

the coating means is slit coating or micro-concave coating;

the fluid shear induction force is 0.1-0.8 Pa;

wherein the coating composition comprises the following components in parts by weight:

0 to 100 portions of monomer

0 to 100 portions of oligomer

50-400 parts of nanosphere

2-40 parts of photoinitiator

1-20 parts of adhesion promoter

1-40 parts of rheological additive

The solids content of the solvent coating composition is maintained at 5-100 wt% to make up the desired amount;

and 2) carrying out ultraviolet curing on the base material containing the nanosphere coating layer surface obtained in the step 1) to obtain the colorful film.

According to the preparation method of the colorful film, the fluid shear induction force generated by the coating means is utilized to complete the periodic arrangement of the nanospheres on the substrate through a one-step method, the colorful effect can be generated, the crosslinking and curing can be rapidly completed under ultraviolet light, and the prepared colorful film has excellent mechanical property and superior adhesive force.

In the step 1), the opening gap of the slit coating is 5-250

E.g. 5

、10

、15

、20

、25

、30

、35

、40

、45

、50

、55

、60

、65

、70

、75

、80

、85

、90

、95

、100

、110

、120

、130

、140

、150

、160

、170

、180

、190

、200

、210

、220

、230

、240

、250

And the like.

The web of the applicator roll in the gravure coating) is 25 to 180 lines/inch, for example, 25 lines/inch, 30 lines/inch, 35 lines/inch, 40 lines/inch, 45 lines/inch, 50 lines/inch, 60 lines/inch, 70 lines/inch, 80 lines/inch, 90 lines/inch, 100 lines/inch, 110 lines/inch, 120 lines/inch, 130 lines/inch, 140 lines/inch, 150 lines/inch, 160 lines/inch, 170 lines/inch, or 180 lines/inch, etc.; the coating thickness is from 5 to 80, for example, 5, 6, 7, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80.

The fluid shear-inducing force, wherein the shear-inducing force is a force capable of generating shear deformation on a material, and the deformation of a liquid caused by the force when the liquid flows is caused, so that the force is called shear force (also called shear-inducing force), and the ratio of the shear force per unit area to the shear force per unit area is called shear strain force, also called shear stress; the specific calculation is shown in the following formula:

wherein F is the acting force on the shear plane and A is the shear plane area.

The fluid shear inducing force is 0.1 to 0.8 Pa, for example, 0.1 Pa, 0.2 Pa, 0.3 Pa, 0.4 Pa, 0.5 Pa, 0.6 Pa, 0.7 Pa, or 0.8 Pa.

The substrate is one of polyester film or glass.

The polyester film is any one or a composite film of at least two of a Polycarbonate (PC) film, a polymethyl methacrylate (PMMA) film, a polyethylene terephthalate (PET) film, a Polyimide (PI) film and a polyethylene naphthalate (PEN) film.

In the step 2), the radiation intensity of the ultraviolet curing is 100-1500 mJ/cm²For example, 100 mJ/cm²、200 mJ/cm²、400 mJ/cm²、800 mJ/cm²、1000 mJ/cm²Or 1500 mJ/cm²And the like.

The coating composition of the colorful film comprises nanospheres, monomers, oligomers, a photoinitiator, an adhesion promoter, a rheological aid and a solvent, has excellent film forming property and moderate viscosity, does not need to be transferred or other complicated processes, can finish the periodic arrangement of the nanospheres on a substrate by adopting a simple coating mode, can generate a colorful effect, and has simple process and high production efficiency; the acrylic monomer and/or oligomer contained in the coating composition can quickly complete crosslinking and curing under ultraviolet light, so that excellent mechanical properties of the coating can be guaranteed; meanwhile, the adhesion promoter contained in the coating composition can generate a bridging effect between the coating and the base material, so that the superior adhesion of the coating on the base material is ensured. Based on the excellent mechanical property and the outstanding adhesive force, the dazzling color film is ensured to have the performance of practical application.

Specifically, the coating composition comprises the following components in parts by weight:

the weight portion of the monomer is 0 to 100 portions, such as 1 portion, 2 portions, 3 portions, 4 portions, 5 portions, 6 portions, 7 portions, 8 portions, 9 portions, 10 portions, 20 portions, 30 portions, 40 portions, 50 portions, 60 portions, 70 portions, 80 portions, 90 portions or 100 portions, and the like.

The oligomer is present in an amount of 0 to 100 parts by weight, for example 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, or the like.

The nanosphere is 50-400 parts by weight, such as 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, 160 parts, 170 parts, 180 parts, 190 parts, 200 parts, 210 parts, 220 parts, 230 parts, 240 parts, 250 parts, 260 parts, 270 parts, 280 parts, 290 parts, 300 parts, 310 parts, 320 parts, 330 parts, 340 parts, 350 parts, 360 parts, 370 parts, 380 parts, 390 parts, or 400 parts, and the like.

The photoinitiator is 2-40 parts by weight, such as 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, and the like.

The adhesion promoter is 1-20 parts by weight, such as 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts or 20 parts, and the like.

The rheological aid is 1 to 40 parts by weight, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, or the like.

The amount of solvent used is such that the solids content of the coating composition A is kept between 5 and 100% by weight.

In the present invention, the solid content refers to the percentage of the total amount of the components except the solvent in the composition. For example, a solid content of 5% in the composition means that the mass of the solvent is 95g and the sum of the masses of the components other than the solvent is 5g in 100g of the composition; the solid content in the composition is 100%, which means that the mass of the solvent is 0g and the sum of the masses of the components other than the solvent is 100g in 100g of the composition.

The nanosphere is prepared by solution or emulsion polymerization, and generally contains a surfactant, an emulsifier, organic small molecules or inorganic small molecules, water or an organic solvent and the like. The nanosphere is any one or a mixture of at least two of polystyrene, polyacrylate and silicon dioxide.

The particle size distribution of the nanospheres is monodispersity; further preferably, the particle size of the nanosphere is 100-1500 nm, for example, 100 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1000 nm, 1100 nm, 1200 nm, 1300 nm, 1400 nm, 1500 nm, etc. Further preferably, the particle size of the nanospheres is 200-1000 nm.

The monomer is any one or a mixture of at least two of acrylic monomers, styrene monomers, maleic anhydride monomers and furan monomers.

The monomer can be one or a mixture of acrylic ester monomers. The acrylate monomer refers to a lipid containing an acrylic structure or a homologue of the lipid, and contains more than one acrylate reaction functional group. Including but not limited to monofunctional monomers: cycloaliphatic methacrylate, tridecyl methacrylate, dicyclopentadiene methacrylate, methoxypolyethylene glycol monomethacrylate, triethylene glycol ethyl ether methacrylate, alkoxydodecyl acrylate, tetrahydrofuran methacrylate, cycloaliphatic acrylate, 2 (2-ethoxy) ethyl acrylate, octadecyl acrylate, tetrahydrofuran acrylate, dodecyl methacrylate, methyl stearyl acrylate, dodecyl acrylate, 2-phenoxyethyl methacrylate, sec-butyl acrylate, isodecyl acrylate, cycloaliphatic acrylate, isobornyl methacrylate, isooctyl acrylate, tridecyl acrylate, caprolactone acrylate, 4) ethoxylated nonylphenol acrylate, methyl stearyl acrylate, 2-phenoxyethyl methacrylate, sec-butyl acrylate, isodecyl acrylate, cyclohexyl acrylate, isobornyl methacrylate, isooctyl acrylate, tridecyl acrylate, caprolactone acrylate, ethoxylated nonylphenol acrylate, and mixtures thereof, Isobornyl acrylate, trimethylolpropane formal acrylate, lauryl acrylate, sec-butyl methacrylate, lauryl methacrylate, methoxy polyethylene glycol methacrylate, alkoxylated tetrahydrofuran acrylate, alkoxylated nonylphenol acrylate, alkoxylated phenol acrylate; including but not limited to difunctional monomers: cyclohexane dimethanol diacrylate, acrylic acid ester, alkoxylated neopentyl glycol diacrylate, ethoxylated bisphenol A dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol (200) dimethacrylate, 1, 3-butanediol diacrylate, 1, 4-butanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, polyethylene glycol (600) dimethacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (400) dimethacrylate, ethylene glycol (1, 6-hexanediol dimethacrylate, ethylene glycol (1, 6-b) dimethacrylate, ethylene glycol (B) dimethacrylate, ethylene glycol (600) dimethacrylate, ethylene glycol (200) diacrylate, ethylene glycol (400) and the like, 1, 12-dodecyl dimethacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate, 1, 3-butanediol dimethacrylate, tripropylene glycol diacrylate, polyethylene glycol (400) diacrylate, (2) ethoxylated bisphenol A dimethacrylate, (3) ethoxylated bisphenol A diacrylate, (10) ethoxylated bisphenol A dimethacrylate, dipropylene glycol diacrylate, ethoxylated (4) bisphenol A dimethacrylate, ethoxylated (6) bisphenol A dimethacrylate, polyethylene glycol (600) diacrylate, tricyclosilane dimethanol diacrylate, (2) propoxylated neopentyl glycol diacrylate, ethoxylated (30) bisphenol A diacrylate; including but not limited to trifunctional monomers: trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanuric acid triacrylate, (20) ethoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, (3) ethoxylated trimethylolpropane triacrylate, (6) ethoxylated trimethylolpropane triacrylate, (9) ethoxylated trimethylolpropane triacrylate, (15) ethoxylated trimethylolpropane triacrylate, (3) glycerol oxypropylate triacrylate; high functionality monomer: dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, di-trimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, (4) ethoxylated pentaerythritol tetraacrylate, and the like, and may further include derivatives of the above acrylic acids.

The oligomer is an acrylate oligomer. Oligomers, also known as oligomers, oligomers or oligomers, are polymers composed of fewer repeating units, with a relative molecular mass between small and high molecular weight. Including but not limited to: aliphatic urethane acrylate, aromatic urethane acrylate, epoxy acrylate, epoxidized soybean oil acrylate, modified epoxy acrylate, epoxy methacrylate, aliphatic silicone acrylate, acid functional acrylate, silicone urethane acrylate, polybutadiene dimethacrylate, polybutadiene diacrylate, polyester acrylate, acrylate polyester, chlorinated polyester acrylate.

The oligomer is preferably any one of epoxy acrylate, polyester acrylate, polyurethane acrylate, polyether acrylate or a mixture of at least two thereof.

The photoinitiator is also called a light curing agent or a photosensitizer, and is used for absorbing light wave energy in a specific wavelength range (ultraviolet light or visible light region) to generate free radicals or cations so as to excite the monomer to be crosslinked, polymerized and cured. The photoinitiator is 2-hydroxy-2-methyl-1-phenyl acetone, 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate, methyl benzoylformate, 1-hydroxycyclohexyl phenyl methyl, diethoxy-phenyl acetophenone, diethoxy acetophenone, dimethoxy phenyl acetophenone, 2, 4-dihydroxy benzophenone, 2,4, 6-trimethyl benzoyl ethoxy phenyl phosphine oxide, 2-di-sec-butyl oxy acetophenone, alpha-hydroxy ketone, hydroxycyclohexyl phenyl ketone, hydroxymethyl phenyl acetone, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholinyl-1-acetone, 1- (4-isopropyl phenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1-one, 2-hydroxy-2-methyl propyl-1-one, methyl-1-hydroxy-phenyl ethyl benzoate, 2-hydroxy-phenyl acetophenone, diethoxy acetophenone, dimethoxy phenyl acetophenone, 2, 4-dihydroxy benzophenone, 2-methyl-1-phenyl ketone, 2-hydroxy-2-methyl-1-phenyl ketone, 2-methyl-phenyl ketone, 2-methyl-1-methyl propyl-1-ketone, 2-methyl-phenyl ketone, 2-methyl-1-methyl-phenyl ketone, 2-methyl-phenyl ketone, 2-ethyl benzoate, 2-methyl-ethyl benzoate, 2-phenyl ketone, 2-ethyl benzoate, 2-phenyl ketone, 2-methyl-phenyl ketone, 2-phenyl ketone, 2-methyl-phenyl ketone, 2-methyl-phenyl ketone, 2-methyl-phenyl ketone, 2-phenyl ketone, 2-ethyl benzoate, 2-methyl-phenyl ketone, 2-ethyl benzoate, 2-phenyl ketone, 2-phenyl ketone, 2-phenyl ketone, 2-phenyl-p-phenyl-2-p-phenyl-p-2-p, Any one or a mixture of at least two of 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide.

The adhesion promoter is a chemical component which can generate or improve the binding force between the base material and the coating, so that the coating has strong adhesion on the base material and can be applied to actual places. The adhesion promoter is any one or a mixture of at least two of CoatOSil 1770, CoatOSil 2287, CoatOSil DRI, CoatOSil MP 200, Silquest A-1170, Silquest A-171, Silquest A-187, Silquest A-1110, Silquest A-1100, Silquest A-186, Silquest A-1871, Silquest A-2120, Silquest A-Link 597, Silquest A-9627, Silquest Y-Y9669, BYK-4509, BYK-4510, BYK-4511, BYK-4512, BYK-C8000 and BYK-4513.

The rheological additive comprises one or a combination of several of the following wetting agents and flatting agents: 0.1-2 parts of wetting agent and 0.1-3 parts of flatting agent; for example, the wetting agent is 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.1 part, 1.2 part, 1.3 part, 1.4 part, 1.5 part, 1.6 part, 1.7 part, 1.8 part, 1.9 part or 2 parts by weight, and the leveling agent is 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, 1.1 part, 1.2 part, 1.3 part, 1.4 part, 1.5 part, 1.6 part, 1.7 part, 1.8 part, 1.9 part, 2 parts, 2.1, 2.2, 2.3 parts, 2.4 parts, 2.5 parts, 2.6 parts, 1.7 parts, 1.8 parts, 2.9 parts, 2.1.1.1.1, 2, 2.2.2, 2, 2.3, 2.6, 2, 2.6, 2.8 parts, 2.2, 2.6, 2, 2.2.6, 2, 2.2.2, 2, 2.6, 2, 2.8, 2.2, 2, 2.2.2, 2, 2.3, 2.6, 2, 2.2, 2, 2.6, 2, 2.3, 2, 2.8, 2, 2.6, or 3, 2.6, or 3 parts by weight. The rheological additive is added to improve the compatibility and stability of each component and improve the coating film forming property.

The wetting agent is used for reducing the interfacial tension between a solid and a liquid, so that a liquid substance can wet the surface of the solid more easily, thereby achieving the purpose of coating. Including but not limited to the designations: at least one of Anti-Terra-203, Anti-Terra-204, Anti-Terra-2005, Anti-Terra-210, Anti-Terra-250, BYK-151, BYK-1162, BYK-1165, BYK-Synergist 2100, BYKUMEN, Disperbyk-163, Dynol 360, Dynol 604, Dynol 607, Dynol 800, Dynol 810, Dynol 960, Dynol 980, Surfynol AD01, Surfynol 82, Surfynol 104, Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485, Surfynol 2502, TEGO WeGO 245, TEBYt 250, TEBYt 260, TEBYt 270, TEWet GO 280, TEGO 345, TEBYK 410K-4100, or mixture of any two of them.

The leveling agent is a substance which effectively reduces the surface tension of a coating film, obtains a uniform, flat and smooth coating in the coating film-forming process and improves the film-forming property of the coating film. Including but not limited to TEGO Glide 440, TEGO Glide 110, TEGO Flow 425, TEGO Glide 482, TEGO Glide 410, EASYTECHST-5050, BYK333, BYK341, BYK349, TERIC 320, BYK348, N-2218, BYK306, BYK307, FS-3100, and any one or a mixture of at least two of cellulose and its derivatives.

The solvent is any one or a mixture of at least two of isopropanol, water, ethanol, methanol, n-propanol, butanediol, acetone and butanone. Further preferably, the solvent is water or isopropanol.

The second purpose of the invention is to provide a colorful film prepared by the preparation method of the first purpose.

Compared with the prior art, the invention has the beneficial effects that:

(1) the preparation method of the colorful film uses a coating technology, can complete the periodic arrangement of the nanospheres on the substrate by one step by utilizing the fluid shear induction force generated by a coating means, and can generate the colorful effect, so the production equipment is simple and the process is simple; after coating, the curing is rapidly finished by means of ultraviolet light, and the production efficiency is high. The colorful film prepared by the preparation method has excellent practicability while ensuring the colorful effect and various mechanical property effects, and particularly has the pencil hardness of 2H-5H and the adhesion of 5B.

(2) The preparation method of the colorful film has great significance for promoting the development of colorful functional materials and expanding the nano coating technology, greatly reduces the application threshold of the nano materials and accelerates the application steps of the nano materials.

Drawings

FIG. 1 is a schematic flow chart of a slit coating process for producing a glare film of the present invention;

FIG. 2 is an enlarged schematic view of a portion of the coating of FIG. 1 in accordance with the present invention;

FIG. 3 is a schematic flow chart of a method for preparing a micro-gravure coating of a glare film according to the present invention;

wherein the reference numbers are as follows:

1-slot coating die; 2-a substrate; 3-nanospheres; 4-nanosphere coated face; 5, an unwinding device; 6-an ultraviolet lamp; 7-a winding device; 8-a coating composition; 9-a dimple coating die; 10-micro-concave coating blade;

wherein the arrows point in the coating direction.

Detailed Description

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached figures 1-3.

Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.

In the following examples and comparative examples, monomers and oligomers were purchased from Satomer and Allnex, wetting, leveling and adhesion promoters were purchased from Chemours, BYK, Evonik, Dow Corning, Momentive and 3M, photoinitiators were purchased from BASF, nanospheres were purchased from Bell, Citriness New materials, Nanjing. The substrate material was from Olympic materials science and technology, Suzhou, Slot-die Coating equipment from Nordson Corporation, gravure Coating from Mirwec Coating, UV curing equipment using the Heraeus F600S UV curing System, USA, and the focus distance of the light source to the substrate surface was 53 mm. Note that the wet thickness described in the following examples and comparative examples is the thickness of the coating composition directly after coating, and the dry thickness is the thickness of the coating composition after evaporation of the solvent, and the specific values are wet thickness × solid content.

The flow schematic diagrams of the slit coating preparation method of the colorful film are shown in fig. 1 and fig. 2, and the preparation method of the colorful film comprises the following steps:

step 1) coating the coating composition 8 on the base material 2 by utilizing a fluid shear induction force generated by a coating means of the slit coating die head 1 to form a microstructure in which nanospheres are periodically arranged, and drying the nanospheres 3 to form a nanosphere coating surface 4 in which the nanospheres are regularly and periodically arranged on the surface of the base material 2;

2) the unreeling device 5 conveys the base material 2 containing the nanosphere coating surface 4 obtained in the step 1) to an ultraviolet lamp 6 for ultraviolet curing, and the colorful film is obtained after being reeled by the reeling device 7. Wherein the arrows in fig. 1 point in the coating direction.

The schematic flow diagram of the slightly concave coating preparation method of the colorful film is shown in fig. 3, and the preparation method of the colorful film comprises the following steps:

step 1) coating the coating composition 8 on the base material 2 by utilizing a fluid shearing induction force generated by a coating means of a micro-concave coating die head 9 and a micro-concave coating scraper 10 to form a microstructure with nanospheres arranged periodically, and regularly and periodically arranging the nanospheres 3 on the surface of the base material 2 after drying to form a nanosphere coating surface 4;

2) and (2) conveying the base material 2 containing the nanosphere coating surface 4 obtained in the step 1) to an ultraviolet lamp 6 for ultraviolet curing, and rolling to obtain the colorful film.

Example 1

This example provides a method for preparing a glare film, wherein the coating composition comprises: tetrahydrofuran methacrylate (SR203) 25 parts, 1, 6-hexanediol dimethacrylate (SR239 NS) 50 parts, (3) ethoxylated trimethylolpropane triacrylate (SR454 NS) 25 parts, photoinitiator 2-hydroxy-2-methyl-1-phenyl acetone 2 parts, adhesion promoter Silquest A-1170 1 part, nanospheres (JNS-PC01-100, diameter 100 nm) 50 parts, leveling agent BYK333 1 part, total solid content of the coating composition 100 wt%, stirring and mixing uniformly.

Uniformly coating the prepared coating composition on a PC (polycarbonate) thin film (with the thickness of 50 microns) by using a slit coating die head (with the wet thickness of 25 microns and the opening gap of 250 microns), wherein the fluid shearing induction force is 0.1 Pa, the final dry thickness of the coating composition is 5 microns, and the periodic regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 100 mJ/cm)²) The curing process is completed.

Example 2

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: tetrahydrofuran acrylate (SR285) is 25 parts, ethylene glycol dimethacrylate (SR206) is 25 parts, trimethylolpropane triacrylate (SR351 NS) is 50 parts, aliphatic urethane acrylate (CN8000 NS) is 100 parts, photoinitiator 2, 4-dihydroxy benzophenone is 2 parts, adhesion promoter Silquest A-186 is 5 parts, nanospheres (JNS-PC05-200, diameter 200 nm) is 100 parts, flatting agent TEGO GLIDE 410 is 2 parts, isopropanol is added to enable the total solid content to be 80 wt%, and the components are stirred and mixed uniformly.

Uniformly coating the prepared coating composition on a PC (polycarbonate) thin film (with the thickness of 100 micrometers) by using a slit coating die head (with the wet thickness of 20 micrometers and the opening gap of 200 micrometers), wherein the fluid shearing induction force is 0.4 Pa, the final dry thickness of the coating composition is 10 micrometers, and the periodic regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 200 mJ/cm)²) The curing process is completed.

Example 3

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: the preparation method comprises the following steps of adding 25 parts of caprolactone acrylate (SR495B NS), 50 parts of 1, 3-butanediol dimethacrylate (SR297), 25 parts of dipentaerythritol pentaacrylate (SR399), 50 parts of urethane acrylate (CN8885 NS), 5 parts of photoinitiator 2, 4-dihydroxybenzophenone, 10 parts of adhesion promoter Silquest A-186, 200 parts of nanospheres (JNS-PC01-260, the diameter of 260 nm) and 4 parts of flatting agent TEGO 425, adding isopropanol to enable the total solid content to be 60 wt%, and uniformly stirring and mixing.

Uniformly coating the prepared coating composition on a PC (polycarbonate) thin film (400 micrometers in thickness) by using a slit coating die head (25 micrometers in wet thickness and 150 micrometers in opening gap), wherein the fluid shearing induction force is 0.6 Pa, the final dry thickness of the coating composition is 21 micrometers, and the periodic regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 400 mJ/cm)²) The curing process is completed.

Example 4

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: 25 parts of isobornyl acrylate (SR506 NS), 25 parts of ethoxylated bisphenol A dimethacrylate (SR150), 50 parts of dipentaerythritol hexaacrylate (DPHA NS), 100 parts of aromatic urethane acrylate (CN9165), 10 parts of photoinitiator Darocur 651, 15 parts of adhesion promoter BYK-4509, 200 parts of nanospheres (JNS-PC05-400 with the diameter of 400 nm) and 10 parts of flatting agent BYK348, adding isopropanol to enable the total solid content of the coating composition to be 40 wt%, and stirring and mixing uniformly.

Uniformly coating the prepared coating composition on a PET (polyethylene terephthalate) film (with the thickness of 50 microns) by using a slit coating die head (with the wet thickness of 25 microns and the opening gap of 100 microns), wherein the fluid shearing induction force is 0.8 Pa, the final dry thickness of the coating composition is 40 microns, and the periodic regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 500 mJ/cm)²) The curing process is completed.

Example 5

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: 50 parts of isooctyl acrylate (SR440), 25 parts of alkoxylated hexanediol diacrylate (CD564), 25 parts of pentaerythritol triacrylate (SR444), 100 parts of epoxy acrylate (CN2204 NS), 20 parts of photoinitiator dimethoxyphenylacetophenone, 20 parts of adhesion promoter BYK-4509, 400 parts of nanospheres (JNS-PC01-550, diameter 550 nm) and 20 parts of flatting agent BYK348, adding isopropanol to enable the total solid content of the coating composition to be 60 wt%, and stirring and mixing uniformly.

Uniformly coating the prepared coating composition on a PET (polyethylene terephthalate) film (the thickness is 100 mu m) by using a slit coating die head (the wet thickness is 25 mu m, the opening gap is 50 mu m), wherein the fluid shearing induction force is 0.6 Pa, the final dry thickness of the coating composition is 60 mu m, and the periodic regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 600 mJ/cm)²) The curing process is completed.

Example 6

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: the preparation method comprises the following steps of taking 100 parts of tricyclosilane dimethanol diacrylate (SR833 NS), 100 parts of epoxidized soybean oil acrylate (CN111), 6 parts of photoinitiator dimethoxyphenylacetophenone, 6 parts of adhesion promoter BYK-C8000, 200 parts of nanospheres (JNS-PC01-550, diameter 550 nm) and 6 parts of flatting agent BYK333, adding isopropanol to enable the total solid content of the coating composition to be 10 wt%, and uniformly stirring and mixing.

Uniformly coating the prepared coating composition on a PET (polyethylene terephthalate) film (the thickness is 250 micrometers) by using a slit coating die head (the wet thickness is 25 micrometers, and the opening gap is 25 micrometers), wherein the fluid shearing induction force is 0.6 Pa, the final dry thickness of the coating composition is 5 micrometers, and the periodic regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 800 mJ/cm)²) The curing process is completed.

Example 7

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: 100 parts of di-trimethylolpropane tetraacrylate (SR355 NS), 100 parts of modified epoxy acrylate (CN118), 6 parts of photoinitiator 2, 2-di-sec-butoxyacetophenone, 12 parts of adhesion promoter Silquest A-1170, 400 parts of nanospheres (JNS-PC02-1, diameter 1000 nm) and 6 parts of flatting agent BYK307, isopropanol is added to enable the total solid content of the coating composition to be 5 wt%, and the coating composition is stirred and mixed uniformly.

Uniformly coating the prepared coating composition on a PMMA plate (with the thickness of 500 microns) by using a slit coating die head (with the wet thickness of 25 microns and the opening gap of 10 microns), wherein the fluid shearing induction force is 0.6 Pa, the final dry thickness of the coating composition is 5 microns, and the periodic regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 1000 mJ/cm)²) The curing process is completed.

Example 8

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: the coating composition is prepared by uniformly stirring and mixing 100 parts of methyl stearate (SR324 NS), 3 parts of ethylene glycol dimethacrylate (SR206), 3 parts of pentaerythritol triacrylate (SR444 NS), 3 parts of polyester acrylate (CN2282), 3 parts of photoinitiator 2, 2-di-sec-butoxyacetophenone, 3 parts of adhesion promoter Silquest A-1170, 50 parts of nanospheres (JNS-PC02-1.2, the diameter of 1200 nm), 1 part of a leveling agent BYK307, and 100 wt% of the total solid content of the coating composition.

Uniformly coating the prepared coating composition on a PMMA (polymethyl methacrylate) film (the thickness is 800 mu m) by using a slit coating die head (the wet thickness is 25 mu m, the opening gap is 5 mu m), wherein the fluid shearing induction force is 0.6 Pa, the final dry thickness of the coating composition is 10 mu m, and the periodic regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 1200 mJ/cm)²) The curing process is completed.

Example 9

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: tetrahydrofuran methacrylate (SR285) is 100 parts, organosilicon polyurethane acrylate (CN990) is 100 parts,

photoinitiator

2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate is 8 parts, adhesion promoter Silquest A-1170 is 6 parts, nanospheres (JNS-PC02-1.5, diameter 1500 nm) is 50 parts, leveling agent BYK349 is 2 parts, isopropanol is added to enable the total solid content of the coating composition to be 50 wt%, and the coating composition is stirred and mixed uniformly.

Uniformly coating the prepared coating composition on a PMMA (polymethyl methacrylate) film (JNS-PC02-1.5, the thickness is 1500 mu m) by using a slit coating die head (the wet thickness is 25 mu m, the opening gap is 250 mu m), the fluid shearing induction force is 0.6 Pa, the final dry thickness of the coating composition is 10 mu m, and the periodic and regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 1500 mJ/cm)²) The curing process is completed.

Example 10

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: the preparation method comprises the following steps of taking 20 parts of 2 (2-ethoxy) ethyl acrylate (SR256), 20 parts of neopentyl glycol diacrylate (SR247), (9) 60 parts of ethoxylated trimethylolpropane triacrylate (SR502 NS), 3 parts of

photoinitiator

2,4, 6-trimethylbenzoylphenyl ethyl phosphonate, 3 parts of adhesion promoter Silquest A-1170, 50 parts of nanospheres (JNS-PC02-2.0, the diameter of 2000 nm) and 10 parts of leveling agent BYK349, adding isopropanol to enable the total solid content of the coating composition to be 40 wt%, and uniformly stirring and mixing.

Uniformly coating the prepared coating composition on glass (the thickness is 500 micrometers) by using a slit coating die head (the wet thickness is 25 micrometers, the opening gap is 250 micrometers), wherein the fluid shearing induction force is 0.6 Pa, the final dry thickness of the coating composition is 16 micrometers, and the periodic regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 300 mJ/cm)²) The curing process is completed.

Example 11

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: 100 parts of aliphatic organic silicon acrylate (CN9800), 3 parts of 2, 4-dihydroxy benzophenone serving as a photoinitiator, 3 parts of an adhesion promoter Silquest A-1170, 100 parts of nanospheres (JNS-PC01-550 with the diameter of 550 nm), 2 parts of a wetting agent TEGO Wet 260 and a flatting agent TEGO GLIDE 425 are added, isopropanol is added to enable the total solid content of the coating composition to be 20 wt%, and the components are stirred and mixed uniformly.

Uniformly coating the prepared coating composition on glass (the thickness is 800 micrometers) by using a slit coating die head (the wet thickness is 50 micrometers, the opening gap is 15 micrometers), wherein the fluid shearing induction force is 0.6 Pa, the final dry thickness of the coating composition is 10 micrometers, and the periodic regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 600 mJ/cm)²) The curing process is completed.

Example 12

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: 10 parts of methoxy polyethylene glycol monomethacrylate (SR550), 45 parts of 1, 6-hexanediol diacrylate (SR238 NS), (20) 45 parts of ethoxylated trimethylolpropane triacrylate (SR415), 10 parts of aliphatic urethane acrylate (CN310 NS), 4 parts of photoinitiator 2, 4-dihydroxybenzophenone, 4 parts of adhesion promoter Silquest A-1170, 200 parts of nanospheres (JNS-PC01-550, the diameter of 550 nm), a wetting agent GO TEWet 270, 2 parts of a leveling agent TEGO GLIDE 482, adding isopropanol to enable the total solid content of the coating composition to be 10 wt%, and uniformly stirring and mixing.

Uniformly coating the prepared coating composition on glass (the thickness is 1000 microns) by using a slit coating die head (the wet thickness is 200 microns, the opening gap is 15 microns), wherein the fluid shearing induction force is 0.6 Pa, the final dry thickness of the coating composition is 20 microns, and the periodic regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 600 mJ/cm)²) The curing process is completed.

Example 13

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: octadecyl acrylate (SR257) is 45 parts, ethylene glycol dimethacrylate (SR206) is 45 parts, trimethylolpropane triacrylate (SR351) is 10 parts, urethane acrylate (CN972) is 20 parts, photoinitiator 2, 4-dihydroxy benzophenone is 4 parts, adhesion promoter Silquest A-1170 is 4 parts, nanospheres (JNS-PC01-550, diameter 550 nm) is 300 parts, wetting agent TEGO Wet 500, leveling agent TEGO 425 is 8 parts, isopropanol is added to enable the total solid content of the coating composition to be 5 wt%, and the coating composition is stirred and mixed uniformly.

Uniformly coating the prepared coating composition on a PMMA surface of a PC/PMMA composite board (the thickness is 800 mu m) by using a slit coating die head (the wet thickness is 200 mu m, the opening gap is 15 mu m), the fluid shearing induction force is 0.6 Pa, the final dry thickness of the coating composition is 10 mu m, and the periodic nanostructure is completedArranging in a regular way; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 600 mJ/cm)²) The curing process is completed.

Example 14

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: the coating composition is prepared by adding isopropanol into 100 parts of alkoxylated phenol acrylate (SR9087), 100 parts of aromatic urethane acrylate (CN9783), 6 parts of photoinitiator hydroxy methyl phenyl acetone, 6 parts of adhesion promoter Silquest A-1170, 100 parts of nanospheres (JNS-PC01-550, diameter 550 nm), 6 parts of wetting agent TEGO Wet 510 and 6 parts of flatting agent TEGO GLIDE 425, and stirring and mixing uniformly, wherein the total solid content of the coating composition is 30 wt%.

Uniformly coating the prepared coating composition on a PMMA (polymethyl methacrylate) surface of a PC/PMMA composite board (the thickness is 1500 mu m) by using a slit coating die head (the wet thickness is 60 mu m, the opening gap is 20 mu m), wherein the fluid shearing induction force is 0.6 Pa, the final dry thickness of the coating composition is 18 mu m, and the periodic and regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 1000 mJ/cm)²) The curing process is completed.

Example 15

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: 100 parts of aliphatic polyurethane acrylate (CN9100 NS), 3 parts of photoinitiator hydroxy methyl phenyl acetone, 3 parts of adhesion promoter Silquest A-1170, 50 parts of nanospheres (JNS-PC01-550, the diameter of 550 nm), a wetting agent TEGO Wet KL245 and a flatting agent TEGO GLIDE 440, adding isopropanol to enable the total solid content of the coating composition to be 30 wt%, and uniformly stirring and mixing.

Uniformly coating the prepared coating composition on a PC thin film (the thickness is 100 mu m) by using a slit coating die head (the wet thickness is 100 mu m, the opening gap is 50 mu m), wherein the fluid shearing induction force is 0.6 Pa, the final dry thickness of the coating composition is 30 mu m, and the periodic nano structure is completedArranging regularly; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 800 mJ/cm)²) The curing process is completed.

Example 16

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: the preparation method comprises the following steps of preparing 30 parts of alkoxylated nonylphenol acrylate (SR614A), 30 parts of dipropylene glycol diacrylate (SR508 NS), 30 parts of trimethylolpropane trimethacrylate (SR350 NS), (4) 10 parts of ethoxylated pentaerythritol tetraacrylate (SR494 NS), 20 parts of aromatic urethane acrylate (CN9167), 4 parts of photoinitiator hydroxymethylphenyl acetone, 4 parts of adhesion promoter Silquest A-1170, 20 weight percent of nanospheres (JNS-PC01-550, diameter of 550 nm), 20 weight percent of wetting agent TEGO IDE Wet 260 and 0.2 weight percent of flatting agent TEGO GL440, adding isopropanol to enable the total solid content of the coating composition to be 30 weight percent, and uniformly stirring and mixing.

Uniformly coating the prepared coating composition on a PEN thin film (the thickness is 100 mu m) by using a slit coating die head (the wet thickness is 50 mu m, the opening gap is 100 mu m), wherein the fluid shearing induction force is 0.6 Pa, the final dry thickness of the coating composition is 15 mu m, and the periodic regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 600 mJ/cm)²) The curing process is completed.

Example 17

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: 10 parts of alkoxylated tetrahydrofuran acrylate (SR611), 30 parts of 1, 3-butanediol dimethacrylate (SR297), (3) 30 parts of ethoxylated trimethylolpropane triacrylate (SR454 NS), 100 parts of polyester acrylate (CN2254 NS), 6 parts of photoinitiator hydroxy methyl phenyl acetone, 6 parts of adhesion promoter Silquest A-1170, 100 parts of nanospheres (JNS-PC01-550 with the diameter of 550 nm), 260 parts of wetting agent TEGO Wet 260 and 20 parts of leveling agent TEGO IDE 440, adding isopropanol to ensure that the total solid content of the coating composition is 30 wt%, and uniformly stirring and mixing.

Uniformly coating the prepared coating composition on a PC (polycarbonate) thin film (with the thickness of 100 micrometers) by using a slit coating die head (with the wet thickness of 50 micrometers and the opening gap of 200 micrometers), wherein the fluid shearing induction force is 0.6 Pa, the final dry thickness of the coating composition is 15 micrometers, and the periodic regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 600 mJ/cm)²) The curing process is completed.

Example 18

This example provides a method for preparing a glare film, wherein the coating composition was prepared as follows: 100 parts of trimethylolpropane triacrylate (SR351 NS), 100 parts of urethane acrylate (CN978 NS), 6 parts of photoinitiator hydroxy methyl phenyl acetone, 200 parts of nanospheres (JNS-PC01-550, the diameter of 550 nm), 12 parts of adhesion promoter Silquest A-1170, 12 parts of wetting agent TEGO Wet 280 and leveling agent TEGO GLIDE 440, adding isopropanol to ensure that the total solid content of the coating composition is 30 wt%, and uniformly stirring and mixing.

Uniformly coating the prepared coating composition on a PC thin film (the thickness is 100 mu m) by using a slit coating die head (the wet thickness is 50 mu m, the opening gap is 20 mu m) to obtain a wire rod, wherein the fluid shearing induction force is 0.6 Pa, the final dry thickness of the coating composition is 15 mu m, and the periodic and regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 300 mJ/cm)²) The curing process is completed.

Example 19

Uniformly coating the prepared coating composition on a PC thin film (the thickness is 100 mu m) by using a micro-concave coating die head (the reticulate pattern of a coating roller is 180 lines/inch, the wet thickness is 5 mu m), wherein the fluid shearing induction force is 0.8 Pa, the final dry thickness of the coating composition is 10 mu m, and the periodic and regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 200 mJ/cm)²) The curing process is completed.

Example 20

Uniformly coating the prepared coating composition on a PC thin film (the thickness is 100 mu m) by using a micro-concave coating die head (the reticulate pattern of a coating roller is 90 lines/inch, the wet thickness is 10 mu m), wherein the fluid shearing induction force is 0.4 Pa, the final dry thickness of the coating composition is 10 mu m, and the periodic and regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 200 mJ/cm)²) The curing process is completed.

Example 21

Uniformly coating the prepared coating composition on a PMMA (polymethyl methacrylate) thin film (the thickness is 800 mu m) by using a micro-concave coating die head (the reticulate pattern of a coating roller is 25 lines/inch, the wet thickness is 80 mu m), the fluid shearing induction force is 0.8 Pa, the final dry thickness of the coating composition is 10 mu m, and the periodic regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 1200 mJ/cm)²) The curing process is completed.

Example 22

Uniformly coating the prepared coating composition on a PEN film (the thickness is 100 mu m) by using a micro-concave coating die head (the reticulate pattern of a coating roller is 90 lines/inch, and the wet thickness is 10 mu m), wherein the fluid shearing induction force is 0.6 Pa, the final dry thickness of the cloth composition is 15 mu m, and the periodic and regular arrangement of the nano structures is completed; drying for 2 minutes at 100 ℃ to complete solvent volatilization and adhesive force formation; finally in an ultraviolet curing system (energy density 600 mJ/cm)²) The curing process is completed.

Comparative example 1

The process for preparing the glare film of this comparative example differs from example 1 in that no adhesion promoter is added to the coating composition.

Comparative example 2

The process for the preparation of the glare film of this comparative example differs from example 1 in that no monomers and oligomers are added to the coating composition.

Comparative example 3

The process for preparing the glare film of this comparative example differs from example 1 in that no monomers, oligomers, and photoinitiators are added to the coating composition.

Comparative example 4

The method for preparing the glare film of this comparative example is different from example 1 in that nanospheres are not added to the coating composition.

Comparative example 5

The process for preparing the glare film of this comparative example differs from example 1 in that no uv curing is performed.

Comparative example 6

The preparation method of the colorful film of the comparative example is different from that of the example 1 in that the nanospheres are replaced by the nano cadmium oxide with the diameter of 100 nm.

Comparative example 7

The preparation method of the dazzling color film of the comparative example is different from that of example 1 in that the particle size of the nanospheres is 10 nm.

Comparative example 8

The preparation method of the dazzling color film of the comparative example is different from that of example 1 in that the particle size of the nanospheres is 3000 nm.

Comparative example 9

The method for preparing the dazzling color film of the comparative example is different from that of example 1 in that the adhesion promoter is replaced by ADP (which is a special polyester compound purchased from Jessica chemical Co., Ltd., Hangzhou).

Comparative example 10

The process for producing the glare film of this comparative example differs from example 1 in that the intensity of the UV-curing radiation is80 mJ/cm²。

Comparative example 11

The method for preparing a glare film of this comparative example is different from example 1 in that the radiation intensity of the UV-curing is 2000 mJ/cm²。

Comparative example 12

The method for preparing a glare film of this comparative example is different from example 1 in that the opening gap using slit coating is 300.

Comparative example 13

The method for preparing the colorful film in the comparative example is different from that in example 1 in that a silk rod coating process (wet thickness of 35 mu m and thread pitch of 10 mu m) is adopted.

Comparative example 14

The method for preparing a glare film of this comparative example is different from example 1 in that the dimpled coating had a texture (number of lines/inch) of 300 corresponding to a coating thickness of 0.5

。

Comparative example 15

The comparative example, a process for the preparation of a iridescent film, differs from example 1 in that the fluid shear inducing force is 0.01 Pa, the rest being the same as in example 1.

Comparative example 16

The preparation method of the comparative example dazzling film is different from that of example 1 in that the fluid shear induction force is 1Pa, and the rest is the same as that of example 1.

The glare films obtained in examples 1 to 22 and comparative examples 1 to 16 were subjected to the performance test, and the test results are shown in table 1. Wherein the pencil hardness is measured using the ASTM D3363 method for the glare film coating, the adhesion is measured using the ASTM D3359 method, the UV-vis reflection spectrum is recorded on a Lamda 900 spectrometer (Perkin Elmer), and the following method is used for the optical properties, i.e. the glare effect: taking a film to be measured (3 cm x 3 cm), wherein the placing angles of the film and incident light are respectively 30 degrees, 40 degrees and 50 degrees, and measuring the peak position in a reflection mode.

As can be seen from Table 1, the colorful film disclosed by the invention has excellent film forming property, moderate viscosity, excellent mechanical property and superior adhesive force, and can be rapidly crosslinked and cured under ultraviolet light.

In comparative example 1, the coating composition without the additive adhesion promoter reduced or lost the adhesion between the coating and the polymeric substrate.

In comparative example 2, the absence of monomers and oligomers in the coating composition resulted in no adhesion and hardness between the coating and the polymeric substrate.

In comparative example 3, the absence of monomers, oligomers and initiators in the coating composition resulted in no curing reaction of the coating and no adhesion and hardness between the coating and the polymeric substrate.

In comparative example 4, the absence of nanospheres in the coating composition resulted in a coating with no glare.

In comparative example 5, the coating composition was not uv-cured, resulting in no curing crosslinking reaction of the coating and no mechanical properties of the coating.

In comparative example 6, inorganic nanospheres were added to the coating composition, which resulted in a non-glare effect of the coating.

In comparative example 7, the diameter of the nanospheres added to the coating composition was 10 nm, which resulted in the generation of a non-glare effect of the coating.

In comparative example 8, the diameter of the added nanospheres in the coating composition was 3000 nm, resulting in a non-glare effect of the coating.

In comparative example 9, the adhesion promoter in the coating composition was ADP (suitable for metal substrate surfaces), which resulted in no adhesion of the coating to the substrate.

In comparative example 10, the coating composition was set to have a low UV radiation energy intensity of 80 mJ/cm during UV curing²Incomplete curing and poor mechanical properties can be caused.

In comparative example 11, the coating composition was set to a high UV radiation energy intensity of 2000 mJ/cm during UV curing²This causes the polymer matrix to be directly broken down.

In comparative example 12, the coating composition was applied with an open gap of 300

This can result in a coating film having no glare effect.

In comparative example 13, in the coating process of the coating composition, a wire rod coating process (wet thickness of 35 μm, thread pitch of 10 μm) is adopted, so that the coating effect is not uniform, and the dazzle color effect is not uniform.

In comparative example 14, the coating composition was applied in a dimple-applied texture of 300 lines/inch corresponding to a coating thickness of 0.5 during the application process

This can result in a coating film having no glare effect.

The fluid shear induction force in comparative example 15 is too small, and the fluid shear induction force in comparative example 16 is too large, so that the nanospheres cannot form a periodic structure, and the coating film has no dazzling effect.

The present invention is illustrated by the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, i.e. it is not meant to imply that the present invention must rely on the above-mentioned detailed process equipment and process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. The preparation method of the colorful film is characterized by comprising the following steps:

step 1): coating the coating composition on a base material by utilizing a fluid shear induction force generated by a coating means to form a microstructure in which nanospheres are periodically arranged, and drying the nanospheres to form a nanosphere coating surface by regularly and periodically arranging the nanospheres on the surface of the base material;

the coating means is micro-concave coating or slit coating; the opening gap of the slit coating is 5-250 microns; the reticulate pattern of the coating roller in the micro-concave coating is 25-180 lines/inch, and the corresponding coating thickness is 5-80 microns;

the nanospheres are any one or a mixture of at least two of polystyrene, polyacrylate and silicon dioxide, and the particle size of the nanospheres is 100-1500 nm;

the fluid shear induction force is 0.1-0.8 Pa;

1-100 parts of monomer

0 to 100 portions of oligomer

50-400 parts of nanosphere

2-40 parts of photoinitiator

1-20 parts of adhesion promoter

1-40 parts of rheological additive

the adhesion promoter is any one or a mixture of at least two of CoatOSil 1770, CoatOSil 2287, CoatOSil DRI, CoatOSil MP 200, Silquest A-1170, Silquest A-171, Silquest A-187, Silquest A-1110, Silquest A-1100, Silquest A-186, Silquest A-1871, Silquest A-2120, Silquest A-Link 597, BYK-4509, BYK-4510, BYK-4511, BK-4512, BK-C8000 and BYK-4513;

step 2): carrying out ultraviolet curing on the base material containing the nanosphere coating layer surface obtained in the step 1), wherein the radiation intensity of the ultraviolet curing is 100-1500 mJ/cm²And obtaining the colorful film.

2. The production method according to claim 1, wherein in step 1), the substrate is any one of a polycarbonate film, a polymethyl methacrylate film, a polyethylene terephthalate film, a polyimide film, a polyethylene naphthalate film, or a composite film of at least two of them, or glass.

3. The production method according to claim 1, wherein the monomer is any one or a mixture of at least two of an acrylic monomer, a styrene monomer, a maleic anhydride monomer and a furan monomer;

the oligomer is an acrylate oligomer;

the solvent is any one or a mixture of at least two of isopropanol, water, ethanol, methanol, n-propanol, butanediol, acetone and butanone.

4. The method according to claim 1, wherein the photoinitiator is 2-hydroxy-2-methyl-1-phenylpropanone, ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, methyl benzoylformate, 1-hydroxycyclohexylphenylketone, diethoxy-phenylacetophenone, diethoxyacetophenone, dimethoxyphenylacetophenone, 2, 4-dihydroxybenzophenone, 2,4, 6-trimethylbenzoylethoxyphenylphosphine oxide, 2-di-sec-butoxyacetophenone, α -hydroxyketone, hydroxycyclohexylphenylketone, hydroxymethylphenylacetone, 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholino-1-propanone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropanone Any one or a mixture of at least two of-1-ketone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, bis (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylpentylphosphine oxide.

5. The method of claim 1, wherein the rheological aid comprises, in parts by weight: 0.1-2 parts of wetting agent and 0.1-3 parts of flatting agent;

the wetting agent is at least one of a mixture of any two of Anti-Terra-203, Anti-Terra-204, Anti-Terra-210, Anti-Terra-250, BYK-151, BYK-1162, BYK-1165, BYK-Synergist 2100, BYKUMEN, Disperbyk-163, Dynol 360, Dynol 604, Dynol 607, Dynol 800, Dynol 810, Dynol 960, Dynol 980, Surfynol AD01, Surfynol 82, Surfynol 104, Surfynol 420, Surfynol 440, Surfynol 465, Surfynol 485, Surfynol 2502, TEGO Wet 245, TEGO Wet 250, TEGO Wet 260, TEGO 270, TEBYnt 280, TEBYnt 500, TEGO Wego 510, TEGO 410K 4000, TEGO K410K 342, BYK-K342, BYNOL K-200, Dynol-K-80, Dynol-B-C1, BYb-B-;

the leveling agent is any one or a mixture of at least two of TEGO Glide 440, TEGO Glide 110, TEGO Flow 425, TEGO Glide 482, TEGO Glide 410, BYK333, BYK341, BYK349, TERIC 320, BYK348, BYK306, BYK307, FS-3100 and cellulose and derivatives thereof.

6. A glare film, characterized by being produced by the production method according to any one of claims 1 to 5.