CN106032444A - Anti-reflection adhesive film and its manufacturing method - Google Patents

Abstract

The anti-reflection glue film is prepared by mixing a monomer material of transparent resin with a colloidal solution of high-dispersity nanospheres, evaporating a solvent of the colloidal solution, and curing the resin through a curing effect to form the anti-reflection glue film with a plurality of non-periodically arranged nanospheres.

Description

Anti-reflection adhesive film and its manufacturing method

【Technical field】

The invention relates to an adhesive film with selective anti-reflection effect on the light band, in particular to an adhesive film formed by mixing nano-scale particles with a resin composition.

【Background technique】

Ordinary resin film, depending on the resin material used and additive components, will have different characteristics, such as: transparent, light-shielding, scratch-resistant, wear-resistant, elastic and conductive. Existing high-tech resin films can have more than two properties at the same time, such as light-shielding, wear-resistant and conductive, but there is no resin film that has two completely different optical properties of transparency and light-shielding . Because transparency requires high light transmittance, and shading requires high light reflectivity, it is not easy to have the effect of high transparent band and high reflective band in one film.

However, industrial applications with this requirement can be seen everywhere, such as glasses, glass patch, lamp coating and white LED packaging industry, etc. For those who need a certain transparent band and reflect a specific band of light at the same time, all of them pursue high transparency. Highly reflective films are also targeted, such as anti-ultraviolet or anti-blue lenses. However, as far as the existing technology is concerned, optical components or transparent substrates are coated with multi-layer dielectric films or metal films, and then various transmission characteristics of light waves are changed layer by layer, including transmission, reflection, absorption, scattering, Polarization and phase change, etc. This kind of multilayer film, which is specially designed to adjust the required characteristics, is the most common user of the so-called anti-reflection film today.

【Content of invention】

The anti-reflective adhesive film of the present invention is a dual-character adhesive film composed of a transparent resin and a plurality of nanospheres arranged aperiodically. By changing the thickness of the adhesive film and the particle size of multiple nanospheres, the wavelength range of the reflected light can be further changed, so that the single film formed by the highly transparent resin composition has a thickness between 0.001mm and 1.0mm, It can have the characteristics of high penetration band and reflection of specific wavelength at the same time.

The preparation method of the anti-reflection adhesive film of the present invention is to mix a plurality of highly dispersed colloidal solutions of nanospheres with a transparent resin monomer material, and after the solvent in the colloidal solution is evaporated, a non-periodic arrangement is formed by curing. Anti-reflective coating of multiple nanospheres.

The anti-reflection adhesive film made by the technology of the present invention can be controlled by controlling the particle size of a plurality of nanospheres within the range of 10nm to 1000nm, and the thickness of the adhesive film is between 0.001mm and 1.0mm, so that the anti-reflection adhesive The film is highly reflective of specific wavelengths. For example, if the non-periodic structure formed by nanoparticles with a specific particle size is able to highly reflect ultraviolet light, the ultraviolet light transmittance can be close to zero, and the anti-reflective adhesive film has high penetration in the visible light range. High efficiency can make the finished product not only have a transparent appearance but also filter out harmful light bands.

Therefore, the present invention can be applied to any film product that needs to reflect a specific wavelength and requires high transparency. It has the advantages of replacing traditional multilayer films and reducing film production costs, and is beneficial to promote the industrial development of the optical film industry.

【Description of drawings】

Fig. 1 is the structural diagram of the adhesive film of the present invention.

Fig. 2 is a structure diagram of the nanosphere of the present invention.

Fig. 3 is a spectrum diagram of the transmittance of adhesive films of different thicknesses according to the present invention.

Fig. 4 is a spectrogram of film transmittance of different particle sizes of the present invention.

Fig. 5 is a schematic diagram of an embodiment of the present invention.

Fig. 6 is a comparison chart of the relative luminous intensity test of the anti-reflection adhesive film of the present invention.

【detailed description】

The anti-reflection adhesive film of the present invention is manufactured by mixing a plurality of highly dispersed nanosphere colloidal solutions with a transparent resin monomer material, and after the solvent of the colloidal solution evaporates, the resin is cured by curing to form Anti-reflective adhesive film with aperiodic arrangement of multiple nanospheres.

In the aforementioned manufacturing method, different material formulations and curing procedures can be used depending on the characteristics of the selected transparent resin, but in the present invention, photo-curable resin, thermal-curable resin or a combination thereof can be selected.

The so-called photocurable resin means that the resin monomer and the photoinitiator are irradiated with ultraviolet light (the wavelength range of 200nm to 400nm is selected), and the photoinitiator first absorbs the energy of ultraviolet radiation to generate free radical electrons. The active center is generated in a very short time, so that the active center can interact with the unsaturated group of the resin monomer, triggering the resin monomer and the diluent molecule (depending on the required film properties, such as the required viscosity, different reactions will be required. The double bond between the additive amount) is broken, and the free radical continuous polymerization reaction is caused continuously, and the cross-linked film is formed.

In the present invention, optional photocurable resin materials include acrylate monomers, acrylate oligomer monomers, or combinations thereof. In this embodiment, acrylate monomers are used, because acrylates have excellent weather resistance, transparency, color retention and mechanical strength, and acrylate monomers can be selected from tripropylene glycol diacrylate (Tripropylene glycol diacrylate, TPGDA ), neopentyl glycol diacrylate (Neopropylene glycol diacrylate, NPGDA), propoxylated neopentyl glycol diacrylate (Propoxylated neopropylene glycol diacrylate, PO-NPGDA), trimethylolpropane triacrylate (Trimethyloipropane triacrylate , TMPTA), ethoxylated trimethylolpropane triacrylate (Ethoxylated trimethyloipropane triacrylate, EO-TMPTA), propoxylated trimethylolpropane triacrylate (Propoxylatedtrimethyloipropane triacrylate, PO-TMPTA), propoxy Propoxylated glyceryl triacrylate (GPTA), di-(trimethylolpropane) tetraacrylate (Di-trimethyloipropane tetraacrylate, di-TMPTA), ethoxylated pentaerythritol tetraacrylate (Ethoxylated pentaerythritol tetraacrylate, EO -PETA), dipentaerythritol hexaacrylate (Dipentaerythritol hexaacrylate, DPHA) or a combination thereof.

However, acrylate oligomer monomers can also be used as photocurable resin materials, such as: epoxy acrylate (Epoxy acrylate, EA), polyurethane acrylate (Urethane acrylate, PUA), polyester acrylate (Polyester acrylate, PEA ), unsaturated polyester acrylate (Unsaturated polyester acrylate, UPE), amino acrylate (Amine acrylate), polysiloxane acrylate (Silicon acrylate) or a combination thereof.

In addition, if a thermosetting resin is used as the transparent resin material, a thermosetting silicone resin can be selected, which is cured by heating in an oven or adding a hardener. However, the thermosetting resin material selected in this embodiment includes methyl silicon, phenyl silicon or a combination thereof.

In the anti-reflection adhesive film of the present invention, a plurality of nanospheres are made of silicon dioxide (Silica, SiO ₂ ), polystyrene (Polystyrene, PS), polydimethylsiloxane (Polydimethylsiloxane) or a combination thereof. The formed nanosphere particles with a particle size of 10nm to 1000nm are made of silicon dioxide in this embodiment.

Also in this embodiment, before the resin monomer is cured to form a film, the added and mixed silica nanosphere particles can be prepared in several ways, for example (1) precipitation method: using water glass (Na ₂ O·nSiO ₂ ) and inorganic acid (such as sulfuric acid) react in a neutral environment; or (2) sol-gel method: the sol-gel method uses silane oxides, alcohols (such as: methanol or ethanol) as solvents, ammonia water As a catalyst, it is prepared by ultrasonic vibration. Of course, it can also be produced by other wet chemical methods, such as hydrothermal method, spray cracking method, electrochemical process, etc., which can be selected according to the scope of application. The nanospheres in this embodiment are produced by sol-gel method.

As for the mixing method of resin and nanosphere colloid, disperser, homogenizer, ultrasonic disperser, bead mill, ball mill or kneading machine can be used to make it evenly mixed.

Regarding the curing effect, if a photocurable resin is selected, a photoinitiator that promotes the curing of the resin is added, and the photoinitiator can be selected from a propiophenone series photoinitiator, a hydroxyketone series photoinitiator, or a benzophenone A series of photoinitiators. Acetophenone (Acetophenone) series of photoinitiators, such as diethoxyacetophenone (2,2-diethoxyacetophenone, DEAP); Hydroxyketone (α-Hydroxy ketone) series of photoinitiators, such as hydroxymethylbenzene 2-Hydroxy-2-methylphenylpropanone (HMPP), hydroxycyclohexyl phenyl ketone (1-Hydroxy-cyclohexyl-phenyl-ketone, HCPK) or combinations thereof; benzophenone (Benzophenone) series photoinitiators, For example, it is trimethylbenzophenone (2,4,6-Trimethylbenzophenone, TMBP), methylbenzophenone (4-Methylbenzophenone, MBP) or a combination thereof. In this embodiment, hydroxyketone series are used as photoinitiators.

The resin and nanosphere colloid after adding the photoinitiator, and then removing the solvent (such as methanol, ethanol, acetone or toluene used to make nanospheres), can be cast, scraped, rolled, and sprayed. , Gravure coating method or curtain coating method, etc., coated on the surface of an appropriate substrate, or molded by mold embossing and other compression molding methods to suppress a specific shape or structure.

Then use UV LED lamps, high-pressure mercury lamps, electrodeless lamps or xenon lamps to irradiate for 2 seconds to 20 minutes, where the illuminance is 5mW/cm ² to 200mW/cm ² , and the amount of ultraviolet light is between 4mJ/cm ² to 2,000mJ In the range of /cm ² , an anti-reflection film can be obtained accordingly.

If the thermal curing resin is selected, no additional photoinitiator is added, and no light curing is required. Instead, heat the coated or molded adhesive in an oven at 100°C to 160°C for 1 to 300 minutes to form an anti-reflective adhesive film (if necessary, a secondary curing procedure can also be added, for example: 150°C oven heating 4 hours); or add a hardener to cure at room temperature.

Please refer to Figure 1 and Figure 2 for the structure of the anti-reflection adhesive film of the present invention. Sexual arrangement, that is, a disordered structure, which is similar to quasi-amorphous array structures (quasiamorphous arrays). Fig. 2 is a nanosphere structure diagram of the present invention, further showing that the particle size of the nanosphere 2 is not uniform, as shown in the nanosphere A and the nanosphere B in the figure, generally speaking, there is a difference range of about 10nm to 20nm, so A disordered structure with non-periodic arrangement can be formed.

Further, the anti-reflection film was subjected to a light transmittance spectrum test. At first, please refer to Fig. 3, and Fig. 3 is the adhesive film transmittance spectrogram of different thicknesses of the present invention, selects and is the silica gel nanosphere of 100nm particle diameter for use in the test, the formed film of different thickness, wherein film 1 ( The thickness is between 0.3mm and 0.5mm) is thicker than the film 2 (the thickness is between 0.1mm and 0.2mm), and the films with different thicknesses have different transmittances for different wavelengths in the visible light range.

Next, carry out light transmittance test with the film that thickness is identical but nanosphere particle diameter is different, as shown in Figure 4, Fig. 4 is the adhesive film transmittance spectrogram of different particle diameters of the present invention, in same film thickness (thickness Between 0.1mm and 0.2mm), when the particle size is 100nm (particle size 1), 150nm (particle size 2), 160nm (particle size 3) and 180nm (particle size 4), films with different particle sizes It can be used to scatter light of different wavelengths, so that the light transmittance in the same wavelength range is different.

Therefore, according to the theory of constructive interference and Rayleigh scattering (Rayleigh scattering), that is, the linear superposition of light waves, and the theoretical basis of particle selective scattering wavelength, it is possible to adjust different film thicknesses and different nanospheres The combination of particle size enables the film to reflect the desired specific wavelength while having high transmittance. As shown in Figure 4, the anti-reflection adhesive film of the present invention can make the light transmittance below 400nm close to zero, and the wavelength range of visible light still has a high transmittance, which is very suitable for applications that require both anti-ultraviolet and high Product of transparency.

Furthermore, the anti-reflection adhesive film of the present invention can also be applied to the fluorescent sheet of the high-power LED lamp module, please refer to FIG. 5 , which is a schematic diagram of an embodiment of the present invention. Generally speaking, the white light of a white LED lamp 3 with a cool color temperature (5000K) is composed of a blue LED and a two-color fluorescent sheet 4 . The anti-reflection adhesive film 5 of the present invention is attached to the surface of the two-color fluorescent sheet 4. In this embodiment, the film thickness of the adhesive film 5 is between 0.1 mm and 0.2 mm, and the particle size of the nanospheres is 100 nm. Result as shown in Figure 6, Fig. 6 is the comparative figure of relative luminous intensity test of the anti-reflection adhesive film of the present invention, makes the control group that does not attach adhesive film 5, after attaching adhesive film (being experimental group) again, its blue light The relative luminous intensity of the wavelength band (wavelength from 400nm to 500nm) decreases by about 15% (absorbance/Absorbance unit), while the red light band (wavelength from 600nm to 800nm) increases by up to 10% (absorbance/Absorbance unit). Reduce the color temperature of 5000K cool white LED lamps to 2700-3000K and become warm LED lamps, producing the function of adjusting the color temperature.

In addition, adding the anti-reflection film on the surface of the fluorescent sheet will also form a white film, which is like a fluorescent lamp cover, which is helpful for LED manufacturers to promote their lamps.

The anti-reflection adhesive film of the present invention can be made according to needs, in addition to the above-mentioned components, but also can further add appropriate additives, such as thermal conductivity additives, flame retardants, pigments, oxidation inhibitors, ultraviolet stabilizers, dispersants, disinfectants, etc. Foaming agent, tackifier, plasticizer and silane coupling agent, etc., and more than one of various known additives to add other special properties.

To sum up, the anti-reflection adhesive film disclosed by the present invention and its manufacturing method can produce highly transparent adhesive films with different reflection bands according to actual needs, meet the needs of various industries, and replace existing multilayer films and colored cellophane etc., and even change the color temperature of lamps, with a wide range of applications, which is expected to make the optical film industry take a big step forward.

【Symbol Description】

1 clear resin

2 nanospheres

3 LED lamps

4 fluorescent sheets

5 film

6 shades

A nanosphere

B nanosphere

Claims (17)

1. an anti-reflection adhesive film, is characterized in that, comprises: a transparent resin, the thickness of which is between 0.001mm and 1.0mm; and A plurality of nanospheres are non-periodically arranged in the transparent resin, and the particle diameter of the nanospheres is 10nm to 1000nm. 2 . The anti-reflective adhesive film according to claim 1 , wherein the particle size of the nanospheres is further 100 nm to 300 nm, and the thickness of the transparent resin is between 0.001 mm to 0.5 mm. 3 . The anti-reflective adhesive film according to claim 1 , wherein the particle diameter of the nanospheres is further 100 nm, and the thickness of the transparent resin is between 0.001 mm and 0.1 mm. 4. The antireflection adhesive film according to claim 1, 2 or 3, wherein the material of the transparent resin comprises photocurable resin, thermosetting resin or a combination thereof. 5 . The anti-reflective adhesive film according to claim 4 , wherein the material of the photocurable resin comprises acrylate monomer, acrylate oligomer monomer or a combination thereof. 6. anti-reflection adhesive film as claimed in claim 5, is characterized in that, this acrylate monomer comprises tripropylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate ester, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, di-(trimethylolpropane hydroxymethylpropane) tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, or combinations thereof. 7. The anti-reflection adhesive film as claimed in claim 5, wherein the acrylate oligomer monomer comprises epoxy acrylate, polyurethane acrylate, polyester acrylate, unsaturated polyester acrylate, amino Acrylates, silicone acrylates or combinations thereof. 8 . The anti-reflection adhesive film as claimed in claim 4 , wherein the material of the thermosetting resin comprises methyl silicon, phenyl silicon or a combination thereof. 9. The anti-reflection adhesive film according to claim 1, 2 or 3, wherein the material of the nanospheres comprises silicon dioxide, polystyrene, polydimethylsiloxane or a combination thereof. 10. A method for making an anti-reflection adhesive film, for making the anti-reflection adhesive film as claimed in claim 1, 2 or 3, characterized in that, it is made of the monomer material of the transparent resin, mixed with highly dispersible The colloidal solution of the plurality of nanospheres is cured to form the anti-reflection adhesive film with the plurality of nanospheres arranged aperiodically. 11. the manufacture method of anti-reflection adhesive film as claimed in claim 10, is characterized in that, the monomer material of this transparent resin is acrylate series monomer material, and further adds a photoinitiator, through ultraviolet light irradiation The curing action forms the anti-reflection adhesive film. 12. The preparation method of the anti-reflection adhesive film as claimed in claim 11, wherein the photoinitiator comprises a propiophenone series photoinitiator, a hydroxyketone series photoinitiator or a benzophenone series photoinitiator agent. 13. The method for making an anti-reflective adhesive film as claimed in claim 12, wherein the propiophenone series photoinitiator comprises diethoxyacetophenone. 14. The method for making an anti-reflective adhesive film according to claim 12, wherein the hydroxyketone series photoinitiator comprises hydroxymethyl phenylacetone, hydroxycyclohexyl phenyl ketone or a combination thereof. 15. The method for making an anti-reflective adhesive film according to claim 12, wherein the benzophenone series photoinitiator comprises trimethylbenzophenone, methylbenzophenone or a combination thereof. 16. The manufacture method of anti-reflective adhesive film as claimed in claim 10, it is characterized in that, the monomer material of this transparent resin is the monomer material of thermosetting resin series further, and is formed by the curing action of oven heating The AR film. 17. The manufacture method of anti-reflective adhesive film as claimed in claim 10, it is characterized in that, the monomer material of this transparent resin is the monomer material of thermosetting resin series further, and add curing agent through this curing action at room temperature Form the anti-reflection adhesive film.