TWI737988B - Light-permeable anti-fouling laminated film - Google Patents

Abstract

A light-permeable antifouling laminated film includes a transparent release substrate, a transparent optical adhesive layer, a transparent substrate, and an antifouling hard coating. The transparent release substrate has a Young's modulus greater than 0.5 GPa and a release force of 10 gf/cm to 60 gf/cm. The transparent optical adhesive layer is arranged on the transparent release substrate. The transparent substrate is arranged on the transparent optical adhesive layer and has a Young's modulus greater than 2 GPa. The anti-fouling hard coating is arranged on the transparent substrate. The light-permeable antifouling laminated film has the advantages of flexibility, foldability, curling, antifouling, scratch resistance, abrasion resistance and high hardness.

Description

Light-permeable anti-fouling laminated film

The present invention relates to a film, in particular to a light-permeable anti-fouling laminated film.

Building materials, automobile exterior parts, glass, paper, furniture, home appliances, optical products, cosmetic containers, various display elements, and semi-finished products of electronic manufacturing processes are widely used with functional hard coatings to protect the surface of these items. In particular, a large number of displays recently used in smart mobile devices, such as liquid crystal displays, active organic light-emitting diode displays, or passive organic light-emitting diode displays, must be protected by the hard coating. The demand for hard coatings with anti-scratch, wear-resistant and anti-fouling functions has increased significantly.

Generally, the hard coating used to protect the display window must have the characteristics of anti-scratch, abrasion resistance, anti-fouling and easy processing. However, the currently commercially available laminated films containing hard coatings only have the characteristics of high hardness, and the laminated films The flexibility of the film is not good. For example, when the laminated film is bent, visual cracks will be generated if the bending radius is more than 5mm, and it cannot be applied to flexible articles that require a bending radius of less than 3mm, especially the flexible type. , Foldable or rollable display.

Therefore, the purpose of the present invention is to provide a light-permeable anti-fouling laminated film with the characteristics of flexibility, foldability, curling, antifouling, scratch resistance, abrasion resistance and high hardness.

Therefore, the light-permeable anti-fouling laminated film of the present invention includes a transparent release substrate, a transparent optical adhesive layer, a transparent substrate, and an anti-fouling hard coating. The transparent release substrate has a Young's modulus greater than 0.5 GPa and a release force of 10 gf/cm to 60 gf/cm. The transparent optical adhesive layer is arranged on the transparent release substrate. The transparent substrate is arranged on the transparent optical adhesive layer and has a Young's modulus greater than 2 GPa. The anti-fouling hard coating is arranged on the transparent substrate.

The effect of the present invention is: through the antifouling hard coating and the transparent substrate, the light-permeable antifouling laminated film has flexibility, foldability, curling, antifouling, scratch resistance, abrasion resistance and high hardness The advantages.

1, the light-transmissive anti-fouling laminated film of the present invention includes a transparent release substrate 1, a transparent optical adhesive layer 2, a transparent substrate 3, and an anti-fouling hard coating 4.

The transparent release substrate 1 is used to protect the transparent optical adhesive layer 2. The transparent release substrate 1 has a Young's modulus greater than 0.5 GPa and a release force of 10 gf/cm to 60 gf/cm. The material of the transparent release substrate 1 is, for example, but not limited to, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, isobutyl cellulose, propylene cellulose, butyl cellulose, Acetyl propylene cellulose, ethylene-vinyl acetate copolymer, polyester, polystyrene, polyamide, polyetherimide, polyacrylic acid, polyimide, polyether turquoise, polyvinyl acetate, polyethylene, poly Propylene, polymethylpentene, polycyclopentene, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polymethyl methacrylate, polyethylene terephthalate, poly Butylene phthalate, polyethylene naphthalate, polycarbonate, polyurethane, or epoxy resin, etc. Preferably, the material of the transparent release substrate 1 is polyethylene terephthalate. The thickness of the transparent release substrate 1 is not particularly limited, for example, 4 μm to 200 μm, preferably 20 μm to 100 μm. The transparent release substrate 1 may have a single-layer structure or a multi-layer structure. When the transparent release substrate 1 has a multilayer structure, the transparent release substrate 1 includes a release layer and a carrier layer. The material of the release layer is, for example, but not limited to, silicone resin, fluororesin, acrylic-melamine resin, polyester resin, polyolefin resin, polypropylene resin, or polyurethane resin. The thickness of the release layer is not particularly limited, for example, 0.5 μm to 20 μm.

The optically clear adhesive (OCA for short) layer 2 is disposed on the transparent release substrate 1. The transparent optical adhesive layer 2 is, for example, an optical pressure sensitive adhesive layer or an optical hot pressure adhesive layer. The transparent optical adhesive layer is, for example, an acrylic optical adhesive layer, an epoxy optical adhesive layer, a polyurethane optical pressure sensitive adhesive layer, or a heat-sealing adhesive layer. The thickness of the transparent optical adhesive layer 2 is not particularly limited. For example, when the transparent optical adhesive layer 2 is an optical pressure sensitive adhesive layer, the thickness of the transparent optical adhesive layer 2 is 5 μm to 50 μm. For example, when the transparent optical adhesive layer 2 is an optical pressure sensitive adhesive layer, When the optical adhesive layer 2 is a heat-sealing adhesive layer, the thickness of the transparent optical adhesive layer 2 is 25 μm to 175 μm. When the transparent release substrate 1 of the light-permeable anti-fouling laminated film is removed, the transparent optical adhesive layer 2 is used for the transparent substrate 3 and, for example, flexible objects, flexible image display devices, Items such as foldable image display devices, rollable image display devices, or components in the above image display devices are connected together.

The transparent substrate 3 is disposed on the transparent optical adhesive layer 2 and has a Young's modulus greater than 2 GPa. By adjusting the thickness and Young's modulus of the transparent substrate 3, the transparent substrate 3 and the anti-fouling hard coating layer 4 are used in conjunction to assist the anti-fouling hard coating layer 4 and enhance the anti-fouling hard coating layer. The hardness and flexibility of the coating 4, therefore, when the transparent substrate 3 and the antifouling hard coating 4 are bent, they can have a bending radius of 3mm or less, and can be bent more than 100,000 times without breaking. Or damage such as cracks. The material of the transparent substrate 3 is, for example, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, isobutyl cellulose, acryl cellulose, butyl cellulose, acetyl propylene fiber Polyethylene, ethylene-vinyl acetate copolymer, polyester, polystyrene, polyamide, polyetherimide, polyacrylic acid, polyimide, polyether turpentine, polyimide, polyethylene, polypropylene, polymethyl Pentene, polycyclopentene, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate Alcohol ester, polyethylene naphthalate, polycarbonate, polyurethane, epoxy resin, or glass, etc.

The antifouling hard coating layer 4 is disposed on the transparent substrate 3. The thickness of the antifouling hard coating layer 4 is not particularly limited, for example, 3 μm to 100 μm. The antifouling hard coating 4 has an elongation at break greater than 5%. The antifouling hard coating 4 has the characteristics of high hardness, antifouling, scratch resistance and wear resistance. In the embodiment of the present invention, the anti-fouling hard coating 4 has a hardness of more than 5H under a load of 750 grams, a surface water contact angle of more than 100 degrees, and wears #0000 steel wool under a load of 1 kg. During the test, it can be subjected to more than 500 times of back and forth rubbing without visible scratches.

The anti-fouling hard coating layer 4 is formed by a photo-curing coating through a photo-curing reaction. The photocurable coating includes photocurable materials, additives, photoinitiators and solvents. The additives include hardeners and antifouling agents. The photocuring reaction is performed using ultraviolet light.

The photocurable material is, for example, a translucent photocurable resin or a photocurable monomer. The translucent photocurable resin can be used alone or in combination of multiple types, and the translucent photocurable resin is, for example, a photocurable acrylate oligomer or a photocurable methacrylate oligomer. The photocurable acrylate oligomer can be used alone or in combination of multiple types, and the photocurable acrylate oligomer is for example epoxy acrylate, urethane acrylate, or polyester acrylate. The photocurable methacrylate oligomer can be used alone or in combination of multiple types. The photocurable methacrylate oligomer is for example epoxy methacrylate, urethane methacrylate, or polymethacrylate. Ester methacrylate and so on. The photocurable monomer is, for example, a monomer having a photoreactive group, and the photoreactive group is an unsaturated group. The unsaturated group is, for example, an acryl group, a methacryl group, a vinyl group, a styryl group, or an allyl group. Preferably, the unsaturated group is acryloyl or methacryloyl. The photocurable monomer can be used alone or in combination of multiple types, and the photocurable monomer is for example neopentyl glycol acrylate, 1,6-hexanediol acrylate, and 1,6-hexanediol methacrylic acid. Ester, propylene glycol diacrylate, propylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, dipropylene glycol diacrylate, dipropylene glycol dimethacrylate, polyethylene glycol diacrylate Ester, polyethylene glycol dimethacrylate, polypropylene glycol acrylate, polypropylene glycol methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, methylolethane triacrylate Acrylate, hydroxymethylethane trimethacrylate, 1,2,4-cyclohexane tetraacrylate, 1,2,4-cyclohexane tetramethacrylate, pentaglycerol triacrylate, pentaglycerol Trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol triacrylate, dipentaerythritol trimethacrylate, pentaerythritol pentaacrylate, pentaerythritol Pentamethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tripentaerythritol triacrylate, tripentaerythritol trimethacrylate, tripentaerythritol Hexacrylate, tripentaerythritol hexamethacrylate, bis(2-hydroxyethyl) isocyanurate diacrylate, bis(2-hydroxyethyl) isocyanurate dimethacrylate, acrylic hydroxy Ethyl, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, isooctyl acrylate, isooctyl methacrylate, isodecyl acrylate , Isodecyl methacrylate, stearyl acrylate, stearyl methacrylate, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, isobornyl acrylate , Or isobornyl methacrylate and so on.

The hardening agent can be used alone or in combination of multiple types, and the hardening agent is for example silica, alumina, zirconia, zeolite, or titanium oxide. The antifouling agent can be used alone or in combination of multiple types, and the antifouling agent can be fluorinated acrylate materials, fluorinated methacrylate materials, perfluoroalkane materials, or perfluoropolyether materials. The fluorinated methacrylate material is, for example, trifluoroethyl methacrylate.

The photoinitiator can be used alone or in combination of multiple types, and the photoinitiator is for example a hydroxyketone-based photoinitiator, an aminoketone-based photoinitiator, or a photoacid-based photoinitiator. The photoinitiator is, for example, 2-methyl-1-[4-(methyl)-1-(methylthio)phenyl]2-morpholine-1-acetone, diphenyl ketone, benzalkonium dimethyl Ketal, 2-hydroxy-2-methyl-1-phenyl-1-one, 4-hydroxycyclophenyl ketone, 2,2-dimethoxy-2-phenyl-acetophenone, anthraquinone Fluorene, triphenylamine, oxazole, 3-methylacetophenone, 4-chloroacetophenone, 4,4-dimethoxyacetophenone, 4,4-diaminobenzophenone, 1- Hydroxycyclohexyl phenyl ketone, benzophenone, or diphenyl (2,4,6-trimethylbenzyl) phosphorus oxide, etc. The 1-hydroxycyclohexyl phenyl ketone is, for example, Irgacure® 184 from Ciba Specialty Chemicals Inc. The solvent can be used singly or in combination of multiple types, and the solvent is, for example, an alcohol-based solvent, a ketone-based solvent, an acetate-based solvent, a hexane-based solvent, or an ether-based solvent. The ketone solvent is, for example, methyl ethyl ketone.

The light-permeable anti-fouling laminated film of the present invention can be used as a surface protective film, and can be applied to, for example, flexible objects, flexible image display devices, foldable image display devices, and rollable image display The device, or the components in the above-mentioned image display device, etc., so that the article can have the characteristics of stain resistance, scratch resistance and abrasion resistance. The material of the flexible object is, for example, diacetyl cellulose, triacetyl cellulose, acetyl cellulose butyrate, isobutyl cellulose, propyl cellulose, butyl cellulose, acetyl cellulose, Ethylene-vinyl acetate copolymer, polyester, polystyrene, polyamide, polyetherimide, polyacrylic acid, polyimide, polyether turpentine, polyvinyl acetate, polyethylene, polypropylene, polymethylpentene , Polycyclopentene, polyvinyl chloride, polyvinyl alcohol, polyvinyl acetal, polyether ketone, polymethyl methacrylate, polyethylene terephthalate, polybutylene terephthalate , Polyethylene naphthalate, polycarbonate, polyurethane, or epoxy resin, etc. The image display device is, for example, a liquid crystal display, an active organic light emitting diode display, or a passive organic light emitting diode display. The components in the image display device are, for example, light-emitting diodes.

Before the present invention is described in detail, it should be noted that in the following description, similar elements are denoted by the same numbers.

The present invention will be further described with the following examples, but it should be understood that these examples are for illustrative purposes only and should not be construed as limitations to the implementation of the present invention.

Preparation Example 1

Using a blender, 100 parts by weight of urethane propionate, 10 parts by weight of dipentaerythritol hexaacrylate, 10 parts by weight of pentaerythritol triacrylate, 30 parts by weight of nanosilica sol, 10 parts by weight Parts of trifluoroethyl methacrylate, 20 parts by weight of methyl ethyl ketone, and 2 parts by weight of Irgacure® 184 (photoinitiator) are mixed, and then filtered with a polypropylene filter to obtain light curing coating.

Preparation Example 2

Using a blender, 100 parts by weight of urethane propionate, 10 parts by weight of dipentaerythritol hexaacrylate, 10 parts by weight of pentaerythritol triacrylate, 50 parts by weight of nano-zeolite sol, 10 parts by weight of Trifluoroethyl methacrylate, 20 parts by weight of methyl ethyl ketone, and 2 parts by weight of Irgacure® 184 (photoinitiator) were mixed, and then filtered with a polypropylene filter membrane to obtain a light-curing coating.

Preparation Example 3

Using a blender, mix 100 parts by weight of urethane propionate, 10 parts by weight of dipentaerythritol hexaacrylate, 10 parts by weight of pentaerythritol triacrylate, 30 parts by weight of dipropanol diacrylate, and 30 parts by weight. Parts of nanosilica sol, 10 parts by weight of trifluoroethyl methacrylate, 20 parts by weight of methyl ethyl ketone, and 2 parts by weight of Irgacure® 184 (photoinitiator) were mixed, and then used The polypropylene filter membrane is filtered to obtain a light-curing paint.

Preparation Example 4

Using a blender, mix 100 parts by weight of urethane propionate, 10 parts by weight of dipentaerythritol hexaacrylate, 10 parts by weight of pentaerythritol triacrylate, 30 parts by weight of dipropanol diacrylate, and 30 parts by weight. Parts of nano zeolite sol, 10 parts by weight of trifluoroethyl methacrylate, 20 parts by weight of methyl ethyl ketone, and 2 parts by weight of Irgacure® 184 (photoinitiator) are mixed, and then, polypropylene is used The filter membrane is filtered to obtain a light-curing paint.

Preparation Example 5

Using a blender, 100 parts by weight of urethane propionate, 10 parts by weight of dipentaerythritol hexaacrylate, 10 parts by weight of pentaerythritol triacrylate, 30 parts by weight of dipropanol diacrylate, 10 parts by weight Parts of trifluoroethyl methacrylate, 20 parts by weight of methyl ethyl ketone, and 2 parts by weight of Irgacure® 184 (photoinitiator) are mixed, and then filtered with a polypropylene filter to obtain light curing coating.

Table 1 Light-curing coating unit: parts by weight Preparation example 1 2 3 4 5 Light curing material Light-curing acrylate oligomer Urethane Acrylate 100 100 100 100 100 Light-curing monomer Dipentaerythritol hexaacrylate 10 10 10 10 10 Pentaerythritol triacrylate 10 10 10 10 20 Dipropanol diacrylate 0 0 30 30 30 additive Hardener Nano silica sol 30 0 30 0 0 Nano Zeolite Sol 0 50 0 50 0 Antifouling agent Trifluoroethyl methacrylate 10 10 10 10 10 Photoinitiator Irgacure® 184 20 20 20 20 20 Solvent Methyl ethyl ketone 2 2 2 2 2

Example 1

The light-curable coating of Preparation Example 1 was coated on the surface of the transparent polyimide substrate 3 with a Young's modulus of 3GP and a thickness of 30 μm to form a pre-coating film. Then, the pre-coating film was irradiated with ultraviolet light to The photocuring reaction is carried out, and an antifouling hard coat layer 4 having a thickness of 50 μm is formed on the transparent substrate 3, thereby obtaining a first laminate. The acrylic pressure sensitive adhesive is applied to a transparent polyethylene terephthalate release substrate 1 with a Young's modulus of 3GP, a release force of 30gf/cm, and a thickness of 50μm, and the A transparent optical adhesive layer 2 with a thickness of 50 μm is formed on the ethylene terephthalate transparent release substrate 1 to obtain a second laminate. The transparent optical adhesive layer 2 of the second laminate was bonded to the transparent substrate 3 of the first laminate, and allowed to stand and mature for 6 days to obtain a light-permeable anti-fouling laminate film.

Example 2

Example 2 is carried out in the same steps as in Example 1, except that the photocurable coating of Preparation Example 2 is used to form the anti-fouling hard coating layer 4.

Example 3

Example 3 is carried out in the same steps as in Example 1, with the main difference being that the photocurable coating of Preparation Example 3 is used to form the anti-fouling hard coating layer 4.

Example 4

Example 4 is carried out in the same steps as in Example 1, except that the photocurable coating of Preparation Example 4 is used to form the anti-fouling hard coating layer 4.

Example 5

Using a co-extrusion equipment, the raw material for the transparent substrate and the photocurable coating of Preparation Example 1 are used to form a first member, and the first member includes a transparent film formed from the raw material for the transparent substrate, and a layer The pre-coating film formed on the surface of the transparent film and formed from the photocurable paint, wherein the raw material for the transparent substrate is polyimide. The first member was placed in an oven set at a temperature of 130°C to 150°C for the first baking treatment to make the transparent film in a semi-dry state, and then the temperature was lowered to 80°C to 90°C for the second time. A second baking treatment to make the transparent film in a completely dried state and at the same time soften the pre-coated film, and then ^{irradiate the pre-coated film with ultraviolet light with an energy of 100 to 3000 mj/cm 2} to perform a photocuring reaction, Then, it is placed in an oven for the third baking treatment to obtain a first laminate, wherein the first laminate includes a transparent polyimide substrate 3 with a Young's modulus of 6GP and a thickness of 80μm and a layer The antifouling hard coat layer 4 having a thickness of 10 μm is provided on the surface of the polyimide transparent substrate 3. The acrylic pressure sensitive adhesive is applied to a polyethylene terephthalate transparent release substrate 1 with a Young's modulus of 2GP, a release force of 5gf/cm, and a thickness of 50μm. A transparent optical adhesive layer 2 with a thickness of 25 μm is formed on the ethylene terephthalate transparent release substrate 1 to obtain a second laminate. The transparent optical adhesive layer 2 of the second laminate was attached to the transparent substrate 3 of the first laminate, and it was allowed to stand and mature for 6 days to obtain a light-permeable anti-fouling laminate film.

Example 6

Example 6 is carried out in the same steps as in Example 5, with the main difference being that the photocurable coating of Preparation Example 2 is used to form the anti-fouling hard coating layer 4 and the polyethylene terephthalate transparent release substrate 1 The release force.

Example 7

Example 7 is carried out in the same steps as in Example 5, the main difference being: the light-curable coating of Preparation Example 3 is used to form the anti-fouling hard coating layer 4, and the polyethylene terephthalate transparent release substrate 1 The release force, the thickness of the transparent optical adhesive layer 2, and the thickness of the anti-fouling hard coating layer 4.

Example 8

Example 8 is carried out in the same steps as in Example 5, but the main difference lies in: using the photocurable coating of Preparation Example 4 to form an anti-fouling hard coating layer 4, and a transparent polyethylene terephthalate release substrate 1 The release force, the thickness of the transparent optical adhesive layer 2, and the thickness of the anti-fouling hard coating layer 4.

Example 9

Example 9 was carried out in the same steps as in Example 5, the main difference being: In Example 9, the polyethylene terephthalate transparent release substrate of the second laminate of Example 5 was used. 1 Replace with a polyimide transparent release substrate, and the Young's modulus is 3GP; the thickness of the transparent substrate 3 is 25 μm and the Young's modulus is 3GP, and the thickness of the anti-fouling hard coating layer 4 is 25 μm.

Example 10

Example 10 was carried out in the same steps as in Example 6, but the main difference was: in Example 10, the polyethylene terephthalate transparent release substrate of the second laminate of Example 6 was used. 1 Replace with a polyimide transparent release substrate; the thickness of the transparent substrate 3 is 30 μm, the Young's modulus is 4 GP, and the thickness of the anti-fouling hard coating layer 4 is 25 μm.

Example 11

Example 11 is carried out in the same steps as in Example 7, but the main difference lies in: In Example 11, the polyethylene terephthalate transparent release substrate of the second laminate of Example 7 is used. 1 Replaced with a polyimide transparent release substrate; the thickness of the transparent substrate 3 is 50 μm and the Young's modulus is 5 GP.

Example 12

Example 12 is carried out in the same steps as in Example 8, but the main difference lies in: In Example 12, the polyethylene terephthalate transparent release substrate of the second laminate of Example 8 is used. 1 Replaced with a polyimide transparent release substrate; the thickness of the anti-fouling hard coating layer 4 is 10 μm.

Comparative example 1

Comparative Example 1 was carried out in the same steps as in Example 1, except that the light-curable coating of Preparation Example 5 was used to form the hard coat layer 4, and the thickness of the hard coat layer was 25 μm; the thickness of the transparent optical adhesive layer 2 The transparent substrate 3 is a polyethylene terephthalate transparent substrate with a thickness of 50 μm and a Young's modulus of 4GP.

Comparative example 2

Comparative Example 2 was carried out in the same steps as in Example 5, the main difference being: the photocurable coating of Preparation Example 5 was used to form the hard coating layer 4, and the thickness of the hard coating layer was 15 μm; The release force of the alcohol ester transparent release substrate 1 is 30gf/cm and the Young’s modulus is 3GP; the thickness of the transparent optical adhesive layer 2 is 12μm; the transparent substrate 3 is a polyethylene terephthalate transparent substrate The thickness is 125μm and the Young's modulus is 4GP.

Comparative example 3

Comparative example 3 is carried out in the same steps as the comparative example 2, the main difference lies in: in the comparative example 3, the polyethylene terephthalate transparent release substrate of the second laminate of the comparative example 2 1. Replace with a polyimide transparent release substrate, and the release force of the polyimide transparent release substrate is 20 gf/cm; the thickness of the transparent optical adhesive layer 2 is 25 μm.

Evaluation item

Pencil hardness test: In order to be able to clearly describe the measurement process, the light-permeable anti-fouling laminated film of Example 1 is described below, and the remaining examples and comparative examples are all measured according to this process. The nibs of pencils of different hardness were pressed against the surface of the antifouling hard coating layer 4 of the light-permeable antifouling laminated film of Example 1 in a direction of 45 degrees and a load of 1 kg, and the antifouling hard coating layer 4 In the direction opposite to the pencils, the surface of the anti-fouling hard coating layer 4 was scratched, and a total of 5 times with pencils of each hardness, and more than 4 times were recorded without scratching the anti-fouling hard coating layer 4 The hardness of the pencil on the surface. The hardness of these pencils is divided into the following grades from the softest to the hardest: 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, 9H .

Flexibility test: In order to be able to clearly describe the measurement process, the light-permeable anti-fouling layer film of Example 1 is described below, and the remaining examples and comparative examples are all measured according to this process. A rod with a diameter of 3 mm was placed on the center of the width of the light-permeable anti-fouling laminate film of Example 1, and then the light-permeable anti-fouling laminate film was bent until the light could penetrate both sides of the anti-fouling laminate film. The bottom of the end touches, and then returns to the original state, repeats the above process until the light penetrating anti-fouling laminated film breaks, and records the number of times before the light penetrating anti-fouling laminated film breaks. Judgment criteria: the frequency is more than 100,000 times as ◎; the frequency is from 50,000 to 100,000 times as ○; the frequency is more than 10,000 times but less than 50,000 times is Δ; the frequency is less than 10,000 times as X.

Antifouling test: Drop water drops on the hard coatings of Examples 1 to 12 and Comparative Examples 1 to 3, and then measure the contact angle with a contact angle analyzer.

Abrasion resistance test: Use an abrasion tester to apply a load of 1 kg to the hard coating layer of the laminate films of Examples 1 to 12 and Comparative Examples 1 to 3, and rub the hard coating layer back and forth with #0000 steel wool. After 1000 times, the degree of surface damage of the hard coat layer was observed.

Table 2 Example 1 2 3 4 5 6 7 8 Transparent release substrate 1 Material Polyethylene terephthalate Polyethylene terephthalate Thickness (μm) 50 50 Young's modulus (GP) 3 2 Release force (gf/cm) 30 5 10 20 20 Transparent optical adhesive layer 2 Material Acrylic pressure sensitive adhesive Acrylic pressure sensitive adhesive Thickness (μm) 50 50 50 50 25 25 12 12 Transparent substrate 3 Material Polyimide Polyimide Thickness (μm) 30 30 50 50 80 Young's modulus (GP) 3 3 4 4 6 Anti-fouling hard coating 4 Preparation example 1 2 3 4 1 2 3 4 Thickness (μm) 50 10 10 15 20 Evaluation item Pencil hardness 5H 5H 6H 7H 6H 6H 7H 8H Flexibility ○ ○ ○ ○ ○ ○ ◎ ◎ Contact angle (degrees) 110 120 110 120 110 120 110 120 Surface damage degree slight slight Not obvious slight without Not obvious slight Not obvious slight without without

table 3 Example Comparative example 9 10 11 12 1 2 3 Transparent release substrate 1 Material Polyimide Polyethylene terephthalate Polyimide Thickness (μm) 50 50 50 50 Young's modulus (GP) 3 3 3 3 Release force (gf/cm) 20 20 20 20 30 30 20 Transparent optical adhesive layer 2 Material Acrylic pressure sensitive adhesive Acrylic pressure sensitive adhesive Thickness (μm) 25 25 12 12 12 12 25 Transparent substrate 3 Material Polyimide Polyethylene terephthalate Thickness (μm) 25 30 50 80 50 125 125 Young's modulus (GP) 3 4 5 6 4 4 4 Anti-fouling hard coating 4 Preparation example 1 2 3 4 5 5 5 Thickness (μm) 25 25 15 10 25 15 15 Evaluation item Pencil hardness 6H 6H 8H 8H 4H 5H 5H Flexibility ○ ◎ ◎ ◎ X △ △ Contact angle (degrees) 110 120 110 120 105 105 105 Surface damage degree Not obvious slight Not obvious slight without without damage slight slight

According to the experimental data in Table 2 and Table 3, compared with Comparative Examples 1 to 3, the pencil hardness of the anti-fouling hard coating layer 4 of the light-permeable anti-fouling laminated film of the present invention is 5H to 8H, which indicates that the light can The anti-fouling hard coating layer 4 that penetrates the anti-fouling laminate film has the characteristics of high hardness. In addition, the number of bending times of the light-permeable anti-fouling laminate film of the present invention is at least 50,000 times, which means that the light-permeable anti-fouling layer of the present invention The laminated film has the characteristics of being highly flexible, foldable, and rollable. Furthermore, the water contact angle of the anti-fouling hard coating layer 4 of the light-permeable anti-fouling laminated film of the present invention is above 110 degrees, which means that the light can be The antifouling hard coat layer 4 penetrating the antifouling laminate film has antifouling properties.

In summary, the light-permeable anti-fouling laminated film of the present invention has the advantages of flexibility, foldability, curling, anti-fouling, scratch resistance, abrasion resistance and high hardness, so it can indeed achieve the purpose of the invention.

However, the above are only examples of the present invention. When the scope of implementation of the present invention cannot be limited by this, all simple equivalent changes and modifications made in accordance with the scope of the patent application of the present invention and the content of the patent specification still belong to Within the scope covered by the patent of the present invention.

1: Transparent release substrate 2: Transparent optical adhesive layer 3: Transparent substrate 4: Anti-fouling hard coating

Other features and effects of the present invention will be clearly presented in the embodiments with reference to the drawings, in which: FIG. 1 is a perspective view of an embodiment of the light-permeable anti-fouling laminated film of the present invention.

1: Transparent release substrate

2: Transparent optical adhesive layer

3: Transparent substrate

4: Anti-fouling hard coating

Claims (1)

A light-permeable anti-fouling laminated film, comprising: a transparent release substrate with a Young's modulus of 2GPa to 3GPa and a release force greater than 10gf/cm and less than 30gf/cm, and is selected from poly(p-phenylene) Ethylene glycol dicarboxylate transparent release substrate or polyimide transparent release substrate; a layer of acrylic transparent optical pressure sensitive adhesive layer is arranged on the transparent release substrate, with a thickness of 12 μm to 25 μm; A layer of polyimide transparent substrate is arranged on the acrylic transparent optical pressure sensitive adhesive layer, and has a Young's modulus of 4GPa to 6GPa, and a thickness of 30μm to 80μm; and a layer of antifouling hard coating, which is arranged The transparent polyimide substrate has a thickness of 10 μm to 25 μm, and is formed by a photo-curable coating through an ultraviolet curing reaction. The photo-curable coating includes a photo-curable material, a nano-zeolite sol hardener, and methacrylic acid. Trifluoroethyl antifouling agent, photoinitiator and solvent. The photocurable material includes urethane acrylate, dipentaerythritol hexaacrylate and pentaerythritol triacrylate.

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