TWI743821B - Anti-fog coating composition, optical film fabricated using the anti-fog coating composition and display device having the optical film - Google Patents

Abstract

An anti-fog coating composition, an optical film fabricated using the anti-fog coating composition and a display device having the optical film are disclosed. An anti-fog coating composition includes two different (meth)acrylic monomers, such as the first (meth)acrylic monomer and the second (meth)acrylic monomer. Each of the first and second (meth)acrylic monomers has a viscosity less than 65 cps at 25℃. Each of the first and second (meth)acrylic monomers has a surface tension from 36 dyne/cm to 42 dyne/cm at 20℃. Also, the first and second (meth)acrylic monomers are mixed at the same weight percentage. The anti-fog coating composition also includes the third (meth)acrylic monomer having a viscosity in a range of 90 cps to 500 cps, and having a surface tension from 36 dyne/cm to 42 dyne/cm at 20℃.

Description

Anti-fog coating composition, optical film prepared and display device with optical film

The present invention relates to a coating composition, a prepared film layer and a display device containing the film layer, and particularly relates to an anti-fog coating composition, the prepared optical film, and a display device with the optical film.

Transparent substrates (such as glass, plastic, etc.) are indispensable materials in people's daily life, work and production. For example, attaching an optical film to the surface of a transparent substrate to provide the required optical applications, or attaching an optical film containing an adhesive layer to the surface of a transparent substrate can have optical functions and prevent splashes and injury after the glass is broken. The explosion-proof function. However, during the use of the transparent substrate, the surface of the substrate is caused by the penetration of water vapor in the high temperature and high humidity environment, which often produces fog/white fog, which causes the light transmittance of the substrate to decrease, which affects the line of sight and brings people’s lives. It causes inconvenience and even danger.

Some embodiments of the present invention disclose an anti-fog coating composition, comprising two different first (meth)acrylic monomers and second (meth)acrylic monomers, each having a viscosity less than 25°C 65 cps, and the surface tension at 20°C is in the range of 36 dyne/cm (dyne/cm) ~ 42 dyne/cm (dyne/cm), where the first (methyl) The acrylic monomer and the second (meth)acrylic acid monomer system are mixed in the same weight percentage and equal ratio (1:1); and the third (meth)acrylic monomer has a viscosity at 25°C Between 90 cps and 500 cps, and the surface tension at a temperature of 20 ℃ is between 36 dyne/cm ~ 42 dyne/cm. The anti-fog coating composition of the embodiment further includes an aliphatic urethane acrylate oligomer.

Some embodiments of the present invention disclose an optical film including a base film and an anti-fog coating formed on the base film, wherein the anti-fog coating is formed by hardening the aforementioned anti-fog coating composition.

Some embodiments of the present invention disclose a display device including a display module, a touch module disposed above the display module, and the aforementioned optical film, wherein the optical film is disposed above the touch module, or Between the touch module and the display module.

In order to prevent fogging on the surface of the substrate, there are usually two methods. The first method is to eliminate water vapor or temperature difference. Although it is difficult to eliminate water vapor in the air, through heating methods, such as power heating or infrared radiation, the surface temperature of the substrate is always higher than the dew point of water vapor. The heating method is expensive and consumes energy. The second method is to change the wettability of the substrate surface, such as making the substrate surface hydrophilic or hydrophobic. When the surface of the substrate is hydrophilic, the contact angle of the substrate surface to water can be reduced, so that the small water droplets condensed on the surface will not form tiny water droplets, but spread on the surface to form a thin film to reduce the diffusion of light. Ensure the transparency of the material. In addition, if a layer of hydrophobic substance is coated on the surface of the material to improve the wet state of the surface, the contact angle will increase. The action of gravity falls down, and the purpose of anti-fog can be achieved.

However, the hydrophilic anti-fog coating has relatively soft properties, so its anti-fogging effect has low timeliness. Furthermore, in the daily use of anti-fogging products, necessary decontamination and wiping are inevitable, but instant anti-fogging products processed by hydrophilic properties are not resistant to rubbing and can only be used as a temporary emergency anti-fogging means. However, the current hydrophobic anti-fog coating has no explosion-proof effect.

In the embodiments of the present disclosure, an anti-fog coating composition, an optical film using the anti-fog coating composition, and a display device using the optical film are proposed. The optical film of the embodiment may be an explosion-proof film. The anti-fog coating composition of the embodiment contains a (meth)acrylic monomer with good hydrophobicity and a multifunctional (meth)acrylic monomer with good water resistance, which can make the surface of the formed film have hydrophobic properties and increase water molecules The contact angle with the surface of the film prevents water vapor from staying on the surface of the film, so as to achieve the purpose of anti-fog or waterproof. Furthermore, the anti-fog coating composition of the embodiment can make the formed optical film layer have the characteristics of scratch resistance and abrasion resistance required by the explosion-proof film at the same time. Therefore, the embodiments of the present disclosure can effectively extend the timeliness of the anti-fog coating, so that the surface of the formed optical film (with explosion-proof effect) not only has hydrophobicity but also achieves anti-fog and waterproof effects, but also has excellent water resistance and resistance. Scratching.

Various embodiments are presented below for detailed description. The embodiments are only used as examples for illustration, and do not limit the scope of the disclosure to be protected. The disclosure can still be implemented with other features, components, methods, and parameters. The embodiments are only used to illustrate the technical features of the present disclosure, and are not used to limit the scope of patent application of the present disclosure. Those with ordinary knowledge in this technical field will be able to make equivalent modifications and changes based on the description in the following specification without departing from the spirit of the present disclosure. Furthermore, the (meth)acrylic monomers mentioned herein refer to acrylic monomers or methacrylic monomers, as known by those skilled in the art.

Some embodiments of the present disclosure relate to an anti-fog coating composition. The anti-fog coating composition contains two different first (meth)acrylic monomers and second (meth)acrylic monomers with good hydrophobicity, wherein the first and second (meth)acrylic monomers are in The viscosity at 25°C is less than 65 cps, and the surface tension at 20°C is in the range of 36 dyne/cm (dyne/cm) ~ 42 dyne/cm (dyne/cm), and Mix in equal proportions (ie 1:1) with the same weight percentage. In some embodiments, the anti-fog coating composition further includes a third (meth)acrylic monomer with good water resistance and multifunctionality, and its viscosity at 25° C. is between 90 cps and 500 cps. The surface tension at a temperature of 20°C is also between 36 dyne/cm and 42 dyne/cm. In some embodiments, the anti-fog coating composition further includes monofunctional or multifunctional aliphatic urethane acrylate oligomers, so that the anti-fog coating composition has abrasion resistance and scratch resistance after film formation, as well as good Water resistance.

According to some embodiments of the present disclosure, the first and second (meth)acrylic monomers have low hydrophobic parameters, and their good hydrophobicity makes the surface of the formed film have excellent hydrophobic properties to increase water molecules The contact angle with the surface of the film layer to prevent water vapor from staying on the surface of the film layer. In some embodiments, 1/2 of the sum of the hydrophobic parameter (XlogP) of the first (meth)acrylic monomer and the hydrophobic parameter (XlogP) of the second (meth)acrylic monomer is less than 1.6.

Furthermore, in some embodiments, the hydrophobic parameter (XlogP) of the third (meth)acrylic monomer is less than 2.5 to further enhance the hydrophobicity of the anti-fog coating composition.

According to some embodiments of the present disclosure, taking the total weight of the first, second, and third (meth)acrylic monomers and the aliphatic urethane acrylate oligomer as 100 wt%, the first ( The content of the meth)acrylic monomer and the second (meth)acrylic monomer is 40wt%-60wt%.

According to some embodiments of the present disclosure, the total weight of the first, second, and third (meth)acrylic monomers and the aliphatic urethane acrylate oligomer is 100 wt%, and the third ( The content of meth)acrylic acid monomer is 20wt% to 30wt%.

Furthermore, the anti-fog coating composition may contain one or more polyfunctional (meth)acrylic monomers. For example, in some embodiments, the anti-fog coating composition further includes a fourth (meth)acrylic monomer that is different from the third (meth)acrylic monomer, wherein the fourth (meth)acrylic monomer is at 25°C. The viscosity at temperature is between 90 cps and 500 cps, and the surface tension at 20°C is between 36 dyne/cm and 42 dyne/cm. Furthermore, the third (meth)acrylic monomer and the fourth (meth)acrylic monomer are mixed with the same weight percentage and the same ratio (1:1). If the total weight of the first, second and mixed third and fourth (meth)acrylic monomers and the aliphatic urethane acrylate oligomer is 100wt%, the mixed third And the total content of the fourth (meth)acrylic monomer is 20wt%~30wt%.

According to the embodiments of the present disclosure, the two different first and second (meth)acrylic monomers contained in the anti-fog coating composition have excellent optical properties and a high surface tension of 36 to 42 dyne/cm Can make the composition have excellent hydrophobicity. In some embodiments, the surface tension of the first (meth)acrylic monomer and the second (meth)acrylic monomer at a temperature of 20° C. is greater than that of the third (meth)acrylic monomer. Surface tension at a temperature of 20°C. However, this disclosure is not limited to this. The third (meth)acrylic monomer with a surface tension of 36~42 dyne/cm at a temperature of 20°C, even if its surface tension is greater than that of the first and second ( The surface tension of the meth)acrylic monomer at a temperature of 20°C may also be used in the examples.

In addition, in some embodiments, the refractive index of any one of the first, second, and third (meth)acrylic monomers contained in the anti-fog coating composition is between 1.46 and 1.51, so that the formed film layer Can have high light transmittance. For example, the optical film formed by the anti-fog coating composition of the examples has a light transmittance of 88% or more.

In some embodiments, the first and second (meth)acrylic acid monomer systems are 2-phenoxyethyl acrylate (2-PEA), diethylene glycol acrylate, and (3) ethoxylated three Any two of hydroxymethyl propane triacrylate (EO ₃ TMPTA); (3) before TMPTA means that the number of ethylene oxide (EO) is 3. Furthermore, it is preferable to use diethylene glycol acrylate (simply expressed as A-1 in the following Table 3) and (3) ethoxylated trimethylolpropane triacrylate (EO ₃ TMPTA) (in the following Table 3 It is simply expressed as A-2) to make equal proportions (1:1 mixing).

According to the embodiments of the present disclosure, the third (meth)acrylic monomer contained in the anti-fog coating composition has excellent optical properties and water resistance, and the high surface tension of 36 to 42 dyne/cm can also make the composition The material has excellent hydrophobicity. Furthermore, the third (meth)acrylic monomer of some embodiments has more excellent weather resistance, abrasion resistance and high hardness.

In the anti-fog coating composition of some embodiments, the viscosity of the third (meth)acrylic monomer contained at 25°C is greater than that of either of the first and second (meth)acrylic monomers at 25°C. Viscosity at temperature. The more the number of functional groups of the third (meth)acrylic monomer, the higher the viscosity. The higher the viscosity, the higher the hardness of the formed optical film, but too high viscosity will also affect the overall thickness of the film. Therefore, the viscosity of the third (meth)acrylic monomer at a temperature of 25° C. does not exceed 500 cps.

In some embodiments, the third and/or fourth (meth)acrylic acid monomer system is pentaerythritol tetraacrylate, (3) propylene oxide glycerol triacrylate (GPTA), and (10) ethoxylated diacrylate. Any one or two of phenol A diacrylate (EO _{10 BPADA).} (3) in front of GPTA indicates that the number of ethylene oxide (EO) is 3, and (10) in front of BPADA indicates that the number of ethylene oxide (EO) is 10. Furthermore, in the following Table 3, (3) propylene oxide glycerol triacrylate is simply represented as A-3, and (10) ethoxylated bisphenol A diacrylate (EO ₁₀ BPADA) is simply represented as A -4, and the anti-fogging coating composition contains A-3 or A-4, or A-3 and A-4 in equal proportions, as a few exemplary (non-limiting) embodiments of this disclosure .

Specifically, the first, second, and third (meth)acrylic monomers contained in the anti-fog coating composition of the examples (the surface tensions are all between 36 and 42 dyne/cm) have excellent hydrophobicity. After the anti-fog coating composition forms a film layer, its surface becomes hydrophobic, and the hydrophobic group factor and water molecules in the composition repel each other, increasing the contact angle between water molecules and the film surface, and making water vapor on the film surface Gradually condense into droplets with a large contact angle, making it difficult to stay on the surface of the film, and will continue to automatically slide off (that is, produce a "lotus effect"), so as to achieve the effect of anti-fogging or waterproofing. Furthermore, the third (meth)acrylic monomer (and/or the fourth (meth)acrylic monomer) of some embodiments has high hardness, excellent weather resistance and abrasion resistance (such as scratch resistance and (Scratch resistance and other characteristics), even if the film formed is repeatedly cleaned and wiped during daily use, it is not easy to cause scratches on the surface of the film, and it has good abrasion resistance.

Therefore, the composition proposed according to the embodiments of the present disclosure can effectively extend the timeliness of the anti-fog coating, so that the surface of the formed optical film (for example, as an explosion-proof film) not only has hydrophobicity but also achieves the effect of anti-fog and waterproof, but also has an explosion-proof film The required sufficient hardness, excellent weather resistance and abrasion resistance, such as scratch resistance and scratch resistance.

The anti-fogging coating composition of the embodiments of the present disclosure may further include other compounds to further improve the anti-fogging and/or abrasion and scratch resistance properties of the composition. For example, in some embodiments, the anti-fog coating composition further includes a monofunctional or multifunctional aliphatic urethane acrylate oligomer. Among them, it is preferable (but not limited) to include a multifunctional hydrophobic aliphatic urethane acrylate oligomer. The monofunctional or multifunctional aliphatic urethane acrylate oligomer has excellent optical properties, and can make the anti-fog coating composition have abrasion resistance and scratch resistance, and good water resistance after film formation. In some embodiments, the content of the aliphatic urethane acrylate oligomer is (meth)acrylic monomers and oligomers (for example, the first, second and third (meth)acrylic monomers and fatty acids). Group urethane acrylate oligomer) 20wt% to 30wt% of the total weight.

In addition, in some embodiments, the monofunctional or multifunctional aliphatic urethane acrylate oligomer contained in the anti-fog coating composition has a refractive index greater than or equal to 1.48, and has non-yellowing properties, so that the formed film The layer can have high light transmittance. For example, the optical film formed by the anti-fog coating composition of the examples has a light transmittance of 88% or more.

According to some embodiments of the present disclosure, the anti-fog coating composition is a light-hardening composition, and therefore, the anti-fog coating composition further includes a photoinitiator. When the anti-fog coating composition is irradiated with ultraviolet light, the photoinitiator is triggered to generate free radicals or cationic reactive groups. These highly reactive free radicals or cationic groups undergo a chain extension reaction with, for example, acrylic monomers or epoxy monomers and/or corresponding oligomers contained in the composition. Since the reactivity of free radical reaction or cationic reaction is very fast, the reactants can complete the reaction within a short time (for example, a few seconds to a few minutes), and form a functional polymer. For example, the examples have Optical film with anti-fog effect.

In some embodiments, the photoinitiator contained in the anti-fog coating composition is a (meth)acrylic monomer and an oligomer (such as the first, second, and third (meth)acrylic monomers). And aliphatic urethane acrylate oligomer) 5wt% of the total weight. In some embodiments, the photoinitiator includes an organic peroxide, an azo compound, or a combination of the foregoing, to induce the anti-fog coating composition to undergo an ultraviolet curing reaction to form an optical film with an anti-fog effect. Among them, the photoinitiator contained in the composition is an aromatic carbonyl compound, such as a phenyl ketone compound, which has a better effect.

In some embodiments, phenyl ketone compounds are used as photoinitiators added to the composition, for example, 1-hydroxycyclohexyl phenyl ketone, 1,2-diphenyl ethylenedione (Benzil) , Benzophenone, Benzoin, the aforementioned ether derivatives, or a combination of the aforementioned. In some examples (such as the following test examples and comparative examples), 1-hydroxycyclohexyl phenyl ketone (trade name IRGACURE 184, purchased from BASF) is used as the photoinitiator.

According to the embodiments of the present disclosure, the anti-fog coating composition may further include other additives, such as additives with polyether-modified acrylic functional groups. In some embodiments, the content of additives is (meth)acrylic monomers and oligomers (for example, the first, second, and third (meth)acrylic monomers and aliphatic urethane acrylate oligomers) 0.05wt%~1wt% of the total weight. Polyether modified acrylic functional group can promote the combination of organic polymer and inorganic mineral surface, so that the composition will retain its strength after long-term use after film formation (such as forming an optical film with anti-fogging effect), and has sufficient Hardness, thereby extending the service life of the film on the application product. In some embodiments, the additive is an organopolydimethylsiloxane having a polyether-modified acrylic functional group.

According to an embodiment of the present disclosure, an optical film is further provided, which includes at least a base film and an anti-fog coating formed on the base film, wherein the anti-fog coating is used to harden the anti-fog coating composition as in the above embodiment And formed. For example, the anti-fog coating composition coated on the base film is irradiated with ultraviolet light to cause the components contained in it to produce a photohardening reaction, and the anti-fog coating is quickly formed on the base film. In some embodiments, the anti-fog coating has a pencil hardness greater than 3H. The anti-fog coating of the embodiment also has an explosion-proof effect.

In addition, in order to facilitate the temporary storage of the optical film and the subsequent bonding between the optical film and the application product (such as a display device), other film layers, such as protective films, adhesives, can be provided on the upper and lower sides of the optical film proposed in the above embodiments. Layer and release film, etc. to form a composite film layer structure. FIG. 1 is a schematic cross-sectional view of a composite film structure including optical films of some embodiments of the disclosure. As shown in FIG. 1, the composite film layer structure 10 includes a base film 100 and an anti-fog coating 120 formed on the first surface 101 of the base film 100 to form the optical film F1 proposed in the foregoing embodiment.

The base film 100 of the embodiment is, for example, a flexible transparent substrate or a transparent optical film. In some embodiments, the base film is made of polyethylene terephthalate (PET), triacetate cellulose (TAC), cycloolefin polymer (COP), Polycarbonate (PC), polymethyl methacrylate (PMMA), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), propylene oxide (PO), co-extrusion Materials such as oriented polypropylene (OPP) or a combination thereof. Since the soft transparent substrate or transparent optical film is penetrated by moisture in a high temperature and high humidity environment, white fog will be generated on the surface of the substrate. Therefore, if the base film 100 is coated and hardened to form an anti-fog coating of the embodiment 120, the optical film F1 can achieve the purpose of anti-fogging. In some embodiments, the thickness of the anti-fog coating 120 is 20 μm-40 μm, and preferably 25 μm-30 μm. The content of the anti-fog coating composition and the film forming method required to form the anti-fog coating 120 of the embodiment have been described above, and the description will not be repeated here.

Referring again to FIG. 1, the composite film layer structure 10 further includes an adhesive layer 140 formed on the second surface 102 (relative to the first surface 101) of the base film 100, and a surface formed on the surface 121 of the anti-fog coating 120 The protective film 160 and the release film 180 formed on the surface 142 of the adhesive layer 140. The adhesive layer 140 is, for example, a pressure sensitive adhesive (PSA) or other suitable adhesive materials. The surface protective film 160 prevents dust from contaminating the anti-fog coating 120 and avoids damage to the anti-fog coating 120 during storage or transportation. The surface protective film 160 can also be removed after the optical film and the application product are set up. The release film 180 covers the adhesive layer 140 to prevent adhesion between the different composite film layer structures 10, and is removed when the optical film and the application product (such as a display device) are to be bonded together.

The optical film of the embodiment can be set above the application product or set inside the application product, and the setting position can be appropriately adjusted according to application requirements. The following is an example of setting the optical film on the top of the application product.

FIG. 2 is a schematic cross-sectional view of a display device according to some embodiments of the disclosure. As shown in FIG. 2, the display device 30 includes a touch display unit 20 and a composite film structure 10' disposed on the touch display unit 20. Wherein, the composite film layer structure 10' includes the base film 100, the anti-fog coating 120 and the adhesion layer 140 as described above. The optical film F1 (ie, the base film 100 and the anti-fog coating 120) of the embodiment is attached to the touch display unit 20 through the adhesive layer 140.

In some embodiments, the touch display unit 20 includes, for example, a display module 200, a polarizing plate 201 (the upper polarizing plate is drawn in the drawing and the lower polarizing plate is omitted), one or more optical film layers 203 located above the polarizing plate 201, four weeks the sealant 205 is located a top surface of the polarizer 201 L _a of an air layer between the optical film and polarizing plate 203 and 201, and 203 are positioned above the optical film touch module 207, wherein the touch module 207 for example, an adhesive layer is attached to L _G 203 on the optical film. Of course, the optical film F1 of the embodiment can also be placed on other types of application products, including the type that can be placed on or inside other touch display units that are different in structure from the touch display unit 20. This disclosure does not apply to this. Don't make any restrictions.

The optical film prepared according to the anti-fog coating composition proposed in the present disclosure has hydrophobicity on its surface and has anti-fog and waterproof functions, and has sufficient hardness, excellent weather resistance and abrasion resistance, and overcomes the current market The anti-fog film sold is not resistant to scratches and scratches. The characteristics of the optical film prepared according to the anti-fog coating composition proposed in the present disclosure are also suitable for application as an explosion-proof film.

In order to make the above and other objectives, features, and advantages of the present disclosure more obvious and understandable, several examples and comparative examples are given below to illustrate the preparation of the anti-fog coating composition. The anti-fog coating composition in these examples is The base film is hardened to form a film, and several tests are performed on these hardened films to analyze and evaluate the characteristics of the film.

In addition, the various detection methods of the cured film characteristics analyzed in the examples and comparative examples are briefly described as follows. In the subsequent analysis of the detection results of the various embodiments and comparative examples, the detection method will not be repeated.

1. Tightness test:

The test method is to use a 100-grid knife to cut the 100-grid on the film, stick it on the surface of the film with 3M (#600) tape, and then quickly pull the tape off for the adhesion test. The classification is based on the amount of film sticking off by the tape.

Observe the surface of the film layer, if no film layer is stuck together by the tape, the grade is 5B; if there is less than 5% of the film layer is stuck together by the tape, the grade is 4B; if there is 5% -15% of the film layer is stuck together by the tape, the grade is 3B; if 15%-35% of the film layer is stuck together by the tape, the grade is 2B; if there is 35%-65% of the film layer If it is stuck together by tape, the grade is 1B; if more than 65% of the film layer is stuck together by tape, the grade is 0B.

2. Initial characteristics of anti-fog film:

The test method is to fill a beaker with hot water at a temperature of 80°C, and cover the anti-fogging surface of the hardened film on the beaker, and observe after 2 minutes whether a water film is formed and does not fog.

3. Anti-fog effect and abrasion resistance test

The test method is to rub the surface with a dust-free paper weighing 300g in water (60 wipes per minute) for a total of 10,000 rubs. After that, fill the beaker with hot water at a temperature of 80°C, and cover the anti-fogging surface of the hardened film on the beaker, and observe whether there is no fogging after 2 minutes.

4. Soaking test:

The test method is to immerse the hardened film in distilled water at a temperature of 30°C and 50°C for 1 day, and then conduct an anti-fogging test. Fill a beaker with hot water at a temperature of 80°C, and cover the anti-fogging surface of the hardened film on the beaker for 2 minutes. Then observe whether there is no fogging.

5. Low temperature test:

The test method is to put the hardened film in a refrigerator at a temperature of -40°C and freeze for 500 hours. After taking it out, observe the anti-fogging function of the film. Fill a beaker with 80°C hot water and cover the anti-fogging surface of the hardened film on the beaker. Observe whether there is no fogging after 2 minutes.

6. High temperature test:

The test method is to hang the anti-fog film vertically, place it in a ring tester with a temperature of 85℃ and a relative humidity of 85%, take it out after 216 hours, and fill it with 80℃ hot water in a beaker to cover the anti-fog surface of the hardened film On the beaker, observe after 2 minutes, and after cutting out 100 grids, test the adhesion with 3M (#600) tape.

7. High temperature and humidity test II:

The test method is to hang the hardened film vertically, place it in a ring tester at a temperature of 85°C, and take it out after 240 hours, fill it with 80°C hot water in a beaker, and cover the anti-fogging surface of the hardened film on the beaker, 2 After a few minutes, observe whether there is no fogging, and after cutting out 100 grids, conduct an adhesion test with 3M (#600) tape to observe whether it peels off.

Eight, penetrating haze

The test method is to test the penetration rate of the hardened film with the spectrometer NDH-5000 (wavelength 450nm~500nm). Among them, a penetration rate greater than 88% is better.

9. Falling ball test:

The test method is to attach the test sample to 8-inch glass (glass thickness 0.7mm), the height of the 4-corner frame is 2mm from the ground, and the kinetic energy of the ball falling is 0.66 joules (J) as the test level, that is, using a steel ball weighing 67g, It falls vertically and freely at a height of 100cm. A total of 5 points are tested for each piece, and each point is tested once. Observe the glass breakage when the sample is hit by a steel ball, and determine the degree of breakage.

10. Pencil hardness test:

According to JIS K5300-1990, the sample is pre-treated: placed in a moisture-proof box with a temperature of 23°C and a relative humidity of 30%-50% for 24 hours.

Pencil hardness test. The pencil hardness test conditions include the selection of 1200# sandpaper and a pencil made by Mitsubishi (grip strength, weight 500g). Set the pencil at 45 degrees, and the moving speed is 0.5mm/sec. Measurement method: longitudinal (Machine Direction, MD), transverse (Transverse Direction, TD) (5).

Take the results 3H, 4H, and 5H in the table as examples. In this pencil hardness test, according to the JIS K5400 pencil hardness test method (when the coating film is scratched), the pencil made by Mitsubishi Japan used in the five scratch test , If there are two or more layers that are considered to have not scratched the substrate or bottom coating film of the sample, use the pencil with the previous pencil hardness mark for the same test, until the selected coating film is scratched by two or two For the pencil above the road, write down the hardness mark which is one digit after the pencil hardness mark.

N/5 display result (N is OK number); Final judgment: If 3/5 or greater in the sampling full-angle hand direction, it is OK.

11. Wear resistance test:

Use an 800g weight to press on ^{steel wool (#0000) with an area size of 4cm 2} to rub the film, counting back and forth as one cycle at a time, for a total of 10 cycles. After the end, judge whether the surface of the film is scratched.

12. Surface tension test:

Using the surface tension meter SIGMA 703D, the method is to use the platinum ring as the sensing interface, immerse the platinum ring in the liquid and slowly pull it up, so that the platinum ring and the liquid form a liquid column, and finally the liquid surface separates from the platinum ring. The platinum ring method is to sense the maximum value of the platinum ring and the liquid sample before the final separation, and convert it to the surface tension value of the liquid.

Table 1 and Table 2 first list the relevant codes and relevant characteristics of the components used in the anti-fog coating composition of the 8 embodiments and 20 comparative examples of this disclosure.

Table 3 lists the component ratios and weight percentages of the anti-fog coating composition in 8 examples and 20 comparative examples of this disclosure. Tables 4 and 5 list the relevant characteristics of the composition and list the above-mentioned components. The film method is the test result of the hardened film made of the composition after a number of tests.

A-2 乙氧化三羥甲基丙烷三丙烯酸酯(EO ₃TMPTA，購自SARTOMER)（SR454）

A-3 丙氧化丙三醇三丙烯酸酯(GPTA)(SR-9020，購自SARTOMER)

A-4 (10)乙氧化双酚A二丙烯酸酯(EO ₁₀BPADA)(SR-580，購自SARTOMER)

A-5 1,6-己二醇二丙烯酸酯(HDDA)(SR-238，購自SARTOMER)

A-6 (30)乙氧化双酚A二丙烯酸酯(EO ₃₀BPADA)(M2300，購自MIWON)

B (5)乙氧化甲基丙烯羥乙酯(CD570，購自SARTOMER)

C-1 丙烯酸聚氨酯(CN968，購自SARTOMER)

C-2 脂肪族聚氨酯丙烯酸酯(CN9013，購自SARTOMER)

D 1-羥基環己基苯基酮(IRGACURE 184，購自BASF)

E 聚醚改性丙烯酸官能基-有機聚二甲基硅氧烷添加劑(UV3500，購自BYK)

Table 1 Codename Ingredients Structural formula A-1 Diethylene glycol acrylate (SR-230, purchased from SARTOMER)

A-2 Ethoxylated trimethylolpropane triacrylate (EO ₃ TMPTA, purchased from SARTOMER) (SR454)

A-3 Propoxyglycerol triacrylate (GPTA) (SR-9020, purchased from SARTOMER)

A-4 (10) Ethoxylated bisphenol A diacrylate (EO ₁₀ BPADA) (SR-580, purchased from SARTOMER)

A-5 1,6-Hexanediol diacrylate (HDDA) (SR-238, purchased from SARTOMER)

A-6 (30) Ethoxylated bisphenol A diacrylate (EO ₃₀ BPADA) (M2300, purchased from MIWON)

B (5) Ethoxylated hydroxyethyl methacrylate (CD570, purchased from SARTOMER)

C-1 Acrylic polyurethane (CN968, purchased from SARTOMER)

C-2 Aliphatic urethane acrylate (CN9013, purchased from SARTOMER)

D 1-Hydroxycyclohexyl phenyl ketone (IRGACURE 184, purchased from BASF)

E Polyether modified acrylic functional group-organic polydimethylsiloxane additive (UV3500, purchased from BYK)

Among them, the above A-1 to A-6 are hydrophobic acrylic monomers, B is hydrophilic acrylic monomers, C-1 and C-2 are polyurethane (meth)acrylic oligomers, and D is a photoinitiator, E is other additives.

The surface tension (mN/m), viscosity (temperature 25°C), glass transition temperature (Tg,°C), refractive index of each component, and related characteristics that can be given to the composition are described in Table 2. Table 2 Codename Surface tension (mN/m) Viscosity (cps, 25℃) Glass transition temperature (℃) Refractive index Hydrophobic parameter (XlogP) Characteristic description A-1 38.2 12 100 1.463 1 Low volatility, high boiling point A-2 39.6 60 -40 1.471 2.2 Good adhesion, high reactivity A-3 36.1 95 18 1.462 2.4 Weather resistance, fast curing, abrasion resistance A-4 42 410 -1 1.516 1.6 Good adhesion, high hardness A-5 35.7 9 43 1.456 2.6 Fast curing, high reactivity A-6 44.3 680 -57 1.493 1.6 Good flexibility B 38.2 51 -15 1.453 0.5 Enhance hydrophilicity C-1 18,000 145 1.486 Low viscosity, scratch resistance, fast curing C-2 37 10,000 (60℃) 102 1.4982 Abrasion resistance, scratch resistance, fast curing D Short-wavelength photoinitiator E With unsaturated double bonds. With high slip

Table 3 lists the component ratios and weight percentages contained in the anti-fog coating compositions of the examples and comparative examples. Among them, the total weight of monomer materials (such as acrylic monomers) and oligomers is 100%, and components D and E are additional components.

table 3 A-1 A-2 A-3 A-4 A-5 A-6 B C-1 C-2 Additional D E Example 1 30% 30% 20% - - - - - 20% 5% 1% Example 2 25% 25% 30% - - - - - 20% 5% 1% Example 3 20% 20% 30% - - - - - 30% 5% 1% Example 4 20% 20% 30% - - - - - 30% 5% 0.1% Example 5 30% 30% - 20% - - - - 20% 5% 1% Example 6 20% 20% - 30% - - - - 30% 5% 1% Example 7 30% 30% 10% 10% - - - - 20% 5% 1% Example 8 30% 30% 5% 5% - - - - 30% 5% 1% Comparative example 1 15% 25% 30% - - - - - 30% 5% 1% Comparative example 2 30.5% 30.5% 19% - - - - - 20% 5% 1% Comparative example 3 19.5% 19.5% 31% - - - - - 30% 5% 1% Comparative example 4 31% 31% 18% - - - - - 20% 5% 1% Comparative example 5 30.5% 30.5% 20% - - - - - 19% 5% 1% Comparative example 6 24.5% 24.5% 20% - - - - - 31% 5% 1% Comparative example 7 30% 30% - - 20% - - - 20% 5% 1% Comparative example 8 20% 20% - - 30% - - - 30% 5% 1% Comparative example 9 30% 30% - - - 20% - - 20% 5% 1% Comparative example 10 20% 20% - - - 30% - - 30% 5% 1% Comparative example 11 20% 20% - - - - 30% - 30% 5% 1% Comparative example 12 20% 20% 30% - - - - 30% - 5% 1% Comparative example 13 30% 30% 20% - - - - - 20% 5% Comparative example 14 30% 30% 20% - - - - - 20% 5% 1.1% Comparative example 15 40% - 20% 20% - - - - 20% 5% 1% Comparative example 16 60% - 20% - - - - - 20% 5% 1% Comparative example 17 - 40% 20% 20% - - - - 20% 5% 1% Comparative Example 18 - 60% 20% - - - - - 20% 5% 1% Comparative Example 19 30% - 25% 25% - - - - 20% 5% 1% Comparative example 20 - 30% 25% 25% - - - - 20% 5% 1%

Furthermore, the surface tension and viscosity of the anti-fog coating composition of each example and comparative example were measured, and the thickness of the cured film prepared by the composition according to the above-mentioned film forming method, and the adhesion test and anti-fog of each cured film were performed. Initial characteristics of fog film, anti-fogging effect, abrasion resistance test, water soaking test. The results are summarized in Table 4.

Table 4 Surface tension (mN/m) Viscosity (cps, 25℃ Thickness (µm) Closeness test Initial characteristics of anti-fog film (form a water film without fogging) Anti-fog effect and abrasion test (10,000 cycles, no fog in anti-fog test) Water soaking test (no fogging) Example 1 36.96 318 twenty two 5B OK OK OK Example 2 36.68 342 26 5B OK OK OK Example 3 36.02 428 34 5B OK OK OK Example 4 36.02 542 38 5B OK OK OK Example 5 38.14 362 32 5B OK OK OK Example 6 37.75 598 40 5B OK OK OK Example 7 36.82 586 40 5B OK OK OK Example 8 36.88 426 33 5B OK OK OK Comparative example 1 36.06 358 27 5B NG - - Comparative example 2 36.99 302 20 4B OK OK OK Comparative example 3 35.87 868 56 100/100 OK OK OK Comparative example 4 37.01 286 18 3B OK NG OK Comparative example 5 37.02 308 twenty one 4B OK OK OK Comparative example 6 36.22 442 35 5B OK OK OK Comparative example 7 36.88 258 16 4B NG NG NG Comparative example 8 35.82 362 32 3B NG NG NG Comparative example 9 38.6 332 25 1B OK NG OK Comparative example 10 38.48 838 55 0B OK NG NG Comparative example 11 35.92 726 46 0B White mist - - Comparative example 12 37.19 580 38 5B NG NG NG Comparative example 13 36.96 320 twenty two 4B OK OK OK Comparative example 14 36.96 322 twenty two 5B OK OK OK Comparative example 15 35.82 850 55 4B OK OK OK Comparative example 16 32.48 280 20 0B OK NG NG Comparative example 17 37.12 1024 68 3B~4B OK OK OK Comparative Example 18 39.22 302 25 3B OK OK OK Comparative Example 19 37.7 686 45 3B~4B - - - Comparative example 20 36.26 772 48 3B~4B - - -

According to the results in Table 4, the viscosity of the anti-fog coating composition of the embodiment at a temperature of 25° C. does not exceed 600 cps, for example, between 300 cps and 600 cps. The thickness of the hardened film prepared with the anti-fog coating composition of the embodiment is between 20 μm and 40 μm. In addition, the hardened film produced by the anti-fog coating composition of the embodiment has no film layer stuck together by the tape during the adhesion test, which belongs to the 5B level.

In addition, the cured film prepared by the anti-fog coating composition of the example was covered on a beaker containing hot water at a temperature of 80° C. for 2 minutes, and a water film was formed without fogging (initial characteristics of the anti-fog film). After rubbing the surface of the hardened film with a dust-free paper weighing 300g in water 10,000 times, then covering the hardened film on a beaker filled with hot water at a temperature of 80℃ for 2 minutes, no fogging occurred (anti-fogging effect and abrasion test) ). After immersing the cured film in distilled water at 30°C and 50°C for 1 day, and covering the cured film on a beaker filled with hot water at 80°C for 2 minutes, there was no fogging phenomenon (soaking test). Therefore, the cured film prepared by the anti-fog coating composition of the examples does indeed have an excellent anti-fog effect, as well as excellent scratch resistance and water resistance.

Furthermore, weather resistance test, penetration test, falling ball test, pencil hardness test, and abrasion resistance test were also performed on the cured film prepared according to the anti-fog coating composition of the embodiment and the comparative example. The test results are summarized in Table 5.

table 5 Weather resistance test Penetration test Drop ball test Pencil hardness test Abrasion resistance test determination 85℃ (no peeling after adhesion test), no fogging after anti-fog test -40℃ (no peeling after adhesion test), no fogging after anti-fog test 85℃ and relative humidity 85% (no peeling after adhesion test), no fogging after anti-fog test Penetration rate (%) Slight ◎ Moderate ○ Severe △ Severe glass splash╳ Pencil hardness (500g) 3H Load per unit area (200g/cm ² ) nothing unusual Example 1 OK OK OK 89.2 ◎ 3H A OK Example 2 OK OK OK 88.8 ◎ 3H A OK Example 3 OK OK OK 88.2 ◎ 3H~4H A OK Example 4 OK OK OK 88.2 ◎ 3H A' OK Example 5 OK OK OK 88.6 ◎ 3H A OK Example 6 OK OK OK 88.4 ◎ 3H A OK Example 7 OK OK OK 88.2 ◎ 3H A OK Example 8 OK OK OK 88.32 ◎ 3H A' OK Comparative example 1 - - - - - - - NG Comparative example 2 NG NG NG 89 ◎ 3H A NG Comparative example 3 OK OK OK 86.8 ◎ 3H A NG Comparative example 4 NG NG NG 89.8 ◎ 2H~3H A NG Comparative example 5 NG NG NG 90.2 ◎~○ 2H A' NG Comparative example 6 OK OK OK 85 ◎ 4H A NG Comparative example 7 NG NG NG 88.2 ○ 2H A' NG Comparative example 8 NG NG NG 80.2 ○~△ 2H B NG Comparative example 9 NG NG NG NG - - - NG Comparative example 10 NG NG NG NG - - - NG Comparative example 11 - - - - - - - NG Comparative example 12 NG NG NG NG ◎ 3H A NG Comparative example 13 OK OK OK 89.6 ◎ 2H A' NG Comparative example 14 OK OK OK 88.21 ◎~○ 3H~4H B NG Comparative example 15 OK OK OK 87.02 ○ 3H~4H B NG Comparative example 16 NG NG NG 89.21 ○~△ 2H B NG Comparative example 17 OK OK OK 86.21 ○~△ 2H B NG Comparative Example 18 OK OK OK 87.28 ○~△ 2H B NG Comparative Example 19 - - - 86.88 - - - NG Comparative example 20 - - - 87.02 - - - NG

In the above abrasion test, the film layer was rubbed with steel wool with a load per unit area of 200g/cm ² and after 10 cycles (one back and forth is one cycle), check whether there are any scars on the surface of the film. A in Table 5 represents 0 scars, A'stands for 1-10 scars, B stands for 11-20 scars, C stands for 21-30 scars, and D stands for more than 30 scars.

In summary, the above-mentioned Table 4-5 summarizes the various test items and comprehensive judgment results of the films prepared in the examples and comparative examples, and the results show that the anti-fog coating composition prepared according to the examples The hardened film passed the aforementioned tests; while the film layer made according to the composition of the comparative example failed all the tests. For example, in Comparative Examples 15-18, only one of the monomer A-1 and the monomer A-2 was used, and the two different monomers A-1 and A-2 were not used in the same proportion by weight (1: 1) Mixed, the falling ball test, pencil hardness and abrasion resistance test all fail to meet the required film characteristics. For another example, in Comparative Example 7-11, only monomer A-1 and monomer A-2 are used, but monomer A-3 or A-4 is not used, the resulting film fails the weather resistance test and the falling ball test. , Pencil hardness test and abrasion resistance test.

Furthermore, according to the results in Table 5, the cured film prepared according to the anti-fog coating composition of the embodiment is either frozen at a low temperature of -40°C (low temperature test) or at a high temperature of 85°C (low temperature test) or at a high temperature of 85°C. After being placed under the humidity of 85% (high temperature and high humidity test) for more than 200 hours, after covering it on a beaker containing hot water at a temperature of 80°C for 2 minutes, there was no fogging, and the hardened film was tested for adhesion. None of the film layers are stuck together and peeled off by the tape. Therefore, the cured film produced by the anti-fog coating composition of the example has excellent weather resistance.

Furthermore, the cured films produced by the anti-fog coating compositions of the examples all have a penetration rate of greater than 88%. Therefore, when the anti-fog coating composition of the embodiment is applied to a transparent substrate, it still has a good transmittance, and will not reduce the transmittance of the substrate and affect the product performance.

In addition, the hardened film produced by the anti-fog coating composition of the embodiment was not damaged or only slightly cracked in the falling ball test, and the pencil hardness test results were all 3H or 3H-4H. Furthermore, use steel wool with a unit area load of 200 g/cm ^{2 to} rub the film layer for 10 cycles (one back and forth is one cycle), observe the film surface of the cured film made of the anti-fog coating composition of the example, and No scars, or only 1-3 scars appear (abrasion test). Therefore, the hardened films of the examples all have sufficient film strength and hardness, and have excellent wear resistance performance.

In summary, the anti-fog coating composition proposed in the embodiments of the present disclosure can effectively prolong the timeliness of the anti-fog coating, so that the surface of the formed film not only has hydrophobicity and achieves anti-fog and waterproof effects, but also has sufficient hardness and excellent The weather resistance and abrasion resistance (in line with such properties as scratch resistance and abrasion resistance required by explosion-proof membranes). Therefore, the anti-fog coating composition proposed in the embodiment of the present disclosure can simultaneously improve the optical and mechanical properties of the film prepared thereon, and can improve the performance of the product in practical application, for example, the optical film layer of the embodiment is provided The products can have anti-fog and explosion-proof effects at the same time, which is of great economic value. In addition, the anti-fog coating composition proposed in the embodiment forms a hardened film layer, and the manufacturing method is simple and does not significantly increase the additional manufacturing cost.

Although the present invention has been disclosed in several preferred embodiments as described above, it is not intended to limit the present invention. Anyone with ordinary knowledge in the art can make any changes and modifications without departing from the spirit and scope of the present invention. Retouching, therefore, the scope of protection of the present invention shall be subject to the scope of the attached patent application.

10, 10 ': the composite film structure 100: a base film 101: a first surface 102: second surface 120: anti-fog coating 140, L _G: 121,142 adhesive layer: surface 160: surface protection film 180: release film F1: optical film 20: The touch display unit 200: The display module 201: polarizer 203: optical film L _A: air layer 205: sealant 207: touch module 30: a display device

FIG. 1 is a schematic cross-sectional view of a composite film structure including optical films of some embodiments of the disclosure. FIG. 2 is a schematic cross-sectional view of a display device according to some embodiments of the disclosure.

10: Composite membrane layer structure

100: base film

101: first surface

102: second surface

120: Anti-fog coating

140: Adhesive layer

121, 142: Surface

160: Surface protective film

180: Release film

F1: Optical film

Claims (19)

An anti-fog coating composition comprising: two different first (meth)acrylic monomers and second (meth)acrylic monomers, the viscosity at 25°C is less than 65cps, and at 20°C The following surface tensions are in the range of 36 dyne/cm ~ 42 dyne/cm, wherein the first (meth)acrylic monomer and the second (meth)acrylic monomer are the same The third (meth)acrylic monomer has a viscosity of 90cps~500cps at 25℃, and its surface tension at 20℃ is 36 dyne. /Cm~42 dyne/cm; and aliphatic urethane acrylate oligomers, wherein the first, second and third (meth)acrylic monomers and the aliphatic urethane acrylate oligomers The total weight of the substance is 100wt%, the content of the first (meth)acrylic monomer and the second (meth)acrylic monomer is 40wt% to 60wt%; and/or the third (former) The content of the base) acrylic monomer is 20% by weight to 30% by weight, and the content of the aliphatic urethane acrylate oligomer is 20% by weight to 30% by weight. The anti-fog coating composition according to claim 1, wherein the hydrophobic parameter (XlogP) of the first (meth)acrylic monomer and the hydrophobic parameter (XlogP) of the second (meth)acrylic monomer are The 1/2 of the total is less than 1.6; and/or the hydrophobic parameter (XlogP) of the third (meth)acrylic monomer is less than 2.5. The anti-fog coating composition according to claim 1, further comprising: a fourth (meth)acrylic monomer different from the third (meth)acrylic monomer, and the fourth (meth)acrylic monomer is The viscosity at 25℃ is 90cps~500cps The surface tension at a temperature of 20°C is between 36 dyne/cm and 42 dyne/cm. The anti-fog coating composition according to claim 3, wherein the third (meth)acrylic monomer and the fourth (meth)acrylic monomer are in the same proportion by weight (1:1) Mixing; and/or the third (meth)acrylic monomer or the fourth (meth)acrylic monomer system is selected from pentaerythritol tetraacrylate, (ethylene oxide number 3) propylene oxide glycerol three Acrylate (GPTA) and (ethylene oxide number 10) ethoxylated bisphenol A diacrylate (EO ₁₀ BPADA) group. The anti-fog coating composition according to claim 1, wherein the surface tension of the first (meth)acrylic monomer and the second (meth)acrylic monomer at a temperature of 20°C are respectively greater than that of the third ( Surface tension of meth)acrylic monomers at a temperature of 20°C. The anti-fog coating composition according to claim 1, wherein the first (meth)acrylic monomer, the second (meth)acrylic monomer, and the third (meth)acrylic monomer are any One has a refractive index between 1.46 and 1.51. The anti-fog coating composition according to claim 1, wherein the aliphatic urethane acrylate oligomer is a monofunctional or multifunctional aliphatic urethane acrylate oligomer, and its refractive index is between 1.46 and 1.51 between. The anti-fog coating composition according to claim 1, wherein the first (meth)acrylic monomer and the second (meth)acrylic monomer system are selected from 2-phenoxyethyl acrylate ( Any two of 2-PEA), diethylene glycol acrylate, and (ethylene oxide number 3) ethoxylated trimethylolpropane triacrylate (EO _{3 TMPTA).} The anti-fog coating composition according to claim 1, further comprising: a photoinitiator, which is the first, second and third (meth)acrylic monomers and the aliphatic urethane acrylate oligomer 5wt% of the total weight, the light start Agents include organic peroxides, azo compounds, or combinations of the foregoing. The anti-fog coating composition according to claim 9, wherein the photoinitiator includes an aromatic carbonyl compound. The anti-fog coating composition according to claim 10, wherein the aromatic carbonyl compound is a phenyl ketone compound. The anti-fog coating composition according to claim 9, wherein the photoinitiator is 1-hydroxycyclohexyl phenyl ketone, 1,2-diphenyl ethylenedione (Benzil), benzophenone ( Benzophenone), Benzoin, the aforementioned ether derivatives, or a combination of the aforementioned. The anti-fog coating composition according to claim 1, further comprising: additives, the content of which is the amount of the first, second and third (meth)acrylic monomers and the aliphatic urethane acrylate oligomer 0.05wt% to 1wt% of the total weight, and the additive has a polyether modified acrylic functional group. The anti-fog coating composition according to claim 13, wherein the additive is an organic polydimethylsiloxane having the polyether-modified acrylic functional group. An optical film, comprising: a base film; and an anti-fog coating formed on the base film, wherein the anti-fog coating is composed of hardening the anti-fog coating described in any one of claims 1 to 14 The thing is formed. The optical film according to claim 15, wherein the anti-fog coating has a pencil hardness greater than 3H; and/or the thickness of the anti-fog coating is 20 μm-40 μm. The optical film described in claim 15 has a light transmittance greater than 88%. The optical film according to claim 15, wherein the base film is a soft transparent optical film. A display device includes: a display module; a touch module arranged above the display module; and the optical film as described in any one of the 15 to 18 patent applications, arranged on the touch Above the control module or between the touch module and the display module.

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