Active energy ray-curable fluorine-containing composition

Abstract

To provide a composition capable of providing a cured film having both high water repellency and high durability.SOLUTION: This invention relates to an active energy ray-curable composition, comprising: (1) inorganic oxide particles having a grain diameter of 300 μm or less; (2) a fluorine-containing polymerizable compound; and (3) a fluorine-free polymerizable compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a novel active energy ray-curable fluorine-containing composition, and in particular to a composition for forming a water-repellent coating film. [Background technology]

[0002] Various water-repellent coating agents are sometimes used to impart water repellency to the surfaces of various materials, such as electronic materials, medical materials, packaging materials, building materials, and clothing. Many compositions containing fluororesins or fluorine compounds are known as such water-repellent coating agents. Among these, a technique has been proposed in which unevenness is imparted to the surface of a coating film to be formed, thereby achieving even higher water repellency.

[0003] For example, a water-repellent coating composition is known that contains a resin solution containing a first fluororesin that can be solidified by drying, and a particle component of a second fluororesin (Patent Document 1).

[0004] Furthermore, for example, a cured film having an uneven surface has been proposed, which is formed using a curable composition containing a compound having a perfluoropolyether group and a curable site, and a curable resin and / or a curable monomer, and further using a mold having an uneven structure (Patent Document 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-216585 [Patent Document 2] JP 2019-2014 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, the method of Patent Document 1 does not provide sufficient durability of the coating film, and when the surface is repeatedly rubbed, the bonding strength between the fine particles or between the fine particles and the resin matrix is ​​weak, which can cause the fine particles to peel off, resulting in the loss of the uneven surface structure over time and a decrease in water repellency.

[0007] Furthermore, the method of Patent Document 2 requires the use of a mold to create the irregularities, and therefore, without such equipment, it is impossible to form a cured film with high water repellency. Moreover, since the irregularities are caused by the cured film itself, there is also a risk that the irregularities will be reduced or lost over time due to wear. On the other hand, if the predetermined irregularities are not formed in such a cured film, high water repellency (particularly a contact angle with water of 150 degrees or more) cannot be obtained.

[0008] Thus, there is a need for the development of technology that will ensure that high water repellency is maintained, but at present such technology has not yet been developed.

[0009] Therefore, a primary object of the present invention is to provide a composition capable of forming a cured film that has both high water repellency and durability. [Means for solving the problem]

[0010] As a result of extensive research into the problems of the prior art, the present inventors discovered that the above object can be achieved by employing a composition that can provide a coating film having a specific structure, and thus completed the present invention.

[0011] That is, the present invention relates to the following active energy ray-curable fluorine-containing composition. 1. An active energy ray-curable composition, (1) inorganic oxide fine particles having a particle size of 300 μm or less; (2) a fluorine-containing polymerizable compound, and (3) fluorine-free polymerizable compounds, An active energy ray-curable fluorine-containing composition comprising: 2. The active energy ray-curable fluorine-containing composition according to item 1, wherein the fluorine-containing polymerizable compound is perfluoropolyether (meth)acrylate. 3. The active energy ray-curable fluorine-containing composition according to item 1 or 2, wherein the fluorine-free polymerizable compound is a fluorine-free (meth)acrylate compound. 4. The active energy ray-curable fluorine-containing composition according to any one of items 1 to 3, wherein the surfaces of the inorganic oxide fine particles are modified with (meth)acryloyl groups. 5. The active energy ray-curable fluorine-containing composition according to any one of items 1 to 4, wherein the content of the inorganic oxide fine particles is 1 to 200 parts by weight per 100 parts by weight of the total of the components of the active energy ray-curable fluorine-containing composition excluding the inorganic oxide fine particles and the solvent. 6. The active energy ray-curable fluorine-containing composition according to any one of items 1 to 5, further comprising a solvent and being liquid in nature. 7. The active energy ray-curable fluorine-containing composition according to any one of items 1 to 6, which is used to form a water-repellent coating film. 8. The active energy ray-curable fluorine-containing composition according to any one of items 1 to 7, further comprising a photopolymerization initiator. [Effects of the Invention]

[0012] According to the present invention, a composition capable of forming a cured film having both high water repellency and durability can be provided. In particular, the composition of the present invention contains a specific curable compound and specific inorganic oxide fine particles, and by curing the composition with active energy rays, a cured film having a predetermined uneven surface and, in some cases, a porous structure can be formed. This makes it possible to obtain high water repellency and high abrasion resistance, and therefore, to maintain high water repellency for a relatively long period of time.

[0013] The active energy ray-curable fluorine-containing composition of the present invention having such characteristics can be widely applied to various materials or products whose surfaces should be imparted with water repellency. [Brief explanation of the drawings]

[0014] [Figure 1] FIG. 2 is a view showing the results of observing the cross section of the cured film obtained in Example 1 with a field emission scanning electron microscope. [Figure 2] FIG. 1 shows the results of observing the cross section of the cured film obtained in Example 32 with a field emission scanning electron microscope. DETAILED DESCRIPTION OF THE INVENTION

[0015] 1. Active energy ray-curable fluorine-containing composition The active energy ray-curable fluorine-containing composition of the present invention (the composition of the present invention) is an active energy ray-curable composition, (1) inorganic oxide fine particles having a particle size of 300 μm or less; (2) a fluorine-containing polymerizable compound, and (3) Fluorine-free polymerizable compounds The present invention is characterized by comprising:

[0016] In the present invention, the term "active energy ray-curable composition" refers to a composition that can be polymerized and cured by active energy rays such as ultraviolet rays and electron beams.

[0017] Each component constituting the composition of the present invention will be specifically described below. In the present invention, unless otherwise specified, acryloyl groups and methacryloyl groups will be collectively referred to as "(meth)acryloyl groups." Acrylates and methacrylates will be collectively referred to as "(meth)acrylates."

[0018] Inorganic oxide fine particles The inorganic oxide fine particles used have a particle size of 300 μm or less. When the composition of the present invention contains such inorganic oxide fine particles, extremely fine irregularities can be formed on the surface of the coating film when the composition is formed into a coating film, which contributes to high water repellency.

[0019] The shape of the inorganic oxide particles is not particularly limited, and may be any shape such as spherical, scaly, needle-like, or irregular, as long as it allows the formation of fine irregularities on the surface.

[0020] The type of inorganic oxide is not particularly limited as long as the above-mentioned effects can be obtained, and examples thereof include inorganic oxides such as silicon oxide, titanium oxide, and aluminum oxide. These inorganic oxides can be used alone or in combination of two or more. As in the above specific examples, in the present invention, inorganic oxides also include metal oxides.

[0021] These inorganic oxide fine particles themselves may be publicly known or commercially available. For example, silicon oxides include those with the product names "AEROSIL 50," "AEROSIL 150," "AEROSIL 200," "AEROSIL 300," "AEROSIL 380," "AEROSIL R972," "AEROSIL R972V," "AEROSIL R972CF," "AEROSIL R974," "AEROSIL RX200," "AEROSIL RY200," "AEROSIL R202," "AEROSIL R805," "AEROSIL R812," and "AEROSIL R812S" (all manufactured by Nippon Aerosil Co., Ltd.), "YA010C," "YA050C," "YC100C," "SO-C1," "SO-C2," "SO-C4," "SO-C5," "SO-C6," "FE9 series," "FEB series," "FED series," and "FEF series" (all manufactured by Admattex Co., Ltd.), and "KYKLOS Examples of titanium oxide include the product name "AEROXIDE TiO2T805" (manufactured by Nippon Aerosil Co., Ltd.). Examples of aluminum oxide include the product name "AEROXIDE Alu C" (manufactured by Nippon Aerosil Co., Ltd.).

[0022] In particular, in the present invention, inorganic oxide fine particles preferably have functional groups on the surface of each particle. For example, polymerizable functional groups (curable functional groups) such as (meth)acryloyl groups, (meth)acryloyloxy groups, epoxy groups, allyl groups, and vinyl groups are preferred. This strengthens the bond between the inorganic oxide fine particles and the resin matrix in the cured film formed by active energy ray curing, resulting in a cured film with superior durability (particularly abrasion resistance). These functional groups can be imparted by surface-treating untreated inorganic oxide fine particles according to a known method. Alternatively, commercially available inorganic oxide fine particles to which such functional groups have been imparted can be used. Examples include products with the product names "AEROSIL R711" and "AEROSIL VP RM50L" (both manufactured by Nippon Aerosil Co., Ltd.).

[0023] The inorganic oxide fine particles to be used may have a particle size of 300 μm or less as described above, but preferably have a particle size of 50 μm or less, more preferably have a particle size of 1 μm or less, and most preferably have a particle size of 200 nm or less. As long as these conditions are met, nanoparticles having an average primary particle size of 1 to 100 nm (particularly 2 to 50 nm) can also be used.

[0024] The composition of the present invention may contain a small amount of particles having a particle size exceeding 300 μm, as long as the effects of the present invention are not impaired. However, it is preferable to remove particles having a particle size exceeding 300 μm by classification or the like.

[0025] In the present invention, the average primary particle size can be measured using a field emission scanning electron microscope (FE-SEM), and if the resolution of the scanning electron microscope is low, it may be measured using another electron microscope such as a transmission electron microscope in combination. Specifically, if the particle shape is spherical, its diameter is considered to be the diameter, and if the particle shape is non-spherical, its longest diameter is considered to be the diameter, and the average value of the diameters of 300 particles randomly selected by observation using a scanning electron microscope or the like is taken to be the average primary particle size.

[0026] The content of inorganic oxide fine particles in the composition of the present invention is not limited, but can be appropriately set within the range of 1 to 200 parts by weight (particularly 5 to 150 parts by weight) per 100 parts by weight of the total components of the composition of the present invention excluding the inorganic oxide fine particles and the solvent (hereinafter, the mixture of these components is also referred to as the "polymerizable mixture"). Therefore, the content of inorganic oxide fine particles in the composition of the present invention can be, for example, about 0.5 to 70% by weight (particularly about 4 to 60% by weight).

[0027] The total of the components of the composition of the present invention excluding the inorganic oxide fine particles and the solvent usually refers to the total (solid content) of the fluorine-containing polymerizable compound, the fluorine-free polymerizable compound, and the photopolymerization initiator.

[0028] A preferred embodiment of the present invention involves the use of two or more inorganic oxide microparticles having different average primary particle diameters within the above particle size range. For example, a first microparticle may be used in combination with a second microparticle having a larger average primary particle diameter than the first microparticles. In this case, the average primary particle diameter of the first microparticles is preferably 1 nm to 20 nm, more preferably 5 nm to 15 nm. The average primary particle diameter of the second microparticles is preferably 21 nm to 200 μm, more preferably 25 nm to 100 μm. The use of two types of microparticles with different sizes ensures the formation of a nanoscale uneven structure (surface unevenness) that contributes to water repellency, a microscale uneven structure (surface unevenness) that contributes to durability, and, in some cases, a porous structure, resulting in further improved water repellency and durability.

[0029] In this case, the content of the first microparticles is preferably 1 part by weight or more and 50 parts by weight or less, and more preferably 10 parts by weight or more and 40 parts by weight or less, relative to 100 parts by weight of the polymerizable mixture. The content of the second microparticles is preferably 1 part by weight or more and 100 parts by weight or less, and more preferably 10 parts by weight or more and 50 parts by weight or less, relative to 100 parts by weight of the polymerizable mixture. If the first microparticles and second microparticles are in these ranges, the water repellency and durability will be even better.

[0030] The material of the first fine particles and the second fine particles is not particularly limited, and they may be the same material or different materials from each other.

[0031] Fluorine-containing polymerizable compounds The fluorine-containing polymerizable compound is a basic component for imparting water repellency to the cured film formed from the composition of the present invention.

[0032] The fluorine-containing polymerizable compound is not particularly limited as long as it has a fluorine-containing organic group and a polymerizable (curable) functional group (polymerizable double bond). The fluorine-containing polymerizable compound includes not only compounds used as monomers before polymerization, but also compounds with relatively large molecular weights, generally called oligomers or macromonomers.

[0033] Examples of the above-mentioned organic group containing fluorine include a) an organic group having a perfluoroalkyl structure, b) an organic group having a perfluoropolyether structure, c) an alkylene group in which some of the hydrogen atoms are substituted with fluorine atoms, etc. Among these, an organic group having a perfluoropolyether structure can be preferably used.

[0034] The perfluoropolyether structure has the repeating unit -[C n F 2n O]- (where n is an integer of 1 or more). These may be linear or branched. Therefore, for example, -CF2-, -CF(CF3)-, -CF2CF2-, -CF2CF2CF2-, -CF(CF3)CF2- -CF(CF3)CF2CF2- -CF(CF3)CF(CF3)CF2- These include, but are not limited to:

[0035] In addition, when the repeating unit is composed of two or more of the above repeating units, each -[C n F 2n O]-groups may be the same as or different from each other.

[0036] The polymerizable functional group bonded to the fluorine-containing organic group is not limited, but particularly preferably used are a (meth)acryloyl group, a (meth)acryloyloxy group, an epoxy group, an allyl group, a vinyl group, etc. The fluorine-containing polymerizable compound may have one or more polymerizable functional groups.

[0037] The polymerizable functional group may be bonded to either the end or the side chain of the fluorine-containing organic group.

[0038] Furthermore, the polymerizable functional group may be directly bonded to the fluorine-containing organic group or may be bonded via another organic group (such as a divalent organic group). Therefore, for example, the polymerizable functional group may be bonded to the fluorine-containing organic group via a urethane bond -COONH-, an ester bond -COO-, or the like. Therefore, for example, perfluoropolyether urethane (meth)acrylate, which has a structure in which a (meth)acryloyl group is bonded to a perfluoropolyether group via a urethane bond, can also be used as the fluorine-containing polymerizable compound.

[0039] The molecular weight of the fluorine-containing polymerizable compound may be, but is not limited to, a number average molecular weight of about 100 to 100,000, and therefore compounds having a number average molecular weight of about 500 to 20,000 can also be used.

[0040] Specific examples of fluorine-containing polymerizable compounds include at least one of perfluoroalkyl (meth)acrylate, perfluoroalkyl vinyl ether, perfluoropolyether (meth)acrylate (particularly perfluoropolyether urethane (meth)acrylate), 1H,1H,2H,2H-tridecafluorooctyl acrylate, etc. Among these, perfluoropolyether (meth)acrylate (particularly perfluoropolyether urethane (meth)acrylate) and the like can be preferably used. These compounds have a highly reactive (meth)acryloyl group and a perfluoropolyether group that is excellent in water and oil repellency, droplet removal properties, etc., so that it is possible to more reliably form a cured film with higher water repellency. These compounds can be used alone or in combination.

[0041] In the present invention, the fluorine-containing polymerizable compound itself can be a known or commercially available one. For example, the perfluoropolyether urethane (meth)acrylate is available under the product names "Fluorolink AD1700" and "Fluorolink MD700" (both manufactured by Solvay Specialty Polymers Japan Ltd.), and the 1H,1H,2H,2H-tridecafluorooctyl acrylate is available under the product name "Viscoat 13F" (manufactured by Osaka Organic Chemical Industry Ltd.).

[0042] The content of the fluorine-containing polymerizable compound is not limited, but is usually preferably 5 to 95 parts by weight, and more preferably 30 to 60 parts by weight, per 100 parts by weight of the polymerizable compound. If the content of the fluorine-containing polymerizable compound is 5 parts by weight or more, the water repellency of the cured film will be higher, and if it is 95 parts by weight or less, a polymerization initiator and the like can be appropriately added, making it easier to cure more reliably.

[0043] Fluorine-free polymerizable compounds The fluorine-free polymerizable compound is a polymerizable compound that does not contain fluorine, and has the effect of more reliably reducing the viscosity of the composition of the present invention when a perfluoropolyether acrylate or the like having a relatively high viscosity is used.

[0044] The type of fluorine-free polymerizable compound is not particularly limited as long as it has one or more polymerizable functional groups (curable functional groups) such as (meth)acryloyl groups, (meth)acryloyloxy groups, epoxy groups, allyl groups, vinyl groups, etc., and does not contain fluorine. The type can be changed depending on the additional performance required for the application, such as adhesion to the substrate, chemical resistance, flexibility, weather resistance, etc. Examples include 1,6-hexanediol diacrylate (HDDA), tetrahydrofurfuryl acrylate (THFA), and amine (meth)acrylate. These compounds can be used alone or in combination.

[0045] The content of the fluorine-free polymerizable compound in the composition of the present invention is preferably set to 0.1 to 90 parts by weight per 100 parts by weight of the polymerizable mixture.

[0046] In addition, in the composition of the present invention, the amine (meth)acrylate plays a role in effectively suppressing inhibition of curing on the surface. From this point of view, the amine (meth)acrylate is preferably contained in an amount of 0.1 to 5 parts by weight per 100 parts by weight of the polymerizable mixture.

[0047] Other additives In the composition of the present invention, particularly when ultraviolet light is used as the active energy ray, a photopolymerization initiator can also be used. The photopolymerization initiator is not particularly limited as long as it can cause polymerization upon ultraviolet light irradiation. Therefore, any type of photopolymerization initiator, such as a cleavage-type polymerization initiator or a hydrogen abstraction-type polymerization initiator, can be used. For example, intramolecular cleavage-type initiators include alkylphenones and oxime esters. For example, hydrogen abstraction-type initiators include benzophenone / amines and thioxanthone / amines. These can be used alone or in combination of two or more. These photopolymerization initiators themselves can be known or commercially available. For example, the product name "Omnirad127" (manufactured by IGM Resins BV) can be mentioned.

[0048] The content of the photopolymerization initiator is not particularly limited, but can usually be about 0.1 to 10 parts by weight per 100 parts by weight of the total of the fluorine-containing polymerizable compound and the fluorine-free polymerizable compound.

[0049] In the composition of the present invention, a solvent can be used as needed for the purpose of adjusting viscosity, etc. The solvent is not particularly limited, and examples thereof include organic solvents such as aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbon solvents such as methylcyclohexane and cyclohexane, ester solvents such as ethyl acetate and butyl acetate, ketone solvents such as methyl ethyl ketone and acetone, and alcohol solvents such as isopropyl alcohol and denatured ethanol. These can be used alone or in combination of two or more.

[0050] The amount of solvent used, when used, is not particularly limited, but can be adjusted appropriately to obtain an appropriate viscosity depending on the coating / painting method, etc., within the range of approximately 10 to 500 parts by weight per 100 parts by weight of the total amount of inorganic oxide microparticles and polymerizable mixture, but is not limited to this.

[0051] The composition of the present invention may contain additives such as colorants (dyes, pigments), antistatic agents, antioxidants, UV absorbers, dispersants, surfactants, leveling agents, surface conditioners, anti-sagging agents, thickeners, antifoaming agents, lubricants, etc., within the range that does not impair the effects of the present invention. When any of these additives also falls under the category of inorganic oxide fine particles, they are included in the content of the inorganic oxide fine particles.

[0052] The composition of the present invention can be prepared by mixing these components uniformly, using a known or commercially available kneader, mixer, or the like.

[0053] 2. Use of active energy ray-curable fluorine-containing composition The composition of the present invention can be effectively used for forming a cured film. The method for forming a cured film using the composition of the present invention is not particularly limited, but for example, a method including: (1) a step of forming a coating film of the composition of the present invention on a substrate (coating film forming step); and (2) a step of irradiating the coating film with active energy rays to cure it, thereby obtaining a cured film (curing step), can be suitably employed.

[0054] Paint film formation process The substrate used in the coating film formation process may be a material to be imparted with water repellency, or a cured film formed on that material or on a portion thereof. Here, water repellency includes not only the ability to repel water, but also the ability to repel ice, ice water, etc. Therefore, the composition of the present invention can be used to prevent adhesion of water or the accumulation of ice, snow, etc.

[0055] The material of the substrate is not particularly limited, and may be, for example, any of synthetic resin, rubber, metal, ceramic, fibrous material (paper, nonwoven fabric, woven fabric, etc.), composite materials thereof, etc. Furthermore, the substrate may be any of a finished product (finished product), a semi-finished product, or the raw material thereof. More specifically, the substrate may be widely applied to such products as packaging materials, daily necessities, building materials, clothing, cosmetics, pharmaceuticals, etc. Furthermore, the substrate may be applied to products (building materials, automobile parts, etc.) used outdoors for waterproofing, preventing ice and snow adhesion, etc., or materials therefor.

[0056] The formation of a coating film can be carried out, for example, by applying the liquid composition of the present invention onto a substrate. The application method is not particularly limited, and can be carried out, for example, by a doctor blade, a bar coater, a brush, a roller, a spray gun, etc. Furthermore, in the present invention, when applying, the above-mentioned application and drying can be repeated two or more times to obtain a predetermined thickness.

[0057] The thickness of the coating film can be appropriately set depending on, for example, the use of the cured film, and can be adjusted so that the thickness of the cured film is, for example, about 0.1 to 1000 μm, but is not limited to this.

[0058] After the coating film is formed, it is preferable to perform a heat treatment for drying as needed. The degree of heat treatment varies depending on the amount of coating in the previous step and the amount of solvent contained in the composition, but whether the solvent has completely evaporated can be determined by visual inspection, odor, etc. If the heat treatment is insufficient, there is a risk of poor curing of the coating film in the subsequent curing step. When heat treatment is performed, it may be performed at, for example, about 50 to 160°C, but is not limited thereto.

[0059] Curing process The active energy rays used in the curing step are not limited, and examples thereof include electron beams, ultraviolet rays, far ultraviolet rays, visible light, infrared rays, etc. These can be irradiated using known or commercially available active energy ray irradiation devices.

[0060] The irradiation conditions can also be set within the range normally adopted. For example, when ultraviolet rays are used as the active energy rays, the ultraviolet irradiation conditions are as follows: a peak irradiance of 10 to 1000 mW / cm 2 The cumulative light intensity is 100-3000mJ / cm 2 However, this is only when an ultraviolet integrating illuminometer with a 365 nm wavelength receiver is used.

[0061] Furthermore, for example, when an electron beam is used as the active energy beam, the electron beam irradiation conditions can be an acceleration voltage of 100 to 300 kV and a dose of about 10 to 100 kGy. [Example]

[0062] The features of the present invention will be described in more detail below with reference to examples and comparative examples. However, the scope of the present invention is not limited to these examples. In the examples, "%" indicates "% by weight" unless otherwise specified.

[0063] Example 1 A polymerizable mixture was prepared by mixing 50 parts by weight of Fluorolink AD1700 (perfluoropolyether acrylate, 70% solids by weight, Solvay Specialty Polymers Japan), 15 parts by weight of Viscoat #230 (1,6-hexanediol diacrylate, Osaka Organic Chemical Industry Ltd.), 50 parts by weight of Viscoat #150 (tetrahydrofurfuryl acrylate, Osaka Organic Chemical Industry Ltd.), 4 parts by weight of Omnirad 127 (cleavage-type polymerization initiator, IGM Resins BV), 1 part by weight of CN371NS (amine acrylate, SARTOMER), and 1 part by weight of benzophenone (photopolymerization initiator, Fujifilm Wako Pure Chemical Industries). To 100 parts by weight of the obtained polymerizable mixture, 10 parts by weight of R711 (methacrylic group surface-modified silica microparticles (average primary particle diameter: 12 nm), AEROSIL), 10 parts by weight of VP RM50L (methacrylic group surface-modified silica microparticles (average primary particle diameter: 40 nm), AEROSIL), and 100 parts by weight of ethyl acetate (Fujifilm Wako Pure Chemical Industries) were added and mixed to obtain a mixed solution. The above mixture was applied to a double-sided adhesive PET film (Toyobo Co., Ltd., Cosmoshine, 100 μm thick) using a No. 8 bar coater. After application, the film was dried at 100°C for 3 minutes to form a coating film on the double-sided adhesive PET film. The coating film was then irradiated with ultraviolet light using a high-pressure mercury UV lamp to form a cured film with a thickness of approximately 1 μm. The UV irradiation conditions were as follows: the coated film was placed on a conveyor and passed under a UV lamp once. The UV irradiance was 200-300 mW / cm peak irradiance. 2 The cumulative amount of light irradiated was 650-800mJ / cm 2 The peak irradiance and the integrated light amount were measured using an Eye ultraviolet integrated illuminance meter (product name: "UVPF-A1" (equipped with a 365 nm photodetector PD-365), manufactured by Iwasaki Electric Co., Ltd.).

[0064] Example 2 A cured film was prepared in the same manner as in Example 1, except that a No. 24 bar coater was used instead of the No. 8 bar coater used in Example 1. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0065] Example 3 A mixed solution was obtained by adding and mixing R711 (20 parts by weight), VP RM50L (20 parts by weight), and ethyl acetate (300 parts by weight) to 100 parts by weight of a polymerizable mixture prepared in the same manner as in Example 1. The mixed solution obtained was coated using a No. 8 bar coater in the same manner as in Example 1, dried, and cured to obtain a cured film.

[0066] Example 4 A cured film was prepared in the same manner as in Example 3, except that a No. 24 bar coater was used instead of the No. 8 bar coater used in Example 3. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0067] Example 5 A mixed solution was obtained by adding R711 (10 parts by weight) and ethyl acetate (100 parts by weight) to and mixing with 100 parts by weight of the polymerizable mixture prepared in the same manner as in Example 1. The mixed solution obtained was coated using a No. 8 bar coater in the same manner as in Example 1, dried, and cured to obtain a cured film.

[0068] Example 6 A cured film was prepared in the same manner as in Example 5, except that a No. 24 bar coater was used instead of the No. 8 bar coater used in Example 5. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0069] Example 7 A mixed solution was obtained by adding and mixing R711 (20 parts by weight) and ethyl acetate (150 parts by weight) to 100 parts by weight of the polymerizable mixture prepared in the same manner as in Example 1. The mixed solution obtained was coated using a No. 8 bar coater in the same manner as in Example 1, dried, and cured to obtain a cured film.

[0070] Example 8 A cured film was prepared in the same manner as in Example 7, except that a No. 24 bar coater was used instead of the No. 8 bar coater used in Example 7. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0071] Example 9 A mixed solution was obtained by adding R711 (40 parts by weight) and ethyl acetate (300 parts by weight) to and mixing with 100 parts by weight of the polymerizable mixture obtained by the same preparation as in Example 1. The mixed solution obtained was coated using a No. 8 bar coater in the same manner as in Example 1, dried, and cured to obtain a cured film.

[0072] Example 10 A cured film was prepared in the same manner as in Example 9, except that a No. 24 bar coater was used instead of the No. 8 bar coater used in Example 9. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0073] Example 11 A mixed solution was obtained by adding VP RM50L (20 parts by weight) and ethyl acetate (100 parts by weight) to and mixing 100 parts by weight of the polymerizable mixture prepared in the same manner as in Example 1. The mixed solution obtained was coated using a No. 8 bar coater in the same manner as in Example 1, dried, and cured to obtain a cured film.

[0074] Example 12 A cured film was prepared in the same manner as in Example 11, except that a No. 24 bar coater was used instead of the No. 8 bar coater used in Example 11. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0075] Example 13 A mixed solution was obtained by adding VP RM50L (40 parts by weight) and ethyl acetate (166 parts by weight) to and mixing with 100 parts by weight of the polymerizable mixture prepared in the same manner as in Example 1. The mixed solution obtained was coated using a No. 8 bar coater in the same manner as in Example 1, dried, and cured to obtain a cured film.

[0076] Example 14 A cured film was prepared in the same manner as in Example 13, except that a No. 24 bar coater was used instead of the No. 8 bar coater used in Example 13. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0077] Example 15 A polymerizable mixture was prepared by mixing AD1700 (10 parts by weight), Viscoat #230 (24.2 parts by weight), Viscoat #150 (80.8 parts by weight), Omnirad 127 (4 parts by weight), CN371NS (1 part by weight), and benzophenone (1 part by weight). To 100 parts by weight of the resulting polymerizable mixture, R711 (5 parts by weight), VP RM50L (5 parts by weight), and ethyl acetate (75 parts by weight) were added and mixed to obtain a mixed solution, which was then coated using a No. 8 bar coater in the same manner as in Example 1, dried, and cured to obtain a cured film.

[0078] Example 16 A cured film was prepared in the same manner as in Example 15, except that a No. 24 bar coater was used instead of the No. 8 bar coater used in Example 15. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0079] Example 17 A mixed solution was obtained by adding and mixing R711 (10 parts by weight), VP RM50L (10 parts by weight), and ethyl acetate (100 parts by weight) to 100 parts by weight of the polymerizable mixture prepared in the same manner as in Example 15. The mixed solution obtained was coated using a No. 8 bar coater in the same manner as in Example 1, dried, and cured to obtain a cured film.

[0080] Example 18 A mixed solution was obtained by adding and mixing R711 (20 parts by weight), VP RM50L (20 parts by weight), and ethyl acetate (300 parts by weight) to 100 parts by weight of the polymerizable mixture prepared in the same manner as in Example 15. The mixed solution obtained was coated using a No. 8 bar coater in the same manner as in Example 1, dried, and cured to obtain a cured film.

[0081] Example 19 A mixed solution was obtained by adding R711 (10 parts by weight) and ethyl acetate (100 parts by weight) to and mixing with 100 parts by weight of the polymerizable mixture prepared in the same manner as in Example 15. The mixed solution obtained was coated using a No. 8 bar coater in the same manner as in Example 1, dried, and cured to obtain a cured film.

[0082] Example 20 A cured film was prepared in the same manner as in Example 19, except that a No. 24 bar coater was used instead of the No. 8 bar coater used in Example 19. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0083] Example 21 A mixed solution was obtained by adding and mixing R711 (20 parts by weight) and ethyl acetate (150 parts by weight) to 100 parts by weight of the polymerizable mixture prepared in the same manner as in Example 15. The mixed solution obtained was coated using a No. 8 bar coater in the same manner as in Example 1, dried, and cured to obtain a cured film.

[0084] Example 22 A cured film was prepared in the same manner as in Example 21, except that a No. 24 bar coater was used instead of the No. 8 bar coater used in Example 21. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0085] Example 23 A mixed solution was obtained by adding VP RM50L (20 parts by weight) and ethyl acetate (100 parts by weight) to and mixing 100 parts by weight of the polymerizable mixture obtained by the same preparation as in Example 15. The mixed solution obtained was coated using a No. 8 bar coater in the same manner as in Example 1, dried, and cured to obtain a cured film.

[0086] Example 24 A mixed solution was obtained by adding VP RM50L (40 parts by weight) and ethyl acetate (166 parts by weight) to and mixing with 100 parts by weight of the polymerizable mixture obtained by the same preparation as in Example 15. The mixed solution obtained was coated using a No. 8 bar coater in the same manner as in Example 1, dried, and cured to obtain a cured film.

[0087] Example 25 A cured film was prepared in the same manner as in Example 24, except that a No. 24 bar coater was used instead of the No. 8 bar coater used in Example 24. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0088] Example 26 A polymerizable mixture was prepared by mixing AD1700 (115 parts by weight), Omnirad127 (4 parts by weight), CN371NS (1 part by weight), and benzophenone (1 part by weight). To 100 parts by weight of the obtained polymerizable mixture, R711 (10 parts by weight), VP RM50L (10 parts by weight), and ethyl acetate (125 parts by weight) were added and mixed to obtain a mixed solution. The mixed solution obtained was coated using a No. 8 bar coater in the same manner as in Example 1, dried, and cured to obtain a cured film.

[0089] Example 27 A cured film was prepared in the same manner as in Example 26, except that a No. 24 bar coater was used instead of the No. 8 bar coater used in Example 26. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0090] Example 28 A mixed solution was obtained by adding R711 (10 parts by weight) and ethyl acetate (66 parts by weight) to 100 parts by weight of the polymerizable mixture prepared in the same manner as in Example 26 and mixing them. The mixed solution was applied using a No. 24 bar coater, dried, and cured in the same manner as in Example 1 to obtain a cured film. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0091] Example 29 A mixed solution was obtained by adding R711 (20 parts by weight) and ethyl acetate (150 parts by weight) to 100 parts by weight of the polymerizable mixture prepared in the same manner as in Example 26. The mixed solution obtained was coated using a No. 8 bar coater in the same manner as in Example 1, dried, and cured to obtain a cured film.

[0092] Example 30 A cured film was prepared in the same manner as in Example 29, except that a No. 24 bar coater was used instead of the No. 8 bar coater used in Example 29. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0093] Example 31 A mixed solution was obtained by adding VP RM50L (20 parts by weight) and ethyl acetate (100 parts by weight) to 100 parts by weight of the polymerizable mixture prepared in the same manner as in Example 26 and mixing them. The mixed solution was applied using a No. 24 bar coater, dried, and cured in the same manner as in Example 1 to obtain a cured film. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0094] Example 32 To 100 parts by weight of the polymerizable mixture prepared in the same manner as in Example 1, 15 parts by weight of R711 (methacrylic group surface-modified silica fine particles (average primary particle diameter: 12 nm), AEROSIL) and 30 parts by weight of acrylic group-modified silica particles (average particle diameter: approximately 20 μm) were added, thereby preparing a mixed solution. The acrylic group-modified silica particles were prepared by surface-modifying KYKLOS FR-2400-TS (average particle size approximately 20 μm, 75 μm sieve (200 mesh), Tatsumori Co., Ltd.) with KBM-5103 (acrylic silane coupling agent, Shin-Etsu Silicones Co., Ltd.) using a known method. The resulting mixed solution was applied, heat-treated, and cured with ultraviolet light in the same manner as in Example 1 to form a cured film.

[0095] Example 33 A polymerizable mixture was prepared by mixing Fluorolink AD1700 (50 parts by weight), Viscoat #230 (15 parts by weight), Viscoat #150 (50 parts by weight), and CN371NS (amine acrylate, SARTOMER) (1 part by weight). The polymerizable mixture of Example 33 was prepared by replacing the polymerizable mixture of Example 1 with the polymerizable mixture without the polymerization initiator. The polymerizable mixture of Example 33 is cured by electron beam, so no initiator is required. To 100 parts by weight of the obtained polymerizable mixture, R711 (10 parts by weight), VP RM50L (10 parts by weight), and ethyl acetate (125 parts by weight) were added and mixed to obtain a mixed liquid. The resulting mixture was applied to a double-sided adhesive PET film using a No. 8 bar coater. After application, the film was dried at 100°C for 3 minutes to form a coating. The coating was then irradiated with electron beams using an electron beam irradiator (CB250, i-Electron Beam Co., Ltd.) to produce a cured film. The electron beam irradiation conditions were an acceleration voltage of 200 kV, an absorbed dose of 30 kGy, and a single irradiation.

[0096] Example 34 A cured film was prepared in the same manner as in Example 33, except that a No. 24 bar coater was used instead of the No. 8 bar coater used in Example 33. However, the drying time was changed to 5 minutes instead of 3 minutes.

[0097] Example 35 To 100 parts by weight of the polymerizable mixture prepared in the same manner as in Example 33, 15 parts by weight of R711 (methacrylic group surface-modified silica fine particles (average primary particle diameter: 12 nm), AEROSIL) were added, 30 parts by weight of acrylic group-modified silica particles (average particle diameter: approximately 20 μm), and 200 parts by weight of ethyl acetate to prepare a mixed solution. The acrylic group-modified silica particles were prepared by surface-modifying KYKLOS FR-2400-TS (average particle size approximately 20 μm, 75 μm sieve (200 mesh), Tatsumori Co., Ltd.) with KBM-5103 (acrylic silane coupling agent, Shin-Etsu Silicones Co., Ltd.) using a known method. The resulting mixed solution was applied, heat-treated and cured with an electron beam in the same manner as in Example 33 to form a cured film.

[0098] [Table 1]

[0099] Comparative Example 1 A 9% solution of amorphous fluororesin (product name "CYTOP", CTX-809A, manufactured by Asahi Glass Co., Ltd.) was diluted using CT-solve 180 to obtain a 1.0% CYTOP solution. TFW3000F, TFW1000, and TFW500 (polytetrafluoroethylene (PTFE) powders with average primary particle diameters of 3 μm, 10 μm, and 25 μm, respectively, manufactured by Seishin Co., Ltd.) were mixed in a 1:1:1 (weight ratio) ratio to obtain a PTFE mixed powder. The PTFE mixed powder was added to the 1.0% CYTOP solution and stirred to obtain a 6.0% PTFE coating solution. The resulting coating solution was applied to a double-sided adhesive PET film using a No. 24 bar coater and then heat-cured at 100°C for 1 hour, followed by 150°C for 3 hours.

[0100] Comparative Example 2 A coating solution and a PTFE mixed powder were prepared in the same manner as in Comparative Example 1. The coating solution was applied to a double-sided adhesive PET film using a No. 24 bar coater, and then a 0.04 m 27 g of PTFE mixed powder was sprinkled evenly on the coated surface (20 cm x 20 cm). That is, 175 g / m 2 The PTFE mixed powder was sprinkled on the laminate so that the laminate amount was 100°C for 1 hour, and then the laminate was heat-cured at 150°C for 3 hours.

[0101] Test Example 1 The treated surface (cured film) of each sample was used as the test surface, and the contact angle of 2.0 μL of pure water was measured using a contact angle measuring device ("DMs-401," manufactured by Kyowa Interface Science Co., Ltd.). The treated surface (cured film) of each sample was used as the test surface. A double paper wiper (Kimwipe S-200 mini, manufactured by Nippon Paper Crecia Co., Ltd.) was attached to the bottom of a 50 g weight with a 4 cm square base. The weight was then placed on the test surface and pulled in one direction parallel to the test surface at approximately 20 cm / sec. The contact angle was measured after each pulling and rubbing. The measurement temperature can be room temperature (e.g., 20°C). Furthermore, in Comparative Example 2, significant PTFE mixed powder detachment occurred after the first friction, and it was determined that the paper wiper surface was not in an appropriate friction state for the second friction, so the paper wiper was replaced for the second friction. Although no particle detachment was observed in the Example, the paper wiper was replaced after the first friction in order to match the conditions of the Example and the Comparative Example. Since no particle detachment was observed after the second or subsequent friction, the paper wiper was not replaced. The number of frictions and the contact angle (unit: degrees) at that time are shown in Tables 2 and 3.

[0102] [Table 2]

[0103] [Table 3]

[0104] As is clear from the results in Table 2, it is possible to form cured films that have both high water repellency and durability in the Examples. After 3 rubbings, most of the Examples showed very high water repellency with a contact angle of 140 degrees or more, and even after 10 rubbings, all of the Examples showed high water repellency with a contact angle of 135 degrees or more. It is also apparent that when inorganic oxide fine particles with different particle sizes are used in combination, higher water repellency durability can be obtained (Examples 2, 4, 27, and 32). Furthermore, even when using the same mixed solution, it was found that the use of the No. 24 bar coater exhibited superior water repellency. The reason for this is presumably that the durability is improved as a result of the formation of rougher irregularities on the cured film surface. On the other hand, looking at the results in Table 3, high water repellency was not obtained in Comparative Example 1. In Comparative Example 2, high water repellency was obtained before rubbing, but the PTFE mixed powder was significantly detached as rubbing continued, and the contact angle decreased significantly after rubbing twice. As described above, it is clear that the present invention can provide a cured film having a surface that exhibits both high durability and high water repellency.

[0105] Test Example 2 The cross sections of the cured films obtained in Examples 1 and 32 were observed with a field emission scanning electron microscope, and the observation results are shown in Figures 1 and 2, respectively. As shown in Figure 1, the inorganic oxide particles filling the inside of the cured film form micro-scale surface irregularities, and nano-scale surface irregularities are further formed on top of these. As shown in Figure 2, it is clear that voids are formed inside the cured film. Even if the outermost surface is slightly worn away, the uneven structure reappears, and high water repellency is maintained. In particular, Figure 1 (Example 1) shows that the ratio of inorganic oxide particles to the polymerizable mixture is relatively low, resulting in the silica being embedded in the polymerizable mixture (cured resin).On the other hand, Figure 2 (Example 32) shows that the ratio of inorganic oxide particles to the polymerizable mixture is high, resulting in a sparse final cured product with an internal void structure.

Claims

1. An active energy ray-curable composition, (1) inorganic oxide fine particles having a particle size of 300 μm or less; (2) Perfluoropolyether (meth)acrylate as a fluorine-containing polymerizable compound; (3) Fluorine-free polymerizable compounds such as 1,6-hexanediol diacrylate (HDDA), tetrahydrofurfuryl acrylate (THFA), and amine (meth)acrylate An active energy ray-curable fluorine-containing composition comprising:

2. 2. The active energy ray-curable fluorine-containing composition according to claim 1, wherein the content of the fluorine-containing polymerizable compound is 5 to 95 parts by weight based on 100 parts by weight of a total of all components of the active energy ray-curable fluorine-containing composition excluding the inorganic oxide fine particles and the solvent.

3. 3. The active energy ray-curable fluorine-containing composition according to claim 1, wherein the content of the amine (meth)acrylate is 0.1 to 5 parts by weight per 100 parts by weight of a total of components of the active energy ray-curable fluorine-containing composition excluding the inorganic oxide fine particles and the solvent.

4. 4. The active energy ray-curable fluorine-containing composition according to claim 1, wherein the surfaces of the inorganic oxide fine particles are modified with (meth)acryloyl groups.

5. 5. The active energy ray-curable fluorine-containing composition according to claim 1, wherein the content of the inorganic oxide fine particles is 1 to 200 parts by weight per 100 parts by weight of the total of components of the active energy ray-curable fluorine-containing composition excluding the inorganic oxide fine particles and the solvent.

6. 6. The active energy ray-radiation type fluorine-containing composition according to claim 1, further comprising a solvent and being in a liquid state.

7. The active energy ray-curable fluorine-containing composition according to any one of claims 1 to 6, which is used to form a water-repellent coating film.

8. The active energy ray-curable fluorine-containing composition according to any one of claims 1 to 7, further comprising a photopolymerization initiator.

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