TW202221074A - Laminated film - Google Patents

Abstract

To provide a film that exhibits the good physical properties of both water repellency and oil repellency while maintaining adhesion to a resin substrate film. Provided is a laminated film having, on a resin substrate film, a coating layer that contains: a binder resin; and fine particles the surfaces of which are hydrophobicized and lipophobicized, wherein the laminated film has a fluorine atom ratio of at least 20 at% in terms of atomic composition ratio, in a region where the depth from the surface of the coating layer of the laminated film is 10 nm, as measured by an X-ray photoelectron spectrometer (ESCA).

Description

Laminated film

The present invention relates to a laminated film. In more detail, it is about a coating laminated film which has water repellency and oil repellency.

Materials exhibiting water and oil repellency on the surface are industrially important in fields requiring antifouling properties. In order to achieve antifouling properties, it is necessary to reduce the interaction between pollutants and the surface of the material. Generally speaking, it is usually achieved by water-repellent or oil-repellent on the surface of the material.

Conventionally, a method has been known in which a thin film having excellent water and oil repellency is produced by using silica particles having voids or particles having voids due to the formation of aggregates (refer to, for example, Patent Documents 1- 2). However, in general, the coating method for imparting water and oil repellency to the film surface has the problems of low adhesion to the substrate and easy peeling of the coating layer, and it is difficult to achieve both sufficient water and oil repellency and compatibility with the substrate. The tightness of the material. [Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2006-106507 Patent Document 2: Japanese Patent Laid-Open No. 2004-272198

[The problem to be solved by the invention]

The present invention was made on the background of the problems of the prior art. That is, an object of the present invention is to provide a film which maintains the adhesiveness with the resin base film and exhibits good physical properties of both water repellency and oil repellency. [means to solve the problem]

The inventors of the present invention have found that the above-mentioned problems can be solved by the means shown below, and have completed the present invention as a result of careful examinations in order to achieve the object. That is, the present invention includes the following configurations. 1. A laminated film, which is a laminated film having a coating layer on a resin base film, the coating layer containing a binder resin and particles whose surfaces are hydrophobicized and oleophobic, wherein X-ray photoelectron spectroscopy (ESCA) is used. In the measurement of , when the atomic composition ratio is determined for a depth region of 10 nm inward from the surface of the coating layer, the ratio of fluorine atoms is 20 at % or more. 2. The laminated film according to the above 1, wherein the resin base film is a polyethylene terephthalate film or a polyethylene naphthalate film. 3. The laminated film according to 1 or 2 above, wherein the average primary particle size of the surface-hydrophobized fine particles is 30 nm to 1 μm. 4. The laminated film according to any one of 1 to 3 above, wherein the binder resin is an acid-modified polyolefin resin or a polyester resin. [Effect of invention]

The laminated film of the present invention exhibits high water and oil repellency when the atomic composition ratio is determined for a depth region of 10 nm from the surface of the coating layer, and the ratio of fluorine atoms is 20 at % or more.

[Form for carrying out the invention]

The present invention is described in detail below. The present invention provides a laminated film having excellent water and oil repellency on the surface of the coating layer, and adhesion between the coating layer and the resin substrate film.

唑、聚苯并噻唑等芳香族系烴系聚合物；聚四氟乙烯、聚二氟亞乙烯等氟系樹脂；環氧樹脂、酚系樹脂、酚醛樹脂、苯并

樹脂等。從透明性與尺寸安定性之觀點而言，該等之中，較佳為包含聚酯樹脂或丙烯酸酯樹脂的薄膜。作為聚酯樹脂，具體而言，可舉出聚對苯二甲酸乙二酯、聚對苯二甲酸丙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯等。從物性之觀點而言，該等之中，較佳為聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯，從物性與成本的平衡之觀點而言，特佳為聚對苯二甲酸乙二酯。 (Resin base film) The laminated film in this invention has a resin base film. The material of the resin base film is not particularly limited, but is preferably a resin film from the viewpoint of handling properties such as flexibility. Examples of the resin constituting the resin film include polyolefins such as polyethylene, polypropylene, polystyrene, and diene-based polymers; polyethylene terephthalate, polypropylene terephthalate, Polybutylene terephthalate, polyethylene naphthalate and other polyesters; nylon 6, nylon 6,6, nylon 6, 10, nylon 12 and other polyamides; polymethacrylic acid Acrylic resins such as methyl esters, polymethacrylates, polymethylacrylates, and polyacrylates; polyacrylic resins, polymethacrylic resins, polyurethane resins; cellulose acetate, Cellulose resins such as ethyl cellulose; polyarylate, polyaramide, polycarbonate, polyphenylene sulfide, polyphenylene ether, polysulfite, polyetherether, polyetheretherketone, polyetherimide, polyimide, polyimide imide, polybenzimidazole, polybenzyl

Aromatic hydrocarbon-based polymers such as azoles and polybenzothiazoles; fluorine-based resins such as polytetrafluoroethylene and polyvinylidene fluoride; epoxy resins, phenolic resins, phenolic resins, benzoic

resin etc. Among these, a film containing a polyester resin or an acrylate resin is preferable from the viewpoint of transparency and dimensional stability. Specific examples of the polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like. From the viewpoint of physical properties, among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and from the viewpoint of balance between physical properties and cost, polyethylene terephthalate is particularly preferable Ethylene formate.

The resin base film may be a single layer, or two or more layers may be laminated. When two or more layers are laminated, the same type or different types of thin films may be laminated. In addition, the resin composition may be laminated on the resin base film. In addition, as long as the effect of this invention is exhibited, various additives can be contained in a resin base film as needed. As an additive, an antioxidant, a lightfast agent, an antigelling agent, an organic wetting agent, an antistatic agent, a ultraviolet absorber, a surfactant, etc. are mentioned, for example. When the resin base film is composed of two or more layers, an additive may be contained in accordance with the function of each layer. In order to improve the handling properties of the resin base film such as sliding property and winding property, inactive particles may be contained in the resin base film.

In the present invention, the thickness of the resin base film is not particularly limited, but is preferably 5 μm or more and 300 μm or less. More preferably, it is 10 μm or more and 280 μm or less, and even more preferably 12 μm or more and 260 μm or less. When it is 5 μm or more, it is easy to coat when the coating layer is laminated, and when it is 300 μm or less, it is advantageous in terms of cost.

As the surface of the resin base film, it may be used without treatment, but it may also be used by performing surface treatments such as plasma treatment, corona treatment, and flame treatment, or applying a primer layer.

(surface hydrophobized particles) The laminated film in the present invention has a coating layer on the resin base film directly or via other layers, and the coating layer contains fine particles whose surfaces are hydrophobicized and oleophobic. The kind of fine particles is not particularly limited. For example, at least one of silicon oxide (silicon dioxide), aluminum oxide, titanium oxide, and zirconium oxide can be used. These may be synthesized via arbitrary compounds, and well-known or commercially available ones may be used. In particular, silicon oxide (silicon dioxide) particles are preferable because they are easy to hydrophobicize and oleophobicize the surface, which will be described later.

The above-mentioned microparticles are those whose surface is hydrophobized or oleophobic, but the method of hydrophobization is not particularly limited. For example, hydrophilic oxide microparticles may be hydrophobized by surface treatment. That is, the hydrophilic oxide fine particles can be surface-treated with an arbitrary reagent such as a silane coupling agent to hydrophobize the surface.

The method of hydrophobizing fine particles represented by silicon oxide fine particles is a surface treatment using various known reagents such as silicone oil, silane coupling agent, and silazane as appropriate. In particular, from the viewpoint of exhibiting excellent water repellency and oil repellency, it is more preferable to introduce 1H,1H,2H,2H-perfluorooctyl, 1H,1H,2H,2H-perfluorodecyl, 1H, Fluorine functional groups represented by 1H,2H,2H-perfluorohexyl, 3,3,3-trifluoropropyl, etc., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl , secondary butyl, tertiary butyl, octyl and other alkyl groups, or alkenyl, alkynyl, vinyl, cyclohexyl, styryl, phenyl, trimethylsilyl, etc. Among them, hydrophobic and oleophobic oxide fine particles into which 1H,1H,2H,2H-perfluorooctyl group is introduced are preferable from the viewpoint of exhibiting more excellent water repellency and oil repellency (oleophobicization), and particularly preferable For the introduction of 1H, 1H, 2H, 2H-perfluorooctyl hydrophobic, oleophobic silicon oxide.

The primary particle diameter of the fine particles in the present invention is preferably 5 nm or more and 2 μm or less, more preferably 20 nm or more and 1.5 μm or less, and even more preferably 30 nm or more and 1 μm or less. If it is 5 nm or more, it becomes easy to form unevenness|corrugation in a coating layer surface layer, and it becomes easy to raise a contact angle mentioned later, and it is preferable. On the other hand, when it is 2 μm or less, it becomes difficult to cause fine particles to fall off from the coating layer, which is preferable, and it becomes easy to maintain the transparency of the resin base film, which is preferable. In addition, in this invention, the magnitude|size of an average primary particle diameter can be determined based on the result of the morphological observation by a microscope, such as a scanning electron microscope or a transmission electron microscope. Specifically, in these microscopic observations, the average of the diameters of arbitrarily selected 20/20 microparticles was defined as the average primary particle size. The average primary particle size of the amorphous particles can be calculated as the equivalent circle diameter. The equivalent circle diameter is the value obtained by dividing the area of the observed particles by π, calculating the square root, and multiplying by 2 times.

In the present invention, as an index of water and oil repellency on the surface of the coating layer of the laminated film, that is, as an index of water repellency and oil repellency on the surface of the microparticles whose surfaces have been hydrophobized and oleophobic. As an index of the modification rate, the measurement result using X-ray photoelectron spectroscopy (ESCA) can be used. Specifically, the atomic composition ratio can be obtained for a depth region of about 10 nm, and the ratio of specific atoms constituting a functional group having water and oil repellency, such as fluorine atoms, can be compared. In the present invention, from the viewpoint of exhibiting excellent water repellency and oil repellency, for example, when a hydrophobic or oleophobic silicon oxide such as 1H,1H,2H,2H-perfluorooctyl is introduced, the The ratio is preferably 20 at% or more. When the fluorine atomic ratio is 20 at % or more, good liquid repellency can be obtained even for a substance with a low surface tension. More preferably, it is 25 at% or more. There is no upper limit for the fluorine atomic ratio, but from the viewpoint of adhesion to the base material, etc., it is preferably 50 at % or less, more preferably 40 at % or less.

(binder resin) The binder resin in the present invention is not particularly limited as long as it is a component that can adhere well to the resin base film. It is preferable to use, for example, polyester resin, acid-modified polyolefin resin, polyurethane resin, epoxy resin, acrylic resin, and the like. Furthermore, from the viewpoint of the adhesiveness with the resin base film, it is preferable to use a polyester resin or an acid-modified polyolefin resin for the first coating layer, and from the viewpoint of preventing a decrease in water and oil repellency, It is particularly preferable to use a polyester resin, an acid-modified polyolefin resin, or an acrylic silicone resin for the second coating layer.

The acid-modified polyolefin resin is preferably at least partially polyolefin or unsaturated carboxylic acid-modified polyolefin, more preferably unsaturated carboxylic acid-modified polypropylene, unsaturated carboxylic acid-modified polyethylene, and most preferably Modified polypropylene for unsaturated carboxylic acid.

As the unsaturated carboxylic acid, maleic acid, fumaric acid, acrylic acid, methacrylic acid, and acid anhydrides thereof are preferred, and maleic anhydride and maleic acid are preferred. By this, a coating layer having high adhesiveness with the resin base film can be formed.

The acid value of the acid-modified olefin resin is preferably 2 mgKOH/g or more and 35 mgKOH/g or less, more preferably 5 mgKOH/g or more and 35 mgKOH/g or less, still more preferably 5 mgKOH/g or more and 25 mgKOH/g. If it is less than the above, the adhesiveness with the resin base film will decrease, and if it is more than the above, if the acid value that causes the reduction in water and oil repellency is larger than the lower limit value, the adhesiveness with the resin or the resin base film will be good. , if the acid value is smaller than the upper limit, the water and oil repellency of the resin itself is active in the liquid repellency of the coating layer, which is better.

The polyester resin used as the binder resin of the coating layer is not particularly limited, and polyester resins of the Toyobo Co., Ltd., Byron series, etc. can be appropriately used.

The binder resin can be mixed with a hardener and used by crosslinking. As the hardener used, isocyanate, epoxy, melamine, and carboxylic acid are preferred, and epoxy and melamine are more preferred. Through these, the transparency of the resin base film can be maintained, and a coating layer containing silicon oxide particles can be formed.

(Other components in the coating layer) The coating layer in the present invention may contain components other than the above-mentioned fine particles. Specifically, binder components, antioxidants, hardeners, light-fastening agents, anti-gelling agents, organic wetting agents, antistatic agents, ultraviolet absorbers, surfactants, etc. are mentioned, and these may be appropriately contained as necessary the ingredients.

Furthermore, from the viewpoint of satisfying the adhesiveness between the coating layer and the resin base film, the thickness of the entire coating layer is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 30 nm or more, and particularly preferably 50 nm or more. The thickness of the entire coating layer is preferably 3 μm or less, more preferably 2 μm or less, still more preferably 1.5 μm or less, and particularly preferably 1.2 μm or less, considering the water and oil repellency of the coating layer surface, economical efficiency, and the like.

The solid content of the coating liquid is preferably 0.5 mass % or more and 20 mass % or less, more preferably 1 mass % or more and 15 mass % or less, and even more preferably 3 mass % or more and 10 mass % or less. Within the above range, the coating surface layer is likely to be exposed due to the unevenness of the fine particles, and the coating properties are also favorable, which is preferable.

The range of the mixing ratio of the particles of the binder resin (binder resin: particles) is preferably 90:10 to 5:95, more preferably 70:30 to 5:95, still more preferably 50:50 to 5:5. 95. Within the above-mentioned range, it is preferable because the concavities and convexities of the fine particles can be formed on the surface, but it is difficult to cause a state in which the self-adhesive comes off.

(solvent) The solvent used for coating is not particularly limited, but is preferably an organic solvent such as water, alcohols, ketones, n-hexane, cyclohexane, toluene, butyl acetate, and glycols, and more preferably Organic solvents such as toluene, cyclohexane, and hexane are preferably toluene. By this, the solubility of the binder resin is high, and a uniform coating liquid can be produced.

(Primary particle size of particles whose surface is hydrophobized) It can be determined based on the results of morphological observation with a microscope, such as a scanning electron microscope or a transmission electron microscope. Specifically, in these microscopic observations, the average of the diameters of arbitrarily selected 20/20 particles was defined as the average primary particle size.

(Measurement method of acid value) The acid value (mgKOH/g-resin) in the present invention is the amount of KOH required to neutralize 1 g of acid-modified polyolefin, and is measured according to the test method of JIS K0070 (1992). Specifically, 100 g of xylene adjusted to a temperature of 100°C. After dissolving 1 g of acid-modified polyolefin, using phenolphthalein as an indicator at the same temperature, a 0.1 mol/L potassium hydroxide ethanol solution [trade name "0.1 mol/L ethanolic potassium hydroxide solution", Wako Pure Chemical Industries, Ltd. system] for titration. At this time, the amount of potassium hydroxide required for the titration was converted into mg, and the acid value (mgKOH/g) was calculated.

(water and oil repellency) The water repellency and oil repellency of the laminated film of the present invention can be evaluated by a known method. Specifically, water repellency can be evaluated by contact angle measurement using water, and oil repellency can be evaluated by contact angle measurement using diiodomethane and decane. In the present invention, the preferable range of the contact angle to water is 100 degrees or more, and more preferably 120 degrees or more. The higher the contact angle of water, the better, and the upper limit is not particularly limited, but in reality, about 170 degrees is the upper limit. When the contact angle of water is 100 degrees or more, excellent water repellency is exhibited, which is more preferable, and when it is 120 degrees or more, the water repellency is equal to or greater than that of a conventional fluororesin sheet represented by polytetrafluoroethylene (PTFE). Aqueous is preferred. Moreover, the range of the preferable contact angle of diiodomethane in this invention is 60 degrees or more, More preferably, it is 90 degrees or more. The larger the contact angle of diiodomethane, the better, and the upper limit is not particularly limited, but in reality, about 160 degrees is the upper limit. When the contact angle of diiodomethane is 60 degrees or more, it is preferable from the viewpoint of imparting oil repellency that can suppress oil stains, etc., and when it is 90 degrees or more, it shows a repellency equal to or more than that of a conventional fluororesin sheet. Oily, so better. In the present invention, the preferred range of the contact angle to decane is 30 degrees or more, and more preferably 40 degrees or more. The higher the contact angle of decane, the better, and the upper limit is not particularly limited, but in reality, about 150 degrees is the upper limit. When the contact angle of decane is 40 degrees or more, excellent oil repellency is exhibited, and it is more preferable, and when it exceeds 40 degrees, it is equal to or more than the conventional fluororesin sheet represented by polytetrafluoroethylene (PTFE). Water repellency is better.

(Manufacturing Steps of Laminated Films) In the production of the laminated film of the present invention, the coating method is not particularly limited. For example, it can be produced by known methods such as roll coating, gravure coating, bar coating, blade coating, spin coating, spray coating, and brush coating. The solvent used for coating by these methods is not particularly limited, and can be appropriately selected and used, for example, water, alcohols, ketones, n-hexane, cyclohexane, toluene, butyl acetate, glycols, etc. organic solvent. These solvents may be used alone, or a plurality of them may be mixed and used. The content of the hydrophobized microparticles on the surface of the solvent can be selected in an arbitrary ratio to obtain a uniform dispersion. A method of drying after coating. Either natural drying or heat drying may be used, but from the viewpoint of industrial production, heat drying is more preferable. The drying temperature is not particularly limited as long as it is a range that does not affect the components contained in the resin substrate film or the coating layer, but is usually preferably 150°C or lower, more preferably 50°C or higher and 140°C or lower. The drying method is not particularly limited, and a known method for drying a film such as a hot plate and a hot air oven can be used. The drying time may be appropriately selected according to other conditions such as the drying temperature, and may be within a range that does not affect the resin base film or the components contained in the coating layer. In addition, the coating step may be a so-called off-line coating method that is performed in a separate step after the resin substrate film is formed, or the coating solution may be applied during the production step of the resin substrate film. A so-called in-line coating method in which a sheet or a uniaxially stretched film is stretched and stretched in at least a uniaxial direction. [Example]

The following specific examples are given to further illustrate the present invention, but the present invention is not limited to the aspects of these examples. First, the evaluation method employed in the present invention will be described.

(Contact angle measurement) The contact angle with respect to a solvent was measured about the coating layer surface of the produced laminated film. A contact angle meter CA-X manufactured by Kyowa Interface Science Co., Ltd. was used for the measurement of the contact angle. As the measurement solvent system, pure water, diiodomethane, and decane were used. For the contact angle of water, 1.8 μL of water droplets were added dropwise, and the measurement was performed after 10 seconds. The contact angle of diiodomethane was measured after 10 seconds by adding dropwise 0.9 μL of diiodomethane, and the contact angle of decane was measured by adding droplet 0.5 μL of decane after 10 seconds.

(Adhesion measurement) The adhesion between the film and the coating layer was determined by a visual test using cellophane tape. A 24 mm wide cellophane tape was attached to the coated surface, and after being strongly pressed with fingers, the presence or absence of peeling of the coating layer at the time of vigorously peeling was visually confirmed. ○: Peeling is not seen ×: No peeling seen

(Measurement of average primary particle size) The average primary particle size of the surface-hydrophobized fine particles is determined based on the results of observation with a scanning electron microscope or a transmission electron microscope. Specifically, in these microscopic observations, the average of the diameters of arbitrarily selected 20/20 microparticles was defined as the average primary particle size. The average primary particle size of the amorphous particles can be calculated as the equivalent circle diameter. The equivalent circle diameter is the value obtained by dividing the area of the observed particles by π, calculating the square root, and multiplying by 2 times.

(ESCA determination of surface hydrophobized and oleophobic particles) The surface hydrophobized and oleophobic particle dispersion was added dropwise onto clean aluminum foil, and dried to form surface hydrophobized particles on the aluminum foil. the film. At this time, it dries quickly without generating surface contamination as much as possible, and sampling is performed immediately for surface composition analysis. As the apparatus, K-Alpha ⁺ (manufactured by Thermo Fisher Scientific) was used. Details of the measurement conditions are shown below. In addition, at the time of analysis, background removal was performed by Shirley's method. In addition, the surface composition ratio was determined as the average value of the measurement results of three or more locations where Al was not detected in the resin base film.・Measurement conditions Excitation X-ray: Monochromatic AlKα-ray X-ray output: 12kV, 6mA Photoelectron extraction angle: 90 degrees Spot size: 400μmΦ Path energy: 50eV Step: 0.1eV

(ESCA Measurement of Coating Layer of Laminated Film) The composition analysis was performed for a depth region of 10 nm from the surface of the coating layer of the laminated film. As the apparatus, K-Alpha ⁺ (manufactured by Thermo Fisher Scientific) was used. Details of the measurement conditions are shown below. In addition, at the time of analysis, background removal was performed by Shirley's method. In addition, the surface composition ratio was set as the average value of the measurement results of three or more places.・Measurement conditions Excitation X-ray: Monochromatic AlKα-ray X-ray output: 12kV, 6mA Photoelectron extraction angle: 90 degrees Spot size: 400μmΦ Path energy: 50eV Step: 0.1eV

The reagents used in the examination of the examples are listed below. ・Byron (registered trademark) RV280 (Toyobo polyester resin) ・MS-001 (Methylated melamine resin manufactured by Sanwa Chemical) ・P-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) ・YD128 (Epoxy resin made by NIPPON STEEL Chemical & Material) ・TETRAD (registered trademark)-X (multifunctional epoxy resin manufactured by Mitsubishi Gas Chemical)

<Production example of acid-modified polyolefin> In a 1 L autoclave, 100 parts by mass of polypropylene, 150 parts by mass of toluene, 8.5 parts by mass of maleic anhydride, and 4 parts by mass of di-tertiary butyl peroxide were added, and the temperature was raised to 140° C., followed by stirring for a further 1 hour. After the completion of the reaction, the reaction liquid was poured into a large amount of methyl ethyl ketone to precipitate resin. The resin was further washed several times with methyl ethyl ketone to remove unreacted maleic anhydride. By drying the obtained resin under reduced pressure, maleic anhydride-modified polypropylene (acid value: 12.7 mgKOH/g, weight average molecular weight: 60,000, Tm: 80°C) was obtained as acid-modified polyolefin.

<Production example of acid-modified polyolefin solution A-1> 10 parts by mass of the acid-modified polyolefin was weighed in a reaction vessel, 90 parts by mass of toluene was added thereto, and the mixture was stirred for 1 hour or more to obtain an acid-modified polyolefin solution A-1 with a solid content concentration of 10 mass %.

<Production example of acid-modified polyolefin solution A-2> 23 parts by mass of acid-modified polyolefin solution A-1, 27 parts by mass of toluene, 0.2 parts by mass of YD128 as a cross-linking agent, and 0.02 parts by mass of TETRAD (registered trademark)-X as a cross-linking catalyst were added to the sample bottle. By stirring at room temperature for 5 minutes, an acid-modified polyolefin solution A-2 having a solid content concentration of 5% by mass was obtained.

<Production example of polyester solution B-1> Polyester solution B-1 was prepared by adding 20 parts by mass of Byron (registered trademark) RV280 (polyester resin made by Toyobo), 90 parts by mass of toluene, and 90 parts by mass of methyl ethyl ketone to the sample bottle, and stirred at room temperature for 1 hour. (solid content concentration 10 mass %).

<Production example of polyester solution B-2> Add 23 parts by mass of polyester solution B-1, 27 parts by mass of toluene, 0.2 part by mass of melamine resin MS-001 as a crosslinking agent, and 0.02 part by mass of p-toluenesulfonic acid (PTS) as a crosslinking catalyst into the sample bottle, By stirring at room temperature for 5 minutes, polyester solution B-2 (solid content concentration 5 mass %) was produced.

<Synthesis method of silica fine particle dispersion liquid D-1> In the reaction container 1, 100 parts by mass of tetraethoxysilane and 439 parts by mass of ethanol were mixed. After mixing 179 parts by mass of ethanol, 13 parts by mass of ammonia water (25%), and 26 parts by mass of deionized water in the reaction container 2, the contents of the reaction container 2 were added dropwise to the reaction container 1 and transferred. At this time, in order to prevent a rapid reaction, dripping was performed over 10 minutes. After the dropwise addition, the reaction solution was left to stand at 20°C for 48 hours. Then, ammonia and water were distilled off to prepare a dispersion liquid of silicon oxide fine particles (average primary particle size: 35 nm). Then, 7.5 parts by mass of 1H, 1H, 2H, 2H-perfluorooctyl trichlorosilane and 7.5 parts by mass of ammonia water (25%) were added and heated at 65° C. for 2 days to prepare 1H, 1H, 2H, 2H-perfluorooctyl trichlorosilane Fluorooctyl-modified silica particle dispersion D-1. In order to confirm the solid content concentration of the silica particle dispersion, 5 g of the silica particle dispersion was weighed in an aluminum cup (1.3 g) and heated in an oven at 150°C for more than 24 hours to remove residual solvent ethanol and water. The aluminum cup after the measurement was removed was 1.55 g, so the solid content in 5 g of the silica particle dispersion liquid was calculated to be 0.25 g, and the solid content concentration of the silica particle dispersion liquid was confirmed to be 5 mass %. Then, when preparing the coating liquid, the ethanol of the silicon oxide fine particle dispersion liquid was removed, and the same amount of toluene as the removed ethanol was added, and it was implemented as a toluene dispersion liquid. Furthermore, as a result of ESCA analysis of the surface-modified silicon oxide particles, C was 17.8 at % and F was 31.9 at %.

<Synthesis method of particle dispersion D-2> In the reaction container 1, 100 parts by mass of tetraethoxysilane and 49 parts by mass of ethanol were mixed. After mixing 60 parts by mass of ethanol, 13 parts by mass of ammonia water (25%), and 536 parts by mass of deionized water in the reaction container 2, the contents of the reaction container 2 were added dropwise to the reaction container 1 and transferred. At this time, in order to prevent a rapid reaction, dripping was performed over 30 minutes. After the dropwise addition, the reaction solution was left to stand at 20°C for 48 hours. Then, ammonia and water were distilled off to prepare a dispersion liquid of silicon oxide fine particles (average primary particle size: 800 nm). Then, 7.5 parts by mass of 1H, 1H, 2H, 2H-perfluorooctyl trichlorosilane and 7.5 parts by mass of ammonia water (25%) were added and heated at 65° C. for 2 days to prepare 1H, 1H, 2H, 2H-perfluorooctyl trichlorosilane Fluorooctyl-modified silica particle dispersion D-2. In order to confirm the solid content concentration of the silica particle dispersion, 5 g of the silica particle dispersion was weighed in an aluminum cup (1.3 g) and heated in an oven at 150°C for more than 24 hours to remove residual solvent ethanol and water. The aluminum cup after the measurement was removed was 1.55 g, so the solid content in 5 g of the silica particle dispersion liquid was calculated to be 0.25 g, and the solid content concentration of the silica particle dispersion liquid was confirmed to be 5 mass %. Then, when preparing the coating liquid, the ethanol of the silicon oxide fine particle dispersion liquid was removed, and the same amount of toluene as the removed ethanol was added, and it was implemented as a toluene dispersion liquid. Furthermore, as a result of ESCA analysis of the surface-modified silicon oxide particles, C was 14.7 at %, and F was 30.7 at %.

<Synthesis method of silica fine particle dispersion liquid D-3> In the reaction container 1, 100 parts by mass of tetraethoxysilane and 439 parts by mass of ethanol were mixed. After mixing 179 parts by mass of ethanol, 13 parts by mass of ammonia water (25%), and 26 parts by mass of deionized water in the reaction container 2, the contents of the reaction container 2 were added dropwise to the reaction container 1 and transferred. At this time, in order to prevent a rapid reaction, dripping was performed over 10 minutes. After the dropwise addition, the reaction solution was left to stand at 20°C for 48 hours. Then, ammonia and water were distilled off to prepare a dispersion liquid of silicon oxide fine particles (average primary particle size: 35 nm). After that, 150 parts by mass of hexamethyldisilazane was added and heated at 65° C. for 2 days to prepare a trimethylsilyl group-modified silicon oxide fine particle dispersion D-3. In order to confirm the solid content concentration of the silica particle dispersion, 5 g of the silica particle dispersion was weighed in an aluminum cup (1.3 g) and heated in an oven at 150°C for more than 24 hours to remove residual solvent ethanol and water. The aluminum cup after the measurement was removed was 1.55 g, so the solid content in 5 g of the silica particle dispersion liquid was calculated to be 0.25 g, and the solid content concentration of the silica particle dispersion liquid was confirmed to be 5 mass %. Then, when preparing the coating liquid, the ethanol of the silicon oxide fine particle dispersion liquid was removed, and the same amount of toluene as the removed ethanol was added, and it was implemented as a toluene dispersion liquid. Furthermore, as a result of ESCA analysis of silicon oxide particles surface-modified with trimethylsilyl groups, C was 8.5 at%, and F was less than 0.1 at%.

<Production Example of Coating Liquid E-1> Into the sample bottle, 40 parts by mass of acid-modified polyolefin solution A-1 (solid content concentration of 10 mass %), 40 mass parts of silica fine particle dispersion D-1 (solid content concentration of 5 mass %), and 44 mass parts of toluene were added and mixed. parts, epoxy hardener YD128 (solid content concentration 100 mass %) 0.2 mass part, catalyst TETRAD-X (solid content concentration 100 mass %) 0.02 mass part, to prepare coating liquid E-1 (solid content concentration 5 mass %) ).

Next, each substance was blended as shown in Table 1, except that it was carried out in the same manner as the coating liquid E-1, and the coating liquids E-2 to E-9 for the second coating layer were mainly produced. Table 1 shows the compositions of coating liquids E-1 to E-9.

[Table 1] The obtained coating solution for the second coating layer resin solution used Silicon oxide particle dispersion used Hardener used catalyst used Blending amount (parts by mass) Left-mentioned resin solution Left-mentioned particle dispersion solvent hardener left catalyst E-1 Acid modified polyolefin A-1 D-1 YD128 TETRAD-X 40 40 44 0.2 0.02 E-2 Acid modified polyolefin A-1 D-1 YD128 TETRAD-X 14 66 18 0.2 0.02 E-3 Polyester solution B-1 D-1 MS-001 PTS 40 40 44 0.2 0.02 E-4 Polyester solution B-1 D-1 MS-001 PTS 14 66 18 0.2 0.02 E-5 Acid modified polyolefin A-1 D-2 YD128 TETRAD-X 40 40 44 0.2 0.02 E-6 Acid modified polyolefin A-1 D-2 YD128 TETRAD-X 14 66 18 0.2 0.02 E-7 Polyester solution B-1 D-2 MS-001 PTS 40 40 44 0.2 0.02 E-8 Polyester solution B-1 D-2 MS-001 PTS 14 66 18 0.2 0.02 E-9 Acid modified polyolefin A-1 D-3 YD128 TETRAD-X 14 66 18 0.2 0.02

＜Production of coating film＞ (Example 1) A bar coater # 5. After coating the polyester solution B-2, it was dried at 120° C. for 10 minutes to form a first coating layer (the thickness of the first coating layer after drying was 0.6 μm). After that, the coating liquid E-1 prepared by the method described in the above-mentioned coating liquid production example was coated with a bar coater #5, and then dried at 110° C. for 60 minutes to prepare a second coating layer, thereby obtaining a coating film. (The film thickness after drying of the second coating layer was 0.6 μm).

(Examples 2 to 12) Hereinafter, the coating liquids of the first coating layer and the second coating layer were changed as shown in Table 2 to obtain the coating films of Examples 2 to 12.

(Example 13) The same procedure as in Example 1 was carried out, except that the resin base film used was changed to a Teonex (registered trademark) film (product number: Q51, thickness 38 μm) made of polyethylene naphthalate. Coated film of Example 13.

(Comparative Example 1) On the corona-treated surface of the PET film E5100, the acid-modified polyolefin solution A-2 was coated with a bar coater #5, and then dried at 120° C. for 1 minute to obtain a coated film.

(Comparative Example 2) A coating film was obtained in the same manner as in Example 1 except that the second coating layer was changed to Coating Liquid E-9. Table 2 summarizes the evaluation results of the respective Examples and Comparative Examples.

[Table 2] Resin base film 1st coating layer 2nd coating layer Contact angle (degrees) F element ratio of coating layer (at%) Adhesion to substrate coating liquid Film thickness after drying (μm) coating liquid Film thickness after drying (μm) The primary average particle size of the particles (nm) water Diiodomethane Decane Example 1 PET E5100 B-2 0.6 E-1 0.6 35 135.4 101.7 33.8 27.3 ○ Example 2 PET E5100 B-2 0.6 E-2 0.6 35 140.2 105.3 40.5 30.7 ○ Example 3 PET E5100 B-2 0.6 E-3 0.6 35 125.3 95.6 33.0 26.5 ○ Example 4 PET E5100 B-2 0.6 E-4 0.6 35 136.8 100.9 40.9 30.3 ○ Example 5 PET E5100 B-2 0.6 E-5 0.6 800 134.9 99.8 34.2 26.8 ○ Example 6 PET E5100 B-2 0.6 E-6 0.6 800 138.7 104.7 38.6 30.1 ○ Example 7 PET E5100 B-2 0.6 E-7 0.6 800 124.2 96.9 34.0 25.9 ○ Example 8 PET E5100 B-2 0.6 E-8 0.6 800 136.8 101.4 39.8 29.7 ○ Example 9 PET E5100 A-2 0.6 E-2 0.6 35 140.8 104.3 39.4 30.9 ○ Example 10 PET E5100 A-2 0.6 E-4 0.6 35 135.4 99.7 41.0 31 ○ Example 11 PET E5100 A-2 0.6 E-6 0.6 800 136.6 103.4 38.0 30.6 ○ Example 12 PET E5100 A-2 0.6 E-8 0.6 800 135.4 103.6 40.1 29.6 ○ Example 13 Teonex Q51 B-2 0.6 E-1 0.6 35 137.8 100.4 34.7 27.0 ○ Comparative Example 1 PET E5100 none - A-2 0.6 - 99.6 53.7 less than 5 less than 0.1 ○ Comparative Example 2 PET E5100 B-2 0.6 E-9 0.6 35 121.3 86.7 less than 5 less than 0.1 ○ [Possibility of Industrial Use]

According to the present invention, it is possible to provide a laminated film having excellent water and oil repellency and exhibiting antifouling properties. The laminated film of the present invention is useful in applications such as packaging, coating, and mold release materials.

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Claims (4)

A laminated film, which is a laminated film with a coating layer on a resin base film, the coating layer contains a binder resin and particles whose surface is hydrophobicized and oleophobic, wherein the measurement by X-ray photoelectron spectroscopy (ESCA) is used. Among them, when the atomic composition ratio is obtained for a depth region of 10 nm inward from the surface of the coating layer, the ratio of fluorine atoms is 20 at % or more. The laminated film of claim 1, wherein the resin base film is a polyethylene terephthalate film or a polyethylene naphthalate film. The laminated film according to claim 1 or 2, wherein the surface hydrophobized microparticles have an average primary particle size of 30 nm to 1 μm. The laminate film according to any one of claims 1 to 3, wherein the binder resin is an acid-modified polyolefin resin or a polyester resin.