TW202214786A - Multilayer film - Google Patents

Abstract

To provide a film which exhibits both good water repellency and good oil repellency, while maintaining adhesion to a resin base film. A multilayer film which comprises a coating layer on a resin base film, said coating layer containing a binder resin and fine particles that have hydrophobized surfaces, wherein if the thickness of the coating layer is divided into 100 equal parts, and the interface between the resin base film and the coating layer is taken as 0, while the outermost surface of the coating layer is taken as 100, the fine particles that have hydrophobized surfaces are unevenly distributed in the parts 30 to 100.

Description

Laminated film

The present invention relates to laminated films. More specifically, it relates to a coated laminated film with water and oil repellency.

Materials that exhibit 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 the pollutants and the material surface, which is usually achieved by water repellency or oil repellency of the material surface.

There is a conventionally known method for producing thin films having excellent water and oil repellency by using silica fine particles having voids or using fine particles having voids by forming aggregates (see, eg, Patent Documents 1 to 2). However, in general, the coating method for imparting water and oil repellency to the surface of a film has problems such as low adhesion to the substrate and easy peeling of the coating layer, making it difficult to achieve both sufficient water and oil repellency , and adhesion to the substrate. [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 has been made on the background of the problems of the related art. That is, an object of the present invention is to provide a film which exhibits favorable physical properties both of water repellency and oil repellency while maintaining the adhesiveness with the resin substrate film. [means to solve the problem]

As a result of earnestly examining to achieve this object, the present inventors found that the above-mentioned problems can be solved by the means shown below, and arrived at the present invention. That is, the present invention includes the following structures. 1. A laminated film, which is a laminated film with an adhesive resin and a coating layer on a resin base film; wherein, the coating layer contains microparticles whose surface is hydrophobized; and when the thickness of the coating layer is increased to 100% When the interface between the resin base film and the coating layer was set to 0 and the outermost surface of the coating layer was set to 100, the surface hydrophobized fine particles were only distributed in the part of 30-100. 2. The laminated film according to the above item 1, wherein the resin base film is a polyethylene terephthalate film or a polyethylene naphthalate film. 3. The laminated film according to the above item 1 or 2, wherein the microparticles whose surfaces are hydrophobized have an average primary particle diameter of 30 nm to 1 μm. 4. The laminated film according to any one of the above items 1 to 3, 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 by allowing the fine particles whose surfaces have been hydrophobized to be distributed on the surface side of the coating layer, and exhibits high adhesion between the coating layer and the resin substrate film sex.

[Form for carrying out the invention]

Hereinafter, the present invention will be described in detail. 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.

樹脂等。該等之中，從透明性與尺寸穩定性的觀點來看，較佳為由聚酯樹脂或丙烯酸酯樹脂構成的薄膜。就聚酯樹脂而言，具體地說，可列舉有：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。該等之中，從物性的觀點來看，較佳為聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯，從物性與成本之平衡這樣的觀點來看，特佳為聚對苯二甲酸乙二酯。 (Resin Base Film) The laminate film in the present invention has a resin base film. The material of the resin base film is not particularly limited, but a resin film is preferable from the viewpoint of workability such as flexibility. The resin constituting the resin film includes, for example, polyolefins such as polyethylene, polypropylene, polystyrene, and diene-based polymers, polyethylene terephthalate, and polypropylene terephthalate. polyester, polybutylene terephthalate, polyethylene naphthalate and other polyesters, nylon 6, nylon 6,6, nylon 6,10, nylon 12 and other polyamides, polyamide Acrylic resins such as methyl methacrylate, polymethacrylates, polymethylacrylates, polyacrylates, etc., polyacrylic resins, polymethacrylic resins, polyurethane resins, cellulose acetate Cellulose resins such as plain, ethyl cellulose, polyarylate, aramid, polycarbonate, polyphenylene sulfide, polyphenylene oxide, polyselenium, polyethersoleum, polyetherether Aromatic hydrocarbon-based polymers such as ketones, polyetherimide, polyimide, polyamideimide, polybenzimidazole, polybenzoxazole, polybenzothiazole, polytetrafluoroethylene, poly Fluorine resins such as polyvinylidene fluoride, epoxy resins, phenol resins, phenolic resins, benzos

resin etc. Among these, from the viewpoint of transparency and dimensional stability, a film composed of a polyester resin or an acrylate resin is preferred. Specific examples of polyester resins include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like. . Among them, from the viewpoint of physical properties, polyethylene terephthalate and polyethylene naphthalate are preferred, and from the viewpoint of balance between physical properties and cost, polyethylene terephthalate is particularly preferred Ethylene Diformate.

The resin base film may be a single layer, or two or more layers may be laminated. When two or more types of layers are laminated, the same type or different types of thin films can be laminated. In addition, a resin base film may be laminated with the resin composition. Furthermore, various additives may be contained in the resin base film as necessary within the range that the effects of the present invention can be achieved. 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, additives can also be contained in accordance with the function of each layer. In order to improve the handleability, such as sliding property and winding property of the resin base film, 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 still 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.

The surface of the resin base film can be used untreated, but one that has been subjected to surface treatments such as plasma treatment, corona treatment, and flame treatment, or that has been subjected to primer coating can also be used.

(fine particles with hydrophobized surface) 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 hydrophobized. The kind of fine particles is not particularly limited. For example, at least one type of silica (silicon dioxide), alumina, titania, and zirconia can be used. These may be synthesized via arbitrary compounds, and well-known or commercially available ones may be used. In particular, silica (silicon dioxide) fine particles are preferred because the surface hydrophobization described later is easy.

The aforementioned fine particles are those whose surfaces are hydrophobized, but the method of hydrophobizing is not particularly limited. For example, hydrophilic oxide fine particles may be obtained by hydrophobizing by surface treatment. That is, hydrophilic oxide fine particles can be surface-treated with an arbitrary agent such as a silane coupling agent, and the surface of which has been hydrophobized can be used.

As a method of hydrophobizing microparticles represented by silica microparticles, surface treatment with various known agents such as silicone oil, silane coupling agents, and silazanes can be suitably used. In particular, from the viewpoint of exhibiting excellent water and oil repellency, it is more preferable to introduce 1H,1H,2H,2H-perfluorooctyl, 1H,1H,2H,2H-perfluorodecyl, Fluorine-based functional groups represented by 1H, 1H, 2H, 2H-perfluorohexyl, 3,3,3-trifluoropropyl, etc., such as methyl, ethyl, n-propyl, isopropyl, n-butyl, Alkyl groups represented by isobutyl, tertiary butyl, tertiary butyl, octyl, etc., or alkenyl, alkynyl, vinyl, cyclohexyl, styryl, phenyl, trimethylsilyl, and the like. Among them, hydrophobic oxide fine particles into which a trimethylsilyl group is introduced are preferable, and hydrophobic silica into which a trimethylsilyl group is introduced is particularly preferred, since they exhibit better water and oil repellency.

In the present invention, the primary particle diameter of the fine particles is preferably 5 nm or more and 2 μm or less, more preferably 20 nm or more and 1.5 μm or less, and still more preferably 30 nm or more and 1 μm or less. If it is 5 nm or more, the formation of concavities and convexities in the surface layer of the coating layer becomes easy, and it is easy to increase the contact angle described later, which is preferable. On the other hand, if it is 2 μm or less, it is preferable because it becomes difficult for the fine particles to fall off from the coating layer, and it is relatively easy to maintain the transparency of the resin base film. good. In addition, in this invention, the magnitude|size of the average diameter of a primary particle can be determined based on the result of 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 20 randomly selected microparticles was defined as the average primary particle diameter. The average primary particle diameter of the amorphous fine particles can be calculated as a circle-equivalent diameter. The equivalent diameter of a circle is the value obtained by dividing the area of the observed microparticles by π, calculating the square root and multiplying by 2 times.

In the present invention, the measurement result by X-ray photoelectron spectroscopy (ESCA) can be used as an index of the modification rate based on the functional group having water repellency and oil repellency in the surface of the hydrophobized microparticles. Specifically, the atomic composition ratio can be obtained for a depth region of about 10 nm, and the ratio of specific atoms (eg, carbon atoms) constituting a functional group having water and oil repellency can be compared. In the present invention, from the viewpoint of exhibiting excellent water and oil repellency, for example, in the case of hydrophobic silica into which trimethylsilyl groups are introduced, the ratio of carbon atoms is preferably 8 at % or more.

(binder resin) The binder resin in the present invention is not particularly limited as long as it is a component capable of making good adhesion 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 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, from the viewpoint of preventing a decrease in water and oil repellency In view of the second coating layer, it is particularly preferable to use polyester resin, acid-modified polyolefin resin, or acrylic silicone resin.

For the acid-modified polyolefin resin, preferably at least a part of it is polyolefin or unsaturated carboxylic acid-modified polyolefin, more preferably unsaturated carboxylic acid-modified polypropylene, unsaturated carboxylic acid-modified polyethylene, and most preferably Preferred is unsaturated carboxylic acid-modified polypropylene.

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 most preferred. With these, it is possible to form a coating layer having high adhesiveness with the resin base film.

The acid value of the acid-modified polyolefin 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 or less. When the acid value of the acid-modified polyolefin resin is 2 mgKOH/g or more, the adhesion to the resin and the resin base film is good, and when the acid value is 35 mgKOH/g or less, the resin itself is used for water and oil repellency. The liquid repellency of the coating layer is thus better.

The polyester resin that can be used as the binder resin for the coating layer is not particularly limited, but Toyobo Co., Ltd.'s Vylon (registered trademark) series polyester resin or the like can be suitably used.

The binder resin can also be mixed with a hardener and used for crosslinking. For the hardener used, isocyanate-based compounds, epoxy-based compounds, melamine-based compounds, and carboxylic acids are preferred, and epoxy-based compounds, Melamine-based compounds. By these, a coating layer containing silica fine particles can be formed while maintaining the transparency of the resin base film.

(other components in the coating) The coating layer in the present invention may contain components other than the above-mentioned fine particles. Specifically, binder components, antioxidants, curing agents, light-fastening agents, anti-gelling agents, organic wetting agents, antistatic agents, ultraviolet absorbers, surfactants, etc. can be mentioned, and it is possible to appropriately contain such ingredients.

(structure of coating layer) In the present invention, when the thickness of the coating layer is divided into equal parts, the interface between the resin substrate film and the coating layer is set to 0, and the outermost surface of the coating layer is set to 100, the above-mentioned surface is preferred. The hydrophobized microparticles only exist in the fraction of 30-100. More preferably, it is 40 or more, and still more preferably 50 or more. If it is 30 or more, since the adhesiveness of a coating layer and a resin base material film will improve, it is preferable.

When the thickness of the coating layer is divided into 100, the interface between the resin substrate film and the coating layer is set to 0, and the outermost surface of the coating layer is set to 100, so that the hydrophobicized microparticles on the surface only partially exist in the The method for the portion of 30 to 100 is not particularly limited, but includes providing a coating layer (hereinafter referred to as the first coating layer) that does not have fine particles whose surface is hydrophobized directly or via other layers on the resin substrate film. coating layer), and further layer a coating layer (second coating layer) with microparticles whose surface is hydrophobized on the first coating layer, and adjust the thickness of the other layers and the first coating layer. It becomes more than 30% of the overall thickness of the coating layer. The upper limit value of the part from 30 to 100 is assumed to be 100, but the lower limit value is preferably 90 or less, more preferably 80 or less, from the viewpoint of preventing the hydrophobized fine particles from falling off.

Furthermore, from the viewpoint of satisfying the adhesion 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, further preferably 30 nm or more, and particularly preferably 50nm or more. In addition, in consideration of water and oil repellency and economical efficiency of the coating layer surface, 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.

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 still more preferably 3 mass % or more and 10 mass % or less. Within the above-mentioned range, the unevenness of the fine particles is likely to be exposed on the coating surface layer, and the coatability is also good, which is preferable for these reasons.

The mixing ratio of the fine particles to the binder resin (binder resin: fine particles) is preferably in the range of 90:10 to 5:95, more preferably 70:30 to 5:95, still more preferably 50:50 to 5:95 . Within the above-mentioned range, the irregularities capable of forming fine particles appear on the surface, but the state of being detached from the binder is less likely to occur, which is preferable for this reason.

(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, More preferred are organic solvents such as toluene, cyclohexane, and hexane, and most preferred is toluene. Due to these, the solubility of the binder resin is high, and a uniform coating liquid can be produced.

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

(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, after dissolving 1 g of acid-modified polyolefin in 100 g of xylene whose temperature was adjusted to 100°C, 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", manufactured by Wako Pure Chemical Industries, Ltd.] was titrated. At this time, the acid value (mgKOH/g) was calculated by converting the amount of potassium hydroxide required for the titration into mg.

(water/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. In the present invention, the preferred range of the contact angle with respect to water is 100 degrees or more, and more preferably 120 degrees or more. The larger the contact angle with respect to water, the better, and the upper limit is not particularly limited, but practically, about 170 degrees is the upper limit. If the contact angle of water is 100 degrees or more, it is preferable because it exhibits excellent water repellency. The water repellency of the same or more is better. Further, in the present invention, the preferred range of the contact angle of diiodomethane is 60 degrees or more, more preferably 90 degrees or more. The larger the contact angle of diiodomethane, the better, and the upper limit is not particularly limited, but in fact, 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 being able to impart oil repellency that can suppress oil stains, etc., and when it is 90 degrees or more, it is equivalent to a conventional fluororesin sheet. The above oil repellency is better.

(Manufacturing step of the laminated film) In the production of the laminated film of the present invention, the method of coating 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 for example, organic solvents such as water, alcohols, ketones, n-hexane, cyclohexane, toluene, butyl acetate, and glycols can be appropriately selected. and use. These solvents may be used alone, or a plurality of them may be mixed and used. The content of the microparticles whose surfaces are hydrophobized with respect to the solvent can be selected in an arbitrary ratio in which a uniform dispersion can be obtained. As 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 does not affect the components contained in the resin base film and 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 the 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 a range that does not affect the components contained in the resin base film and the coating layer. In addition, the coating step may be a so-called off-line coating method, which is performed in a separate step after the resin base film is formed, or may be a process in which the resin base film is produced. The coating liquid is applied to an unstretched sheet or a uniaxially stretched film and stretched in at least a uniaxial direction, so-called in-line coating method. [Example]

Hereinafter, the present invention will be further described with reference to specific examples, 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. For the measurement of the contact angle, a contact angle meter CA-X manufactured by Kyowa Interface Science Co., Ltd. was used. For the measurement solvent, pure water and diiodomethane were used. The contact angle of water (hereinafter sometimes abbreviated as WCA) was measured by dropping 1.8 μL of water droplets after 10 seconds. The contact angle of diiodomethane (hereinafter abbreviated as DCA in some cases) was measured after 10 seconds after dropping a droplet of 0.9 μL of diiodomethane.

(Adhesion measurement) The adhesion between the film and the coating layer was determined by a visual test using cellophane tape. Cellophane tape with a width of 24 mm was attached to the coated surface, and after being pressed firmly with a finger, the presence or absence of peeling of the coating layer was visually confirmed when peeled off strongly.

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

(ESCA measurement of surface hydrophobized microparticles) The surface hydrophobized microparticle dispersion was dropped onto a clean aluminum foil, dried, and a thin film of the surface hydrophobized microparticles was formed on the aluminum foil. At this time, drying was performed quickly so as not to cause surface contamination as much as possible, and the sample was immediately sampled for surface composition analysis. For the device, K-Alpha ⁺ (manufactured by Thermo Fisher Scientific) was used. Details of the measurement conditions are shown below. In addition, at the time of analysis, the background removal was performed by the Shirley method. In addition, the surface composition ratio was set 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 line X-ray output: 12kV, 6mA Photoelectron escape angle: 90 degrees Spot size: 400μmΦ Pass energy: 50eV Step: 0.1eV

The reagents used in the study of the examples are listed below. ・Vylon (registered trademark) RV280 (Toyobo polyester resin) ・Symac (registered trademark) US-350 (Acrylic polysiloxane resin, manufactured by Toagosei Industries, solid content concentration 30% by mass) ・MS-001 (Methylated melamine resin manufactured by Sanwa Chemical Co., Ltd.) ・YD128 (Epoxy resin manufactured by NIPPON STEEL Chemical & Material) ・TETRAD (registered trademark)-X (multifunctional epoxy resin manufactured by Mitsubishi Gas Chemical) ・Millionate (registered trademark) MR-001 (Isocyanate-based crosslinking agent manufactured by Tosoh) ・KS-1260 (manufactured by Sakai Chemical Industry Co., Ltd., butyl tin dilaurate)

<Production example of acid-modified polyolefin> To 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 further 1 hour. After the completion of the reaction, the reaction solution was put 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 of 12.7 mgKOH/g, weight average molecular weight of 60,000, Tm of 80° C.) was obtained as an acid-modified polyolefin.

<Production example of acid-modified polyolefin solution A-1> 10 parts by mass of the aforementioned acid-modified polyolefin was weighed into a reaction vessel, 90 parts by mass of toluene was added thereto, and the mixture was stirred for more than 1 hour 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> 20 parts by mass of Vylon (registered trademark) RV280 (polyester resin manufactured by Toyobo Co., Ltd.), 90 parts by mass of toluene, and 90 parts by mass of methyl ethyl ketone were added to the sample bottle, and the mixture was stirred at room temperature for 1 hour to prepare a polyester solution B-1 (solid ingredient concentration 10% by mass).

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

<Production example of silicone resin solution C-1> 100 parts by mass of Symac (registered trademark) US-350, 100 parts by mass of toluene, and 100 parts by mass of methyl ethyl ketone were added to the sample bottle, followed by stirring at room temperature for 1 hour to prepare a silicone resin solution C-1 (solid content concentration). 10% by mass).

<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 reaction container 2, the contents of reaction container 2 were dropped into reaction container 1 and transferred. At this time, in order to prevent a violent reaction, dripping was performed for 10 minutes. After the dropping was completed, the reaction solution was left to stand at 20°C for 48 hours. Then, ammonia and water were distilled off by distillation, and a silica fine particle dispersion liquid (average primary particle diameter 35 nm) was produced. Then, 150 parts by mass of hexamethyldisilazane was added, and the mixture was heated at 65° C. for 2 days, thereby producing a silica fine particle dispersion D-1 modified with a trimethylsilyl group. In order to confirm the solid content concentration of the silica fine particle dispersion liquid, 5 g of the silica fine particle dispersion liquid was weighed in an aluminum cup (1.3 g) and heated in an oven at 150°C for more than 24 hours to remove the residual solvent ethanol. with water. If the aluminum cup after removal was measured, it was 1.55 g, so the solid content in 5 g of the silica fine particle dispersion liquid was calculated to be 0.25 g, and it was confirmed that the solid content concentration of the silica fine particle dispersion liquid was 5 mass %. Then, when preparing the coating liquid, the ethanol of the silica fine particle dispersion liquid was removed, and the same amount of toluene as the removed ethanol was added to prepare a toluene dispersion liquid and implemented. Furthermore, as a result of ESCA-based analysis of silica microparticles surface-modified with trimethylsilyl groups, C (carbon atom) was 8.5 at%.

<Synthesis method of fine particle dispersion liquid 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 reaction container 2, the contents of reaction container 2 were dropped into reaction container 1 and transferred. At this time, in order to prevent a violent reaction, dripping took 30 minutes. After the dropping was completed, the reaction solution was left to stand at 20°C for 48 hours. Then, ammonia and water were distilled off by distillation, and a silica fine particle dispersion liquid (average primary particle diameter 800 nm) was produced. Then, 150 mass parts of hexamethyldisilazane was added, and it heated at 65 degreeC for 2 days, and produced the silica fine particle dispersion liquid D-2 modified with a trimethylsilyl group. In order to confirm the solid content concentration of the silica fine particle dispersion liquid, 5 g of the silica fine particle dispersion liquid 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. with water. When the aluminum cup after removal was measured, it was 1.55 g, so the solid content in 5 g of the silica fine particle dispersion liquid was calculated to be 0.25 g, and it was confirmed that the solid content concentration of the silica fine particle dispersion liquid was 5 mass %. Then, when preparing the coating liquid, the ethanol of the silica fine particle dispersion liquid was removed, and the same amount of toluene as the removed ethanol was added to prepare a toluene dispersion liquid and implemented. Furthermore, as a result of ESCA-based analysis of silica microparticles surface-modified with trimethylsilyl groups, C (carbon atoms) was 9.0 at%.

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

Hereinafter, except that each substance was blended as shown in Table 1, it carried out similarly to coating liquid E-1, and mainly produced the coating liquids E-2 to E-12 for 2nd coating layers. Table 1 shows the compositions of coating liquids E-1 to E-12.

[Table 1] The obtained coating liquid for the second coating layer resin solution used Silica microparticle dispersion used Hardener used catalyst used Blending amount (parts by mass) Left-mentioned resin solution Left-mentioned microparticle 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 44 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 44 0.2 0.02 E-5 Silicone Resin Solution C-1 D-1 Millionate MR-200 KS-1260 40 40 44 0.2 0.02 E-6 Silicone Resin Solution C-1 D-1 Millionate MR-200 KS-1260 14 66 44 0.2 0.02 E-7 Acid Modified Polyolefin A-1 D-2 YD128 TETRAD-X 40 40 44 0.2 0.02 E-8 Acid Modified Polyolefin A-1 D-2 YD128 TETRAD-X 14 66 44 0.2 0.02 E-9 Polyester solution B-1 D-2 MS-001 PTS 40 40 44 0.2 0.02 E-10 Polyester solution B-1 D-2 MS-001 PTS 14 66 44 0.2 0.02 E-11 Silicone Resin Solution C-1 D-2 Millionate MR-200 KS-1260 40 40 44 0.2 0.02 E-12 Silicone Resin Solution C-1 D-2 Millionate MR-200 KS-1260 14 66 44 0.2 0.02

<Production of coating film> (Example 1) A bar coater # 5. After applying the polyester solution B-2, the first coating layer was produced by drying at 120° C. for 10 minutes (the thickness of the first coating layer after drying was 0.6 μm). After that, after coating the coating liquid E-1 produced by the method described in the above-mentioned production example of the coating liquid by the bar coater #5, it was dried at 110° C. for 60 minutes to produce the second coating. A coating layer was formed to obtain a coating film (the thickness of the second coating layer after drying was 0.6 μm).

(Examples 2 to 18) Hereinafter, the coating films of Examples 2 to 18 were obtained by changing the coating liquid of the first coating layer and the second coating layer, and the film thickness after drying of the two coating layers as shown in Table 2.

(Example 19) 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) which is a film made of polyethylene naphthalate. Coated film of Example 19.

(Comparative Example 1) A coated film was obtained by coating the acid-modified polyolefin solution A-2 on the corona-treated surface of the PET film E5100 using a bar coater #5, and drying at 120° C. for 1 minute.

(Comparative Example 2) A coated film was obtained by applying the coating liquid E-2 used in Example 2 to the corona-treated surface of the PET film E5100 with a bar coater #5, and then drying it at 110° C. for 60 minutes. .

(Comparative Example 3) Except having changed the film thickness after drying of the 1st coating layer and the 2nd coating layer as described in Table 2, it carried out similarly to Example 1, and obtained the coating thin film. 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) Adhesion to substrate coating liquid Film thickness after drying (μm) coating liquid Film thickness after drying (μm) Primary average particle size of fine particles (nm) WCA DCA Example 1 PET E5100 Polyester solution B-2 0.6 E-1 0.6 35 106.1 62.7 ○ Example 2 PET E5100 Polyester solution B-2 0.6 E-2 0.6 35 121.3 86.7 ○ Example 3 PET E5100 Polyester solution B-2 0.6 E-3 0.6 35 102.4 61.2 ○ Example 4 PET E5100 Polyester solution B-2 0.6 E-4 0.6 35 126.4 81.6 ○ Example 5 PET E5100 Polyester solution B-2 0.6 E-5 0.6 35 107 84.5 ○ Example 6 PET E5100 Polyester solution B-2 0.6 E-6 0.6 35 116.2 84.4 ○ Example 7 PET E5100 Polyester solution B-2 0.6 E-7 0.6 800 102.5 54.9 ○ Example 8 PET E5100 Polyester solution B-2 0.6 E-8 0.6 800 120.7 86.9 ○ Example 9 PET E5100 Polyester solution B-2 0.6 E-9 0.6 800 103.4 60.2 ○ Example 10 PET E5100 Polyester solution B-2 0.6 E-10 0.6 800 126 82.6 ○ Example 11 PET E5100 Polyester solution B-2 0.6 E-11 0.6 800 106.5 84.2 ○ Example 12 PET E5100 Polyester solution B-2 0.6 E-12 0.6 800 115.8 86.0 ○ Example 13 PET E5100 Polyester solution B-2 0.4 E-1 0.8 35 108.5 68.1 ○ Example 14 PET E5100 Polyester solution B-2 1.0 E-1 0.2 35 106.4 67.0 ○ Example 13 PET E5100 Acid-modified polyolefin A-2 0.6 E-2 0.6 35 121.5 83.8 ○ Example 14 PET E5100 Acid-modified polyolefin A-2 0.6 E-4 0.6 35 125.2 80.3 ○ Example 15 PET E5100 Acid-modified polyolefin A-2 0.6 E-6 0.6 35 118.1 82.3 ○ Example 16 PET E5100 Acid-modified polyolefin A-2 0.6 E-8 0.6 800 123 90 ○ Example 17 PET E5100 Acid-modified polyolefin A-2 0.6 E-10 0.6 800 126.8 81.9 ○ Example 18 PET E5100 Acid-modified polyolefin A-2 0.6 E-12 0.6 800 114.6 84.5 ○ Example 19 Teonex Q51 Polyester solution B-2 0.6 E-1 0.6 35 107.3 85.2 ○ Comparative Example 1 PET E5100 none - Acid-modified polyolefin A-2 0.6 - 99.6 53.7 ○ Comparative Example 2 PET E5100 none - E-1 0.6 35 120.5 87.2 × Comparative Example 3 PET E5100 Polyester solution B-2 0.2 E-1 1.0 35 106.8 65.5 × [Possibility of Industrial Use]

According to the present invention, a laminated film having excellent water and oil repellency and showing antifouling properties can be provided. The laminated film of the present invention is useful in applications such as packaging, coating, and release material.

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Claims (4)

A laminated film, which is a laminated film with a binder resin and a coating layer on a resin base film; wherein, the coating layer contains microparticles whose surfaces are hydrophobized; and when the thickness of the coating layer is divided into hundred equal parts , and the interface between the resin base film and the coating layer is set to 0, and the outermost surface of the coating layer is set to 100, the surface hydrophobized fine particles are only distributed in the part of 30-100. 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 microparticles whose surfaces are hydrophobized have an average diameter of primary particles ranging from 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.