WO2022049900A1

WO2022049900A1 - Laminated film

Info

Publication number: WO2022049900A1
Application number: PCT/JP2021/026323
Authority: WO
Inventors: 美唯妃林; 雅樹箭原; 浩司山田
Original assignee: 東洋紡株式会社
Priority date: 2020-09-02
Filing date: 2021-07-13
Publication date: 2022-03-10
Also published as: TW202221074A; JPWO2022049900A1

Abstract

[Problem] 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. [Solution] 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. More specifically, the present invention relates to a coated laminated film having water and oil repellency.

Materials that show water and oil repellency on the surface are industrially important in fields where antifouling properties are required. In order to achieve antifouling property, it is necessary to reduce the interaction between the pollutant and the surface of the material, and it is generally achieved by making the surface of the material water-repellent or oil-repellent.

Conventionally, a method of producing a film having excellent water repellency and oil repellency by using silica fine particles having voids or by using fine particles having voids by forming an aggregate is known (for example, Patent Document 1). See ~ 2). However, in general, the coating method for imparting water and oil repellency to the film surface has a problem that the adhesiveness to the base material is low and the coating layer easily falls off, so that sufficient water repellency and oil repellency are obtained. It was difficult to achieve both oil repellency and adhesion to the substrate.

Japanese Unexamined Patent Publication No. 2006-106507 Japanese Unexamined Patent Publication No. 2004-272198

The present invention has been made against the background of the problems of the prior art. That is, an object of the present invention is to provide a film that exhibits good physical properties in terms of both water repellency and oil repellency while maintaining adhesion to a resin base film.

As a result of diligent studies to achieve such an object, the present inventor has found that the above problems can be solved by the means shown below, and has arrived at the present invention. That is, the present invention has the following configuration.
1. 1. It is a laminated film having a coating layer containing a binder resin and fine particles whose surface is hydrophobicized and sparsely oiled on a resin base film, and is 10 nm from the surface of the coating layer as measured by an X-ray photoelectron spectrometer (ESCA). A laminated film in which the ratio of fluorine atoms is 20 at% or more when the atomic composition ratio is determined for the depth region of.
2. 2. The laminated film according to the first aspect, wherein the resin base film is a polyethylene terephthalate film or a polyethylene naphthalate film.
3. 3. The laminated film according to the first or second above, wherein the primary particle average diameter of the fine particles having a hydrophobic surface is 30 nm to 1 μm.
4. The laminated film according to any one of the above 1 to 3, wherein the binder resin is an acid-modified polyolefin resin or a polyester resin.

The laminated film of the present invention exhibits high water repellency 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.

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 base film.

(Resin base film)
The laminated film in the present invention has a resin base film. The material of this resin base film is not particularly limited, but the resin film is preferable from the viewpoint of handleability such as flexibility. Examples of the resin constituting the resin film include polyethylene, polypropylene, polyolefins such as polystyrene and diene polymers, polyesters such as polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, nylon 6, nylon 6,6. , Polyamides such as Nylon 6, 10, Nylon 12, Polymethylmethacrylate, Polymethacrylic acid esters, Polymethylacrylate, Polyacrylic acid esters and other acrylate-based resins, Polyacrylic acid-based resins, Polymethacrylic acid-based resins, Polyurethane-based resin, cellulose-based resin such as cellulose acetate, ethyl cellulose, polyarylate, aramid, polycarbonate, polyphenylene sulfide, polyphenylene oxide, polysulfone, polyether sulfone, polyether ether ketone, polyetherimide, polyimide, polyamideimide, polybenzimidazole , Aromatic hydrocarbon polymers such as polybenzoxazole and polybenzthiazole, fluororesins such as polytetrafluoroethylene and polyvinylidenefluoride, epoxy resins, phenolic resins, novolak resins, benzoxazine resins and the like. Of these, a film made of 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, and polyethylene naphthalate. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable from the viewpoint of physical properties, and polyethylene terephthalate is particularly preferable from the viewpoint of the balance between physical properties and cost.

The resin base film may be a single layer, or two or more types of layers may be laminated. When two or more layers are laminated, the same or different films can be laminated. Further, the resin composition may be laminated on the resin base film. Further, various additives can be contained in the resin base film, if necessary, as long as the effects of the present invention are exhibited. Examples of the additive include antioxidants, lightfasteners, antigelling agents, organic wetting agents, antistatic agents, ultraviolet absorbers, surfactants and the like. When the resin base film is composed of two or more layers, additives may be contained depending on the function of each layer. In order to improve the handleability such as slipperiness and winding property of the resin base film, the resin base film may contain inert particles.

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. It is more preferably 10 μm or more and 280 μm or less, and further preferably 12 μm or more and 260 μm or less. If it is 5 μm or more, it is easy to apply when laminating the coating layer, and if it is 300 μm or less, it is advantageous in terms of cost.

The surface of the resin base film may be used untreated, but surface treatments such as plasma treatment, corona treatment, and flame treatment, and those coated with a primer layer can also be used.

(Fine particles with a hydrophobic surface)
The laminated film in the present invention has a coating layer directly on the resin base film or via another layer, and the coating layer contains fine particles having a hydrophobic or oleicified surface. The type of fine particles is not particularly limited. For example, at least one of silica (silicon dioxide), alumina, titania, zirconia and the like can be used. These may be synthesized via any compound, or known or commercially available ones may be used. In particular, silica (silicon dioxide) fine particles are preferable because they can easily make the surface hydrophobic and oleophobic, which will be described later.

The surface of the fine particles is made hydrophobic and sparsely oiled, but the method of making the fine particles is not particularly limited, and for example, hydrophilic oxide fine particles may be made hydrophobic by surface treatment. That is, a hydrophilic oxide fine particle is surface-treated with an arbitrary reagent such as a silane coupling agent, and the surface is made hydrophobic.

As a method for hydrophobizing fine particles represented by silica fine particles, surface treatment with various known reagents such as silicon oil, a silane coupling agent and silazane is preferably used. In particular, from the viewpoint of exhibiting excellent water and oil repellency, 1H, 1H, 2H, 2H-perfluorooctyl group, 1H, 1H, 2H, 2H-perfluorodecyl group, 1H, 1H, 2H, 2H are exhibited on the surface. -Fluorofunctional groups typified by perfluorohexyl group, 3,3,3-trifluoropropyl group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- It is more preferable to introduce an alkyl group typified by a butyl group, a tert-butyl group, an octyl group and the like, an alkenyl group, an alkynyl group, a vinyl group, a cyclohexyl group, a styryl group, a phenyl group, a trimethylsilyl group and the like. Among these, hydrophobic and oleophilic oxide fine particles into which a 1H, 1H, 2H, 2H-perfluorooctyl group is introduced are preferable because they exhibit more excellent water repellency and oil repellency (oil sparseness), 1H and 1H. , 2H, 2H-hydrophobic and oleophilic silica with a perfluorooctyl group introduced is particularly preferred.

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 further preferably 30 nm or more and 1 μm or less. When it is 5 nm or more, it is easy to form irregularities on the surface layer of the coating layer, and it is easy to increase the contact angle described later, which is preferable. On the other hand, when it is 2 μm or less, it is preferable because fine particles are less likely to fall off from the coating layer, and it is also preferable because it is easy to maintain the transparency of the resin base film. In the present invention, the size of the average primary particle diameter can be determined as a result of morphological observation with a microscope using a scanning electron microscope, a transmission electron microscope, or the like. Specifically, the average diameter of 20 fine particles arbitrarily selected in these microscopic observations is defined as the average primary particle diameter. The average diameter of the primary particles of amorphous fine particles can be calculated as the equivalent diameter of a circle. The equivalent circle diameter is a value obtained by dividing the area of the observed fine particles by π, calculating the square root, and doubling it.

In the present invention, as an index of water repellency and oil repellency on the surface of the coating layer of the laminated film, that is, as an index of the modification rate by a functional group having water repellency and oil repellency on the surface of fine particles whose surface is hydrophobic or sparsely oiled. , The measurement result by the X-ray photoelectron spectrometer (ESCA) can be used. Specifically, the atomic composition ratio can be determined for a depth region of about 10 nm, and the ratio of specific atoms constituting a water-repellent / oil-repellent functional group, for example, a fluorine atom can be compared. In the present invention, from the viewpoint of exhibiting excellent water and oil repellency, for example, in the case of hydrophobic or oleophobic silica into which a 1H, 1H, 2H, 2H-perfluorooctyl group or the like is introduced, the ratio of fluorine atoms Is preferably 20 at% or more. When the fluorine atom ratio is 20 at% or more, good liquid repellency can be obtained even for a substance having a low surface tension. More preferably, it is 25 at% or more. Although there is no upper limit to the fluorine atom ratio, it is preferably 50 at% or less, and more preferably 40 at% or less, from the viewpoint of adhesion to the substrate and the like.

(Binder resin)
The binder resin in the present invention is not particularly limited as long as it is a component that can be well adhered to the resin base film. For example, it is preferable to use a polyester resin, an acid-modified polyolefin resin, a polyurethane resin, an epoxy resin, an acrylic resin, or the like. Further, from the viewpoint of adhesion to 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 deterioration of water repellency and oil repellency, polyester is used for the second coating layer. It is particularly preferable to use a resin, an acid-modified polyolefin resin, or an acrylic silicone resin.

The acid-modified polyolefin resin preferably has at least a part of polyolefin or unsaturated carboxylic acid-modified polyolefin, more preferably unsaturated carboxylic acid-modified polypropylene and unsaturated carboxylic acid-modified polyethylene, and most preferably unsaturated carboxylic acid-modified polypropylene. ..

As the unsaturated carboxylic acid, maleic acid, fumaric acid, acrylic acid, methacrylic acid, and acid anhydrides thereof are preferable, and maleic anhydride and maleic acid are most preferable. From these, it can be said that a coating layer having high adhesion to 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, and further preferably 5 mgKOH / g or more and 25 mgKOH / g. If it is less than the above, the adhesion to the resin base film is lowered, and if it is more than the above, the acid value leading to the deterioration of water repellency and oil repellency is larger than the lower limit, and the adhesion to the resin or the resin base film is good. When the acid value is smaller than the upper limit, the water and oil repellency of the resin itself is utilized in the liquid repellency of the coating layer, which is preferable.

The polyester resin used as the binder resin for the coating layer is not particularly limited, but a polyester resin of the Byron series manufactured by Toyobo Co., Ltd. is preferably used.

The binder resin may be used by mixing and cross-linking a curing agent, and isocyanate, epoxy, melamine and carboxylic acid are preferable, and epoxy and melamine are more preferable as the curing agent to be used. As a result, it is possible to form a coating layer containing silica fine particles while maintaining the transparency of the resin base film.

(Other components in the coating layer)
The coating layer in the present invention may contain components other than the fine particles. Specific examples thereof include a binder component, an antioxidant, a curing agent, a light resistant agent, an antioxidant, an organic wetting agent, an antistatic agent, an ultraviolet absorber, a surfactant, and the like, and these components may be used as required. Can be appropriately contained.

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 from the viewpoint of satisfying the adhesion between the coating layer and the resin base film. That is all. 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, particularly preferably 1.5 μm or less in consideration of water and oil repellency and economic efficiency of the surface of the coating layer. Is 1.2 μm or less.

The solid content of the coating liquid is preferably 0.5% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and further preferably 3% by mass or more and 10% by mass or less. Within the above range, the unevenness of the fine particles is easily exposed on the surface layer of the coating, and the coatability is also good, which is preferable.

The range of the mixing ratio of the fine particles to the binder resin (binder resin: fine particles) is preferably 90:10 to 5:95, more preferably 70:30 to 5:95, and further preferably 50:50 to 5. : 95. Within the above range, unevenness of fine particles appears on the surface, but it is preferable because it can form a state in which it is unlikely to fall off from the binder.

(solvent)
The solvent used for coating is not particularly limited, and for example, organic solvents such as water, alcohols, ketones, normal hexane, cyclohexane, toluene, butyl acetate and glycols are preferable, and toluene, cyclohexane, hexane and the like are preferable. The organic solvent of hexane is more preferable, and toluene is most preferable. As a result, the binder resin has high solubility and a uniform coating liquid can be produced.

(Primary particle diameter of fine particles with hydrophobic surface)
It can be determined as a result of morphological observation with a microscope using a scanning electron microscope, a transmission electron microscope, or the like. Specifically, the average of the diameters of 20 particles arbitrarily selected in these microscopic observations is defined as the primary particle average diameter.

(Measuring 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 the acid-modified polyolefin, and was 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 has been adjusted to 100 ° C., a 0.1 mol / L potassium hydroxide ethanol solution using phenolphthalein as an indicator at the same temperature [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 titration into mg.

(Water and oil repellency)
The water and oil repellency of the laminated film according to the present invention can be evaluated by a known method. Specifically, the water repellency can be evaluated by the contact angle measurement using water, and the oil repellency can be evaluated by the contact angle measurement using diiodomethane or decane. The range of the preferable contact angle with water in the present invention is more preferably 120 degrees or more than 100 degrees or more. The larger the contact angle with water, the better, and the upper limit is not particularly limited, but in reality, the upper limit is about 170 degrees. A water contact angle of 100 degrees or more is preferable because it exhibits excellent water repellency, and a water contact angle of 120 degrees or more is equivalent to or higher than that of a conventional fluororesin sheet typified by polytetrafluoroethylene (PTFE). It is more preferable because it is water-based. Further, the range of the preferred contact angle of diiodomethane in the present invention 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 reality, the upper limit is about 160 degrees. When the contact angle of diiodomethane is 60 degrees or more, it is preferable from the viewpoint of imparting oil repellency capable of suppressing oil stains, etc., and when it is 90 degrees or more, the oil repellency equal to or higher than that of the conventional fluorine-based resin sheet is obtained. It is more preferable because it is shown. The range of the contact angle with respect to the decan preferred in the present invention is more preferably 40 degrees or more than 30 degrees or more. The larger the contact angle with the decan, the better, and the upper limit is not particularly limited, but in reality, the upper limit is about 150 degrees. When the contact angle of Decan is 40 degrees or more, it is preferable because it shows excellent oil repellency, and when it exceeds 40 degrees, it has water repellency equal to or higher than that of a conventional fluororesin sheet typified by polytetrafluoroethylene (PTFE). It is more preferable because it shows.

(Manufacturing process of laminated film)
In the production of the laminated film of the present invention, the coating method is not particularly limited. For example, it can be produced according to a known method such as roll coating, gravure coating, bar coating, doctor 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, normal hexane, cyclohexane, toluene, butyl acetate, and glycols are appropriately selected and used. can do. These solvents may be used alone or in combination of two or more. The content of the fine particles having a hydrophobic surface with respect to the solvent can be selected at any ratio at which a uniform dispersion can be obtained. The method of drying after coating may be either natural drying or heat drying, 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 or the coating layer, but is usually preferably 150 ° C. or lower, and 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 or a hot air oven, can be used. The drying time is appropriately selected depending on other conditions such as the drying temperature, but may be any range as long as it does not affect the components contained in the resin base film or the coating layer. Further, the coating step may be a so-called offline coating method performed in a separate step after the resin base film is formed, or the coating liquid is applied to the unstretched sheet or the uniaxially stretched film in the resin base film manufacturing step. It may be a so-called in-line coating method in which the film is applied and stretched in at least one axial direction.

Hereinafter, the present invention will be further described with reference to specific examples, but the present invention is not limited to the embodiments of these examples. First, the evaluation method adopted in the present invention will be described.

(Measurement of contact angle)
The contact angle with respect to the solvent was measured on the surface of the coating layer of the produced laminated film. A contact angle meter CA-X manufactured by Kyowa Interface Science Co., Ltd. was used for the contact angle measurement. Pure water, diiodomethane, and decane were used as measurement solvents. The contact angle of water was measured after 10 seconds by dropping 1.8 μL of water droplets. The contact angle of diiodomethane was measured by dropping 0.9 μL of droplets of diiodomethane, and the contact angle of decan was measured 10 seconds after dropping 0.5 μL of droplets of decan.

(Adhesion measurement)
The adhesiveness between the film and the coating layer was judged by a visual test using cellophane tape. A cellophane tape having a width of 24 mm was attached to the coated surface, and after strongly crimping with a finger, it was visually confirmed whether or not the coating layer was peeled off when it was vigorously peeled off.
〇: No peeling is seen ×: No peeling is seen

(Measurement of average primary particle diameter)
The average diameter of the primary particles of the fine particles having a hydrophobic surface was determined as a result of observation with a scanning electron microscope or a transmission electron microscope. Specifically, the average diameter of 20 fine particles arbitrarily selected in these microscopic observations was taken as the average diameter of the primary particles. The average diameter of the primary particles of amorphous fine particles can be calculated as the equivalent diameter of a circle. The equivalent circle diameter is a value obtained by dividing the area of the observed fine particles by π, calculating the square root, and doubling it.

(ESCA measurement of fine particles whose surface is hydrophobized and sparsely oiled)
A fine particle dispersion having a hydrophobic and oil-free surface was dropped onto a clean aluminum foil and dried to form a thin film of fine particles having a hydrophobic surface on the aluminum foil. At this time, the surface was dried promptly so as not to cause surface contamination as much as possible, and immediately sampled and used for surface composition analysis.
As an apparatus, K-Alpha ⁺ (manufactured by Thermo Fisher Scientific) was used. Details of the measurement conditions are shown below. At the time of analysis, the background was removed by the shillley method. The surface composition ratio was the average value of the measurement results of three or more sites where Al was not detected in the resin base film.
-Measurement conditions Excited X-ray: Monochrome AlKα line X-ray output: 12 kV, 6 mA
Photoelectron escape angle: 90 degrees Spot size: 400 μmΦ
Path energy: 50eV
Step: 0.1eV

(ESCA measurement of the coating layer of the laminated film)
The composition was analyzed for a depth region of 10 nm from the surface of the coating layer of the laminated film.
As an apparatus, K-Alpha ⁺ (manufactured by Thermo Fisher Scientific) was used. Details of the measurement conditions are shown below. At the time of analysis, the background was removed by the shillley method. The surface composition ratio was the average value of the measurement results of three or more points.
-Measurement conditions Excited X-ray: Monochrome AlKα line X-ray output: 12 kV, 6 mA
Photoelectron escape angle: 90 degrees Spot size: 400 μmΦ
Path energy: 50eV
Step: 0.1eV

The reagents used at the time of studying the examples are listed below.
-Byron (registered trademark) RV280 (polyester resin manufactured by Toyobo)
・ MS-001 (Methylated melamine resin manufactured by Sanwa Chemical Co., Ltd.)
・ P-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry)
・ YD128 (Epoxy resin manufactured by Nittetsu Chemical & Materials)
-TETRAD (registered trademark) -X (multifunctional epoxy resin manufactured by Mitsubishi Gas Chemical Company)

<Production example of acid-modified polyolefin>
To 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-tert-butyl peroxide were added, the temperature was raised to 140 ° C., and the mixture was further stirred for 1 hour. After completion of the reaction, the reaction solution was put into a large amount of methyl ethyl ketone to precipitate a resin. The resin was further washed with methyl ethyl ketone several times to remove unreacted maleic anhydride. The obtained resin was dried under reduced pressure to obtain maleic anhydride-modified polypropylene (acid value 12.7 mgKOH / g, weight average molecular weight 60,000, Tm80 ° C.), which is an acid-modified polyolefin.

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

<Production example of acid-modified polyolefin solution A-2>
To the sample bottle, add 23 parts by mass of the 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®-X as a cross-linking catalyst. 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>
To a sample bottle, add 20 parts by mass of Byron (registered trademark) RV280 (Toyobo polyester resin), 90 parts by mass of toluene, and 90 parts by mass of methyl ethyl ketone, and stir at room temperature for 1 hour to make a polyester solution B-1 (solid content concentration 10% by mass). %) Was prepared.

<Production example of polyester solution B-2>
To the sample bottle, add 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 cross-linking agent, and 0.02 parts by mass of paratoluene sulfonic acid (PTS) as a cross-linking catalyst. , The polyester solution B-2 (solid content concentration 5% by mass) was prepared by stirring at room temperature for 5 minutes.

<Synthesis method of silica fine particle dispersion liquid D-1>
100 parts by mass of tetraethoxysilane and 439 parts by mass of ethanol were mixed in the reaction vessel 1. 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 vessel 2, the contents of the reaction vessel 2 were dropped and transferred to the reaction vessel 1. At this time, it was added dropwise over 10 minutes to prevent a sudden reaction. After completion of the dropping, the reaction solution was left at 20 ° C. for 48 hours. Then, ammonia and water were distilled off to prepare a silica fine particle dispersion (average primary particle diameter of 35 nm). Then, 7.5 parts by mass of 1H, 1H, 2H, 2H-perfluorooctyltrichlorosilane and 7.5 parts by mass of aqueous ammonia (25%) were added, and the mixture was heated at 65 ° C. for 2 days to obtain 1H, 1H, A silica fine particle dispersion D-1 modified with a 2H, 2H-perfluorooctyl group was prepared. In order to confirm the solid content concentration of the silica fine particle dispersion, 5 grams of the silica fine particle dispersion is measured in an aluminum cup (1.3 g) and heated in an oven at 150 ° C. for 24 hours or more to obtain ethanol as a residual solvent. And removed the water. Since the weight of the removed aluminum cup was 1.55 g, the solid content in 5 g of the silica fine particle dispersion could be calculated to be 0.25 g, and the solid content concentration of the silica fine particle dispersion was confirmed to be 5% by mass. .. After that, when preparing the coating liquid, ethanol was removed from the silica fine particle dispersion liquid, and the same amount of toluene as the removed ethanol was added to carry out as a toluene dispersion liquid. The results of analysis of the surface-modified silica fine particles by ESCA were 17.8 at% for C and 31.9 at% for F.

<Synthesis method of fine particle dispersion liquid D-2>
100 parts by mass of tetraethoxysilane and 49 parts by mass of ethanol were mixed in the reaction vessel 1. 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 vessel 2, the contents of the reaction vessel 2 were dropped and transferred to the reaction vessel 1. At this time, it was added dropwise over 30 minutes to prevent a sudden reaction. After completion of the dropping, the reaction solution was left at 20 ° C. for 48 hours. Then, ammonia and water were distilled off to prepare a silica fine particle dispersion (average primary particle diameter 800 nm). Then, 7.5 parts by mass of 1H, 1H, 2H, 2H-perfluorooctyltrichlorosilane and 7.5 parts by mass of aqueous ammonia (25%) were added, and the mixture was heated at 65 ° C. for 2 days to obtain 1H, 1H, A silica fine particle dispersion D-2 modified with a 2H, 2H-perfluorooctyl group was prepared. In order to confirm the solid content concentration of the silica fine particle dispersion, 5 grams of the silica fine particle dispersion is measured in an aluminum cup (1.3 g) and heated in an oven at 150 ° C. for 24 hours or more to obtain ethanol as a residual solvent. And removed the water. Since the weight of the removed aluminum cup was 1.55 g, the solid content in 5 g of the silica fine particle dispersion could be calculated to be 0.25 g, and the solid content concentration of the silica fine particle dispersion was confirmed to be 5% by mass. .. After that, when preparing the coating liquid, ethanol was removed from the silica fine particle dispersion liquid, and the same amount of toluene as the removed ethanol was added to carry out as a toluene dispersion liquid. As a result of analysis of the surface-modified silica fine particles by ESCA, C was 14.7 at% and F was 30.7 at%.

<Synthesis method of silica fine particle dispersion liquid D-3>
100 parts by mass of tetraethoxysilane and 439 parts by mass of ethanol were mixed in the reaction vessel 1. 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 vessel 2, the contents of the reaction vessel 2 were dropped and transferred to the reaction vessel 1. At this time, it was added dropwise over 10 minutes to prevent a sudden reaction. After completion of the dropping, the reaction solution was left at 20 ° C. for 48 hours. Then, ammonia and water were distilled off to prepare a silica fine particle dispersion (average primary particle diameter of 35 nm). Then, 150 parts by mass of hexamethyldisilazane was added and heated at 65 ° C. for 2 days to prepare a silica fine particle dispersion D-3 modified with a trimethylsilyl group. In order to confirm the solid content concentration of the silica fine particle dispersion, 5 grams of the silica fine particle dispersion is measured in an aluminum cup (1.3 g) and heated in an oven at 150 ° C. for 24 hours or more to obtain ethanol as a residual solvent. And removed the water. Since the weight of the removed aluminum cup was 1.55 g, the solid content in 5 g of the silica fine particle dispersion could be calculated to be 0.25 g, and the solid content concentration of the silica fine particle dispersion was confirmed to be 5% by mass. .. After that, when preparing the coating liquid, ethanol was removed from the silica fine particle dispersion liquid, and the same amount of toluene as the removed ethanol was added to carry out as a toluene dispersion liquid. As a result of analysis by ESCA of silica fine particles surface-modified with a trimethylsilyl group, C was 8.5 at% and F was less than 0.1 at%.

<Production example of coating liquid E-1>
40 parts by mass of acid-modified polyolefin solution A-1 (solid content concentration 10% by mass), 40 parts by mass of silica fine particle dispersion D-1 (solid content concentration 5% by mass), 44 parts by mass of toluene, epoxy curing agent YD128 in a sample bottle. Coating liquid E-1 (solid content concentration 5% by mass) by adding 0.2 part by mass (solid content concentration 100% by mass) and 0.02 part by mass of catalyst TETRAD-X (solid content concentration 100% by mass) and mixing. Was produced.

Hereinafter, E-9 was prepared mainly from the coating liquid E-2 for the second coating layer in the same manner as the coating liquid E-1 except that each substance was blended as shown in Table 1. Table 1 shows the compositions of the coating liquids E-1 to E-9.

<Making a coating film>
(Example 1)
Polyester solution B using bar coater # 5 on the corona-treated surface of Toyobo ester (registered trademark) film (product number: E5100, thickness: 75 μm), which is a film of polyethylene terephthalate (hereinafter sometimes referred to as PET film). After applying -2, the first coating layer was prepared by drying at 120 ° C. for 10 minutes (the thickness of the first coating layer after drying was 0.6 μm). Then, the coating liquid E-1 prepared by the method described in the above-mentioned production example of the coating liquid is coated with bar coater # 5, and then dried at 110 ° C. for 60 minutes to prepare a second coating layer. A coating film was obtained (the film thickness of the second coating layer after drying 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 coating film of Example 13 was used in the same manner as in Example 1 except that the resin base film used was changed to Theonex (registered trademark) film (product number: Q51, thickness 38 μm) made of polyethylene naphthalate. Obtained.

(Comparative Example 1)
An acid-modified polyolefin solution A-2 was applied to the corona-treated surface of the PET film E5100 using 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 exactly the same manner as in Example 1 except that the second coating layer was changed to the coating liquid E-9. Table 2 summarizes the evaluation results of each example and comparative example.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a laminated film having excellent water and oil repellency and exhibiting antifouling property. The laminated film according to the present invention can be applied to applications such as packaging, coating, and mold release materials, and is useful.

Claims

It is a laminated film having a coating layer containing a binder resin and fine particles whose surface is hydrophobicized and sparsely oiled on a resin base film, and is 10 nm from the surface of the coating layer as measured by an X-ray photoelectron spectrometer (ESCA). A laminated film in which the ratio of fluorine atoms is 20 at% or more when the atomic composition ratio is determined for the depth region of.
The laminated film according to 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 primary particle average diameter of the fine particles having a hydrophobic surface is 30 nm to 1 μm.
The laminated film according to any one of claims 1 to 3, wherein the binder resin is an acid-modified polyolefin resin or a polyester resin.