JP2014000697A - Water and oil-repellent antifouling film, method for manufacturing water and oil-repellent antifouling film, and water and oil-repellent antifouling plate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water and oil-repellent antifouling film which has excellent water repellency and oil repellency, and also has high antifouling property, scratch resistance and weather resistance; a method for manufacturing the water and oil-repellent antifouling film having high productivity; and a water and oil-repellent antifouling plate using the same.SOLUTION: The water and oil-repellent antifouling film has a water and oil-repellent layer on one face side of a resin substrate. The water and oil-repellent layer includes at least a binder, fine particles and a compound having water and oil-repellency. The surface of the water and oil-repellent layer has a root mean square roughness Rq which is measured in conformity to JIS B 0601-2001 in a range of 5-50 nm.

Description

  The present invention relates to a water / oil repellent antifouling film excellent in durability and water / oil repellency, a method for producing the same, and a water / oil repellent antifouling plate using the same.

  Conventionally, a wide range of studies have been conducted on methods for imparting surface modification functions such as water repellency, oil repellency, and antifouling properties to the surface of inorganic substrates such as glass, ceramics, and metals using various surface treatment agents. ing.

  As a method for imparting water repellency or oil repellency on these substrates, the water repellency of the substrate surface is improved, the dirt component is prevented from adhering to the substrate surface, and the surface energy is small on the substrate surface. Designs have been made to increase the contact angle of the substrate surface with water by applying a paint such as a material such as a silicone resin, a polyester resin, or a fluororesin. By adopting such a configuration, the surface of the base material is made water-repellent, it is difficult to be stained, antistatic property is imparted to the inside of the base material or the surface of the base material, and the surface potential is lowered, thereby causing contamination by static electricity. There is a method for preventing adhesion of dust and the like. Such a method can be said to be a method of preventing the adhesion of dirt on the surface of the base material or imparting surface characteristics that facilitate removal of the adhered dirt.

  When the compound group used for providing the above characteristics is roughly classified, a fluorine-based compound, a silicone-based compound (for example, polysiloxane and the like), and a hybrid compound thereof can be given. Among these, a compound group that has been attracting particular attention recently is a hybrid compound of a fluorine compound and a silicone (polysiloxane) compound.

  Specifically, as a method of applying a fluorine-based compound, for example, in JP-A-7-102187, a water-repellent paint in which a fluoroalkyl group-containing radical polymerization monomer is dispersed in a thermosetting matrix resin, etc. However, these materials have problems such as low compatibility between the fluororesin and other resins, and low durability and antifouling properties.

  On the other hand, as a silicone compound, for example, in Japanese Patent Publication No. 4-103668, a plastic material in which a silicone compound is mixed is proposed, but the compatibility between the silicone resin and other resins is also low, Moreover, it cannot be said that the water repellency obtained is sufficient. Japanese Patent Application Laid-Open No. 63-67828 discloses a method for treating a surface using an organosiloxane solution and in the presence of an inorganic acid catalyst or an organic acid catalyst, but requires an acid catalyst. And the problem that the polysiloxane structure obtained by the hydrolysis-condensation reaction of the alkoxysilyl group is incomplete.

  As a compound group obtained by hybridizing a fluorine compound and a silicone (polysiloxane) compound, JP-A-7-53919 discloses water repellency / oil repellency / antifouling by a perfluorooxyalkylene group-containing silane compound. In addition, JP-A-58-172245 discloses a material having a water-repellent surface by treating the surface of an inorganic substrate with a silane coupling agent containing a perfluoro group. The technology is described. However, in order to complete the hydrolysis-condensation reaction of the silane coupling agent, an acid catalyst is required. In addition, the crosslinking reaction does not proceed unless sufficient heating is performed, and the durability due to incomplete reaction is low. Had.

  Silane compounds and siloxane compounds having a fluorine-containing organic group such as a perfluoroalkyl group have been widely studied as surface treatment agents such as metals, glass, and ceramics, water repellents, and oil repellents. However, in general, these compounds give a hardened film by a dehydration condensation reaction of only the silicon-bonded alkoxy group, and are inferior in curability and durability on the substrate surface such as wear resistance. There was a problem of being. In addition, many of the fluorine-containing compounds that serve as these reaction reagents have a problem of high production costs.

  In addition to the water- and oil-repellent agents and antifouling agents based on the functional compounds as described above, the fluorine-containing resin compounds are also attracting attention. For example, fluorine-based polymers such as polytetrafluoroethylene (hereinafter abbreviated as PTFE) have various fields of use due to their excellent water repellency. However, PTFT itself has low moldability and resin strength (too stiff), low adhesion to substrates derived from low surface energy, and low solubility in solvents. As a result, compatibility with other resins is also achieved. It was bad. In addition, PTFT has a problem of an expensive material.

  As an attempt to improve the above-mentioned problems of PTFT, JP-A-7-133325 and the like describe that a fluoroethylene monomer and a vinyl ester monomer are copolymerized to form a surface modifier or a water / oil repellent. . This is a solvent-soluble fluorine-based polymer obtained by copolymerizing a fluoroolefin and a hydrocarbon-based monomer such as vinyl ether or vinyl ester, improving the problem of PTFE and being inexpensive. However, the amount of water repellency and oil repellency obtained is low due to copolymerization with other general-purpose resin monomers, and the main applications are in the field of protective coatings for buildings and civil engineering structures that require weather resistance and durability. Met.

  On the other hand, the contamination caused by the contaminants adhering to the material surface not only impairs the aesthetics but also reduces the function of the material surface due to the progress of contamination. As a result, in order to prevent contamination, it is necessary to reduce the adhesion (interaction) of contaminants, and this is generally achieved by making the material surface hydrophilic or oil repellent.

  Conventionally, as a film having water repellency and antifouling property, a film obtained by wet coating (wet film formation) with a fluorine compound layer on the outermost surface to impart water repellency and antifouling property (for example, , See Patent Document 1). However, in the surface coating method using an organic compound, the surface hardness and durability obtained are low, and it is necessary to improve them.

  In order to solve these problems, a method using a silica layer having excellent water repellency and antifouling properties and low surface free energy has been studied. This silica layer is used to improve the surface hardness and durability described above. Promising. However, when a silica layer having water repellency and antifouling properties is coated on a support to obtain a film having water repellency and antifouling properties, the surface energy of the silica layer is small, so There is a problem that the adhesion is reduced.

  In order to improve the adhesion between the support and the surface silica layer, a method is disclosed in which an adhesion silica layer having a carbon content of less than 20 atomic% is provided as an intermediate layer between the support and the surface silica layer ( For example, see Patent Document 2.) In this method, the adhesion between the support and the surface silica layer is improved by providing an adhesion silica layer having a large surface free energy between the surface silica layer and the support. However, in the disclosed method, it cannot be said that the adhesiveness is sufficient, and furthermore, the surface energy, water repellency, and antifouling properties vary greatly depending on the carbon content, so that it is difficult to control the characteristics. There was a problem.

  Furthermore, application of a super water-repellent film having a concavo-convex structure on its surface is disclosed for automobile window glass (see, for example, Patent Document 3). However, the super water-repellent film obtained by the disclosed method has a problem that it is difficult to achieve both water repellency and scratch resistance.

JP 2000-284102 A JP 2002-113805 A JP 2007-144917 A

  The present invention has been made in view of the above problems, and a solution to the problem is water and oil repellency prevention having excellent water repellency and oil repellency and having high antifouling properties, scratch resistance and weather resistance. An object is to provide a dirty film, a method for producing a water- and oil-repellent antifouling film having high productivity, and a water- and oil-repellent antifouling plate using the same.

  As a result of intensive studies in view of the above problems, the present inventor has a water / oil repellent layer on one surface side of the resin base material, and the water / oil repellent layer has at least a binder, fine particles and water / oil repellent properties. A water- and oil-repellent antifouling film, characterized in that it is formed by controlling the root mean square roughness Rq of the surface of the water- and oil-repellent layer to be in a specific range. It has been found that a water and oil repellent antifouling film having excellent water repellency and oil repellency, and having high antifouling properties, scratch resistance and weather resistance can be realized. .

  That is, the said subject of this invention is solved by the following means.

  1. A water / oil repellent antifouling film having a water / oil repellent layer on one side of a resin substrate, the water / oil repellent layer containing at least a binder, fine particles and a compound having water / oil repellent properties. And the surface of the water / oil repellent layer has a root mean square roughness Rq measured in accordance with JIS B 0601-2001 in the range of 5 to 50 nm. the film.

  2. 2. The water / oil repellent antifouling film according to item 1, wherein 70% to 95% of the outermost surface of the water / oil repellent layer is covered with the water / oil repellent compound.

  3. The water-repellent and oil-repellent layer has a pencil hardness measured in accordance with JIS K 5600-5-4 in the range of H to 5H. Oil-based antifouling film.

  4). 4. The binder according to any one of items 1 to 3, wherein the binder is a polymer compound having a metalloxane skeleton containing at least one atom selected from silicon, aluminum, zirconium and titanium. Water and oil repellent antifouling film.

  5. The fine particles are at least one kind of inorganic oxide fine particles selected from silica, alumina, titanium oxide, zinc oxide, and zirconium oxide, according to any one of items 1 to 4, Water and oil repellent antifouling film.

  6). 6. The water / oil repellent antifouling film according to any one of items 1 to 5, wherein the fine particles have an average particle diameter in the range of 10 to 100 nm.

  7). The water / oil repellency antifouling film according to any one of items 1 to 6, wherein the water / oil repellency compound is a fluorine-containing compound or an organosilicon compound.

  8). 7. The water / oil / oil repellent antifouling according to item 6, wherein the water / oil / oil repellent compound covering 70% to 95% of the outermost surface of the water / oil repellent layer is a fluorine-containing compound. the film.

  9. The water / oil repellent antifouling film according to any one of items 1 to 8, further comprising a hard coat layer between the water / oil repellent layer and the resin substrate.

  10. The water repellent according to any one of items 1 to 9, wherein the resin base material has an adhesive layer on a surface opposite to the surface having the water and oil repellent layer. Oil repellent antifouling film.

11. A method for producing a water / oil repellent antifouling film for producing the water / oil repellent antifouling film according to any one of items 1 to 10,
On the resin substrate, a water / oil repellent layer forming coating solution containing fine particles and a binder having a metalloxane skeleton is applied and dried to form layer A, and then the surface of layer A is subjected to high pressure under atmospheric pressure. A method for producing a water- and oil-repellent antifouling film, comprising applying a surface modification treatment by applying energy, and further forming a water- and oil-repellent layer through a step of adsorbing a compound having water and oil repellency .

  12 12. The method for producing a water / oil repellent antifouling film according to item 11, wherein the water / oil repellent compound is a fluorine-containing compound or an organosilicon compound.

  13. A water / oil repellency characterized in that the water / oil repellency antifouling film according to any one of Items 1 to 10 is bonded to a surface of a self-supporting substrate. Antifouling board.

  14 14. The water / oil repellent antifouling plate according to item 13, wherein the self-supporting substrate is at least one selected from plate glass, a resin substrate, a metal substrate, and a metal-resin composite plate.

  By the above means of the present invention, a water / oil repellent antifouling film having excellent water repellency and oil repellency and having high antifouling properties, scratch resistance and weather resistance, and water / oil repellency having high productivity. A method for producing an antifouling film and a water / oil repellent antifouling plate using the same can be provided.

  It is presumed that the above problem can be solved by the configuration defined in the present invention for the following reason.

  The technical feature of the present invention is that the water / oil repellency correlated with antifouling property has a very strong correlation with the root mean square roughness Rq, which is the basis of the technical idea of the present application. It is in. In general, the surface roughness index includes arithmetic average roughness Ra and ten-point average roughness Rz. The root mean square roughness Rq has a particularly strong correlation with water and oil repellency. It is speculated that the object and effect of the present invention could be achieved by setting the root mean square roughness Rq within a desired range.

Schematic sectional view showing an example of the layer structure of the water / oil repellent antifouling film of the present invention Schematic sectional view showing an example of the structure of a water / oil repellent antifouling plate provided with the water / oil repellent antifouling film of the present invention

  The water / oil repellent antifouling film of the present invention is a water / oil repellent antifouling film having a water / oil repellent layer on one side of a resin substrate, wherein the water / oil repellent antifouling layer is at least a binder, The root mean square roughness Rq measured in accordance with JIS B 0601-2001 is in the range of 5 to 50 nm, containing fine particles and a compound having water and oil repellency, and the surface of the water and oil repellency layer measured according to JIS B 0601-2001. Thus, it is possible to realize a water / oil repellent antifouling film which exhibits excellent water repellency and oil repellency and has high antifouling properties, scratch resistance and weather resistance. This feature is a technical feature common to the inventions according to claims 1 to 13.

  As an embodiment of the present invention, 70 to 95% of the outermost surface of the water / oil repellent layer is coated with the compound having the water / oil repellency from the viewpoint that the effects of the present invention can be further expressed. It is preferable that In the present invention, the outermost surface of the water / oil repellent layer is the side opposite to the surface on the resin substrate side, and in many cases, the surface in contact with the atmosphere. Moreover, it is preferable that the pencil hardness which the said water / oil repellent layer measured based on JISK5600-5-4 is the range of H-5H. The binder is preferably a polymer compound having a metalloxane skeleton containing at least one atom selected from silicon, aluminum, zirconium and titanium as a metal atom. The fine particles are preferably at least one inorganic oxide fine particle selected from silica, alumina, titanium oxide, zinc oxide and zirconium oxide. The average particle size of the fine particles is preferably in the range of 10 to 100 nm.

  The compound having water and oil repellency is preferably a fluorine-containing compound or an organosilicon compound. Furthermore, the water- and oil-repellent compound that covers a region of 70 to 95% of the outermost surface of the water- and oil-repellent layer is preferably a fluorine-containing compound.

  Furthermore, it is preferable that the water / oil repellent antifouling film has a hard coat layer between the water / oil repellent layer and the resin substrate. Moreover, it is preferable that the said resin base material has an adhesion layer in the surface on the opposite side to the surface which has the said water / oil repellent layer.

  Further, in the method for producing a water / oil repellent antifouling film of the present invention, a coating liquid for forming a water / oil repellent layer containing fine particles and a binder having a metalloxane skeleton is applied onto a resin substrate and dried. After forming A, the surface of the layer A is etched by applying high energy under atmospheric pressure, and a water- and oil-repellent layer is formed through a process of adsorbing a compound having water- and oil-repellency. It is characterized by doing. Furthermore, in the method for producing a water / oil repellent antifouling film of the present invention, it is a preferred embodiment that the compound having water / oil repellency is a fluorine-containing compound or an organosilicon compound.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, "-" shown in this invention is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

<Layer structure of water / oil repellent antifouling film>
FIG. 1 is a schematic cross-sectional view showing an example of the layer structure of the water / oil repellent antifouling film of the present invention.

  In FIG. 1, a water / oil repellent antifouling film 1 of the present invention (hereinafter also simply referred to as “antifouling film”) has at least one binder, fine particles and water repellent repellent on at least one surface side of a resin substrate 2. It is the structure which has the water- and oil-repellent layer 3 containing the compound which has oiliness.

  Furthermore, as shown in FIG. 1, the structure which provides the hard-coat layer 4 between the resin base material 2 and the water / oil repellent layer 3, or the surface which has the water / oil repellent layer 3 of the resin base material 2 It is a preferable aspect to have a configuration having the adhesive layer 5 on the surface opposite to the surface.

<Characteristic values of water / oil repellent layer>
The antifouling film of the present invention is characterized in that the root mean square roughness Rq measured according to JIS B 0601-2001 on the surface of the water / oil repellent layer is in the range of 5 to 50 nm. Furthermore, it is preferable that the pencil hardness measured based on JISK5600-5-4 is the range of H-5H.

[Root mean square roughness Rq]
In the present invention, the root mean square roughness (Rq) of the surface of the water / oil repellent layer is 5 to 50 nm, and preferably 10 to 45 nm. In the present invention, as a method of bringing the root mean square roughness (Rq) of the surface of the water / oil repellent layer to the range specified above, it is preferable to appropriately select fine particles used for forming the water / oil repellent layer.

  The root-mean-square roughness Rq in the present invention represents that described in JIS B 0601-2001, which is a JIS standard, and is represented by the following formula. Formerly, it is an index called RMS (Root Mean Square).

  In the formula, lr represents a reference length. x is a coordinate representing an arbitrary position, and Z (x) represents the height of the roughness curve at the coordinate x.

  As long as it conforms to the above JIS B 0601-2001, the method for deriving Rq is not particularly limited, but in the present invention, values measured at a cutoff λc of 2.5 mm and an evaluation length of 12.5 mm are used.

  In addition, as a specific measuring device of the root mean square roughness Rq, it is calculated from the height difference of the water / oil repellent layer surface using an atomic force microscope, for example, a simple AFM (Nanopics, manufactured by Seiko Instruments Inc.). Or the surface roughness of the surface of the water / oil repellent layer is measured using a laser microscope VK-9710 (manufactured by Keyence Corporation). Subsequently, the root mean square roughness Rq can be calculated using the analysis software attached to the VK-9710.

[Pencil hardness test]
In the present invention, the pencil hardness of the surface of the water / oil repellent layer is preferably in the range of H to 5H. In the present invention, the method for achieving the pencil hardness of the surface of the water / oil repellent layer as defined above can be achieved by appropriately selecting the binder and fine particles constituting the water / oil repellent layer.

The pencil hardness referred to in the present invention is a pencil hardness measured in accordance with JIS K 5600-5-4 (corresponding international standard: ISO15184), and the pencil core is pressed against the surface of the water / oil repellent layer to move it. The scratch hardness of the surface of the water / oil repellent layer is represented by the hardness of the pencil core (6B to HB to 6H) depending on whether or not there is a mark. For example, it can be measured according to the following method (mechanical method): 1) Device used: A pencil is set at an angle of 45 degrees on a wheeled block, and the sample surface is run. For example, a pencil hardness tester manufactured by Toyo Seiki Co., Ltd. can be used.

2) Specifications of the device ・ Load load at the tip of the pencil: 750 ± 10 g
・ Used pencil: Mitsubishi Pencil Uni (6B ~ HB ~ 6H)
・ Adjusting the lead of the pencil: Only the xylem is shaved, and the core is kept without being shaved. The tip maintains an angle of 90 degrees, and the surface is polished with abrasive paper to form a smooth and circular cross section.

3) Measuring method It is confirmed with a level attached to the apparatus that the apparatus used for mounting the pencil at an angle of 45 degrees is horizontal with respect to the surface of the water and oil repellent layer.

    2. A device with a pencil attached to the surface of a water- and oil-repellent layer of an antifouling film conditioned at a temperature of 23 ° C. and a relative humidity of 55% for 2 hours or more at a speed of 0.5 to 1.0 mm / s is about 7 mm. Travel the distance.

    3. Judgment: If there is a scratch or the like, the pencil scale is softened and a pencil scale without scratches is obtained. On the other hand, if there is no scratch or the like, the pencil scale is hardened, the pencil scale that is scratched is searched, the hardest pencil scale that is not scratched is found, and this is set as the evaluation rank of the pencil test.

[Measurement of water / oil repellent layer coverage of compound having water / oil repellency]
In the water / oil repellent layer according to the present invention, the water / oil repellent compound constituting the water / oil repellent layer covers an area of 70 to 95% of the surface of the water / oil repellent layer. Is a preferred embodiment.

  The atom covering the surface of the water / oil repellent layer is an atom having a strong surface orientation, for example, a fluorine atom or a silicon atom. As a method of achieving the coverage defined in the present invention, a method of forming a water / oil repellency layer with a binder and fine particles and then applying a water / oil repellency compound and performing a super water repellency treatment is preferable. .

  In the present invention, an X-ray photoelectron spectrometer (XRD JPS-9200, manufactured by JEOL Ltd.) or an X-ray photoelectron spectrometer is used as a method for measuring the coverage of a compound having water and oil repellency on the surface of the water and oil repellent layer. (Shimadzu Corporation, ESCA 850 type) is used, the atomic composition ratio is obtained for a region of φ100 μm and a depth of 5 nm, and the specific atom constituting the compound having water and oil repellency, for example, the atomic density of fluorine atoms, The area occupied by the surface of the compound having water / oil repellency is calculated to determine the water / oil repellency layer coverage by the compound having water / oil repellency.

<Constituent elements of water / oil repellent antifouling film>
In the water / oil repellent antifouling film of the present invention, the water repellency referred to in the present invention means “super water repellency”. In the present invention, “super water repellency (characteristic)” means that the contact angle with water on the surface of the water / oil repellent layer is 150 ° or more. In the present invention, the root mean square roughness (Rq) Means that the surface of the water / oil repellent layer having a concavo-convex structure in a range of 5 to 50 nm has a contact angle with water of 150 ° or more. In the present invention, in order to achieve the surface of the water / oil repellent layer having a contact angle with water of 150 ° or more, a compound having water / oil repellency is used when forming the water / oil repellent layer, The method of achieving by adjusting formation conditions so that the compound which has oiliness orients in the surface area | region of 70 to 95% of a water- and oil-repellent layer is preferable.

  The contact angle with water as used in the present invention means a static contact angle with respect to water applied to the surface of the water / oil repellent layer. For example, the measurement sample is placed in an environment of 25 ° C. and 55% RH for 3 hours. After adjusting the humidity above, using a contact angle measuring device (CONTACT ANGLE METER CA-Z) manufactured by Kyowa Interface Science Co., Ltd., 3 μl of pure water was dropped in the above environment, and the angle after 20 seconds was measured. It is. The measurement was repeated seven times, and the contact angle with water was calculated as an average value of five times excluding the upper limit and the lower limit twice.

  Similarly, in the water / oil repellent antifouling film of the present invention, the oil repellency referred to in the present invention means “super oil repellency”.

The super oil repellent surface referred to in the present invention can basically be formed with the same concept as the super water repellent surface described above. However, the super oil repellent surface must have a higher surface roughness and a higher surface roughness than the super water repellent surface. This is because the surface free energy of oil is generally as low as about 30 mJ / m ² compared to the surface free energy of water (72 mJ / m ² ). However, in essence, the super-oil-repellent surface is a super-water-repellent surface, and the surface of the water- and oil-repellent layer having a concavo-convex structure having a root mean square roughness (Rq) in the range of 5 to 50 nm is An element having a low free energy, for example, a fluorine atom, specifically, —CF ₃ terminal is arranged as densely as possible. Therefore, on the surface of the water / oil repellent layer according to the present invention, for example, it is achieved by adjusting the forming conditions to be applied so that a compound containing a fluorine atom is oriented in a surface area of 70 to 95%. be able to.

  Next, details of the water / oil repellent layer and the resin substrate constituting the antifouling film of the present invention, and the hard coat layer and adhesive layer that can be suitably incorporated will be described.

[1] Water / oil repellent layer The water / oil repellent layer according to the present invention comprises at least a binder, fine particles and a compound having water / oil repellency.

(1) Binder The binder applicable to the water / oil repellent layer according to the present invention is not particularly limited, but is a polymer having a metalloxane skeleton containing at least one atom selected from silicon, aluminum, zirconium and titanium. A compound is preferred.

  In consideration of the case where the antifouling film of the present invention is applied to a car window of an automobile, the binder applicable to the water / oil repellent layer according to the present invention is preferably a highly transparent binder. . High transparency as used in the present invention means that the transparent binder is formed under the condition that the film thickness after drying is 150 μm, and the transmittance measured with light having a wavelength of 550 nm is 70% or more, preferably Is 80% or more, more preferably 90% or more.

  The metalloxane skeleton in the present invention is a skeleton having a bond between a metal atom and an oxygen atom, that is, a MO bond, and the polymetalloxane is a polymer having a repeating main chain skeleton of this MO bond. A sol-gel method is preferable as a method for polymerizing the compound. Examples of the polymetalloxane include polysiloxane, polytitanoxane, polyaluminoxane, polyzircoxane and the like.

<1-1> Polymer compound having a metalloxane skeleton Examples of materials having a metalloxane skeleton include polymethoxane such as silicon, titanium, zirconium, and aluminum, or polysilazane, perhydropolysilazane, alkoxysilane, alkylalkoxysilane, and polysiloxane. A compound having a metalloxane skeleton containing at least one element selected from silicon, aluminum, zirconium and titanium is preferable.

The binder having a metalloxane skeleton according to the present invention is preferably a polysiloxane, a polytitanoxane, a polyaluminoxane, or a polyzirconoxane composed of a polymetalloxane formed from a metal alkoxide. Metal alkoxides include Si (OC ₂ H ₅ ) ₄ , Al (OC ₂ H ₅ ) ₄ , Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (iso-OC ₃ H ₇ ) ₄ , Ti Single metal alkoxides such as (OC ₄ H ₉ ) ₄ , Zr (OC ₂ H ₅ ) ₄ , Zr (iso-OC ₃ H ₇ ) ₄ , Zr (OC ₄ H ₉ ) ₄ can be mentioned.

  Among the above, polysiloxane is preferable, and polysiloxane represented by the following general formula (1) is particularly preferable.

In formula (1), R ¹¹ and R ¹² may be the same or different and each represents an organic group such as a hydrogen atom, an alkyl group, or an aryl group.

  Examples of the polysiloxane include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltoxioxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycid. Xylpropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyl Hydrolyzable silyl such as methyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane Hydrolyzed silane compounds, organosilica sols in which silicic acid fine particles are stably dispersed in an organic solvent, or those obtained by adding the above-mentioned silane compounds having radical polymerizability to organosilica sols, etc. be able to. However, the present invention is not limited to this.

<1-2> Sol-Gel Method It is preferable to apply a method in which an inorganic oxide is formed by a thermosetting reaction using a sol-gel method as at least the binder according to the present invention.

The sol-gel method is a method of forming an inorganic oxide from an organic metal compound that is a precursor of an inorganic oxide. In other words, a metal alkoxide, which is a kind of organometallic compound, is used as a starting material, and after the solution is hydrolyzed and polycondensed to form a sol, the reaction is further gelled by moisture in the air, etc. A thing is obtained. For example, in the process of forming a silica glass film, when tetraethoxysilane (Si (OC ₂ H ₅ ) ₄ ), which is a metal alkoxide of silicon, is used, tetraethoxysilane is dissolved in a solvent such as alcohol, and a catalyst such as an acid is used. By adding a small amount of water and mixing well, a liquid polysiloxane sol is formed according to the following reaction formula.

Hydrolysis reaction Si (OC ₂ H ₅ ) ₄ + 4H ₂ O → Si (OH) ₄ + 4C ₂ H ₅ OH
Dehydration condensation reaction nSi (OH) ₄ → [SiO ₂ ] n + 2nH ₂ O
When a polysiloxane sol is applied to a resin substrate and dried, the volume of the sol shrinks with the evaporation of water and ethyl alcohol (C ₂ H ₅ OH) generated by the solvent and reaction. Residual OH groups at the ends of the polymer undergo a dehydration condensation reaction and are bonded, and the coating film becomes a gel (solidified body). Furthermore, when the obtained gel film is baked to strengthen the bond between the polysiloxane particles, a strong gel film can be obtained.

  In the sol-gel method, the above-described organometallic compound may be used for the reaction as it is, but it is preferably diluted with a solvent for easy control of the reaction. The dilution solvent may be any solvent that can dissolve the organometallic compound and can be uniformly mixed with water. Preferred examples of such a solvent for dilution include aliphatic lower alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol, and mixtures thereof. Further, a mixed solvent of butanol, cellosolve, and butyl cellosolve, or a mixed solvent of xylol, cellosolve acetate, methyl isobutyl ketone, and cyclohexane may be used.

(2) Fine particles The fine particles used for forming the water / oil repellent layer of the water / oil repellent antifouling film of the present invention are not particularly limited, but are preferably inorganic fine particles composed of an inorganic oxide. As oxide fine particles, the metal constituting the metal oxide is Li, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Rb. Sr, Y, Nb, Zr, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Ta, Hf, W, Ir, Tl, Pb, Bi, etc. Silicon oxide, titanium oxide, zinc oxide, aluminum oxide, zirconium oxide, hafnium oxide, niobium oxide, tantalum oxide, magnesium oxide, calcium oxide, strontium oxide, barium oxide, indium oxide, tin oxide In the present invention, the inorganic oxide fine particles are preferably at least one transparent inorganic oxide fine particle selected from silica, alumina, titanium oxide, zinc oxide and zirconium oxide. . The fine particles according to the present invention preferably have high transparency.

  The shape of the fine particles applied to the water / oil repellent layer according to the present invention is preferably a spherical shape or a rugby ball shape.

  Further, the mean particle diameter of the fine particles is in the range of 10 to 180 nm, and the root mean square roughness Rq of the surface of the water / oil repellent layer defined in the present invention can be controlled in the range of 5 to 50 nm. It is preferable from a viewpoint, More preferably, it is the range of 10-100 nm.

  If the average particle diameter is 10 nm or more, the root mean square roughness Rq can be 5 nm or more, and sufficient surface roughness can be ensured. Moreover, if an average particle diameter is 180 nm or less, the root mean square roughness Rq can be 50 nm or less, and the transparency of an antifouling film is not impaired.

  Moreover, in the water / oil repellent layer according to the present invention, the proportion of fine particles when the binder having the metalloxane skeleton is 100% by mass is preferably in the range of 30 to 90% by mass.

(3) Compound having water and oil repellency In the water and oil repellency layer according to the present invention, 70 to 95% of the outermost surface of the water and oil repellency layer is coated with a compound having water and oil repellency. It is a preferable embodiment from the viewpoint of achieving super water repellency. In particular, the surface content of the specific element constituting the compound having water and oil repellency, particularly fluorine element or silicon atom, is preferably 40 to 60 atomic% of the outermost surface of the water and oil repellent layer. .

  In the present invention, the compound having water and oil repellency is preferably a fluorine-containing compound or an organic silicon compound, and further, the water repellency that covers 70 to 95% of the outermost surface of the water and oil repellency layer. The compound having oil repellency is preferably a fluorine-containing compound containing a fluorine atom.

  Specific examples of the water- and oil-repellent compounds applicable to the present invention include fluorine-based surfactants and silicone-based compounds.

  The fluorosurfactant is not particularly limited and can be obtained as a commercial product. For example, Surflon S-381, S-382, SC-101, SC-102, SC-103, SC-104 (Asahi Glass Co., Ltd.), Florad FC-430, FC-431, FC-173 (Fluorochemical-Sumitomo 3M), F-Top EF352, EF301, EF303 (Shin-Akita Kasei Co., Ltd.) , Schwegau Fluer 8035, 8036 (manufactured by Schwegman), BM1000, BM1100 (manufactured by BM Himmy), Megafuck F-171, F-470 (all manufactured by DIC Corporation), and the like. .

  Moreover, as a fluorine compound with antifouling property, OPTOOL DAC, DSX (manufactured by Daikin Industries), FS-1010, 7010 (manufactured by Fluoro Technology), ZX-058-A, 212, 201, 202, 214-A, 101 (Fuji Kasei Kogyo Co., Ltd.) and the like.

  As the silicone compound, commercially available silicone surfactants manufactured by Toray Dow Corning, Shin-Etsu Chemical, Big Chemie Japan, and GE Toshiba Silicone can also be used.

  In the water / oil repellent layer according to the present invention, as a method of containing these water / oil repellent compounds, it can be directly added to the water / oil repellent layer forming coating solution. From the viewpoint of aligning and coating 70 to 95% of the outermost surface of the water / oil repellent layer with a compound having water / oil repellency, the resin substrate contains fine particles and a binder having a metalloxane skeleton. It is preferable to apply the water / oil repellent layer forming coating solution and then immerse it in a solution containing a compound having water and oil repellency at a predetermined concentration.

  At this time, the surface coverage of the compound having water / oil repellency can be controlled by appropriately adjusting the concentration of the compound having water / oil repellency in the solution. Although it varies depending on the compound to be applied, it is generally in the range of 0.5 to 10% by mass, preferably in the range of 1.0 to 5.0% by mass.

(4) Other Additives Various conventionally known additives can be used for the water / oil repellent layer according to the present invention or the resin substrate described later.

(UV absorber)
As the ultraviolet absorber, an organic ultraviolet absorber or an inorganic ultraviolet absorber can be used, and an inorganic ultraviolet absorber is preferable.

  As the inorganic ultraviolet absorber, a metal oxide is preferable. Preferred metal oxides include titanium oxide, zinc oxide, cerium oxide, iron oxide, or a mixture thereof.

  Further, from the viewpoint of improving the transparency of the surface layer containing the inorganic ultraviolet absorber, the inorganic ultraviolet absorber preferably has an average particle size in the range of 5 to 150 nm, particularly preferably. Is an average particle size in the range of 10 to 100 nm, and is a metal oxide particle having a maximum particle size distribution of 150 nm or less. Such coated or uncoated metal oxide pigments are described in more detail in patent application EP-A-0 518 773.

  Examples of the inorganic ultraviolet absorber include Sicotrans Red L2815 (iron oxide; manufactured by BASF), CeO-X01 (cerium oxide; manufactured by Iox Co., Ltd.), NANOFINE-50 (zinc oxide; manufactured by Sakai Chemical Industry Co., Ltd.), and STR. -60 (titanium oxide; manufactured by Sakai Chemical Industry Co., Ltd.), CM-1000 (manufactured by iron oxide chemilite industry Co., Ltd.), CERIGUARD S-3018-02 (cerium oxide manufactured by Daito Kasei Kogyo Co., Ltd.), MZ-300 (zinc oxide) TA-KA Co., Ltd.), MT-700B (titanium oxide manufactured by TAICA CO., LTD.) And the like are commercially available.

  The particle size of the inorganic ultraviolet absorber can be measured by LB-550 (manufactured by Horiba, Ltd.) which is a dynamic light scattering particle size distribution measuring device, and the number average particle size is obtained from the output of the measurement result. be able to.

(Antioxidant)
As the antioxidant, it is preferable to use a phenol-based antioxidant, a thiol-based antioxidant, and a phosphite-based antioxidant.

  Examples of phenolic antioxidants include 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 2,2′-methylenebis (4-ethyl-6-t-). Butylphenol), tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 2,6-di-t-butyl-p-cresol, 4,4 '-Thiobis (3-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), 1,3,5-tris (3', 5'-di-t -Butyl-4'-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propio , Triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis [1,1-di-methyl-2- [β- (3 -T-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] -2,4,8,10-tetraoxoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4 , 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like. In particular, the phenolic antioxidant preferably has a molecular weight of 550 or more.

  Examples of the thiol antioxidant include distearyl-3,3′-thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thiopropionate), and the like.

  Examples of the phosphite antioxidant include tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,6-di-t-butylphenyl) pentaerythritol. Diphosphite, bis- (2,6-di-t-butyl-4-methylphenyl) -pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylene-diphosphonite 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite and the like.

  In addition, the said antioxidant and the following light stabilizer can also be used together.

  Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 1-methyl- 8- (1,2,2,6,6-pentamethyl-4-piperidyl) -sebacate, 1- [2- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl ] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6, 6-tetramethyl Piperidine, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, triethylenediamine, 8-acetyl-3-dodecyl-7,7,9 , 9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione.

  Other nickel-based UV stabilizers include [2,2′-thiobis (4-t-octylphenolate)]-2-ethylhexylamine nickel (II), nickel complex-3,5-di-t-butyl-4- Hydroxybenzyl phosphate monoethylate, nickel dibutyl-dithiocarbamate and the like can also be used.

  In particular, the hindered amine light stabilizer is preferably a hindered amine light stabilizer containing only a tertiary amine, specifically, bis (1,2,2,6,6-pentamethyl-4-piperidyl). Sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate, or A condensate of 1,2,2,6,6-pentamethyl-4-piperidinol / tridecyl alcohol and 1,2,3,4-butanetetracarboxylic acid is preferred.

[Resin substrate]
Various conventionally known resin films can be used as the resin base material. For example, cellulose ester film, polyester film, polycarbonate film, polyarylate film, polysulfone (including polyethersulfone) film, polyethylene terephthalate, polyethylene naphthalate polyester film, polyethylene film, polypropylene film, cellophane, Cellulose diacetate film, cellulose triacetate film, cellulose acetate propionate film, cellulose acetate butyrate film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, syndiotactic polystyrene film, polycarbonate film, norbornene resin film , Polymethylpentenef Can Lum, polyether ketone film, polyether ketone imide film, a polyamide film, a fluororesin film, a nylon film, polymethyl methacrylate film, and acrylic films. Among these, a polycarbonate film, a polyester film, a norbornene resin film, and a cellulose ester film are preferable.

  In particular, it is preferable to use a polyester film or a cellulose ester film, and it may be a film manufactured by melt casting or a film manufactured by solution casting.

  The thickness of the resin base material is preferably an appropriate thickness according to the type and purpose of the resin. For example, it is generally in the range of 5 to 450 μm. Preferably it is 10-200 micrometers, More preferably, it is 20-100 micrometers.

[Hard coat layer]
In the antifouling film of the present invention, a structure in which a hard coat layer is provided between the water / oil repellent layer and the resin substrate improves the adhesion between the water / oil repellent layer and the resin substrate. From the viewpoint of obtaining higher film hardness.

  The material constituting the hard coat layer according to the present invention is not particularly limited as long as transparency, weather resistance, hardness, mechanical strength and the like can be obtained.

  Examples of the hard coat layer include acrylic resins, urethane resins, melamine resins, epoxy resins, organic silicate compounds, and silicone resins that have been conventionally used as hard coat constituent materials. From the viewpoint of the film hardness obtained and the affinity with the water / oil repellent layer composed of the inorganic polymer and inorganic fine particles formed thereon, the hard coat layer is preferably composed of an inorganic material.

  As the inorganic material constituting the hard coat layer according to the present invention, it is preferable to apply the same inorganic polymer as that used for forming the water / oil repellent layer according to the present invention, for example, silicon, aluminum, zirconium and titanium. And a polymer compound having a metalloxane skeleton containing at least one element selected from the group consisting of:

  Further, as an inorganic substance constituting the hard coat layer, polysilazane can be applied and formed, and a heat-cured film can be formed. When the hard coat precursor contains polysilazane, for example, after applying a solution with a catalyst added to an organic solvent containing polysilazane represented by the following general formula (1) as necessary, the solvent is evaporated. The polysilazane layer having a layer thickness of 0.05 to 3.0 μm is formed on the resin substrate. Then, a glass-like transparent hard coat film is formed on the resin substrate by locally heating the polysilazane layer in the presence of oxygen, active oxygen, and in some cases nitrogen in an atmosphere containing water vapor. can do.

General formula (1)
-(SiR ¹ R ² -NR ³ ) _n-
In the above general formula (1), R ¹ , R ² , and R ³ are the same or different, and independently of each other, hydrogen, or an optionally substituted alkyl group, aryl group, vinyl group, or (trialkoxy) Silyl) alkyl groups, preferably hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, phenyl, vinyl or 3- (triethoxysilyl) propyl, 3- (trimethoxysilylpropyl) Represents a group selected from the group consisting of In this case, n is an integer, and n is determined so that polysilazane has a number average molecular weight of 150 to 150,000 g / mol.

  As catalysts, preferably basic catalysts, in particular N, N-diethylethanolamine, N, N-dimethylethanolamine, triethanolamine, triethylamine, 3-morpholinopropylamine or N-heterocyclic compounds are used. . The catalyst concentration is usually in the range of 0.1 to 10 mol%, preferably 0.5 to 7 mol%, based on polysilazane.

In one preferred embodiment, a solution containing perhydropolysilazane in which all of R ¹ , R ² and R ^{3 in} the general formula (1) are hydrogen atoms is used.

(Adhesive layer)
In the antifouling film of this invention, it is preferable to have an adhesion layer in the surface on the opposite side to the surface which provided the water- and oil-repellent layer of the resin base material.

  The adhesive layer provided on the back surface of the antifouling film pastes the water / oil repellent antifouling film of the present invention and the self-supporting substrate when producing the water / oil repellent antifouling film plate of the present invention. It has a function to match.

  The constituent material of the adhesive layer is not particularly limited, and for example, any of a dry laminating agent, a wet laminating agent, an adhesive, a heat seal agent, a hot melt agent, and the like is used. As the adhesive, for example, a polyester resin, a urethane resin, a polyvinyl acetate resin, an acrylic resin, a nitrile rubber, or the like is used. The laminating method is not particularly limited, and for example, it is preferable to carry out the roll method continuously from the viewpoint of economy and productivity. Moreover, it is preferable that the thickness of an adhesion layer is the range of about 1-100 micrometers normally from viewpoints, such as an adhesion effect and a drying rate.

  It is preferable that the adhesive layer provided on the back surface of the antifouling film of the present invention further has a separate film on the surface thereof.

  That is, as a method for providing an adhesive layer on the back surface of the antifouling film of the present invention, as a first step, the constituent material of the adhesive layer is applied on a separate film to form an adhesive layer. As a second step, the adhesive layer formed on the separate film is bonded to the back surface of the antifouling film of the present invention with the separate film attached thereto to form an adhesive layer. Thereafter, the separation film is left as it is, and the adhesive layer surface is protected until a water / oil repellent antifouling film plate is produced. As a third step, the separate film provided on the surface of the adhesive layer is peeled off and bonded to a self-supporting substrate to produce a water / oil repellent antifouling film plate.

  As a separate film, what can protect the adhesiveness of the adhesion layer is sufficient, for example, acrylic film or sheet, polycarbonate film or sheet, polyarylate film or sheet, polyethylene naphthalate film or sheet, polyethylene terephthalate film Or resin film or sheet such as sheet, fluorine film, resin film or sheet kneaded with titanium oxide, silica, aluminum powder, copper powder, etc., coating the resin kneaded with these, and depositing metal such as aluminum on metal A resin film or sheet that has been subjected to surface processing such as scouring is used. Although the thickness of a separate film does not have a restriction | limiting in particular, Usually, it is preferable that it is the range of 12-250 micrometers.

<< Production Method of Water / Oil Repellent Antifouling Film >>
As a method for producing the water / oil repellent antifouling film of the present invention,
1) Step 1 of forming a layer A by applying and drying a water / oil repellent layer forming coating solution containing fine particles and a binder having a metalloxane skeleton on a resin substrate;
2) Step 2 of subjecting the surface of the layer A to surface modification treatment by applying high energy under atmospheric pressure,
3) Step 3 for adsorbing a compound having water and oil repellency;
And a water / oil repellent layer is formed.

  In step 1, a fine particle, a binder having a metalloxane skeleton, and if necessary, an ultraviolet absorber, a stabilizer and a solvent are mixed, and then dissolved by heating to prepare a coating solution for forming a water / oil repellent layer. A coating liquid for forming a water / oil repellent layer is applied onto a resin substrate and then dried by heating to form layer A.

  As the coating method used for coating the coating liquid for forming the water / oil repellent layer, a wet coating method is applied, for example, a gravure coating method, a reverse coating method, a die coating method, a bar coating method, an extrusion method, a dip method, a slide. A hopper method or the like can be applied.

  In step 2, the layer A formed on the resin substrate is subjected to surface modification treatment by applying high energy under atmospheric pressure.

  Examples of the surface modification treatment include dry processes such as corona treatment, atmospheric pressure plasma treatment, oxygen plasma treatment, ultraviolet irradiation treatment, ozone treatment, excimer lamp treatment, and heat treatment, sodium hydroxide, potassium hydroxide, and ethanolamine. A wet process such as an alkali treatment by the like. In the present invention, among these, corona treatment, atmospheric pressure plasma treatment, and excimer lamp treatment that can be performed under atmospheric pressure are preferable from the viewpoint of production efficiency.

The corona treatment applicable to the present invention is a treatment performed by applying a high voltage of 1 kV or more between the electrodes under atmospheric pressure and discharging, such as Kasuga Electric Co., Ltd. or Toyo Electric Co., Ltd. Can be carried out using a commercially available apparatus. The frequency used for the corona treatment used in the present invention is a frequency of 20 kHz to 100 kHz, and a frequency of 30 kHz to 60 kHz is preferable. When the frequency is lowered, the uniformity of the corona treatment is deteriorated and unevenness of the corona treatment occurs. In addition, when the frequency is increased, there is no particular problem when performing high-output corona treatment, but when performing low-output corona treatment, it is difficult to perform stable processing, resulting in uneven processing. Will occur. The output of the corona treatment is 1 to 5 w · min. / M ² but ² to 4 w · min. An output of / m ² is preferred. The distance between the electrode and the film is 5 mm or more and 50 mm or less, preferably 10 mm or more and 35 mm or less. When the gap is opened, a higher voltage is required to maintain a constant output, and unevenness is likely to occur. On the other hand, if the gap is too narrow, the applied voltage becomes too low and unevenness is likely to occur. Furthermore, when the film is transported and continuously processed, the film comes into contact with the electrodes and scratches are generated.

  As the atmospheric pressure plasma treatment applicable to the present invention, for example, the treatment method and atmospheric pressure plasma described in JP-A-2004-68143, 2003-49272, WO 02/48428, etc. A processing device can be mentioned.

  An example of the modification process using an excimer lamp that can be applied to the present invention is a process by irradiation with vacuum ultraviolet rays. The treatment with vacuum ultraviolet irradiation uses light energy of 100 to 200 nm, preferably light energy with a wavelength of 100 to 180 nm, which is larger than the interatomic bonding force in the silazane compound, and bonds of atoms are only photons called photon processes. This is a method of forming a silicon oxide film at a relatively low temperature by causing an oxidation reaction with active oxygen or ozone to proceed while cutting directly.

  As a vacuum ultraviolet light source required for this, a rare gas excimer lamp is preferably used.

1. Excimer light is laser light using a rare gas excimer or a hetero excimer as an operating medium. Since noble gas atoms such as Xe, Kr, Ar, Ne and the like are chemically bonded to form no molecule, they are called inert gases. However, a rare gas atom (excited atom) that has gained energy by discharge or the like can combine with other atoms to form a molecule. When the rare gas is xenon, e + Xe → e + Xe ^*
Xe ^* + Xe + Xe → Xe ₂ ^* + Xe
Thus, when the excited excimer molecule Xe ₂ ^* transitions to the ground state, excimer light of 172 nm is emitted. A feature of the excimer lamp is that the radiation is concentrated on one wavelength, and since only the necessary light is not emitted, the efficiency is high.

  The Xe excimer lamp is excellent in luminous efficiency because it emits ultraviolet light having a short wavelength of 172 nm at a single wavelength. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen. In addition, it is known that the energy of light having a short wavelength of 172 nm for dissociating the bonds of organic substances has high ability. Due to the high energy of the active oxygen, ozone and ultraviolet radiation, the polysilazane film can be modified in a short time. Therefore, compared to low-pressure mercury lamps with a wavelength of 185 nm and 254 nm and plasma cleaning, the process time is shortened due to high throughput, the equipment area is reduced, and organic materials, plastic substrates, resin films, etc. that are easily damaged by heat are irradiated. It is possible.

  Finally, as step 3, the sample on which layer A is formed is immersed in a solution containing the above-mentioned compound having water and oil repellency, and a 70 to 95% region on the outermost surface has a compound having water and oil repellency. The water / oil / oil repellent antifouling film of the present invention is produced by forming a super water / oil / oil repellent layer coated with constituent atoms, for example, fluorine atoms.

《Water and oil repellent antifouling plate》
The water / oil repellent antifouling plate of the present invention is characterized in that the water / oil repellent antifouling film of the present invention is bonded to the surface of a self-supporting substrate. Preferably, it is the structure bonded together through the adhesion layer which a water / oil repellent antifouling film has. Furthermore, the self-supporting substrate applied to the water / oil / oil repellent antifouling plate of the present invention is preferably at least one selected from plate glass, a resin substrate, a metal substrate, and a metal-resin composite plate.

[Self-supporting substrate]
The self-supporting base material referred to in the present invention, when cut to the size used as the base material of the water- and oil-repellent antifouling plate of the present invention, by supporting the opposite edge portions, This represents a base material having a rigidity sufficient to support the base material.

  In the water / oil repellent antifouling plate of the present invention, the plate glass (also referred to as a glass substrate) applicable as a self-supporting substrate is not particularly limited, and has functional groups (hydroxy group, amino group, thiol on the surface). An alkali-containing glass substrate such as an inorganic glass or organic glass having a group, etc.), a soda lime silicate glass substrate, an alkali-free glass substrate such as a borosilicate glass substrate, and the like.

The glass substrate may be laminated glass, tempered glass, or the like, and a film or the like may be formed on the surface by various methods such as vapor deposition, sputtering, or wet method. The surface of the glass substrate may be pretreated before forming the film. Examples of the pretreatment include acid treatment with diluted hydrofluoric acid, sulfuric acid, nitric acid, hydrochloric acid, etc., alkali with sodium hydroxide aqueous solution, etc. There are processes such as plasma irradiation, corona irradiation, and electron beam irradiation. When the surface of the glass substrate is pretreated, the adhesion between the surface of the glass substrate and the film can be improved.
In the water- and oil-repellent antifouling plate of the present invention, examples of the resin substrate applicable as a self-supporting substrate include polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyethylene, polypropylene, cellophane, cellulose diacetate, and cellulose. Cellulose esters such as triacetate, cellulose acetate butyrate, cellulose acetate propionate, cellulose acetate phthalate, cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin , Polymethylpentene, polyetherketone, polyimide, polyethersulfone, polysulfones, polyetherke N'imido, polyamide, fluorine resin, nylon, polymethyl methacrylate, and an organic-inorganic hybrid resins such as acrylic or polyarylates, or these resins and silica.

  In the water / oil repellent antifouling plate of the present invention, examples of the metal substrate applicable as a self-supporting substrate include, for example, steel plate, copper plate, aluminum plate, aluminum plated steel plate, aluminum alloy plated steel plate, copper plated steel plate, tin. Examples thereof include a plated steel plate, a chrome plated steel plate, and a stainless steel plate.

  The self-supporting substrate according to the present invention preferably has one of the following configurations A and B.

A: A substrate having a pair of metal flat plates and an intermediate layer provided between the metal flat plates, the intermediate layer being a layer having a hollow structure or a resin material B: a resin material layer having a hollow structure It is the board | substrate comprised from these.

  The base material constituting the water / oil / oil repellent antifouling plate has self-supporting properties so that when the water / oil / oil repellent antifouling film is bonded, it has excellent handleability and holds the water / oil / oil repellent antifouling film. Since the holding member can have a simple configuration, the water / oil repellent antifouling plate can be reduced in weight.

  As in the configuration A, the self-supporting base material is composed of a pair of metal flat plates and an intermediate layer provided between the metal flat plates, and the intermediate layer is a layer having a hollow structure or a resin material When the substrate is composed of only a metal flat plate by having a high flatness due to the metal flat plate, and the intermediate layer is formed of a layer having a hollow structure or a resin material. In comparison, the base material can be significantly reduced in weight, and the rigidity can be further increased by the relatively lightweight intermediate layer, so that the substrate can be light and self-supporting. Even when a layer made of a resin material is used as the intermediate layer, the weight can be further reduced by using a layer of a resin material having a hollow structure.

  In addition, when the intermediate layer has a hollow structure, the intermediate layer functions as a heat insulating material, so that the temperature change of the metal flat plate on the back surface is prevented from being transmitted to the water / oil / oil repellent antifouling film, and condensation is prevented. It is possible to prevent or suppress deterioration due to heat.

  As the metal flat plate forming the surface layer of configuration A, the above steel plate, copper plate, aluminum plate, aluminum plated steel plate, aluminum alloy plated steel plate, copper plated steel plate, tin plated steel plate, chrome plated steel plate, stainless steel plate, etc. A metal material having high conductivity can be preferably used. In the present invention, it is particularly preferable to use a plated steel plate, a stainless steel plate, an aluminum plate or the like having good corrosion resistance.

  When the intermediate layer of Configuration A has a hollow structure, a material such as a metal, an inorganic material (glass or the like), or a resin can be used. As the hollow structure, a cellular structure made of a foamed resin, a three-dimensional structure having a wall surface made of a metal, an inorganic material, or a resin material (such as a honeycomb structure), a resin material to which hollow fine particles are added, or the like can be used. The cellular structure of the foamed resin refers to a material in which a gas is finely dispersed in a resin material and formed into a foamed or porous shape, and a known foamed resin material can be used as the material. Polyurethane, polyethylene, polystyrene and the like are preferably used. The honeycomb structure represents a general three-dimensional structure composed of a plurality of small spaces surrounded by side walls. When the hollow structure is a three-dimensional structure having a wall surface made of a resin material, examples of the resin material forming the wall surface include homopolymers or copolymers of olefins such as ethylene, propylene, butene, isoprene pentene, and methylpentene. Polymers such as polyolefin (for example, polypropylene, high density polyethylene), polyamide, polystyrene, polyvinyl chloride, polyacrylonitrile, acrylic derivatives such as ethylene-ethyl acrylate copolymer, polycarbonate, acetic acid such as ethylene-vinyl acetate copolymer Preferred are terpolymers such as vinyl copolymers, ionomers, ethylene-propylene-dienes, and thermoplastic resins such as ABS resins, polyolefin oxides, and polyacetals. In addition, these may be used individually by 1 type, or may mix and use 2 or more types. In particular, among thermoplastic resins, olefin-based resins or resins mainly composed of olefin-based resins, polypropylene-based resins or resins based mainly on polypropylene-based resins are excellent in balance between mechanical strength and moldability. preferable. The resin material may contain an additive. Examples of the additive include silica, mica, talc, calcium carbonate, glass fiber, carbon fiber, and other inorganic fillers, plasticizers, stabilizers, colorants, charging agents. An inhibitor, a flame retardant, a foaming agent, etc. are mentioned.

  In addition, the intermediate layer can be a layer made of a resin plate. In this case, the resin material constituting the intermediate layer is the same as the material constituting the resin base material of the above-described water / oil repellent antifouling film. Can be preferably used.

  The intermediate layer does not need to be provided in all regions of the base material, and may be provided in a part of the region as long as the flatness of the metal flat plate and the self-supporting property as the base material can be ensured. When the intermediate layer has the above-described three-dimensional structure, it is preferable to provide the three-dimensional structure in a region of about 90 to 95% with respect to the area of the metal flat plate. It is preferable to provide it.

  As in the configuration B, the self-supporting base material can be a layer made of a resin material having a hollow structure. When the base material is made of a resin material only, a certain amount of thickness is required to obtain a degree of rigidity sufficient to provide self-supporting properties. By giving the material a hollow structure, it is possible to reduce the weight while providing self-supporting properties. When a layer made of a resin material having a hollow structure is used, it is preferable to provide a resin sheet having a smooth surface as the surface layer and use the resin material having a hollow structure as the intermediate layer. As the material of this resin sheet, the same material as that constituting the resin base material of the above-mentioned water / oil repellent antifouling film can be preferably used, and as the resin material constituting the hollow structure, the above-mentioned foam material Alternatively, the same resin material as that used for the three-dimensional structure can be preferably used.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, although the display of "%" is used in an Example, unless otherwise indicated, "mass%" is represented.

《Preparation of water and oil repellent antifouling film》
[Production of Water / Oil Repellent Antifouling Film 1: Comparative Example]
(1) Preparation of Base Material A biaxially stretched polyethylene terephthalate film (A4100, manufactured by Toyobo Co., Ltd., hereinafter abbreviated as PET) having a film thickness of 100 μm is used as a lithographic magnetron sputtering apparatus (manufactured by Shibaura Eletech). CFS-10-EP70) was used, and oxygen glow treatment was performed under the following conditions to obtain a PET support 1 subjected to surface treatment.

<Oxygen glow treatment conditions>
Initial vacuum degree: 1.2 × 10 ⁻³ Pa
Oxygen pressure: 0.9 Pa
Radio frequency (RF) glow: 1.5 kW
Processing time: 60 sec
(2) Formation of graft polymer layer 1: production of support A Next, a mixed solution of N, N-dimethylacrylamide, methacryloxypropyltriethoxysilane and ethanol (N, N-dimethylacrylamide: methacryloxypropyltriethoxysilane) = 1: 1 (molar ratio), concentration: 50 mass%) was bubbled with nitrogen. The PET support 1 was immersed in this mixed solution at 70 ° C. for 7 hours. After the immersion, the PET support 1 is thoroughly washed with ethanol, and the graft polymer chain having a silane coupling group and an amide group, which are specific element alkoxide groups, is directly bonded to the surface of the PET support 1 in the structure. A graft polymer layer was formed. The PET support having this graft polymer layer was designated as support A.

(3) Preparation of organic-inorganic hybrid film A: Formation of organic-inorganic composite layer a On the obtained support A, it is composed of the following ethanol, water, tetraethoxysilane, phosphoric acid, colloidal silica, and polyvinyl alcohol. The coating liquid composition 1 is prepared and stirred at room temperature for 24 hours, and then applied using a bar coater, and heated and dried at 100 ° C. for 10 minutes to form the organic-inorganic composite layer a. An organic-inorganic hybrid film A was produced.

<Coating liquid composition 1>
Tetraethoxysilane (crosslinking agent) 0.90g
Ethanol 3.70g
8.70g of pure water
Phosphoric acid aqueous solution (0.85 mass% aqueous solution) 1.30 g
Colloidal silica (volume average particle size: 1.4 μm) 0.36 g
Polyvinyl alcohol aqueous solution (95% saponified, 10% by mass aqueous solution) 3.00 g
(4) Water-repellent treatment: Preparation of water- and oil-repellent antifouling film The organic-inorganic hybrid film A prepared above was added to 0.1% by mass of 1H, 1H, 2H, 2H perfluorodecyltrichlorosilane / hexane solution. After being immersed for 10 minutes, the water-repellent / oil-repellent antifouling film 1 having a water-repellent treatment layer was produced by pulling up and heating and drying (100 ° C., 30 minutes). The total film thickness of the formed water repellent layer and the organic-inorganic composite layer a was 2.5 μm.

[Preparation of Water / Oil Repellent Antifouling Film 2: Present Invention]
(1) Formation of coating layer b 30% by mass isopropyl alcohol dispersion (IPA-ST-ZL, isopropyl alcohol-dispersed spherical colloidal silica, solid containing silica particles (organosilica sol) having an average particle diameter of 100 nm as the fine particle dispersion. 30%, Nissan Chemical Industry Co., Ltd.) and, as a binder, a silicate coating liquid (product of Colcoat, product name: Colcoat PX, silicate weight average molecular weight: 20) , 3,000 to 30,000), and diluted and dispersed in isopropyl alcohol to obtain a coating solution b having a binder: fine particles = 30: 70 (mass ratio) and a solid content of 5%. Furthermore, 0.01 mol / L of hydrochloric acid was added as a condensation catalyst for the sol-gel reaction. After applying this coating solution b on one surface side of a 100 μm-thick biaxially stretched polyethylene terephthalate film (A4300, manufactured by Toyobo Co., Ltd.) using a bar coater so that the dry film thickness is 150 nm. It dried and further after-cured for 10 minutes at 120 degreeC continuously, and the coating layer b was formed.

(surface treatment)
Next, oxygen plasma treatment was performed on the formed coating layer b surface side using an oxygen plasma treatment apparatus (Samco Co., Ltd., PC-300K). Further, a 1.0 mass% solution of a fluorine-based chemical adsorption solution (OPTOOL DSX, fluorine-substituted alkyl group-containing organosilicon compound, manufactured by Daikin Industries) is applied to the surface of the coating layer b subjected to the oxygen plasma treatment with a bar coater and dried. Thus, a fluorine monomolecular film was formed to produce a water / oil repellent antifouling film 2.

[Preparation of Water / Oil Repellent Antifouling Film 3: Present Invention]
In the production of the water / oil repellent antifouling film 2, silica particles having an average particle size of 100 nm (IPA-ST-ZL) used in the preparation of the coating layer b were replaced with silica particles having an average particle size of 50 nm (30% by mass). A water / oil / oil repellent antifouling film 3 was produced by the same method except that the coating layer c was formed using the coating solution c changed to isopropyl alcohol dispersion (IPA-ST-L, Nissan Chemical Industries, Ltd.). .

[Preparation of Water / Oil Repellent Antifouling Film 4: Present Invention]
In the production of the water / oil repellent antifouling film 2, silica particles having an average particle size of 100 nm (IPA-ST-ZL) used in the preparation of the coating layer b were replaced with silica particles having an average particle size of 10 nm (30% by mass). A water / oil / oil repellent antifouling film 4 was produced by the same method except that the coating layer d was formed using the coating solution d changed to isopropyl alcohol dispersion (IPA-ST series, Nissan Chemical Industries, Ltd.).

[Production of Water / Oil Repellent Antifouling Film 5: Present Invention]
In the preparation of the water / oil repellent antifouling film 2, silica particles having an average particle size of 100 nm (IPA-ST-ZL) used in the preparation of the coating layer b were replaced with silica particles having an average particle size of 150 nm (30% by mass). A water / oil / oil repellent antifouling film 5 was produced by the same method except that the coating layer e was formed using the coating solution e changed to isopropyl alcohol dispersion, IPA-ST series, Nissan Chemical Industries, Ltd.).

[Preparation of Water / Oil Repellent Antifouling Film 6: Present Invention]
In preparation of the water / oil repellent antifouling film 2, a water / oil repellent antifouling film 6 was prepared using the coating liquid composition 2 prepared using the following metal alkoxide instead of the coating layer b.

(Preparation of coating liquid composition 2)
10 g of titanium (IV) tetra-n-butoxide [Ti (O (CH ₂ ) ₃ CH ₃ ) ₄ , manufactured by Wako Pure Chemical Industries, Ltd.], which is a metal alkoxide, is diluted with 100 ml of 1-propanol as a solvent and stirred. Thus, a titanium alkoxide solution was prepared. Next, 7 g of benzoylacetone [CH ₃ —CO—CH ₂ —CO—Ph, manufactured by Wako Pure Chemical Industries, Ltd.] is added as a complexing agent and stirred at room temperature for 1 hour to form a chelate with the titanium alkoxide. To prepare a binder. To this, 2 ml of water was added and stirred for 2 hours. Further, using silica particles having an average particle diameter of 100 nm (supra, IPA-ST-ZL), a coating solution f having a binder: fine particles = 30: 70 (mass ratio) and a solid content of 5.0% is obtained. It was.

  The coating solution f was applied to one surface side of a 100 μm-thick biaxially stretched polyethylene terephthalate film (A4300, manufactured by Toyobo Co., Ltd.) using a bar coater so that the dry film thickness was 150 nm. After that, the coating film f was formed by irradiating light with a wavelength of 360 nm for 7 minutes using an ultrahigh pressure mercury lamp. Next, surface treatment was performed in the same manner as in the production of the water / oil repellent antifouling film 2 to produce a water / oil repellent antifouling film 6.

[Preparation of Water / Oil Repellent Antifouling Film 7: Present Invention]
In the production of the water / oil repellent antifouling film 2, silica particles (IPA-ST-ZL) having an average particle size of 100 nm used in the preparation of the coating layer b were used, and alumina particles having an average particle size of 100 nm (Daimei Chemical Industry). A water- and oil-repellent antifouling film 7 was prepared in the same manner except that the coating layer g was formed using the coating solution g changed to low-temperature sinterable alumina TM-D series).

[Preparation of Water / Oil Repellent Antifouling Film 8: Present Invention]
In the production of the water / oil repellent antifouling film 2, before forming the coating layer b, it is a hydrolyzed / dehydrated condensation compound of tetraethoxylane on a biaxially stretched polyethylene terephthalate film (A4300) having a thickness of 100 μm. Using a silicate coating solution (manufactured by Colcoat Co., Ltd., product name: Colcoat PX, weight average molecular weight of silicate: 20,000 to 30,000), coating and coating using a bar coater under the condition that the dry film thickness is 3.0 μm A water / oil / oil repellent antifouling film 8 having a hard coat layer provided between the resin substrate and the water / oil repellent layer was prepared in the same manner except that it was dried and provided with a hard coat layer.

[Preparation of Water / Oil Repellent Antifouling Film 9: Present Invention]
In the production of the water / oil repellent antifouling film 8, the surface treatment method was changed to corona discharge treatment (irradiation conditions: 3 kW / m) instead of oxygen plasma. Film 9 was produced.

[Preparation of Water / Oil Repellent Antifouling Film 10: Present Invention]
In the production of the water / oil repellent antifouling film 2, the concentration of the fluorine-based chemical adsorption liquid (OPTOOL DSX, fluorine-substituted alkyl group-containing organosilicon compound, manufactured by Daikin Industries) used for the surface treatment was changed to 0.1% by mass. A water / oil repellent antifouling film 10 was produced in the same manner except that.

[Production of Water / Oil Repellent Antifouling Film 11: Present Invention]
In the production of the water / oil repellent antifouling film 2, the binder silicate coating solution (colcoat PX) used in the preparation of the coating layer b was changed to Zr (OC ₂ H ₅ ) ₄ which is a metal alkoxide. Thus, an oil-repellent antifouling film 11 was produced.

[Preparation of Water / Oil Repellent Antifouling Film 12: Present Invention]
In the production of the water / oil repellent antifouling film 2, the binder silicate coating solution (colcoat PX) used in the preparation of the coating layer b was changed to Al (OC ₂ H ₅ ) ₄ which is a metal alkoxide. Thus, an oil-repellent antifouling film 12 was produced.

[Preparation of Water / Oil Repellent Antifouling Film 13: Present Invention]
In the production of the water / oil repellent antifouling film 2, the silica particles (IPA-ST-ZL) having an average particle diameter of 100 nm used in the preparation of the coating layer b were changed to titanium oxide particles having an average particle diameter of 100 nm. A water / oil repellent antifouling film 13 was prepared in the same manner except for the above.

[Production of Water / Oil Repellent Antifouling Film 14: Present Invention]
In the production of the water / oil repellent antifouling film 2, the silica particles (IPA-ST-ZL) having an average particle diameter of 100 nm used in the preparation of the coating layer b were changed to zinc oxide particles having an average particle diameter of 100 nm. A water and oil repellent antifouling film 14 was prepared in the same manner except for the above.

[Preparation of Water / Oil Repellent Antifouling Film 15: Present Invention]
In the production of the water / oil repellent antifouling film 2, the silica particles (IPA-ST-ZL) having an average particle size of 100 nm used in the preparation of the coating layer b were changed to zirconium oxide particles having an average particle size of 100 nm. A water and oil repellent antifouling film 16 was produced in the same manner except for the above.

[Production of Water / Oil Repellent Antifouling Film 16: Comparative Example]
In the production of the water / oil repellent antifouling film 2, silica particles (IPA-ST-ZL) having an average particle diameter of 100 nm used in the preparation of the coating layer b were replaced with silica particles having an average particle diameter of 200 nm (30% by mass). A water / oil repellent antifouling film 16 was prepared in the same manner except that the coating layer was formed using a coating solution changed to isopropyl alcohol dispersion, IPA-ST series, Nissan Chemical Industries, Ltd.).

[Production of Water / Oil Repellent Antifouling Film 17: Comparative Example]
In the production of the water / oil repellent antifouling film 10, silica particles (IPA-ST-ZL) having an average particle diameter of 100 nm used in the preparation of the coating layer b were replaced with silica particles having an average particle diameter of 200 nm (30% by mass). A water / oil / oil repellent antifouling film 17 was produced in the same manner except that the coating layer was formed using a coating solution changed to isopropyl alcohol dispersion, IPA-ST series, Nissan Chemical Industries, Ltd.).

(Formation of adhesive layer)
On a separate film, one part of a platinum catalyst was added to 100 parts of an addition reaction type silicone pressure-sensitive adhesive having a weight average molecular weight of 500,000 to form a 35 mass% toluene solution under the condition that the dry film thickness was 25 μm. And heated at 130 ° C. for 5 minutes to form a silicone-based adhesive layer (Si-based).

  Next, the water- and oil-repellent properties of the water- and oil-repellent antifouling films prepared above are bonded to the surface of the resin substrate opposite to the surface on which the water- and oil-repellent layers are formed, and the water- and oil-repellent properties have an adhesive layer. Antifouling films 1A to 17A were prepared.

<Measurement of each characteristic value>
For each of the produced water / oil repellent antifouling films, the following characteristic values were measured, and the obtained results are shown in Table 1.

(Measurement of root mean square roughness Rq)
The root mean square roughness Rq (nm) of the surface of the water / oil repellent layer of each water / oil repellent antifouling film was measured using a simple AFM (nanopics, manufactured by Seiko Instruments Inc.), with a cutoff λc of 2.5 mm and an evaluation length. The measurement was performed under the condition of 12.5 mm.

(Measurement of surface coverage (surface atom density) of fluorine-containing compounds)
About the water / oil repellent layer surface of each water / oil repellent antifouling film, an X-ray photoelectron spectrometer (XRD JPS-9200, manufactured by JEOL Ltd.) was used. The composition ratio of fluorine atoms attributable to the fluorine compound was determined, and the surface coverage of the fluorine-containing compound was calculated from the atom density of the fluorine atoms.

<< Production of water and oil repellent antifouling boards >>
After peeling off the separate film provided on the surface of the adhesive layer of the water- and oil-repellent antifouling films 1A to 17A produced above, the adhesive layer was bonded to a float glass surface of 10 × 10 cm and a thickness of 3 mm. Water / oil repellent antifouling plates 1 to 17 were prepared.

<Evaluation of water / oil repellent antifouling plate>
Each of the following evaluations was performed on the water- and oil-repellent antifouling plates 1 to 17 produced above.

[Evaluation of super water repellency and light resistance 1]
(Evaluation 1: Measurement of contact angle immediately after fabrication)
Each water / oil repellent antifouling plate produced above was conditioned for 3 hours or more in an environment of 25 ° C. and 55% RH, and then contact angle measuring device (CONTACT manufactured by Kyowa Interface Science Co., Ltd.) in the same environment. (ANGLE METER CA-Z), 3 μl of pure water was dropped on the surface of the water / oil repellent layer, and the angle after 20 seconds was measured. The measurement was repeated seven times, and the contact angle immediately after the production was obtained as an average value of five times excluding the upper limit and the lower limit twice.

(Evaluation 2: Evaluation of light resistance 1)
Each of the produced water / oil repellent antifouling plates was irradiated for 2000 hours using a super xenon irradiation device (manufactured by Suga Test Instruments), and then the contact angle after Xe light irradiation was measured by the same method as described above. It represents that it is excellent in light resistance, so that the fall of a numerical value is small with respect to the contact angle of the evaluation 1.

[Evaluation of adhesion and light resistance 2]
(Evaluation 1: Evaluation of adhesion immediately after production)
Each water / oil repellent antifouling plate produced above is conditioned for 3 hours or more in an environment of 25 ° C. and 55% RH, and then in accordance with JIS K 5400 for the surface of the water / oil repellent layer in the same environment. Then, after attaching 100 mm square grids of 1 mm square with a rotary cutter and crimping cello tape (manufactured by Nichiban Co., Ltd., registered trademark), a peeling test at 90 degrees was performed three times at a speed of 30000 mm / min. The evaluation was performed by measuring the number (%) of cells remaining after the peel test.

(Evaluation 2: Evaluation of light resistance 2)
Each water / oil repellent antifouling plate produced above was irradiated for 2000 hours using a super xenon irradiation device (manufactured by Suga Test Instruments), and then the adhesion after Xe light irradiation was evaluated in the same manner as described above. It was. It represents that it is excellent in light resistance, so that the fall of a numerical value is small with respect to the adhesiveness (mesh residual rate) of evaluation 1.

[Evaluation of pencil hardness]
Each water / oil repellent antifouling plate prepared above was conditioned for 3 hours or more in an environment of 25 ° C. and 55% RH, and in accordance with JIS K 5600-5-4 (ISO15184) under the same environment, Using a pencil hardness tester (manufactured by Toyo Seiki Co., Ltd.), the pencil hardness at a load of 750 g was measured.

  The results obtained as described above are shown in Table 2.

  As is apparent from the results shown in Table 2, the water / oil / oil repellent antifouling plate of the present invention that satisfies the conditions defined in the present invention has higher super water repellency and light resistance (after light irradiation) than the comparative example. It can be seen that the surface layer is excellent in contact angle and adhesion) and has a high hardness.

DESCRIPTION OF SYMBOLS 1 Water repellent / oil repellent antifouling film 2 Resin base material 3 Water / oil repellent repellent layer 4 Hard coat layer 5 Adhesive layer 6 Water repellent / oil repellent antifouling plate 7 Self-supporting substrate

Claims (14)

  A water / oil repellent antifouling film having a water / oil repellent layer on one side of a resin substrate, the water / oil repellent layer containing at least a binder, fine particles and a compound having water / oil repellent properties. And the surface of the water / oil repellent layer has a root mean square roughness Rq measured in accordance with JIS B 0601-2001 in the range of 5 to 50 nm. the film.   2. The water / oil repellent antifouling film according to claim 1, wherein an area of 70 to 95% of the outermost surface of the water / oil repellent layer is covered with the water / oil repellent compound.   The water repellent and water repellent layer according to claim 1 or 2, wherein the water and oil repellent layer has a pencil hardness measured in accordance with JIS K 5600-5-4 in a range of H to 5H. Oil-based antifouling film.   4. The polymer according to claim 1, wherein the binder is a polymer compound having a metalloxane skeleton containing at least one atom selected from silicon, aluminum, zirconium, and titanium. Water and oil repellent antifouling film.   The fine particles are at least one inorganic oxide fine particle selected from silica, alumina, titanium oxide, zinc oxide, and zirconium oxide, according to any one of claims 1 to 4. Water and oil repellent antifouling film.   6. The water / oil repellent antifouling film according to claim 1, wherein an average particle diameter of the fine particles is in a range of 10 to 100 nm.   The water / oil repellent antifouling film according to any one of claims 1 to 6, wherein the water / oil repellent compound is a fluorine-containing compound or an organosilicon compound.   8. The water / oil repellency preventive agent according to claim 7, wherein the water / oil repellency compound covering 70% to 95% of the outermost surface of the water / oil repellency layer is the fluorine-containing compound. Dirty film.   The water / oil repellent antifouling film according to any one of claims 1 to 8, further comprising a hard coat layer between the water / oil repellent layer and the resin base material.   The water repellent according to any one of claims 1 to 9, wherein the resin base material has an adhesive layer on a surface opposite to a surface having the water and oil repellent layer. Oil repellent antifouling film. A method for producing a water / oil repellent antifouling film for producing the water / oil repellent antifouling film according to any one of claims 1 to 10,
On the resin substrate, a water / oil repellent layer forming coating solution containing fine particles and a binder having a metalloxane skeleton is applied and dried to form layer A, and then the surface of layer A is subjected to high pressure under atmospheric pressure. A method for producing a water- and oil-repellent antifouling film, comprising applying a surface modification treatment by applying energy, and further forming a water- and oil-repellent layer through a step of adsorbing a compound having water and oil repellency .   The method for producing a water- and oil-repellent antifouling film according to claim 11, wherein the water- and oil-repellent compound is a fluorine-containing compound or an organosilicon compound.   A water / oil repellent property comprising the water / oil repellent antifouling film according to any one of claims 1 to 10 bonded to a surface of a self-supporting substrate. Antifouling board.   The water / oil / oil repellent antifouling plate according to claim 13, wherein the self-supporting substrate is at least one selected from a plate glass, a resin substrate, a metal substrate, and a metal-resin composite plate.

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