WO2017122561A1 - Water-repellent coating material - Google Patents

Abstract

[Problem] To provide, at low cost, a surface treatment material which, when being formulated as a coating liquid that does not contain an acid or an alkali and is easily used even by ordinary household users, which can be applied at room temperature, which can form a coating having excellent water repellency, which allows, through dry wiping, easy removal of excessive dried solid matter formed by components not involved in the formation of the coating, and which can be used on the surface of a plastic, a metal, or glass, such as, for example, automotive window glasses, building windows, automotive coated surfaces, automotive lamp covers, kitchen equipment, kitchen utensils, exhaust devices attached to kitchen equipment, display plates, bathroom equipment, washroom equipment, medical facilities, medical machines and tools, mirrors, eyeglasses, inkjet printer components, and electronic circuit boards. [Solution] The problem is solved, and particularly, water repellency is dramatically improved, by a neutral coating liquid obtained by including only a small amount of a fluorine-containing alcohol compound into a base polymer in a surface-modifying coating liquid.

Description

Water-sliding coating material

The present invention is a surface modifier that can be applied on the surface of a base material such as metal, plastic, glass, etc. at room temperature without using acid or alkali, and can easily form a layer that imparts an excellent water-sliding function. The present invention relates to a water-slidable coating material.

In a general living environment, there are certain facilities, devices, machine tools, etc. that have desirable or required water repellency. For example, automobile window glass, building windows, automobile paint surfaces, automobile light covers, kitchen equipment, kitchen utensils, exhaust devices attached to kitchen equipment, display boards, bathing facilities, wash facilities, medical facilities, medical Machine tools, mirrors, eyeglasses, inkjet printer parts, electronic circuit boards, etc. Conventionally, when water repellency is imparted to an object that requires such water repellency, a method of increasing the water contact angle on the surface of the object is usually used to make it difficult to wet. Typically, surface coating is performed with a so-called hydrophobic material such as a silicone compound or a resin, a fluorine resin, or a polyolefin resin.

By the way, when water adheres to the surface of the object that has been subjected to such surface hydrophobization treatment, the water is repelled into spherical water droplets, and large water droplets fall due to their own weight, while small water droplets remain strongly adhered to the object surface. There is often a phenomenon that it remains and does not fall even if the attached surface is tilted vertically. Therefore, in the above treatment, it is difficult to obtain a dry surface free from water droplets unless it is forcibly removed by a mechanical method such as wiping off adhering water droplets.

That is, when the surface energy of the substrate is lowered to improve water repellency, the water on the substrate does not spread and forms water droplets. For this reason, although the area | region exposed without being coat | covered with the water droplet is ensured, the fine water droplet still remained on the base material. This residual water droplet causes an adverse effect of irregularly reflecting light to deteriorate visibility. For example, even in a window glass of an automobile, even if visibility is ensured in an exposed area that is not covered with water droplets, minute water droplets still remain dispersed in the window glass and diffusely reflect light. The situation becomes difficult to check. In addition, the minute dust remaining in the water droplets remains on the base material after drying the water droplets, causing dirt.

Patent Document 1 (Japanese Patent Application Laid-Open No. 5-301742) proposes a composition containing an amino-modified silicone oil and a cationic surfactant. The composition of this document is simply sprayed or applied to the glass surface and does not require any spreading or wiping, so it is easy to work and exhibits excellent water repellency. This is a method for forming a film. However, although this method is excellent in workability and water repellency, the sliding of water droplets, that is, the water slidability is not satisfactory.

Patent Document 2 (Japanese Patent Application Laid-Open No. 2000-144056) describes a silicone compound having a hydrolyzable functional group at the terminal, or a silicone compound having a hydrolyzable functional group at the terminal and a fluoroalkyl group at the other end. Then, the functional layer obtained by dissolving the acid and water in the solvent, applying the mixed solution obtained by mixing and stirring to the surface of the base material, and then drying is chemically formed by the base surface and the siloxane bond. There has been proposed a surface-treated substrate excellent in water droplet sliding property, characterized in that it is bonded to the surface. However, the method of this document requires a baking treatment and cannot be used for a substrate having a low heat-resistant temperature, and also requires equipment for the treatment, and no one can easily form a film.

In Patent Document 3 (Japanese Patent Laid-Open No. 2002-097192), a functional layer having a water droplet removal property and a water droplet mobility is formed on the surface of a glass substrate to form a water droplet falling angle of 5 to 30 ° and 1 mm. The surface treatment agent is effective only for glass substrates, and various acids such as inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid, etc. In addition, organic acids such as formic acid, sulfonic acid, and methanesulfonic acid need to coexist, and there are disadvantages that are difficult for general users such as households to use.

Further, in Patent Document 4 (Japanese Patent Laid-Open No. 2014-21085), by adding a silicon-containing polymer having a specific structure to an active energy ray-curable coating liquid, a hard coat excellent in water repellency as well as water slidability. However, there is a drawback that an ultraviolet curing machine is required at the time of coating, and the cost is high, and it is difficult to cope with coating on a large area. Furthermore, in Patent Document 5 (Japanese Patent Laid-Open No. 2015-010221), the sliding property when hydrophobic fine particles are distributed on the surface of a resin molding is examined, and the hydrophobic fine particles having a BET specific surface area larger than 300 m ² / g. However, there is a problem in antifouling properties because the coating layer is porous.

JP-A-5-301742 JP 2000-144056 A JP 2002-097192 A JP 2014-21085A JP2015-010221A

The present invention has been made to solve the above problems, and does not contain acid or alkali as a surface treatment material, and can be safely used by ordinary users who do not have special facilities, environments, and skills, such as metals, plastics, and glass. It is possible to provide a water-slidable coating material that can be applied to the surface of a base material and can form a coating film that can eliminate water droplets quickly and with a simple and inexpensive method. It is.

In addition, a coating with excellent water repellency, water slidability and durability can be formed by applying a treatment agent and drying at room temperature without any special treatment such as heating or ultraviolet irradiation. An object of the present invention is to provide a water slidable coating material which can provide water slidability and can easily remove excess dried solid matter by a simple operation such as dry wiping.

In order to solve the above-mentioned problems, the applicant has found that the water repellency is drastically improved by slightly containing a fluorine-containing alcohol compound in the surface-modified coating film. That is, the said subject is achieved by the structure of the following this invention.

(1) A water-slidable coating material that contains one or more base resins and a fluorine-containing alcohol compound containing two or more OH groups and forms a coating film.
(2) The slidable coating material according to (1), wherein the fluorine-containing alcohol compound is represented by the following formula (1).

(In Formula (1), R ¹ and R ^{1 ′} are OH groups or CH ² OH groups, R ² and R ^{2 ′} are 0 to 3 OH groups and 0 or 1 or more F atoms. ~ 5 alkyleneoxy groups, R ³ and R ^{3 '} contain one or more F and carbon chains of 1 to 5 carbon atoms, R ⁴ contains one or more F and carbon atoms of 1 to 10 carbon atoms The chains i and i ′ are integers of 0 to 5 which may be the same or different, j and j ′ may be natural numbers of 1 to 5 and may be the same or different, and k is an integer of 0 to 20 is there.)
(3) The slidable coating material according to (1) or (2), wherein the fluorine-containing alcohol compound has a molecular weight of 500 g / mol to 2000 g / mol.
(4) In the formula (1), R ¹ and R ^{1 ′} are OH groups, R ² and R ^{2 ′} contain 1 to 3 OH groups and contain 0 or 1 or more F An alkyleneoxy group having 1 to 4 carbon atoms, R ³ and R ^{3 ′} are 2 to 10 F and 1 to 5 carbon chains, and R ⁴ contains 2 to 10 F. The water-slidable coating material according to any one of the above (1) to (3), which is a carbon chain having 1 to 10 carbon atoms and k is an integer of 1 to 15.
(5) The water-slidable coating material according to any one of (1) to (4), wherein the base resin contains fluorine or is a fluorine-based resin.
(6) The fluororesin is PVF (polyvinyl fluoride), PTFE (polytetrafluoroethylene (tetrafluoroethylene)), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoropropylene copolymer). (4.6 fluoride)), ETFE (tetrafluoroethylene / ethylene copolymer), PVDF (polyvinylidene fluoride (difluoride)), PCTFE (polychlorotrifluoroethylene (trifluoride)), ECTFE (chlorotrifluoro) The water-slidable coating material according to any one of the above (1) to (5), which is any one of (ethylene / ethylene copolymer).
(7) The water-slidable coating material according to any one of the above (1) to (6), wherein the content of the fluorinated alcohol compound relative to the base resin is 0.001 ppm to 100 ppm.
(8) The water-slidable coating material according to any one of the above (1) to (7), wherein when the formed coating surface is inclined by 30 degrees with respect to the horizontal plane, the speed at which the water droplet slides is 0.3 mm / s or more.
(9) The water-slidable coating material according to any one of (1) to (8) above, wherein the water contact angle of the formed coating surface is 70 degrees or more.
(10) The water-slidable coating material according to any one of (1) to (9), wherein the water sliding angle of the formed coating surface is less than 70 degrees.
(11) The water-slidable coating material according to any one of the above (1) to (10), wherein a film is formed on the surface of a base material made of plastic, metal, or glass.

According to the present invention, a minute water droplet hardly remains on the surface, and a film capable of quickly removing the water droplet can be formed by a simple and inexpensive method, and the surface lubricity of a substrate such as metal, plastic, glass, etc. has jumped. In addition, it can be applied at room temperature, and does not require a special curing process, and is useful in mass production at low cost.

It is a graph which shows the sliding-down (falling) speed of the water of Example 3.

The water-slidable coating material of the present invention contains at least one or two or more base resins and a fluorine-containing alcohol compound containing two or more OH groups.

In order to give the water-repellent coating material water-repellent properties, a low surface energy substance such as a fluorine-containing resin may be used. Although the water-slidable coating material can be composed of an inorganic material or the like, a resin material is preferable from the viewpoint of easy formation of a film and cost. By using a resin composition in which a fluorine-containing alcohol compound is added to a base resin material (base resin), a coating material that can be easily formed and handled at low cost can be obtained. As described above, in the present invention, the water-repellent property can be remarkably improved by adding the fluorinated alcohol compound to the film of the water-slidable coating material.

In order to improve water repellency, it is not sufficient to simply increase the fluorine on the coating surface. In the surface hydrophobization treatment, for example, the surface is coated with a hydrophobic material such as a silicone compound or resin, fluorine resin, polyolefin resin, etc., and when water adheres to the object surface subjected to such treatment, The water is repelled into spherical water droplets. At this time, a large water droplet falls due to its own weight, but a small water droplet remains strongly adhered to the object surface and does not fall even when the adhered surface is tilted vertically.

Thus, if there is only a hydrophobic group on the surface of the coated surface, fine water droplets remain attached to the coated surface even if the coated surface of the substrate is vertical. Therefore, when a hydrophilic group, for example, an OH group is oriented on the coat surface, the water droplets are easily moved by the hydrophilic OH group, and the finely dispersed water droplets are moved and bonded to increase the weight and flow easily. Some general fluororesins contain OH groups, but in such resins, the OH groups are usually oriented on the substrate side and are difficult to appear on the surface side. When a fluorine-containing alcohol compound is added to the water slidable coating material, the hydrophilic OH group contained in the slidable coating material is oriented on the surface side, and the water droplets are likely to move. Similarly, the fluorine contained in the fluorinated alcohol-based compound can also be expected to increase the surface fluorine element and further improve the water repellency.

The fluorine-containing alcohol compound will be described in more detail. It is a linear compound containing two or more OH groups, preferably having 5 or more carbon atoms, and one or more oxygen is present in the linear skeleton. An ether bond may be formed. Further, the fluorine bonded to the linear skeleton is preferably 10 or more, more preferably 16 or more. The OH groups exist at both ends of the skeleton main chain, but 1 to 4 substituents may be further present in the skeleton.

More specifically, the fluorine-containing alcohol compound is preferably a compound represented by the following formula (1).

In the formula (1), R ¹ and R ^{1 ′} are OH groups or CH ² OH groups, R ² and R ^{2 ′} are 0 to 3, preferably 1 to 3 OH groups, and F is 0 or 1 or more. It is an alkyleneoxy group having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms. R ³ and R ^{3 ′} are one or more F and a carbon chain having 1 to 5 carbon atoms. R ¹ and R ^{1 ′} , R ² and R ^{2 ′} , R ³ and R ^{3 ′} may be the same or different. R ⁴ is a carbon chain containing 1 or more F and having 1 to 10 carbon atoms. i and i ′ are integers of 0 to 5, which may be the same or different; j and j ′ may be integers of 1 to 5 and may be the same or different; k is an integer of 0 to 20, preferably 1 to 15, more preferably 2 to 10. The number of fluorine contained in R ² and R ^{2 ′} , R ³ and R ^{3 ′,} or R ⁴ is preferably 2 to 10, more preferably 4 to 10.

The greater the number of fluorine contained in R ² and R ^{2 ′} , R ³ and R ^{3 ′} or R ⁴ , the better the water repellency. Further, when the number of OH groups contained in R ² and R ^{2 ′} is larger to some extent, water droplets flow more easily. However, if the number is too large, there is a tendency to inhibit water repellency. Further, it is considered that as k is increased to some extent, OH groups and F are more easily oriented on the coating surface. As described above, the molecular weight of the fluorine-containing alcohol-based compound is preferably such that k has a certain size, and therefore the molecular weight is preferably large, specifically 600 or more, more preferably 700 or more, and even 900 or more. The upper limit is about 2000 or less.

Examples of the fluorine-containing alcohol compound include the following compounds. For example, HOCH ₂ CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ OCF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₂ CF ₂ CF ₂ CF ₂ CH ₂ OH HOCH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₃ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₄ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₅ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₆ CF _{2 CF 2 CF 2 CH 2 OH} , HOCH 2 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 7 CF 2 CF 2 CF 2 CH 2 OH, HO _{H 2 CF 2 CF 2 O (} CF 2 CF 2 CF 2 O) 8 CF 2 CF 2 CF 2 CH 2 OH, HOCH 2 CF 2 CF 2 O (CF 2 CF 2 CF 2 O) 9 CF 2 CF 2 CF 2 CH ₂ OH, HOCH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₁₀ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₂₀ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ O) ₂ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF ₂ CF ₂ OCF ₂ OCF ₂ CF ₂ CF ₂ CH _{2 OH, HOCH 2 CF 2 CF} 2 OCHFOCF 2 CF 2 CF 2 CH 2 OH, HOCH 2 CF 2 CF 2 O (CF 2 O) 3 CF _{CF 2 CF 2 CH 2 OH,} HOCH 2 CF 2 CF 2 O (CF 2 O) 4 CF 2 CF 2 CF 2 CH 2 OH, HOCH 2 CF 2 CF 2 O (CF 2 O) 4 CF 2 CF 2 CF 2 _{CH 2 OH, HOCH 2 CF 2} CF 2 O (CF 2 O) 5 CF 2 CF 2 CF 2 CH 2 OH, HOCH 2 CF 2 CF 2 O (CF 2 O) 10 CF 2 CF 2 CF 2 CH 2 OH, HOCH ₂ CF ₂ CF ₂ O (CF ₂ O) ₁₅ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF ₂ CF ₂ O (CF ₂ O) ₂₀ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF _{2 CF 2 OCF (CH 3) CF} 2 OCF 2 CF 2 CF 2 CH 2 OH, HOCH 2 CF 2 CF 2 O (CF (CH 3) CF 2 O) 2 C _{2 CF 2 CF 2 CH 2 OH} , HOCH 2 CF 2 CF 2 O (CF (CH 3) CF 2 O) 5 CF 2 CF 2 CF 2 CH 2 OH, HOCH 2 CF 2 CF 2 O (CF (CH 3) CF ₂ O) ₁₀ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF ₂ CF ₂ O (CF (CH ₃ ) CF ₂ O) ₁₅ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF ₂ CF ₂ O _{(CF (CH 3) CF 2} O) 20 CF 2 CF 2 CF 2 CH 2 OH, HOCH 2 CF 2 CF 2 OCF (CF 3) CF 2 OCF 2 CF 2 CF 2 CH 2 OH, HOCH 2 CF 2 CF 2 _{O (CF (CF 3) CF} 2 O) 2 CF 2 CF 2 CF 2 CH 2 OH, HOCH 2 CF 2 CF 2 O (CF (CF 3) CF 2 O) 3 C _{2 CF 2 CF 2 CH 2 OH} , HOCH 2 CF 2 CF 2 O (CF (CF 3) CF 2 O) 4 CF 2 CF 2 CF 2 CH 2 OH, HOCH 2 CF 2 CF 2 O (CF (CF 3) CF ₂ O) ₅ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) ₁₀ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) ₁₅ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF ₂ CF ₂ O (CF (CF ₃ ) CF ₂ O) ₂₀ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH _{2 CF 2 CF 2 O (CF} 2 CF 2 CF 2 CF 2 CF 2 O) 2 CF 2 CF 2 CF 2 CH 2 OH, HOCH 2 CF 2 CF 2 O (CF 2 CF _{CF 2 CF 2 CF 2 CF 2} CF 2 CF 2 CF 2 CF 2 O) 2 CF 2 CF 2 CF 2 CH 2 OH, HOCH 2 CF 2 CF 2 O (CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF ₂ CF ₂ CF ₂ CF ₂ O) ₁₀ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ O) ₂₀ CF ₂ CF ₂ CF ₂ CH ₂ OH, HOCH ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF (CF ₃ ) CF ₂ CF ₂ CF ₂ O) ₂₀ CF ₂ CF ₂ CF ₂ CH _{2 OH, HOCH 2 CF 2 CF} 2 O (CF (CF 3) CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 CF 2 O) 20 CF _{CF 2 CF 2 CH 2 OH,} HOCH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 OCF 2 CF 2 CF 2 CF 2 OCH 2 CH (OH) CH 2 OH, _{HOCH 2 CH (OH) CH 2} OCH 2 CF 2 CF 2 CF 2 O (CF 2 CF 2 CF 2 CF 2 O) 2 CF 2 CF 2 CF 2 CF 2 OCH 2 CH (OH) CH 2 OH, HOCH 2 CH _{(OH) CH 2 OCH 2 CF} 2 CF 2 CF 2 O (CF 2 CF 2 CF 2 CF 2 O) 3 CF 2 CF 2 CF 2 CF 2 OCH 2 CH (OH) CH 2 OH, HOCH 2 CH (OH) _{CH 2 OCH 2 CF 2 CF 2} CF 2 O (CF 2 CF 2 CF 2 CF 2 O) 4 CF 2 CF 2 CF 2 CF 2 OCH 2 C _{(OH) CH 2 OH, HOCH} 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 O (CF 2 CF 2 CF 2 CF 2 O) 5 CF 2 CF 2 CF 2 CF 2 OCH 2 CH (OH) _{CH 2 OH, HOCH 2 CH (} OH) CH 2 OCH 2 CF 2 CF 2 CF 2 O (CF 2 CF 2 CF 2
CF ₂ O) ₁₀ CF ₂ CF ₂ CF ₂ CF ₂ OCH ₂ CH (OH) CH ₂ OH, HOCH ₂ CH (OH) CH ₂ OCH ₂ CF ₂ CF ₂ CF ₂ O (CF ₂ CF ₂ CF ₂ CF ₂ O _{) 15 CF 2 CF 2 CF 2} CF 2 OCH 2 CH (OH) CH 2 OH, HOCH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 O (CF 2 CF 2 CF 2 CF 2 O) 20 CF _{2 CF 2 CF 2 CF 2 OCH} 2 CH (OH) CH 2 OH, HOCH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 O (CF 2 CF 2 CF 2 CF 2 O) 2 CF 2 CF 2 _{CF 2 CF 2 OCH 2 (OH} ) CH 2 CH 2 OH, HOCH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 OCF 2 OCF _{CF 2 CF 2 CF 2 OCH 2} CH (OH) CH 2 OH, HOCH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 O (CF 2 O) 2 CF 2 CF 2 CF 2 CF 2 OCH 2 CH _{(OH) CH 2 OH, HOCH} 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 O (CF 2 O) 3 CF 2 CF 2 CF 2 CF 2 OCH 2 CH (OH) CH 2 OH, HOCH 2 _{CH (OH) CH 2 OCH 2} CF 2 CF 2 CF 2 O (CF 2 O) 4 CF 2 CF 2 CF 2 CF 2 OCH 2 CH (OH) CH 2 OH, HOCH 2 CH (OH) CH 2 OCH 2 CF _{2 CF 2 CF 2 O (CF} 2 O) 5 CF 2 CF 2 CF 2 CF 2 OCH 2 CH (OH) CH 2 OH, HOCH 2 CH (OH) CH _{OCH 2 CF 2 CF 2 CF 2} O (CF 2 O) 6 CF 2 CF 2 CF 2 CF 2 OCH 2 CH (OH) CH 2 OH, HOCH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 O (CF ₂ O) ₇ CF ₂ CF ₂ CF ₂ CF ₂ OCH ₂ CH (OH) CH ₂ OH, HOCH ₂ CH (OH) CH ₂ OCH ₂ CF ₂ CF ₂ CF ₂ O (CF ₂ O) ₈ CF ₂ CF ₂ CF ₂ CF ₂ OCH ₂ CH (OH) CH ₂ OH, HOCH ₂ CH (OH) CH ₂ OCH ₂ CF ₂ CF ₂ CF ₂ O (CF ₂ O) ₉ CF ₂ CF ₂ CF ₂ CF ₂ OCH ₂ CH ( _{OH) CH 2 OH, HOCH 2} CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 O (CF 2 O) 10 CF 2 CF 2 CF 2 CF 2 OC _{2 CH (OH) CH 2 OH} , HOCH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 O (CF 2 O) 15 CF 2 CF 2 CF 2 CF 2 OCH 2 CH (OH) CH 2 OH, _{HOCH 2 CH (OH) CH 2} OCH 2 CF 2 CF 2 CF 2 O (CF 2 O) 20 CF 2 CF 2 CF 2 CF 2 OCH 2 CH (OH) CH 2 OH, HOCH 2 CH (OH) CH 2 OCH _{2 CF 2 CF 2 CF 2 O} (CF 2 O) 2 CF 2 CF 2 CF 2 CF 2 CH 2 OH, HOCH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 O (CF 2 O) 2 CF _{2 CF 2 CF 2 CF 2 (} OCH 2 CH (OH)) 2 CH 2 OH, HOCH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 O (C _{2 O) 2 CF 2 CF 2} CF 2 CF 2 (OCH 2 CH (OH)) 3 CH 2 OH, HOCH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 O (CF 2 O) 2 CF 2 CF ₂ CF ₂ CF ₂ (OCH ₂ CH (OH)) ₄ CH ₂ OH, HOCH ₂ CH (OH) CH ₂ OCH ₂ CF ₂ CF ₂ CF ₂ O (CF ₂ O) ₂ CF ₂ CF ₂ CF ₂ CF ₂ (OCH ₂ CH (OH)) ₅ CH ₂ OH, HOCH ₂ CH (OH) CH ₂ OCH ₂ CF ₂ CF ₂ CF ₂ O (CF ₂ O) ₂ CF ₂ CF ₂ CF ₂ CF ₂ (OCH ₂ CH (OH _{)) 5 OH, HOCH 2 CH} (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 O (CF 2 O) 2 OCH 2 CH (OH) CH 2 OH, HOCH 2 CH (O _{H) CH 2 OCH 2 CF 2} CF 2 CF 2 O (CF 2 O) 2 (CF 2 CF 2 CF 2 CF 2) 2 OCH 2 CH (OH) CH 2 OH, HOCH 2 CH (OH) CH 2 OCH 2 CF ₂ CF ₂ CF ₂ O (CF ₂ O) ₂ (CF ₂ CF ₂ CF ₂ CF ₂ ) ₃ OCH ₂ CH (OH) CH ₂ OH, HOCH ₂ CH (OH) CH ₂ OCH ₂ CF ₂ CF ₂ CF ₂ O (CF ₂ O) ₂ (CF ₂ CF ₂ CF ₂ CF ₂ ) ₄ OCH ₂ CH (OH) CH ₂ OH, HOCH ₂ CH (OH) CH ₂ OCH ₂ CF ₂ CF ₂ CF ₂ O (CF ₂ O) _{2 (CF 2 CF 2 CF 2} CF 2) 5 OCH 2 CH (OH) CH 2 OH, HOCH 2 CH (OH) CH 2 OCH 2 CF 2 CF 2 CF 2 O (CF 2 O) ₂ (CF ₂ CF ₂ CF ₂ CF ₂ ) ₁₀ OCH ₂ CH (OH) CH ₂ OH, HOCH ₂ CH (OH) CH ₂ OCH ₂ CF ₂ CF ₂ CF ₂ O (CF ₂ O) ₂ (CF ₂ CF ₂ CF ₂ CF ₂ ) ₁₅ OCH ₂ CH (OH) CH ₂ OH, HOCH ₂ CH (OH) CH ₂ OCH ₂ CF ₂ CF ₂ CF ₂ O (CF ₂ O) ₂ (CF ₂ CF ₂ CF ₂ CF ₂ ) _{20 OCH 2 CH (OH) CH 2} OH, HOCH 2 (CH (OH) CH 2 O) 2 CH 2 CF 2 CF 2 CF 2 O (CF 2 O) 2 (CF 2 CF 2 CF 2 CF 2) 2 OCH 2 _{CH (OH) CH 2 OH,} HOCH 2 (CH (OH) CH 2 O) 2 CH 2 CF 2 CF 2 CF 2 O (CF 2 O) 2 (CF 2 CF 2 CF 2 CF 2) _{OCH 2 CH (OH) CH 2} OH, HOCH 2 (CH (OH) CH 2 O) 2 CH 2 CF 2 CF 2 CF 2 O (CF 2 O) 2 (CF 2 CF 2 CF 2 CF 2) 4 OCH 2 CH (OH) CH ₂ OH, HOCH ₂ (CH (OH) CH ₂ O) ₂ CH ₂ CF ₂ CF ₂ CF ₂ O (CF ₂ O) ₂ (CF ₂ CF ₂ CF ₂ CF ₂ ) ₅ OCH ₂ CH ( OH) CH ₂ OH and the like, and a mixture of two or more of these compounds may be used.

The content of the fluorinated alcohol compound with respect to the base resin is preferably 0.001 ppm or more and 100 ppm or less, more preferably 0.005 ppm or more and 50 ppm or less, and particularly preferably 0.01 ppm or more and 10 ppm or less by mass ratio. It is. Even if the fluorine-containing alcohol compound is added in excess of the above upper limit, there is a tendency that the effect is not further improved.

As the base resin material, any of solvent dilution type, thermosetting type, and ultraviolet curable type resins can be used.

The solvent dilution type resin means a resin in which the precursor of the coating film is not chemically changed even after the coating is formed. The thermosetting resin means that the precursor of the coating is cured by heat. The term “resin” refers to a resin in which the precursor of the coating is cured by ultraviolet rays. These resins are exemplified below, but the present invention is not limited thereby.

Solvent-diluted resin: The base resin solid component, which is the main component for forming a film, and the fluorinated alcohol compound are dissolved in advance, and the film can be formed by applying to a substrate and evaporating the solvent. Examples of the solid content used in the solvent dilution type include acrylic resin, epoxy resin, PC (polycarbonate), TAC (triacetyl cellulose), PET (polyethylene terephthalate), PVA (polyvinyl alcohol), PVB (polyvinyl butyral), and PEI. (Polyetherimide), polyester, EVA (ethylene-vinyl acetate copolymer), PCV (polyvinyl chloride), PI (polyimide), PA (polyamide), PU (polyurethane), PE (polyethylene), PP (polypropylene), PS (Polystyrene), PAN (polyacrylonitrile), butyral resin, ABS (acrylonitrile-butadiene-styrene copolymer); PVF (polyvinyl fluoride), PTFE (polytetrafluoroethylene (tetrafluoroethylene) ), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoropropylene copolymer (4.6 fluoride)), ETFE (tetrafluoroethylene / ethylene copolymer), PVDF (polyvinylidene fluoride) (Difluoride)), PCTFE (polychlorotrifluoroethylene (trifluoride)), ECTFE (chlorotrifluoroethylene-ethylene copolymer) and other fluororesins; silicone resins, etc., one or more of these It can be used by mixing. Among them, PVF (polyvinyl fluoride), PTFE (polytetrafluoroethylene (tetrafluoroethylene)), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoropropylene copolymer (4.6) Fluoride)), ETFE (tetrafluoroethylene / ethylene copolymer), PVDF (polyvinylidene fluoride (difluoride)), PCTFE (polychlorotrifluoroethylene (trifluoride)), ECTFE (chlorotrifluoroethylene / ethylene copolymer) ) And other fluorine-based resins are excellent in water repellency, and are excellent in the characteristics described above. Among these fluororesins, ETFE (ethylene-tetrafluoroethylene copolymer) and PVF (polyvinyl fluoride) are preferable. Further, when used for a translucent substrate, an amorphous fluororesin (amorphous fluoropolymer) is also preferable. On the other hand, even when other resins are used, a certain degree of effect can be obtained, so that these can be used depending on the use conditions. Furthermore, the resin composition etc. which provided active energy ray curability, such as the following thermosetting or ultraviolet rays, etc. can be used for these.

Thermosetting resin: The base resin solids, the main component of the film, and the fluorinated alcohol-based compound are dissolved in advance. After the solvent is evaporated on the substrate, the coated surface is heated above room temperature. A film can be obtained. Examples of the solid content used in the thermosetting type include polymers such as epoxy resins, melamine resins, urea resins, urethane resins, and polyimide resins, and fluororesins, silazane resins, and silicone resins. Two or more kinds can be mixed and used.

Examples of the thermal initiator include azo compounds such as AIBN (azobisisobutyronitrile) and dimethyl-2,2′-azobis (2-methylpropionate), ketone peroxide, peroxyketal, hydroperoxide, Compounds such as diallyl peroxide, diacyl peroxide, peroxyester, peroxycarbonate or derivatives thereof are preferred, and commercially available products such as Parroyl O, Parroyl L, Parroyl S, Paroctyl O, Parroyl SA, Perhexa manufactured by NOF CORPORATION 250, perhexyl O, niper PMB, perbutyl O, niper BMT, niper BW, perbutyl IB, perhexa MC, perhexa TMH, perhexa HC, perhexa C, pertetra A, perhexyl I, perbutyl MA, perbutyl 3 5, Perbutyl L, Perhexa 25 mT, Perbutyl I, Perbutyl E, Perhexyl Z, Perhexa V, Perbutyl P, Percumyl D, PERHEXYL D, Perhexa 25B, Perbutyl D, Pamenta H, etc. Pahekishin 25B is used.

UV curable resin: The base resin solids, which is the main component of the film, and the fluorine-containing alcohol compound are dissolved in advance, and after applying to the substrate and evaporating the solvent, the application surface is irradiated with UV. A cured film is formed to obtain the desired module. Examples of the solid content used in the ultraviolet curable type include silicone resins, acrylic resins, unsaturated polyester resins, epoxy resins, fluororesins, oxetane resins, and polyvinyl ether resins. Use one or more of these. Can do.

Examples of the photopolymerization initiator include IRGACURE 651, IRGACURE 184, DAROCUR 1173, IRGACURE 2959, IRGACURE 127, IIRGACURE 907, IIRGACURE 369, IIRGACURE 379, DAROCURE TPO, IRGACURE 819, IRGACURE 819, IRGACURE 819, IRGACURE 819, IRGACURE 819, IRGACURE 819 Lucirin TPO and Lucirin TPO-L can be used alone or in admixture of two or more.

In order to promote photocuring, for example, a ketone compound such as benzophenone, a dye such as rose bengal, or a conjugated compound such as fluorene, pyrene, or fullerene is used as a photosensitizer, and the mass ratio to the photoinitiator is 0. 0.05 to 3 times the amount can be used with the photoinitiator.

In light curing, high pressure mercury lamp, constant pressure mercury lamp, thallium lamp, indium lamp, metal halide lamp, xenon lamp, ultraviolet LED, blue LED, white LED, excimer lamp manufactured by Harrison Toshiba Lighting, H valve manufactured by Fusion, H plus valve In addition to light emitted from the D bulb, V bulb, Q bulb, M bulb, etc., it is also possible to use sunlight. In addition, as a method of curing in the absence of oxygen, there is a case where the curing is performed in an atmosphere of nitrogen gas, carbon dioxide gas, helium gas or the like.

Further, in the photocuring, ultraviolet rays of 200 to 400 nm are preferably irradiated in the range of 0.1 to 1000 mJ / cm ² . Moreover, it is more preferable to irradiate the energy ray active for curing by dividing it into a plurality of times. That is, when the first irradiation is performed for about 1/20 to 1/3 of the total irradiation amount and the necessary remaining amount is irradiated for the second and subsequent times, a cured product having smaller birefringence can be obtained. The irradiation time can be appropriately adjusted according to the amount of resin and the degree of curing, and is usually adjusted between about 1 second and 10 minutes.

Base resins that can be used for the water slidable coating material of the present invention are commercially available products such as Teflon (registered trademark) AF series (DuPont), Tedlar series (DuPont), Fullon series (Asahi Glass), Saipan. Top (manufactured by Asahi Glass Co., Ltd.), Hyflon series (manufactured by Solvay Solexis), THV series (manufactured by Sumitomo 3M), Neoflon series (manufactured by Daikin Industries), Opt-Ace (manufactured by Daikin Industries), Kainer series (Arkema) ), Dyneon series (Dyneon), Marvell Coat (Mitsubishi Gas Chemical), F Top Series (Mitsubishi Materials Electronics), SFC (AGC Seikagaku), etc. It can be used alone or in combination of two or more.

The photopolymerization initiator or thermal polymerization initiator used as necessary during curing is used in the range of 0.001 to 30% by mass with respect to the total content of the base resin and the fluorinated alcohol compound. Is recommended, and it is preferably used in the range of 0.01 to 20% by mass, more preferably 0.1 to 10% by mass.

The solvent in which the solid content used as a solvent dilution type, thermosetting type, or ultraviolet curable type and the fluorinated alcohol compound are dissolved in advance is particularly a solvent that can dissolve or disperse the solid content. It is not limited. Specifically, CF ₃ CH ₂ OH, F (CF ₂ ) ₂ CH ₂ OH, (CF ₃ ) ₂ CHOH, F (CF ₂ ) ₃ CH ₂ OH, F (CF ₂ ) ₄ C ₂ H ₅ OH, Fluorine alcohol solvents such as H (CF ₂ ) ₂ CH ₂ OH, H (CF ₂ ) ₃ CH ₂ OH, H (CF ₂ ) ₄ CH ₂ OH, and fluorine-containing fragrances such as perfluorobenzene and meta-xylene hexafluoride Group solvents, CF ₄ (HFC-14), CHClF ₂ (HCFC-22), CHF ₃ (HFC-23), CH ₂ CF ₂ (HFC-32), CF ₃ CF ₃ (PFC-116), CF ₂ ClCFCl ₂ (CFC-113), C ₃ HClF ₅ (HCFC-225), CH ₂ FCF ₃ (HFC-134a), CH ₃ CF ₃ (HFC-143a), CH ₃ CHF ₂ (HFC-152a), CH ₃ CCl ₂ F (HC _{C-141b), CH 3 CClF} 2 (HCFC-142b), such as a fluorocarbon-based solvent such as _{C 4 F 8 (PFC-C318} ) are exemplified. The dilution rate may be adjusted to an optimum dilution rate depending on the resin and solvent to be used, the thickness of the coating film to be formed, and the drying conditions. Usually, for film formation, the solid component is adjusted to 30 to 0.05% by mass in the adjusted solvent.

Further, for example, xylene, toluene, Solvesso 100, Solvesso 150, hydrocarbon solvents such as hexane, methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, Ester solvents such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol acetate, diethylene glycol acetate, dimethyl ether, diethyl ether, dibutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono Butyl ether, ethylene glycol dimethyl ether , Ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, tetrahydrofuran and other ether solvents, methyl ethyl ketone, methyl isobutyl ketone, acetone Ketone solvents such as N, N-dimethylacetamide, N-methylacetamide, acetamide, N, N-dimethylformamide, N, N-diethylformamide, amide solvents such as N-methylformamide, and sulfonic acids such as dimethylsulfoxide Ester solvent, methanol, ethanol , Isopropanol, butanol, ethylene glycol, diethylene glycol, polyethylene glycol (polymerization degree 3 to 100) are exemplified, can be used as a mixture thereof alone, or two or more kinds.

Of these, the various alcohol solvents, fluorine solvents, ketone solvents, and ester solvents are preferred from the viewpoint of solubility, coating film appearance, and storage stability, and in particular, methanol, ethanol, isopropanol, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, cellosolve acetate, butyl acetate, ethyl acetate, perfluorobenzene, metaxylene hexafluoride, HCFC-142b, HCFC-225, CFC-113, HFC-134a, HFC-143a, HFC-142b alone Or it is preferable to mix and use 2 or more types.

Furthermore, when forming a coating on a structural member, if there is a gap between the substrates, the coating may be formed in the gaps between these substrates. Specifically, a technique of soaking the solution of the coating component is effective, and it is preferable to use a solvent dilution type or a thermosetting type for the solid content provided to the coating at that time.

Further, in the present invention, fumed silica may be added in addition to the above components. By containing fumed silica, durability such as scratch resistance of the obtained thin film is improved. The fumed silica that can be used in the present invention preferably has an average primary particle size of 1 to 100 nm and a specific surface area of 10 to 1000 m ² / g, more preferably an average primary particle size of 3 to 50 nm, The specific surface area is 40 to 400 m ² / g. Specifically, if it is fumed silica manufactured by Evonik Group, use 200, 300, R202, R805, R812, R812S, RX200, RY200, R972, R972CF, 90G, 200V, 200CF, 200FAD, 300CF, etc. Can do. Such fumed silica is preferably added in the range of 0.01 to 10% by mass relative to the total amount of the composition. In addition to fumed silica, particulate titania, zirconia, alumina, silica-alumina and the like may be used alone or in admixture of two or more.

Furthermore, in the present invention, in addition to the above components, an alkoxysilane containing a fluoroalkyl group having 1 to 10 carbon atoms, preferably 2 to 6 carbon atoms may be added. For example, CF ₃ (CH ₂ ) ₉ Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₈ Si (OCH ₂ CH ₃ ) ₃ , CF ₃ (CH ₂ ) ₇ Si (OCH ₃ ) ₃ , (CF ₃ ) ₂ CHSi (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ CH ₂ Si (OCH ₃ ) ₃ , (CF ₃ ) ₂ CHSi (OCH ₂ CH ₃ ) ₃ , CF ₃ (CH ₂ ) ₆ Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₅ Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₄ Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₃ Si (OCH ₃ ) ₃ , CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ Si (OCH ₃ ) ₃ , CH ₃ (CF ₂ ) ₇ Si (OCH ₃ ) ₃ , CH ₃ CF ₂ (CH _{2) 7 Si (OCH 3)} 3, CH 3 CF 2 (CH 2) 6 Si (OCH 3) 3, CF 3 (CH 2) 6 Si (OCH (C _{3) 2) 3,} etc. may be mixed singly or two or a.

The content of these alkoxysilane compounds may be added so that the total amount of fluorine atoms contained in the resin material excluding the solvent component is at least 5% by mass, more preferably 10% by mass, and still more preferably 30%. What is necessary is just to add so that it may become mass% or more. The upper limit is not particularly restricted, but if it is too much, there may be an adverse effect on light transmission and adhesion to the substrate, so fluorine atoms derived from all compounds contained in the coating resin material Should be added so that the total amount of is 40% by mass or less.

In the present invention, the above resin materials, an organic solvent, and, if necessary, a photopolymerization initiator or a thermal polymerization initiator are mixed, and a resin composition solution is adjusted to obtain a coating solution for forming a film. An antireflection film can be formed by applying the resin composition solution onto the surface of a member and curing it by irradiation with radiation energy such as light or heating.

When applying solvent-diluted, thermosetting, or UV-curable solids, the above solution is soaked in cloth or paper, etc. A method can be selected. Specifically, printing methods such as screen printing, gravure coating method, reverse coating method, bar coating method, spray coating method, knife coating method, roll coating method, die coating method, etc. can be used. (Flow coating), spin coating method, CVD method, mist-CVD method and the like may be used, and a coating film can be obtained by selecting an optimum one from these methods to form a coating film.

The film thickness of the coating film to be formed is not particularly restricted and may be about the same as that of a coating film formed from a normal resin material. Specifically, it may be about 1 to 500 μm. It is also possible to adjust to the desired physical properties by adjusting the film thickness of the coat layer. What is necessary is just to adjust the solid content concentration of the composition solution for application | coating so that it may become a desired film thickness with the specific instrument and apparatus to be used, the viscosity of a solution, the speed | rate of a spinner, time permitted for application | coating, etc.

<Water contact angle>
As the contact angle of the coating film with water in the present invention is larger, the water repellency is improved, the substrate can be prevented from being wetted, and the initial performance can be maintained for a long time even outdoors. Moreover, the dirt adhering to the substrate can be easily removed. The contact angle can be measured with a contact angle meter. The preferable range of the water contact angle of the coating is less likely to be wet and less likely to spread if the contact angle is 70 ° or more. Preferably, the measurement temperature and the measurement humidity are 20 ° C. to 50 ° C. and 20% RH to 50% RH. And greater than 75 degrees and less than 180 degrees, more preferably greater than 80 degrees and less than 150 degrees, and even more preferably greater than 80 degrees and less than 140 degrees.

Measure the contact angle using the 1 / 2θ method. That is, the solid-liquid interface / horizontal line and the tangent line at the edge of the droplet, and the angle formed by these two lines is θA (contact angle). Assuming that the angle formed by the two lines is θB (measurement angle), the contact angle is obtained because the measurement angle is ½ of the contact angle.

<Water sliding (falling) angle>
In the present invention, the smaller the sliding (falling) angle of the film with respect to water, the better the water repellency and the superior water repellency, and the initial performance can be maintained outdoors for a long time. The sliding angle can be measured with a sliding angle meter. For example, the coating surface of each member is kept horizontal and water droplets are adhered, and the coating surface is tilted little by little and the angle with respect to the horizontal where the water droplet slides is measured. In the present invention, the preferred sliding angle is 0.5 degree or more and less than 70 degree, more preferably 0.5 degree or more and 60 degree or less, particularly 1 degree or more and 55 degree or less.

<Water sliding (falling) speed>
As the sliding (falling) speed of the water adhering to the coating film in the present invention increases, the water repellency improves and the wetting of the substrate can be prevented, and the initial performance can be maintained for a long time outdoors. The sliding speed can be measured with a sliding speed meter. For example, water droplets are adhered in a horizontal state without tilting the coating surface of each member, and the coating surface is tilted little by little and the angle with respect to the horizontal where the water droplet slides and the speed of the water droplet at that time are measured. As a preferred sliding speed, when the angle at which the coating surface is inclined is 20 to 60 degrees with respect to the horizontal, the speed at which the water drops slide is 0.3 mm / s or more, more preferably 0.4 mm / s or more and 1 m. / s or less, particularly preferably 0.5 mm / s or more, and the upper limit thereof is 1 m / s or less although not particularly restricted. The water droplet used for the measurement is preferably about 3 μL to 30 μL. The sliding speed of the water can be obtained by photographing the falling water drop with a high-speed camera. For example, the moving distance from the start of sliding down to an arbitrary time, specifically after 1 second (after 1000 milliseconds), may be measured and obtained from the slope of the time versus distance. At this time, the tracer particles may be mixed in the water droplets and the tracer may be measured.

<Refractive index>
When the refractive index of the coating itself applied to the substrate in the present invention is the same as that of the transparent substrate member that is a structural member, the appearance when the coating is applied can maintain the same state as before applying the coating. In addition, when the refractive index of the coating is smaller than the refractive index of the base material, the reflection (shine) of the member by external light is suppressed due to the antireflection effect, and a high-class feeling is increased, or the effect of increasing the incident light and improving the internal illuminance Can be expected.

<Light transmittance>
When the light transmittance of the coating itself in the present invention is the same as that of a transparent substrate member, the appearance when the coating is applied can maintain the same state as before applying the coating. Moreover, when the light transmittance of a film is larger than a base material, the transparency of a base material surface improves and the calm appearance is obtained, The effect which increases incident light and increases internal illumination can be expected.

<Base material>
Examples of the material of the substrate used in the present invention include metal, glass, and plastic. For example, aluminum, stainless steel, glass, polycarbonate, acrylic, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyimide (PI). Such materials are used. Examples include polytetrafluoroethylene, polyvinyl fluoride (PVF), polyethylene terephthalate (PET), polyethylene (PE), polypropylene (PP), polyethylene-propylene (EP,) acrylonitrile-butadiene-styrene copolymer (ABS), etc. The A structure formed using one or more of these materials serves as a base material, and a water-repellent coating material film is formed on the surface thereof, thereby imparting water repellency to the structure.

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

[Example 1]
A compound represented by the following formula (2) having a molecular weight of about 700 g / mol as a fluorine-containing alcohol compound was dispersed in Teflon (registered trademark) AF1601S so that the content relative to the base resin solid content (AF1600) was 1 ppm. A glass plate (Schott B270, size 100 mm × 100 mm, thickness 1 mm: each of the following examples, so that the cloth is soaked and the thickness of the coating is about 0.02 to 0.2 μm, The same was applied to the comparative example) and then allowed to stand at room temperature and dried to obtain a coating film for evaluation. Moreover, the excessive dry matter by the component which did not participate in formation of a coat film during coating could be easily removed by dry wiping.

The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH), sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of this coating film for evaluation were measured. They were 103.3 degrees, 13.7 degrees, and 2.1 mm / s, respectively. The sliding speed of any water droplet was determined by measuring the moving distance from the start of sliding down to 1 second (1000 milliseconds later) and the slope.

[Comparative Example 1]
In Example 1, except that the compound represented by the formula (2) was not added, the solution obtained in the same manner as in Example 1 was soaked into a cloth, and the thickness of the film was about 0.02 to 0.2 μm. After coating on a glass plate (Schott B270, size 100 mm × 100 mm, thickness 1 mm), it was allowed to stand at room temperature and dried to obtain a coating film for evaluation. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH), sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of this coating film for evaluation were measured. They were 104.3 degrees, 14.8 degrees, and 0.20 mm / s, respectively.

[Comparative Example 2]
1,7-bis (2,2-diacryloxymethyl-butyloxy) -2,2,3,4,4,5,6,6,8,8,9,9,10,10-tetradecafluoro- Adamantane: 1 g, AIBN (2,2′-azobisisobutyronitrile): 50 mg, methyl isobutyl ketone: 40 g, Nippon Kayaku DPHA: 500 mg was put into a 100 mL flask to dissolve each component. The interior was purged with nitrogen and stirred at 50 ° C. for 30 minutes to obtain a coating solution.

Next, the obtained solution was soaked into a cloth, applied in the same manner as in Example 1, and then allowed to stand at room temperature and dried to obtain a coating film for evaluation. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH), sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of this coating film for evaluation were measured. They were 100.5 degrees, 5.7 degrees, and 0.28 mm / s, respectively.

[Example 2]
Teflon (registered trademark) so that the content of the compound represented by the following formula (3) having a molecular weight of about 700 g / mol as a fluorine-containing alcohol compound with respect to the base resin solid content (AF1600) is 2 ppm by mass ratio (hereinafter the same). ) Dispersed in AF1601S. A glass plate (Schott B270, size 100 mm × 100 mm, thickness 1 mm: each of the following examples, so that the cloth is soaked and the thickness of the coating is about 0.02 to 0.2 μm, The same was applied to the comparative example) and then allowed to stand at room temperature and dried to obtain a coating film for evaluation. In addition, it was confirmed that excess dry solids due to components that were not involved in the formation of the coat film during coating could be easily removed by dry wiping.

The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH), sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of this coating film for evaluation were measured. They were 103.2 degrees, 12.5 degrees, and 5.4 mm / s, respectively.

Example 3
In Example 1, except that the concentration of the compound represented by the formula (2) was changed to 2, 3, and 4 ppm, each of the coating film samples for evaluation 3-2, Sample 3-3, Sample 3-4 was created. The sample of Example 1 was Sample 3-1. A sample 2-1 in which the content of the formula (3) in Example 2 was 2 ppm was also prepared. Furthermore, as the comparative sample 1 and the comparative sample 2, the coating film samples for evaluation obtained in Comparative Example 1 and Comparative Example 2 were prepared. Moreover, it confirmed that the excessive dry matter by the component which was not concerned in formation of a coat film during coating in each Example sample can be easily removed by dry wiping. On the other hand, since all of the comparative sample samples could not be removed easily by wiping with dry wiping, they were removed using the solvent used for adjusting the coating solution.

The results of measuring the water sliding (falling) speed (measured at a water droplet amount of 15 μL, room temperature of 20 ° C., humidity of 40% RH) when the obtained base material of each evaluation sample is inclined at 30 ° are shown in FIG. It is shown in 1. The Y axis in FIG. 1 is the moving distance (millimeter) of the leading end of the water droplet, and the X axis is the elapsed time (millisecond). The sliding (falling) speed was obtained from the averaged inclination. From the results obtained, the effect was also observed in sample 3-1 obtained in Example 1, but samples 3-2 to 3 in which the concentration of the compound represented by formula (2) was increased to 2, 3, and 4 ppm were obtained. In 3-4, the sliding speed is increased in proportion to the concentration of the compound. Furthermore, it was found that Sample 2-2 obtained in Example 2 further improved the water sliding effect.

Example 4
A coating film for evaluation was obtained in the same manner as in Example 1 except that the compound represented by the formula (2) in Example 1 had a molecular weight of about 1200 g / mol. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH), sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of this coating film for evaluation were measured. They were 102.1 degrees, 11.5 degrees, and 12.3 mm / s, respectively.

Example 5
A coating film for evaluation was obtained in the same manner as in Example 1 except that the compound represented by the formula (2) in Example 1 had a molecular weight of about 1500 g / mol. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH), sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of this coating film for evaluation were measured. They were 103.7 degrees, 10.5 degrees, and 15.1 mm / s, respectively.

Example 6
A compound represented by the formula (2) in Example 1 was made to have a molecular weight of about 700 g / mol, and 1 ppm of this was dispersed in a manner similar to Example 1 using a 4% by mass polymethylmethacrylate butyl acetate solution. A coating film for evaluation was obtained. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH), sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of the coating film for evaluation are 103.2 ° each. 12.7 degrees and 3.1 mm / s.

Example 7
The compound represented by the formula (2) of Example 1 was made to have a molecular weight of about 700 g / mol, and 1 ppm of this was dispersed in a similar manner as in Example 1 using a 4 mass% PS (polystyrene) tetrahydrofuran solution. A coating film for evaluation was obtained. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH), sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of this evaluation coating film 94.2 ° each. 21.7 degrees and 1.3 mm / s.

[Comparative Example 3]
A coating film for evaluation was obtained in the same manner as in Example 1 except that a 4 mass% PS (polystyrene) tetrahydrofuran solution was not added and the compound represented by the formula (2) was not added. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH), sliding speed (slope angle 50 °, 25 ° C., 40% RH) of the coating film for evaluation are 85.2 ° each. It was 42.1 degrees and 0.02 mm / s.

Example 8
A compound represented by the formula (2) in Example 1 having a molecular weight of about 700 g / mol and dispersed in 1 ppm was used in the same manner as in Example 1 by using a 4 mass% PU (polyurethane) tetrahydrofuran solution. A coating film for evaluation was obtained. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH) and sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of this coating film for evaluation were 93.2 ° each. 21.7 degrees and 3.3 mm / s.

[Comparative Example 4]
A coating film for evaluation was obtained in the same manner as in Example 1 except that a 4 mass% PU (polyurethane) tetrahydrofuran solution was not added and the compound represented by the formula (2) was not added. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH), sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of this coating film for evaluation are 79.2 degrees. 49.1 degrees and 0.011 mm / s.

Example 9
A compound represented by the formula (2) in Example 1 was made to have a molecular weight of about 700 g / mol, and 1 ppm of this was dispersed in a 4 mass% PE (polyethylene) tetrahydrofuran solution in the same manner as in Example 1. A coating film for evaluation was obtained. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH), sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of this coating film for evaluation are 90.2 ° each. 26.7 degrees and 2.3 mm / s.

[Comparative Example 5]
A coating film for evaluation was obtained in the same manner as in Example 1 except that a 4 mass% PE (polyethylene) tetrahydrofuran solution was not added and the compound represented by the formula (2) was not added. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH) and sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of the coating film for evaluation are 89.2 ° each. 45.1 degrees and 0.015 mm / s.

Example 10
A compound represented by the formula (2) in Example 1 having a molecular weight of about 700 g / mol and dispersed in 1 ppm was used in the same manner as in Example 1 by using a 4 mass% PP (polypropylene) tetrahydrofuran solution. A coating film for evaluation was obtained. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH), sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of the coating film for evaluation are 95.2 ° each. 23.7 degrees and 2.4 mm / s.

[Comparative Example 6]
A coating film for evaluation was obtained in the same manner as in Example 1 except that a 4 mass% PP (polypropylene) tetrahydrofuran solution was not added and the compound represented by formula (2) was not added. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH), sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of this coating film for evaluation are 92.2 ° each. It was 40.1 degrees and 0.02 mm / s.

Example 11
Using a tetrahydrofuran solution of 4% by mass EVA (ethylene-vinyl acetate copolymer) in which the compound represented by the formula (2) in Example 1 has a molecular weight of about 700 g / mol and 1 ppm is dispersed, Example 1 and A coating film for evaluation was obtained in the same manner. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH) and sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of this coating film for evaluation are 55.2 ° each. 52.7 degrees and 0.4 mm / s.

[Comparative Example 7]
A coating film for evaluation was obtained in the same manner as in Example 1 except that a 4 mass% EVA (ethylene-vinyl acetate copolymer) tetrahydrofuran solution was used and the compound represented by the formula (2) was not added. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH) and sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of this evaluation coating film are 42.2 ° each. 60.1 degrees and 0.001 mm / s.

Example 12
Similar to Example 1 using a 4 mass% ethyl acetate solution of PDMS (dimethylpolysiloxane) in which the compound represented by formula (2) in Example 1 had a molecular weight of about 700 g / mol and 1 ppm was dispersed. A coating film for evaluation was obtained by various methods. The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH), sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of the coating film for evaluation were 110.1 ° each. 22.7 degrees and 2.4 mm / s.

[Comparative Example 8]
A coating film for evaluation was obtained in the same manner as in Example 1 except that a compound represented by the formula (2) was not added using a 4 mass% ethyl acetate solution of PDMS (dimethylpolysiloxane). The water contact angle (25 ° C., 40% RH), sliding angle (25 ° C., 40% RH), sliding speed (inclination angle 50 °, 25 ° C., 40% RH) of the coating film for evaluation are 102.2 ° each. 28.1 degrees and 1.1 mm / s.

As can be seen from the above examples, when the compound of the present invention was added, all the base resins used were improved in water repellency properties such as water contact angle, sliding angle, and sliding speed. In particular, it has also been found that the properties of fluorine-based resins and silicone resins are excellent.

By coating at room temperature with a neutral coating solution, it is possible to form a film with excellent lubricity, and it is possible to easily remove excess dry matter due to components that did not participate in the film formation by dry wiping is there. For this reason, as a resin or metal or glass surface such as plastic, for example, automobile window glass, automobile paint surface, automobile light cover, building window, kitchen equipment, kitchenware, exhaust device attached to kitchen equipment, Surface treatment materials that can be used for a wide range of applications such as bathing facilities, wash facilities, medical facilities, medical equipment, mirrors, eyeglasses, inkjet printer parts, and electronic circuit boards can be provided at low cost, which is industrially useful.

Claims (11)

A water-slidable coating material that contains one or more base resins and a fluorine-containing alcohol-based compound containing two or more OH groups to form a coating film. The water-slidable coating material according to claim 1, wherein the fluorine-containing alcohol compound is represented by the following formula (1).

(In Formula (1), R ¹ and R ^{1 ′} are OH groups or CH ² OH groups, R ² and R ^{2 ′} are 0 to 3 OH groups and 0 or 1 or more F atoms. ~ 5 alkyleneoxy groups, R ³ and R ^{3 '} contain one or more F and carbon chains of 1 to 5 carbon atoms, R ⁴ contains one or more F and carbon atoms of 1 to 10 carbon atoms The chains i and i ′ are integers of 0 to 5 which may be the same or different, j and j ′ may be natural numbers of 1 to 5 and may be the same or different, and k is an integer of 0 to 20 is there.) The water-slidable coating material according to claim 1 or 2, wherein the fluorine-containing alcohol compound has a molecular weight of 500 g / mol to 2000 g / mol. In the formula (1), R ¹ and R ^{1 ′} are OH groups, R ² and R ^{2 ′} contain 1 to 3 OH groups and contain 0 or 1 or more F 1 carbon atoms Or 4 alkyleneoxy groups, R ³ and R ^{3 ′} are carbon chains of 2 to 10 F and 1 to 5 carbon atoms, R ⁴ contains 2 to 10 F and 1 carbon atoms The water-slidable coating material according to any one of claims 1 to 3, which has -10 carbon chains and k is an integer of 1-15. The water-slidable coating material according to any one of claims 1 to 4, wherein the base resin contains fluorine or is a fluorine-based resin. The fluororesin is PVF (polyvinyl fluoride), PTFE (polytetrafluoroethylene (tetrafluoroethylene)), PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene / hexafluoropropylene copolymer (4. Hexafluoride)), ETFE (tetrafluoroethylene / ethylene copolymer), PVDF (polyvinylidene fluoride (difluoride)), PCTFE (polychlorotrifluoroethylene (trifluoride)), ECTFE (chlorotrifluoroethylene / ethylene) The water-slidable coating material according to any one of claims 1 to 5, which is a copolymer). The water-slidable coating material according to any one of claims 1 to 6, wherein the content of the fluorine-containing alcohol compound relative to the base resin is 0.001 ppm or more and 100 ppm or less. The water slidable coating material according to any one of claims 1 to 7, wherein a sliding speed of a water droplet is 0.3 mm / s or more when the formed coating surface is inclined by 30 degrees with respect to a horizontal plane. The water-slidable coating material according to any one of claims 1 to 8, wherein the water contact angle of the formed coating surface is 70 degrees or more. The water-slidable coating material according to any one of claims 1 to 9, wherein the water sliding angle of the formed coating surface is less than 70 degrees. The water-slidable coating material according to any one of claims 1 to 10, wherein a coating film is formed on the surface of a base material made of plastic, metal or glass.

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